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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
51

Efficiency and Selectivity in the Chlorate Process

Lindberg, Aleksandra January 2021 (has links)
This licentiate thesis presents experimental studies concerning two parts of the electrochemical cell in the chlorate process: a cathode and an anode. Newly synthesized MnOx electrodes were investigated for the cathodic reaction, hydrogen evolution reaction (HER) in the chlorate process. In industry addition of toxic and carcinogenic chromium (VI) as sodium dichromate provides high efficiency. Here undesirable addition of sodium dichromate was avoided while high cathodic efficiency was achieved. Cathodic efficiency and selectivity towards HER, achieved by the MnOx electrodes annealed at different temperatures, were measured by means of mass spectrometry (MS).  The second study investigated oxygen evolution in the chlorate process, which is an anodic side reaction. The evolution of oxygen decreases anodic efficiency and also presents a safety risk due to occurrence of HER in the undivided cell. We followed the amount of produced oxygen by two types of the electrode TiRu, similar to that industrially used, and synthesized TiRuSnSb, by means of MS. The produced oxygen amount was compared to the amount produced by Pt. To our best knowledge, this was the first study that successfully disentangles three different sources of oxygen with good time resolution. Oxygen is produced by homogenous hypochlorite decomposition, heterogeneously by different catalysts present in the electrolyte solution and anodically during the electrolysis i.e. electrochemically. Different electrode materials catalyzed hypochlorite decomposition differently and led to a different volume of oxygen produced. / Denna licentiatavhandling redogör för experimentella studier av tvådelar av den elektrokemiska cell som används i kloratprocessen:katoden och anoden. Syntetiserade MnOx elektroder utvärderades för katodreaktionen,vätgasutveckling, i kloratprocessen. Industriellt tillsätts giftigt ochcancerogent krom(IV) som natriumdikromat för hög verkningsgrad. Denna studie uteslöt oönskad tillsats av natriumdikromat samtidigt som hög katodisk effektivitet erhölls. Katodisk effektivitet och selektivitet för vätgasutveckling, med MnOx elektroder,värmebehandlade vid olika temperaturer, uppmättes med masspektrometer. I den andra studien undersöktes syrgasutveckling i kloratprocessen,vilket är en anodisk sidoreaktion. Syrgasutvecklingen minskar den anodiska effektiviteten och utgör en säkerhetsrisk med anledning avden pågående vätgasutvecklingen i den odelade cellen. Vi uppmättemängden producerad syrgas med två olika elektroder TiRu, liknandeden som industriellt används, och syntetiserad TiRuSnSb, med masspektrometer. Den producerade syrgasmängden jämfördes med mängden producerat på Pt. Såvitt vi vet var detta den första studiesom särskiljer på tre olika syrgaskällor med god tidsupplösning. Syrgas produceras homogent av hypokloritsönderfall, heterogent av olika katalysatorer närvarande i elektrolyten och anodiskt vid elektrolys dvs. elektrokemiskt. Olika elektrodmaterial katalyserade hypokloritsönderfall olika och producerade olika volym syrgas. / <p>QC 2021-04-28</p>
52

The Development of Appropriate Brine Electrolysers for Disinfection of Rural water supplies

