Construction of a New Perbromate-Selective Electrode. Kinetic Study of the Iron(II)- Perbromate Reaction and Microdetermination of Iron

Abstract

A perbromate- selective membrane electrode with a liquid membrane of crystal violet-perbromate dissolved in chlorobenzene is described, The liquid membrane electrode exhibits rapid and near Nernstian response to perbromate activity from 10^?5 to 10^?2 M. The response is unaffected by pH in the range 2–10, Major interferences are periodate and perchlorate. A kinetic study of the iron(II)- perbromate reaction was carried out with the perbromate electrode, A potentiometric method is described for the determination of 50–500 μg of iron (II) with relative errors and standard deviations of 1–2%.     

Development and analytical applications of a new liquid-membrane 3,5-dinitrosalicylate-selective electrode

A 3,5-dinitrosalicylate (DNS)-selective electrode with a liquid membrane of either tetraphenyIphosphonium-DNSH dissolved in p-nitrocumene or dimethyldioctadecylammonium-DNSH dissolved in 1-decanol is described. The liquid membrane electrode exhibits rapid and near-Nemstian response to DNSH- activity from 10^-2 to 10^-5 M. The response is unaffected by pH in the range 2.5–6.5. The electrode has been successfully applied in the direct potentiometric titration of iron(III) and copper(II) with EDTA and in the indirect titrimetric determination of aluminium(III) and nickel(II). It is also useful in titrations of bulky quaternary cations such as cetyltrimethylammonium, cetylpyridinium and didodecyldimethylamnionium ions with DNSHNa.     

Potentiometric determination of nicotine in tobacco products with a nicotine-sensitive liquid membrane electrode

A simple potentiometric method with standard additions is described for the rapid determination of nicotine in tobacco products. A nicotine-sensitive electrode with a liquid membrane of nicotine hydrogen tetra(m-chlorophenyl)borate dissolved in o-nitrotoluene is used. The electrode exhibits near-Nernstian response to monoprotonated nicotine cation activity from 0.08 to 10^-5 M, in the pH range 4–7. Nicotine down to 2 mg per g of sample can be determined with a standard deviation of about 0.5 mg of nicotine. Comparison with an official method gave satisfactory results.     

Construction,assessment and applications of a dichromate-selective liquid membrane electrode based on tetrapentylammonium dichromate

A dichromate-selective liquid-membrane electrode based on tetrapentylammonium dichromate dissolved in 2-nitrotoluene is described. The electrode exhibits rapid and linear response to the activity of Cr(VI) anions in the range 5 × 10^?4–2 × 10.2 M dichromate; the slopes of the calibration graphs depend on the acidity. The electrode is useful for end-point indication in titrations of iron(II), arsenic(III), ascorbic acid, thiobarbituric acid, thiourea, and cysteine with dichromate. The electrode is also used as indicator electrode in a potentiometric reaction-rate method for the determination of hydroxyl-containing organic compounds, based on their oxidation by dichromate in acidic solution; ethanol, isopropanol, ethylene glycol, propylene glycol, butylene glycol, and several carbohydrates were determined with a mean error of 1%. The method is applied to determine the ethanol content of alcoholic beverages. Kinetic data are given for the dichromate/ethanol reaction.     

Kinetic study of the tartaric acid-periodate reaction: Determination of tartaric acid using an improved periodate-selective electrode

The preparation of an improved liquid-membrane periodate-selective electrode is described. The electrode exhibits rapid and near-Nernstian response in the range 2 × 10⁻⁶-10⁻² M. The electrode was used to monitor the course of the tartaric acid-periodate reaction. A potentiometric reaction rate method for the rapid and accurate determination of tartaric acid has been developed. A total of 0.4–120 μmol of tartaric acid has been determined with relative error of about 2.0%. The method has been applied to the determination of tartaric acid in pharmaceutical preparations and to the determination of small amounts of tartaric acid in impure citric acid.     

Electro-Catalytic Oxidation of Ascorbic Acid at a Cobalt-Salen Polymer Modified Electrode and Analytical Applications

ABSTRACT

The preparation and electrochemical characteristics of electrodes modified by cobalt complexes of N, N' - bis(salicylidene)-ethane -1, 2- diamine (salen) are described. A cobalt-salen polymer film modified electrode has strong electro-catalytic effects for the oxidation of ascorbic acid. The anodic peak potential of ascorbic acid shifted negatively for 400 m V. The catalytic reaction rate constant determined by rotating disk experiments is 7.08×10⁵ mol s^?1 cm^3. The catalytic mechanism and the effect of film thickness are discussed. A sensitive voltammetric response for ascorbic acid was obtained covering a linear range from 1.0×10^?6 to 1.0×10^?3 mol-L^?1 The modified electrode showed good stability and reproducibility. The electrode was used to the determination of ascorbic acid in fruit juices and showed promising results compared with conventional methods. The electro-catalytic effect of several metal-salen complexes and a similar Schiff base derivative for ascorbic acid was compared.     

