The electrochemistry of ferrocene in non-aqueous solvents

the electrochemical oxidation of ferrocene on Pt in dimethylformamide, ethanol, propylene carbonate and their aqueous solutions was studied at 25°C. The concentration of the supporting electrolyte, NaClO4, was varied from 0.1 to 0.5 M. The results show that the electrode process may be described as a quasi-reversible one-electron charge transfer, followed by slow decomposition of the oxidized species. © 1987.

Influence of the heat treatment in the electrochemical corrosion of Al-Zn-Mg alloys

The localized corrosion of Al-(5.03%)Zn-(1.67%)Mg-(0.23%)Cu alloys and high purity Al has been studied using electrochemical techniques, optical microscopy, SEM and EDX. The samples were previously submitted to different heat treatments in which coherent and incoherent MgZn 2 precipitates with different distribution and aggregation degree were produced. The influence of NaCl and Na 2SO 4, dissolved oxygen, immersion time and convection were studied. In NaCl solutions, pitting potentials for the alloys were more negative than for aluminium, indicating an increase in their susceptibility to localized corrosion. Moreover, annealed and cold-rolled alloys presented more negative pitting and repassivation potentials than those submitted to age hardening with direct or interrupted quenching. In annealed and cold-rolled samples, pit nucleation and propagation takes place in the zones where MgZn 2 is accumulated. In the case of the age-hardened alloys, a double pitting behaviour is observed, the first one in the magnesium and zinc enriched regions and the second in the matrix. While the cold water quenched alloy is susceptible to stress corrosion craking, the alloy submitted to the interrupted quenching process is less susceptible to intergranular attack. The sulphate ion shifts the pitting potential of aluminium and the alloys by chloride towards more positive values because it impedes local accumulations of the latter. © 1992 Chapman & Hall.

Electrochemical behavior of a nitrobenzenesulfonyl derivative of aniline in aqueous solution

The electrochemical behavior of aniline protected by a nitrobenzene sulphonyl group in aqueous solution at a mercury electrode is reported. At pH < 10 the compound was reduced in a single well-defined step. Reduction of the nitro group involving a preceding protonation step was postulated. Two reduction steps are present at higher pH (pH > 11). Controlled potential electrolysis confirms that the reduction of the nitro group in a four-electron step to N-phenyl-4-hydroxylamine sulphonamide is always the preponderant process. ©1997 Soc. Bras. Química.

Preparation, characterization and electrochemical studies of dinuclear copper(II) complexes with pseudohalides and bidentate amines on platinum electrode in acetonitrile

The complexes: [Cu(N 3) 2(N,N-diEten)] 2, [Cu(N 3) 2(tmeen)] 2, [Cu(N 3)(NCO)(N,N-diEten)] 2, [Cu(N 3) 2(N,N′-diMeen)] 2 and [Cu(N 3)(NCO)(tmeen)] 2 were prepared, characterized and their electrochemical behavior was investigated by cyclic voltammetry and controlled potential electrolysis. Cyclic voltammograms for all complexes studied are similar and exhibit one pair of current peaks in the range of -0.65 to +0.0 V. The number of electrons obtained from controlled potential electrolysis at ca. -0.55 V for all compounds was 1.8 ≤ n ≤ 2.1, indicating that both copper(II) metallic centres in the molecule were reduced to copper (I). Comparing the peak potential values for these complexes one can observe that the redox process corresponding to copper(II)/copper(I) couple is slightly influenced by the σ-basicity of the ligands. © 1997 Soc. Bras. Química.

The behaviour of resin-bond diamond wheels in the grinding of advanced ceramics

Results are reported of the behaviour of the plane tangential grinding process using diamond grinding wheels. Grinding performance is analysed in terms of the wear behaviour of the wheel in the grinding of ceramic. Discussion of the results concentrates on the wear mechanism of the diamond wheel and the process of material removal.

Advanced ceramics: Evaluation of the mechanism of stock removal and ground surface quality

The aim of this work is to evaluate the mechanism of stock removal and the ground surface quality of advanced ceramics grounded by a plane tangential grinding process with diamond grinding wheels. The analysis of the grinding performance was done regarding the cutting surface wear behavior of the grinding wheel for ceramic workpieces. The discussion about the results emphasized the wear mechanism of the grinding wheel cutting surface and the cutting phenomenology of the grinding process. The grounded surface was evaluated using Scanning Electron Microscopy (SEM). © 1999 Society of Automotive Engineers, Inc.

Advanced ceramics: Evaluation of the mechanism of stock removal and ground surface quality

The aim of this work is to evaluate the mechanism of stock removal and the ground surface quality of advanced ceramics machined by a surface grinding process using diamond grinding wheels. The analysis of the grinding performance was done regarding the cutting surface wear behavior of the grinding wheel for ceramic workpieces. The ground surface was evaluated using Scanning Electron Microscopy (SEM). As a result it can be said that the mechanism of material removal in the grinding of ceramic is largely one of brittle fracture. The increase of the hmax can reduce the tangential force required by the process. Although, it results in an increase in the surface damage, reducing the mechanical properties of the ground component.

