Diagramas de Ellingham e de Van't Hoff: algumas considerações

The main subject of this article is to show the parallelism betwen the Ellingham and Van't Hoff diagrams. The first one is a graphic representation of the changes in the standard Gibbs free energy (deltarGtheta) as a function of T and was introduced by Ellingham in 1944, in order to study metallurgic processes involving oxides and sulphides. On the other hand, the Van't Hoff diagram is a representation of the function ln K versus (1/T). The equivalence between both diagrams is easily demonstrated, making simple mathematical manipulations. In order to show the parallelism between both diagrams, they are presented briefly and two examples are discussed. The comparison of the both diagrams surely will be helpful to students and teachers in their learning and teaching activities, and will certainly enrich important aspects of chemical thermodynamics.

Teores de nutrientes na alface irrigada com água residuária aplicada por sistemas de irrigação

A trial was carried out to evaluate the chemical composition in the aerial part of lettuce, cv. 'Elisa', irrigated with wastewater treated with constructed wetland and source deposit water, grown on a Rhodic Hapludox Soil, using the irrigation systems sprinkle, subsurface drip and surface drip irrigation. The experiment was carried out from August 17th to October 3rd of 2001 and the chemical analyses of the lettuce were accomplished to 47 days after transplanting of the seedling. The aerial part of the lettuce was analyzed as for the levels of total nitrogen, nitrate, phosphorus, potassium, calcium, magnesium, sulfur, iron, manganese, copper, zinc, sodium, boron, cobalt and molybdenum. The sodium and the sulfur presented higher levels than the maximum suitable in the aerial part of the lettuce and the smallest level of magnesium, while other chemical elements analyzed were normal and appropriate considering the standard for well-nourished plants, not being influenced by the water type. The sodium was the chemical element that presented the highest levels in the aerial part of the lettuce in the treatments irrigated with wastewater, presenting significant difference in relationship to the treatments irrigated with source deposit water in the three irrigation systems. The use of the different irrigation systems by the application of wastewater treated with constructed wetland did not interfere in the levels of nutrients in the aerial part of the lettuce.

Weekend/weekday differences in concentrations of ozone, nox, and non-methane hydrocarbon in the metropolitan area of São Paulo

Ozone and inhalable particulate matter are the major air pollutants in the Metropolitan Area of São Paulo, Brazil, a region that has more than 19 million inhabitants and approximately 7 million registered vehicles. Proximity of roadways, adjacent land use, and local circulation are just some of the factors that can affect the results of monitoring of pollutant concentrations. The so-called weekend effect (higher ozone concentrations on weekends than on weekdays) might be related to the fact that concentrations of ozone precursors, such as nitrogen oxides (NOx) and Non Methane-Hydrocarbon (NMHC), are relatively lower on weekends. This phenomenon has been reported in some areas of the United States since the 1970s. The differences between the concentrations of ozone in period of weekend and weekday, were obtained from analysis of data hourly average of CETESB for 2004, studied the precursors to the formation of troposphere ozone, the meteorological variables and traffic profile for RMSP. Because of the proximity to sources of emissions from the station Pinheiros showed higher concentrations of NO and NO² and greater variations to the periods weekend and weekday. With fewer vehicles circulating during the weekend, and consequently less emission of pollutants, it has cleaner air and less concentration of NO and NO², there is the ideal setting to the formation of troposphere ozone, despite the lower concentration of NO². The proximity with the source emissions, aided by the increased availability of solar radiation and the presence of ozone precursors, were factors conditions for the occurrence of weekend effect.

Óxidos do tipo perovskita para reação de redução de no com CO

In this work, the perovskite-type oxides LaNiO3, LaMnO3, La0,7Sr0,3NiO3 and La0,7Sr0,3MnO3 were prepared by co-precipitation and tested in the NO reduction with CO at 400 and 500 ºC for 10 h. The catalysts were characterized by X-ray diffraction, temperature programmed reduction with hydrogen, nitrogen adsorption and chemical analysis. The nonstoichiometric oxygen was quantified by temperature programmed reduction, and the catalytic tests showed that the La0,7Sr0,3MnO3 catalyst presented the higher performance for the reduction reaction of NO with CO. The partial substitution of lanthanum by strontium increased the NO conversion and the N2 yield.

Reaproveitamento de óxidos de manganês de pilhas descartadas para eletrocatálise da reação de redução de oxigênio em meio básico

The oxygen reduction reaction was studied in alkaline media using manganese oxides obtained from spent batteries as electrocatalysts. Three processes were used to recover manganese oxides from spent batteries. The particles obtained were in the range from 8 to 11 nm. The electrochemical experiments indicated a good electrocatalytic activity toward oxygen reduction using the different samples and showing approximately a direct transference of 4 electrons during the process. Even though all the processes were efficient, the best result was observed for the prepared sample using reactants of low cost.