Kinetic determination of ascorbic acid by the 2,6-dichlorophenolindophenol reaction with a stopped-flow technique.

The reaction of ascorbic acid with 2.6-dichlorophenolindophenol is applied for the kinetic determination of ascorbic acid in 0.05M oxalic acid. Stopped-flow techniques are used; the concentrations of the reactants of the second-order reaction can be adjusted so that the transmittance signal remains nearly invariant for a wide range of voltage. Theoretical and experimental results are in very good agreement. Analytical working curves are presented for the determination of ascorbic acid in the ranges 5.0·10^-4–1.0·10^-2M and 5.0·10^-5–1.0-·10^-3M with errors of 1.0% and 2.2%. respectively. The method is simple, fast and sensitive.     

Direct potentiometric titration of thiosulfate,thiourea, and ascorbic acid with lodate using an iodide ion-selective electrode

A potentiometric method has been developed for the semi-automatic direct titration of thiourea, thiosulfate, and ascorbic acid with potassium iodate in strongly acidic solutions using an iodide ion-selective electrode to monitor the reaction and locate the endpoint. The method is simple, fast, precise, and accurate. Amounts ranging from 0.15–1.5 mg of thiourea (3.9 × 10^?4–3.9 × 10^?3, M), 0.3–3.0 mg of thiosulfate (5.4 × 10^?4–5.4 × 10^?3, M), and 0.5–5.0 mg of ascorbic acid (5.7 × 10^?4–5.7 × 10^?3, M) have been determined with an average error of about 1%. The method has been applied to the determination of ascorbic acid in tablets. Results checked closely with those obtained with a standard titrimetric method.     

Electrochemical synthesis of polyaniline in surface-attached poly(acrylic acid) network, and its application to the electrocatalytic oxidation of ascorbic acid

Acrylic acid was first electropolymerized on the surface of a gold electrode. Then, polyaniline (PANI) was electrodeposited on the poly(acrylic acid) (PAA) network to give a PANI–PAA composite film. Scanning electron microscopy and electrochemical studies confirmed the formation of PANI–PAA composite which exhibited excellent electroactivity over a wide pH range. The electro-oxidation of ascorbic acid (AA) was studied in detail. The modified electrode exhibits significantly reduced oxidation overpotential. The response towards AA is linear in the range 1.0 μM to 9.3 mM (R?=?0.9997, n?=?33) at a potential of 0.1 V (vs. SCE). The sensitivity is 207 μA mM^-1 cm^-2, and the detection limit is 1.0 μM (S/N?=?3). Interferences by uric acid and dopamine are negligible. The electrode thus enables sensitive and selective determination of AA, with a performance superior to many other PANI–based ascorbate sensors.     

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.     

Determination of L-Ascorbic Acid by Adsorption Potentiometry with Carbon Paste Electrode

Abstract

This paper reports the potentiometric measurement of ascorbic acid in the solution of 0.10 mol/L NaOH-0.1 mol/L NaCl using carbon paste (the mixture of spectroscopic graphite powder and di-iso-octyl phthalate) electrode(room temperature 15°C), with the linear range 7.0 × 10^?7 × 4.0 × 10^?5mol/L, average response slope 95mV/decade and detection limit 1 × 10^?7mol/L. Phenol, sulfite, Mn²⁺ and so on pose no interference to the measurement of ascorbic acid. This method is characterized by fine selectivity, reproducibility and accuracy. The potential response behavior is caused chiefly by chemisorption of ascorbic acid to the surface of the carbon.

Each year yields a number of papers concerning the determination of ascorbic acid by various methods, including gas chromatographymass spectrometry¹, capillary electrophoresis², spectrophotometry³, voltammetry⁴, titrimetric method⁵, biosensor⁶ and so on, Each method has its merits and defects in analyzing different samples. M. Petersson⁷ worked out the potentiometric sensor for determining ascorbic acid by modifying monolayer of ferrocene upon the surface of half-oxidized platinum electrode with an average response slope 50±8.8mV/decade, but this sensor suffers from inadequate selectivity. In our study, carbon paste electrode (without ionophore) is applied in the determination of ascorbic acid by potentiometry with an average response slope 95mV/decade. This method displays fine selectivity, accuracy, convenience and rapidity of determination.     