Siguba, Maxhobandile January 2005 (has links)
>Magister Scientiae - MSc / A comparative study of electrolysers using different anodic materials for the electrolysis of brine (sodium chloride) for the production of sodium hypochlorite as a source of A comparative study of electrolysers using different anodic materials for the electrolysis of brine (sodium chloride) for the production of sodium hypochlorite as a source of available chlorine for disinfection of rural water supplies has been undertaken. The electrolyser design used was tubular in form, having two chambers i.e. anode inside and cathode outside, separated by a tubular inorganic ceramic membrane. The anode was made of titanium rod coated with a thin layer of platinum and a further coat of metal oxide. The cathode was made of stainless steel wire. available chlorine for disinfection of rural water supplies has been undertaken. The electrolyser design used was tubular in form, having two chambers i.e. anode inside and cathode outside, separated by a tubular inorganic ceramic membrane. The anode was made of titanium rod coated with a thin layer of platinum and a further coat of metal oxide. The cathode was made of stainless steel wire. An assessment of these electrolysers was undertaken by studying the effects of some variable parameters i.e. current, voltage and sodium chloride concentration. The flow rate was kept unchanged at 50ml/h anolyte and 140ml/h catholyte since it was found to be optimum flow rate for chlorine generation. Figures of merit of the electrolysers were calculated on the basis of three sets of measurements. Analytical methods used for the determination of sodium hypochlorite concentration were iodometric and N, N-Diethyl-p- Phenylenediamine (DPD) titration methods. The DPD titration method was used to determine the chlorine concentration of less than 1mg/L, while the iodometric titration method was used to determine chlorine concentration of ImgIL and above. Sodium chlorate present in the hypochlorite solution was also determined using a spectrophotometric method. The cobalt oxide electrolyser has been shown to be superior as compared to the ruthenium dioxide and manganese dioxide electrolysers in terms of hypochlorite generation. Sodium chlorate was present but at concentration levels not hazardous for use in dosing water for drinking purposes. Analysis of hydroxyl radicals was undertaken since there were claims that these are produced during brine electrolysis. Hydroxyl radical analysis was not successful, since sodium hypochlorite and hypochlorous acid interfere using the analytical method described in this study.
53

Intimt eller sexuellt deepfakematerial? : En analys av fenomenet ‘deepfake pornografi’ som digitalt sexuellt övergrepp inom det EU-rättsliga området / Intimate or sexual deepfake material? : An analysis of the phenomenon ’deepfake pornography’ as virtual sexual abuse in the legal framework of the European Union

Skoghag, Emelie January 2023 (has links)
No description available.
54

Utökade ansvarsbestämmelser i lagen om digitala tjänster– vad innebär de egentligen för onlinemarknadsplatser?

Dellnäs, Julia January 2024 (has links)
This paper reviews the responsibilities and liability of online marketplaces within the Digital Services Act (DSA) framework. The DSA, proposed by the European Union, represents a comprehensive legislative initiative to regulate digital platforms and intermediaries, with a particular emphasis on online marketplaces. Specifically, the focus of this paper is on the obligations imposed on online marketplaces, shedding light on the regulatory landscape governing their conduct and responsibilities. This paper aims to examine the implications of the extended responsibilities of online marketplaces under the DSA. The analysis explores potential changes in their levels of responsibility, obligations, and measures for handling user-generated content. Through this, the aim is to contribute to the debate on regulating digital platforms, shedding light on key aspects of online marketplace responsibilities. This is performed using a critical policy analysis methodology, examining the legal content of the DSA regulation, and analysing the practical consequences of its implementation, with a special focus on how the DSA ensures a responsible and sustainable retail environment and what the increased requirements mean for online marketplaces in practice.
55

TRATAMIENTO ELECTROQUÍMICO DE DISOLUCIONES DE TINTURAS OBTENIDAS A PARTIR DE LA MEZCLA DE COLORANTES REACTIVOS BIFUNCIONALES HIDROLIZADOS

