Preparação e caracterização do complexo cobaloxima e sua utilização na construção de um eletrodo modificado: um experimento eletroquímico no curso de graduação

The present experiment describes the preparation, characterization of n-butyl(pyridil)cobaloxime complex and its electrochemical property. The infrared and uv-visible absorption spectra were used to characterize the complex obtained. The infrared spectrum of the compound showed characteristics bands that indicated the formation of the Co-C chemical bond formation. The electronic absorption spectrum in acetonitrile showed transition bands attributed to p-p*, metal-to-ligand charge transfer, d-d transitions and charge transfer Co-C. The electrochemical property was investigated by the pulse differential voltammetry technique. Two oxidation processes: Co(I)/Co(II) at -423 mV and Co(II)/Co(III) at 752 mV were observed.

Utilização do TEMPO (N-oxil-2,2,6,6-tetrametilpiperidina) na oxidação de álcoois primários e secundários

The oxidation of alcohols to obtain ketones, aldehydes or carboxylic acids is a fundamental transformation in organic synthesis and many reagents are known for these conversions. However, there is still a demand for mild and selective reagents for the oxidation of alcohols in the presence of other functional groups. As an alternative, the nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) has been demonstrated to be a useful reagent for the transformation of alcohols. The oxidation of alcohols using TEMPO is often efficient, fast, selective, made in mild conditions and can tolerate sensitive functional groups. In this article we report different methodologies using TEMPO in the oxidation of alcohols.

Utilização de um eletrodo de grafite-epóxi recoberto com [Zn(FEN)3][tetratris(4-clorofenil) borato]2 sensível a zinco(II) em meio 1,10-fenantrolina como eletrodo indicador em titulações potenciométricas de precipitação

The construction and analytical evaluation of a coated graphite-epoxy electrode sensitive to the zinc-1,10-phenantroline complex based on the [Zn(fen)3][tetrakis(4-chlorophenyl)borate]2 incorporated into a poly(vinylchloride) (PVC) matrix are described. A thin membrane film of this ion-pair, dibutylphthalate (DBPh) and PVC were deposited directly onto an electrically conductive graphite-epoxy support located inside a Perspex® tube. The best PVC polymeric membrane contains 65% (m/m) DBPh, 30% (m/m) PVC and 5% (m/m) of the ion-pair. This electrode shows a response of 19.5 mV dec-1 over the zinc(II) concentration range of 1.0 x 10-5 to 1.0 x 10-3 mol L-1 in 1,10-phenantroline medium, at pH 6.0. The response time was less than 20 seconds and the lifetime of this electrode was more than four months (over 1200 determinations by each polymeric membrane). It was successfully used as an indicator electrode in the potentiometric precipitation titration of zinc(II) ions.

Utilização de regressão multivariada para avaliação espectrofotométrica da demanda química de oxigênio em amostras de relevância ambiental

In this work, a partial least squares regression routine was used to develop a multivariate calibration model to predict the chemical oxygen demand (COD) in substrates of environmental relevance (paper effluents and landfill leachates) from UV-Vis spectral data. The calibration models permit the fast determination of the COD with typical relative errors lower by 10% with respect to the conventional methodology.

Utilização de reações foto-Fenton na prevenção de contaminações agrícolas

In this work the application of the photo-Fenton process for the treatment of washing water of herbicide containers using solar energy was studied. The influence of the H2O2 concentration and the iron source on the degradation of tebuthiuron and diuron was investigated. The degradation efficiency was strongly affected by the iron source. Using ferrioxalate, total mineralization of diuron and tebuthiuron was obtained either for the individual compounds or for a mixture containing both herbicides, while when using Fe(NO3)3, the maximum mineralization reached for both herbicides was only 50%.

Utilização de RMN de ¹H na determinação da configuração absoluta de álcoois

This review reports the determination of absolute configuration of primary and secondary alcohols by ¹H NMR spectroscopy, using the Mosher method. This method consists in the derivatization of an alcohol possessig unknown absolute configuration with one or both enantiomers of an auxiliary reagent. The resulting diastereoisomer spectra are registered and compared, and the chemical shift differences (DdR,S = deltaR - deltaS) are measured. The determination of the absolute configuration of the alcohol molecule is based on the correlation between its chiral center and the auxiliary reagent's chiral center. Therefore, the determination of the absolute configuration depends on aromatic ring shielding effects on the substituents of the alcohol as evidenced by the ¹H NMR spectrum.

Utilização de técnicas eletroanalíticas na determinação de pesticidas em alimentos

The aim of this work is to discuss selected applications of electroanalytical techniques for the detection of pesticides in foods and beverages, published in the last ten years. The applications involved different working electrodes for the electroanalytical determination of pesticides, namely amperometric biosensors, cholinesterase-based biosensors, polymer-modified electrodes, ultramicroelectrodes and hanging mercury drop electrodes. They were used for several voltammetric and amperometric techniques in different analytical procedures for the detection and quantification of different classes of pesticides in different food matrices.

