Portugaliae
Electrochimica Acta

2,3,6,7,10,11-hexadecahexoxytriphenylene was synthesized by electrochemical oxidation of 1,2-didecahexoxybenzene in dichloromethane-tetrabutylammonium tetrafluoroborate (TBATFB) on platinum electrode. A green, adherent, insoluble deposit was grown on the Pt electrode surface. The deposit was isolated and characterized using Fourier Transform Infrared (FTIR) Spectroscopy and Nuclear Magnetic Resonance (NMR). The results suggest that the deposit shows a decahexoxy triphenylene structure, associated to the anion of the supporting electrolyte.

A new way for deriving the fundamental equation of the electrochemistry has been developed in the potential range in which Butler-Volmer behaviour is found. In this approach the frequency factor is considered to be a function of the potential instead of the activation energy. The frequency factor is calculated by means of a classical statistical mechanics treatment giving rise to a new definition for the symmetry factor. A new expression for the standard rate constant in adiabatic heterogeneous charge transfer reactions has been derived.

The effect of oil soluble commercial corrosion inhibitors (OSCI) on the growth of bacteria and its corrosion inhibition efficiency were investigated. Corrosion inhibition efficiency was studied by rotating cage test and the nature of biodegradation of corrosion inhibitor was also analyzed by using FTIR, NMR and GC-MS. This isolate has the capacity to degrade the aromatic and aliphatic hydrocarbon present in the corrosion inhibitors. The degraded products of corrosion inhibitors and bacterial activity determine the electrochemical behaviour of API 5LX steel. The influence of bacterial activity on degradation of corrosion inhibitor and its influence on corrosion of API 5LX have been evaluated by employing weight loss techniques and electrochemical studies. The present study also emphasizes the importance of evaluation of oil soluble corrosion inhibitor in stagnant model (flow loop test) and discusses the demerits of the oil soluble corrosion inhibitors in petroleum product pipeline.

In this preliminary work, for the first time, the electrochemical oxygen reduction reaction (ORR) was investigated using cyclic voltammetry (CV) on the electrodeposited manganese oxide (MnOx)-modified glass carbon electrode (MnOx-GC) at room temperature ionic liquids (RTILs) of EMIBF4, i.e., 1-ethyl-3-methylimidazolium tetrafluorobroate (EMIBF4). The results demonstrated that, after being modified by MnOx on GC, the reduction peak current of oxygen was increased to some extent, while the oxidation peak current, corresponding to the oxidation of superoxide anion, O2-, was attenuated in some degree, suggesting that MnOx catalyzed ORR in RTILs of EMIBF4, which is consistent with the results obtained in aqueous solution. To accelerate the electron transfer rate, multi-walled carbon nanotubes (MWCNTs) were modified on GC, and then MnOx was electrodeposited onto the MWCNTs-modified GC electrode to give rise to the MnOx /MWCNTs–modified GC electrode; consequently, the improved standard rate constant, κs, originated from the modified MWCNTs, along with the modification of electrodeposited MnOx, showed us a satisfactory electrocatalysis for ORR in RTILs of EMIBF4. In addition, not only for the MnOx-modified GC but also for the MnOx/ MWCNTs-modified GC, there is a novel small oxidation peak appearing at –0.2 V vs. solid Ag/AgCl, implying that the catalysis of MnOx for ORR in EMIBF4 is somewhat different from that observed in aqueous solution, though the exact interpretation is not achieved in this preliminary work. Initiating the catalysis of MnOx on ORR in RTILs is the main contribution of this work. Further discussions are in progress.

In order to investigate the electrochemical behaviour and morphology under different experimental conditions of poly-N-methylpyrrole doped with sodium p-toluensulphonate (NaTsO) in aqueous medium, the doped polymer was potentiostatically synthesized at four potential values: 0.6, 0.8, 0.9 and 1.0 V. The morphological study reveals a compact texture in these polymeric films; after being submitted to a positive potential those films were wrinkled. Cyclic voltammetry was used to characterize polymer films (pNMPy/TsO). The corresponding voltammograms revealed a reversible doping/de-doping process in those films obtained at ηp = 0.8 V. Different parameters such as: negative potential limit (Ei), positive potential limit (Ef), sweep rate (v) and continuous cycling were varied.

The effect of some mono azo dyes compounds on the dissolution of aluminium in 0.01 M NaOH solutions was studied using weight loss and galvanostatic polarization techniques. The percentage inhibition efficiency was found to increase with increasing concentration of inhibitor and with decreasing temperature. The inhibition mechanism was discussed on the basis of the formation of complex compound adsorbed on the metal surface. The adsorption process follows Frumkin isotherm. The effect of temperature on the rate of corrosion in the absence and presence of these compounds was also studied. Some activated thermodynamic parameters were computed.

A novel electrochemical sensor has been developed for the determination of nimesulide. The sensor is based on the NIM- molybdophosphoric acid (MPA) as the electroactive material in PVC matrix in presence of bis(2-ethyl hexyl) phthalate (BEP) as a plasticizer. The sensor showed a fast, stable, near Nernstian response for 1  10-2 –1  10-6 M NIM over the pH range 5 – 8 with a slope 55.6 0.5m V/decade and the response time is < 45 s. Selectivity coefficient data for some common ions show negligible interferences. The sensor was successfully applied for the determination of NIM in tablet and the results obtained are in good agreement with those obtained by the official method.

The glassy carbon electrode (GCE) modified with cobalt nitroprusside (CoNP) was prepared by electrochemical method. The CoNP modified electrode (ME) prepared electrochemically on a GCE in two-step. The electrochemical behavior of the modified electrode was studied by cyclic voltammetric technique. The cyclic voltammogram of CoNP showed a redox couple with formal potential [E0 =(Epa+Epc)/2] of 500 mV vs. SCE. The electrocatalytic oxidation of nitrite was studied on the CoNP modified glassy carbon electrode. The CoNP films on the glassy carbon electrode show an excellent electrocatalytic activity toward the oxidation of nitrite in 0.5 mol L-1 KNO3. Hydrodynamic amperometry was used to the detection of nitrite with CoNP. The linear detection limit of the CoNP elctrode for NO2- was from 20×10-6 to 220×10-4 mol L-1 and the detection limit was 10×10-6 mol L-1 (S/N=3).