Orts Maiques, Francisco José 01 September 2017 (has links)
ELECTROCHEMICAL TREATMENT OF DYE DISSOLUTIONS OBTAINED FROM THE MIXTURE OF HYDROLYZED BIFUNCTIONAL REACTIVE DYES In this Doctoral Thesis the degradation of the three reactive dyestuffs that make up the Tricromia Procion HEXL is studied by applying the oxidation-reduction electrochemical treatment to 125mA/cm2 in a filter-press cell using a stainless steel cathode, and as anode, an Ti / SnO2-Sb-Pt type DSA electrode are used. The degree of decolorization / mineralization is evaluated by Total Organic Carbon (TOC), Total Nitrogen (TN) and Chemical Oxygen Demand (COD), data that also allow us to know Average Oxidation State (AOS) at the end of each as well as information on the efficiency in each case through the Carbon Oxidation State (COS), State of Average Oxidation (EOP), Instantaneous Currente Efficiency (ICE) and Average Current Efficiency (ACE). The kinetics of discoloration and the evolution of the generated intermediates have been studied through measurements of High Resolution Liquid Chromatography (HPLC). The spectra obtained through UV-Visible Spectroscopy and FTIR allows us to follow the discoloration from the initial and final state of the solutions after the electrolysis. The main objective is to obtain discolored water with organic matter contents significantly lower than the initial values and to study the possibility of reuse of these purified waste water in subsequent dyeing processes. In this first part of the work we studied the electrochemical treatment for the degradation of these dyes using solutions with the hydrolyzed dyes. Na2SO4 is used as electrolyte. Next, we study the degradation and electrochemical behavior of baths containing the dyes: Procion Yellow HEXL, Procion Crimson HEXL and Procion Navy HEXL after the dyeing of cotton fabrics. Dyes are made at the laboratory level, subsequently the waters resulting from these dye baths are subjected to an electrochemical oxidation-reduction treatment at 125mA / cm2 in a filter-press cell. Proceed to study and to verify that these treated waters can be reused in later dyes obtaining acceptable values of equalization in the dyed tissues. We perform a color equalization study of the cotton fabrics tinted with the dyes of the Tricromia Procion HEXL, using solutions with different proportions of distilled water and recovery water and verify the equalization of the same, the data that we obtain from this study indicate us that good results are obtained from mixtures of 70% recovery water and 30% water. The color differences obtained in the fabrics dyed in the reuses are below the maximum limit of acceptance of color differences in the textile industry, which is one unit (DECMC(2:1) ¿ 1). Subsequently we study the degradation and mineralization of the bath resulting from the dyeing of cotton fabrics at the laboratory level with a mixture of the colorants the Tricromia Procion HEXL using NaCl as electrolyte by subjecting these baths to a treatment Oxide-reduction electrochemical at 125mA/cm2 in a filter-press cell. In all cases a decrease of COD, TOC and TN is obtained, AOS and COS data indicate that the oxidation state of Carbon in all solutions increases, the ACE and COS results show that the process takes place in a way efficient. The discoloration kinetics of all processes correspond to pseudo-first order, UV-Visible spectroscopy reveals that the bands corresponding to the chromophore group of the dyes are eliminated. This treatment of successive dyes and discolorations could be a viable alternative in the purification of actual textile effluents containing this type of dyes. / TRATAMIENTO ELECTROQUÍMICO DE DISOLUCIONES DE TINTURAS OBTENIDAS A PARTIR DE LA MEZCLA DE COLORANTES REACTIVOS BIFUNCIONALES HIDROLIZADOS Se estudia la degradación de los tres colorantes reactivos bifuncionales que