Portugaliae
Electrochimica Acta

This work is part of the DURACON project, in which it is characterized the concretes exposed durability in the present iberoamerican environmental conditions, being based in the exhibition of armed specimens in at least two different atmospheres, a marine and an urban, in each iberoamerican participant country. The results obtained by exposing these armed concrete specimens to the environmental conditions of the city Chihuahua, Mexico, during the first 15 months of exhibition, will be discussed in this work. Two concretes were designed, one with a relationship w/c (water/cement) = 0.65, and the other one with w/c = 0.45, and three cover thickness (1.5, 2.0 and 3.0 cm). Tests were mainly based in measuring electrochemical parameters that allowed evaluating the corrosion kinetics of the bars, by means of potential corrosion measurements and implementing the technique of linear resistance polarization in order to determine the corrosion rate. All this information will permit, with the use of specific models, to design durable concrete structures, and to repair appropriately those already existent, what will rebound in a decrease of the economic losses that at the moment is causing the phenomenon of corrosion in our country.

The present work shows the results of the electrochemical evaluation of reinforced concrete specimens exposed in 3 to 5% Na2SO4 solutions during four months exhibition. The concrete was elaborated with water/cement ratio (w/c) of 0.4, 0.5 and 0.6. The electrochemical evaluation was carried out using the lineal resistance polarization technique. The results of these tests show that the biggest attack for Na2SO4 was presented in the specimens of 0.5 and 0.6 w/c ratio. Also, they showed a passive tendency after curing. On the other hand the Rp curves analysis, shows that in all the evaluated specimens a great corrosion rate was presented during the curing stage and after some time the system tends to be stabilized approximately in 0.05 mm/yr.

This research was made to determine the corrosion rate of the copper cable used in grounding and lightning systems, at the electrical generation plants from the Costarrican Electrical Institute. The methods used were linear polarization resistance (LPR), and the weight loss one. This report includes both, laboratory and field tests of corrosion rates, using as electrolytes two products commercially available. Moreover, some electrochemical experiments were developed at the laboratory, in order to know the reaction mechanisms. The goal of this study was to generate criteria for the maintenance and/or the substitution of copper cables according to their deterioration. The results showed that the corrosion rate in "A" is at least ten times higher than in "B". In addition, several samples in the "A" electrolyte had pitting corrosion. The study indicates that from the point of view of the corrosion it is preferable to use product "B" like filling, since the generalized corrosion of copper is lower and in addition localized damage does not appear.

Methanol electrooxidation was investigated on tailored Pt-Ru-polyaniline catalysts prepared applying dynamic potential routines. The electrodes characterized by SEM, EDX and TEM present a uniform distribution of metal particles about 100 nm in size, composed of Ru and Pt on the fibrous polymer matrix. The effect of concentration in the range 0.05-1 M and temperature in the range 20 to 60 ºC on the methanol electrooxidation rate was determined. The apparent activation energy depends on the catalyst Ru content.

Carbon pencil electrodes are proposed as supporting material for the fabrication of disposable devices through surface modification by bismuth plating and polyaniline formation. The surface characteristics were assessed by fractal analysis under semi-infinite linear diffusion employing a soluble molecular probe, and scanning electron microscopic analysis. The results indicate that the surface topography for bismuth-modified electrodes corresponds to a 2-dimensional smooth surface, while for polyaniline-modified electrodes, a surface fractal dimension of 2.76 was obtained. These topographic characteristics indicate that bismuth-modified carbon electrodes are suitable for anodic stripping analysis, and polyaniline ones, due to the surface irregularities, may result a good supporting material for biomolecules attachment.

An integral analysis was carried out on the results obtained in laboratory experiments on electro-remediation of soils using two heavy metal-contaminated volcanic soils from the region of Antioquia, Colombia. Measurements of pH, conductivity, and pollutant concentration were made on each soil. The results were related to the structural characteristics of the soils employed in the experiments. Under the present experimental conditions it was shown that the soil with the lower concentration of organic matter had a lower pH regulatory capacity, that treatment without using wash solutions was more efficient for the mobilization of the metals, and that the particular characteristics of each soil conditioned the efficiency of the treatment.

Studies of soil resistance suggest that this type of measurement when carried out simultaneously with decontamination treatment, serves as a rapid method for analyzing the behavior of different soils under study, especially when an electric field is not applied.The variation observed in the first step of electro-remediation is related to the ionic content of the segments adjacent to the electrodes. The use of a wash flow facilitates the formation of "ionic batches" near the electrodes. The soil with the higher content of organic material shows lower resistance in the first stage of the treatment. Measuring the electrolysis current without the use of wash flow, together with the other experimental parameters, allows the evaluation of the soil characteristics in experiments of relatively short duration.