A surface modification for hydrogen storage intermetallic particles by sol-gel method

A new process for the surface modification of hydrogen storage intermetallic particles used as anode material in secondary batteries is proposed in this article. The copper oxide particles coverage obtained by the sol-gel method is proposed to produce, under operational conditions of a Ni-MH battery, a metallic framework that tolerates the volume changes in charge/discharge cycles and does not inhibit the hydrogen absorption. Furthermore it was noticed an enhancement on the discharge capacity of the electrode material that can be related to a new hydrogen storage phase or to an inhibition of the surface oxidation promoted by the film coverage.

Electrochemical sensors: A powerful tool in analytical chemistry

Potentiometric, amperometric and conductometric electrochemical sensors have found a number of interesting applications in the areas of environmental, industrial, and clinical analyses. This review presents a general overview of the three main types of electrochemical sensors, describing fundamental aspects, developments and their contribution to the area of analytical chemistry, relating relevant aspects of the development of electrochemical sensors in Brazil.

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH > 7. © 2003 Elsevier Ltd. All rights reserved.

Photoelectrocatalytic production of active chlorine on nanocrystalline titanium dioxide thin-film electrodes

The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L-1 of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L-1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.

Decolourization of anthraquinone reactive dye by electrochemical reduction on reticulated glassy carbon electrode

The electrochemistry reduction for the removal of Reactive Blue 4 (RB4) dye from aqueous solution using reticulated glassy carbon electrode is investigated. At pH < 8.0 the anthraquinone group of the RB4 dye are reduced in one cathodic step to hidroquinone after a reversible two-electron process involving a precedent two protons reaction. A stable semiquinone is detected by spectrophotometric technique. At pH > 8.0 the reduction process involves two reversible 2-electron steps, whose species are generated by a protonation equilibrium of anthraquinone group. The results shows that 60% of color removal was obtained after 3 hours of RB4 dye electrolysis at acidic and neutral conditions and only 37% at alkaline conditions. Simultaneously 64% of total organic carbon was removed after electrolysis at pH 2.0.

Voltammetric determination of dipyrone using a N,N′- ethylenebis(salicylideneaminato)oxovanadium(IV) modified carbon-paste electrode

The preparation and electrochemical characterization of a carbon paste electrode modified with N.N′-ethylenebis(salicylideneiminato) oxovanadium(IV) complex ([VO(Salen)]) as well as its behavior as electrocatalyst toward the oxidation of dipyrone were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of dipyrone were explored using cyclic voltammetry. The voltammetric response of the modified electrode is based on two reactions. One electrochemical related to the oxidation of the metallic center of the [VO(Salen)] and the other involving the chemical redox process involving the oxidized form of the complex and the reduced form of dipyrone. The best voltammetric response was observed for a paste composition of 25% (m/m) [VO(Salen)], KCl solution pH from 5.5 to 8.0 as the electrolyte and potential scan rate of 10 mV s-1 in the presence of dipyrone. A linear voltammetric response for dipyrone was obtained in the concentration range from 9.9 × 106 to 2.8 × 10 -3 mol L-1, with a detection limit of 7.2 × 10 -6 mol L-1. Among of several compounds tested as potential interference, only ascorbic acid presented some interference. The proposed electrode is useful for the quality control and routine analysis of dipyrone in pharmaceutical formulations.

Photo-oxidation of polyphenylenevinylene chains in Langmuir-Blodgett and cast films

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.

Electrical devices obtained from polymeric precursors process

Nowadays, many investments have been made in the area of superconductor materials, with the aim to improve their potential technological applications. Applications on the energy transport using cables, to get high resolution images in the medicine use high magnetic fields, high speed signals use superconductor devices all of them are in crescent evidence and they are showing that the future is coming and next for this new kind of materials. Obviously that everything of this is possible due to the increasing of research with new materials, where the synthesis, characterization and applications are of the mainly objective of these researches. The production of cable for the energy transport has been in advanced stage as the bulks production is too. However, the film production that to aim at the electronic devices area is not as developed or it still need expensive investments. Thinking about that, we are developing a research where we may increase the relation of cost/benefits. Thereby, we are applying the polymeric precursors method to obtain films that will be used in the built of electronic devices. Thin films (mono and multilayers, on crystalline or metallic substrates, controlled thickness) of the BSCCO system have been obtained from dip coating deposition process with excellent results in terms of preferential orientation, controlled thickness, a large area, which may indicate future applications. Based on these results, we present an electrical circuit and their principal characteristics as superconductor transition (85K), transport current density and structure. DC four probes method, scanning electron microscopy, digital optical microscopy and X-ray diffractometry were some techniques used for the characterization of this superconductor electric device. © 2006 Materials Research Society.