componen la Tricromía Procion HEXL mediante la aplicación del tratamiento electroquímico de óxido-reducción a 125mA/cm2 en una célula filtro-prensa empleando un cátodo de acero inoxidable, y como ánodo se utiliza un electrodo tipo DSA de Ti/SnO2-Sb-Pt. Se evalúa el grado de decoloración/mineralización mediante medidas de Carbono Orgánico Total (COT), Nitrógeno Total (TN) y Demanda Química de Oxigeno (DQO), datos que además nos permiten conocer el Estado de Oxidación Promedio (EOP) al final de cada electrolisis, así como información de la eficiencia en cada caso a través del Estado de Oxidación del Carbono (EOC), Eficiencia en Corriente Instantanea (ECI) y Eficiencia en Corriente Promedio (ECP). La cinética de decoloración y la evolución de los intermedios generados se han estudiado a través medidas de Cromatografía Liquida de Alta Resolución (HPLC). Los espectros obtenidos a través de Espectroscopia UV-Visible y FTIR nos permiten hacer un seguimiento de la decoloración desde el estado inicial y final de las disoluciones tras la electrolisis. El objetivo principal es obtener aguas decoloradas con contenidos en materia orgánica sensiblemente inferiores a los valores iniciales y estudiar la posibilidad de reutilización de esas aguas residuales depuradas en posteriores procesos de tintura. En la primera parte del trabajo se estudió el tratamiento electroquímico para la degradación de estos colorantes empleando disoluciones con los colorantes hidrolizados. Se utiliza Na2SO4 como electrolito. Seguidamente se estudia la degradación y comportamiento electroquímico de baños que contienen los colorantes: Procion Yellow HEXL, Procion Crimson HEXL y Procion Navy HEXL tras la tintura de tejidos de algodón. Se realizan tinturas a nivel de laboratorio, posteriormente las aguas resultantes de estos baños de tintura se someten a un tratamiento electroquímico de óxido-reducción a 125mA/ cm2 en una célula filtro-prensa. Se procede a estudiar y verificar que estas aguas tratadas pueden ser reutilizadas en posteriores tinturas obteniendo valores aceptables de igualación en los tejidos teñidos. Se realiza un estudio de igualación del color de los tejidos de algodón tintados con los colorantes de la Tricromía Procion HEXL, utilizando disoluciones con distintas proporciones de agua destilada y agua de recuperación y comprobando la igualación de las mismas, los datos obtenidos en este estudio nos indican que se consiguen buenos resultados a partir de mezclas de 70% agua de recuperación y 30% agua. Las diferencias de color obtenidas en los tejidos tintados en cuatro reutilizaciones son inferiores al límite máximo de aceptación de diferencias de color en la industria textil, que es de una unidad (DECMC(2:1) ¿ 1). Posteriormente hemos estudiado la degradación y mineralización del baño resultante de la tintura de tejidos de algodón a nivel de laboratorio con una mezcla de los colorantes de la Tricromía Procion HEXL utilizando NaCl como electrolito al someterlos a un tratamiento electroquímico de óxido-reducción a 125mA/ cm2 en una célula filtro-prensa. En todos los casos se obtiene una disminución de DQO, COT y TN, los datos de EOP y EOC nos indican que aumenta el Estado de Oxidación del Carbono en todas las disoluciones, los resultados de ECP y EOC demuestran que el proceso tiene lugar de forma eficiente. La cinética de decoloración de todos los procesos corresponde a pseudo-primer orden, la espectroscopia UV-Visible revela que las bandas correspondientes al grupo cromóforo de los colorantes son eliminadas. Este tratamiento de sucesivas tinturas y decoloraciones podría ser una alternativa viable en la depuración de efluentes textiles reales que contienen es / TRACTAMENT ELECTROQUÍMIC DE DISSOLUCIONS DE TINTURES OBTINGUDES A PARTIR DE LA MESCLA DE COLORANTS REACTIUS BIFUNCIONALES HIDROLITZATS En la present Tesi Doctoral s'estudia la degradació