Simultaneous Determination of Ascorbic Acid and Uric Acid by Using a PVC/TTF‐TCNQ Composite Electrode as Detector in a FIA System

A PVC/TTF‐TCNQ composite electrode has been employed as detector in a flow injection system. The proposed method allows the simultaneous detection of ascorbic acid (AA) and uric acid (UA) in mixtures by using a FIA system in a simple manner, without pre‐treatment or modified electrode. This method is based on the amperometric determination of (a) ascorbic acid at 0.15 V and (b) both analytes at 0.35 V, being the response linear in the range 1×10^?2–4×10^?4 M for both analytes with detection limits (S/N=3) of 1.2×10^?4 M and 8.1×10^?5 M for AA and UA, respectively.     

Construction of a Triphenyltetrazolium Liquid Membrane Ion Selective Electrode and its Analytical Application to the Assay of Vitamin C

 The construction of a liquid triphenyltetrazolium cation (TT⁺) ion-selective electrode (ISE) based on [TT⁺]₃[P(W₃O₁₀)₄] salt dissolved in 2-nitrotoluene is described. The liquid membrane electrode exhibits a rapid and almost Nernstian response to triphenyltetrazolium cations in the concentration range from 2×10⁻⁴ to 1×10⁻² mol l⁻¹. The Nernstian slope is 56–58 mV decade⁻¹ which remains constant for at least two months. The response is virtually unaffected by pH changes in the range 3–12. Major interferents are periodate and malate. Deviation from linearity is also observed in the presence of bromide, iodide and thiocyanate, due to their precipitation with triphenyltetrazolium cations. Analytical applications such as direct potentiometry for the determination of TT⁺ in aqueous solutions and indirect potentiometry for the assay of ascorbic acid (vitamin C) in pharmaceutical preparations are described. Ascorbic acid in the range of 150–500 mg l⁻¹, under specified experimental conditions, can be determined with mean relative error of 1.9%. Received February 25, 2000. Revision April 4, 2000.     

Triiodide PVC Membrane Electrode Based on a Charge‐Transfer Complex of Iodine with Ditertbutyl‐Dicyclohexyl‐18‐Crown‐6

A new triiodide ion‐selective electrode based on a charge‐transfer complex of iodine with ditertbutyl‐dicyclohexyl‐18‐crown‐6 (t‐Bu)₂DC18C6 as membrane carrier was prepared. The electrode has a linear dynamic range from 6.3 × 10^?3‐5 × 10^?6 with a Nernstian response of 58.6 ± 1 mV decade^?1 and a detection limit of 1.3 × 10^?6 M. The response time of the sensor was 25 s. The membrane could be used for two months without any divergence in potentials. The electrode exhibits an anti‐Hofmeistetr selectivity sequence with a preference for triiodide at pH 2.0‐10.0. The response mechanism of the electrode was investigated by Uv‐Vis spectroscopic technique. The electrode can be used for the determination of ascorbic acid in orange juice.     

Synthesis and characterization of activated carbon–ethylenediamine–cobalt(II) tetracarboxyphthalocyanine conjugate for catalytic oxidation of ascorbic acid

We report on the synthesis and characterization of activated carbon–ethylenediamine–cobalt(II) tetracarboxyphthalocyanine conjugate (AC–CONHCH₂CH₂NH₂–CoPc) and its electrocatalytic behavior for oxidation of ascorbic acid. Ultraviolet–visible (UV–Vis), Fourier-transform infrared (FTIR), and electrochemical impedance spectroscopies, and cyclic and square-wave voltammetry were used to characterize the electrode modifiers and modified glassy carbon electrode. The limit of detection was found to be 0.26 µm using 3δ notation. The linear dynamic range was from 1.5 × 10^?4 to 1 × 10^?2 M with electrode sensitivity of 0.01 A mol^?1 L cm^?2. A Tafel slope of 200.8 mV decade^?1 was found. The concentration of ascorbic acid in the tablet was 0.034 M. Oxalic acid showed no interference in ascorbic acid determination.     

