To mitigate microbial activity in swimming pools and to assure hygienic safety for bathers, pool systems have a re-circulating water system ensuring continuous water treatment and disinfection by chlorination. A major drawback associated with the use of chlorine as disinfectant is its potential to react with organic matter (OM) present in pool water to form potentially harmful disinfection by-products (DBP). In this thesis, the treatment performance of different combinations of conventional and novel treatment processes was compared using a pilot scale swimming pool model that was operated under reproducible and fully controlled conditions. The quality of the pool water was determined in means of volatile DBPs and the concentration and composition of dissolved organic carbon (DOC). Further, overall apparent reaction rates for the removal of monochloramine (MCA), a DBP found in pool water, in granular activated carbon (GAC) beds were determined using a fixed-bed reactor system operated under conditions typical for swimming pool water treatment. The reaction rates as well as the type of reaction products formed were correlated with physico-chemical properties of the tested GACs.

The diploma thesis focuses on the water distribution system functioning without chlorine-based disinfectant. This thesis contains research of documented cases of examples of drinking water distribution systems both abroad and in the Czech Republic, which do not use disinfectants. Moreover, the thesis pay attention to chlorine and its effects on bacteria. The thesis deals with the first assessment of water supply structure, which determines whether the water supply structure is suitable for operating without disinfectant. The thesis describes the process of transition to the disinfectant-free operation and determines the undesired events, which may occur with the ending of the use of disinfectant. As a part of the research, the thesis examines the water supply system in village Kateřinice, to determine if it is suitable for operation without disinfectant.

To mitigate microbial activity in swimming pools and to assure hygienic safety for bathers, pool systems have a re-circulating water system ensuring continuous water treatment and disinfection by chlorination. A major drawback associated with the use of chlorine as disinfectant is its potential to react with organic matter (OM) present in pool water to form potentially harmful disinfection by-products (DBP). In this thesis, the treatment performance of different combinations of conventional and novel treatment processes was compared using a pilot scale swimming pool model that was operated under reproducible and fully controlled conditions. The quality of the pool water was determined in means of volatile DBPs and the concentration and composition of dissolved organic carbon (DOC). Further, overall apparent reaction rates for the removal of monochloramine (MCA), a DBP found in pool water, in granular activated carbon (GAC) beds were determined using a fixed-bed reactor system operated under conditions typical for swimming pool water treatment. The reaction rates as well as the type of reaction products formed were correlated with physico-chemical properties of the tested GACs.

Chlor-alkali electrolysis indicates significant demand response potential, accounting for over 2% of Germany’s total elec-tricity demand. To fully analyze this potential, digital models or digital twins are necessary. In this study, we use the IRPopt modeling framework to develop a digital model of an electrolysis process and examine the cost-optimal load shifting application in the day-ahead spot and balancing reserve market for various price scenarios (2019, 2030, 2040). We also investigate the associated CO2 emissions. Combined optimization at both markets results in greater and more robust cost savings of 16.1% but cannibalizes the savings that are possible through optimization separately at each market. In future scenarios, the shares of savings from spot and reserve market could potentially reverse. CO2 savings between 2.5% and 9.2% appear only through optimization at the spot market and could even turn negative if optimized solely at the reserve market.