dels tres colorants reactius bifuncionals que componen la Tricromia Procion HEXL mitjançant l'aplicació del tractament electroquímic d'òxid-reducció a 125mA/cm2 en una cèl¿lula filtre-premsa emprant un càtode d'acer inoxidable, i com a ànode s'utilitza un elèctrode tipus DSA de Ti/SnO2-Sb-Pt. S'avalua el grau de decoloració/mineralització mitjantçant mesures de Carboni Orgànic Total (COT), Nitrogen Total (TN) i Demanda Química d'Oxigen (DQO), dades que a més ens permeten conéixer l'Estat d'Oxidació Mitjana (EOM) al final de cada electròlisi, així com informació de l'eficiència en cada cas a través de l'Estat d'Oxidació del Carboni (EOC) , Eficiència en Corrent Instantània (ECI) i Eficiència en Corrent Mitjana (ECM). La cinètica de decoloració i l'evolució dels intermedis generats s'han estudiat a través de mesures de Cromatografia Liquida d'Alta Resolució (HPLC). Els espectres obtinguts a través d'Espectroscòpia UV-Visible i FTIR ens permet fer un seguiment de la decoloració des de l'estat inicial i final de les dissolucions després de l'electròlisi. L'objectiu principal és obtindre aigües decolorades amb continguts en matèria orgànica sensiblement inferiors als valors inicials i estudiar la possibilitat de reutilització d'eixes aigües residuals depurades en posteriors processos de tintura. A la primera part del treball es va estudiar el tractament electroquímic per a la degradació d'estos colorants emprant dissolucions amb els colorants hidrolitzats. S¿utilitza Na2SO4 com electròlit. A continuació s'estudia la degradació i comportament electroquímic de banys que contenen els colorants: Procion Yellow HEXL, Procion Crimson HEXL i Procion Navy HEXL després de la tintura de teixits de cotó. Es realitzen tintures a nivell de laboratori, posteriorment les aigües resultants d'estos banys de tintura se sotmeten a un tractament electroquímic d'òxid-reducció a 125mA/cm2 en una cèl¿lula filtre-premsa. Procedim a estudiar i verificar que estes aigües tractades poden ser reutilitzades en posteriors tintures aconseguint valors acceptables d'igualació en els teixits tenyits. Es realitza un estudi d'igualació del color dels teixits de cotó tintats amb els colorants de la Tricromia Procion HEXL, utilitzant dissolucions amb distintes proporcions d'aigua destil¿lada i aigua de recuperació i comprovant la igualació de les mateixes, les dades obtingudes en este estudi ens indiquen que s¿aconsegueixen bons resultats a partir de mescles de 70% aigua de recuperació i 30% aigua. Les diferències de color obtingudes en els teixits tintats en les quatre reutilitzacions són inferiors al límit màxim d'acceptació de diferències de color en la indústria tèxtil que és d'una unitat (DECMC(2:1) ¿ 1). Posteriorment hem estudiat la degradació i mineralització del bany resultant de la tintura de teixits de cotó a nivell de laboratori amb una mescla dels colorants de la Tricromia Procion HEXL, utilitzant NaCl com a electròlit al sotmetre'ls a un tractament electroquímic d'òxid-reducció a 125mA/cm2 en una cèl¿lula filtre-premsa. En tots els casos s'obté una disminució de DQO, COT i TN, les dades d'EOP i EOC ens indiquen que augmenta l'estat d'Oxidació del Carboni en totes les dissolucions, els resultats d'ECP i EOC demostren que el procés té lloc de forma eficient. La cinètica de decoloració de tots els processos correspon a pseudo-primer ordre, l'espectroscòpia UV-Visible revela que les bandes corresponents al grup cromóforo dels colorants són eliminades. Este tractament de successives tintures i decoloracions podria ser una alternativa viable en la depuració d'efluents tèxtils reals que contenen este tipus de colorants. / Orts Maiques, FJ. (2017). TRATAMIENTO ELECTROQUÍMICO DE DISOLUCIONES DE TINTURAS OBTENIDAS A PARTIR DE LA MEZCLA DE COLORANTES REACTIVOS BIFUNCIONALES HIDROLIZADOS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/86153
56