Análise quiral por espectrometria de massas através da utilização do método cinético

Novel and quantitative mass spectrometry methods for rapid and accurate enantiomeric excess determination are presented. These methodologies use electrospray ionization (ESI) and mass spectrometry (MS) to detect and analyze, via collision-induced dissociation (CID), mass-selected transition metal complexes that promote enantio especific interactions. The data from CID are conveniently treated by the kinetic method, a sensitive linear free energy method of treating mass spectrometric results. Four different variations of this methodology are described: single ratio method (S R), quotient ratio method (Q R), fixed ligand method (S Rfixed), and quotient ratio method with fixed ligand (Q Rfixed). These individual methods are compared and their main features discussed in detail.

Princípio e utilização da técnica de efeito miragem de concentração

The aim of this work is to present the theoretical and experimental aspects of the mirage effect technique. We are especially interested in the concentration mirage effect, which is a powerful tool in the study of electrochemical reactions that produce ionic movements close to electrodes and to get some fundamental information on mass transport and charge transfer during electrochemical processes. Limitations of this technique are discussed as well as the recent attempts to overcome them.

Utilização de um monitor de vídeo como fonte de alta tensão para eletroforese capilar

This article describes the use of a conventional CRT monitor as a high voltage power supply for capillary electrophoresis. With this monitor, a 23-kV high voltage with a ripple of 1.32% was observed. The reproducibility of the applied high voltage was evaluated by measuring the standard deviations of peak area and migration time for five consecutive injections of a test mixture containing potassium, sodium, and lithium cations at 50 mmol L-1. The errors were about 2.5% and 0.6% for peak area and migration time, respectively. The maximum current tested was about 180 mA, which covers most capillary electrophoresis applications. This system has been successfully used for several months, maintaining the desired level of performance.

Utilização da múltipla voltametria de onda quadrada na determinação eletroanalítica de compostos orgânicos e inorgânicos

This paper reports the development of multiple square wave voltammetry and the possibilities of its use for electroanalytical determinations of organic and inorganic compounds with the improvement of the signal-to-noise ratios and detection limits 2-3 orders of magnitude lower than those obtained with conventional square wave voltammetry. The theoretical aspects and analytical applications were demonstrated as an increased analytical response (current) and application of different pulse modes for different redox processes. Preliminary results obtained for several redox systems using different electrode surfaces are shown, demonstrating also that MSWV represents an excellent alternative for the determination of ultra-traces of organic and inorganic compounds.

Utilização da extração em fase sólida (SPE) na determinação de hidrocarbonetos policíclicos aromáticos em matrizes aquosas ambientais

Polycyclic aromatic hydrocarbons (PAHs) are a great environmental concern mainly because of their toxic, mutagenic and carcinogenic potential. This paper reports utilization of the solid-phase extraction (SPE) technique to determine PAHs in environmental aqueous matrices. The recovery from environmental aqueous matrices fortified with PAHs varied from 63.7 to 93.1% for atmospheric liquid precipitation, from 38.3 to 95.1% for superficial river water, and from 71.0 to 95.5% for marine water. No negative matrix effect was observed for the recovery of PAHs from atmospheric liquid precipitation and marine water, but was observed for superficial river water, particularly for PAHs possessing 5 and 6 aromatic rings.

Utilização de zeólitas sintetizadas a partir de xisto retortado na remoção de arsênio em águas contaminadas

The solid by-product of the oil shale processing (PETROBRAS - Brazil) was used as raw material to synthesize zeolites A and faujasite. Alkaline fusion followed by hydrothermal treatment was the synthesis procedure used, and five different starting material compositions were obtained. The more crystalline zeolite-type materials synthesized, the pretreated oil shale ash and commercial zeolites were used as adsorbents in the purification of pollutant solutions with arsenic. The zeolite-type material composed of a mixture of zeolite A (42.6%) and faujasite (52.9%) presented an ion exchange capacity comparable to the pure zeolites A and faujasite, much better than the pretreated ash.

Utilização de solos locais para tratamento de efluentes do refino de petróleo contendo metais

The employment of local soils for extraction of metallic elements was evaluated through batch tests to treat wastewaters generated in a petroleum refinery plant in southern Brazil. Clay and organic carbon content and clay mineralogy provide these soils, in principle, with moderate metal retention capacity. The following retention order was established: Cr3+ > Pb2+ > Cu2+ > Hg2+ > Cd2+, with total amount of metals retained varying from 36 to 65 meq kg-1. The results show the high efficiency of local soils for extracting metals from liquid effluents through sorption and precipitation processes under acid pH conditions.

Utilização de modelagem numérica para o estudo da dispersão de poluentes emitidos pela usina termoelétrica Presidente Médici

The purpose of the present study is to evaluate the atmospheric behavior in the dispersion of the pollutants SO2, PM10 and NOx emitted by the President Medici power plant in Candiota, RS. The RAMS atmospheric model was applied and the simulations were conducted from april in 20 to 24, 2004. The concentrations of the pollutants simulated by RAMS were compared with the data measured at the air quality monitoring stations. The results showed significant influence of the emissions generated by the power plant on the concentration of the pollutants.