Portugaliae
Electrochimica Acta

The cyclic voltammetric study on the electro-oxidation of methanol on 30 % Pt and 20 % Pt +10 % Ru catalysts supported on Vulcan XC-72 was carried out in 0.5 M H2SO4. Kinetic parameters such as exchange current density, Tafel slope and heterogeneous rate constants were calculated. The 30 % Pt showed a higher apparent catalytic activity for the electro-oxidation of methanol as compared with 20 % Pt + 10 % Ru catalyst. The presence of Ru did not contribute significantly towards the apparent catalytic activity of a catalyst for the electro-oxidation of methanol but it may be useful to prevent the catalyst from CO poisoning. Thermodynamic parameters, ΔH*, ΔS*, and ΔG298* have been evaluated. The values of ΔH* and ΔG298* were positive showing that the electro-oxidation of methanol is an endothermic and non-spontaneous process.

The corrosion of mild steel in H2SO4 was studied using gravimetric, gasometric and IR methods. The results indicate that the rate of corrosion of mild steel in H2SO4 increases with increase in the concentration of the acid and that ethanol extracts of the seeds and leaves of Azadirachta indica inhibit the corrosion of mild steel in H2SO4. Inhibition efficiencies of the leaves and seeds extract range from 82.62 to 94.24% and from 60.55 to 84.78%, respectively. The inhibition potential of these extracts is attributed to the presence of tannin, saponin, glycoside, anthraquinone, flavonone and other phytochemicals in the extracts. IR study confirms that the inhibitors are adsorption inhibitors and the adsorption of the inhibitors on mild steel surface is exothermic, spontaneous and consistent with the assumptions of Flory-Huggins adsorption isotherm. Based on the values of the activation, free energy of adsorption and the variation of inhibition efficiency with temperature, a physical adsorption mechanism is proposed for the adsorption of ethanol extract of leaves and seeds of Azadirachta indica on the surface of mild steel.

New developments in the utilization of a laccase based polyphenolic biosensor were done in order to optimize its application in wines. Laccase was immobilized on polyether sulphone membranes and applied on an Universal Sensors (US) electrode base system containing a platinum working electrode and silver, silver chloride electrode. Caffeic acid was dissolved either in tartarate standard buffer solution at pH 3.5 or in 12% ethanol tartarate standard buffer solution at pH 3.5. The referred values of pH and ethanol percentage are the average values of table wines. Wines from different regions of Portugal, namely Grão Vasco (Dão), A P_Cabernet (Setúbal), C P_Castelo de Syrah (Setúbal), Ol (Alentejo), A P (Alentejo) and Quinta dos Poços (Douro), were studied. Grão Vasco was taken as a reference. It was observed that Grão Vasco (Dão) wine presented a caffeic acid equivalent concentration superior to the other studied wines, followed by a Douro wine: Quinta dos Poços (values of 17.00 and 12.18 mg/L, respectively, were found). It was also possible to verify that the two latter referred wines did not inhibit the biosensor, which could be reused after having been dipped in those wines. However, the wines from Setúbal and Alentejo, studied in this work, have a caffeic acid equivalent concentration lower than the other two mentioned before and seemed to inhibit the system, since the biosensor response decreased after being used in them. It was, thus, not possible to do several assays with the same membrane, when those wines were used. Reproducibilities were better for caffeic acid standard solutions, Grão Vasco and Quinta dos Poços wines, than for the other wines. In fact RSDs (Relative standard deviations) of the order of 1.1, 1.4 and 5.0% were obtained for caffeic acid standard solution, Grão Vasco and Quinta dos Poços wines, whereas 20% was found in the Setúbal and Alentejo studied wines. Two particular wines, A P_Cabernet and A P, were studied in more detail. Cyclic voltammograms and biosensor responses of these two wines indicate that A P has more caffeic acid equivalents than the A P_Cabernet.

