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Química Nova, Volume: 21, Issue: 3, Published: 1998
  • Editorial

    Freitas, Luiz Carlos Gomide
  • When sulfate is present in high concentrations, it acts as an inhibitor in the production of methane (biogas formation) in anaerobic biodigestion processes Artigo

    Prada, Sílvio Miranda; Guekezian, Márcia; Suárez-Iha, Maria Encarnación. V.

    Abstract in English:

    In this way it is very important to know the sulfate concentration in vinasse samples before to make the biodigestor design. A previous developed and indirect method (Anal. Chim. Acta. 1996, 329, 197), was used to determine sulfate in samples of vinasse, after previous treatments, done in order to eliminate organic matter with hydrogen peroxide 30% and concentrated nitric acid mixture (3:1), under heating. Interferent cationic ions were isolated by using ion exchange columns. The results obtained for some samples from Araraquara and Penápolis are here presented. The phosphate concentration was also determined.
  • Determination of phosphorus in steel samples by graphite furnace atomic absorption spectrometry Artigo

    Curtius, Adilson José

    Abstract in English:

    A method for the determination of phosphorus in steel samples by graphite furnace atomic absorption spectrometry, using the Zeeman effect background correction and the STPF conditions is proposed. The effect of iron (III) on the phosphorus signal was studied. It was verified, through the pyrolysis temperature curves, that iron (III) is an efficient chemical modifier, thermically stabilizing phosphorus up to 1400ºC. The phosphorus signal increases with the iron (III) concentration, but in the range, which corresponds to the usual concentrations of iron in the sample solutions, the increase is small. Phosphorus was determined in three standard reference materials, after its dissolution in a mixture of hydrochloric and perchloric acids in a PTFE bomb. The agreement with the certified concentration values was excellent. Iron (III) was added to the reference analytical solutions prepared in the blank of the dissolution, while the sample solutions were measured directly, since they already contained the modifier. The detection limit (k = 2) was 0.0042% of phosphorus in the steel sample.
  • Quantium theoretical model for the physical adsorption of He by solid Xe Artigo

    Morgon, Nelson Henrique; Soares, Álvaro Guedes

    Abstract in English:

    This article introduces a simplified model for the theoretical study of the physical adsorption process of gaseous He on the planes (100) and (111) of the solid Xe matrix, whose crystalline structure is face centered cubic (fcc). The Ab initio calculations were carried out at the MP2 level of theory employing basis sets obtained through the Generator Coordinate Method, where the core electrons were represented by a pseudopotential. The calculated adsorption energies for the (100) and (111) faces are 5,39 and 4,18 kJ/mol, respectively. This simplified model is expected to be suitable for treating complex systems of applied interest.
  • Thermal analyasis kinetics for non-isothermal reactions of solids Artigo

    Pimentel, André Silva; Arbilla, Graciela

    Abstract in English:

    In this work, a computer program called Thermal Kinetics was implemented to simulate thermal analysis experiments by numerical integration of the kinetics equations. The computer program was tested in two different examples: non-isothermal transformation of a Cu-Al alloy and non-isothermal decomposition of calcium oxalate monohydrated. In spite of the rather crude approximations of the model, the simulated profiles are very similar to the experimental curves. Both, the dalpha /dt and the dalpha /dT profiles reproduce the experimental transition temperatures with an error smaller than 25%.
  • Selective hydrolysis of carboxyamides of asparagine and glutamine residues of collagen: preparation and characterization of anionic collagen matrices for biomaterial applications Artigo

    Lacerda, Cristina; Plepis, Ana Maria de Guzzi; Goissis, Gilberto

    Abstract in English:

    This work describes the selective hydrolysis of carboxyamide groups of asparagine and glutamine of collagen matrices for the preparation of negatively charged collagen biomaterials. The reaction was performed in the presence of chloride and sulfate salts of alkaline and alkaline earth metals in aqueous dimethylsulfoxide solution and, selectively hydrolysis of carboxyamide groups of collagen matrices was promoted without cleavage of the peptide bond. The result is a new collagen material with controlled increase in negative charge content. Although triple helix secondary structure of tropocollagen was preserved, significative changes in thermal stabilities were observed in association with a new pattern of tropocollagen macromolecular association, particularly in respect microfibril assembly, thus providing at physiological pH a new type of collagen structure for biomaterial preparation, characterized by different charge and structural contents .
  • Discrepancies over the onset of surfactant monomer aggregation interpreted by fluorescence, conductivity and surface tension methods

