Clarisse Maria Sartori Piatnicki

Enlarged electrochemical window in dialkyl-imidazolium cation based room-temperature air and water-stable molten salts

The electrochemical windows of the ionic liquids 1-n-butyl-3-methyl imidazolium tetrafluoroborate (BMI+)(BF4−) and 1-butyl-3-methyl imidazolium hexafluorophosphate (BMI+)(PF6−) have been investigated at platinum, vitreous carbon, tungsten and gold electrodes. The lowest current densities and widest electrochemical windows were found on tungsten and vitreous carbon 6.10 and 5.45 V for (BMI+)(BF4−) and >7.10 and 6.35 V for (BMI+)(PF6−), respectively.

Electrochemical behaviour of iron in neutral solutions of acetate and benzoate anions

The electrochemical behaviour of iron in pH 6 aqueous solutions of benzoate and acetate anions mixed in varying concentrations and constant ionic strength was investigated. For that purpose cyclic voltammetric experiments were carried out at a disc electrode either static and/or rotating. A high surface coverage is observed in the presence of benzoate anions, thus favouring the establishment of a passive state. The overall process is discussed in terms of a three-dimensional film, the growth mechanism of which is under diffusion and migration control. It was also observed that the addition of chloride ions to the mixed electrolyte solutions containing increasing benzoate concentration shifts the breakdown potential and the repassivation potential toward more positive values.

Removal of Cd2+ ion from diluted aqueous solutions by electrodeposition on reticulated vitreous carbon electrodes

ion in the solution was monitored after each experiment by anodic stripping voltammetry at a hanging mercury drop electrode.

Removal of Cd+2 from aqueous solutions onto polypyrrole coated reticulated vitreous carbon eletrodes

The development of simple methods for removal of heavy metals from aqueous samples is a relevant field of research. In this connection, the electrodeposition of the Cd+2 ion, one of the most toxic species for animals and human beings, was investigated in aerated pH 4.8 sulfuric-sulfate solutions. In potentiostatic conditions, the maximum rate of cadmium deposition at a neutral polypyrrole (PPy0) coated reticulated vitreous carbon (RVC) working electrode occurs at -3.0 V vs. the saturated calomel reference electrode (SCE). Moreover, the conversion rate depends both on the applied potential and on the mass transport regime, and, for solutions containing 10 mg L-1 of Cd2+, the highest removal efficiency achieved is 84% after 90 min of electrolysis. The concentration decay of the Cd+2 ion in the solution was monitored by anodic stripping voltammetry (ASV) at a hanging mercury drop electrode. Besides, metallic cadmium deposited onto the polypyrrole modified RVC electrode was evidenced by Scanning Electron Microscopy (SEM) analysis using the backscattered electron image (BEI) technique and by Energy Dispersive Spectrometry (EDS).

Role of the co-surfactant nature in soybean w/o microemulsions.

The influence of the co-surfactant on physicochemical properties of w/o soybean oil microemulsions (MEs) has been studied. In spite of the similarity in phase diagrams, the MEs display remarkable differences when examined by electrical conductivity, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and linear voltammetry. When different short-chain alcohols were employed as co-surfactants, together with sodium dodecyl sulfate (SDS) as surfactant, the DLS results indicated the systems to be monodisperse. Both the electrical conductivity of the MEs and the hydrodynamic radii of the droplets (R(H)) increased with water content while R(H) diminished as temperature increased, no aggregation or percolation of the droplets being observed. In comparison to w/o MEs prepared with 3-methyl-1-butanol, those prepared with 1-pentanol presented higher electrical conductivity and larger limiting currents at a Pt ultramicroelectrode for oxidation of the water occluded into the particles. Finally, from the electrochemical viewpoint the use of 1-pentanol is recommended, no advantage being gained by using any of the other tested alcohols.

Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel

This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample.

Removal of Cu(II) from dilute solutions at polypyrrole modified electrodes

The removal of Cu2+ ion from dilute acidic solutions containing dissolved oxygen was investigated through its spontaneous and potentiostatic reduction at Pt and reticulated vitreous carbon (RVC) electrodes recovered with reduced polypyrrole (PPy0). It was observed that the spontaneous Cu2+ ion reduction occurs only at the Pt/PPy0 electrode. In the electroreduction procedure, a removal efficiency of 99.8% was achieved with the RVC–PPy0 electrode after 30 min of electrolysis at −0.40 V vs. a saturated calomel reference electrode. The removal efficiency of Cu2+ ion from the solution was evaluated by monitoring its concentration decay through linear voltammetric measurements at a Pt ultramicroelectrode and/or by flame atomic absorption spectrometry. Due to its high efficiency and simplicity, the electroreduction procedure at the RVC–PPy0 electrode may become advantageous in the removal of low-level concentrations of copper from pretreated industrial wastes.

