Potential oscillation generated by formaldehyde oxidation in the presence of dissolved oxygen

The influence of dissolved oxygen on the potential oscillation patterns is investigated during the oxidation of 0.1 M formaldehyde on polycrystalline platinum in an acidic solution at 315 K under galvanostatic conditions. We have found that, with increasing dissolved oxygen concentration from 0 to 1 mM, chaotic oscillations persist to appear as well as periodic ones, both oscillations show fluctuations in their amplitude and the period length doubles. Voltammograms show that a current peak appears at ca. 0.6 V and becomes large, which is found to be due to the oxidation of the adsorbed CO with oxygen but not due to the slowing down of the formation velocity of the adsorbed CO. The results are discussed regarding the conditions for the appearance of chaos.     

Chloride selective potentiometric sensor based on a newly synthesized hydrogen bonding anion receptor

A new potentiometric chloride sensor based on the use of anion receptor 2-(1-H-imidazo [4,5-f][1,10]phenanthroline-2-yl)-6methoxyphenol (HIPM) in poly(vinyl chloride) (PVC) matrix is reported. Effect of various plasticizers: 2-nitrophenyloctylether (o-NPOE), di-n-butylphthalate (DBP), diethyl phthalate (DEP), dioctylpthalate (DOP), tri-n-butyl phosphates (TBP), chloronapthalene (CN) and cation excluder, cetryltrimethylammoniumbromide (CTAB) was studied. The best performance was obtained with a membrane composition of PVC: o-NPOE:HIPM: CTAB ratio (w/w, %) of 31:60:7:3. The sensor exhibits significantly enhanced selectivity towards chloride over the concentration range 5.0 × 10⁻⁸ to 1.0 × 10⁻¹ M with a lower detection limit of 1.0 × 10⁻⁸ M and a Nernstian slope of 59.8 mV decade⁻¹ of activity. Influence of the membrane composition and possible interfering ions was investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability are demonstrated. The sensor shows response time of <10 s and can be used for about 3 months without any considerable divergence in their potential response. Selectivity coefficients determined with matched potential method (MPM) indicate high selectivity for chloride. The proposed electrode shows fairly good discrimination of chloride from anions. It was successfully applied to determination of chloride ion in packed drinking water. The electrode can be used in the pH range of 6.5-8.0 and mixtures containing up to 20% (v/v) non-aqueous content. It was used as an indicator electrode in potentiometric titration of chloride ion against silver nitrate.     

Novel all-solid-state copper(II) microelectrode based on a dithiomacrocycle as a neutral carrier

A novel dithiomacrocycle (4-phenyl-11-decanoyl-1,7-dithia-11-azacyclotetradecane-4-sulfide) has been synthesized and used as a new ionophore in order to develop a plasticized poly(vinyl chloride) membrane for copper ion detection. The performance of these novel planar copper(II)-selective potentiometric microelectrodes was investigated using potentiometric measurements. The developed microelectrodes exhibits a good linear response of 29.5 ± 1 mV per decade within the concentration range of 1.0 × 10⁻⁶ to 1.0 × 10⁻² M (r = 0.9995) of Cu²⁺. The detection limit was determined as 5.62 × 10⁻⁷ M and the selectivity coefficients for possible interfering cations were evaluated. The microelectrodes are suitable for use with aqueous solutions of pH 3.5-6.0 and were found to be insensitive to the nature of the anions used in the sample.     

Effect of Ni content on the corrosion behavior of Cu-Ni alloys in neutral chloride solutions

The effect of systematic increase of Ni content on the electrochemical behavior of the Cu-Ni alloys in neutral chloride solutions was investigated. The pitting corrosion behavior of Cu-Ni alloys with different Ni contents, namely, 5, 10, 30 and 65 mass% Ni, in a stagnant 0.6 mol dm⁻³ NaCl solution of pH 7.0 was studied. The effect of chloride ion concentration on the electrochemical behavior of these alloys was also investigated. The results show that the increase in nickel content decreases the corrosion rate of the alloys in the neutral chloride solution. The increase of chloride concentration up to 0.3 mol dm⁻³ increases the corrosion rate. At higher concentrations ([Cl⁻] > 0.3 mol dm⁻³) the corrosion rate decreases due to the hydrolysis of Cu(I) chloride to form the passive Cu(I) oxide film. The breakdown potential depends on the chloride ion concentration and the nickel content of the alloy. For these investigations conventional electrochemical techniques and electrochemical impedance spectroscopy (EIS) were used. The impedance measurements have shown that the increase of the Ni content and the immersion time of the alloys in the chloride solution increase the corrosion resistance of the alloys. The experimental impedance data were fitted to theoretical values according to a proposed equivalent circuit model.     

