Portugaliae
Electrochimica Acta

The inhibition behavior of chromate ions towards corrosion and dezincification of α-brass (Cu/Zn: 64/36) in acetate buffer solutions (pH 2.4, 7.0 and 8.5) containing 3% sodium chloride was studied. Weight loss and solution analysis were used for a long period (four weeks) and electrochemical polarization for a short period (one hour). Chromate accelerated corrosion and dezincification at pH 2.4 by acting as depolarizer but chromate suppressed efficiently the corrosion and dezincification at pH 8.5. At pH 7.0 the corrosion and dezincification suppressed in the presence of chromate but the inhibition action started to deteriorate at chromate concentration less than 0.005 mol/L. The inhibition effect is attributed to adsorption of chromate ions on the corroding surface and improvement of the passivity. Chromate led to an increase in the concentration of copper species in solution due to the formation of the more soluble CuCrO4 than Cu2O, which contributed to the apparent suppression of dezincification.

The electrochemical behavior of Cu-(0.5-13 wt.%)Al alloys in K2SO4 0.5 mol dm-3 (m = 1.5 M, pH 2-5) was studied using open-circuit potential (Eoc) measurements and polarization curves, in order to know the conditions of copper oxides formation, influence of Al concentration and solution pH on the electrode processes. The open-circuit potential measurements with time indicated that the Eoc decreases with the Al content, due to the lower Al potential compared to Cu. The electrode potentials decrease ca. 20 mV per unity of solution pH as increase pH of the solution. The polarization curves showed changes with the increase of Al concentration. For alloys with up to 3 wt.%Al the obtained Tafel anodic coefficient was 40 mV/decade for low potentials region (E < -320 mV) and 130 mV/decade for the other region (-320 < E/mV < -250), indicating that up to this concentration there is no considerable change in the electrochemical behavior of the alloys, when compared to pure Cu. For alloys with an Al content from 8 to 13 wt.% the Tafel anodic coefficient was 60 mV/decade. No influence of the solution pH on the Tafel anodic coefficient was observed.

The electrochemical behaviour of coated Cr3C2-NiCr steel in aerated 0.5 M H2SO4 solution was studied by means of electrochemical ac and dc measurements. The structural characterisation of the coated steel, before and after electrochemical tests, was also performed in order to identify the mechanism of the electrolyte penetration through the coating up to the steel substrate, causing its corrosion. This characterisation may also help to explain electrochemical results. Three types of Cr3C2-NiCr coatings performed by a High Velocity Oxy-Fuel Spraying system (HVOF) were analysed. The facility for the electrolyte penetration through the coating and the corresponding electrochemical behaviour of the samples were strongly influenced by the spray parameters used and heat treatment applied. It was observed that heat-treated coatings (Q1 and Q3) showed better corrosion resistance than the as-sprayed coating (A). For coatings Q1 and Q3, the electrolyte did not reach the steel substrate during the measurement, leading to a better protection of the steel substrate against corrosion.

Cyclic voltammetry and surface analysis techniques (EDX microanalysis, mapping of elements and SEM images) have been used to study the solid state reactions of Ir in blank solution or Hg(I)-containing solution. The studies in KNO3/HNO3 solution permit to suggest the formation of a thin oxide layer film deposited in the substrate. The RCV process exhibits the decrease of capacitive current associated to the substrate surface restructuring. The electro deposition of Hg occurs initially in UPD condition from Hg(I)-containing solution, C[Hg(I)] = 3.51x10-7 mol/L. The electro deposition of bulk mercury occurs from Hg(I)-containing solution, C[Hg(I)] = 3.51x10-5 mol/L. It was observed the deposition of Hg in the substrate in open circuit for all employed conditions.

A new amperometric biosensor for lactose determinaion in raw milk was developed through the simultaneous immobilization of β-galactosidase and galactose oxidase on a derivatised polyethersulphone membrane. β-galactosidase catalyses the hydrolysis of lactose into galactose and glucose and galactose oxidase catalyses the oxidation of galactose into galactonic acid and H2O2. The membranes with the two immobilized enzymes were then used in an amperometric sensor, by oxidation of the H2O2 formed, at a Pt electrode of an Universal Sensors electrode base system. The sensitivity and the reproducibility of the biosensor thus formed were found to be 6.81 and 0.72 nA.M-1, respectively. Biosensors were found to be stable for 20 days.

The zinc electrochemical behaviour from sulphate and sulphate-gluconate baths was studied both on a vitreous carbon and a copper electrode. The voltammetric response depends on the complexing agent concentration, the electrode material, the pH and the cathodic potential limit. The reduction of zinc ions proceeds with hydrogen evolution, and at less negative potentials on the copper electrode than on the vitreous carbon electrode, specially in absence of gluconate. Gluconate decreases the efficiency of the process. On the other hand, gluconate favours zinc electrodeposition on vitreous carbon but retards it on copper.

