Selenium (Se) is a trace element essential to the nutrition of animals. On the other hand, in a narrow concentration range, Se can cause toxicity. The presence of Se in food is related to the concentration of the element in soil. Thus, the knowledge of the Se amount and its behavior in soil are very important to the better manage the environment and to prevent toxicological problems and human deficiency. The objectives of this study were: (i) to quantify the natural content of Se in some Brazilian soils and correlates them with soil attributes; (ii) to evaluate the adsorption of selenite and selenate as a function of pH and Se concentration in tropical soils; (iii) to adjust the constant capacitance model to describe the Se adsorption in tropical soil as compared to empiric models. Se concentrations ranged from <0.08 to 1.61 mg kg-1, with a mean of 0.19 mg kg-1. Concentrations of Se in the samples collected in the superficial layers were positively correlated to cationic exchange capacity, as well as to clay, organic matter and oxide contents of the soils. In the subsurface samples, only pH and aluminum oxide content were correlated with Se concentrations. Most samples with the highest Se concentrations were derived from sedimentary parent material. Se(IV) adsorption was high for all soils, decreased with increasing pH and was strongly correlated to organic matter and Fe and Al oxides contents. On the other hand, Se(VI) adsorption was very low at pH values commonly found in agricultural soils, except for the highly weathered Rhodic Acrudox which was positively correlated with the gibbsite content. The constant capacitance model fit the Se(IV) and Se(VI) adsorption data well, and was similar to Langmuir and Freundlich empirical models. Optimizations of mono and bidentate complexation and surface protonation constant were used for the Se(IV) adsorption data. For Se(VI), optimizations for the two monodentate species were employed. / O selênio (Se) é um elemento traço essencial a nutrição animal. Por outro lado, o limiar de concentração entre suficiente e tóxico é estreito. A presença de Se nos alimentos está relacionada à sua concentração no solo. Deste modo, conhecer a quantidade e o comportamento do Se no solo é muito importante para um correto manejo ambiental, previnindo problemas toxicológicos e deficiência em humanos. Os objetivos deste estudo foram: (i) quantificar os conteúdos naturais de Se em solos brasileiros e correlacioná-los com seus atributos; (ii) avaliar a adsorção de selenito e selenato em função da variação do pH e da concentração de Se em solos tropicais; (iii) ajustar o modelo de capacitancia constante para descrever a adsorção de Se em solos tropicais comparado a modelos empíricos. As concentrações de Se variaram de <0,08 - 1,61 mg kg-1, com média de 0,19 mg kg-1. As concentrações de Se nas amostras coletadas nas camadas superficiais do solo foram positivamente correlacionadas com a capacidade de troca catiônica, bem como os teores de argila, matéria orgânica e óxidos de Fe e Al do solos. Nas amostras subsuperficiais, apenas pH e teor de óxido de alumínio foram correlacionadas com as concentrações de Se. A maioria das amostras com maiores concentrações de selênio foram provenientes de material de origem sedimentar. A adsorção de Se(IV) foi elevada para todos os solos, diminuiu com o aumento do pH e foi fortemente correlacionada com teores de matéria orgânica e de óxidos de Fe e de Al. Por outro lado, a adsorção de Se(VI) foi muito baixa em valores de pH normalmente encontrados em solos agrícolas, excepto para o Latossolo Vermelho acriférrico, que foi positivamente correlacionada com o teor de gibbsita dos solos. O modelo de capacitância constante ajustou-se bem aos resultados de adsorção Se(IV) e Se(VI), com ajuste similar aos modelos empíricos de Langmuir e de Freundlich. Para os resultados de adsorção de Se(IV) foram utilizadas otimizações das constantes de complexação mono e bidentadas e da constante de protonação de superfície. Para Se(VI), foram empregadas otimizações para as duas espécies de monodentadas.

