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O níquel e o cobalto são dois metais de ampla utilização na indústria mundial, principalmente na produção de aços inoxidáveis e ligas metálicas no caso do níquel, e baterias e superligas no caso do cobalto; estes dois metais são encontrados associados na natureza, cerca de 55% da produção mundial de cobalto é derivada da mineração de níquel. Porém, devido a estes elementos apresentarem comportamento químico similar em soluções aquosas, a sua purificação se torna difícil, impulsionando pesquisas voltadas para o melhoramento dos processos existentes para este fim. Dentre estes processos podemos citar a extração por solventes, e para um melhor entendimento da purificação de níquel e cobalto a partir dessa técnica, foi realizado esse estudo, o qual tem como objetivo estudar os complexos organometálicos formados na etapa de extração. A fase aquosa utilizada para a realização deste estudo é um licor sintético de lixiviação que contém níquel, cobalto, manganês, cobre, magnésio e cálcio na sua composição química. Por outro lado, a fase orgânica foi preparada com os extratantes ácidos Cyanex 272, Versatic 10 e D2EHPA de forma individual, assim como as suas misturas, como são: [Cy15-Ve5], [Cy10-Ve10], [Cy5-Ve15], [Cy15-DH5], [Cy10-DH10], [Cy5-DH15], [Ve15-DH5], [Ve10-DH10] e [Ve5-DH15]. Com o intuito de compreender a interação entre o extratante e o íon metálico (complexo organometálico), foi determinada a estequiometria dos complexos através dos métodos de análises da inclinação e o método da variação contínua (método de Job) e a caracterização foi feita utilizando as técnicas de espectrofotometria UV-Vis, espectroscopia FT-IR e termogravimetria (TG/DTG/DSC). Através dos resultados obtidos nos ensaios de extração, foram escolhidos os sistemas, [Cy15-Ve5] e [Cy10-DH10] para realizar o estudo dos complexos organometálicos. O método da variação contínua mostrou a participação de duas moléculas de extratante na complexação de cobalto em todas as fases orgânicas estudadas, com exceção do Versatic 10, a qual apresentou o envolvimento de 5 moléculas. Na complexação de níquel, foram encontradas uma molécula com D2EHPA e [Cy10-DH10], duas moléculas com Cyanex 272 e [Cy15-Ve5] e três moléculas com Versatic 10. As análises por UV-Vis forneceram o número de coordenação dos complexos organometálicos de níquel e cobalto formados tanto na solução aquosa como nas diferentes fases orgânicas estudadas. Através destes resultados determinou-se que o níquel apresentou uma simetria octaédrica nas condições testadas (fase aquosa e fases orgânicas), já o cobalto apresentou uma simetria octaédrica na solução aquosa e no Versatic 10, e simetria tetraédrica nas outras condições (Cyanex 272, D2EHPA e mistura dos extratantes). Por outro lado, as análises de infravermelho (FT-IR) mostraram que a extração do íon metálico é realizada através do mecanismo de troca catiônica (substituição do hidrogênio da ligação P-O-H). As análises termogravimétricas forneceram as temperaturas de decomposição dos complexos e, a presença ou não de moléculas de água no mesmo. Através destes resultados foi confirmado que os complexos de níquel se tratam de complexos hidratados, com exceção do complexo [Ni-Versatic 10], o qual corresponde a um complexo desidratado. Entretanto, os complexos organometálicos formados com o cobalto, são complexos desidratados, ou seja, que os sítios de coordenação estão completamente preenchidos por moléculas de extratante. / Nickel and cobalt are two metals widely used in the world industry, mainly in the production of stainless steel like an alloy element in the case of nickel, and both batteries and super alloys in the case of cobalt. These metals are found associated in nature and about 55% world production of cobalt is derived from the nickel mining. Due their similar chemical behavior in aqueous solution, its purification becomes difficult, encouraging research to improve the current processes, such as, the solvent extraction. In order to have a better understanding about both nickel and cobalt purification through this technique, this study has been carried out to evaluate the organometallic complexes formed during the extraction stage. The aqueous phase used in this study is a synthetic leach liquor containing in its chemical composition nickel, cobalt, manganese, copper, magnesium