The electrochemical intramolecular cyclisation of allyl 2-bromophenyl ethers in N,N'-dimethylformamide at constant current in a diaphragmless cell has been developed using Ni(II) and Co(II) complexes as electron-transfer mediators. Cyclic compounds are obtained in good yields under appropriate experimental conditions.

Iron disulphide molten salt electrochemical cells are among the most promising technological options for batteries. The electrochemical behaviour of pyrite allies excellent cathodic characteristics to optimal performance and low operational costs. The cathodic iron disulphide mechanism involves many processes, encompassing from polysulphides formation to the reduction of iron to the metallic state. The use of X-ray diffraction together with scanning electronic microscopy analysis on cells of the Li/KCl-LiCl/FeS2 system made possible to identify intrinsic and extrinsic parameters to the electrochemical process involved in the establishment of the polysulphides stoichiometry. It is necessary to note that the augmentation of the cell's internal resistance and loss of electrical capacity are directly related with the formation of these same substances. Researches in the electrochemistry of these phenomena aim to elucidate the cathodic interphase processes and the effect of every reaction in the global mechanism.

On the basis of an ohmic model and a Tafel equation describing relations between current density and overpotentials in the film and at the metal/film interface, respectively, it is shown that a quantitative analysis of galvanostatic transients for the growth of passivating ultra-thin films on the so-called non-noble metals can be obtained. As an example, the growth of ZnO on Zn in a boric/borate buffer solution is considered. In this case, the values of the transfer coefficient and the exchange current density of the reaction at the metal/film interface were found to be 1.2 and 0.11 mA cm-2, respectively. It was shown that a single, first film occurred at low current densities and two films at high ones. The ionic resistivity inside the single, first film, during the transients, has an initial constant value region followed by a final increase indicating the aging process. For this variation the evolution of the point defect concentrations is taken into account. For the variation of the ionic resistivity with the galvanostatic current density two types of behaviors were found, depending on the current density. An interpretation of these results is advanced in terms of the concentrations, mobilities and recombination rate of point defects inside the film.

CoFe films were electrodeposited on platinum and copper from an acidic sulfate bath. The deposits surface morphology was analyzed using SEM and composition was determined by XPS. For deposition potentials lower than -0.80 V (SCE), the anodic stripping voltammogram showed a complex anodic current peak evidencing the complexity of the deposition process. Analysis of the deposition current transient curves showed that the nature of the substrate influenced the kinetic of the process: it was observed an instantaneous nucleation on Pt and a progressive nucleation on Cu. Pure cobalt and cobalt-iron films formed on Pt and on Cu presented binding energies for Co2p3/2 signal corresponding to cobalt oxide, while the Fe2p3/2 signal is related to metallic iron. The corresponding metallic cobalt was observed for the Co2p3/2 signal with binding energy of about 778.0 eV.

The degradation of a reactive blue 4 dye in acidic solution has been compared using electrochemical reduction and oxidation at reticulated vitreous carbon electrode (RVC) and Ti/SnO2/SbOx (3%mol)/RuO2 (30%mol) electrodes and photo-Fenton method under UV irradiation. The reduction of RB4 dye at -0.6 V on RVC electrode results in 50% of color removal and up to 64% of TOC removal. The direct oxidation of RB4 dye at +1 V on RVC promotes only the oxidation of amine group and there is no color removal. On SnO2 electrode, 58% TOC was removed and the decolorization is around 100 % after 1 hour of electrolysis at 2.4 V indicating good efficiency. Best performance was obtained by photo-Fenton method that indicates 80% elimination of TOC and 100% of color removal but the method requires oxidant addition and time of rest to remove the generated residues.

Cyclic voltammetry and controlled potential electrolysis, and other analytical techniques were used to study the reactions of mercury with iridium oxides formed by repetitive cyclic voltammetry (RCV) or by controlled potential electrolysis (CPE) on pure iridium substrate. The oxides were formed in a Hg(I)-containing solution. The SEM images, XPS spectra and CV obtained after the RCV treatment showed a more attacked surface with less mercury on the Ir. On the contrary, the SEM images, XPS spectra and the CV for the electrode prepared by CPE indicated a less attacked surface with more Hg. The oxides formed when the CPE condition was applied inhibited the UPD of mercury.

