Desproporcionamento de tolueno sobre zeólitas tipo mordenita - atividade e seletividade na obtenção de xilenos

A sodium mordenite zeolite (Na-MOR) was synthesized and modified by dealumination with chloridric acid solution (H-MOR). X-Ray Diffraction (XRD), Inductive Coupled Plasm (ICP) and Scanning Electron Micrograph (SEM) techniques were used for sample characterization. The zeolite catalytic behavior was evaluated through toluene disproportionation at 435°C. It was verified that mordenites were very selective for the disproportionation reaction and the samples with higher aluminum content showed larger initial activity, however, these samples showed too a higher deactivation velocity due to a blockage of the unidimensional porous system of the zeolite by coke deposits. The selectivity to xylene isomers was practically not influenced by the Si/Al ratio and changed with the time on stream, due to coke formation. Transition state shape selectivity inside the mordenite pores is also discussed.

Estudo semi-empírico de ácidos hidroxâmicos: ácido formoidroxâmico e derivados do aleloquímico dimboa

Open chain hydroxamic acid (Hx) can exist as Z and E diastereomers of two tautomers, hydroxamic acid and hydroximic acid. The conformational stability of the formohydroxamic acid isomers evaluated by PM3 compared better to ab initio results from the literature than AM1 results. Structural data of the cyclic Hx 2,4-dihydroxy-7-metoxy-2H-1,4-benzoxazin-3(4 H)-one (DIMBOA) obtained by both semiempirical methods compared well to ab initio results. pKa data from the literature for derivatives of the aldolic isomer of DIMBOA were compared to the stability of the anions resulting from the loss of protons of their phenol and hydroxamic acid groups, determined as the difference in heat of formation between anionic and neutral forms, calculated by AM1 and PM3 methods. Good correlations between theoretical and experimental data were obtained for both semiempirical methods.

Transferência de elétrons em sistemas inorgânicos de valência mista

This article reports on some basic and conceptual principles concerning electron transfer (ET) and/or intervalence transfer (IT) phenomena in inorganic mixed-valence systems.

Extração de esteróides em frutos de Ottonia martiana Miq., Piperaceae, com gás liqüefeito

A new extraction method for sterols was tested in fruits of Ottonia martiana Miq., a shrub belonging to the family Piperaceae, popularly known as "anestésica" due to the use of its roots and aerial parts, in alcoholic preparations, in treatment of odontological problems. For this purpose, a portable extraction equipment was developed, to operate with liquified gases, which showed to be practical, fast and effective, besides being economical and ecological. In the chromatographic analysis of the extracts obtained in this equipment, it was demonstrated the presence of two sterols, isomers of b-sitosterol and stigmasterol.

Estabilidade relativa de alcenos: análise dos critérios encontrados nos livros textos de graduação e uma proposta de explicação operacional para alcenos dissubstituídos

Despite of being used as thermodynamic criterion to rank alkene stability in a number of undergraduate textbooks, the heat of hydrogenation does not describe adequately the relative stability of disubstituted alkenes. In this work, both the heat of formation and the heat of combustion were used as thermodynamic criteria to rank correctly the stability of alkenes according to the degree of alkyl substitution and also in the disubstituted series (geminal > trans > cis). An operational model based on molecular orbital and valence bond representations of hyperconjugation is proposed to show how this effect can explain the order of stability of this class of compounds.

Métodos para análise de ácido clorogênico

This paper describes the analytical methods for determination of total chlorogenic acid (CGA) and their individual isomers. Spectrofotometric methods are adequate for total CGA analysis in green coffee but they can provide inflated results for coffee products. High pressure liquid chromatography (HPLC) with gel permeation column and ultraviolet (UV) monitoring is adequate for the simultaneous analysis of total CGA, alkaloids and sugars in coffee products. HPLC-UV-reversed phase is a simple, rapid and precise method for the determination of the individual isomers of CGA. Gas chromatography (GC) also is applied to the analysis of the individual isomers but phenolic acids need to be derivatized before analysis. Both HPLC- and GC-mass spectrometry provide an unequivocal identification of the individual isomers. The capillary electrophoresis method is simple, rapid and adequate to the simultaneous analysis of polyphenols and xanthines. Advantages and limitations of each method are discussed throughout the text.

Remoção de metais pesados de efluentes aquosos pela zeólita natural escolecita - influência da temperatura e do pH na adsorção em sistemas monoelementares

Cation exchange capabilities of a Brazilian natural zeolite, identified as scolecite, were evaluated for application in wastewater control. We investigated the process of sorption of chromium(III), nickel(II), cadmium(II) and manganese(II) in synthetic aqueous effluents, including adsorption isotherms of single-metal solutions. The natural zeolite showed the ability to take up the tested heavy metals in the order Cr(III) > Cd(II) > Ni(II) > Mn(II), and this could be related to the valence and the hydration radius of the metal cations. The influence of temperature (25, 40 and 60 ºC) and initial pH value (from 4 to 6) was also evaluated. It was found that the adsorption increased substantially when the temperature was raised to 60 ºC and that maximum adsorption capacity was observed at pH 6. These results demonstrate that scolecite can be used for removal of heavy metals from aqueous effluents, under optimized conditions.