Les systèmes à base de biopolymères à faible teneur en humidité sont couramment rencontrés dans les aliments. Bien entendu, il est primordial de comprendre les bases physiques de leur qualité: texture, performances dans le temps ou en fonction de leur composition. Le vieillissement physique des systèmes composites rend les changements survenant dans le stockage des produits comestibles difficiles à prévoir. Les objectifs de ce travail étaient d'évaluer l'incidence de la présence de saccharose et de la teneur en eau de fabrication sur les propriétés physico-chimiques du produit fini. La stabilité physique de ces matériaux a été contrôlée grâce à une étude à différentes échelles moléculaires. Ensuite, les relations entre les données multi-échelles ont été examinées. L'effet du saccharose (0 à 20%) et de l'eau d'alimentation (10 et 15%) sur les mélanges d'extrusion a été étudié à l'aide d'un extrudeur double vis conduit dans les mêmes conditions. Les propriétés physiques et microstructurales des produits extrudés expansés ont été examinées sous diverses conditions d'humidité relative. La réduction des teneurs en sucre et en eau d’alimentation a fait augmenter la pression et l’énergie mécanique spécifique, ce qui a réduit la dégradation de l’amidon et augmenté la viscosité dans l’extrudeur en particulier à la teneur en eau la plus élevée. L'augmentation de la pression dans l’extrudeur a entraîné une expansion plus importante des extrudés. Par contre, la technique d'imagerie neutronique montré que le saccharose réduisait la taille des pores, et donc augmentait la densité apparente et ce qui était particulièrement évident en utilisant. Cette technique a été appliquée pour la première fois sur des produits extrudés. Les images de tomographie 2D ont indiqué des différences structurelles internes entre les extrudés à différentes teneurs en saccharose et stockés à humidité relative différente. Toutefois, l'analyse d'images 3D a montré que l'impact de ces facteurs sur la distribution de la taille des pores et le taux de porosité n'était pas significatif. En fin d'extrusion, les échantillons étaient à l'état amorphe à la suite de la gélatinisation de l'amidon et de la fonte du sucre. Leursrs propriétés thermiques ont été analysées par analyse enthalpique différentielle (AED) et les températures e transition vitreuse ont été étudiées. Les thermogrammess d’AED ont été minutieusement étudiés via une déconvolution de la dérivée première de la variation d’enthalpie. Cette approche a mis en évidence que les systèmes composites étudiés présentaient des phases multiples avec des transitions vitreuses distinctes. Ces dernières sont associées à une phase riche en polymère (amidon principalement) et / ou à une phase riche en plastifiant (sucre) dont le comportement dépendait de la teneur en eau de l'échantillon. Les isothermes de sorption ont montré qu’aux faibles Aw et pour une valeur donnée, a la teneur en eau des extrudés diminuait avec l’augmentation des teneurs en saccharose et que l'effet inverse était observé aux aw élevées. L’étude de la cinétique apparente de lala diffusion de l'eau a mis en évidence deux sites de sorption différents. Le premier est caractérisé par une cinétique quasi constante qui pourrait correspondre à un phénomène d'adsorption à la surface. Le second site présente d’abord un ralentissement initial de la cinétique de sorption, tandis qu’une forte augmentation est constatée lorsque la teneur en eau était plus élevée. Ce comportement peut être lié à un effondrement de la structure. Une étude par RMN à cyclage de champ rapide à basse fréquence a montré que les temps de relaxation dépendaient de la teneur en saccharose et en eau. Une carte de stabilité a été tracée pour modéliser les évolutions rhéologiques des matrices avec la teneur en eau en lien avec les transitions de phases des matériaux (...). / Low-moisture biopolymer-based systems are commonly encountered in food. Obviously, understanding the physical basis of their quality: e.g texture, or performance over time or as a function of their composition is of primary importance. The objectives of this work were to evaluate how the presence of sucrose and water content affects physico-chemical properties. The physical stability of these materials were monitored through an insight at different molecular scales. Then the relations between the multi-scale studies were investigated. The effect of sucrose (0–20%) and feed water (10 and 15%) on extrusion blends was studied using a twin screw extruder under the same processing settings. The physical and microstructural properties of extruded products were examined at various RH. Reducing both sugar levels and feed water increased die pressure and specific mechanical energy, as a consequence, it reduced starch degradation and increased in viscosity. The effect was more pronounced with increasing feed water content. The increased die pressure resulted in higher expansion of the porous extrudates. Sucrose was shown to increase the bulk density and reduce the pore size, this was particularly evident by using neutron imaging technique. This technique was applied for the first time in extrudate. 