Determinação direta de crômio em açúcar e leite por espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

A fast and direct method for the determination of Cr in milk and cane sugar suspensions using graphite furnace atomic absorption spectrometry with Zeeman-effect background correction is described. No sample pre-treatment was necessary, minimizing the risk of contamination. The concentration of chromium in cane sugar was evaluated using Cr reference solutions prepared in 1% v/v HNO3 solution. The milk samples were introduced into the furnace with a mixture of amines for avoiding the autosampler blockage and foaming of milk. Chromium determination in milk was based on the standard additions method (SAM). The limit of detection and characteristic mass for cane sugar sample (30 muL) were 0,13 ng/ml and 4,3 pg, and for milk sample (10 muL) were 0,23 ng/ml and 7,8 pg, respectively. The graphite tube lifetime was 300 firings for sugar-cane sample and 100 firings for milk sample. The heating program was implemented in 68 s.

Determinação direta de selênio em água de coco e em leite de coco utilizando espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

Selenium is both essential and toxic to man and animals, depending on the concentration and the ingested form. Most fruits and vegetables are poor sources of selenium, but coconut can be a good selenium source. Samples were suspended (1 + 4 v/v) in a mixture of tertiary amines soluble in water (10% v/v CFA-C). This simple sample treatment avoided contamination and decreased the analysis time. The standard additions method was adopted for quantification. The action of the autosampler was improved by the presence of the amines mixture in the suspension. A Varian model AA-800 atomic absorption spectrometer equipped with a graphite furnace and a GTA 100 autosampler was used for selenium determination in coconut water and coconut milk. Background correction was performed by means of the Zeeman effect. Pyrolytically coated graphite tubes were employed. Using Pd as chemical modifier, the pyrolysis and the atomization temperatures were set at 1400 and 2200ºC, respectively. For six samples, the selenium concentration in coconut water varied from 6.5 to 21.0 mug L-1 and in coconut milk from 24.2 to 25.1 mug L-1. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values are in the 99.5-102.3% range. The main advantage of the proposed method is that it can be directly applied without sample decomposition.

Avaliacão de programas de aquecimento para espectrometria de absorção atômica com atomizacão eletrotérmica em filamento de tungstênio

A tungsten coil atomizer was used to investigate the effect of heating programs with constant or variable drying temperatures on the atomization of Al, Cd, Cr and Pb. The variation of the surface temperature in the tungsten coil furnace can occur during each heating step due to the design of the power supply, that may apply constant voltages during a programmed time. For volatile elements (Cd), losses in sensitivity were observed when the program with a variable temperature was used. On the other hand, these effects are negligible for less volatile elements (Al and Cr) and any tested program, in different acidic media, could be used without appreciable changes in sensitivities. The results allow the establishment of proper heating programs for elements with different thermochemical behavior in the tungsten coil atomizer.

Síntese de nanotubos de carbono de parede simples por sublimação de grafite em atmosfera de hélio

Macroscopic samples of fullerene nanostructures are obtained in a modified arc furnace using the electric arc method with a Helium atmosphere at low pressures. High purity graphite rods are used as electrodes but, when drilled and the orifices filled with powders of transition metals (Fe, Co, Ni) acting as catalysts, the resulting particles are carbon nanostructures of the fullerene family, known as Single Wall Nanotubes (SWNTs). They have typical diameters of 1.4 nm, lengths up to tenths of microns and they are arranged together in bundles containing several SWNTs. Those samples are observed and analyzed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques.

A geração química de vapor em espectrometria atômica

The historical development of atomic spectrometry techniques based on chemical vapor generation by both batch and flow injection sampling formats is presented. Detection via atomic absorption spectrometry (AAS), microwave induced plasma optical emission spectrometry (MIP-OES), inductively coupled plasma optical emission spectrometry (ICP-OES) , inductively coupled plasma mass spectrometry (ICP-MS) and furnace atomic nonthermal excitation spectrometry (FANES) are considered. Hydride generation is separately considered in contrast to other methods of generation of volatile derivatives. Hg ¾ CVAAS (cold vapor atomic absorption spectrometry) is not considered here. The current state-of-the-art, including extension, advantages and limitations of this approach is discussed.