Elektronické zabezpečení zdravotnické dokumentace v prostředí zdravotnického IS / Security of Electronic Documentation in Medical Environment

Hauserová, Markéta January 2012 (has links)
Thesis is analyzing czech laws which are related to medical documentation. Describes the points  which are mandatory for information system, so the medical documentation can be stored electronically. Includes various algorithms for implementation of certain electronic signature and for  identification of person. This thesis deals with asymmetric cryptography, specifically RSA, DSA, and ECDSA. Describes the hash functions and their functions and their characteristics. Describes the principle of the certificate, ways of its obtaining, invalidation and their formats. Analyzes medical information system and suggests ways to create a program for signing medical records. Then based on that analysis, the program is implemented. At the conclusion of the work is discussed, if created program meets the criteria.
57

Intimt eller sexuellt deepfakematerial? : En analys av fenomenet ‘deepfake pornografi’ som digitalt sexuellt övergrepp inom det EU-rättsliga området / Intimate or sexual deepfake material? : An analysis of the phenomenon ’deepfake pornography’ as virtual sexual abuse in the legal framework of the European Union

Skoghag, Emelie January 2023 (has links)
No description available.
58

Digital Pre-distortion for Interference Reduction in Dynamic Spectrum Access Networks

Fu, Zhu 23 April 2014 (has links)
Given the ever increasing reliance of today’s society on ubiquitous wireless access, the paradigm of dynamic spectrum access (DSA) as been proposed and implemented for utilizing the limited wireless spectrum more efficiently. Orthogonal frequency division multiplexing (OFDM) is growing in popularity for adoption into wireless services employing DSA frame- work, due to its high bandwidth efficiency and resiliency to multipath fading. While these advantages have been proven for many wireless applications, including LTE-Advanced and numerous IEEE wireless standards, one potential drawback of OFDM or its non-contiguous variant, NC-OFDM, is that it exhibits high peak-to-average power ratios (PAPR), which can induce in-band and out-of-band (OOB) distortions when the peaks of the waveform enter the compression region of the transmitter power amplifier (PA). Such OOB emissions can interfere with existing neighboring transmissions, and thereby severely deteriorate the reliability of the DSA network. A performance-enhancing digital pre-distortion (DPD) technique compensating for PA and in-phase/quadrature (I/Q) modulator distortions is proposed in this dissertation. Al- though substantial research efforts into designing DPD schemes have already been presented in the open literature, there still exists numerous opportunities to further improve upon the performance of OOB suppression for NC-OFDM transmission in the presence of RF front-end impairments. A set of orthogonal polynomial basis functions is proposed in this dissertation together with a simplified joint DPD structure. A performance analysis is presented to show that the OOB emissions is reduced to approximately 50 dBc with proposed algorithms employed during NC-OFDM transmission. Furthermore, a novel and intuitive DPD solution that can minimize the power regrowth at any pre-specified frequency in the spurious domain is proposed in this dissertation. Conventional DPD methods have been proven to be able to effectively reduce the OOB emissions that fall on top of adjacent channels. However more spectral emissions in more distant frequency ranges are generated by employing such DPD solutions, which are potentially in violation of the spurious emission limit. At the same time, the emissions in adjacent channel must be kept under the OOB limit. To the best of the author’s knowledge, there has not been extensive research conducted on this topic. Mathematical derivation procedures of the proposed algorithm are provided for both memoryless nonlinear model and memory-based nonlinear model. Simulation results show that the proposed method is able to provide a good balance of OOB emissions and emissions in the far out spurious domain, by reducing the spurious emissions by 4-5 dB while maintaining the adjacent channel leakage ratio (ACLR) improvement by at least 10 dB, comparing to the PA output spectrum without any DPD.
59

Contributions à l'étude de détection des bandes libres dans le contexte de la radio intelligente.