and calcium. On the other hand, the organic phase was prepared using the acidic extractants, as such: Cyanex 272, Versatic 10 and D2EHPA, as well as their mixtures [Cy15 Ve5], [Cy10-Ve10], [Cy5 Ve15], [Cy15-DH5], [Cy10-DH10], [Cy5 DH15], [Ve15-DH5], [Ve10-DH10] and [Ve5-DH15]. In order to understand the interaction between extractant molecule and metal ion (organometallic complex), the complex stoichiometry was determinate through two methods, such as: slope analysis and the continuous variation (Job´s method). Furthermore, the complex characterization was carried out using some techniques, spectrophotometry UV Vis, spectroscopy FT-IR and thermogravimetry (TG/DTG/DSC). The systems [Cy15-Ve5] and [Cy10-DH10] have been chosen in order to study the organometallic complexes formed. The continuous variation method has shown the participation of two extractant molecules in the complexation of cobalt in all organic phases studied in this work, except for the Versatic 10, where was observed the involvement of 5 molecules to form the complex. On the other hand, to form the nickel complex, when the D2EHPA and [Cy10-DH10] were used, five molecules were involved in the complex formation process. Furthermore, two molecules are present in the complex if Cyanex 272 or [Cy15-Ve5] are used like extractant and, when the Versatic 10 is used, three molecules are necessary to form the organometallic complex. The UV-Vis analysis provided the coordination number of the organometallic complexes of nickel and cobalt formed in both the aqueous and all organic phases chosen. It was determined that nickel showed an octahedral symmetry in both aqueous phase and organic phases, whereas the cobalt exhibited an octahedral symmetry both the aqueous solution and Versatic 10, and a tetrahedral symmetry in the other conditions (Cyanex 272, D2EHPA and extractants mixtures). Moreover, the infrared (FT-IR) analysis showed that the metal ion extraction is performed through the cation exchange mechanism (hydrogen substitution of P-O-H bond). Lastly, the thermogravimetric analysis provided the complexes decomposition temperatures and the presence or absence of water molecules. It was confirmed that nickel complexes are hydrated, except for the [Ni-Versatic 10] complex, which corresponds to a dehydrated complex. However, all organometallic complexes with cobalt are dehydrated complexes, that is, coordination sites are completely filled with extractant molecules.

The syntheses and characterisation of di(cyclohexylmethyl), di(2-cyclohexylethyl), di(2-methylcyclohexyl) and di(4-methylcyclohexyl) phosphoric acids; cyclohexylmethyl phosphonic acid monocyclohexylmethyl ester, di(cyclohexylmethyl), di(4-methylcyclohexyl), di(4-tert- butylcyclohexyl), di(3-methylcyclohexyl), di(3,5-dimethylcyclohexy) and di(2-methylcyclohexyl) phosphinic acids are reported. Problems encountered and how they were resolved during the preparation of the above organophosphorus acids are reported and discussed in detail. These acids are then evaluated as potential hydrometallurgical extractants, for the separation of cobalt from nickel in acid leach liquors, and compared with two commercially available extractants, namely di(2-ethylhexyl)phosphoric acid (D2EHPA) and di(2,4-4- trimethylpentyl)phosphinic acid (Cyanex 272). The effects of variablest such as metal feed solution concentration, extractant concentration, diluent, modifier and temperature are examined experimentally in order to determine which factors are important for optimisation of an extraction system. The extraction characteristics for each acid as a function of pH are presented graphically and the pHO 5 values, distribution coefficients and separation factors are calculated. The dialkylphosphinic acids are found to exhibit much greater selectivity, for cobalt over nickel, than the dialkylphosphoric acids. It is postulated, that steric crowding of the phosphorus atom, by the hydrocarbon groups attached to the phosphorus, increases the selectivity of an extractant. This effect is particularly apparent in the dialkylphosphinic acids with di(2-methylcyclohexyl)phosphinic acid giving the best selectivity; much better than the commercially available Cyanex 272. Several of the dialkylphosphinic acids, evaluated as extractants in this thesis, are protected by a British Patent Application.