Water in soybean oil microemulsions as medium for electrochemical measurements

Microemulsions of water in soybean oil (w/o ME) were prepared with sodium dodecyl sulfate (SDS) as surfactant and amyl or isoamyl alcohol, as co-surfactants. Microemulsions containing 40.0% oil, 43.2% alcohol, 10.8% SDS and 6.0% water in weight, in the ratio 1:4 [SDS]:[alcohol] showed the highest thermodynamic stability. The aqueous droplet size and its diffusion coefficient Dw/o in the ME were determined through dynamic light scattering (DLS). Voltammetric measurements in the ME at a Pt disk ultramicroelectrode (ume) evidenced the oxidation of both water and ferrocene (Fc), and the reduction of oleic acid. The Dw/o values calculated from the limiting current being lower than the ones obtained from DLS indicate that water oxidation probably requires diffusion towards the electrode of both the droplets and the water molecules from inside the droplets. The results show that electroanalytical determinations can be carried out in w/o ME.

Direct determination of oleic acid in soybean oil by capacitively coupled contactless conductivity detection capillary electrophoresis in an oil-miscible KOH/1-propanol/methanol medium

The aim of this work was to develop a quick direct analytical technique for the determination of oleic acid content in soybean oil by non-aqueous capillary electrophoresis with capacitively coupled contactless conductivity detection. The oil-miscible background electrolyte was a mixture of methanol/1-propanol (1:6 v/v) containing 4 × 10-2 mol L-1 KOH and 10% (v/v) ethylene glycol. Samples of 50 g L-1 soybean oil were prepared directly in the background electrolyte added with 1.33 × 10-3 g L-1 of salicylic acid as internal standard. Quantitative tests were performed by adding to the samples pure oleic acid in the range from 0.53 to 2.13 × 10-3 mol L-1. Under negative polarity anionic solutes moved faster than the electro-osmotic flow so that oleic acid was detected in 16 minutes. The limits of detection and quantification were, respectively, 24 and 81 µmol L-1. Such results demonstrate that, unlike required by other methods, low levels of oleic acid can be quantitatively determined in soybean oil without prior extraction.

Physical chemical properties and kinetics of redox processes in water/soybean oil microemulsions

Microemulsoes de agua em oleo (ME w/o) constituidas de agua, oleo de soja, SDS (dodecil sulfato de sodio) e diversos alcoois de cadeia curta foram caracterizadas sob o ponto de vista fisico-quimico e de propriedades eletroanaliticas. Foram testados diferentes co-surfactantes e razoes surfactante:cosurfactante, sendo a ME com a composicao mais favoravel utilizada para estudar a cinetica de processos redox. Para tanto, realizaram-se medidas de voltametria ciclica utilizando como eletrodo de trabalho um ultramicroeletrodo de disco de Pt e, como eletrodo de referencia e auxiliar, foram usados Ag/AgCl e Pt, respectivamente, e ferroceno como uma sonda. Verificou-se que a estabilidade termodinâmica das MEs aumenta com o conteudo de co-surfactante. A estrutura molecular e a solubilidade em agua do co-surfactante afetam a condutividade eletrica e o raio hidrodinâmico das MEs. Devido aos baixos coeficientes de difusao observados na ME, foi possivel a realizacao de medidas em estado transiente usando velocidades de varredura convencionais. A oxidacao do ferroceno na ME demonstrou ocorrer em condicoes de quasi-reversibilidade. Assim, foi demonstrada a possibilidade de realizar estudos por voltametria ciclica em oleos vegetais sob a forma de ME w/o. Water/oil microemulsions (w/o ME) constituted by water, soybean oil, SDS (sodium dodecyl sulfate) and several short-chain alcohols were characterized from the viewpoint of its physical-chemical and electroanalytical properties. Different co-surfactants and surfactant:co-surfactant ratios were used, and the ME with the most favourable composition was used to study the kinetics of redox processes. For this purpose, cyclic voltammetry measurements using a Pt disk working ultramicroelectrode, an Ag/AgCl reference electrode and a Pt auxiliary electrode, and ferrocene as a probe, were performed. It was verified that the thermodynamic stability of the MEs increases with the co-surfactant content. The molecular structure and water solubility of the co-surfactant affect the electrical conductivity and the hydrodynamic radio of the MEs. Owing to the low diffusion coefficients verified in the MEs, measurements in transient state using conventional sweeping rates could be performed. Ferrocene oxidation in the ME has been demonstrated to proceed in quasi-reversibility conditions. Thus, the possibility of carrying out studies of cyclic voltammetry in vegetable oils under the w/o ME form was demonstrated.