Khalaf, Ziad 08 February 2013 (has links) (PDF)
Les systèmes de communications sans fil ne cessent de se multiplier pour devenir incontournables de nos jours. Cette croissance cause une augmentation de la demande des ressources spectrales, qui sont devenues de plus en plus rares. Afin de résoudre ce problème de pénurie de fréquences, Joseph Mitola III, en 2000, a introduit l'idée de l'allocation dynamique du spectre. Il définit ainsi le terme " Cognitive Radio " (Radio Intelligente), qui est largement pressenti pour être le prochain Big Bang dans les futures communications sans fil [1]. Dans le cadre de ce travail on s'intéresse à la problématique du spectrum sensing qui est la détection de présence des Utilisateurs Primaires dans un spectre sous licence, dans le contexte de la radio intelligente. L'objectif de ce travail est de proposer des méthodes de détection efficaces à faible complexité et/ou à faible temps d'observation et ceci en utilisant le minimum d'information a priori sur le signal à détecter. Dans la première partie on traite le problème de détection d'un signal aléatoire dans le bruit. Deux grandes méthodes de détection sont utilisées : la détection d'énergie ou radiomètre et la détection cyclostationnaire. Dans notre contexte, ces méthodes sont plus complémentaires que concurrentes. Nous proposons une architecture hybride de détection des bandes libres, qui combine la simplicité du radiomètre et la robustesse des détecteurs cyclostationnaires. Deux méthodes de détection sont proposées qui se basent sur cette même architecture. Grâce au caractère adaptatif de l'architecture, la détection évolue au cours du temps pour tendre vers la complexité du détecteur d'énergie avec des performances proches du détecteur cyclostationnaire ou du radiomètre selon la méthode utilisée et l'environnement de travail. Dans un second temps on exploite la propriété parcimonieuse de la Fonction d'Autocorrelation Cyclique (FAC) pour proposer un nouvel estimateur aveugle qui se base sur le compressed sensing afin d'estimer le Vecteur d'Autocorrelation Cyclique (VAC), qui est un vecteur particulier de la Fonction d'Autocorrelation Cyclique pour un délai fixe. On montre par simulation que ce nouvel estimateur donne de meilleures performances que celles obtenues avec l'estimateur classique, qui est non aveugle et ceci dans les mêmes conditions et en utilisant le même nombre d'échantillons. On utilise l'estimateur proposé, pour proposer deux détecteurs aveugles utilisant moins d'échantillons que nécessite le détecteur temporel de second ordre de [2] qui se base sur l'estimateur classique de la FAC. Le premier détecteur exploite uniquement la propriété de parcimonie du VAC tandis que le second détecteur exploite en plus de la parcimonie la propriété de symétrie du VAC, lui permettant ainsi d'obtenir de meilleures performances. Ces deux détecteurs outre qu'ils sont aveugles sont plus performants que le détecteur non aveugle de [2] dans le cas d'un faible nombre d'échantillons.
60

Eletroxidação de cloranfenicol e outros poluentes organicos utilizando reatores eletroquimicos, constituidos de anodos tipo DSA ou de diamante dopado com boro (DDB) / Electrooxidation of chloramphenicol and otherpollutants using electrochemical reactors composed with a DSA type anode or a boron-doped diamond anode