Biosensor for determination of hydrogen peroxide based on catalase activity of human erythrocytes

A hydrogen peroxide biosensor based on human erythrocytes is described. Erythrocytes are retained on the surface of an oxygen electrode by a semipermeable membrane. The response is based on the catalase activity of the erythrocytes. The sensitivity of 10^?4 mol 1^?1 and linearity from 1.5×10^?4 to 5×10^?3 mol^?1 are comparable to those of analogous enzyme biosensors for hydrogen peroxide determination. The greatest advantages of this biosensor are its easy preparation and a lifetime of 2 months together with good reproducibility (relative standard deviation <5%) and selectivity; only ascorbic acid appeared to interfere with the measurements.     

Solid contact Zn2+ -selective electrode with low detection limit and stable and reversible potential

A new solid contact Zn²⁺ polyvinylchloride membrane sensor with 2-(2-Hydroxy-1-naphthylazo)-1,3,4 -thiadiazole as an ionophore has been prepared. For the electrode construction, ionic liquids, alkylmethylimidazolium chlorides are used as transducer media and as a lipophilic ionic membrane component. The addition of ionic liquid to the membrane phase was found to reduce membrane resistance and determine the potential of an internal reference Ag/AgCl electrode. The electrode with the membrane composition: ionophore: PVC: o-NPOE: ionic liquid in the percentage ratio of (wt.) 1:30:66:3, respectively, exhibited the best performance, having a slope of 29.8 mV decade^?1 in the concentration range 3×10^?7–1×10^?1 M. The detection limit is 6.9×10^?8 M. It has a fast response time of 5–7 s and exhibits stable and reproducible potential. It has a fast response time of 5–7 s and exhibits stable and reproducible potential, which does not depend on pH in the range 3.8–8.0. The proposed sensor shows a good and satisfactory selectivity towards Zn²⁺ ion in comparison with other cations including alkali, alkaline earth, transition and heavy metal ions. It was successfully applied for direct determination of zinc ions in tap water and as an indicator electrode in potentiometric titration of Zn²⁺ ions with EDTA.      

New PVC-membrane electrode based on charge-transfer inclusion complex between I2 and 1,4,8,11-tetraazacyclotetracdecane for selective determination of I3 − ions

A new triiodide ion-selective electrode based on charge-transfer complex of iodine with 1,4,8,11-tetraazacyclotetracdecane as membrane carrier was prepared. The best performance of electrode observed with the membrane having the ligand–PVC–NPOE–NaTPB composition 3.0:33:66:0.5 mg which worked well over a wide concentration range 2.8 × 10^?6–1.4 × 10^?1 M with a Nernstian slope of 59.6 ± 0.3 mV per decade and a detection limit of 1.2 × 10^?6 M. This electrode showed a response time of 25 s and was used over a period of 2 months. The electrode exhibits an anti-Hofmeister selectivity sequence with a performance for triiodide at pH 1.5–10.2. The response mechanism of the electrode was investigated by UV–Vis spectroscopic technique. The electrode was successfully applied as an indicator electrode in the potentiometric titration of ascorbic acid and hydroquinone in drugs.     

Preparation and properties of a carbonate ion-selective membrane electrode

A liquid membrane ion-selective electrode has been prepared for the measurement of carbonate ion activities in solutions containing high levels of hydrogen carbonate and chloride. The electrode exhibits Nernstian response in the approximate range 1O^-2–1O^-7M carbonate, and has a fast response and low noise level under most conditions. In the physiologically important pH region, hydroxide ion does not interfere. Detailed information is given on the composition and properties of the active membrane phase.     

Electrochemical Behavior of Chloranil Chemically Modified Carbon Paste Electrode. Application to the Electrocatalytic Determination of Ascorbic Acid

A p‐chloranil modified carbon paste electrode was constructed and the electrochemical behavior of this electrode was studied in the aqueous solution with different pH. From the E_1/2–pH diagram for this compound the values of formal potential E^0' and pK_a of some different redox and acid‐base couples depending on the solution pH were estimated. The diffusion coefficient, D, value for p‐chloranil was estimated 1.5×10^?7 cm² s^?1. It has been shown by direct current cyclic voltammetry and double potential step chronoamperometry, that this p‐chloranil incorporated carbon paste electrode, can catalyze the oxidation of ascorbic acid in the aqueous buffered solution. Under the optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such an electrode occurs at a potential about 325 mV less positive than that at an unmodified carbon past electrode. The catalytic oxidation peak currents was linearly dependent on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 7×10^?5 M–4×10^?3 M of ascorbic acid with a correlation coefficient of 0.9998. The limit of detection (3σ) was determined as 3.5×10 ^?5 M. This method was used as simple, selective and precise voltammetric method for determination of ascorbic acid in pharmaceutical preparations.