Desenvolvimento de uma unidade laboratorial para quantificação de BTX como poluentes atmosféricos, usando microextração em fase sólida

This dissertation aims the development of an experimental device to determine quantitatively the content of benzene, toluene and xylenes (BTX) in the atmosphere. BTX are extremely volatile solvents, and therefore play an important role in atmospheric chemistry, being precursors in the tropospheric ozone formation. In this work a BTX new standard gas was produced in nitrogen for stagnant systems. The aim of this dissertation is to develop a new method, simple and cheaper, to quantify and monitor BTX in air using solid phase microextraction/ gas chromatography/mass spectrometry (SPME/CG/MS). The features of the calibration method proposed are presented in this dissertation. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fiber exposed for 10 min standard gas mixtures. It is observed that the main parameters that affect the extraction process are sampling time and concentration. The results of the BTX multicomponent system studied have shown a linear and a nonlinear range. In the non-linear range, it is remarkable the effect of competition by selective adsorption with the following affinity order p-xylene > toluene > benzene. This behavior represents a limitation of the method, however being in accordance with the literature. Furthermore, this behavior does not prevent the application of the technique out of the non-linear region to quantify the BTX contents in the atmosphere.

Extração de ferro da cera de carnaúba utilizando sistemas microemulsionados

The constant search for biodegradable materials for applications in several fields shows that carnauba wax can be a viable alternative in the manufacturing of biolubricants. Carnauba wax is the unique among the natural waxes to have a combination of properties of great importance. In previous studies it was verified the presence of metals in wax composition that can harm the oxidative stability of lubricants. Considering these factors, it was decided to develop a research to evaluate iron removal from carnauba wax, using microemulsion systems (Me) and perform the optimization of parameters, such as: extraction pH, temperature, extraction time, among others. Iron concentration was determined by atomic absorption and, to perform this analysis, sample digestion in microwave oven was used, showing that this process was very efficient. It was performed some analysis in order to characterize the wax sample, such as: attenuated total reflectance infrared spectroscopy (ATR-IR), thermogravimetry (TG), differential scanning calorimetry (DSC), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy (SEM) and melting point (FP). The microemulsion systems were composed by: coconut oil as surfactant, n-butanol as cosurfactant, kerosene and/or heptanes as oil phase, distilled water as water phase. The pH chosen for this study was 4.5 and the metal extraction was performed in finite experiments. To evaluate Me extraction it was performed a factorial design for systems with heptane and kerosene as oil phase, also investigating the influence of temperature time and wax/Me ratio, that showed an statistically significant answer for iron extraction at 95% confidence level. The best result was obtained at 60°C, 10 hours contact time and 1: 10 wax/Me ratio, in both systems with kerosene and heptanes as oil phase. The best extraction occurred with kerosene as oil phase, with 54% iron removal

Determinação de dados de equilíbrio de fases para sistemas aquosos com eletrólitos

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer s ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Equilíbrio líquido-líquido de sistemas aquosos com tensoativos polietoxilados: dados experimentais e modelagem

The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ° C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease

Sistemas microemulsionados aplicados à remoção da cor de efluente têxtil

Effluent color resulting from textile dyeing processes has been one of the biggest environmental problems faced by the textile industry. In particular, reactive dyes are highly resistant to conventional wastewater treatment methods. New technologies have been contemplated, some of which have been applied in industrial treatment plants, but color removal has not been efficiently attained. Since microemulsion systems provide good results in heavy metals and proteins extraction processes, their use in dyes extraction has been suggested and investigated. In this work, a real textile wastewater from an exhaustion dyebath has been treated, which contains the following reactive dyes: Procion Yellow H-E4R (CI Reactive Yellow 84), Procion Blue H-ERD (CI Reactive Blue 160) and Procion Red H-E3B (CI Reactive Red 120), in addition to auxiliary compounds normally found in dyeing processes with reactive dyes. The dyes Remazol Blue RR and Remazol Turquoise Blue G (Reactive Blue 21) have also been examined in view of the presence of heavy metals in these molecules. The microemulsion system comprised dodecyl ammonium chloride (as a cationic surfactant), water or wastewater as aqueous phase, kerosene as oil phase, and one of the following alcohols as cosurfactant: isoamyl alcohol, n-butyl alcohol and n-octyl alcohol. The pseudo-ternary diagrams were constructed in order to define Winsor s equilibrium regions. The influence of parameters such as pH, C/S (cosurfactant/surfactant) ratio, distribution coefficient, initial dye concentration, salinity, temperature, phases relative amounts, loading capacity of the microemulsion phase and dye reextraction rate has also been investigated. An experimental planning (Scheffé Net) was used to optimize the extraction process. The removal of color and metals reached levels as high as 99%

