Modelagem dos processos químicos em plasmas de misturas gasosas usadas na corrosão de silício. Parte 2: SF6 / O2

In this work, a numerical modeling analysis of the gas-phase decomposition of SF6 / O2 mixtures, in the presence of silicon, was performed. The relative importance of individual processes and the effect of the parameters' uncertainties were determined. The model was compared with experimental data for the plasma etching of silicon and with the calculated results for the CF4 / O2 system. In both systems the main etching agent is the fluorine atom and the concentration of the major species depends on the composition of the mixture. The etching rate is greater for SF6 / O2.

Pervaporação: uma técnica de separação contínua não-cromatográfica

A brief discussion of the non-chromatographic continuous separation techniques is presented emphasizing the pervaporation process. It makes interesting choices for implementing various preliminary operations of the analytical process in order to accommodate the raw sample to the measuring instrument. Discussions include the perceived advantages and disadvantages, the underlying principles of pervaporation process, the flexible module and fields of application.

Identificação de componentes de óleos voláteis: Análise espectroscópica de misturas de sesquiterpenos

This paper describes a chromatographic method to fractionate volatile oils and to identify their sesquiterpenic constituents. The fractionation process includes flash chromatography over silica gel and chromatography over silica gel/AgNO3, utilising pentane, CH2Cl2 and/or acetone as eluents. GC chromatograms were obtained in order to get the relative percentage of each constituent in the volatile oils, to get the retention time value of them as well as to analyse and combine the fractions eluted from the columns. Such procedure afford mixtures of sesquiterpenes which are analysed by GC/MS, 13C and ¹H NMR.

Química orgânica experimental: integração de teoria, experimento e análise

A new approach for teaching in basic experimental organic chemistry is presented. Experimental work goes on parallel to theoretical lectures leading to an immediate application of theoretical concepts transmitted therein. One day/week is dedicated exclusively to the organic laboratory. Reactions are proposed as problems to be solved; the student has to deduce the structure of the product on the basis of his observations, the analytical data and his mechanistical knowledge. 70 different experiments, divided in 7 thematical chapters, are presented. All experiments require the analysis and discussion of 1H and 13C NMR, IR and UV spectra. Additional questions about each reaction have to be answered by the student in his written report. Laboratory safety is garanteed by the exclusion or substitution of hazardous and toxic reagents. Microscale preparations are adopted in most cases to lower the cost of materials and the amount of waste. Recycling of many reaction products as starting materials in other experiments reduces the need for commercial reagents and allows the execution of longer reaction sequences. Only unexpensive standard laboratory equipment and simple glassware are required. All experiments include instructions for the save treatment or disposal of chemical waste.

Elementos da dinâmica química ao nível da teoria variacional do estado de transição com correções interpoladas

In this article are presented some fundamental elements of the conventional and of the variational transition state theories which are needed to carried out calculations of semi-classical chemical dynamics. Some important bottlenecks in building reliable potential energy surfaces using electronic structure calculations are also discussed. It is put emphasis on the methodology of the variational transition state theory with interpolated corrections (VTST-IC), and its application in the calculations of the rate constants and of the kinetic isotope effect (KIE) of CH4 + Cl « CH3 + HCl reaction.

Triterpenos da resina de Protium heptaphyllum March (B0urseraceae): caracterização em misturas binárias

Eight triterpenes, maniladiol, breine, ursa-9(11):12-dien-3beta-ol, oleana-9(11):12-dien-3beta-ol, 3alpha-hydroxy-tirucalla-8,24-dien-21-oic acid, 3alpha-hydroxy-tirucalla-7,24-dien-21-oic, alpha and beta amyrines were isolated as binary mixtures obtained from the chloroform extract of the oil-resin of Protium heptaphyllum March. The identification of the compounds was based mainly in 13C NMR data and mass spectra. The diene and the tetracyclic acid triterpenes were not reported before in the literature as constituents of the studied resin.

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.

Índices de reatividade química a partir da teoria do funcional de densidade: formalismo e perspectivas

The fundaments of the modern Density Functional Theory (DFT), its basic theorems, principles and methodology are presented. This review also discuss important and widely used concepts in chemistry but that had not been precisely defined until the development of the DFT. These concepts were proposed and used from an empirical base, but now their precise definition are well established in the DFT formalism. Concepts such as chemical potential (electronegativity), hardness, softness and Fukui function are presented and their consequences to the understanding of chemical reactivity are discussed.