Offdesign operation of kraft recovery boiler

A model to solve heat and mass balances during the offdesign load calculations was created. These equations are complex and nonlinear. The main new ideas used in the created offdesign model of a kraft recovery boiler are the use of heat flows as torn iteration variables instead of the current practice of using the mass flows, vectorizing equation solving, thus speeding up the process, using non dimensional variables for solving the multiple heat transfer surface problem and using a new procedure for calculating pressure losses. Recovery boiler heat and mass balances are reduced to vector form. It is shown that these vectorized equations can be solved virtually without iteration. The iteration speed is enhanced by the use of the derived method of calculating multiple heat transfer surfaces simultaneously. To achieve this quick convergence the heat flows were used as the torn iteration parameters. A new method to handle pressure loss calculations with linearization was presented. This method enabled less time to be spent calculating pressure losses. The derived vector representation of the steam generator was used to calculate offdesign operation parameters for a 3000 tds/d example recovery boiler. The model was used to study recovery boiler part load operation and the effect of the black liquor dry solids increase on recovery boiler dimensioning. Heat flows to surface elements for part load calculations can be closely approximated with a previously defined exponent function. The exponential method can be used for the prediction of fouling in kraft recovery boilers. For similar furnaces the firing of 80 % dry solids liquor produces lower hearth heat release rate than the 65 % dry solids liquor if we fire at constant steam flow. The furnace outlet temperatures show that capacity increase with firing rate increase produces higher loadings than capacity increase with dry solids increase. The economizers, boiler banks and furnaces can be dimensioned smaller if we increase the black liquor dry solids content. The main problem with increased black liquor dry solids content is the decrease in the heat available to superheat. Whenever possible the furnace exit temperature should be increased by decreasing the furnace height. The increase in the furnace exit temperature is usually opposed because of fear of increased corrosion.

Espectrofotometría de absorción atómica con tubo en la llama: aplicación en la determinación total de cadmio, plomo y zinc en aguas frescas, agua de mar y sedimentos marinos

Thermospray flame furnace Atomic Absorption Spectrometry (TS-FF-AAS) was used for the total determination of Cd, Pb and Zn in fresh water and seawater samples at µg L-1 levels, and in marine sediment samples at µg g-1 levels. Using a sample loop of 50 µL and a peristaltic pump the samples were transported into the metallic tube placed over an air/acetylene flame, through a ceramic capillary (o.d. = 3.2 mm) containing two parallel internal orifices (i.d = 0.5 mm). The detection limits determined for Cd, Pb and Zn using a synthetic water matrix (2.5% m/v NaCl, 0.5% m/v MgCl2 and 0.8% m/v CaCl2) were 0.32 µg L-1; 2.6 µg L-1 and 0.21 µg L-1 respectively. The methodology by TS-FF-AAS was validated by determination of Cd, Pb and Zn in certified reference materials of water and marine sediment, and the t-test for differences between means was applied. No statistically significant differences were established in fresh water and seawater (p>0.05), whereas differences became apparent in marine sediment (p<0.03).

Estudo do nitrogênio na combustão do gás natural

Nitrogen content in natural gas was studied in experimental and computational investigations to identify its influence on the emission level of exhaust gases from combustion facilities. Changes in natural gas composition with different N2 concentrations may result from introducing a new source gas into the system. An industrial burner fired at 75 kW, housed in a laboratory-scale furnace, was employed for runs where the natural gas/N2 proportion was varied. The exhaust and in-furnace measurements of temperature and gas concentrations were performed for different combustion scenarios, varying N2 content from 1-10 %v. Results have shown that the contamination of natural gas with nitrogen reduced the peak flame temperature, the concentration of unstable species, the NO X emission level and the heat transfer rate to the furnace walls, resulting from the recombination reactions.

Determinação direta de molibdênio em comprimidos polivitamínicos por voltametria em meio não aquoso

Adsorptive stripping voltammetry carried out in a homogeneous ternary solvent composed of N,N-dimethylformamide, water and ethanol, with alpha-benzoinoxime (alphaBO) as the complexing agent for Mo(VI) and a 0.5 mol L-1 acetic acid - sodium acetate buffer as supporting electrolyte was successfully used for the determination of molybdenum in polyvitamin-polymineral tablets. Tablet samples were analyzed and the results were compared with those obtained both by graphite furnace atomic absorption and by recovery tests, with good correlations, indicating that this may be considered as an alternative procedure for routine determination of Mo(VI) in pharmaceutical samples.

Modern recovery boiler design criteria

Engineering and pricing of large recovery boiler were studied in this work. Engineering was carried out with Anita 4.2 which is an engineering program of Andritz. Key initial values were chosen with previous studies. Primary target of this work was to find out the consequences that furnace dimensions and furnace screen vertical part has to boiler pricing. Boilers that were engineered had different rate of furnace width and depth and different heat transfer plate count. Boiler balances were invariable. Boilers with different vertical screen construction were also calculated. First variation was boiler with vertical screen up to furnace roof. Other variation was to connect vertical screen to Pre-boiler generating bank inlet tubes. Total prices were calculated to engineered boilers. Pricing was sort out to heat transfers, high pressure pipes, steel structures, auxiliary equipments and civil/structural costs. This study did not notice parts of the boiler which costs do not vary with the construction of the boiler. Heat transfers had the largest share of costs. Boiler building had the most significant differences between the boilers. Furnace screen had also significant role especially to costs of the boiler building.

