Portugaliae
Electrochimica Acta

Metal recovery by reduction of metal ions present in model solutions, containing one or more heavy metals, was performed. To prepare the model solutions, sulfates and/or chlorides of Cu(II), Cd(II), Pb(II) and Zn(II) were used, at pH 3.5. Assays were run in a one or two compartments cell, at different applied potentials, using a steel plate as cathode, a platinum plate as anode and an Ag/AgCl, KClsat as reference electrode. The metal recovery yield was determined by atomic absorption spectroscopy. The phases corresponding to the metallic deposits were identified by X-ray diffraction. For the solutions containing just one metal ion, the best metal recoveries and the corresponding applied potentials, obtained in a one cell compartment, were the following: Cu(II) 99% at E = - 100 mV; Pb(II) 99% at E = - 800 mV; Cd(II) 93% at E = - 900 mV; and Zn(II) 38% at E = - 1300 mV. The metal removals from the mixed solution of four heavy metals, after 4 consecutive chronoamperometries, performed in a one compartment cell, at the best applied potentials determined with the solutions containing only one metal ion, were the following: Cu(II) 99%; Pb(II) 68%; Cd(II) 92%; and Zn(II) 10%.

The present work reports the results concerning the development and implementation of the first electrochemical biosensor for acrylamide determination, based on a direct biochemical interaction between the analyte and intact bacterial cells, with intracellular enzymatic activity. The biological recognition element consisted of whole cells of Pseudomonas aeruginosa containing intracellular amidase activity, which catalyses the hydrolysis of acrylamide producing ammonium ion (NH4+) and acrylic acid. The transduction process was accomplished by means of an ammonium ion selective electrode. Whole cells were firstly immobilized on single discs of polymeric membranes, such as polyethersulphone, nylon and polycarbonate, which were, then, attached to the surface of the selective electrode. However, it was observed a significant loss of cells each time the biosensor was used, namely at the beginning of the assay, when the membranes were attached to the ammonium electrode, and after the assay, when removed for storage purposes. This evidence determined a premature decrease in the biosensor’s stability. Instead of using single membrane discs, a “sandwich” design, with two membrane discs was considered. This way the cells remain contained between the membranes, never contacting the electrode’s surface, preventing their premature loss. Consequently, the activity of the biosensor could be maintained for longer periods of time. The analytical performance of the biosensor was evaluated. The best results were obtained when polyethersulphone double membranes were used. A typical response of 120 mV (after 6 min reaction time), a Nernstian slope of 48 mV/decade, a limit of detection of 6.31×10-4 M and a half-life time of 27 days, are examples of some figures of merit observed for this biosensor.

Electroless nickel coatings possess several advantages over electroplating such as ability to coat any material and with uniform thickness. Besides, these coatings are used mainly for their wear resistance and corrosion resistance applications. The present study addresses the corrosion behavior of the coating based on electrical impedance spectroscopy. The effect of the four parameters viz. bath temperature, reducing agent concentration, nickel source concentration and annealing temperature, on the electrochemical characteristics (charge transfer resistance and double layer capacitance) are studied with the help of Taguchi method and grey relational analysis. It is found that the bath temperature has the most significant influence on the corrosion behavior of the coating followed by nickel source concentration. The microstructural characterization of the coating is done with the help of scanning electron microscope, X-ray diffraction analysis and energy dispersive X-ray analysis.

The structure and properties of the passive film formed on the surface of AISI 316 stainless steel in aqueous ethanoic acid have been investigated using EIS. Experiments were carried out at 30 ºC in different concentrations of ethanoic acid. Effects on the film properties due to the change of electrode potential, exposure durations and addition of chloride ions to the electrolyte were also studied. Impedance parameters were determined using simple model and equivalent electrical circuit. Results suggest the formation of multilayered passive film on the steel surface. The film possessed dual structure. Inner layers were thin and compact, whereas the outer layer was porous and defective. The measured capacitive behavior was of non ideal nature and hence replaced by constant phase element or CPE. Formation of the passive film and the change in its structure has been explained using impedance parameters.

The inhibition of copper corrosion in 1 M HNO3 by (E)-(4-(4-methoxybenzylideneamino)-4H-1, 2, 4-triazole-3, 5-diyl) dimethanol (MBATD) was investigated by polarization, ac impedance, adsorption studies, quantum chemical calculations, molecular dynamics methods and surface morphological studies. Polarization studies showed that MBATD acts as a mixed type inhibitor. Adsorption followed the Langmuir isotherm with negative value of free energy. Various thermodynamic and kinetic parameters were calculated to understand the energy changes associated during the inhibition process. The correlation between inhibitive effect and molecular structure is ascertained by quantum chemical calculations using density functional theory and Fukui functions. The molecular dynamics method has also been used to simulate the adsorption of inhibitor molecule on the metal surface.