    Costa, Maria de Fátima Carvalho; Froehner, Sandro José; Ruzza, Ângelo Adolfo; Santos, Sônia de Fátima; Zanette, Dino

    Abstract in English:

    Molecular probe techniques have made important contributions to the determination of microstructure of surfactant assemblies such as size, stability, micropolarity and conformation. Conductivity and surface tension were used to determine the critical aggregation concentration (cac) of polymer-surfactant complexes and the critical micellar concentration (cmc) of aqueous micellar aggregates. The results are compared with those of fluorescent techniques. Several surfactant systems were examined, 1-butanol-sodium dodecylsulfate (SDS) mixtures, solutions containing poly(ethylene oxide)-SDS, poly(vinylpyrrolidone)-SDS and poly(acrylic acid)-alkyltrimethylammonium bromide complexes. We found differences between the cac and cmc values obtained by conductivity or surface tension and those obtained by techniques which use hydrophobic probe.
  • Physical and chemical characterization of vermicompost from bovine manure and evaluation of competitive retention of copper and zinc Artigo

    Lamim, Soraida Sozzi Miguel; Jordão, Cláudio Pereira; Brune, Walter; Pereira, José Luiz; Bellato, Carlos Roberto

    Abstract in English:

    The physical and chemical characterization of vermicompost from bovine manure has been studied. It was examined the pH and cation exchangeable capacity (CEC), organic matter content, electric conductivity and elementary and XRD analyses, among other characteristics. The vermicompost was then applied to the retention and competition of metal micronutrients and pollutants (Cu and Zn) from metal nitrate solutions. The retention was affected by both the pH and adsorption time, while the competitive character of these metals for the substrate was relevant to each pH examined.
  • Anodic niobium oxide films: electrochromic effect and electrointercalation reaction kinetics Artigo

    Maranhão, Silvanna L. de Albuquerque; Torresi, Roberto M.

    Abstract in English:

    The aim of this work is to study the electrochromism and the reaction kinetics of lithium electrointercalation in anodic niobium oxide films. The oxide grown in an acid environment by application of an alternating potential shows interference colour (iridescence) and when reduced in lithium perclorate/PC solution, the intercalation of Li+ ions and electrons causes a reversible colour change (electrochromism), characterized here by electrochemical and optical measurements. A model where the reaction kinetics is dominated by diffusion of ionic pairs (Li+, e-) in the oxide film permitted the reproduction of current and absorbance temporal dependence, confirming the relationship between the electrochromic and electrochemical reactions. From the results obtained, a relation was established where the colour change is associated to the reduction of Nb+5 to Nb+4 ions with simultaneous cations injection.
  • Simultaneous determinations of nickel and cobalt: a review Revisão

    Antunes, Patrícia Alexandra; Breviglieri, Susete Trazzi; Chierice, Gilberto Orivaldo; Cavalheiro, Éder Tadeu Gomes

    Abstract in English:

    The simultaneous determination of cobalt and nickel is a classical analytical problem. A great number of reagents associated with several techniques of analysis have been applied to achieve this determination. In this review 117 references, which appeared between 1996-1980, are described and classified according to the technique applied.
  • Layered double hydroxides: structure, synthesis, properties and applications Revisão

    Crepaldi, Eduardo Luis; Valim, João Barros

    Abstract in English:

    The layered double hydroxides, known as anionic clays and represented by the general formula [M2+1-x M3+x (OH) 2]x+ Am-x/m·nH 2O, are a group of materials which are of much interest currently. They present a variety of potential applications as adsorbents, catalysts and catalyst support, ion-exchangers, antacids and as a polymer stabilizer. It is possible to obtain a broad variety of layered double hydroxides (LDHs), depending on the identity and ratio of the cations M2+ and M3+, as well as the interlamelar anion. The aim of this review is to give out some information about this class of materials, concerning to the synthesis, characterization, properties and applications.
  • Approaches in asymmetric synthesis Divulgação

    Pinheiro, Sergio; Ferreira, Vítor F.