Estudo da influência de tensoativos em sistemas microemulsionados na extração de gálio e alumínio

Gallium is an important material used in the electronic industry whose demand in the world market is increasing in view of its potential applications. A selective technique is required to allow for the production of the metal, separated from aluminium. Due to the fact that microemulsions constitute an attractive alternative to metal extraction procedures, microemulsified systems have been employed as gallium-selective extraction agents. Two surfactants have been synthesized: sodium 12-N,N-diethylamino-9,10-dihydroxyestearate (AMINE) and saponified coconut oil (SCO), both produced from raw materials readily available in Northeastern Brazil. Also, the commercial extraction agent KELEX-100, conventionally used with the same purpose, has been used in this work for comparison. The optimization of the extraction process with microemulsions was carried out by investigating the influence of some parameters, namely the type of cosurfactant, the cosurfactant/surfactant (C/S) ratio, the pH and concentration of metals in the aqueous phase. Pseudoternary diagrams, which are representative of the microemulsified systems under study, have been constructed in order to establish the boundaries of the regions where the several Winsor systems are formed. An experimental planning methodology (Scheffé Net) has been used to optimize the extraction. The extraction percentage values were as high as 100% for gallium and 99.99% for aluminium for the system with KELEX-100; 96.6% for gallium and 98.8% for aluminium for the system containing AMINE; and 88% for gallium and 85% for aluminium for the system with SCO. The microemulsified system chosen for presenting the best results in gallium extraction was composed by SCO/isoamyl alcohol/kerosene/Bayer licquor with a C/S ratio of 28 and pH of the original aqueous phase of 6.0. The selectivity that has not been observed in the extraction stage was accomplished in the reextraction process using HCl. For the KELEX-100 system, gallium was reextracted at 100% with 6M HCl and aluminium was reextracted at 100% with 0.8M HCl. For the AMINE system, the reextraction percentages were also 100% for both metals, using 6M HCl for gallium and 0.5M HCl for aluminium. On the other hand, the reextraction percentages for the system with SCO were as high as 84% for gallium and 92% for aluminium, with HCl in the same concentrations as those used in the AMINE system. Finally, an optimized system was applied in the gallium extraction process employing a reciprocating perforated-plates extractor. As a result, the metal content was extracted at a recovery rate of 95% for gallium and 97% for aluminium

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Propriedades dos sistemas de numeração: uma sequência didática em uma abordagem histórica

This paper aims to describe the construction and validation of a notebook of activities whose content is a didactic sequence that makes use of the study of ancient numbering systems as compared to the object of our decimal positional numbering system Arabic. This is on the assumption that the comparison with a system different from our own might provide a better understanding of our own numbering system, but also help in the process of arithmetic operations of addition, subtraction and multiplication, since it will force us to think in ways that are not routinely object of our attention. The systems covered in the study were the Egyptian hieroglyphic system of numbering, the numbering system Greek alphabet and Roman numbering system, always compared to our numbering system. The following teachung is presented structured in the form of our activities, so-called exercise set and common tasks around a former same numbering system. In its final stage of preparation, the sequence with the participation of 26 primary school teachers of basic education