Otimização da reação de interesterificação química do óleo de palma

The Brazilian market has been showing a growing concern with nutritional values of oil components of foods. Chemical interesterification is a promising alternative to the current processes of modifying the consistency of oils. Chemical interesterification of deodorized palm oil was studied on a laboratory scale. The best results were obtained with 0.4% MeONa and heating for 20 min at 100 °C. These conditions are based on the largest variation in triacylglycerols as compared to a control. The trisaturated values varied from 6.2 to 9.9%, showing that the consistency of the oil improved for it to be used in margarines, without the formation of trans isomers.

Efeito do processo de descafeinação com diclorometano sobre a composição química dos cafés arábica e robusta antes e após a torração

The decaffeinated coffee market has been expanding increasingly in the last years. During decaffeination, aroma precursors and bioactive compounds may be extracted. In the present study we evaluate the changes in the chemical composition of C. arabica and C. canephora produced by decaffeination using dichloromethane. A significant change in the chemical composition of both C. arabica and C. canephora species was observed, with differences between species and degrees of roasting. Major changes were observed in sucrose, protein and trigonelline contents after decaffeination. Changes in the levels of total chlorogenic acids and in their isomers distribution were also observed. Lipids and total carbohydrates were not affected as much. The sensory and biological implications of these changes need to be investigated.

Determinação do perfil de compostos voláteis e avaliação do sabor e aroma de bebidas produzidas a partir da erva-mate (Ilex paraguariensis)

Volatile compounds from green and roasted yerba mate were analyzed by gas chromatography/mass spectrometry and the flavor profile from yerba mate beverages was determined by descriptive quantitative analyses. The main compounds tentatively identified in green mate were linalool, alpha-terpineol and trans-linalool oxide and in roasted mate were (E,Z)-2,4-heptadienal isomers and 5-methylfurfural. Green mate infusion was qualified as having bitter taste and aroma as well as green grass aroma while roasted mate was defined as having a smooth, slightly burnt aroma. The relationship between the tentatively identified compounds and flavor must be determined by olfatometric analysis.

Interesterificação química: alternativa para obtenção de gorduras zero trans

The function of lipids in human nutrition has been intensively debated in the last decade.This context reinforces the concern about controlling the trans fat ingestion, due to its negative implications on health. Interesterification provides an important alternative to modify the consistency of oils and fats without causing formation of trans isomers. This article reports research done towards production of zero trans fats by chemical interesterification, for different industrial purposes. Aspects related to the effect of trans fats on diet, their impact on health and modifications in Brazilian legislation are also covered.

Uma introdução à espectroscopia atômica: II - o espectro do sódio

The present article is devoted to Chemistry or Physics undergraduate students, given their difficulty to understand fundamental concepts and technical language used in atomic spectroscopy and quantum mechanics. An easy approach is shown in the treatment of the emission spectrum of the sodium atom without any involved calculations. In a previous article, the hydrogen spectrum was considered and the energy degeneracy of the angular momentum quantum number was observed. For the sodium spectrum, due to the valence electron penetration into internal shells, a breakdown of this degeneracy occurs and a dependence of this penetration on the angular momentum quantum number is observed. The eigenvalues are determined introducing the quantum defect correction (Rydberg correction) in the denominator of the Balmer equation, and the energy diagram is obtained. The intensity ratio for the observed doublets is explained by introducing new wave functions, containing the magnetic quantum number of the total angular momentum.

Organochlorine pesticides in Piracicaba river basin (São Paulo/Brazil): a survey of sediment, bivalve and fish

The main objective of this paper was to evaluate the level of occurrence of the organochlorine compounds in samples of sediments, bivalves and two fish species collected in the Piracicaba River basin (São Paulo, Brazil). The isomers alpha and gamma of HCH and Heptachlor were most frequently detected in samples of sediments and specimens of bivalve and fish. Therefore, although the levels of these compounds found were not critically high, they are still found in the environment. This fact suggests that they are still being used, despite the fact that the use of these compounds was outlawed more than twenty years ago.

Adsorção de arsênio(V) pela quitosana ferro - III reticulada

The removal of As(V) by a crosslinked iron(III)-chitosan adsorbent was evaluated under various conditions. The adsorption capacity of CH-FeCL was around 54 mg/g of As(V). The kinetics of adsorption obeys a pseudo-first-order model with rate constants equal to 0.022, 0.028, and 0.033 min-1 at 15, 25 and 35 ºC respectively. Adsorption data were well described by the Langmuir model, although they could be modeled also by the Langmuir-Freundlich equation. The maximum adsorption capacity, calculated with the Langmuir model, was 127 mg g-1 of As(V). The inhibition by competing anions is dependant on their kind and valence.

A química orgânica na consolidação dos conceitos de átomo e molécula

The present work discusses the appearance of the concepts of valence and molecular structure, and describes the appropriation and evolution of the concept of molecule in the period following the publication of Avogadro's Hypothesis. The point of reference is the development of what became known as Organic Chemistry, which encompassed Pharmacy, Physiological Chemistry, Animal and Plant Chemistry, Chemistry of Dyestuffs, Agricultural Chemistry, and the fledgling Organic Synthesis industry in the early 19th century. The theories formulated in these areas and the quest for accurate atomic weights led to those concepts of valence and molecular structure and to a precise differentiation between atom and molecule.