Expired ranitidine was tested as a corrosion inhibitor for mild steel in 1 M HCl using different techniques: weight loss, potentiodynamic polarization, open circuit potential and electrochemical impedance spectroscopy. The polarization resistance (Rp) value increased with increase in the concentration of the inhibitor. Results obtained revealed that ranitidine performed excellently as a corrosion inhibitor for mild steel in this medium at 303 K. The protection efficiency increased with increasing inhibitor concentration. The maximum protection efficiency of 90% has been obtained at 400 ppm. On the other hand, the efficiency decreases with increasing temperature. The adsorption of the inhibitor on the mild steel surface followed Langmuir adsorption isotherm model. The activation and thermodynamic parameters of dissolution and adsorption were calculated and discussed. The negative value of ∆Gads (-40 kJ mol-1) indicates spontaneous chemical adsorption. Results obtained from polarization, EIS and weight loss measurements are in good agreement with each other.

The effect of five compounds of ethoxylated fatty esters with different number of ethylene oxide units on the corrosion of copper in 1 M HNO3 solution has been studied using weight loss and galvanostatic polarization techniques. The inhibition efficiency was found to increase with increasing concentration and number of ethylene oxide units per molecule. Inhibition effect was explained on the basis of adsorption of ethoxylated fatty esters on the metal surface through their ethoxy groups. The adsorption process was found to follow Temkin adsorption isotherm. Polarization data suggested that the used additives act as mixed type inhibitors. It was found also that the ethoxylated fatty esters provide a good protection to copper against pitting corrosion in chloride containing solutions.

The corrosion resistance of three stainless steel materials, namely, stainless steel (SS), stainless steel electroplated with zinc (SS-Zn) and stainless steel electroplated with zinc followed by blue passivation (BP), has been evaluated in an aqueous solution containing 3.5% NaCl. A potentiodynamic polarization study and AC impedance spectra have been used to investigate the corrosion behaviour of these metals. The corrosion resistance of these materials in 3.5% NaCl increased in the following order: SS>SS+Zn+BP >SS+Zn.

The emeraldine base (EB) was synthesized by chemically oxidative polymerization using ammonium persulphate as an oxidant in hydrochloride aqueous medium. The polymer was chemically deposited on mild steel specimens using tetra methyl urea (TMU) as solvent through solvent evaporation method. The coating of polypyrrole (PPy) on carbon steel was deposited by chemical polymerization. A bi-layered polymer coating comprising of inner coat of PPy with top coat of EB (PPy/EB) was also deposited on mild steel following identical procedure. The deposited EB, PPy and PPy/EB coatings were characterized by Fourier Transform Infrared (FTIR) Spectroscopy and Scanning Electron Microscopy (SEM). The anticorrosive properties of single and bi-layered coatings was investigated in major corrosive environments such as 0.1 M HCl, 5% NaCl solution, artificial seawater, distilled water, tap water and open atmosphere by conducting various corrosion tests which include: immersion test, open circuit potential measurements, potentiodynamic polarization measurements, and atmospheric exposure test. The results of immersion tests showed that the PPy/EB coating gave best protection in all media under investigation, the protection efficiency being in the range of 72 to 79% after 30 days of immersion. The result of OCP measurements showed significant positive shift in the corrosion potential for single as well as bi-layered coatings in all corrosive medium under investigation; the bi-layered coating showing more positive corrosion potential. The potentiodynamic polarization studies also confirmed lower corrosion rates for PPy/EB coating than the single polymer coatings.

Sediments can sink or deliver elements to water column. Iron is considered an essential element for the development of cyanobacteria and a limitant to phytoplankton growth. Studies on the chemical speciation of iron in seawater have been conducted, but there is no information about its chemical speciation in pore water, as reported here. This paper presents a voltammetric method to analyze dissolved iron and its chemical speciation in sediment pore water, using adsorptive cathodic stripping voltammetry (AdCSV) and the technique of competitive ligand exchange (CLE-AdCSV), respectively. The limit of detection (LOD = 0.30E−6 M), the quantification (LOQ = 0.90E−6 M), precision (RSD = 4.9%) and accuracy (98%), were calculated from experiments using certified reference material SLRS-4 (National Research Council Canada). The chemical speciation of pore water from sediment samples collected during April 2009, in the Patos Lagoon Estuary (RS, Brazil), was analyzed for the first time, revealing that the ratio (labile iron to dissolved iron) is significantly lower in pore water extracted from sediments of the upper layer (0 to −5 cm), than from the overlaying water or of the pore water extracted from sediments of the lower layer (−15 to −20 cm).

