Comportamento da atomização eletrotérmica de ouro, prata, bismuto, cádmio, chumbo e estanho em soluções aquosas e em etanol, a partir de diferentes superfícies atomizadoras

The atomization behavior of Au, Ag, Bi, Cd, Pb, and Sn from pyrolitic graphite coating (L'vov platform) with the use Pd and Mg solutions, and zirconium coated platform with the analytes in nitric acid 0.2% v/v and in ethanol was investigated. In ethanol medium, the sensitivity gain was three-fold for Bi and Cd using Zr as modifier. Without modifier, the ethanol medium is appropriate only for Au and Cd. In nitric acid medium, the Zr coated platform elevates sensitivity at least two-fold for Bi and Cd. The method was applied to the determination of Ag, Au and Bi of certified steel samples, after on-line preconcentration, sorption on a minicolumn filled with C-18 bonded to silica gel and elution with ethanol. The concentrations obtained agreed with the recommended values.

Estrutura e propriedades de elipticinas

The ellipticines constitute a broad class of molecules with antitumor activity. In the present work we analyzed the structure and properties of a series of ellipticine derivatives in the gas phase and in solution using quantum mechanical and Monte Carlo methods. The results showed a good correlation between the solvation energies in water obtained with the continuum model and the Monte Carlo simulation. Molecular descriptors were considered in the development of QSAR models using the DNA association constant (log Kapp) as biological data. The results showed that the DNA binding is dominated by electronic parameters, with small contributions from the molecular volume and area.

Estudo espectroscópico de complexos de Eu3+, Tb3+ E Gd3+ com ligantes derivados de ácidos dicarboxílicos

Complexes of Eu3+, Tb3+ and Gd3+ with dipicolinic acid, chelidamic acid and chelidonic acid have been synthesized in order to study the effect of the substituent groups on the luminescence of the lanthanide complexes. The luminescence of the Eu3+ and Tb3+ complexes was quantified by quantum yield measurements. The complexes of Gd3+ have been used to determine the energies of the triplet states of the ligands. The Tb3+ complex synthesized with dipicolinic acid presented the highest quantum yield due to the energy difference between the triplet state of the dipicolinic acid and the emitting level of the Tb3+ ion.

O emprego de quitosana quimicamente modificada com anidrido succínico na adsorção de azul de metileno

The adsorption capacity of alpha-chitosan and its modified form with succinic anhydride was compared with the traditional adsorbent active carbon by using the dye methylene blue, employed in the textile industry. The isotherms for both biopolymers were classified as SSA systems in the Giles model, more specifically in L class and subgroup 3. The dye concentration in the supernatant in the adsorption assay was determined through electronic spectroscopy. By calorimetric titration thermodynamic data of the interaction between methyene blue and the chemically modified chitosan at the solid/liquid interface were obtained. The enthalpy of the dye/chitosan interaction gave 2.47 ± 0.02 kJ mol-1 with an equilibrium constant of 7350 ± 10 and for the carbon/dye interaction this constant gave 5951 ± 8. The spontaneity of these adsorptions are reflected by the free Gibbs energies of -22.1 ± 0.4 and -21.5 ± 0.2 kJ mol-1, respectively, found for these systems. This new adsorbent derived from a natural polysaccharide is as efficient as activated carbon. However 97% of the bonded dye can be eluted by sodium chloride solution, while this same operation elutes only 42% from carbon. Chitosan is efficient in dye removal with the additional advantage of being cheap, non-toxic, biocompatible and biodegradable.

Funciones termodinámicas relativas a la transferencia del ketoprófen desde el agua hasta algunos sistemas orgánicos

The thermodynamics of molal partitioning of ketoprofen (KTP) was studied in cyclohexane/buffer (CH/W), octanol/buffer (ROH/W), and dimyristoyl phosphatidylcholine (DMPC), dipalmitoyl phosphatidylcholine (DPPC), and egg lecithin (EGG/W) liposome systems. In all cases the partition coefficients (Kmo/w)were greater than unity; therefore the standard free energies of transfer were negative indicating affinity of KTP for organic media. The Kmo/w values were approximately seventy-fold higher in the ROH/W system compared with the CH/W system. On the other hand, the Kmo/w values were approximately ten or fifty-fold higher in the liposomes compared with the ROH/W system. In all cases, the standard enthalpies and entropies of transfer of KTP were positive indicating some degree of participation of the hydrophobic hydration on partitioning processes.

O emprego da termogravimetria para determinar a energia de ativação do processo de combustão de óleos combustíveis

Activation energy (Ea) is a parameter that can be applied to make predictions about the quality of oils to be used in an ICO engine. In this study, Ea was determined by thermogravimetry following two different procedures: ASTM E 1641 and Model-free kinetics. The energies were calculated in the low temperature oxidation (LTO) region for three Brazilian fuel oils (denominated A, B and C) and the results were equal using both methods: 43 kJ mol-1 (alpha=0.1 to 0.9) for oil A, 48 kJ mol-1 (alpha=0.1 to 0.5) and 65 kJ mol-1 (alpha=0.5 to 0.9) for oil B, and 58 kJ mol-1 (alpha=0.1 to 0.5) and 65 kJ mol-1 (alpha=0.5 to 0.9) for oil C. It was concluded that, among the oils studied, sample A was potentially the best option concerning the behavior in the LTO region.

