Use of multivariate experimental designs for optimizing the reductive degradation of an azo dye in the presence of redox mediators

The optimization of the anaerobic degradation of the azo dye Remazol golden yellow RNL was performed according to multivariate experimental designs: a 2² full-factorial design and a central composite design (CCD). The CCD revealed that the best incubation conditions (90% color removal) for the degradation of the azo dye (50 mg L- 1) were achieved with 350 mg L- 1 of yeast extract and 45 mL of anaerobic supernatant (free cell extract) produced from the incubation of 650 mg L- 1 of anaerobic microorganisms and 250 mg L- 1 of glucose. A first-order kinetics model best fit the experimental data (k = 0.0837 h- 1, R² = 0.9263).

UTILIZAÇÃO DO COMPÓSITO NANOESTRUTURADO SIO2/TIO2NA FOTODEGRADAÇÃO DE CORANTES TÊXTEIS COM LUZ SOLAR NATURAL

SiO2/TiO2 nanostructured composites with three different ratios of Si:Ti were prepared using the sol-gel method. These materials were characterized using energy dispersive X-ray fluorescence, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, photoluminescence, Raman with Fourier transform infrared spectroscopy, and the specific surface area. The band gaps of materials were determined by diffuse reflectance spectra, and the values of 3.20 ± 0.01, 2.92 ± 0.02, and 2.85 ± 0.01 eV were obtained as a result of the proportional increases in the amount of Ti within the composite. The materials exhibit only the anatase (TiO2) crystalline phase and have crystalline domains ranging from 4 to 5 nm. The photodegradation process of methylene blue, royal blue GRL, and golden yellow GL dyes were studied with respect to their contact times, pH variations within the solution, and the variations in the dye concentration of the solution in response to only sunlight. The maximum amount of time for the mineralization of dyes was 90 min. The kinetics of the process follows an apparently first order model, in which the obtained rate constant values were 5.72 × 10-2 min-1 for methylene blue, 6.44 × 10-2min-1 for royal blue GRL, and 1.07 × 10-1min-1 for golden yellow.

RESSONÂNCIA MAGNÉTICA NUCLEAR DE SUBSTÂNCIAS ORGANOFLUORADAS: UM DESAFIO NO ENSINO DE ESPECTROSCOPIA

Nuclear magnetic resonance is a technique that is widely used for elucidating and characterizing organic substances. Organofluorine substances have applications in many areas from drugs to liquid crystals, but their NMR spectra are often challenging due to fluoride coupling with other nuclei. For this reason, NMR spectra of this class of substances are not commonly covered in undergraduate and graduate chemistry courses and related fields. Thus, the aim of this work was the presentation and discussion of 1H, 13C, and 19F NMR spectra of eleven organofluorine substances which, in the case of 1H and 13C nuclei, showed classic patterns of first-order coupling and the effects of the fluorine nucleus in different chemical and magnetic environments. In addition, the observation of long distance coupling constants was possible through the use of apodization functions in the processing of the spectra. It is expected that the examples presented herein can be utilized and discussed in undergraduate and graduate NMR spectroscopy disciplines and thus improve the teaching and future research of organofluorine compounds.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

Simulating the performance of paper machine control

The topic of this thesis is the simulation of a combination of several control and data assimilation methods, meant to be used for controlling the quality of paper in a paper machine. Paper making is a very complex process and the information obtained from the web is sparse. A paper web scanner can only measure a zig zag path on the web. An assimilation method is needed to process estimates for Machine Direction (MD) and Cross Direction (CD) profiles of the web. Quality control is based on these measurements. There is an increasing need for intelligent methods to assist in data assimilation. The target of this thesis is to study how such intelligent assimilation methods are affecting paper web quality. This work is based on a paper web simulator, which has been developed in the TEKES funded MASI NoTes project. The simulator is a valuable tool in comparing different assimilation methods. The thesis contains the comparison of four different assimilation methods. These data assimilation methods are a first order Bayesian model estimator, an ARMA model based on a higher order Bayesian estimator, a Fourier transform based Kalman filter estimator and a simple block estimator. The last one can be considered to be close to current operational methods. From these methods Bayesian, ARMA and Kalman all seem to have advantages over the commercial one. The Kalman and ARMA estimators seems to be best in overall performance.

