Portugaliae
Electrochimica Acta

The effect of different concentrations of 1,3-dihydroxypropane (DHP) on the electrodeposition of copper powder from acidified copper sulphate solution has been studied at different temperatures and different speeds of rotation. Copper powder was electrodeposited onto rotating cylinder electrode (RCE) that made of pure copper. The inhibition percentage, P, in the electrodeposited copper powder was 0.00 – 92.91%, depending on the experimental variables. P was affected by temperature and mole fraction of DHP, while rotation did not show any influence whatsoever. Values of the activation energy of electrodeposition process, Ea, were found to be less than 28 k J mol-1 indicating diffusion controlled process. The overall mass transfer correlations under the present conditions have been obtained using the dimensional analysis method. The data were valid for 80 < Sh (Sh = Sherwood number) < 3970, 290 < Sc (Sc = Schmidt number) < 59284 and 271 < Re (Re = Reynolds number) < 52705 and the results agreed with the previous studies of mass transfer to rotating cylinders in turbulent flow regimes. Experimental determination of the solution critical velocity was obtained for blank and 20% (v/v) DHP solutions at 298 K. The effect of time, DHP content, temperature and the speed of rotation on the morphological changes of the electrodeposited copper powder as well as deposits composition and particle size have been studied. Various particle sizes ranged 60.5 – 203.4 nm were obtained, characterized by EDS and XRD and found to be pure copper with small amount of oxygen. Different topographs proved that the rate of copper electrodeposition increased by increasing time, temperature and the speed of rotation. In addition, they proved that the deposition rate decreased by adding DHP to the solution. Therefore, the results obtained by SEM supported those results obtained by electrochemical measurements. The morphological structure of deposited copper powder from 20% (v/v) DHP at 1000 rpm and 298 K was unique, rounded-crystalline aggregates with voids.

This work presents the results of corrosion inhibition of muntz alloy (63% Cu,  37% Zn) in 1.0 M HCl by water extracts of some naturally occurring plants. These are: outer brown skin of onion (A), onion bulb (B), the cloves of garlic bulb (C), orange peels (D), and henna leaves (E). The techniques of measurements for the determination of the amount of each zinc and copper dissolved from the alloy in the aggressive solution were: weight-loss, galvanostatic polarization, linear polarization and atomic absorption spectroscopy. From these measurements the values of surface coverage, , and inhibition efficiency were calculated. It was found that the investigated extracts have high inhibition efficiency on the corrosion of muntz alloy in 1.0 M HCl. Their inhibition efficiency decreases according to the order: C > D > E > B > A. These extracts behave as mixed inhibitors, i.e., they affect both the cathodic and anodic processes. The activation energy of corrosion was calculated in absence and in presence of extracts. It was found that the presence of extracts in 1.0 M HCl solutions increases the values of activation energy of corrosion in that order of their inhibition efficiency. The inhibiting effect of these extracts results from their adsorption on the electrode surface via the adsorption centers of the compounds present in the extracts. The adsorption of these extracts onto the surface of muntz follows Frumkin,s isotherm. The atomic absorption spectroscopic measurements showed that the presence of these extracts greatly inhibits the preferential dissolution of zinc from the alloy and the occurrence of simultaneous dissolution of both zinc and copper.

The effect of natural occurring extract of artemisia on the corrosion of steel in 0.5 M H2SO4 in the temperature range 298 – 353 K is studied by weight loss method, electrochemical polarisation and linear polarisation Rp measurements. Results obtained reveal that extract reduces the corrosion rate. The inhibition efficiency increases with the increase of artemisia content at 10 g/L to reach 95% and 99% at 298 and 353 K, respectively. Results obtained by gravimetric and electrochemical polarisation are in good agreement. Polarisation studies clearly reveal that the presence of the natural artemisia does not change the mechanism of the hydrogen evolution reaction and acts as a mixed type inhibitor. The inhibition efficiency increases with temperature. The adsorption of artemisia on the steel follows Langmuir adsorption isotherm.