Made available in DSpace on 2014-06-11T19:23:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-28Bitstream added on 2014-06-13T20:10:45Z : No. of bitstreams: 1 godoi_lm_me_jabo.pdf: 221877 bytes, checksum: d6a13644f869b633dd790316dd00f0f4 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Para conhecer o potencial de plantas de cobertura no fornecimento de nitrogênio para o milho, em sistema de plantio direto, foi avaliado o N potencialmente mineralizável (N0) do solo por meio de ensaio de incubação aeróbia de longa duração e o N disponível por meio dos extratores químicos KCl a quente, Dakota do Sul modificado e tampão fosfato borato a pH 11,2. Foram utilizadas amostras de solo de experimento a campo, instalado em área de Latossolo Vermelho argiloso e conduzido em delineamento em blocos casualizados, com cinco tratamentos: testemunha com vegetação espontânea, sorgo, milheto, mucuna-preta e feijão-de-porco, e cinco repetições. A coleta de solo nas parcelas foi feita após a dessecação das plantas de cobertura e antes do cultivo de milho, nos anos agrícolas de 2007/2008 e 2008/2009. O solo coletado, representativo da profundidade de 0 a 10 cm, foi utilizado no ensaio de incubação aeróbia, em experimento em vasos, com milho, e para as análises químicas. A eficiência dos extratores foi avaliada por meio de testes de correlação, empregando como variáveis de referência o N0 e o N mineralizado acumulado por 30 semanas, obtidos no ensaio de incubação aeróbia, e a produção de matéria seca e o N acumulado na parte aérea do milho, obtidos no experimento em vasos. As plantas de cobertura não diferem entre si quanto ao potencial de fornecimento de N para o milho. O método do KCl a quente é capaz de predizer a mineralização de N, porém os métodos químicos avaliados para predizer o N disponível não são eficientes / Aiming to determine the potential of cover crops to supply nitrogen for corn in no-tillage system, it was evaluated the soil potentially mineralizable N (N0) by long-term aerobic incubation and available N by chemical extractants (hot KCl, modified South Dakota and pH 11.2 phosphate-borate buffer). Soil samples were collected from a field experiment, installed in an Udox and carried out in a randomized block design with five treatments (control with spontaneous vegetation, Sorghum bicolor, Pennicetum glaucum, Mucuna aterrima and Canavalia ensiformis) and five replications. Plots soil sampling was made after the cover crops desiccation and before growing the corn in the agricultural seasons of 2007/2008 and 2008/2009. Soil samples collected from 0 to10 cm depth were used for long-term aerobic incubation, pots experiment with corn, and for soil chemical analysis. Extractants efficiency was evaluated by correlation tests, using as reference the N0 and the mineralized accumulated N over 30 weeks obtained from long-term aerobic incubation, dry matter production and N accumulated in maize shoots, obtained from pots experiment. Cover crops do not differ in their potential to supply nitrogen for corn. Hot KCl is able to predict the N mineralization but the chemical methods evaluated to predict the available nitrogen are not efficients

O níquel e o cobalto são dois metais de ampla utilização na indústria mundial, principalmente na produção de aços inoxidáveis e ligas metálicas no caso do níquel, e baterias e superligas no caso do cobalto; estes dois metais são encontrados associados na natureza, cerca de 55% da produção mundial de cobalto é derivada da mineração de níquel. Porém, devido a estes elementos apresentarem comportamento químico similar em soluções aquosas, a sua purificação se torna difícil, impulsionando pesquisas voltadas para o melhoramento dos processos existentes para este fim. Dentre estes processos podemos citar a extração por solventes, e para um melhor entendimento da purificação de níquel e cobalto a partir dessa técnica, foi realizado esse estudo, o qual tem como objetivo estudar os complexos organometálicos formados na etapa de extração. A fase aquosa utilizada para a realização deste estudo é um licor sintético de lixiviação que contém níquel, cobalto, manganês, cobre, magnésio e cálcio na sua composição química. Por outro lado, a fase orgânica foi preparada com os extratantes ácidos Cyanex 272, Versatic 10 e D2EHPA de forma individual, assim como as suas misturas, como são: [Cy15-Ve5], [Cy10-Ve10], [Cy5-Ve15], [Cy15-DH5], [Cy10-DH10], [Cy5-DH15], [Ve15-DH5], [Ve10-DH10] e [Ve5-DH15]. Com o intuito de compreender a interação entre o extratante e o íon metálico (complexo organometálico), foi determinada a estequiometria dos complexos através dos métodos de análises da inclinação e o método da variação contínua (método de Job) e a caracterização foi feita utilizando as técnicas de espectrofotometria UV-Vis, espectroscopia FT-IR e termogravimetria (TG/DTG/DSC). Através