Novel miniaturized polyvinyl chloride (PVC) membrane sensors in all-solid state graphite and platinum wire supports were developed, electrochemically evaluated and used for the assay of orphenadrine citrate (ORP). The ORP sensors were based on the formation of an ion-association complex between the drug cation and tetrakis(4-chlorophenyl)borate (TpClPB) anionic exchanger as electroactive material dispersed in a PVC matrix. Linear responses of 1E-2 - 1E-5 M and 1E-2-1E-4 M with cationic slopes of 56.4 mV and 53.6 mV over the pH range 4-7 were obtained by using the ORP-coated graphite (sensor 1) and platinum wire (sensor 2) membrane sensors, respectively. The proposed methods displayed useful analytical characteristics for the determination of ORP in Norflex® tablets with average recoveries of 100.01±0.83, 100.09±0.90, and in plasma with average recoveries of 99.4±0.97 and 98.55±0.82, for sensor 1 and 2, respectively. The methods were also used to determine the intact drug in the presence of its degradate and thus could be used as stability indicating methods. The results obtained by the proposed procedures were statistically analyzed and compared with those obtained by using an official method. No significant difference for both accuracy and precision was observed.

The electrochemical reduction behavior of cefepime and cefpirome has been studied using cyclic voltammetry in Britton Robinson (BR) buffer ranging from pH 2.0 to 12.0. Cefepime and cefpirome are found to give two well defined peaks and these peaks are attributed to the reduction of the azomethine group (>C=N-) by two electron process in two steps. Kinetic parameters such as diffusion coefficient (D) and forward rate constant (Kof,h) values are evaluated and a reduction mechanism is proposed. The result indicates that the process of both the compounds is irreversible and diffusion controlled. A simple and rapid differential pulse polarographic method has been developed for the determination of cefepime and cefpirome in pharmaceutical formulations and spiked urine samples using the standard addition method. The lower detection limits are found to be 4.6E-8 M and 8.52E-8 M for cefepime and cefpirome, respectively.

The present paper contains the results relative to the reaction of NiO with Na2SO4 in presence of SO2 (g) at 1100 and 1200 K. Nickel oxide (NiO) is produced by the oxidation of metal alloys in many industrial operations. The oxidation of metal and metal oxides in presence of molten salts and gas environment at high temperature is often called as hot corrosion. In this investigation the studies have been carried out taking into consideration the influence of SO2 partial pressure. The thermo-gravimetric studies have been carried out as a function of Na2SO4 concentration in the mixture. The reaction products identified by XRD analysis and surface morphologies of the products were discussed on the basis of metallographic and scanning electron microscopic (SEM) studies. The pH of the aqueous solutions of the reaction products were measured to observe the changes in the system with varying the Na2SO4 concentration. A quantitative estimation of soluble metal ions has also been carried out with the help of an atomic absorption spectrophotometer. The possibility of chemical reaction is established by thermodynamic calculations of free energies of the reaction products.

This work presents the optimization process of mercury determination by Anodic Stripping Voltammetry (ASV), using a glassy carbon modified with a gold film as working electrode, in samples extracted by aqua regia. The samples may contain Cu, Fe or Pb in high concentrations. In these conditions the usual Hg determination by ASV is almost impossible. The effects of the supporting electrolyte on the sensitivity of the method and chloride and nitrate ions concentration were studied. Supporting electrolyte was selected between: HCl, HNO3, HClO4 and CH3COOH. Our results show that the best sensibility is obtained with HClO4 0.10 M. High chloride concentration decreases the useful potential window and the peak current. However, small chloride additions are required to obtain high peak currents because chloride prevents Au film poisoning. Another interference studied was that of Cu and Fe. This kind of interference can be avoided if the sample in the electrochemical cell is exchanged for fresh electrolytic solution (HCl 0.01 M -HClO4 0.10 M) before the stripping step.

The inhibition of corrosion of 304 SS in 2 N HCl solutions by N – furfuryl – N' phenyl thiourea (FPTU) has been investigated using potentiodynamic polarization techniques. The results obtained reveal that FPTU performs excellently as anodic inhibitor (IE> 93%) for 304 SS in HCl solution. The inhibitor functions through adsorption following Temkin’s adsorption isotherm, and the inhibition was governed by physisorption mechanism. The thermodynamic parameters deduced for the adsorption process reveal spontaneous adsorption of the compound on the alloy steel surface.

