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Many important atmospheric processes are determined by the chemical composition of aerosols, including organic material. Dicarboxylic acids are a commonly detected class of organic material in urban, rural, and remote sites across the globe. Understanding the surface behavior of these molecules is imperative in characterizing the atmospheric fate of these molecules in aerosols, especially at an aerosol surface. In fact, little is known about their orientation, solvation, or pH dependence. This dissertation explores in molecular level detail the concentration and pH behavior of low molecular weight dicarboxylic acids at the air/water interface, which is used as a model for an aerosol surface. The solvation of the carboxylic head groups is shown to be dependent upon the length of the alkyl backbone. Indeed, the solvation of the head groups changes dramatically from very weakly solvated to typical surface solvation to near bulk solvation as the backbone increases. The orientation and conformation at the surface is fully explored to explain these differences in solvation. The pH dependence of surface adsorption is characterized, and it is shown that some acids are only surface active if they are fully protonated while others may still be surface active in singly or fully deprotonated forms. Using a combination of vibrational sum frequency spectroscopy (VSFS), surface tension, and computational modeling, the behavior at the air/water interface of four of the most relevant surface-active dicarboxylic acids (malonic, succinic, glutaric, and adipic acid) is completely described. VSFS, a surface specific optical technique, provides details about the solvation, orientation, and number density at the surface while surface tension measurements provide corollary information about the surface density. The use of computational modeling aids and confirms the spectral analysis while also providing molecular level details about the surface adsorption of the acids studied. By investigating the concentration and pH dependence of these molecules, molecular level detail is obtained which enables a complete description of these acids at an air/water interface and provides pertinent surface information on these atmospherically important organic molecules. This dissertation includes both previously published and unpublished co-authored material.

Quantum chemistry has nowadays become a powerful and efficient tool that can be successfully used for studies of biosystems. It is therefore possibleto model the enzyme active-site and the reactions undergoing into it, as well as obtaining quite accurate energetic profiles. Important conclusions can be drawn from such profiles about the  plausibility of different putative mechanisms. Density Functional Theory is used in the present thesis for investigation of the catalytic mechanism of dioxygenase metallo-enzymes and synthetic model complexes. Three enzymes were studied – Homoprotocatechuate 2,3-dioxygenase isolated from Brevibacterium fuscum (Bf 2,3-HPCD), Manganese-Dependent Homoprotocatechuate 2,3-Dioxygenase (MndD) and Homogentisate Dioxygenase (HGD). Models consisting of 55 to 208 atoms have been built from X-ray crystal structures and used in the calculations. The computed energies were put in energy curves and were used for estimation of the feasibility of the suggested reaction mechanisms. A non-heme [(L4Me4)Fe(III)]+3 complex that mimics the reactivity of intradiol dioxygenases, and a heme [T(o-Cl)PPFe] complex catalyzing the stepwise oxidation of cyclohexane to adipic acid, were also studied. For the enzymes and the non-heme biomimetic complex the reaction was found to follow a mechanism that was previously suggested for extradiol and intradiol dioxygenases – ordered substrates binding and formation of peroxo species, which further undergoes homolytic O-O bond cleavage. Different reaction steps appear to be rate limiting in the particular cases: proton transfer from the substrate to the peroxide in Bf 2,3-HPCD, the formation of the peroxo bridge in HGD and the biomimetic complex, and notably, spin transition in MndD. The catalytic oxidation of cyclohexane to adipic acid in the presence of molecular oxygen as oxidant was studied, a reaction of great importance for the chemical industry. Reaction mechanism is suggested, involving several consecutive oxidative steps. The highest calculated enthalpy of activation is 17.8 kcal/mol for the second oxidative step. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: In progress, Paper 5: In progress