Os Polímeros como Sistemas Complexos

Neste trabalho, através de simulações computacionais, identificamos os fenômenos físicos associados ao crescimento e a dinâmica de polímeros como sistemas complexos exibindo comportamentos não linearidades, caos, criticalidade auto-organizada, entre outros. No primeiro capítulo, iniciamos com uma breve introdução onde descrevemos alguns conceitos básicos importantes ao entendimento do nosso trabalho. O capítulo 2 consiste na descrição do nosso estudo da distribuição de segmentos num polímero ramificado. Baseado em cálculos semelhantes aos usados em cadeias poliméricas lineares, utilizamos o modelo de crescimento para polímeros ramificados (Branched Polymer Growth Model - BPGM) proposto por Lucena et al., e analisamos a distribuição de probabilidade dos monômeros num polímero ramificado em 2 dimensões, até então desconhecida. No capítulo seguinte estudamos a classe de universalidade dos polímeros ramificados gerados pelo BPGM. Utilizando simulações computacionais em 3 dimensões do modelo proposto por Lucena et al., calculamos algumas dimensões críticas (dimensões fractal, mínima e química) para tentar elucidar a questão da classe de universalidade. Ainda neste Capítulo, descrevemos um novo modelo para a simulação de polímeros ramificados que foi por nós desenvolvido de modo a poupar esforço computacional. Em seguida, no capítulo 4 estudamos o comportamento caótico do crescimento de polímeros gerados pelo BPGM. Partimos de polímeros criticamente organizados e utilizamos uma técnica muito semelhante aquela usada em transições de fase em Modelos de Ising para estudar propagação de danos chamada de Distância de Hamming. Vimos que a distância de Hamming para o caso dos polímeros ramificados se comporta como uma lei de potência, indicando um caráter não-extensivo na dinâmica de crescimento. No Capítulo 5 analisamos o movimento molecular de cadeias poliméricas na presença de obstáculos e de gradientes de potenciais. Usamos um modelo generalizado de reptação para estudar a difusão de polímeros lineares em meios desordenados. Investigamos a evolução temporal destas cadeias em redes quadradas e medimos os tempos característicos de transporte t. Finalizamos esta dissertação com um capítulo contendo a conclusão geral denoss o trabalho (Capítulo 6), mais dois apêndices (Apêndices A e B) contendo a fenomenologia básica para alguns conceitos que utilizaremos ao longo desta tese (Fractais e Percolação respectivamente) e um terceiro e ´ultimo apêndice (Apêndice C) contendo uma descrição de um programa de computador para simular o crescimentos de polímeros ramificados em uma rede quadrada

Determinacão do período orbital de sistemas binários clipsantes

In this work is presented a new method for the determination of the orbital period (Porb) of eclipsing binary systems based on the wavelet technique. This method is applied on 18 eclipsing binary systems detected by the CoRoT (Convection Rotation and planetary transits) satellite. The periods obtained by wavelet were compared with those obtained by the conventional methods: box Fitting (EEBLS) for detached and semi-detached eclipsing binaries; and polynomial methods (ANOVA) for contact binary systems. Comparing the phase diagrams obtained by the different techniques the wavelet method determine better Porb compared with EEBLS. In the case of contact binary systems the wavelet method shows most of the times better results than the ANOVA method but when the number of data per orbital cicle is small ANOVA gives more accurate results. Thus, the wavelet technique seems to be a great tool for the analysis of data with the quality and precision given by CoRoT and the incoming photometric missions.

Fases magnéticas de sistemas nanoestruturados de terras-raras

There is presently a worldwide interest in artificial magnetic systems which guide research activities in universities and companies. Thin films and multilayers have a central role, revealing new magnetic phases which often lead to breakthroughs and new technology standards, never thought otherwise. Surface and confinement effects cause large impact in the magnetic phases of magnetic materials with bulk spatially periodic patterns. New magnetic phases are expected to form in thin film thicknesses comparable to the length of the intrinsic bulk magnetic unit cell. Helimagnetic materials are prototypes in this respect, since the bulk magnetic phases consist in periodic patterns with the length of the helical pitch. In this thesis we study the magnetic phases of thin rare-earth films, with surfaces oriented along the (002) direction. The thesis includes the investigation of the magnetic phases of thin Dy and Ho films, as well as the thermal hysteresis cycles of Dy thin films. The investigation of the thermal hysteresis cycles of thin Dy films has been done in collaboration with the Laboratory of Magnetic Materials of the University of Texas, at Arlington. The theoretical modeling is based on a self-consistent theory developed by the Group of Magnetism of UFRN. Contributions from the first and second neighbors exchange energy, from the anisotropy energy and the Zeeman energy are calculated in a set of nonequivalent magnetic ions, and the equilibrium magnetic phases, from the Curie temperature up to the Nèel temperature, are determined in a self-consistent manner, resulting in a vanishing torque in the magnetic ions at all planes across the thin film. Our results reproduce the known isothermal and iso-field curves of bulk Dy and Ho, and the known spin-slip phases of Ho, and indicate that: (i) the confinement in thin films leads to a new magnetic phase, with alternate helicity, which leads to the measured thermal hysteresis of Dy ultrathin films, with thicknesses ranging from 4 nm to 16 nm; (ii) thin Dy films have anisotropy dominated surface lock-in phases, with alignment of surface spins along the anisotropy easy axis directions, similar to the known spin-slip phases of Ho ( which form in the bulk and are commensurate to the crystal lattice); and (iii) the confinement in thin films change considerably the spin-slip patterns of Ho.