Two microsized graphite-design sensors based on ionophore technique, polyvinyl chloride carboxylated (PVC-COOH) and β-cyclodextrin (β-CD), are used for fabrication of two membrane sensors for the two studied drugs, metronidazole (MZ), sensor 1, and spiramycin (SP), sensor 2. Fast and stable Nernstian responses near 1E-5 - 1E-3 M for MZ and 1E-5-1E-2 M for SP over pH range 5.5-7.5 for the two electrodes reveal the performance characteristics of these electrodes which have been evaluated according to IUPAC recommendations. The aim of this work is to develop a new, simple, accurate and precise method for the determination of MZ and SP in their binary mixtures, which can be applied in routine quality control. The method is successively applied for the determination of the two drugs in their pharmaceutical formulations. Validation of the method according to the quality assurance standards shows suitability of the proposed electrodes for the use in the quality control assessment of these drugs. The recovery percentages for the determination of the two drugs by the two proposed selective electrodes are 99.86 ± 0.249 % and 99.69 ± 0.856% for sensors 1 and 2, respectively. Statistical comparison between the results obtained by this method and the reported one is done and no significant difference is found.

Bright nickel deposits were electrolytically applied on steel in the nickel Watts bath. The effect of some operational parameters on metal deposition in bright nickel plating was investigated. The investigation indicated that the weight of bright nickel deposited on metal during the process of electroplating was affected by plating temperature, voltage, current density, plating bath pH and plating time. The study established that the deposition of best bright nickel was obtained at a plating temperature of 56 ºC, current density of 6 A/dm2 and plating time of 18 minutes. Brightener is used in applications requiring outstanding appearance with minimum thickness of applied nickel plating. It can also be used for heavy deposit applications because it exhibits unparalleled ductility and low stress. Brightener was used in this study to determine the best nickel plating in the process. Boric acid was added for fixing the bath pH. The compositions of the brightener and nickel solution used are included in the text.

The performance of triethylenetetramine-tribenzylidene (TTTB) and triethylenetetramine-trisalicylidene (TTTS) as corrosion inhibitors for zinc in hydrochloric acid is investigated. At lower concentrations, both inhibitors accelerate the attack but inhibit corrosion at higher concentrations, e.g., 96–100% with 1.0% concentration in 0.5 M and 1.0 M HCl. The efficiency of TTTB decreases while that of TTTS remains almost constant (≥ 99.7%) up to 120 minutes and in the temperature range 35 – 65 ºC. The activation energies are higher in inhibited than in plain acid with both inhibitors. The free energy of adsorption (ΔGads) and heat of adsorption (Qads) are negative, which suggests that there is spontaneous adsorption on metal surface, and from the values of (ΔGads) and (Qads), the values of entropy of adsorption (ΔSads) were calculated. Galvanostatic polarization shows that corrosion is under mixed control with predominance of the cathodic part. In uninhibited 1.0 M HCl, complete cathodic protection is achieved at a current density of 4.2224 Adm-2, but in presence of these inhibitors, much lower current densities are required. Plot of log (θ/1-θ) versus log Cinh gives a straight line, suggesting that inhibitors cover both the anodic and cathodic regions through general adsorption following Langmuir isotherm. The mechanism of inhibition has been proposed.

Two sensitive voltammetric techniques (adsorptive and catalytic cathodic stripping) are described for the determination of timonacic, in the presence of copper or nickel ions, respectively. The measured peaks which correspond to the reduction or copper (I) or nickel – timonacic complexes are measured at -773 and -782 mV, respectively. The different experimental parameters have been carefully studied. The methods have been fully validated. The detection limits were 1.5 and 13.6 ng mL-1, respectively. The methods have been applied for the determination of timonacic in pharmaceutical tablets. The obtained results have been compared statistically with those obtained from a published method.

Essential oil from fennel (Foeniculum vulgare) (FM) was tested as corrosion inhibitor of carbon steel in 1 M HCl using electrochemical impedance spectroscopy (EIS), Tafel polarisation methods and weight loss measurements. The results show that the increase of the charge-transfer resistance (Rct) with the oil concentration supports the molecules of oil adsorption on the metallic surface. The polarization plots reveal that the addition of natural oil shifts the cathodic and anodic branches towards lower currents. Such shifts indicate that FM oil acts as a mixed-type inhibitor. The global rate of corrosion estimated by weight loss measurements confirms the above results. The inhibition efficiency attains a maximum of 76 % at 3 mL/L, but decreases with the rise of temperature. The analysis of FM oil, obtained by hydro-distillation, using Gas Chromatography (GC) and Gas Chromatography/Mass Spectrometry (GC/MS) showed that the major components were limonene (20.8 %) and β-pinene (17.8%). The adsorption of FM on the steel surface has been discussed according to the chemical composition of the oil, giving an explanation to the obtained results.