Orientador: Osvaldir Pereira Taranto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T05:10:47Z (GMT). No. of bitstreams: 1 Ribeiro_MarinadosSantos_M.pdf: 1906759 bytes, checksum: 068fcf7b154ad2dedadfc296efb7fbde (MD5) Previous issue date: 2005 / Resumo: O leito fluidizado pulsado rotativo (LFPR) tem sido estudado como uma alternativa para a fluidização de materiais que são difíceis de processar em leito fluidizado convencional (LFC). O LFPR é um leito fluidizado convencional modificado pela adição de um disco rotativo com uma abertura 60º abaixo do distribuidor. O disco rotativo assegura uma alimentação cíclica do gás no leito, fornecendo uma força extra para fluidizar as partículas. Tal característica torna o LFPR atrativo para o uso no processo de secagem, pois realça a transferência de calor e massa. No entanto, a freqüência da pulsação do gás no interior do leito depende da freqüência de rotação do disco. O objetivo deste trabalho foi estudar o comportamento fluidodinâmico de partículas secas e úmidas em um LFPR e compará-lo com os resultados obtidos em um LFC. As partículas selecionadas para o estudo foram celulose microcristalina e ácido adípico, e os parâmetros estudados foram: a carga da partícula, a freqüência de rotação do disco e o teor de umidade inicial. Verificou-se que em freqüência da rotação do disco baixa, jorros alternados se formaram, alternado com as regiões de leito fixo. Quando a freqüência da rotação do disco era elevada, o sistema todo fluidizou de uma maneira similar a um leito fluidizado convencional. Constatou-se que pode-se empregar o LFPR para processar materiais que apresentam características coesivas em condições inviáveis em LFC. A velocidade mínima de fluidização para o LFPR foi menor do que a obtida para o LFC, o que evidencia as condições mais fáceis de fluidização no primeiro equipamento e sua aplicabilidade ao processo de secagem / Abstract: The rotating-pulsed fluidized bed (RPFB) has been studied as an alternative for fluidization of materials that are difficult to operate in the Conventional Fluidized Bed (CFB). The RPFB apparatus is a conventional fluidized bed modified by the addition of a rotating plate with a 60º opening just below the distributor. The rotating plate insures a cyclic feed of the fluidizing gas into the bed, providing an extra force to fluidize the particles. This characteristics becomes the RPFB attractive for use in drying process, enhancing heat and mass transfer. In this way, the frequency of pulsed gas purges in the bottom of the bed depends upon the frequency of the rotating disk. The objective of this present work was to study the fluid dynamic behavior of both dry and moist particulate samples in a RPFB and compare with the results from a CFB. Selected samples were microcrystalline cellulose and adipic acid. The parameters used for the study were: particle load, disc rotation frequency and initial sample moisture content. It was possible to verify that when the disk rotation frequency was low, rotating spouts were formed, alternated with fixed bed regions. When disk rotation frequency was high, the total system was fluidized in a manner similar to a conventional fluidized bed. It was observed the RPFB can be used to material with cohesive characteristics, this conditions is not usual to CFB. The minimum fluidization velocity for the RPFB was lower than that for the CFB, which evidences the easier fluidization conditions in the first apparatus and its applicability to drying process / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / Strict environmental regulation on flue gas emission has led to the implementation of FGD technologies in power stations. Wet FGD technology is commonly used because it has high SO2 removal efficiency, high sorbent utilization and due to availability of the sorbent (limestone) used. SO2 is removed by passing flue gas through the absorber where it reacts with the slurry containing calcium ions which is obtained by dissolution. This study presents the findings of the dissolution of a calcium-based material (limestone) for wet FGD process. This was done using a pH stat apparatus and adipic acid as acid titrant. Adipic acid was used because of its buffering effect in wet FGD process. The conditions used for this study are similar to what is encountered in a wet FGD process. The extent of dissolution was determined by analyzing the amount of calcium ions in solution at different dissolution periods. The dissolution kinetics were correlated to the shrinking core model and it was found out that chemical reaction at the surface of the particle is the rate controlling step. This study also investigated the dissolution of coal fly ash and bottom ash. Their dissolution kinetics showed that the diffusion through the product layer was the rate controlling step due to an ash layer formed around the particle. The formation of ash layer was attributed to pozzolanic reaction products which is calcium-alumino-silicate (anorthite) compounds were formed after dissolution. The effect of fly ash on the dissolution of rate of limestone was also studied using response surface methodology. Limestone reactivity was found to increase with increase in the amount of fly ash added and the pH was found to be strong function of the rate constant compared to other dissolution variables. The presence of silica and alumina in fly ash led to a significant increase in the specific surface area due to hydration products formed after dissolution. / Eskom