2D tomography images indicated internal structural differences between extrudates containing different sucrose content and stored at low and high % RH, while 3D image analysis showed impact of these factors on pore size distribution and % porosity were not significant. The extruded samples were in the amorphous state as a result of starch gelatinization and sugar melting. Their thermal properties were analyzed with DSC and their Tg were studied. The DSC thermograms were thoroughly studied through a Gaussian deconvolution of the first derivative of their heat low. This approach evidenced a multiple phase behavior with different glass transitions in composite systems. They were associated with either a polymer-rich phase and/or a plasticizer-rich phase which behavior depended on the sample water content. Physical aging accompanied with an increase in rigidity at low aw, resulted in an increased bulk density and more pronounced with increasing sucrose content. Sorption isotherms showed the water content of extrudates decreased when product contains high sucrose at low aw range and the inverse effect was observed at high aw. Apparent kinetics of water diffusion showed two different sorption sites, the first kinetics was almost constant and could be adsorption phenomena at the surface. The second one reflected first an initial slowing in dynamics whereas a sharp increase was found at higher water content. Addition of sucrose or water decreased both Tgs in extrudates. Young's modulus showed water acts as anti-plasticizer at low aw, while it shows a plasticizing effect at high aw. A stability map can explain the brittle-ductile transition occurred below Tg. Fast field cycling NMR study at low frequency highlighted that T1 depended on sucrose and water content. T1 and T2 measured using Low field NMR decrease as a function of water content, while the impact pf sucrose were not significant. T2 showing a minimum probably indicating the exchange of protons of water and macromolecules in composite system. The impact of sucrose content was not significant for T1 and for T2 at low water content. FFC NMR showed T1 results consistent with the LF NMR measurement.In conclusion, physicochemical studies of the influence of water and sucrose content on glassy materials showed that the material properties can be investigated at different levels from the macro- to the microscopic scale and these results clearly presented the need for complementary techniques to probe the dynamics in the glassy state of heterogeneous food systems that could be facilitated to manage the stability during storage of this type of dry products.

Svenska Aerogel AB has developed the material Quartzene® which is of the typeprecipitated silica and contains calcium - magnesium silicate ((Ca, Mg) SiO3). Thematerial is used for molecular filtration of contaminated air. Qartzene™, which is inpellet form, is porous and has a high internal surface which is a requirement for themolecular filtration. With the use of various impregnations, filtration can affect thedesired outcome. As an example Quartzene® can be impregnated with Potassiumhydroxide and clear the air of Sulfur dioxide, SO2 (Svenska Aerogel AB, n.d).Svenska Aerogel AB has developed Quartzene® further and new areas of application hasarosee, one of these areas is how the material function within dehumidification. Thepurpose of this study is to research and analyze how different impregnation salts effecthow Quartzene® function in terms of moisture absorption and moisture desorption.Quartzene® is a hygroscopic material, which is a material that easily absorbs and exudatesmoisture from the air. Materials with high porosity absorb moisture by adsorption andcapillary condensation. A hygroscopic material strives for equilibrium with ambientenvironment which is illustrated in a sorption curve where moisture absorption is set inrelation to relative humidity. In this study the jar method is used to measure moistureabsorption, this is shown with the use of sorption curves. The jar method uses saturatesalt solutions to create environments whit a set relative humidity. Quartzene® – pellets areplaced in jars and weighed at regular intervals to determine the moisture absorption.The results of this study indicate that impregnations affect the way that Quartzene®function in terms of moisture absorption and moisture desorption. Some of theimpregnations affect the material to absorb more moisture than Quartzene® that has notbeen impregnated, while others affect the material to absorb less moisture. The resultsalso show that sodium – based impregnation gives similar results as Quartzene® that hasnot been impregnated.

The aim of this study was to determine the adsorption capacity of activated carbon and organo-zeolites for removal of pesticides in water. In order to prepare organo-zeolite, two kinds of cationic surfactants, namely, hexadecyltrimethyl ammonium bromide (HTAB) and dodecyltrimethyl ammonium bromide (DTAB) were used. Adsorption studies of cationic surfactant on zeolite were investigated in respect to initial concentration of cationic surfactant, time, and temperature. It has been found that the best fitted isotherm equation was Langmuir equation. The observed adsorption rates were found to be equal to the second order kinetic model. The activation energies of cationic surfactant adsorption was determined by using Arrhenius equation.