Efeitos de substituintes na ligação de hidrogênio do 3-hidroxipropenal

The effect of substituents on the energies and geometries of 3-hydroxypropenal was studied using the B3LYP/6-311++G(d,p) model. The hydrogen bond energies indicate that the strongest donors and the weakest acceptors present the highest and the weakest hydrogen bonds, respectively, indicating the validity of the Madsen RAHB model. Geometric parameters indicate that the intensity of the hydrogen bond is proportional to the resonance, as suggested by the RHAB model. The effect of substituents diverges from the model proposed by Gilli et al. Sometimes the results indicate that the donor or acceptor effect is more important than the point of substitution.

Determinação dos parâmetros de arrhenius da reação de sorção do dióxido de enxofre por calcário

Sulfur emission in coal power generation is a matter of great environmental concern and limestone sorbents are widely used for reducing such emissions. Thermogravimetry was applied to determine the effects of the type of limestone (calcite and dolomite), particle size (530 and 650 µm) and atmosphere (air and nitrogen) on the kinetics of SO2 sorption by limestone. Isothermal experiments were performed for different temperatures (650 to 950 ºC), at local atmospheric pressure. The apparent activation energies, as indicated by the slope of the Arrhenius plot, resulted between 3.03 and 4.45 kJ mol-1 for the calcite, and 11.24 kJ mol-1 for the dolomite.

Cinética de redução do catalisador CuO/ZnO/Al2O3

The reduction kinetics of a CuO/ZnO/Al2O3 catalyst by hydrogen was investigated isothermally and by temperature programmed reduction (TPR). Two reducible Cu2+ species were detected; the first one was identified as CuO bulk and the other as Cu2+ strongly interacting with alumina, possibly in the form of copper aluminate. The activation energies for the reduction of these two species were 60 and 90 kJ mol-1, respectively, and the reaction order with respect to hydrogen was one. The isothermal reduction data showed that the isotropic growth model is the most appropriate to describe the reaction rate data for both Cu2+ species.

Determinação simultânea de As, Cd e Pb em amostras de água purificada para hemodiálise por espectrometria de absorção atômica com forno de grafite, após otimização multivariada baseada no uso de planejamento experimental

This paper reports the development of a methodology for simultaneously determining As, Cd and Pb, employing GF AAS with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of pyrolysis and atomization temperatures and the amount of chemical modifiers were studied. Factorial and central composite designs were used to optimize these variables. Precision and accuracy of the method were investigated using Natural Water Reference material, Nist SRM 1640. Results are in agreement with certified values at the 95% confidence limit when the Student t-test is used. This methodology was used for quality control of purified water for hemodialysis.

Cloração do anisol, tolueno e nitrobenzeno com ácido tricloroisocianúrico (ATCI): aspectos computacionais sobre a reatividade e regiosseletividade

We present in this educational article a theoretical analysis based on DFT/B3LYP 6-311++G (d,p) and ab initio MP2/6-311++G(d,p) computational calculation about the reactivity and the regioselectivity on the chlorination reaction of anisole, toluene and nitrobenzene, using trichloroisocyanuric acid (TICA) as donor of Cl+. The H.O.M.O. / L.U.M.O. energy and N.B.O. atomic charges of various aromatic systems were calculated in ab initio level. The energies of the reagents and intermediaries were calculated using D.F.T.. These results have been presented as a quantitative example for the S E A mechanism, in the undergraduate organic chemistry disciplines.

Metodologia AGOA: a modelagem de clusters de hidratação no complexo aziridina···ácido fluorídrico

We present a theoretical study of solvent effect on C2H5N···HF hydrogen-bonded complex through the application of the AGOA methodology. By using the TIP4P model to orientate the configuration of water molecules, the hydration clusters generated by AGOA were obtained through the analysis of the molecular electrostatic potential (MEP) of solute (C2H5N···HF). Thereby, it was calculated the hydration energies on positive and negative MEP fields, which are maxima (PEMmax) and minima (PEMmin) when represent the -CH2- methylene groups and hydrofluoric acid, respectively. By taking into account the higher and lower hydration energy values of -370.6 kJ mol-1 and -74.3 kJ mol-1 for PEMmax and PEMmin of the C2H5N···HF, our analysis shows that these results corroborate the open ring reaction of aziridine, in which the preferential attack of water molecules occurs at the methylene groups of this heterocyclic.

Determinação de As, Cd e Pb em amêndoas e mesocarpo de babaçu, sapucaia, xixá e castanha-do-pará por espectrometria de absorção atômica

This work describes methods for the simultaneous determination of Cd and Pb by graphite furnace atomic absorption spectrometry and As by hydride generation atomic absorption spectrometry in Brazilian nuts. The samples (~ 0.300 g) were digested to clear solutions in a closed vessel microwave oven. The pyrolysis and atomization temperatures for simultaneous determinations of Cd and Pb were 1100 and 2100 °C, respectively, using 0.5% (w v-1) NH4H2PO4 + 0.03% (w v-1) Mg(NO3)2 as chemical modifier. The limits of detection (3Δ) were 3.8 μg kg-1 for As, 0.86 μg kg-1 for Cd and 13 μg kg-1 for Pb. The reliability of the entire procedures was confirmed by peach leaves (No. 1547 - NIST) certified reference material analysis and addition and recovery tests. The found concentrations presented no statistical differences at the 95% confidence level.

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.

O valor energético dos alimentos: exemplo de uma determinação experimental, usando calorimetria de combustão

The energies involved in the combustion, under atmosphere of oxygen, of breakfast cereals and dehydrate powdered whole milk samples, were determined by combustion calorimetry. This practical work, in the field of human nutrition, involved the characterization of the nutritional composition and the combustion of samples of the two foods that are part of the alimentary diet, namely, at breakfast. The obtained results allowed to assess the energy value printed in the foods labels and discuss the way those values are estimated.