Spitzer, Marcos 30 September 2005 (has links)
Orientador: Rodnei Bertazzoli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-05T06:46:31Z (GMT). No. of bitstreams: 1 Spitzer_Marcos_D.pdf: 1019872 bytes, checksum: 57974ac02038eb53169c99987a119811 (MD5) Previous issue date: 2005 / Resumo: O método de oxidação eletroquímica foi aplicado a soluções aquosas contendo cloranfenicol (CAP) e outros compostos orgânicos. Para isso, utilizou-se um anodo de óxido condutor, comercial, tipo DSA®, de composição 70TiO2-30RuO2 e um anodo de diamante dopado com boro (DDB) tipo comercial. Cada anodo foi instalado em um reator tipo filtro-presa, em escala de bancada, para processamento de 2 a 3 L de solução em modo de batelo-reciclo. Inicialmente, nos reatores construídos foram realizados estudos voltamétricos, em modo hidrodinâmico. Sobre um catodo de aço inoxidável, antes da evolução de H2, observou-se a redução do grupo NO2 do CAP a HO-NH- a pH=5, e em potenciais anódicos, sobre o DSA®, observou-se o início reação de evolução de O2 a partir de 1 V vs. ECS e que a presença de CAP reduz as correntes de evolução de O2. Sobre o DDB, o CAP é oxidado a partir de 0,6 V resultado na passivação do anodo. A partir de 2,2 V observa-se o início da evolução de O2 sobre o DDB, resultando na eliminação do filme passivador. Em seguida, eletrólises exaustivas foram realizadas, em modo galvanostático, com ambos os anodos, dentro da região de evolução de O2. Cinéticas de pseudo-primeira ordem foram observadas dos decaimentos ds CAP sobre o DSA®, na faixa de 50 a 180 mA cm-2, e sobre o DDB, na faixa de 10 a 30 mA cm-2. Os decaimentos da demanda química de O2 (DQO) e do carbono orgânico total (COT) também apresentaram essa cinética quando as reações de oxidação sobre o DDB tornavam-se controladas pelos processos de transporte de massa. A partir de eletrólises de soluções de K2SO4 com o DDB observou-se a geração de H2O2. Os números adimensionais Sherwood (Se), Reynolds (Re) e Schmidt (Sc) foram determinados a partir de dados de transporte de massa obtidos a partir de cinéticas da degradação do CAP em função da vazão. No reator composto de DSA® observou-se um regime de fluxo laminar a baixo de Re = 2000 e um regime de fluxo turbulento acima desse valor, como esperado para um reator de placas paralelas. No reator de DDB, devido o aumento da área da secção transversal do compartimento entre eletrodos, há uma elevação de turbulência da face do anodo, impedindo a formação de um regime de fluxo laminar bem definido. Utilizando um efluente real contendo fenóis e derivados, foram aplicadas valores apropriados de densidade de corrente (Jap) para aumento dos valores de eficiência de corrente e diminuição dos índices de consumo energético. Aplicando-se um perfil exponencial de Jap (t) obteve-se um rendimento de corrente médio de 95 % e um consumo de 23,5 kWh por kg de O2. Com isso foi possível propor um método de operação de reatores de DDB para elevação dos índices de eficiência. De modo geral, os anodos de Ti/70TiO2-30RuO2 e de DDB ótimos desempenhos para a eletroxidação de cloranfenicol (CAP) e outros compostos orgânicos e para redução da DQO e do COT / Abstract: Electrochemical oxidation was used as a method for organic pollutant degradation in aqueous media. In the technique was used in solutions containing chloramphenicol (CAP) and phenolic compounds. A commercial DSA® type anode, of composition 70TiO2-30RuO2, and a boron-doped diamond anode (BDD) were used. Each anode was mounted in a filter-press type reactor connected to a recirculating flow system with 3 L of capacity. Initially, voltammetric studies were carried out with electrochemical reactors operating in hydrodynamic mode. On the DSA® type anode O2 evolution reaction was observed after 1 V vs. SCE and the current densities for O2 evolution decreased when chloramphenicol was present in solution. On stainless steel cathode, before H2 evolution, reduction of NO2 group to HO-NH- group was observed for CAP molecule, at pH = 5. On DDB, the anode was passived with an organic film at potentials from 0.6 V. Current responses on DDB anode were restored after anodic treatments within O2 evolution range of potentials. On BDD, O2 evolution took place after 2.2 V vs SCE. Galvanostatic experiments were carried out within the range of potentials for O2 evolution. Pseudo-first order kinetics were observed for CAP concentration decay on the DSA® anode, when current densities (Jap) were ranged from 50 to 180 mA cm-2, and from 10 to 30 mA cm-2 on DDB anode. Chemical oxygen demand (COD) and total organic carbon (TOC) showed linear concentration decays when the oxidation reactions were controlled by charge transfer process and it showed exponential decays when these reactions were controlled by mass transfer process. H2O2 production on DDB anode was investigated as function of Jap. Dimensionless numbers and their mass transfer figures of merit were studied from mass transport data of CAP decays as function of several flow rates. In the reactor composed by DSA® anode, a laminar flow was observed below Reynolds (Re) equal 2000 and a turbulent flow was observed above this value. In the BDD reactor, the transition between laminar and turbulent flow was not observed. Using a real effluent composed by phenols and derivates, appropriate values of Jap was applied on DDB reactor to increase the anodic efficiency and to reduce the energy consumption per kg of O2. Applying an exponential profile of Jap in galvanostatic experiments, an anodic efficiency of 95% was reached, corresponding to an energy consumption of 23,5 kWh per kg of O2. From these results an operation method of BDD reactors arose in order to increase the performance of this electrochemical device. Good performances were observed when DSA® and BDD anodes were used in electrochemical oxidation of chloramphenicol and other organic pollutants, especially in BDD case / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

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