Structural and electrochemical characterization of a cobalt phthalocyanine bulk-modified SiO2/SnO2 carbon ceramic electrode

A cobalt phthalocyanine bulk-modified carbon ceramic composite has been prepared by using sol-gel processing, and characterized by BET surface area, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy. A water-soluble 3-n-propylpyridinium chloride silsesquioxane (SiPyCl), an ion exchanger polymer, was employed to attach cobalt(II) tetrasulfophthalocyanine (CoTsPc) and prevent its leakage, as well as, to ensure adequate dispersion in the sol-gel network. The modified electrode built in a rigid disk-format displayed good electrocatalytic behavior towards the oxidation of oxalic acid at 0.84 V (SCE), as evidenced by the enhancement of the anodic current peak intensity when the concentration of oxalic acid was increased. A linear response was found in the range of 1.6 × 10⁻⁵ to 1.5 × 10⁻³ mol l⁻¹ with a detection limit of 7.1 × 10⁻⁶ mol l⁻¹.     

Effect of Bi(III) concentration on the stripping voltammetric response of in situ bismuth-coated carbon paste and gold electrodes

The effect of Bi(III) concentration (over the wide concentration range of 10⁻⁷ to 10⁻⁴ M) on the determination of Pb and Cd metal ions (in the 10⁻⁸ to 10⁻⁵ M range), by means of anodic stripping voltammetry (ASV) at in situ bismuth-coated carbon paste (CPE) and gold electrodes, has been studied. It is shown that in square wave anodic stripping voltammetry (SWASV) experiments the sensitivity of the technique generally depends on the Bi(III)-to-metal ion concentration ratio. It was found that, unlike the usually recommended at least 10-fold Hg(II) excess in anodic stripping experiments at in situ prepared mercury film electrodes, Bi(III)-to-metal ion ratios less than 10 are either optimal or equally effective at CPE and Au electrode substrates. Detection limits down to 0.1 μg L⁻¹ for Pb(II) and 0.15 μg L⁻¹ for Cd(II) were estimated at CPEs under conditions of small or moderate Bi(III) excess. Depending on Bi(III) concentration and deposition time, multiple stripping peaks attributed to Bi were recorded (especially in the case of Au substrates), indicating various forms of Bi deposits.     

PVC membrane and coated graphite potentiometric sensors based on 1-phenyl-3-pyridin-2-yl-thiourea for selective determination of iron(III)

The construction and performance characteristics of PVC membrane (PME) and coated graphite (CGE) Fe³⁺ ion selective electrodes based on 1-phenyl-3-pyridin-2-yl-thiourea (PPT) are described. The electrodes exhibit a Nernstian slope of 20.2 ± 0.8 (CGE) and 19.9 ± 0.4 (PME) mV decade⁻¹ of activity in Fe³⁺ ion over a wide concentration range from 3.0 × 10⁻⁷ to 1.0 × 10⁻² M for CGE and 6.9 × 10⁻⁷ to 1.0 × 10⁻² M Fe³⁺ for PME. The lower detection limits by CGE and PME are 2.0 × 10⁻⁷ and 3.9 × 10⁻⁷ M, respectively, in the pH range of 1.8-5.6 for PME and 1.8-5.8 for CGE with a fast response time (<10 s). The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the PME. The PME showed the working temperature range of 22-55 °C with isothermal temperature coefficient of 1.33 × 10⁻³ V/°C and it was also used in non-aqueous solvents. The electrodes were successfully applied to determine iron(III) in water samples.     