Three polyvinylchloride (PVC) membrane sensors for the determination of moexipril hydrochloride were prepared and characterized. The sensors are based on the use of the ion association complexes of moexipril cation with either ammonium reineckate (sensor 1) or tetraphenyl borate (sensor 2) or phosphotungistic acid (sensor 3) counter anions as ion exchange sites in the PVC matrix. The performance characteristics of these sensors were evaluated according to IUPAC recommendations, which reveal a fast, stable and linear response for moexipril over the concentration range of 10-6 to 10-2 M for the three sensors with cationic slopes of 29.1, 30.1 and 30.2 mV per concentration decade for the three sensors, respectively. The direct potentiometric determination of moexipril hydrochloride using the proposed sensors gave recoveries % of 99.64 ± 0.34, 99.34 ± 0.56 and 99.68 ± 0.42 for the three sensors, respectively. The sensors were used for determination of moexipril hydrochloride in pharmaceutical formulations and in plasma. Validation of the method shows suitability of the proposed sensors for use in quality control assessment of moexipril hydrochloride. The obtained results were in a good agreement with those obtained using the reported spectrophotometric method.

Aluminium metal matrix composites (AMMCs) are now gaining their usage in aerospace and automotive industries. Because of their inherent nature, difficult to machine, they find very little applications in other sectors. Even non traditional processes like Laser Jet Machining and Electro Discharge Machining result in significant sub surface damage to the work. In this paper, an attempt is made to machine the A356/SiCp composite work material using Electro Chemical Machining process. Silicon carbide with an average particle size of 40 microns is tried in three different proportions, namely 5%, 10% and 15% by weight. Taguchi’s L27 orthogonal array is chosen to design the experiments and 54 trials are conducted to study the effect of various parameters like applied voltage, electrolyte concentration, feed rate and percentage reinforcement on maximizing the material removal rate. ANOVA results have shown that all the four selected factors are significant and from the S/N graph the optimum level of each factor is chosen. A mathematical model is also developed using the regression method. Confirmation experiment is conducted and found that the data obtained have close match with the data predicted using the model.

This paper reviews some recent canonical Monte Carlo simulations of the Au(210)/H2O interface using a DFT force field developed by us. New results are reported on the solvent contribution to the potential of mean force (PMF) for the phenol adsorption, from a dilute aqueous solution, onto the Au(210) surface. The Monte Carlo simulations show the common features normally observed in the simulation of water in contact with metallic surfaces, where the water molecules adsorb forming bilayers. The molecules adsorbed over the Top gold sites form hydrogen bonds between the first and second solvent layers. The PMF calculations indicate that the phenol molecule penetrates the solvent layers with the aromatic ring in a perpendicular configuration and the oxygen atom pointing to the surface. The PMF results also suggest the existence of hydrogen bonds between the phenol molecule and the first solvent layer of the water molecules adsorbed onto the Top sites.

The numerical method for the simulation of linear scan voltammetry on the rotating disk electrode is adjusted to the problem of irreversible redox reaction between the adsorbed catalyst and the dissolved reactant under transient conditions. The response consists of the wave and the maximum. The peak current depends on the scan rate in linear scan voltammetry, while the limiting current of the wave depends on the rate of rotation of the working electrode. The rate constant of catalytic reaction is determined from the kinetic current under steady-state conditions.

The corrosion inhibition of aluminium by Ipomoea involcrata (IP) in 1 M NaOH was rapidly assessed using the gasometric technique at 30 and 60 oC . Results obtained showed that Ipomoea involcrata acts as an inhibitor for aluminium corrosion in 1 M NaOH. Inhibition efficiency increased with increase in concentration of IP up to 55.0 % at 50 v/v% and decreased with increase in temperature. The adsorption of IP was in accord with Langmuir adsorption isotherm at the studied temperatures. A mechanism of physical adsorption is proposed from the calculated values of Ea, Qads and ΔGads.