<p>Nicaragua is a country in which the toxic metal contamination of freshwater resources has become an increasingly important problem in certain regions posing a threat to the environment as well as to human health. Among the metals found in the waters of Nicaragua, arsenic is one of the most problematic since its long time consumption is connected to serious health problems such as cancer and neurological disorders. The arsenic contamination of water recourses in Nicaragua is mostly attributable natural factors, even though anthropogenic activities including gold mining may be a contributing factor.</p><p>In this work the biopolymer Chitosan was studied as a potential adsorption material for the removal of arsenic from aqueous solutions for water treatment design purposes.</p><p>The Chitosan used in this study was extracted from shrimp shells with an overall yield of 40% and a deacetylation grade of 59%. The maximum adsorption capacity was determined to 20.9 mg As/g at a controlled pH of 5.5 using the Langmuir isotherm. The adsorption was found to be strongly pH dependant with a fourfold increase in adsorption capacity when pH was well under the pKa of Chitosan. The pH dependence indicates that ionic exchange was the most important mechanism. No difference in adsorption capacity with respect to the initial pH of the solution was detected in the pH range 3-7. This was attributed to the ability of Chitosan to act as a weak base in water solutions.</p><p>The arsenic was desorbed from Chitosan using NaOH, (NH4) 2SO 4 and NaCl, with a 1M NaOH solution being the most efficient displaying a concentration ratio of 1.08. The NaOH and (NH4) 2SO 4 solutions displayed a steep desorption curvature with a large fraction of the arsenic being easily desorbed. The arsenic was, however, not completely desorbed from the Chitosan implying that the adsorption capacity would decrease for the coming cycles. Being a biopolymer the Chitosan is quite easily degraded in acid and alkali solutions, which might be a limiting step for the process applicability.</p>

A return-period analysis of annual peak spring break-up and open-water levels for 136 Water Survey of Canada hydrometric stations was used to classify rivers across Canada and to assess the physical controls on peak break-up water-levels. According to the peak water-level river-regime classification and subsequent analysis, 32% of rivers were classified as spring break-up dominated, characterized by low elevations and slopes and large basin sizes while 45% were open-water dominated and associated with alpine environments of high elevations and channel slopes, and smaller basin sizes. The remaining 23% of rivers were classified as a mixed regime. A spatial and temporal analysis (1969-2006) of the river ice break-up season using hydrometric variables of timing and water levels, never before assessed at the northern Canada-wide scale, revealed significant declines in break-up water levels and significant trends towards earlier and prolonged break-up in western and central Canada. The spatial and temporal influence of air temperature on break-up timing was assessed using the spring 0°C isotherm, which revealed a significant positive relationship but no spatial patterns. In the case of major ocean/atmosphere oscillations, significant negative (positive) correlations indicate that break-up occurs earlier (later) during the positive phases of the Pacific North American Pattern (El Niño Southern Oscillation) over most of western Canada. Fewer significant positive correlations show that break-up occurs later during the positive phases of the Arctic Oscillation and North Atlantic Oscillation in eastern Canada. / Graduate

Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2017-11-09T18:52:41Z No. of bitstreams: 2 Dissertação - Mário Nogueira Ferreira - 2017.pdf: 2817458 bytes, checksum: 535476b53a39b1dd6638afd630c66c93 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-11-13T12:09:24Z (GMT) No. of bitstreams: 2 Dissertação - Mário Nogueira Ferreira - 2017.pdf: 2817458 bytes, checksum: 535476b53a39b1dd6638afd630c66c93 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-11-13T12:09:24Z (GMT). No. of bitstreams: 2 Dissertação - Mário Nogueira Ferreira - 2017.pdf: 2817458 bytes, checksum: 535476b53a39b1dd6638afd630c66c93 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-05-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The objective of this work was to characterize the pulp + jabuticaba shell, the foams of the formulations (F1, F2, F3, F4) and the pulp + jabuticaba shell powder by the foam layer method. It was used jabuticaba of the variety M. cauliflora sp (jabuticaba sabará), harvest 2016. The pulp + jabuticaba bark were characterized as centesimal composition, hydrogenation potential, total titratable acidity, total soluble solids, energy value, water activity and color (a*, b *, L *, h * and C *). The foam was characterized regarding density, the percentage of expansion, stability, and fraction of drained volume, drying curves and mathematical modeling. The pulp + bark of jabuticaba powder was also characterized for the adsorption isotherm, scanning electron microscopy (SEM), antioxidant potential by the DPPH method, ABTS and FRAP, total phenolics, condensed and hydrolyzed tannins, absorption indexes and solubility in water (AI/SW) and milk (IAL / ISL) and oil absorption index (OAI). It was observed that the moisture content, SST, pH, acidity, water activity and color did not change, while all other analyzes were influenced. Formulation F3 was the one that best fit the foam evaluation criteria. The model of Wang and Singh presented the lowest reduced chi-square (χ²) and the highest coefficients of determination (R²), whereas the Page model obtained higher values for the drying rate and lower values for the internal resistance to the formulation F3. It was verified that the formulation F3 presented greater reduction of the moisture ratio as a function of time compared to the other formulations during processing. Therefore, a model can be adjusted in certain bands and not in others, which limits the application of empirical models. The results obtained in this study demonstrate that the pulp foam drying + jabuticaba bark can make a promising alternative in the post harvest of this important fruit since it allows the retention of nutritional components of interest in this product and thus increases the consumption Of this product in powder form. / Objetivou-se com este trabalho caracterizar a polpa+casca de jabuticaba, as espumas das formulações (F1, F2, F3, F4) e da polpa+casca de jabuticaba em pó pelo método de camada em espuma. Utilizou-se jabuticaba da variedade M. cauliflora sp (jabuticaba sabará), safra 2016. A polpa+casca de jabuticaba foram caracterizadas quanto à composição centesimal, pH, acidez total titulável, sólidos solúveis totais, valor energético, atividade de água e cor (a*, b*, L*, h* e C*). A espuma foi caracterizada quanto à densidade, percentual de expansão, estabilidade e fração do volume drenado, curvas de secagem e modelagem matemática. A polpa+casca de jabuticaba em pó foi caracterizada também quanto à isoterma de adsorção, microscopia eletrônica de varredura (MEV), capacidade antioxidante pelo método de DPPH, ABTS e FRAP, fenólicos totais, taninos condensados e hidrolisáveis, índices de absorção e solubilidade em água (IAA/ISA) e em leite (IAL/ISL) e índice de absorção em óleo (IAO). Observou-se que os teores de umidade, SST, pH, acidez, atividade de água e cor não sofreram alterações, enquanto que todas as demais análises foram influenciadas. A formulação F3 foi a que se enquadrou melhor nos critérios de avaliação das espumas. O Wang e Singh foi o que apresentou os menores qui-quadrado reduzido (χ²) e os maiores coeficientes de determinação (R²), já o modelo de Page obteve maiores valores para a taxa de secagem e menores valores para a resistência interna para a formulação F3. Verificou-se que a formulação F3 apresentou maior redução da razão de umidade em função do tempo comparado com as demais formulações durante o processamento. Portanto, um modelo pode-se ajustar em determinadas faixas e não em outras, o que limita a aplicação de modelos empíricos. Os resultados obtidos neste estudo demonstram que a secagem em camada de espuma de polpa+casca de jabuticaba pode tornar uma alternativa promissora na pós-colheita dessa importante fruta, uma vez que, possibilita a retenção de componentes nutricionais de interesse neste produto e assim aumenta o consumo deste produto na forma de pó.