Nitrate ion effect on the passive film breakdown and current oscillations at iron surfaces polarized in chloride-containing sulfuric acid solutions

Current oscillatory phenomena have been used to study the effect of nitrates on pitting corrosion of passive iron surfaces in chloride-containing sulfuric acid solutions. From the quasi steady-state current-potential and potentiostatic current-time curves of the Fe | 0.75 M H₂SO₄+10 mM Cl⁻ system it is deduced that at lower potentials nitrates stimulate pitting acting as activators of the oxide dissolution. At higher potentials nitrates act as passivators causing a sudden passivation of Fe during a mass-transport controlled process across a salt film. Current oscillations appear over a wide potential region. The oscillation period as well as the induction period of time occurring before the onset of oscillation, both decrease by increasing the nitrate concentration. The effect of nitrates at lower and higher potentials is discussed in terms of the electrochemical and redox reactions of nitrate ions.     

Preparation and characterization of the dopamine film electrochemically deposited on a gold template and its applications for dopamine sensing in aqueous solution

A dopamine polymer film was electrogenerated on the bare gold template from a 5 × 10⁻³ M dopamine solution in phosphate buffer at pH 7 and next subjected to overoxidation in 0.1 M sodium hydroxide solution. The overoxidized dopamine polymer film obtained shows good permeability to cationic species and was used for quantitative determination of dopamine. A linear relationship between dopamine concentration and current response was obtained in the range of 1 × 10⁻⁶ M to 6 × 10⁻⁴ M with the detection limit 2 × 10⁻⁷ M. The results have shown that using the overoxidized dopamine film it is possible to perform electrochemical analysis of dopamine without interference of ascorbic and uric acids, which is the major limitation in dopamine determination. The modified electrode shows good selectivity, sensitivity, reproducibility and high stability.     

Cu(II) complexes as receptor molecules for development of new chloride sensors

Highly sensitive and selective chloride polymeric membrane sensors are developed that employ Cu(II) complexes as anion carriers. Optimized membrane sensors showed a near-Nernstian response towards chloride anion over a wide concentration range of 2.5 × 10⁻⁵ to 1.0 × 10⁻¹ M and have micromolar level detection limits. These sensors have fast response time and work well in the pH range of 4.2-9.6. They exhibited enhanced potentiometric selectivity for chloride over other anions, including more lipophilic anions such as perchlorate, thiocyanate, nitrate, etc. Response characteristics (e.g. detection limit, linear range, response slope and selectivity) of these sensors remain essentially the same over a period of ∼5 months, reflecting remarkable stability.     

Direct determination of aluminium in foods and pharmaceutical preparations by potentiometry using an AlMCM-41 modified polymeric membrane sensor

A potentiometric aluminium sensor, based on the use AlMCM-41 as a neutral carrier, in poly(vinyl chloride) (PVC) matrix, is reported. The sensor exhibits significantly enhanced selectivity toward Al³⁺ ions over the concentration range 1.0 × 10⁻⁷ to 1.0 × 10⁻¹ M with a detection limit of 8.6 × 10⁻⁸ M and a Nernstian slope of 19.5 ± 0.4 mV/decade of activity. The best performance was obtained with membrane composition 30% poly(vinyl chloride), 67% acetophenone, 3% ionophore and 2 mL tetrahydrofuran. Fast and stable response, good reproducibility and long-term stability are demonstrated. The response time of the sensor is ∼10 s and membrane could be used over a period of 3 months without any considerable divergence in potentials. Selectivity coefficients were determined by matched potential method (MPM). The AlMCM-41-based sensor is suitable for use in aqueous solution of pH 3-6. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the electrode. It was used to determine Al³⁺ in drugs and food products.     

High sensitive simultaneous determination of catechol and hydroquinone at mesoporous carbon CMK-3 electrode in comparison with multi-walled carbon nanotubes and Vulcan XC-72 carbon electrodes