In this work, the formation and effects of chlorate ion were studied over hydrogen evolution reaction (HER), focusing for the chlorine and alkalis production by diaphragm process, using a pilot and bench cells, respectively. Studies in pilot cell revealed that chlorate formation is dependent of NaOH concentration in liquor and brine dwelling time. It was also observed that the NaOH concentration increase in the cathodic side provoked decreasing of diaphragm structure lifetime. This phenomenon reduced the blockage efficiency to back migration and consequently, increasing NaOH concentration in the anodic chamber, further increase in the undesirable parallels reaction rate, for example, the chlorate formation. After formation of chlorate in the anodic chamber the migration to the cathodic side is inevitable. Therefore to complete the studies we decided to verify the influence the chlorate, in bench cell, in the cathodic side, specifically for HER process. Potential polarization experiments in presence of chlorate, evidenced effects of HER wave displacement over SAE1020 mild steel carbon steel plate employed in industrial cells for chlorine and alkalis production using diaphragm process. Alternatively to SAE1020, other duplex alloys like SAF2205, SAF2304 and SAF2507 were also investigated. SAF2205 alloy presented a very interesting electrocatalytic response for HER. Pilot cell results pointed for the problem detected with the NaOH migration to the anodic side of cell, and invoked the single possibility to solve this problem - the changing of diaphragm cell separator. Bench experiments revealed chlorate influence on HER over SAE1020 carbon steel, claiming for urgent developing of alternative materials/cathodes with chlorate-immune character. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Esse trabalho estuda a formação e os efeitos de íon clorato sobre a reação de desprendimento de hidrogênio (RDH) com ênfase para a produção de cloro-soda por processo de diafragma, com a utilização de célula piloto e de bancada, respectivamente. Os estudos em célula piloto revelaram que a formação de clorato é dependente da concentração de hidróxido de sódio no licor de célula e do tempo de residência da salmoura. Observou-se também que o aumento da concentração de hidróxido de sódio no lado catódico provoca envelhecimento prematuro da estrutura do diafragma, e este fenômeno reduz a eficiência do bloqueio à back migration de forma mais intensa. Esta perda de eficiência promove uma maior alcalinização do anólito, e consequentemente, um aumento nas velocidades das reações paralelas indesejáveis, como por exemplo, a formação de clorato. Uma vez formado clorato no compartimento anódico, sua percolação para o lado catódico é inevitável. Por essa razão, optou-se por fazer estudos de bancada do processo catódico, particularmente na região de RDH. Os dados de polarização revelaram a dependência da RDH em presença de clorato sobre o aço carbono SAE1020, atualmente empregado nas células industriais no processo de diafragma para produção de cloro-soda. Alternativamente ao SAE1020, foram estudadas as ligas duplex SAF2205, SAF2304 e SAF2507. Os estudos de polarização mostraram a dependência da RDH para as ligas SAF2304 e SAF2507, por outro lado, a liga SAF2205 apresentou resposta eletrocatalítica para o desprendimento de hidrogênio. Os estudos em célula piloto mostram que a queda de rendimento de produção é observada de forma mais imediata na parte anódica do processo, e fica evidenciada a importância de otimização do separador de diafragma. Nos experimentos de bancada foi constatada a influência do clorato sobre a RDH para o SAE1020, mostrando a necessidade de materiais alternativos que não apresentem susceptibilidade em presença de clorato.

This Master´s thesis deals with heterogeneous photochlorination of polyolefins and especially with the photochlorination of polypropylene itself. In the theoretical part the available information about properties, manufactory and application of chlorinated polyolefins, specifically polyethylene and polypropylene, is provided. The basic principles of the photochemistry are described, which are further applied to the issue of photochemistry chain reactions and photochemical halogenations, mainly photochlorinations. The practical part includes design and realization of few types of equipment for the heterogeneous photochlorination of polypropylene done at low temperatures (to 50° C) by gaseous chlorine in bulk or chlorine suspended in suspension of PP in CCl4. Series of chlorination was accomplished, which was varied in the type of PP, in the way of dosage Cl2 and in the period of high pressure mercury lamp irradiation (1–90 minutes). The chlorine content in prepared samples was determined by the gravimetry with ATR-FTIR spectroscopy, as well as by the Shöniger combustion method. Their accuracies were than compared. The chlorine content dependence on the period of chlorination and on the porosity of initial PP was established.