    Abstract in English:

    The approaches in asymmetric synthesis as the chiron approach, chiral auxiliaries, chiral reagents and asymmetric catalysis are described in a simplified way.
  • Mechanism reactions of photodegradation of organic compounds catalyzed by TiO2 Divulgação

    Ziolli, Roberta Lourenço; Jardim, Wilson F.

    Abstract in English:

    Conventional technology used in the treatment of wastewater has been pointed as a major environmental problem for sustainable development, since minimization is not addressed accordingly. Advanced oxidation processes (AOP), based on the formation of hydroxyl radical (•OH), a powerful oxidant agent, have been considered to be a potential technology for the destruction of many toxic compounds. Photocatalysis using solar light, an AOP, has been studied for nearly 20 years and recently attracted great interest as a clean-up technology. However, solar detoxification processes have not yet achieved commercial success. This article presents an overview of reaction mechanisms at the surface of semiconductors used as photocatalysts (specially TiO2), when heterogeneous photocatalysis is used to remove hazardous compounds from contaminated sites.
  • The chemistry of peroxynitrite, a biological toxin<a name=TOP1></a>

    Koppenol, W. H.

    Abstract in English:

    Oxyradicals play a tole in several diseases. While for several decades the hydroxyl radical - produced via the Fenton reaction - has been considered the species that initiates oxyradical damage, new findings suggest that much of this damage can be ascribed to peroxynitrite, O=NOO-, formed from the reaction of the superoxide anion with nitrogen monoxide near activated macrophages. The rate constant for the reaction of this reaction has been investigated by flash photolysis and was found to be significantly higher than previously described in the literature, 1.9 x 10(10) M-1s-1. Studies of the isomerization to nitrate resulted in the discovery of a complex between peroxynitrite and its protonated form with a stability constant of 1 x 10(4) M-1. Some of the harmful reaction of peroxynitrous acid have been ascribed to the hydroxyl radical as a product of homolysis of the O-O bond during the conversion to nitrate. Kinetics of the isomerization reaction as a function of pressure show that the activation volume is only +1.5+1.0 ml mol-1, which is inconsistent with homolysis. Instead, an intermediate, possibly a distorted trans-isomer of O=NOOH could be responsible for the harmful reactions of peroxynitrite.
  • Phosphorescence lifetime in polymer relaxation studies: phase resolution method Nota Técnica

    Talhavini, M.; Atvars, T. D. Z.

    Abstract in English:

    We describe in this work a simple experimental set up to perform time dependent luminescence experiments in time scales from mili-seconds to seconds, based on the phase resolution of the emission signal. This system is composed by modulation of a continuous light source with an external chopper controlled by a lock-in amplifier. We exemplified the utility of the system in studies of phosphorecence emission using benzophenone dissolved in polystyrene and since the phosphorescence intensity and lifetime are temperature-dependent processes, we also studied polymer relaxation processes in the temperature range from 20 to 400K. A software that drives the spectrofluorimeter and controls both the cryosystem and the lock-in amplifier was developed.
  • Molecules in three dimensions: a stereoscope for the personal computer Nota Técnica

    Constantino, Mauricio Gomes; Silva, Gil Valdo José da; Pelisson, Marcelo Miguel Martins

    Abstract in English:

    In this paper we describe how to make a very simple stereoscope for observation of molecular models produced by several recent computer programmes. With this instrument, constructed essentially with four mirrors, the chemist can visualize molecular models in three dimensions directly from the personal computer monitor screen.
  • The ground fault circuit interrupter and its utility in the chemical laboratory Nota Técnica

    Li, Rosamaria Wu Chia; Gruber, Jonas; Lucca, Marco Antonio de; Lisboa, Alcides S.