Made available in DSpace on 2016-08-19T12:56:32Z (GMT). No. of bitstreams: 1 Rosiane Silva Penha.pdf: 1185030 bytes, checksum: 1245e0f7f26361b970082d5de61de02b (MD5) Previous issue date: 2009-01-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Adsorption of some metal ions (Co2+, Ni2+, Cu2+ e Zn2+) from aqueous solutions (pH 5.0) onto in nature rice husk (0.088 <  < 0.177 mm) was investigated. All experiments were conducted by the batch adsorption techniques at room temperature (28  1°C) and under constant stirring. The adsorption amounts were determined using atomic absorption spectroscopy. The Adsorption data were studied using two well-known adsorption models: Langmuir and Freundlich. The results showed that the metal ions uptake processes mediated by rice husks were fitted Freundlich isotherm model, suggesting that all adsorptions are governed by weak electrostatic interactions. According to the equilibrium studies, the selectivity sequence can be given as: Ni2+ (0.08 mmol g-1) < Co2+ (0.16 mmol g-1) < Zn2+ (0.40 mmol g-1) < Cu2+ (0.89 mmol g-1). This result showed that natural rice rusk holds good potential to remove such metal ions from wastewater. The effect of chemical pretreatment of rice husk on adsorption was also investigated. In nature rice husk (IN) was pretreated with phosphoric acid (AF); phosphoric acid and urea (AFU) and sodium metaperiodate (MP). AFU was the best adsorbent for all metal ions investigated [Ni2+ (0,96 mmol g-1) < Cu2+ (1,20 mmol g-1) < Co2+ (1,59 mmol g-1) < Zn2+(1,80 mmol g-1)]. In addition, in nature rice husk was characterized by chemical-bromatological analyses (humidity, ash, protein, carbohydrate, starch, lipid and fibers), scanning electron microscopy, solid-state 13C NMR and specific BET surface area. Some properties of in nature and pretreated samples were studied by infrared spectroscopy, thermogravimetric analysis, X-ray diffractometry, and elemental analyses. The results showed only marginal changes among them. / Investigou-se a adsorção de alguns íons de metais (Co2+, Ni2+, Cu2+ e Zn2+) a partir de soluções aquosas (pH 5,0), em casca de arroz in natura (IN) (0,088 <  < 0,177 mm). Todos os experimentos foram conduzidos em batelada, a temperatura ambiente (28  1°C) e sob agitação constante. Dois modelos de isotermas foram aplicados aos resultados experimentais: o de Langmuir e o de Freundlich. Os resultados mostraram que as adsorções seguem o modelo da isoterma de Freundlich. De acordo com os estudos de equilíbrio, a seletividade observada para a matriz in natura foi: Ni2+ (0,08 mmol g-1) < Co2+ (0,16 mmol g-1) < Zn2+ (0,40 mmol g-1) < Cu2+ (0,89 mmol g-1). Este resultado mostrou que a matriz tem bom potencial para remover os íons citados de efluentes aquosos. O efeito do pré-tratamento químico na casca de arroz foi também investigado a fim de melhorar a capacidade de adsorção da casca de arroz. A matriz in natura foi tratada com ácido fosfórico (AF), ácido fosfórico e uréia (AFU) e metaperiodato de sódio (MP). Dentre os adsorventes examinados, AFU foi o que melhor adsorveu todas as espécies de íons de metais investigadas [Ni2+ (0,96 mmol g-1) < Cu2+ (1,20 mmol g-1) < Co2+ (1,59 mmol g-1) < Zn2+(1,80 mmol g-1)]. A matriz IN foi caracterizada por análise bromatológica (umidade, cinzas, proteínas, carboidratos, amido, lipídios e fibras), microscopia eletrônica de varredura, ressonância magnética nuclear (13C) e área superficial específica. Todas as matrizes foram caracterizadas por infravermelho, análise termogravimétrica, difratometria de raios-X e análise elementar (CHN). Os resultados mostraram apenas pequenas variações entre as matrizes investigadas.