Liuottajasäiliön hönkien käsittely täytekappalepesurilla

Soodakattilan liuottajasäiliön hönkä on ongelmallinen kaasu sen sisältävän suuren vesihöyrypitoisuuden, pölyn sekä rikkiyhdisteiden vuoksi. Nykyisin sitä ei voida johtaa ilmakehään käsittelemättömänä. Tässä diplomityössä kuvatun järjestelmän avulla liuottajasäiliön hönkä hävitetään soodakattilan tulipesässä. Liuottajasäiliöstä tulevasta höngästä poistetaan kosteutta sekä kiintoaineita jäähdyttämällä sitä täytekappalepesurissa. Tähän diplomityöhön liittyen suunniteltiin koeohjelma. Kokeiden tarkoituksena on tarkastella sekä hönkäpesurin että koko järjestelmän toimintaa erilaisilla kaasun ja nesteen virtauksilla. Lisäksi koeohjelmaan otettiin mukaan höngän esipesurin, sulan hajotushöyryn ja kiertonesteen lämmönsiirtimen toiminnan vaikutus koko järjestelmään. Diplomityössä kuvattujen kokeiden tuloksia ei julkaista tässä työssä. Lopuksi työssä on tarkasteltu höngän ja kiertonesteen laadun vaikutusta täytekappalepesurin sekä koko järjestelmän toimintaan.

A three dimensional study of heat transfer in a supercritical circulating fluidized bed combustor

From the boiler design point of view, it is imperative to know and understand the operation of the boiler. Since comprehensive measurement of a large furnace is impossible, the furnace can be modeled in order to study its behavior and phenomena. This requires the used model to be validated to correspond with the physical furnace behavior. In this thesis, a three dimensional furnace model is validated to match a bituminous coal utilizing, supercritical once-through circulating fluidized bed combustor based on measurement data. The validated model is used for analyzing the furnace heat transfer. Other heat transfer analysis methods are energy balance method based on tube surface temperature measurements and a method based on measured temperature difference between the tube crest and the fin. The latter method was developed in the thesis using Fluent-software. In the theory part, literature is reviewed and the fundamental aspects of circulating fluidized bed are discussed. These aspects are solid particle behavior in fluidization known as hydrodynamics, behavior of fuel and combustion and heat transfer. Fundamental aspects of modeling are also presented.

Análise direta de sólidos por espectrometria de absorção atômica com atomização em forno de grafite: uma revisão

This is a review of direct analysis using solid sampling graphite furnace atomic absorption spectrometry. Greater emphasis is dedicated to sample preparation, sample homogeneity, calibration and its application to microanalysis and micro-homogeneity studies. The main advantages and some difficulties related to the applicability of this technique are discussed. A literature search on the application of solid sampling graphite furnace atomic absorption spectrometry in trace element determination in many kinds of samples, including biological, clinical, technological and environmental ones, is also presented.

Uma estratégia adaptada para síntese de magnetita

Chemical reactions in the solid state are often not included in undergraduate chemistry curricula, due to requirements for special laboratory facilities such as ovens and precision weighing balances. This work aims to describe novel and relatively simple magnetite chemical syntheses in dry medium, which could also be used as an alternative for freshmen chemistry experiments. The proposed reaction was carried out in a muffle furnace by heating (i) a sol-gel preparation and (ii) natural hematite, under nitrogen atmosphere at 400 ºC. The synthesized magnetite was characterized with powder X-ray diffraction and Mössbauer spectroscopy. Results show that magnetite samples have chemical properties as well as crystalline structure quite similar to those of standard natural magnetite.

Arinakattilan lämmönsiirron laskentamallin kehittäminen

Kattilalaitosten polttoaineen syötössä ilmenevät häiriöt ja biopolttoaineiden laatuvaihtelut aiheuttavat epävakaata palamista ja tekevät prosessin hallinnasta vaikeampaa. Polttoaineen laatuvaihtelut vaikuttavat koko prosessiin ja näkyvät lopulta myös höyryntuotannossa. Kompensoinnilla pyritään estämään häiriöiden suuret vaikutukset höyryn tuotantoon. Tarkoituksena on saada kattilan toiminta ja tehon tuotanto tasaisemmaksi ja helpommin hallittavaksi. Tässä diplomityössä tarkastellaan polttoaineen ominaisuuksien, säteilylämmönsiirron sekä säätöjen vaikutusta toisiinsa ja merkitystä kattilan toiminnan kannalta. Työssä muodostetaan säteilylämmönsiirron laskentamalli arinakattilan tulipesälle käyttäen hyväksi hyvin sekoittuneen tulipesän menetelmää. Menetelmällä voidaan määrittääsavukaasujen keskimääräinen lämpötila tulipesässä, lämpövirta tulipesän seiniin tai poltossa vapautuva lämpöteho. Mallin avulla voidaan paremmin ymmärtää prosessin käyttäytymistä polttoaineen laadun muuttuessa sekä helpottaa ja nopeuttaa kattilan käyttäytymisen ennustamista. Laskentamalli tehtiin Excel –laskentaohjelmaan, jossa se testataan. Verifioinnin jälkeen malli on tarkoitus siirtää toimimaan apros –simulointiympäristöön.