Cálculo ab initio de intensidades Raman dinâmicas utilizando a teoria da resposta linear

In this paper a methodology for the computation of Raman scattering cross-sections and depolarization ratios within the Placzek Polarizability Theory is described. The polarizability gradients are derived from the values of the dynamic polarizabilities computed at the excitation frequencies using ab initio Linear Response Theory. A sample application of the computational program, at the HF, MP2 and CCSD levels of theory, is presented for H2O and NH3. The results show that high correlated levels of theory are needed to achieve good agreement with experimental data.

Propriedades eletrônicas e estruturais do PbTiO3: teoria do funcional de densidade aplicada a modelos periódicos

Calculations based on density functional theory at the B3LYP hybrid functional level applied to periodic models have been performed to characterize the structural and electronic properties of PbTiO3. Two different slab terminations (PbO and TiO2) have been considered to obtain and discuss the results of band structure, density of states, charge distribution on bulk and surface relaxation. It is observed that the relaxation processes are most prominent for the Ti and Pb surface atoms. The electron density maps confirm the partial covalent character of the Ti-O bonds. The calculated optical band gap and other results are in agreement with experimental data.

Espectros eletrônicos de alguns complexos de geometria octaédrica de Ni2+: uma introdução prática à teoria do campo cristalino no curso de graduação

The experiment introduces the undergraduate students to the crystal field theory. The electronic spectra of the octahedral complexes of [Ni(L)n]2+ (L = H2O, dmso, NH3 and en) obtained in the experiment are used to calculate 10Dq and B parameters. The experiment shows how the parameters can be calculated and correlated with the nature of the ligands and the field intensities produced.

O modelamento estatístico de misturas: experimento tutorial usando voltametria de redissolução anódica

This work illustrates the modeling procedure for a solvent mixture using the simplex- centroid approach. The selected experiment was the optimization of the peak current observed in the direct determination of nickel by anodic stripping voltammetry (ASV) in a solvent mixture composed of N,N-dimethylformamide, ethanol and water. The text is presented in a tutorial way, showing in detail the several steps which must be followed in such a process. Since not all possible mixtures lead to a measurable instrumental response, pseudocomponents had to be used to rescale the experimental design. This also allows to show how to apply this tool, usually troublesome for non-specialists in mixture modeling procedures.

Desenvolvimento e validação de metodologia de análise de misturas biodiesel: diesel utilizando cromatografia gasosa-espectrometria de massas

The aim of this work was to develop and validate a method of analysis of biodiesel:diesel blends using HRGC-MS in SIM mode. The proposed method is applicable to biodiesel from linoleic oils, such as soybean oil. The following results were obtained: linearity over the methyl linoleate concentration range of 250-2500 mg L-1 (R² > 0.999); limits of detection and quantification of 2 and 5 mg L-1, respectively; recovery from 82 to 96% of biodiesel in diesel and repeatability < 2% (RSD). Comparison between two operators showed that it is not necessary the same operator to do the analysis.

Determinação de misturas de sulfametoxazol e trimetoprima por espectroscopia eletrônica multivariada

In this work a multivariate spectroscopic methodology is proposed for quantitative determination of sulfamethoxazole and trimethoprim in pharmaceutical associations. The multivariate model was developed by partial least-squares regression, using twenty synthetic mixtures and the spectral region between 190 and 350 nm. In the validation stage, which involved the analysis of five synthetic mixtures, prediction errors lower that 3% were observed. The predictive capacity of the multivariate models is seriously affected by spectral changes induced by pH variations, a fact that acquires a great significance in the analysis of real samples (pharmaceuticals) that contain chemical additives.

Efeito antagônico do ferro e do zinco em uma formulação de alimentação enteral utilizando planejamento de misturas da metodologia de superfície de resposta

Nutritional therapy with enteral diets became substantially specialized over the last years. This work's aim was to study the effect of the components of a formulation: fiber, calcium and medium-chain triglycerides for dialysability of minerals. Analysis of multiple variables was carried out using response surface methodology. The level curve showed an antagonic effect of interaction between iron and zinc. TCM was the variable responsible for characterizing competition between the two minerals in the formulation. More studies on foods are needed for knowing the effecs of minerals in formulations.