The electropolymerization of phenylacetylene on a Pt electrode has been carried out in two different solvents, acetonitryle and propylene carbonate. The kinetic study carried out leads to values in the kinetic parameters which are significantly different in both solvents. The values deduced for na, Z (reaction order with respect to the phenylacetylene concentration) and activation enthalpy and entropy, were 0.75, 1, 25.3 kJ mol-1 and -87.0 J mol-1 K-1, respectively, in acetonitrile, and 0.25, 0.5, 33.6 kJ mol-1 and -105 J mol-1 K-1, when working in propylene carbonate. The discrepancy in the values can be explained as a consequence of the change in the initiation step of the polymerisation induced by the adsorption of the acetonitryle molecules. The product obtained was isolated, purified and characterised to be formed by a polyenic chain with a linear trans structure. The average molar mass of the product was 3095, corresponding to a polymer formed from around 30 units of monomer.

A few non-aqueous dipolar aprotic solvents of medium to high permittivities, low viscosities and large temperature intervals between freezing and boiling points have been used to prepare electrolyte solutions applicable to primary and rechargeable high energy batteries. Lithium perchlorate is a salt often chosen to obtain those systems. In this work low temperature effects on conductivities and association constants of LiClO4 and Et4NBr in six different solvents have been analyzed, using the tetraethylammonium bromide salt for comparative reasons. The temperature interval was -30 ºC to 10 ºC. A few thermodynamic functions resulting from KA, T variations were determined being the results discussed on this basis. The accuracy and precision of results are high; whenever possible they are compared with others previously published.

Os estudos cronoamperométricos foram motivados pela observação de histerese de corrente nos perfis de redução dos voltamogramas realizados no sistema Sn/bicarnonato, já que é sabido na literatura que a presença de histerese é considerada indicativo de ocorrência de processos de nucleação. A ocorrência de nucleação foi verificada mediante técnica cronoamperométrica quando filmes eletrogerados na região de passivação são reduzidos. Empregando rotinas de análise de mínimos quadrados não lineares, foi obtido o ajuste entre os resultados experimentais e os calculados usando modelos teóricos que descrevem a nucleação eletroquímica. Assim, a eletrorredução do filme formado no extremo inferior da região estudada, pode ser explicada em termos de difusão e nucleação progressiva e crescimento 3-D controlado por transferência de carga. Por outro lado, a redução do filme electrogerado no extremo superior segue o modelo de nucleação progressiva e crescimento 3-D controlado por transferência de carga, com a presença de tempo de indução. A análise da variação dos parâmetros modelísticos com o tamanho do degrau de potencial permitiu estabelecer a influência dos valores das constantes de velocidade paralela e perpendicular à superfície para cada caso experimental.

The effect of the presence of CO2 and H2S in the well water used in the petroleum plant on corrosion of carbon steel has been tested using impedance measurements. Carbon dioxide leads to decrease in the resistivity of the film developed on the metallic surface, while the effect of hydrogen sulfide is less pronounced. Scanning electron micrographs have shown that corrosion products cover only small part of metallic surface in water containing CO2. Studies under polarization conditions will allow concluding that the dissolved gases in the well water reduce the ability of the film to protect the metal against corrosion. The influence of the oxoanions and halide ions on the corrosion rate of steel has also been analyzed.

The effect of iodide ions on the corrosion inhibition of mild steel in 0.5 M sulfuric acid in the presence of poly(4-vinylpyridine) (p4vp) was studied by weight loss and different electrochemical techniques such as electrochemical impedance spectroscopy, potentiodynamic polarization and polarization resistance measurements. The obtained results showed that poly(4-vinylpyridine) effectively reduces the corrosion rate of mild steel. The addition of potassium iodide (KI) enhanced the inhibition efficiency (P%). The synergism parameter (Sp) calculated from inhibition efficiency was found to be greater than unity, suggesting that the phenomenon of synergism exists between P4VP and iodide ions. The adsorption of p4vp alone and in combination with KI followed Frumkin adsorption isotherm. The effect of temperature indicated that the inhibition efficiency of p4vp decreases with increasing temperature. Study of temperature effect showed also that inhibition efficiency of (P4VP + KI) does not depend on temperature. The apparent activation energies in the absence and in the presence of P4Vp and ( P4VP + KI ) were determined.