Extração seletiva de metais pesados em sedimentos de fundo do Rio Tietê, São Paulo

Sediment samples from Tietê river were submitted to chemical and sequential extractions of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn). It was followed a single extraction by using 0.1 mol L-1 hydrochloric acid and a sequential procedure to evaluate possible chemical associations described as exchangeable, carbonate, reducible oxides, sulfide, organic matter and residual fractions. High concentrations of heavy metals were determined at Pirapora reservoir, which is closer to the Metropolitan Area of São Paulo while for Barra Bonita reservoir, the results showed low concentrations for such elements. Acid volatile sulfides, grain size distribution and carbon contents were also determined.

Natural antioxidant from yerba maté (Ilex paraguariensis St. Hil.) prevents hamburger peroxidation

The aim of this study was to evaluate whether yerba maté alcoholic extracts at very low concentrations (0.01 and 0.1%), prevent/retard lipid peroxidation in beef hamburgers without impairing sensory acceptability. For this TBARs and hexanal levels, fatty acid profile and cholesterol oxides were evaluated as oxidation parameters in beef hamburgers during 90 days' storage. The addition of 0.01% yerba maté ethanolic extracts proved inefficient in restraining the lipid peroxidation while the addition of 0.1% resulted in efficient antioxidant activity. Sensory evaluation of hamburger containing 0.1% yerba maté ethanolic extracts showed good acceptability. Yerba maté ethanolic extracts could entirely or partially replace the phenolic synthetic antioxidants in beef hamburgers only when used at above legally allowed concentrations for antioxidant additives (0.01%).

Efeito do beneficiamento sobre o valor nutricional do peixe mandim (Arius spixii)

Com o objetivo de avaliar o efeito do beneficiamento sobre o valor nutricional do peixe mandim (Arius spixii) comercializado em Maceió-AL, determinaram-se nas suas formas in natura e beneficiada (salgado-seco) a composição centesimal, valor calórico, cloretos, perfil de ácidos graxos e colesterol, sendo também analisada a ocorrência de óxidos de colesterol. Os resultados obtidos para o mandim in natura e beneficiado, respectivamente, de umidade (70,13% e 40,31%), proteínas (51,73% e 38,07%, base seca), carboidratos (4,67% e 2,24%, base seca), calorias (486 kcal/100g e 367 kcal/100g, base seca), ácidos graxos (poliinsaturados 14,54% e 15,49%, ômega-3 8,51% e 6,51%), colesterol (82,66 mg/100g e 61,30 mg/100g) e óxidos (7-cetocolesterol 8,31 µg/g e 17,90 µg/g), permitiram concluir que o beneficiamento favoreceu alterações significativas no valor nutricional do mandim.

Effect of Alloying Elements on Thermal Diffusivity of Gray Cast Iron Used in Automotive Brake Disks

The purpose of this work was to experimentally investigate the thermal diffusivity of four different gray cast iron alloys, regularly used to produce brake disks for automotive vehicles. Thermal diffusivity measurements were performed at temperatures ranging from room temperature to 600 A degrees C. The influence of the thermal conductivity on the thermomechanical fatigue life is also briefly presented. The measurements were sensitive to the influence of the carbon equivalent and alloying elements, such as molybdenum, copper and chromium. Molybdenum, unlike copper, lowered the thermal diffusivity of the gray cast iron, and alloy E (without molybdenum), besides presenting a relatively low carbon equivalent content and an increase in the values of the thermal diffusivity, presented the best performance during the thermomechanical fatigue. The molybdenum present in alloys B and C did not fulfill the expectations of providing the best thermomechanical fatigue behavior. Consequently, its elimination in the gray cast iron alloy for this application will result in a significant economy.

Deficiência em micronutrientes em mudas de sangra d'agua (Croton urucurana, Baill.)

This study had the following objectives: to induce and describe symptoms of deficiency of boron (B), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo) and zinc (Zn), determining the effect on the mineral composition of leaves. The experiment was developed in a green house and used diagnosis technique by subtraction. The experimental design usedn was a randomized blocks, with seven treatments and three replicates. It was verified that micronutrient omission led to morphological alterations which, in turn, caused visual symptoms. The symptoms caused by the omission of Cu, Mn and Zn were the first to appear, and were followed by those of B, Fe and Mo. The omission of B, Mn and Zn was responsible for the more pronounced reduction in height and stem diameter.

