Portugaliae
Electrochimica Acta

Azetidinone ester is the key intermediate during the synthesis of injectable cephalosporin compounds. This intermediate is undergoing electrochemical reaction during the process of conversion from penicillin to cephalosporin. The CV and RRDE studies clearly indicate that electro-reduction of this compound is taking place in three steps under the condition. The first two peaks correspond to the two, one electron transfers and the third one is due to the proton addition from the non-aqueous solvent. And during the process, the cyclisation is also taking place in order to neutralise the charge. Further CV and RRDE studies with the addition of small amount of water to the above system clearly confirm the mechanism. This was very well confirmed by the FTIR analysis of the product obtained from the bulk electrolysis.

The purpose of optimization consists in establishing suitable values for the operational parameters of a process, in order to achieve the results of that process to the greatest possible advantages. These ideal operating conditions are known as the optimum. The process parameters are current density, temperature, concentration, electrode materials, flow rate, cell voltage, mixing and diaphragm and engineering quantities are like current efficiency, space-time yield, energy consumption, yield and conversion. There are several possible targets in optimization of process and the main aim is to get maximum yield, high current efficiency, high purity and minimum energy consumption for mediated electrochemical oxidation. Mediated electro oxidation or indirect electrosynthesis is a cyclic process involving electrochemical generation of cerium(IV) and uses that agent to effect a chemical reaction. Cerium(IV) has attracted attention in electroorganic synthesis for synthesis of aldehydes and quinones.

The characteristics of corrosion inhibitors of the tolitriazole (TTA) for the carbon steel 1008, covered by zinc or tricationic phosphate (Mn, Zn, Ni), in the means of H2SO4 0.1 mol L-1 and NaCl 0.5 mol L-1, were investigated by physical and electrochemical methods. The results obtained in the absence of the inibidor TTA showed that the corrosion protection properties of the tricationic phosphate (Ptri) are better than those observed for the zinc phosphate (PZn), probably due to the presence of vacancies in the layer of PZn. The curves of anodic polarization presented current densities (j) smaller for the steel phosphatized with Ptri, when compared with the metal substrate without phosphate and with PZn. The results of impedance electrochemistry (IE) showed a polarization resistance (Rp) larger for the electrodes phosphatized with Ptri. The electrochemistry measurements of the samples of steel phosphatized, with PZn and/or Ptri, in the presence of [TTA] = 1x10-3 mol L-1, present smaller j and larger Rp when compared with the absence of TTA. In the process of phosphatization of the carbon steel with PZn + TTA, it was observed similar j and Rp in the samples of steel phosphatized with Ptri without TTA. These results suggest that the bathing of zinc phosphate with [TTA] = 1x10-3 mol L-1 can substitute the well known industrial bathing of tricationic phosphate. Corrosion testing by Salt Spray of steel phosphatized with PZn and PZn + TTA, painted with white polyester ink, confirmed the eletrochemical results.

It was developed a very sensitive analytical method to determine molybdenum in water and food grains, using the linear sweep voltammetry technique, with adsorptive preconcentration of a Mo(VI) 8-hydroxyquinoline complex, in an acetate buffer media of pH = 3.5 and KClO3 0.5 mol/L as a support electrolyte. The linear range of the methodology goes from 1.0 hg/L to 10 mg/L, with a limit of detection of 0.3 hg/L and quantification of 1.0 hg/L. The methodology is suitable in the range of mg/L and hg/L. The method was applied to grinded samples of rice, beans, lentil seeds and chickpeas with the following result: 6.2 mg/kg in lentil seeds, 6.0 mg/kg in chickpeas, 3.2 mg/kg in red beans, and 1.7 mg/kg in rice.

Some of the aluminium complexes are electroactive at positive potentials, being necessary a carbon vitreous electrode to their quantitative determination. Nevertheless the aluminium alizarine complex could be measured at negative potential with a mercury hanging electrode, but this complex is not electroactive at negative potential; instead of that, the residual alizarin non complex could be measured. The kinetic complex is very slow, so it is necessary to heat at 80 0C, for five minutes. The study of experimental conditions of complex formation was established at pH 9.25 and is determinant in the complex formation; besides, the buffers employed should be of high regulatory capacity to obtain derivative formation. The optimization of the measurement experimental conditions was done by square wave voltammetry (SWV). Detection limit got using standard deviation of seven blank solutions was 3 mg /L, the variation coefficient was 8%, and the mean recovery for 16 mg /L was 97%. The calibration curves were done in a linear interval of 8 to 64 mg /L. The method application to water samples is possible after previous evaporation.

Inside the construction industry, in the area of sea water retention structures, the chlorides contamination is a main cause of the corrosion, because in the concrete they could form macro cells upon repairing and applying a mortar free of this ion, forming anodes in the repaired zones, and thus increasing corrosion. In the reinforcements are commonly formed corrosion products because the concrete is exposed to mechanical, physical, chemical or biological conditions that commit and shorten their performance. As a consequence, it is important to determine their useful life and that of the made repairs, using electrochemical techniques that allow determining the level of protection, the effect of the macro cells in the corrosive process of the reinforcement, and the mechanism of deterioration in the structures. The present work was carried out using six beams with preoxided reinforcements, six precracking and one beam blank. After curing, those beams were exposed to accelerated cycles of deterioration for causing the cracking of the concrete, making possible to observe their electrochemical behaviour. The tests carried out were corrosion potential and corrosion rate, through the resistance to the polarization technique.