Kinetic evaluation of the dehydration of Yb(III) Lu(III) and Y(III) 4-chlorobenzylidenepyruvate by thermogravimetry (TG)

The dehydration kinetic of Yb, Lu and Y 4-chlorobenzylidenepyruvate was studied by using thermogravimetry and the kinetics parameters obtained by Flynn and Wall method suggest that the dehydration step follows a first order mechanism. The activation energies calculated were 103.6, 96.6 and 97.2 kJ/mol and the lifetime considering the temperature of 31 and 101 º C for the dehydration of these compounds were 23, 26, 31 minutes and 0.6, 1.3 and 1.4 seconds, respectively. The results have similar values and suggest that the water is attached in the same way.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

A study on the inhibition of mild steel corrosion in hydrochloric acid by pyridoxol hydrochloride

The inhibition of the corrosion of mild steel in 2M hydrochloric acid solutions by Pyridoxol hydrochloride (PXO) has been studied using weight loss and hydrogen evolution techniques. The inhibitor (PXO) exhibited highest inhibition efficiency of 71.93% at the highest inhibitor concentration of 1.0 x 10-2M investigated and a temperature of 303K from weight loss result. Also, inhibition was found to increase with increasing concentration of the inhibitor and decreasing temperature. A first order type of mechanism has been deduced from the kinetic treatment of the weight loss results and the process of inhibition attributed to physical adsorption. The results obtained from the two techniques show that pyridoxol hydrochloride could serve as an effective inhibitor of the corrosion of mild steel in HCl acid solution. The compound obeys the Langmuir adsorption isotherm equation.

Metaanin muodostumisen mallintaminen kaatopaikalla

Methane-rich landfill gas is generated when biodegradable organic wastes disposed of in landfills decompose under anaerobic conditions. Methane is a significant greenhouse gas, and landfills are its major source in Finland. Methane production in landfill depends on many factors such as the composition of waste and landfill conditions, and it can vary a lot temporally and spatially. Methane generation from waste can be estimated with various models. In this thesis three spreadsheet applications, a reaction equation and a triangular model for estimating the gas generation were introduced. The spreadsheet models introduced are IPCC Waste Model (2006), Metaanilaskentamalli by Jouko Petäjä of Finnish Environment Institute and LandGEM (3.02) of U.S. Environmental Protection Agency. All these are based on the first order decay (FOD) method. Gas recovery methods and gas emission measurements were also examined. Vertical wells and horizontal trenches are the most commonly used gas collection systems. Emission measurements chamber method, tracer method, soil core and isotope measurements, micrometeorological mass-balance and eddy covariance methods and gas measuring FID-technology were discussed. Methane production at Ämmässuo landfill of HSY Helsinki Region Environmental Services Authority was estimated with methane generation models and the results were compared with the volumes of collected gas. All spreadsheet models underestimated the methane generation at some point. LandGEM with default parameters and Metaanilaskentamalli with modified parameters corresponded best with the gas recovery numbers. Reason for the differences between evaluated and collected volumes could be e.g. that the parameter values of the degradable organic carbon (DOC) and the fraction of decomposable degradable organic carbon (DOCf) do not represent the real values well enough. Notable uncertainty is associated with the modelling results and model parameters. However, no simple explanation for the discovered differences can be given within this thesis.

Vaihtosuuntaajan reaaliaikainen lämpömalli

Vaihtosuuntaajan IGBT-moduulin liitosten lämpötiloja ei voida suoraan mitata, joten niiden arviointiin tarvitaan reaaliaikainen lämpömalli. Tässä työssä on tavoitteena kehittää tähän tarkoitukseen C-kielellä implementoitu ratkaisu, joka on riittävän tarkka ja samalla mahdollisimman laskennallisesti tehokas. Ohjelmallisen toteutuksen täytyy myös sopia erilaisille moduulityypeille ja sen on tarvittaessa otettava huomioon saman moduulin muiden sirujen lämmittävä vaikutus toisiinsa. Kirjallisuuskatsauksen perusteella valitaan olemassa olevista lämpömalleista käytännön toteutuksen pohjaksi lämpöimpedanssimatriisiin perustuva malli. Lämpöimpedanssimatriisista tehdään Simulink-ohjelmalla s-tason simulointimalli, jota käytetään referenssinä muun muassa implementoinnin tarkkuuden verifiointiin. Lämpömalli tarvitsee tiedon vaihtosuuntaajan häviöistä, joten työssä on selvitetty eri vaihtoehtoja häviölaskentaan. Lämpömallin kehittäminen s-tason mallista valmiiksi C-kieliseksi koodiksi on kuvattu tarkasti. Ensin s-tason malli diskretoidaan z-tasoon. Z-tason siirtofunktiot muutetaan puolestaan ensimmäisen kertaluvun differenssiyhtälöiksi. Työssä kehitetty monen aikatason lämpömalli saadaan jakamalla ensimmäisen kertaluvun differenssiyhtälöt eri aikatasoille suoritettavaksi sen mukaan, mikä niiden kuvaileman termin vaatima päivitysnopeus on. Tällainen toteutus voi parhaimmillaan kuluttaa alle viidesosan kellojaksoja verrattuna suoraviivaiseen yhden aikatason toteutukseen. Implementoinnin tarkkuus on hyvä. Implementoinnin vaatimia suoritusaikoja testattiin Texas Instrumentsin TMS320C6727- prosessorilla (300 MHz). Esimerkkimallin laskemisen määritettiin kuluttavan vaihtosuuntaajan toimiessa 5 kHz kytkentätaajuudella vain 0,4 % prosessorin kellojaksoista. Toteutuksen tarkkuus ja laskentakapasiteetin vähäinen vaatimus mahdollistavat lämpömallin käyttämisen lämpösuojaukseen ja lisäämisen osaksi muuta jo prosessorilla olemassa olevaa systeemiä.