    Abstract in English:

    The use of GFCI, ground-fault circuit interrupter, in the chemical laboratory is described, to improve the electrical safety of equipments such as rotary evaporators and constant temperature baths.
  • The application of a new temperature controllable spectroelectrochemical cell to the study of electrochromic polymers Nota Técnica

    Härtinger, Stefan; Machado, Dirnei Aparecido; De Paoli, Marco-A.

    Abstract in English:

    The construction of a temperature controllable spectroelectrochemical cell is described. Its use in the analysis of the thermodynamic and structural parameters of the electrochromic process of poly(3-methyl thiophene) in the temperature range between -40ºC and 60ºC is given as an example of application.
  • Controlled atmosphere system for gas sensors characterization Nota Técnica

    Andrade, Ricardo L. T.; Lindino, Cleber A.; Bulhões, Luis Otavio de Sousa

    Abstract in English:

    This paper describes a sample holder for the electrical measurement of oxides or conducting polymers in the form of pellets or films which are used as gas sensors. The system makes it possible to control the sample temperature, the gas pressure and composition. The temperature in the sample can be changed from 25ºC to 450ºC, and the gas pressure in the chamber is controlled between 5 ¥ 10-4 and 1000 mbar. The performance of the system in resistance measurements of doped tin oxide pellets and polyaniline films deposited on platinum electrodes for methane is analyzed.
  • Was there any science in eighteenth-century Brazil? Assuntos Gerais

    Filgueiras, Carlos A. L.

    Abstract in English:

    In the past decade several articles have been published in this journal and elsewhere by different authors, dealing with the institutionalization of science in Brazil, its origins and subsequent history. The emphasis has often been directed to the work of Brazilian scientists working abroad, to foreigners in Brazil, or to a few private individuals within the country, as well as to cultural, social, economic and political considerations. Much of the attention has also been focused on "academic" science, rather than on empirical or technical developments. The present article presents some of these situations, particularly in the mining district, where the application of technology, sometimes quite up-to-date for the time, tended to blur somewhat the distinction between science and its applications. It is hoped that this may start a debate which will enrich our historiography in this field and be of interest to those who want to assess Brazil's position in the history of science.
  • Degradation of the surface of a metasilicate glass due to atmosphere moisture

    Ziemath, Ervino Carlos

    Abstract in English:

    Glasses with low silica content are very susceptible to suffer pronounced degradation when exposed to room atmosphere during short times. In this work the results of the degradation of the surface of a metasilicate glass with composition 2Na2O.1CaO.3SiO2 are presented. Optical and scanning electron microscopy observations, X-ray diffraction, infrared and Raman microprobe spectroscopic measurements of the modified surface of this glass show strong evidences that it is formed essentially by a crystalline carbonate layer.
  • Study of the optical properties of TeO2-PbO-TiO2 glass system

    Cuevas, Raul F.; Paula, Ana M. de; Cesar, Carlos L.; Barbosa, Luiz C.; Alves, Oswaldo L.

    Abstract in English:

    We describe the preparation and some optical properties of high refractive index TeO2-PbO-TiO2 glass system. Highly homogeneous glasses were obtained by agitating the mixture during the melting process in an alumina crucible. The characterization was done by X-ray diffraction, Raman scattering, light absorption and linear refractive index measurements. The results show a change in the glass structure as the PbO content increases: the TeO4 trigonal bipyramids characteristics of TeO2 glasses transform into TeO3 trigonal pyramids. However, the measured refractive indices are almost independent of the glass composition. We show that third-order nonlinear optical susceptibilities calculated from the measured refractive indices using Lines' theoretical model are also independent of the glass composition.
  • Caracterization of OF Nb2O5 thin films with electrochromic properties Assuntos Gerais

    Avellaneda, C. O.; Aegerter, M. A.; Pawlicka, A.