The simultaneous voltammetric determination of catechol (CC) and hydroquinone (HQ) has been achieved at a mesoporous carbon CMK-3 modified electrode in phosphate buffer solution (pH 7.0). At the electrode both CC and HQ can cause a pair of quasi-reversible and well-defined redox peaks and their peak potential difference increases. In comparison with multi-walled carbon nanotubes (MWCNTs) and Vulcan XC-72 carbon modified electrodes the CMK-3 modified electrode shows larger peak currents and higher adsorbed amounts for the two dihydroxybenzene isomers. This is related to the higher specific surface area of CMK-3. Under the optimized conditions, the linear concentration ranges for CC and HQ are 5 × 10⁻⁷ to 3.5 × 10⁻⁵ M and 1 × 10⁻⁶ to 3 × 10⁻⁵ M, respectively. In the presence of 5 μM isomer, the linear concentration range of CC (or HQ) is 5 × 10⁻⁷ to 2.5 × 10⁻⁵ M (or 5 × 10⁻⁷ to 2.0 × 10⁻⁵ M). The sensitivity for CC or HQ is 41 A M⁻¹ cm⁻² or 52 A M⁻¹ cm⁻², which is close to that without isomer. The detection limits (S/N = 3) for CC and HQ are 1 × 10⁻⁷ M after preconcentration on open circuit for 240 s.     

A novel potentiometric sensor for promethazine based on a molecularly imprinted polymer (MIP): The role of MIP structure on the sensor performance

A novel potentiometric sensor based on a molecularly imprinted polymer (MIP) for determination of promethazine (PMZ) was prepared. Promethazine MIP particles were prepared and dispersed in 2-nitrophenyloctyl ether and then embedded in a polyvinyl chloride matrix. The effect of the monomers type on the sensor performance was investigated, and an important role for this parameter was shown. It was shown that the membrane electrode with a MIP prepared by vinylbenzene and divinylbenzene had a better performance in comparison to membrane electrodes containing MIPs prepared with methacrylic acid-ethylene glycol dimethacrylate or vinylbenzene-ethylene glycol dimethacrylate. After optimization, the membrane electrode constructed with a MIP of vinylbenzene-divinylbenzene exhibited a Nernstian response (31.2 ± 1.0 mV decade⁻¹) over a wide concentration range, from 5.0 × 10⁻⁷ to 1.0 × 10⁻¹ M, with a low detection limit of 1.0 × 10⁻⁷ M and a response time of ∼50 s. The method has the requisite accuracy, sensitivity and precision to assay PMZ in syrup samples and biological fluids.     

Effect of halogen ions on platinum dissolution under potential cycling in 0.5 M H2SO4 solution

The effect of ppm level of chloride and fluoride ions on the dissolution of electrochemically deposited Pt with two different thickness has been studied by using electrochemical quartz crystal microbalance (EQCM) and ICP-Mass analysis in combination with atomic force microscopy (AFM). A mass loss due to dissolution of Pt as chloride complexes was observed in as low as 10 ppm [Cl⁻] at 1.06 V versus SHE. Fluoride ion did not have any effect on the dissolution of Pt in as high as 1000 ppm [F⁻]. From the comparison of EQCM, ICP-Mass and AFM images, it was revealed that amount of platinum dissolution under potential cycling greatly depended on chloride concentration and morphology of deposited Pt layers. When Pt dissolution was induced by Cl⁻ ions, the amount of dissolved Pt did not depend on the particle size of the deposited Pt. On the other hand, in the absence of Cl⁻ induced dissolution, i.e. when oxide formation was dominant, the particle size of the deposited Pt greatly affected the amount of dissolved Pt. This was explained by considering the increase of overpotential for the reduction of chloride complex due to its high stability in chloride solution.     

Nucleation of Sn and Sn-Cu alloys on Pt during electrodeposition from Sn-citrate and Sn-Cu-citrate solutions