In this work the characteristics of corrosion and inhibition of 1008 stainless steel in 0.5 mol.L-1 H2SO4 were investigated by physical and electrochemical methods. Organic compounds containing the heteroatom of N as benzotriazole (BTAH), tolytriazole (TTAH) and mixtures of BTAH + TTAH were used as corrosion inhibitors. The techniques used were: open circuit potential, anodic potentiodynamic polarization measurements, chronoamperometry, electrochemical impedance spectroscopy, weight loss and optical microscopy. The anodic polarization showed that the increase of both concentrations BTAH or TTAH diminishes the current density in all the potential anodic range studied; these results together with the weight loss measurements suggest that the inhibitors act by blocking the surface and that the interaction among them is only of destructive nature when inhibiting efficiency is approximated 100%, revealing that at low concentration both inhibitors act without affecting the mechanisms of the cathodic processes, but the anodic polarization curves in presence of the TTAH showed a strong inhibitive effect in all the potential range studied. However, both gravimetric and electrochemical results suggest a synergic effect for the inhibitive efficiency of the mixture 1x10-3 mol.L-1 BTAH + 1x10-3 mol.L-1 TTAH.

This work is centered on the study of the corrosion inhibition of copper in 1 M HNO3 by N-phenyl oxalic dihydrazide (PODH) and oxalic N-phenylhydrazide N’-phenylthiosemicarbazide (OPHPT) synthesized in our laboratory. The inhibition efficiency obtained by chemical (weight loss) and electrochemical (potentiodynamic polarization) techniques shows that these compounds are very good inhibitors. Polarization curves indicate that OPHPT acts as a mixed type inhibitor while PODH acts on the cathodic reaction. The adsorption of these inhibitors is found to obey Langmuir adsorption isotherm. The thermodynamic functions of adsorption and dissolution processes were calculated.

The inhibitive action of the extract of Ficus nitida leaves toward general and pitting corrosion of C-steel, nickel and zinc in different aqueous media was investigated. Weight loss measurements, potentiostatic and potentiodynamic polarization techniques were used in this study. It was found that the presence of ficus extract in the corrosive media (acidic, neutral or alkaline) decreases the corrosion rates of the three tested metals. The inhibition efficiency increases as the extract concentration is increased. The inhibition efficiency depends on the type of corroded metal and on the corrosive solution. It was also found that the presence of ficus extract in the chloride containing solution shifts the pitting potentials of the tested metals toward the noble direction. The inhibitive action of ficus extract is discussed in view of adsorption of its components, the poly aromatic compounds, friedelin, epifriedelanol and nitidol, on the metal surface. It was found that such adsorption follows Langmuir adsorption isotherm. The calculated values of the free energy of adsorption indicated that the adsorption process is spontaneous.

Theoretical analyses show that in a sampled dc polarography on the static mercury drop electrode the response may consist of a pre-wave and a main wave that are separated by a minimum. This is a general characteristic of electrode reactions complicated by strong adsorption of the product. A steep pre-wave and the minimum are the indications of Frumkin isotherm. A flat plateau of the pre-wave is a special case of the steep plateau which appears at lower reactant concentrations. If the adsorption is weak, the pre-wave and the main wave are usually merged into a single wave.

A modified electrodialytic cell integrates electrodialysis and reduction of metal ions. The cell is able to recover metallic copper from wastewater containing 1000 ppm cupric ions and bring the concentration down to about 1 ppm. The kinetic data of decreasing copper ion concentration fit well in first order kinetics and allow calculation of the over all reaction rate constant. Effect of several parameters, namely, width of wastewater compartment, applied potential and concentration of anolyte and catholyte solution; on the over all reaction rate constant and specific energy consumption were studied. The best combination of parameters results in an overall rate constant of 7.84 × 10-4 sec-1 and specific energy consumption of 48.18 kW-h/kg copper.