Die Pyrolyse ausgewählter Polysiloxane und Poly(chlor)silane erzeugt meso- und mikroporöses SiC, welches als Hochtemperatur-beständiges Material für Filter, Katalysatorträger und Sensoren ein hohes Anwendungspotential besitzt. Der Pyrolyseprozess bis 1500 °C wird thermogravimetrisch und massenspektrometrisch verfolgt und die resultierenden "Bulk"-Pyrolysate mittels DRIFT-Messungen, Elementaranalyse, XRD, N2-Adsorption und FESEM charakterisiert. Zusammensetzung, Kristallinität und Poreneigenschaften des precursorabgeleiteten SiC lassen sich über die Precursorart sowie über die Pyrolysetemperatur und -dauer steuern. Die Poren entstehen je nach Precursor zwischen 1200 und 1500 °C. Im Falle von mesoporösen Pyrolysaten wird die Porenbildung in erster Linie durch die Abgabe gasförmiger Reaktionsprodukte hervorgerufen. Die Porengrößen dieser Produkte liegen zwischen 6 und 12 nm und die spezifische Oberfläche beträgt bis zu 270 m2/g. Bei den mikroporösen Pyrolysaten, gekennzeichnet durch Poren von 1,5 nm Größe und spezifischen Oberflächen bis 530 m2/g, werden die Poreneigenschaften vor allem durch den im Überschuss vorhandenen elementaren Kohlenstoff geprägt.

Raman spectra of aqueous lanthanum perchlorate, triflate (trifluorosulfonate), chloride and nitrate solutions were measured over a broad concentration (0.121–3.050 mol Lˉ¹) range at room temperature (23 °C). A very weak mode at 343 cmˉ¹ with a full width at half height at 49 cmˉ¹ in the isotropic spectrum suggests that the nona-aqua La(III) ion is thermodynamically stable in dilute perchlorate solutions (∼0.2 mol Lˉ¹) while in concentrated perchlorate solutions outer-sphere ion pairs and contact ion pairs are formed. The La³⁺ nona-hydrate was also detected in a 1.2 mol Lˉ¹ La(CF₃SO₃)₃(aq). In lanthanum chloride solutions chloro-complex formation was detected over the measured concentration range from 0.5–3.050 mol Lˉ¹. The chloro-complexes in LaCl₃(aq) are fairly weak and disappear with dilution. At a concentration <0.1 mol Lˉ¹ almost all complexes disappeared. In LaCl₃ solutions, with additional HCl, a series of chloro-complexes of the type [La(OH₂)₉₋nCln]⁺³⁻ⁿ (n = 1–3) were formed. The La(NO₃)₃(aq) spectra were compared with a spectrum of a 0.409 mol Lˉ¹ NaNO₃(aq) and it was concluded that in La(NO₃)₃(aq) over the concentration range from 0.121–1.844 mol Lˉ¹, nitrato-complexes, [La(OH₂)₉₋n-(NO₃)n]⁺³⁻ⁿ (n = 1, 2) were formed. These nitrato-complexes are quite weak and disappear with dilution <0.01 mol Lˉ¹. DFT geometry optimizations and frequency calculations are reported for a lanthanumnona-hydrate with a polarizable dielectric continuum in order to take the solvent into account. The bond distances and angles for the cluster geometry of [La(OH₂)₉]³⁺ with the polarizable dielectric continuum are in good agreement with data from recent structural experimental measurements and high quality simulations. The DFT frequency of the La–O stretching mode at 328.2 cmˉ¹, is only slightly smaller than the experimental one.