This paper describes the use of a FIA system for the automatic determination of uric acid in urine, using a tubular amperometric detector. In this system, glassy carbon electrodes of tubular configuration were activated by successive cyclical scans from - 0.30 to 2.00 V versus Ag/AgCl reference electrode in 0.50 mol.L-1 sulphuric acid solution. Samples were diluted in supporting electrolyte before analysis and no other pre-treatment was employed. Such dilution enabled the matrix effects to be reduced and therefore improving the sensitivity provided by the activation step that allows the uric acid (UA) to be detected at lower concentration levels after dilution. Uric acid determination was performed in a single channel FIA manifold, which provided reproducibility of sample transport to the detector and enabled a sampling rate of 120 samples per hour to be achieved. The tubular configuration of the cell offered robustness to the system since it was rigidly fixed to the manifold, allowing the manifold to be generalised for routine analysis application. The results obtained with the FIA system for UA determination in urine were compared with those from the enzymatic method used in clinical analysis laboratories. No statistical difference between methods was found at the 95% confidence level. Relative deviations between both methods were within ± 4% and the proposed system showed good repeatability (about 3%, n = 10).

The electronic structure of the passive films formed on stainless steels of different chemical composition in artificial sea water is examined by capacitance measurements (Mott-Schottky approach) and photo-electrochemistry. Analytical characterization is carried out by Auger Electron Spectroscopy. The influence of the main alloying elements (Cr, Ni) on the development of space charge regions, which can be described as a depletion or accumulation layers are discussed.

The electrochemical removal of the textile dye C. I. Direct Red 80 (DR80) was carried out using three different materials as anodes: iron, polypyrrole (PPy) and boron doped diamond (BDD). Iron electrodes are consumed during the electrolysis, and promote flocculation/coagulation of the dye. Polypyrrole, a conducting polymer, was prepared by chemical/electrochemical precipitation over a cotton cloth; it enables the precipitation of the dissolved dye through a conversion reaction in a less soluble compound. Boron doped diamond electrode was used to achieve the complete mineralization of the dye. Bulk electrolysis were studied using Na2SO4 as electrolyte. In the case of the PPy electrode, NH4NO3 was also used as electrolyte. The variation of the dye concentration was followed by UV-visible absorbance measurements and chemical oxygen demand (COD) tests were also performed, to compare the rates of colour and COD removal in each case. From the COD measurements over the time of electrolysis, using the BDD anode, a mass transfer coefficient for the DR80 molecule was determined. The obtained results show an almost complete colour removal for all the electrodes tested and a COD removal between 50 and 90 %, being the best results obtained with the BDD electrode.

In the present work, the electronic structure of the passive film formed on austenitic stainless steel of the 304 type and its implications on the initiation of localised corrosion are investigated taking into account concepts developed in semiconductor physics and semiconductor electrochemistry. Capacitance measurements (Mott-Schottky approach), show that the susceptibility of AISI 304 stainless steel to stress corrosion cracking (SCC) in boiling chloride containing aqueous solutions is closely linked to the formation of a chromium rich passive oxide film with p-type semiconductivity. A small polarisation is required to drastically change the electric field at the film-electrolyte interface, as a consequence of the high doping level of the passive film. Initiation of the SCC phenomenon is described as the consequence of localised changes in the semiconductive properties of the passive film.

Iron nitroprusside, Fe(II)NP was incorporated into a carbon paste electrode and the electrochemical studies were performed by cyclic voltammetry. The cyclic voltammogram of the modified electrode, Fe(II)NP showed two redox couples ( E½ox)1 = 0.24 and (E½ox)2 = 0.85 V vs. SCE attributed to Fe(II)/Fe(III) and Fe(II)(CN)5NO / Fe(III)(CN)5NO, respectively. The redox couple at (E½ox)1 = 0.24 V presents an electrocatalytic response for ascorbic acid. The modified paste electrode exhibits a decrease of 180 mV in the ascorbic acid oxidation. The modified graphite paste electrode gives a linear range from 1.0 × 10-3 to 2.6 × 10-2 mol L-1 of ascorbic acid with a detection limit of 1.4 × 10-3 (±1.2%) mol L-1 (n =3). The electrocatalytic oxidation of ascorbic acid compounds by the mediator has been used for the determination of ascorbic acid in a commercially pharmaceutical available product.