Estudo de sistemas complexos com interações de longo alcance : percolação, redes e tráfego

In this thesis we investigate physical problems which present a high degree of complexity using tools and models of Statistical Mechanics. We give a special attention to systems with long-range interactions, such as one-dimensional long-range bondpercolation, complex networks without metric and vehicular traffic. The flux in linear chain (percolation) with bond between first neighbor only happens if pc = 1, but when we consider long-range interactions , the situation is completely different, i.e., the transitions between the percolating phase and non-percolating phase happens for pc < 1. This kind of transition happens even when the system is diluted ( dilution of sites ). Some of these effects are investigated in this work, for example, the extensivity of the system, the relation between critical properties and the dilution, etc. In particular we show that the dilution does not change the universality of the system. In another work, we analyze the implications of using a power law quality distribution for vertices in the growth dynamics of a network studied by Bianconi and Barabási. It incorporates in the preferential attachment the different ability (fitness) of the nodes to compete for links. Finally, we study the vehicular traffic on road networks when it is submitted to an increasing flux of cars. In this way, we develop two models which enable the analysis of the total flux on each road as well as the flux leaving the system and the behavior of the total number of congested roads

Estudo de propriedades críticas em sistemas complexos: método de procura automática em sistemas tipo Ising e percolação de longo alcance

The new technique for automatic search of the order parameters and critical properties is applied to several well-know physical systems, testing the efficiency of such a procedure, in order to apply it for complex systems in general. The automatic-search method is combined with Monte Carlo simulations, which makes use of a given dynamical rule for the time evolution of the system. In the problems inves¬tigated, the Metropolis and Glauber dynamics produced essentially equivalent results. We present a brief introduction to critical phenomena and phase transitions. We describe the automatic-search method and discuss some previous works, where the method has been applied successfully. We apply the method for the ferromagnetic fsing model, computing the critical fron¬tiers and the magnetization exponent (3 for several geometric lattices. We also apply the method for the site-diluted ferromagnetic Ising model on a square lattice, computing its critical frontier, as well as the magnetization exponent f3 and the susceptibility exponent 7. We verify that the universality class of the system remains unchanged when the site dilution is introduced. We study the problem of long-range bond percolation in a diluted linear chain and discuss the non-extensivity questions inherent to long-range-interaction systems. Finally we present our conclusions and possible extensions of this work

Propriedades críticas de sistemas fora do equilíbrio via simulação Monte Carlo

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Caracterização dos acoplamentos fase-amplitude na região CA1 do hopocampo

Brain oscillation are not completely independent, but able to interact with each other through cross-frequency coupling (CFC) in at least four different ways: power-to-power, phase-to-phase, phase-to-frequency and phase-to-power. Recent evidence suggests that not only the rhythms per se, but also their interactions are involved in the execution of cognitive tasks, mainly those requiring selective attention, information flow and memory consolidation. It was recently proposed that fast gamma oscillations (60 150 Hz) convey spatial information from the medial entorhinal cortex to the CA1 region of the hippocampus by means of theta (4-12 Hz) phase coupling. Despite these findings, however, little is known about general characteristics of CFCs in several brain regions. In this work we recorded local field potentials using multielectrode arrays aimed at the CA1 region of the dorsal hippocampus for chronic recording. Cross-frequency coupling was evaluated by using comodulogram analysis, a CFC tool recently developted (Tort et al. 2008, Tort et al. 2010). All data analyses were performed using MATLAB (MathWorks Inc). Here we describe two functionally distinct oscillations within the fast gamma frequency range, both coupled to the theta rhythm during active exploration and REM sleep: an oscillation with peak activity at ~80 Hz, and a faster oscillation centered at ~140 Hz. The two oscillations are differentially modulated by the phase of theta depending on the CA1 layer; theta-80 Hz coupling is strongest at stratum lacunosum-moleculare, while theta-140 Hz coupling is strongest at stratum oriens-alveus. This laminar profile suggests that the ~80 Hz oscillation originates from entorhinal cortex inputs to deeper CA1 layers, while the ~140 Hz oscillation reflects CA1 activity in superficial layers. We further show that the ~140 Hz oscillation differs from sharp-wave associated ripple oscillations in several key characteristics. Our results demonstrate the existence of novel theta-associated high-frequency oscillations, and suggest a redefinition of fast gamma oscillations