Estudos da eletrodeposição de metais em regime de subtensão

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

Estudo das partículas totais em suspensão e metais associados em áreas urbanas

This work aims at the study of the air quality determination regarding the total suspended particles (TSP) and the associated metals in the counties of Charqueadas and Sapucaia do Sul at the state of Rio Grande do Sul. The TSP samples were collected using high volume samplers and the analysis of the metallic elements was accomplished through ICP-AES. The results revealed that the TSP concentrations, found in the two studied regions, have exceded the current air quality patterns established by the Brazilian Legislation. They also revealed high levels of several of the elements being attributed to the presence of anthropogenic sources. The correlation between meteorological data (speed and wind direction) and TSP concentrations were significant and revealed strong influence in particle dispersion.

Uma rota alternativa para a síntese de PPh2Si(CH3)3 segundo Appel; preparação e purificação dePPh2H (Ph = fenila)

The unexpected low yield in the Appel's synthesis of PPh2Si(CH3)3 can be attributed to the presence of phenyllithium and its interfering reactions. The method was carried out with hydrolysis of the products formed by the reaction of PPh3 with metallic lithium, phenyllithium and lithiumdiphenylphosphide. PPh2Si(CH3)3 was obtained by subsequent reaction of the resulting diphenylphosphin with elemental lithium and ClSi(CH3)3.

Estudo da adsorção de hidrogênio e sulfeto na superfície de paládio: aspectos experimentais (eletroquímica) e teóricos (ab initio e Teoria do Funcional da Densidade)

The adsorption of H and S2- species on Pd (100) has been studied with ab initio, density-functional calculations and electrochemical methods. A cluster of five Pd atoms with a frozen geometry described the surface. The computational calculations were performed through the GAUSSIAN94 program, and the basis functions adapted to a pseudo-potential obtained by using the Generator Coordinate Method adapted to the this program. Using the cyclic voltammetry technique through a Model 283 Potentiostat/Galvanostat E.G.&G-PAR obtained the electrochemical results. The calculated chemisorption geometry has a Pd-H distance of 1.55Å, and the potential energy surface was calculated using the Becke3P86//(GCM/DFT/SBK) methodology. The adsorption of S2- ions on Pd surface obtained both through comparison between the experimental and theoretical results, at MP2 level, suggest a S2- absorption into the metallic cluster. The produced Pd-(S2-) system was show to be very stable under the employed experimental conditions. The paper has shows the powerful aid of computational methods to interpret adsorption experimental data.

Um potencial de interação para o estudo de materiais e simulações por dinâmica molecular

The Vashishta-Rahman effective interaction potential, based on the Pauling's concept of "ionic radii", has been successfully employed to investigate structural and dynamical properties of different classes of material. By celebrating Pauling's birth centenary, we review the building up of the Vashishta-Rahman potential and we present molecular-dynamics simulation results for structure and dynamics of superionic materials, chalcogenide glasses and metallic oxides.

A bench arc-furnace facility for fullerene and single-wall nanotubes synthesis

A metallic-sample arc-furnace was modified to synthesize fullerenes and nanotubes. The (reversible) changes and the process for producing single-wall nanotubes (SWNTs) are described.

Estudo do biomaterial Ti-6Al-4V empregando-se técnicas eletroquímicas e XPS

The Ti-6Al-4V alloy used as biomaterial has been used over the last years. The literature shows controversies concerning the kind and the chemical composition of the film naturally and elctrochemically formed on the surface of the titanium alloy. The presente work studies the film composition before and after the electrochemical polarization tests using the x Ray photoelectron spectroscopy (XPS) technique. The results showed that the film naturally formed on the metallic surface is constituted of a variety of oxides which do not cover the whole surface of the metallic alloy and therefore, metallic Ti, Al and V can be found on the uncovered areas. The tests of XPS made after the polarization up to 4V (SCE) showed that the electrochemically formed film is constituted only of TiO2 and that the peak current observed around 1,5 V (SCE) is due to the oxidation of any kind of titanium oxide or the growth of the film.

Reciclagem de cobre proveniente de analisador automático de carbono e nitrogênio

Isotopic and elemental analysis of N, C and S in liquid and solid samples has been simplified with the advent of automated systems. The simplest method of automation for this kind of analysis involves an elemental analyzer interfaced directly to the ion source of an IRMS (Isotope Ratio Mass Spectrometry). In the analyzer reduction system, an expressive amount of oxidized copper is generated as solid residue. This material is normally imported and the price is very high. A methodology was proposed for the recovery of metallic copper in order to recycle this reagent in the reduction system of a GC-IRMS, using the hydrogen gas in the vacuum line. Results show that it is possible to obtain a recycle of about 95 % of the initial metallic copper used in the reduction system.

Geração sonoquímica de oxidantes em solução aquosa saturada de tetracloreto de carbono

In this work the CCl4 degradation in aqueous solution by sonication with 40 kHz commercial ultrasonic bath was investigated. Sonochemical degradation of CCl4 occur by the cleavage of C-Cl bond into the cavitation bubbles. Oxidation reactions and the pH decreasing in the bulk solution during sonication were attributed to chlorine radicals produced by CCl4 sonolysis, leading to increase the chloride concentration. The formation of oxidizing agents was evaluated employing I- and Fe2+ ion solutions, converted to I2 and HIO, and Fe3+, respectively. The amount of chloride and hydronium ions produced after 3 min of irradiation was 11.52 and 12.19 mmol, respectively, suggesting that the same reaction was involved to produce these ions. Fe2+ oxidation and the pH variation were monitored to estimate chlorine radical formation rate in the presence (0.107 mumol s-1) and absence (0.092 mumol s-1) of metallic ion during the first minute of sonication.