It is known that when water is a product in reactions catalysed by cation exchange resins, it inhibits the reaction rate much more than predicted by the reverse reaction or dilution effects. In this work the inhibiting effect is ascribed to the preferential association of the catalytically active sites with water. In the derivation of the kinetic model, a Freundlich type adsorption isotherm was used to quantify the number of sites occupied by water. This is combined with a power law expression for the reaction rate. The resultant expression can accurately predict the reaction rate for various initial concentrations of water and mesityl oxide. Even when water was initially added to the reaction mixture, this model still gave an absolute average error of 6.5% compared to a 54.6% error when the same approach was followed but with the more popular Langmuir isotherm to describe site deactivation. The kinetic expression previously proposed for this reaction system by Klein and Banchero also failed when water was added to the reaction mixture and gave an average error of 71.1%. The procedure used to derive the model is therefore suggested for all cation exchange catalysed reactions where water is one of the products. / Dissertation (MSc)--University of Pretoria, 2005. / Chemical Engineering / unrestricted

L’utilisation des combustibles fossiles (énergies non renouvelables) est responsable de l’augmentation de la concentration en gaz à effet de serre dans l’atmosphère. Lors de l'examen des solutions de rechange, l’hydrogène comme vecteur énergétique est le plus séduisant. Le stockage de l’hydrogène en phase solide sous forme d’hydrures, est l’une des solutions non polluantes futures pour le stockage et le transport de l’énergie. Parmi les matériaux candidats, le borohydrure de sodium (NaBH4) et l’hydrure de magnésium (MgH2) ont été sélectionnés au vu de leur capacité gravimétrique élevée en hydrogène. La réaction d'hydrolyse de NaBH4 a été étudiée dans un calorimètre en phase liquide couplée à un compteur à gaz, afin de suivre en même temps, la cinétique de production d’hydrogène et l’évolution de la chaleur de réaction. Nous avons préparé des catalyseurs à base de cobalt supporté sur différents supports (hydrotalcites, KF/Al2O3, hétéropolyanions) ayant des propriétés acido-basiques différentes. Les supports et les catalyseurs à base de cobalt ont été caractérisés par DRX, MEB+EDX, ICP et BET. Co/hétéropolyanions a montré une cinétique très élevée pour la production d'hydrogène accompagnée d'une conversion totale dans la réaction d'hydrolyse. L’absorption et la désorption de l’hydrogène ont été étudiées sur l’hydrure de magnésium. Afin d’améliorer la cinétique de sorption de MgH2, nous avons préparé des mélanges MgH2-MT (MT = métal de transition Co, Ni, Fe, Cr, Mn), MgH2-MTmélangé (MT = métal de transition Co, Ni, Fe,), MgH2-MTnano (MT = métal de transition Conano, Ninano, Fenano, Cunano, Znnano) et MgH2-nLiBH4-MTnano (MT = métal de transition Conano, Ninano, Fenano) par broyage à billes de haute énergie. Leurs propriétés physico-chimiques ont été étudiées par DRX et MEB+EDX. La température de désorption de l’hydrogène et la quantité d’hydrogène dégagée ont été étudiées par TPD. La cinétique d’absorption de l’hydrogène et la réversibilité du stockage de l’hydrogène ont été étudiées par isotherme PCT pour le système MgH2-MTnano. MgH2-10-Ninano présente la meilleure propriété de stockage réversible de l’hydrogène, MgH2-10-Conano et MgH2- 10-Fenano sont aussi de bons candidats potentiels / The use of fossil fuels (non-renewable) is the main raison of increasing the green house in the atmosphere. Among the considered alternatives, hydrogen is seen as the most attractive energy carrier. The storage of the hydrogen in the solid phase in the form of hydrides is one of the clean future solutions for storage and transport of energy. Among potential materials, sodium borohydride (NaBH4) and magnesium hydride (MgH2) were selected regarding their high hydrogen gravimetric capacity. The hydrolysis reaction of NaBH4 was studied in a liquid phase calorimetry coupled to a gas-meter, in order to monitor simultaneously the kinetics of the hydrogen production and the evolution of the reaction heat. We prepared cobalt supported catalysts using various supports (hydrotalcites, KF/Al2O3, heteropolyanions) with different acid-base properties. The supports and the catalysts were characterized by XRD, SEM+EDX, ICP and BET. Co/heteropolyanions showed a very high kinetics for the production of hydrogen accompanied by a total conversion in the hydrolysis reaction. The absorption and desorption of hydrogen were studied using magnesium hydride. In order to improve the sorption kinetics of MgH2, we have prepared the MgH2-MT (MT= transition metal Co, Ni, Fe, Cr, Mn), MgH2-MTmixture (MT= transition metal Co, Ni, Fe), MgH2-MTnano (MT = transition metal Conano, Ninano, Fenano, Cunano, Znnano) and MgH2-nLiBH4-MTnano (MT = transition metal Conano, Ninano, Fenano) mixtures by high energy ball milling. Their physicochemical properties were studied by XRD and SEM+EDX. The temperature of hydrogen desorption and the amount of hydrogen generated were investigated by TPD. The kinetics of hydrogen absorption and the reversibility of hydrogen storage were investigated with PCT isotherm for the system of MgH2-MTnano. The sample MgH2-10-Ninano presents the best property for reversible hydrogen storage; MgH2- 10-Conano and MgH2-10-Fenano are also good potential candidates