Expressiveness and definability in circumscription

We investigate expressiveness and definability issues with respect to minimal models, particularly in the scope of Circumscription. First, we give a proof of the failure of the Löwenheim-Skolem Theorem for Circumscription. Then we show that, if the class of P; Z-minimal models of a first-order sentence is Δ-elementary, then it is elementary. That is, whenever the circumscription of a first-order sentence is equivalent to a first-order theory, then it is equivalent to a finitely axiomatizable one. This means that classes of models of circumscribed theories are either elementary or not Δ-elementary. Finally, using the previous result, we prove that, whenever a relation Pi is defined in the class of P; Z-minimal models of a first-order sentence Φ and whenever such class of P; Z-minimal models is Δ-elementary, then there is an explicit definition ψ for Pi such that the class of P; Z-minimal models of Φ is the class of models of Φ ∧ ψ. In order words, the circumscription of P in Φ with Z varied can be replaced by Φ plus this explicit definition ψ for Pi.

DYNAMICS OF LEAF FALL FROM RIPARIAN VEGETATION AND THE ACCUMULATION IN BENTHIC STOCK IN NEOTROPICAL STREAMS1

ABSTRACT Considering the importance of the riparian vegetation leaves as an energetic source to first order streams, the aim of the present study was to evaluate the leaf biomass contribution to the system and its temporal dynamics. With this purpose, monthly samples from July 2008 to June 2009 were collected using four sampling devices installed in three streams, in order to collect the vertical, lateral and terrestrial loads, and the benthic stock. We tested the following hypothesis: (1) leaf biomass input is higher after hydric stress periods; and (2) benthic stock biomass increase with higher loads from vertical and lateral entrances. Leaves represented 71.9% (on average) of all sampled allochthonous matter, with seasonal significant variation along the studied year. Peaks of leaf input were registered in September-October, after an increase in rainfall, and also in January, after a decrease in rainfall. Leaf input was higher in the lateral load.

Modeling study of limestone reactions in fluidized bed conditions

Traditionally limestone has been used for the flue gas desulfurization in fluidized bed combustion. Recently, several studies have been carried out to examine the use of limestone in applications which enable the removal of carbon dioxide from the combustion gases, such as calcium looping technology and oxy-fuel combustion. In these processes interlinked limestone reactions occur but the reaction mechanisms and kinetics are not yet fully understood. To examine these phenomena, analytical and numerical models have been created. In this work, the limestone reactions were studied with aid of one-dimensional numerical particle model. The model describes a single limestone particle in the process as a function of time, the progress of the reactions and the mass and energy transfer in the particle. The model-based results were compared with experimental laboratory scale BFB results. It was observed that by increasing the temperature from 850 °C to 950 °C the calcination was enhanced but the sulfate conversion was no more improved. A higher sulfur dioxide concentration accelerated the sulfation reaction and based on the modeling, the sulfation is first order with respect to SO2. The reaction order of O2 seems to become zero at high oxygen concentrations.

Performance of an anaerobic-aerobic reactor and kinetic study of organic matter removal of cattle slaughterhouse effluent

This paper sought to evaluate the behavior of an upflow Anaerobic-Aerobic Fixed Bed Reactor (AAFBR) in the treatment of cattle slaughterhouse effluent and determine apparent kinetic constants of the organic matter removal. The AAFBR was operated with no recirculation (Phase I) and with 50% of effluent recirculation (Phase II), with θ of 11h and 8h. In terms of pH, bicarbonate alkalinity and volatile acids, the results indicated the reactor ability to maintain favorable conditions for the biological processes involved in the organic matter removal in both operational phases. The average removal efficiencies of organic matter along the reactor height, expressed in terms of raw COD, were 49% and 68% in Phase I and 54% and 86% in Phase II for θ of 11h and 8h, respectively. The results of the filtered COD indicated removal efficiency of 52% and k = 0.0857h-1 to θ of 11h and 42% and k = 0.0880h-1 to θ of 8h in the Phase I. In Phase II, the removal efficiencies were 59% and 51% to θ of 11h and 8h, with k = 0.1238h-1 and k = 0.1075 h-1, respectively. The first order kinetic model showed good adjustment and described adequately the kinetics of organic matter removal for θ of 11h, with r² equal to 0.9734 and 0.9591 to the Phases I and II, respectively.

Battery Cell Modeling for Battery Management System

Usage of batteries as energy storage is emerging in automotive and mobile working machine applications in future. When battery systems become larger, battery management becomes an essential part of the application concerning fault situations of the battery and safety of the user. A properly designed battery management system extends one charge cycle of battery pack and the whole life time of the battery pack. In this thesis main objectives and principles of BMS are studied and first order Thevenin’s model of the lithium-titanate battery cell is built based on laboratory measurements. The battery cell model is then verified by comparing the battery cell model and the actual battery cell and its suitability for use in BMS is studied.