This will enable Pb(II) determination optimisation, regarding environmental aspects of the perpetuation of Quercus suber Montado (similar to Forest). It will also allow a more profound toxicological quality control of corks (barks). These two last referred aspects are very related ones, once accepted that the more advanced could the certification of the quality patterns of corks (barks) be, more will be the sustainability of Quercus suber ecosystem. Which we believe can be done, amongst other vectors, by studying such an important environmental issue as heavy metals. It is shown that Pb(II) quantification in the cork (bark) of Quercus suber tree (Cork Oak) is possible, using Differential Pulse Anodic Stripping Voltammetry (DPASV). The samples digestion was made in a mixture of H2O2 and HNO3 1:8, in a closed recipient at approximately 90 ºC. The measures were made in NaCl 0.1 M, using a Hanging Mercury Drop Electrode, a Glassy-Carbon Rod Counter Electrode, and an Ag/AgCl/KCl 3M reference electrode, after a 180 s deposition step. The results have shown the determination of a coherent stripping potential of -0.405 V (SD=0.0005 V), and a fine linear adjustment after the standard addition method (R2 = 0.997). They have also revealed the interest of further studies. The need to test other electroanalysis requisites was understood, and imposed by the proof of the complex nature of the matrix.

The behaviour of the neutral alkynyl complexes trans-[FeBr(L)(depe)2] (L = -C=C-C(=CH2)Ph 1a, -C=C-CPh2(H) 1b; depe = Et2PCH2CH2PEt2) is studied by cyclic voltammetry and the electrochemical PL and EL ligand parameters for the alkynyl ligands are estimated showing that they behave as very strong net electron-donors.

Erratum to “Electrochemical Behavior of Pt(IV) on Mercury Electrode in the Presence of Dimethylglyoxime” Volume 20, Issue: 4, Year: 2002, pp.179-189.

The rate of copper dissolution in presence of phosphoric acid tert-butanol electropolishing mixtures was studied by measuring the limiting current which represents the rate of electropolishing. The rate of dissolution decreases by increasing phosphoric acid concentration, electrode height and the mole fraction of alcohol. The data show that addition of tert-butanol to phosphoric acid decreases the rate of dissolution of copper by an amount ranging from 68 % to 90 % depending on the dielectric constant of mixtures. Thermodynamic parameters are given.

A solid of Fe2O3 based carbon-epoxy composite electrode was investigated for use as a potentiometric pH sensor. The electrode was constructed with a mixture of sulfated iron(III) oxide, carbon power and epoxy resin that was deposited directly onto a glass tube. The effect of composition (Fe2O3, carbon and epoxy resin) on the electrode response and its calibration curve (mV/pH) were investigated. The analytical behaviour of the electrode in acid-base titrations was compared with that of a glass electrode. A linear response from pH 1.7 to 12.2 with a slope of -39.7 ± 0.6 mV/pH (at 25 ºC) was observed.

The formation and stability of alkali metal complexes with crown ethers containing an anthraquinone unit has been investigated in methanol and acetonitrile solutions by potentiometric methods. Complexes of 1:1 stoichiometry were observed for all the studied systems; 2:1 complexes were only detected for the larger alkali cations (Rb+ and Cs+) and with the ligand with the larger macrocyclic cavity (AQ21C7). The 1:1 complexes with the highest stability are formed by K+ ion with the AQ18C6 ligand and by Cs+ ion with the AQ21C7 ligand. In the alkali cation group and in both solvents, the stability of the 1:1 complexes was found to vary in the following order, Li+ < Na+ < K+ > Rb+ > Cs+ with AQ18C6 ligand and Li+ < Na+ < K+ < Rb+ < Cs+ with AQ21C7 ligand. The stability of the complexes of AQ21C7 is smaller than those of their AQ18C6 analogues. The stability of the silver complexes of AQ18C6 and AQ21C7 was found to be smaller than that of the alkali metal complexes of comparable size. The incorporation of an anthraquinone unit in crown ethers induces some loss of complexation stability for all cations, but the cation selectivity is not changed. The results obtained are analysed and discussed regarding the effects of the relative sizes of the cations and macrocyclic cavity of the ligands, solvating ability of the solvents towards the cation and influence of the anthraquinone unit.

The electrochemical behavior of Pt(IV) ions in the presence of dimethylglyoxime has been investigated using adsorptive stripping voltammetric method. The results indicated that the platinum is reduced from its adsorbed state as bis-dimethylglyoxi-mate platinum(IV) complex. The peak current is linearly proportional to the Pt(IV) concentration in the solution, thus representing the basis for a quantitative analysis. Various experimental parameters affecting the stripping response, indicating pH, the ligand concentration or the accumulation time and potential, and the scan rate, were studied to obtain a highly linear response. From the results the scheme for the reduction process of the platinum dimethylglyoximate complex in acidic media is presented.