    Abstract in English:

    The sols for thin electrochromic coatings of Nb2O5 were obtained by synthesis of the niobium butoxide from BuONa and NbCl5. The ~300nm thick films were deposited by dip-coating technique from the alkoxide solution and calcined at 560ºC in O2 atmosphere during 3 hours. The particles size of niobium oxide (V) powder (~20mm) was obtained from x-ray diffraction using the Scherrer equation. The coatings were characterized by cyclic voltammetry and cronoamperommetry techniques. The spectral variation of the optical transmittance were determined in situ as a function of the cyclical potencial and memory effect. The insertion process of lithium is reversible and change the film color from transparent (T=80%) to dark blue (T=20%).
  • Stabilization of fluoroindate glasses by magnesium fluoride and other heavy metal fluorides

    Costa, B. J.; Soufiane, A.; Messaddeq, Y.

    Abstract in English:

    Their extended transparency in the IR makes them attractive for use as optical fibers for CO laser power delivery and optical amplification. This paper firstly describes the spectacular stabilizing effect of MgF2 on the binary system InF3-BaF2. The investigation of the InF3-BaF2-MgF2 system led to samples up to 5mm in thickness. Further optimization of this system was achieved by incorporation of limited amounts of other fluorides and resulted in increased resistence to devitrification. The second approach of this work was concerned to the investigation of the pseudo-ternary system InF3-GdF3-GaF3 at constant concentrations of ZnF2-SrF2-BaF2-NaF. Several compositions were studied in this system. The samples presented a better thermal stability when compared to other families of fluoride glasses. Therefore, these glasses seem to be very promising for the fabrication of special optical fibers. Thermal data are reported.
  • New compositions of fluoroindate glasses with higher chemical resistance

    Costa, B. J.; Soufiane, A.; Messaddeq, Y.

    Abstract in English:

    In this paper, glasses in the systems In-Ba-Mg and In-Ba-Zn-Sr-Mg were water leachead at 80ºC showing surface degradation after 72 hours of leaching. The extent of such degradation is determined by the solubility and the concentration of the elemental fluorides that constitute the glasses. The formation of a layer of crystallized phases on the surface of the samples was observed. Small weight losses were registered and the absence of water on the glass matrix after the attack suggested that the use of MgF2 in the systems studied can lead to better results against moisture corrosion when compared to other fluoride glasses such as the fluorozirconates.
  • Generation and control of the primary light colors in glasses for full color devices Assuntos Gerais

    Silva, José Expedito C.; Malta, Oscar L.; Sá, Gilberto F. de; Santa-Cruz, Petrus A.

    Abstract in English:

    We are working in a new multi-doped glassy material to generate simultaneously the three primary light color (by addition) of the visible spectrum, with the control of the intensity of each one, allowing the simulation of any color: a full-color generator device. Tm+3, Tb+3 and Eu+3 ions were used (0.01 to 5,0 mol%) as blue, green and red narrow line emitters. A wide color gamut was obtained under ultraviolet excitation by varying the material composition. The chromaticity diagram is covered, including the white simulation.
  • Optical characterization of sol-gel glasses derived from Eu3+ complex-forming precursors

    Costa, Vilma C.; Vasconcelos, Wander L.; Bray, Kevin L.

    Abstract in English:

    Fabrication of new optical devices based upon the incorporation of rare earth ions via sol-gel methods depends on elimination of dopant ion clusters and residual hydroxyl groups from the final material. The optical absorption and/or luminescence properties of luminescent rare earth ions are influenced by the local bonding environment and the distribution of the rare-earth dopants in the matrix. Typically, dopants are incorporated into gel via dissolution of soluble species into the initial precursor sol. In this work, Eu3+ is used as optical probe, to assess changes in the local environment. Results of emission, excitation, fluorescence line narrowing and lifetimes studies of Eu3+-doped gels derived from Si(OCH3)4 and fluorinated/chelate Eu3+ precursors are presented. The precursors used in the sol-gel synthesis were: tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) Eu(III), Eu (III) trifluoromethanesulfonate, Eu(III) acetylacetonate hydrate, Eu (III) trifluoroacetate trihidrate, tris (2,2,6,6-tetramethyl-3,5- heptanedionate) Eu(III) and Eu(NO3)3.6H2O. The results were interpreted in terms of the evolution of the Eu3+ fluorescence in systems varying from solution to the gels densified to 800ºC. The lifetimes studies indicate that the fluorinated precursors are effective at reducing the water content in densified gels.
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