Portugaliae
Electrochimica Acta

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.

The semiconducting properties of anodic passive films formed on polycrystalline copper in aqueous borax solutions, pH 9.2, are studied using electrochemical impedance spectroscopy (EIS) and voltammetry. The semiconducting nature of the cuprous passive layer is analysed in the potential region near de rest potential as a function of the electrode potential and the presence of CO dissolved in the electrolyte. The oxide formation is explained as a sequence of Cu2O growth, cation adsorption, Cu(II), and dissolution steps similarly to previous reported investigationsfor the metal in CO free solutions. The different growth conditions change the defect or excess of cations accumulated in the outer side of the cuprous layer/electrolyte interface leading to different semiconducting properties.

Pt-Ru/C, Pt-Dy and Pt-Ru-Mo/C electrocatalysts prepared by Bönnemann´s method have been studied as porous thin films on high surface area carbon electrodes, in order to evaluate their electroactivity on CO desorption in PEM fuel cells. For comparison electrode precursor powders with and without thermal treatment were considered. Cyclic voltammetry showed that addition of Mo in the well-established Pt/Ru system is very promising for methanol oxidation. In order to compare the electroactivity of different catalysts a normalization procedure based on the amount of Pt was used.

The rate of copper II/zinc cementation from copper sulphate solutions in the absence and in the presence of methanol (CH3OH) and dimethyl sulphoxide (DMSO) has been studied and the reaction was found to follow first-order kinetics. The influence of several parameters on the course of the reaction, such as cylinder rotation speed, initial concentration of Cu2+ ions, temperature and concentration of organic solvent, was investigated. In the case of CH3OH, rotating zinc cylinder was used, while in the presence of DMSO stationary zinc sheet and rotating zinc cylinder were used. It was found that (1) the percentage inhibition caused by methanol ranged from 10.70 to 58.38 depending on the concentration of the alcohol used; (2) the rate of cementation in the presence of DMSO using rotating zinc cylinder > the rate of cementation in the presence of DMSO using stationary zinc sheet; (3) the rate of cementation on zinc cylinder in the presence of DMSO < the rate of cementation in the presence of CH3OH. Different reaction conditions, and the physical properties of solutions are studied to obtain dimensionless correlation among all these parameters. Thermodynamic parameters ΔS*, ΔH* and ΔG* were studied.

The inhibition of mild steel corrosion in 1N sulphuric acid was studied in the presence of various concentrations (10-150 ppm) of substituted dithiobiurets and their molybdenum and tungsten complexes at 25 °C. All the compounds behaved as ambiodic corrosion inhibitors for mild steel and were considered to inhibit the corrosion by getting adsorbed on the surface. The inhibition efficiencies (IEs) of the complexes, in general, were found to be appreciably higher than those of corresponding ligands. However, the IE values of the complexes of molybdenum and tungsten of the same ligand did not differ much in their magnitude indicating thereby that the nature of central metal ions hardly influenced the inhibition efficiency. The slight difference in the IEs of the complexes at a given concentration seems to be caused by the slight difference in their size. The variation in IEs of different derivatives of ligands has been attributed to change in their size, number of active sites for adsorption and the electron density on these active sites. Scanning Electron Microscopy was used to study the surface of corroded and inhibited specimens.

The ionic conductivity of lithium based solid polymer films prepared from poly (ethylene oxide) (PEO) and lithium hexafluoarsenate (LiAsF6) with varying compositions of plasticizers likedibutyl sebacate (DBS) and ethylene carbonate (EC) was measured by AC impedance method. Polymer film composition viz. (PEO)8-LiAsF6-(DBS)0.4-(EC)0.1 has been evaluated as an optimum composition as evidenced from its high conductivity and freestanding ability. The high conductivity observed for the polymer electrolyte with this composition has been attributed to an enhanced amorphous character and a reduced energy barrier to the segmental motion of lithium ions in the matrix. The temperature dependence of conductivity on the polymer films, with and without plasticizers, appears to obey the Arrhenius law. However, the activation energy of the plasticized polymer film is 0.81 KJ/mol, a value considerably lower than 10 KJ/mol obtained for the unplasticized electrolyte, making the polymer to be a prospective candidate as lithium-ion conducting electrolyte for rechargeable lithium batteries.

Guar gum was tested as corrosion inhibitor for carbon steel in 1 M H2SO4 solution using weight loss and Tafel polarization techniques. The results showed that the inhibition efficiency increases with the increasing of the guar gum concentration, which act as an inhibitor of the mixed type. The inhibition action of guar gum was discussed in terms of its horizontal adsorption on the metal surface. The adsorption follows Langmuir adsorption isotherm. The effect of the presence of chloride ion in pitting corrosion was analyzed by the potentiodynamic anodic polarization technique. The pitting corrosion potential changes with the concentration of Cl- ion according to a sigmoid S-shaped curve. This behaviour was explained on the basis of the formation of passivatable, active and continuously propagated pits.