6H-1,2-Oxazines were functionalised at the C-C double bond by 1,3-dipolar cycloadditions and halogenation reactions. The reactions were carried out with 6-ethoxy-3-phenyl-6H-1,2-oxazine, 6-ethoxy-3-ethoxycarbonyl-6H-1,2-oxazine and 6-ethoxy-3-trifluoromethyl-6H-1,2-oxazine. The cycloadditions of 6H-1,2-oxazines were performed with nitrile oxides, nitrile imines, nitrile ylides, diazoalkanes, azomethine ylides and a nitrone. High diastereoselectivity was observed, induced by the steric hindrance of the ethoxy group at the 6H-1,2-oxazines. The cycloadditions occur with high regioselectivity. In addition, the constitutions of the bicycles were predicted by the frontier-orbital model using the semi-empirical PM3-method, and subsequently compared with those of the isolated products. The low strength of the N-O bond of 1,2-oxazines can often be used for mild hydrogenolysis reactions, but the reductions of the biheterocycles obtained here were not selective and led in most cases to decomposition. For the derivatives of 3-ethoxycarbonyl-3a,7a-dihydro-4H-isoxazolo[5,4-d]-1,2-oxazine the conversion of the five-membered ring into cis-configurated &amp;amp;#945;-hydroxynitriles (saponification and decarboxylation) was demonstrated. Finally, the 4-chloro- and 4-bromo-6H-1,2-oxazines were prepared in good yields. Investigations with palladium catalysed coupling reactions were initiated. The halogen of 4-bromo-6H-1,2-oxazines was substituted by the phenyl group of benzolboronic acid using the Suzuki method. / Im Verlauf dieser Arbeit wurden 6H-1,2-Oxazine an der C-C-Doppelbindung durch 1,3-dipolare Cycloadditionen und Halogenierungen funktionalisiert. Als Modellsubstrate für die 6H-1,2-Oxazine wurden 6-Ethoxy-3-phenyl-6H-1,2-oxazin, 6-Ethoxy-3-ethoxycarbonyl-6H-1,2-oxazin und 6-Ethoxy-3-trifluormethyl-6H-1,2-oxazin eingesetzt. Die 6H-1,2-Oxazine konnten bei den Cycloadditionen erfolgreich mit Nitriloxiden, Nitriliminen, Nitrilyliden, Diazoverbindungen, Azomethinyliden und einem Nitron umgesetzt werden, wobei die Ausbeuten stark variieren. Die Reaktionen verliefen mit hoher Regioselektivität. Durch die sterische Abschirmung der Ethoxygruppe an den 6H-1,2-Oxazinen (Briefumschlagskonformation der 6H-1,2-Oxazine und pseudoaxiale Ausrichtung der Ethoxygruppe) wurde ebenfalls eine hohe Diastereoselektivität beobachtet. Ergänzend wurden die Konstitutionen der Cycloaddukte mit der semiempirischen PM3-Methode auf Basis des Grenzorbitalmodells vorhergesagt und mit denen der isolierten Biheterocyclen verglichen. Die dargestellten Cycloaddukte sollten unter Ausnutzung der geringen Bindungsenergie der N-O-Bindung hydrogenolysiert werden. Die Reduktionen waren jedoch im allgemeinen nicht selektiv, so daß die Umsetzungen zu komplexen Produktgemischen führten. Für die 3-Ethoxycarbonyl-3a,7a-dihydro-4H-isoxazolo[5,4-d]-1,2-oxazinderivate wurde ferner der Abbau des Fünfringes (Verseifung und Decarboxylierung) in cis-konfigurierte &amp;amp;#945;-Hydroxynitrile beschrieben. Die 4-Chlor- und 4-Brom-6H-1,2-oxazine konnten in guten Ausbeuten unter milden Reaktionsbedingungen dargestellt werden. Anschließend wurden mit den bromierten Verbindungen verschiedene palladiumkatalysierte Kupplungsreaktionen getestet. Durch die Methode von Suzuki konnte das Halogen der 4-Brom-6H-1,2-oxazine durch den Phenylrest der Benzolboronsäure substituiert werden.

Gegenstand der vorliegenden Arbeit sind Versuche zur Synthese von 1-Azido-1 alkinen (Ethinylaziden). Diese instabilen Verbindungen zersetzen sich leicht unter Stickstoffabspaltung zu hochreaktiven Carbenen, welche mit verschiedenen Reagenzien, explizit Tolan, Cyclooctin, DMSO sowie DMF, abgefangen werden konnten. Obwohl eine direkte spektroskopische Beobachtung der Titelverbindungen mittels Tieftemperatur-NMR-Spektroskopie nicht verwirklicht werden konnte, gelang der eindeutige Nachweis von Ethinylaziden via deren 1,3-dipolarer Cycloaddition mit dem hochgespannten cyclischen Alkin Cyclooctin. Als Strategie für die Synthese der Titelverbindungen wurden sowohl Substitutionsreaktionen ausgehend von (Chlorethinyl)aromaten als auch Eliminierungsreaktionen ausgehend von substituierten Vinylaziden herangezogen. Es konnten zahlreiche Sulfoxonium-Ylide sowie alpha-Oxocarbonsäureamide als eindeutige Folgeprodukte der Titelverbindungen isoliert und vollständig – größtenteils sogar anhand von Röntgeneinkristallstrukturanalysen – charakterisiert werden.