Walter Charleton (1620 - 1707) e sua Teoria Atômica

Several authors in the 17th century used the atomic hypothesis to explain observable phenomena. This paper analyzes some ideas about chemical transformation proposed by the English physician Walter Charleton. In Physiologia Epicuro-Gassendo-Charltoniana (London, 1654), Charleton examined philosophical aspects of the atomic theory, and suggested that the best explanation for all natural phenomena would be only in terms of atoms and their motions. Sometimes, however, he had to attribute to the atoms some kind of "internal virtue", to explain more complex properties of the matter. His idea of "element", and the little use of experimentation and quantification, also limited the range of Charleton's theory.

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.

Uma abordagem robusta de cálculo aplicada a um sistema potenciométrico de medida de concentrações hidrogeniônicas em soluções aquosas

The data analyzed in this work were generated following the methodology developed by Molina et al.(J. Electroanal. Chem., 1979) for the calibration of a potentiometric system of measurement of hydrogen-ion concentrations resulting from neutralizations, at 25 ºC, of acidic or alkaline solutions at constant ionic strength (0.1 mol.l-1) held with NaClO4. The observed data present a serious deviation in relation to the mathematical model derived from the Nernst equation, for pH values ranging from 3 to 11, where pH=-log[H+]. We show that the minimization of the sum of the absolute values of the residuals gives estimates that are not influenced by outlying values.

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.

Construção de uma fonte de corrente e de uma sonda para medida de condutividade pelo método da sonda de quatro pontas

This paper describes the construction of an eletrical current source and of a probe to be used in the measurement of eletrical conductivity through a four-point probe method. These pieces of equipments can be obtained at the low price of US$ 50.00 and are adequate for eletrical conductivity measurements in the semiconductor range, that is from 10-1 to 10-6 S cm-1.

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 ensino de química quântica e o computador na perspectiva de projetos

This paper aims to discuss and reflect about the use of computers in the teaching of Quantum Chemistry. A course on Computational Quantum Chemistry concentrating on Medicinal Chemistry projects was developed for undergraduate and graduate students. The results showed that students got more motivated and involved when there is an articulation between theory and practice. This work presents an alternative way to teach Theoretical Chemistry using projects.

De Svante Arrhenius ao peagâmetro digital: 100 anos de medida de acidez

This work describes the establishment of the concept of pH and the evolution of its measurement. The origin of the pH definition can be found in the development of the chemistry of aqueous solutions during the XIXth century. The electrolytic dissociation theory by Svante Arrhenius played a central role. After the proposal of the pH scale by Sörensen, many years were necessary for the acceptance of this new parameter among chemists in general. Its importance was first recognized in biochemistry and related areas. Twenty years after, its importance had been recognized in many industrial and laboratorial practices. The previous methods were based on colorimetric and electrometric methods, but both suffered from many problems. Acceptance of pH in Chemistry was only possible after the development of experimental trustable measurements. The invention of the pH meter was the primordial step.

Aplicação da química quântica computacional no estudo de processos químicos envolvidos em espectrometria de massas

The field of application of mass spectrometry (MS) has increased considerably due to the development of ionization techniques. Other factors that have stimulated the use of MS are the tandem mass spectrometry (MS/MS) and sequential mass spectrometry (MSn) techniques. However, the interpretation of the MS/MS and MSn data may lead to speculative conclusions. Thus, various quantum chemical methods have been applied for obtaining high quality thermochemical data in gas phase. In this review, we show some applications of computational quantum chemistry to understand the formation and fragmentation of gaseous ions of organic compounds in a MS analysis.

Extracción y medida de peroxidasa en pulpa de arazá (Eugenia stipitata MC Vaugh)

A technique for both extraction and activity measurement of peroxidase extracted from arazá (Eugenia stipitata Mc Vaugh) is described. Peroxidase from arazá pulp fruit was extracted using a combination of protein precipitation with acetone and extraction with 50 mM sodium buffer phosphate (pH 6.0). Optimum activity using guaiacol as H-donor was obtained at pH from 5.0 to 6.5, temperature from 60 to 75 °C, H2O2 between 10 to 15 mM and guaiacol from 80 to 160 mM. Thermal inactivation showed a first-order inactivation kinetic. Reactivation was observed when extracts were heated at 80 °C and afterwards incubated at 25 °C.

Modelos da Química Quântica no espaço de momento: diferentes representações de um mesmo sistema

The conventional approach to simple quantum chemistry models is contrasted with that known as momentum representation, where the wavefunctions are momentum dependent. Since the physical interactions are the same, state energies should not change, and whence the energy differences correlating with the real world as spectral lines or bands. We emphasize that one representation is not more fundamental than the other, and the choice is a matter of mathematical convenience. As spatial localization is rooted in our brains, to think in terms of the momentum present us a great mental challenge that can lead to complementary perspectives of a model.