By cyclic voltammetry the active/passive transition of Nb electrode has been investigated in concentration range from 0.1 M to 10 M aqueous solutions of H2SO4 and KOH. Results indicate the strong influence of the concentration and electrolyte nature to the active/passive transitions and stability of passive films. Depending on electrolyte concentrations, at potential of 1 V the calculated thickness of passive films varied from 2.2 nm to 3.2 nm. For the same concentrations of H2SO4 and KOH the formed passive films in KOH are thicker than in H2SO4. By multiple cycle sequences in which the final anodic potential is gradually enlarged, the barrier properties of passive films on Nb electrode were confirmed. In the first positive scan after the active/passive transition, no cathodic or reactivation peaks for both 1 M H2SO4 and KOH were observed. Only for higher concentrations of KOH (> 2 M) the small reactivation process was recorded. In concentration of 5 M and 10 M KOH, if after the passive film formation the Nb electrodes were maintained for 15 min at cathodic potential of -1.55 (SHE), the cyclic voltammograms indicated the complete dissolution of passive films. The voltammetric data have confirmed that the Nb electrode is more resistant in concentrated H2SO4 than in concentrated KOH solutions.

In Honour of Prof. João Cabral

Advanced electrochemical oxidation processes (AEOPs) constitute promising technologies for the treatment of organic pollutants in waters. They are based on the production of oxidant hydroxyl radical (•OH) from water oxidation on the surface of a high O2-overvoltage anode and/or from Fenton’s reaction between added Fe2+ and hydrogen peroxide electrogenerated at the cathode by two-electron O2 reduction. In this paper, fundamentals of AEOPs such as anodic oxidation, electro-Fenton, photoelectro-Fenton and peroxi-coagulation are described, and comparative degradation of aqueous solutions with aromatic pollutants, such as aniline, 4-chlorophenol and several chlorophenoxyacetic and chlorobenzoic acids, in 0.05 M Na2SO4 + H2SO4 of pH 3.0 by these techniques using an undivided electrolytic cell with an O2-diffusion cathode under galvanostatic conditions is discussed. The decay kinetics of chlorophenoxyacetic acids and the evolution of their aromatic intermediates and generated carboxylic acids are also reported to clarify their mineralization processes by the different AEOPs. Anodic oxidation with a Pt anode yields poor decontamination of pollutants, while alternative anodic oxidation with a boron-doped diamond (BDD) anode leads to total mineralization of all solutions due to the greater production of •OH on the BDD surface. Electro-Fenton with a Pt anode has high oxidation ability at short electrolysis times, but the formation of stable Fe3+-oxalate complexes limits the degradation of aromatic contaminants. These products are completely oxidized in electro-Fenton with a BDD anode or photodecomposed by the action of UVA light in photoelectro-Fenton with a Pt anode. Peroxi-coagulation with an Fe anode also gives fast degradation with generation of small amounts of stable Fe3+ complexes, since organics are mainly retained in the Fe(OH)3 precipitate formed.

The presence of soluble salts (particularly sulphates and chlorides) at the metal/paint interface is known to have a detrimental effect on the integrity of most paint systems. Though this is a long-standing problem, it has recently come to receive greater attention from the protective coatings industry. International Standards Organization (ISO) has for some time been trying to develop a standard about guidance levels for water-soluble salt contamination before the application of paints and related products. In the paper the following points are reviewed: degradation mechanisms, nature and sources of soluble salts, their distribution on the metallic surface, the joint action of chlorides and sulphates, the effect of the joint presence of rust, new methodologies for sample preparation with known levels of soluble salts, measuring soluble salts, establishment of threshold levels, removal of salts and new suitable coating systems for applying on substrates contaminated with soluble salts.

This review was erected to describe briefly proteins and processes responsible for the formation of the nativ-folded thioproteins in the pro- and eucariotic cells. This issue has a significant importance due to many dieases and misfunctions caused by misfolded enzymes having low or inactive structure. On the other hand the reduction of the yield of the correctly folded enzymes in the bacterias causing health problems, we can have a needed tool for medical care. This review contains also a short list of an electrochemical methods for the detection and the quantification of the most important thioproteins.