The initial stages of Sn and Sn-Cu electrodeposition from Sn-citrate and Sn-Cu-citrate solutions on Pt were studied using both current-controlled and potential-controlled electrochemical techniques. For both Sn-citrate and Sn-Cu-citrate solutions, when the current density is controlled to lower than 15 mA/cm², potentials remain almost constant which is appropriate to plate dense and uniform films. When the current density is controlled to between 25 and 35 mA/cm², potentials drop quickly initially, followed by a gradual increase to a constant value. When current density is controlled to higher than 50 mA/cm², potential oscillation happens, and significant hydrogen evolution prevents the formation of dense and continuous Sn and Sn-Cu films. A constant transition time constant indicates a diffusion-controlled process. The diffusion coefficient calculated from the Sand equation is about 3.8 × 10⁻⁶ cm²/s for the Sn-citrate solution and 4.1 × 10⁻⁶ cm²/s for the Sn-Cu-citrate solution. The morphology of both Sn and Sn-Cu deposits plated under different potentials was examined by atomic force microscopy (AFM) and the distribution of each element were analyzed using Auger imaging. Analysis of both the electrochemical results at −0.72, −1.1 and −1.5 V and AFM images for both Sn and Sn-Cu deposits at −1.1 and −1.5 V suggested progressive nucleation controlled by diffusion for both Sn and Sn-Cu electrodeposition. Tin reacted with Pt to form PtSn₄, and co-deposited with Cu to form Cu₆Sn₅ during nucleation, with more Sn forming at higher applied potentials.     

Studies on the electrochemical behavior of 3-nitrobenzaldehyde thiosemicarbazone at glass carbon electrode modified with nano-γ-Al2O3

Nano-γ-Al₂O₃ is dispersed onto the glass carbon electrode (GCE) by polishing. This nanostructured modified GCE exhibits a great enhancement to the redox responses of 3-nitrobenzaldehyde thiosemicarbazone (3-NBT). In comparison with bare GCE, 3-NBT gives a more sensitive voltammetric response because of the nanoparticle’s unique properties. The lowest detectable concentration (3σ) of 3-NBT is estimated to be 1.18 × 10⁻⁶ M (accumulation for 4 min). The linear relationship between peak current and concentration of 3-NBT holds in the range 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁴ M (r = 0.9981). The electrochemical properties of 3-NBT on this modified electrode have been investigated with various electrochemical methods. The results indicate that the transference of one electron and one proton involves electrode radical reaction processes I and II, respectively. The coverage value (Γ) of 1.62 × 10⁻⁹ mol cm⁻² was calculated and the electrochemical parameters, diffusion coefficient D (2.54 × 10⁻³ cm² s⁻¹, 2.03 × 10⁻³ cm² s⁻¹) and reaction rate constant k_s (5.9573 s⁻¹, 7.15 × 10⁻² cm s⁻¹) were obtained for quasi-reversible system I and irreversible system II, respectively.     

Electrochemical behavior of folic acid at calixarene based chemically modified electrodes and its determination by adsorptive stripping voltammetry

Voltammetric behavior of folic acid at plain carbon paste electrode and electrode modified with calixarenes has been studied. Two peaks for irreversible oxidation were observed. Out of the three calixarenes chosen for modification of the electrodes, p-tert-butyl-calix[6]arene modified electrode (CME-6) was found to have better sensitivity for folic acid. Chronocoulometric and differential pulse voltammetric studies reveal that folic acid can assemble at CME-6 to form a monolayer whose electron transfer rate is 0.00273 s⁻¹ with 2-electron/2-proton transfer for the peak at +0.71 V against SCE. An adsorption equilibrium constant of 5 × 10³ l/mol for maximum surface coverage of 2.89 × 10⁻¹⁰ mol/cm² was obtained. The current is found to be rectilinear with concentration by differential pulse voltammetry. However, linearity in the lower range of concentration 8.79 × 10⁻¹² M to 1.93 × 10⁻⁹ M with correlation coefficient of 0.9920 was achieved by adsorptive stripping voltammetry. The limit of detection obtained was found to be 1.24 × 10⁻¹² M. This method was used for the determination of folic acid in a variety of samples, viz. serum, asparagus, spinach, oranges and multivitamin preparations.     

A potentiometric and voltammetric sensor based on polypyrrole film with electrochemically induced recognition sites for detection of silver ion

