A new treatment technology, called Advanced Reduction Process (ARP), was developed by combining UV irradiation with reducing reagents to produce highly reactive species that degrade contaminants rapidly. Vinyl chloride (VC) and 1,2-dichloroethane (1,2-DCA) pose threats to humans and the environment due to their high toxicity and carcinogenicity. In this study, batch experiments were conducted under anaerobic conditions to investigate the degradations of VC and 1,2-DCA with various ARP that combined UV with dithionite, sulfite, sulfide or ferrous iron. Complete degradation of both target compounds was achieved by all ARP and the reactions were found to follow pseudo-first-order decay kinetics. The effects of pH, sulfite dose, UV light intensity and initial contaminant concentration on the degradation kinetics were investigated in the photochemical degradation of VC and 1,2-DCA by the sulfite/UV ARP. The rate constants were generally promoted by raising the solution pH. The optimal pH conditions for VC and 1,2-DCA degradation were pH 9 and pH 11,respectively. Higher sulfite dose and light intensity were found to increase the rate constants linearly for both target contaminants. A near reciprocal relation between the rate constant and initial concentration of target compounds was observed in the degradation of 1,2-DCA. The rate constant was observed to be generally independent of VC concentration, but with a slight increase at lower concentrations. A degradation mechanism was proposed that described reactions between target contaminants and reactive species such as the sulfite radical and hydrated electron that were produced in the photolysis of sulfite solution. A mechanistic model that described major reactions in the ARP system was developed and explained the dependence of the rate constant on those experimental factors. Chloride ion and chloroethane were detected as the major degradation products at acid and neutral pH. An increase in pH promoted the extent of dechlorination with complete dechlorination being observed at pH 11 for both VC and 1,2-DCA. Due to the rapid degradation kinetics in these ARPs, this new treatment technology may be applied to remove various contaminants in water and wastewater.

Orientador: Pedro Luiz Onófrio Volpe / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T00:32:39Z (GMT). No. of bitstreams: 1 Perles_CarlosEduardo_D.pdf: 6498150 bytes, checksum: 75103c2ae445898658bf6015728f7fbe (MD5) Previous issue date: 2010 / Resumo: A idéia do trabalho desenvolvido surgiu da observação causal de um fenômeno, no qual partículas de sílicas amorfas eram arrastadas paralelamente às linhas de um campo elétrico DC ao qual esse material foi submetido. É um estudo inédito, não havendo nenhum relato na literatura, de forma que todo o instrumental foi exclusivamente projetado e montado em laboratório para possibilitar o desenvolvimento do trabalho proposto. Realizou-se um estudo científico completo do fenômeno observado, com a seguinte seqüência: observação do fenômeno proposição de modelo exploração do potencial de aplicação. As primeiras observações permitiram concluir que o arraste das partículas de sílica gel ao longo do campo elétrico só ocorria quando as partículas estavam hidratadas e que cargas elétricas eram ¿armazenadas¿ sobre essas partículas até atingirem um valor crítico no qual a força eletrostática agindo sobre elas superava as forças opostas (gravitacional e capilar). O fluxo de partículas entre os dois eletrodos gerava uma corrente elétrica através do sistema. Observações posteriores indicaram que, embora o filme de água superficial fosse essencial para a ocorrência do fenômeno, a taxa de transporte de cargas aumentava até determinado ponto com a diminuição da camada de hidratação. Resultados indicaram que não havia evidências de processos faradaícos ocorrendo, sugerindo que o fenômeno ocorre por injeção de elétrons diretamente na banda de condução do filme de água organizado sobre a sílica, com a formação de hidratos eletrônicos. Observações experimentais sob desidratação gradual dessas partículas, permitiram o estabelecimento de relações quantitativas entre os parâmetros obtidos das curvas experimentais e propriedades superficiais da sílica, como área específica, sugerindo o potencial de aplicação do fenômeno numa possível técnica analítica / Abstract: This work was developed based on a casual observation of an electrostatic phenomenon, in which particles of amorphous silica were dragged by a DC electric field in which that material was submitted. It is a study without absolutely any report in the literature and, thus, all the necessary instrumental was exclusively projected and assembled in the laboratory to make possible the development of this project. In this work a complete scientific study was performed to understand this phenomenon, following the sequence: phenomenon observation proposal of model exploration of the application potential. The first experimental data allowed to conclude that only hydrated silica particles are dragged by the electric field and that electric charges were stored on those particles until a value in wich the electric force overcame the opposite forces acting on the particles (gravitational and capillary). This flow of particles between the two metallic electrodes generates, in the system, an electric current. Subsequent experimental experiments confirmed that the superficial water layer was essential for the occurrence of the phenomenon, however, but the capacity to transport the charges increased with the decrease of the hydration layer. It was also possible to conclude that there are no evidences of redox reactions happening, indicating that the phenomenon occurs due the injection of electrons in the conduction band of the structured water film on the silica surface, by forming hydrated electrons (H2O)n -. The obtained data of the curves of electric current vs. time during gradual dehydration (flow of dry air 1 L min) allowed to establish quantitative relationships between obtained parameters of the experimental curves and the silica surface properties, as specific area, indicating a strong potential of application of this phenomenon in analytical techniques / Doutorado / Físico-Química / Doutor em Ciências