Local atomic structure in tetragonal pure ZrO(2) nanopowders

The local atomic structures around the Zr atom of pure (undoped) ZrO(2) nanopowders with different average crystallite sizes, ranging from 7 to 40 nm, have been investigated. The nanopowders were synthesized by different wet-chemical routes, but all exhibit the high-temperature tetragonal phase stabilized at room temperature, as established by synchrotron radiation X-ray diffraction. The extended X-ray absorption fine structure (EXAFS) technique was applied to analyze the local structure around the Zr atoms. Several authors have studied this system using the EXAFS technique without obtaining a good agreement between crystallographic and EXAFS data. In this work, it is shown that the local structure of ZrO(2) nanopowders can be described by a model consisting of two oxygen subshells (4 + 4 atoms) with different Zr-O distances, in agreement with those independently determined by X-ray diffraction. However, the EXAFS study shows that the second oxygen subshell exhibits a Debye-Waller (DW) parameter much higher than that of the first oxygen subshell, a result that cannot be explained by the crystallographic model accepted for the tetragonal phase of zirconia-based materials. However, as proposed by other authors, the difference in the DW parameters between the two oxygen subshells around the Zr atoms can be explained by the existence of oxygen displacements perpendicular to the z direction; these mainly affect the second oxygen subshell because of the directional character of the EXAFS DW parameter, in contradiction to the crystallographic value. It is also established that this model is similar to another model having three oxygen subshells, with a 4 + 2 + 2 distribution of atoms, with only one DW parameter for all oxygen subshells. Both models are in good agreement with the crystal structure determined by X-ray diffraction experiments.

Synchrotron X-ray powder diffraction and extended X-ray absorption fine structure spectroscopy studies on nanocrystalline ZrO(2)-CaO solid solutions

The crystal structure and the local atomic order of a series of nanocrystalline ZrO(2)-CaO solid solutions with varying CaO content were studied by synchrotron radiation X-ray powder diffraction and extended X-ray absorption fine structure (EXAFS) spectroscopy. These samples were synthesized by a pH-controlled nitrate-glycine gel-combustion process. For CaO contents up to 8 mol%, the t' form of the tetragonal phase (c/a > 1) was identified, whereas for 10 and 12 mol% CaO, the t '' form (c/a=1; oxygen anions displaced from their ideal positions in the cubic phase) was detected. Finally, the cubic phase was observed for solid solutions with CaO content of 14 mol% CaO or higher. The t'/t '' and t ''/cubic compositional boundaries were determined to be at 9 (1) and 13 (1) mol% CaO, respectively. The EXAFS study demonstrated that this transition is related to a tetragonal-to-cubic symmetry change of the first oxygen coordination shell around the Zr atoms.

High-temperature X-ray powder diffraction study of the tetragonal-cubic phase transition in nanocrystalline, compositionally homogeneous ZrO2-CeO2 solid solutions

Crystal structure of compositionally homogeneous, nanocrystalline ZrO2-CeO2 solutions was investigated by X-ray powder diffraction as a function of temperature for compositions between 50 and 65 mol % CeO2 center dot ZrO2-50 and 60 mol % CeO2 solid solutions, which exhibit the t'-form of the tetragonal phase at room temperature, transform into the cubic phase in two steps: t'-to-t '' followed by t ''-to-cubic. But the ZrO2-65 mol % CeO2, which exhibits the t ''-form, transforms directly to the cubic phase. The results suggest that t'-to-t '' transition is of first order, but t ''-to-cubic seems to be of second order. (C) 2008 International Centre for Diffraction Data.

High performance magnetic separation of gold nanoparticles for catalytic oxidation of alcohols

We present the magnetic separation approach to facilitate the recovery of gold nanoparticle (AuNP) catalysts. The use of magnetically recoverable supports for the immobilization of AuNPs instead of traditional oxides, polymers or carbon based solids guarantees facile, clean, fast and efficient separation of the catalyst at the end of the reaction cycle. Magnetic separation can be considered an environmentally benign separation approach, since it minimizes the use of auxiliary substances and energy for achieving catalyst recovery. The catalyst preparation is based on the immobilization of Au(3+) on the surface of core-shell silica-coated magnetite nanoparticles, followed by metal reduction using two different methods. AuNPs were prepared by thermal reduction in air and by hydrogen reduction at mild temperature. Interestingly, the mean particle size of the supported AuNPs was similar (ca. 5.9 nm), but the polydispersity of the samples is quite different. The catalytic activity of both catalysts in the aerobic oxidation of alcohols was investigated and a distinct selectivity for benzyl alcohol oxidation was observed.

Clean preparation of methyl esters in one-step oxidative esterification of primary alcohols catalyzed by supported gold nanoparticles

Methyl esters were prepared by the clean, one-step catalytic esterification of primary alcohols using molecular oxygen as a green oxidant and a newly developed SiO(2)-supported gold nanoparticle catalyst. The catalyst was highly active and selective in a broad range of pressure and temperature. At 3 atm O(2) and 130 degrees C benzyl alcohol was converted to methyl benzoate with 100% conversion and 100% selectivity in 4 h of reaction. This catalytic process is much ""greener"" than the conventional reaction routes because it avoids the use of stoichiometric environmentally unfriendly oxidants, usually required for alcohol oxidation, and the use of strong acids or excess of reactants or constant removal of products required to shift the equilibrium to the desired esterification product.