Based on the principles of the technique of electroremediation (electrochemical decontamination), experiments were carried out with the purpose to determine the buffer capacity of two soils from the region of Antioquia, Colombia, using a new method. These studies included the analysis of variation of the conductivity and residual pH in selected soils, after application of an electric field. From the different obtained parameters a function was defined combining the values of pH in zones close to the cathodic chamber with the corresponding one to the blank. This function allows obtaining a measurement of the buffer capacity of the soils. In this case the function represents the easiness for changing the pH when the electric field is applied and therefore it would not only have agricultural utility, but also to evaluate the behaviour in the case of a electrochemical decontamination treatment. The observed variations in the function are in agreement with those obtained when acid or bases solutions are added to soils.

Sex hormones like 17ß-estradiol (ßES) and progesterone have shown rapid non-genomic vasodilator effects, which could be involved in the protection of cardiovascular system. However, the precise mechanism by which this effect occurs has not been elucidated yet, even if Ca2+ influx inhibition seems to be implicated. The aim of this study was to study the influence of ßES and progesterone on the L-type Ca2+ current measured by whole cell voltage-clamp in A7r5 cells. Voltage-operated Ca2+ currents were elicited by square-step voltage pulses and pharmacologically characterized as L-type currents by (-)-Bay K8644 (BAY) and nifedipine. Both ßES and progesterone (1-100 µM), rapidly and reversibly inhibited, in a concentration dependent manner, either non-stimulated or BAY-stimulated Ca2+ currents registered in A7r5 cells. These results suggest that ßES and progesterone inhibit L-type voltage-operated Ca2+ channels through a non-genomic pathway. Consequently, these hormones inhibit the Ca2+ entry into smooth muscle cells from rat aorta, an effect that can contribute for the protection of the cardiovascular system.

The electrochemical behaviour of the new vanadium(IV) complex [VCl3(SO3Cpz3)] (pz = pyrazolyl), obtained by reaction of VCl3 with Li[SO3Cpz3], investigated by cyclic voltammetry and controlled potential electrolysis is reported and compared with those of hydrotris(pyrazolyl)borate vanadium(IV) complexes.

A FIA system with electrochemical detection was developed for the automatic determination of paracetamol in pharmaceutical formulations. The analytical difficulties caused by adsorption of matrix excipients in the electrode surface were surpassed by an on-line electrochemical regeneration of the glassy carbon tubular electrode, using the carrier solution, enabling the renewal of the electrode surface in a simple and rapid way. A single channel FIA manifold was developed, which provided reproducibility of sample transport to the detector and minimized the contact time between samples and electrode surface, thus reducing its cleaning frequency and permitting a high sampling rate to be achieved. Furthermore, the physical characteristics of the electrochemical cell permitted its easy incorporation in the FIA manifold, offering robustness to the system, and allowed it to be generalized to routine analysis applications. With the optimized parameters, a linear correlation between paracetamol concentration and peak current intensity was obtained up to 4  10-4 mol L-1, with a detection limit of 2.5  10-5 mol L-1. Paracetamol was quantified in pharmaceutical dosage forms and the results were compared to those obtained for the official spectrophotometric method (BP 1998). Correlation between the results obtained by both methods was linear and no statistical difference between methods was found at the 95% confidence level.

The electrochemical oxidation of four different azo dyes, C.I. Acid Orange 7 (AO7), C. I. Direct Red 254 (DR254), C. I. Direct Red 80 (DR80) and Yellow Gold Sandolan (YGS), was performed using as anode material an oxide with a perovskite like structure, BaPb0.9Sb0.1O3-δ. Bulk electrolysis was studied using Na2SO4 as electrolyte, at a current density of 5 mA cm-2. UV-Visible absorbance measurements, Chemical Oxygen Demand (COD), Total Organic Carbon (TOC) and High Performance Liquid Chromatography (HPLC) analysis were performed, in order to follow the colour and COD removals and the mineralization index. The obtained results show an almost complete colour removal for the solutions containing AO7, DR254 or DR80, after 24 h essay. For these dyes, after 96 h electrodegradation experiment, COD removals between 30 and 70 % and TOC removals ranging from 15 to 40 % were obtained. However, for the experimental conditions used, the electrodegradation of YGS was not possible.