Conducting polypyrrole membranes were deposited on glassy carbon electrodes by electropolymerizing pyrrole in the presence of Eriochrome Blue-Black B (EBB) as the counter anion. The electrodes were then subjected to several oxidation/reduction potential steps in pure silver nitrate solution for successive accumulation/stripping of silver species. This electrochemically mediated doping/templating generated selective recognition elements in the EBB/PPy film for silver ions. The resulting sensor exhibited a considerable enhancement in the potentiometric and voltammetric response characteristics: extending the linear dynamic range and lowering the detection limit. In the potentiometric mode, the sensor showed highly reproducible response with a Nernstian slope of 58.5 ± 0.3 mV per decade of Ag⁺ activity over a linear range spanning seven orders of magnitude (1 × 10⁻⁸ to 1 × 10⁻¹ M Ag⁺), with a detection limit of ∼6 × 10⁻⁹ M. The electrodes demonstrated high selectivity over a large number of cations including alkali, alkaline earth and several transition and heavy metal ions, and could be used over a wide pH range of 1-8.5. The EBB/PPy modified electrode was also used for preconcentration and differential pulse anodic stripping voltammetric (DPASV) measurements. The DPASV peak current was dependent on the concentration of Ag⁺ over the range 3 × 10⁻¹⁰ to 1 × 10⁻⁴ M. The presence of 1000-fold excess of Cd²⁺, Cu²⁺, Cr³⁺, Co²⁺, Mn²⁺, Fe²⁺, Fe³⁺, Ni²⁺ and Pb²⁺ can be tolerated in the determination of silver ion.     

A study of the photocatalytic degradation of metamitron in ZnO water suspensions

The photocatalytic degradation of the herbicide metamitron in water using ZnO under Osram ULTRA-VITALUX® lamp light was studied. The effect of the operational parameters such as initial concentration of catalyst, initial metamitron concentration, initial salt concentration (NaCl, Na₂CO₃ and Na₂SO₄) and pH was studied. The optimal concentration of catalyst was found to be 2.0 g/l. First-order rate constants were calculated for the uncatalysed reactions. On the base of the Langmuir-Hinshelwood mechanism, a pseudo first-order kinetic model was illustrated and the adsorption equilibrium constant and the rate constant of the surface reaction were calculated (0.119 l mg^− 1 and 0.836 mg l^− 1 min^− 1, respectively). The photodegradation rate was higher in acidic than in alkaline conditions. When salt effect was studied, it was found that sodium carbonate was the most powerful inhibitor used, while sodium chloride was the weakest one. A negligible inhibition was observed when the concentration of sodium chloride was 20 mM.The rate of photodecomposition of metamitron was measured using UV spectroscopy and HPLC, while its mineralization was followed using ion chromatography (IC), as well as total organic carbon (TOC) and total nitrogen (TN) analysis.Under the employed conditions, almost complete disappearance of 9 mg/ml of herbicide, 56% TOC and 34% TN removal, occurred within 4 h. The ion chromatography results showed that the mineralization led to ammonium, nitrite and nitrate ions during the process.     

Amperometric tyrosinase biosensor based on Fe3O4 nanoparticles-coated carbon nanotubes nanocomposite for rapid detection of coliforms

A tyrosinase (Tyr) biosensor was developed based on Fe₃O₄ magnetic nanoparticles (MNPs)-coated carbon nanotubes (CNTs) nanocomposite and further applied to detect the concentration of coliforms with flow injection assay (FIA) system. Negatively charged MNPs were absorbed onto the surface of CNTs which were wrapped with cationic polyelectrolyte poly(dimethyldiallylammonium chloride) (PDDA). The Fe₃O₄ MNPs-coated CNTs nanocomposite was modified on the surface of the glassy carbon electrode (GCE), and Tyr was loaded on the modified electrode by glutaraldehyde. The immobilization matrix provided a good microenvironment for retaining the bioactivity of Tyr, and CNTs incorporated into the nanocomposite led to the improved electrochemical detection of phenol. The Tyr biosensor showed broad linear response of 1.0 × 10⁻⁸-3.9 × 10⁻⁵ M, low detection limit of 5.0 × 10⁻⁹ M and high sensitivity of 516 mA/M for the determination of phenol. Moreover, the biosensor integrated with a FIA system was used to monitor coliforms, represented by Escherichia coli (E. coli). The detection principle was based on determination of phenol which was produced by enzymatic reaction in the E. coli solution. Under the optimal conditions, the current responses obtained in the FIA system were proportional to the concentration of bacteria ranging from 20 to 1 × 10⁵ cfu/mL with detection limit of 10 cfu/mL and the overall assay time of about 4 h. The developed biosensor with the FIA system was well suited for quick and automatic clinical diagnostics and water quality analysis.