Determinação de Mn, Cu e Zn em matrizes salinas após separação e pré-concentração usando Amberlite XAD-7 impregnada com Vermelho de Alizarina S

The aim of this work was to explore the possibility of the application of a non-ionic resin obtained by impregnation of Alizarin Red S (VAS) in Amberlite XAD-7 for manganese, copper and zinc separation and preconcentration in saline matrices. For these system, the metals were quantitatively retained, in the pH range 8.5-10.0, by using 0.50 g of solid phase, stirring time of five minutes and a total mass up to 200 mug of each cation. The sorbed elements were subsequently eluted and a fifty-fold, ten-fold and ten-fold preconcentration factor for to Zn, Cu and Mn were obtained, respectively.

Avaliando a contaminação por elementos traço em atividades de maricultura: resultados parciais de um estudo de caso realizado na ilha de Santa Catarina, Brasil

Adopting the perspective of human health risk assessment, an interdisciplinary research group has been investigating since 1998 the quality of mussels and oysters cultivated in coastal zones of Santa Catarina State. Evaluation of physico-chemical parameters considered relevant in measuring the degree of eutrophication showed values compatible with the dynamics of well balanced environmental systems. Concentrations of metallic and semi-metallic elements in seawater and bivalves were found to be similar to or lower than those found in Chile, Greenland and the USA. Further investigations focusing upon sediments will provide new and useful data for the management of sustainable mariculture strategies in Brazil.

Catalisadores Ni/Al2O3 promovidos com molibdênio para a reação de reforma a vapor de metano

Mo-promoted Ni/Al2O3 catalysts for the methane steam reforming reaction were studied in this work. The Ni/Al2O3 catalysts were prepared by precipitation and molibdenum was added by impregnation up to 2%wt. The solids were tested using a micro-reactor under two H2Ov/C conditions and were characterized by ICP-OES, XRD, N2 adsoption, H2 chemisorption and TPR. NiO and NiAl2O4 phases were observed and the metallic area decreased with the increase of the Mo content. From the catalytic tests high stability was verified for H2Ov/C=4.0. On the other hand, only the catalyst containing 0,05% Mo stayed stable during 30 hours of the test at H2Ov/C=2.0.

Espectrometria de massas com ionização por "electrospray" aplicada ao estudo de espécies inorgânicas e organometálicas

Although electrospray ionization mass spectrometry (ES-MS) has been extensively applied to study organic and biochemical species, it is also specially suitable to study inorganic and organo-metallic species. Such species, even those that are low-volatile or thermo-unstable, can be easily ionized or simply transferred from liquid to gas phase by electrospray. However, chemical transformations frequently occur during the process. This paper discusses the fundamental aspects of electrospray ionization as well as its analytical applicability to inorganic and organo-metallic species in order to spread the technique and make its characteristics more familiar to potential users.

Procedimentos para recuperação de Ag de resíduos líquidos e sólidos

A simple procedure for recovering Ag, generated as residual solutions, from three different analytical methods, is presented. Based on the rate of the total Ag mass recovered, to the initial one in the initial residual solutions, efficiency as high as 97,9 ± 2,9% was obtained in the process. The purity of Ag, as Ag2O, was verified by employing this reagent in the determination of S in plant tissue. This leads to the generation of a solid metallic Ag as waste. In this situation, an 88,7 ± 0,6% Ag recovery was acquired, when a HNO3 solution was employed as solvent.

Novos materiais à base de nanofibras de carbono como suporte de catalisador na decomposição da hidrazina

Today satellites propulsion is based on the use of monopropellant and/or bipropellant chemical systems. The maneuvering of satellite is based on the hydrazine decomposition micropropulsors catalyzed by metallic iridium supported on g-alumina. This reaction is a surface reaction and is strongly exothermic and implies that the operation of the micropropulsor is controlled by the mass and heat diffusions. For this reason and for the fact that the propulsor operation is frequently in pulsed regime, the catalyst should support high pressure and temperature variations within a short time period. The performance and the durability of the commercial catalyst are jeopardized by the low thermal conductivity of the alumina. The low thermal conductivity of the alumina support restricts the heat diffusion and leads to the formation of hot spots on the catalyst surface causing the metal sintering and/or fractures of the support, resulting in loss of the activity and catalyst destruction. This work presents the synthesis and characterization of new carbon composite support for the active element iridium, in substitution of the commercial catalysts alumina based support. These supports are constituted of carbon nanofibers (30 to 40 nm diameter) supported on a macroscopic carbon felt. These materials present high thermal conductivity and mechanical resistance, as well as the easiness to be shaped with different macroscopic shapes. The mechanical stability and the performance of the iridium supported on the carbon composite support, evaluated in a laboratory scale test in hydrazine decomposition reaction, are superior compared to the commercial catalyst.