dos resultados obtidos nos ensaios de extração, foram escolhidos os sistemas, [Cy15-Ve5] e [Cy10-DH10] para realizar o estudo dos complexos organometálicos. O método da variação contínua mostrou a participação de duas moléculas de extratante na complexação de cobalto em todas as fases orgânicas estudadas, com exceção do Versatic 10, a qual apresentou o envolvimento de 5 moléculas. Na complexação de níquel, foram encontradas uma molécula com D2EHPA e [Cy10-DH10], duas moléculas com Cyanex 272 e [Cy15-Ve5] e três moléculas com Versatic 10. As análises por UV-Vis forneceram o número de coordenação dos complexos organometálicos de níquel e cobalto formados tanto na solução aquosa como nas diferentes fases orgânicas estudadas. Através destes resultados determinou-se que o níquel apresentou uma simetria octaédrica nas condições testadas (fase aquosa e fases orgânicas), já o cobalto apresentou uma simetria octaédrica na solução aquosa e no Versatic 10, e simetria tetraédrica nas outras condições (Cyanex 272, D2EHPA e mistura dos extratantes). Por outro lado, as análises de infravermelho (FT-IR) mostraram que a extração do íon metálico é realizada através do mecanismo de troca catiônica (substituição do hidrogênio da ligação P-O-H). As análises termogravimétricas forneceram as temperaturas de decomposição dos complexos e, a presença ou não de moléculas de água no mesmo. Através destes resultados foi confirmado que os complexos de níquel se tratam de complexos hidratados, com exceção do complexo [Ni-Versatic 10], o qual corresponde a um complexo desidratado. Entretanto, os complexos organometálicos formados com o cobalto, são complexos desidratados, ou seja, que os sítios de coordenação estão completamente preenchidos por moléculas de extratante. / Nickel and cobalt are two metals widely used in the world industry, mainly in the production of stainless steel like an alloy element in the case of nickel, and both batteries and super alloys in the case of cobalt. These metals are found associated in nature and about 55% world production of cobalt is derived from the nickel mining. Due their similar chemical behavior in aqueous solution, its purification becomes difficult, encouraging research to improve the current processes, such as, the solvent extraction. In order to have a better understanding about both nickel and cobalt purification through this technique, this study has been carried out to evaluate the organometallic complexes formed during the extraction stage. The aqueous phase used in this study is a synthetic leach liquor containing in its chemical composition nickel, cobalt, manganese, copper, magnesium and calcium. On the other hand, the organic phase was prepared using the acidic extractants, as such: Cyanex 272, Versatic 10 and D2EHPA, as well as their mixtures [Cy15 Ve5], [Cy10-Ve10], [Cy5 Ve15], [Cy15-DH5], [Cy10-DH10], [Cy5 DH15], [Ve15-DH5], [Ve10-DH10] and [Ve5-DH15]. In order to understand the interaction between extractant molecule and metal ion (organometallic complex), the complex stoichiometry was determinate through two methods, such as: slope analysis and the continuous variation (Job´s method). Furthermore, the complex characterization was carried out using some techniques, spectrophotometry UV Vis, spectroscopy FT-IR and thermogravimetry (TG/DTG/DSC). The systems [Cy15-Ve5] and [Cy10-DH10] have been chosen in order to study the organometallic complexes formed. The continuous variation method has shown the participation of two extractant molecules in the complexation of cobalt in all organic phases studied in this work, except for the Versatic 10, where was observed the involvement of 5 molecules to form the complex. On the other hand, to form the nickel complex, when the D2EHPA and [Cy10-DH10] were used, five molecules were involved in the complex formation process. Furthermore, two molecules are present in the complex if Cyanex 272 or [Cy15-Ve5] are used like extractant and, when the Versatic 10 is used, three molecules are necessary to form the organometallic complex. The UV-Vis analysis provided the coordination number of the organometallic complexes of nickel and cobalt formed in both the aqueous and all organic phases chosen. It was determined that nickel showed an octahedral symmetry in both aqueous phase and organic phases, whereas the cobalt exhibited an octahedral symmetry both the aqueous solution and Versatic 10, and a tetrahedral symmetry in the other conditions (Cyanex 272, D2EHPA and extractants mixtures). Moreover, the infrared (FT-IR) analysis showed that the metal ion extraction is performed through the cation exchange mechanism (hydrogen substitution of P-O-H bond). Lastly, the thermogravimetric analysis provided the complexes decomposition temperatures and the presence or absence of water molecules. It was confirmed that nickel complexes are hydrated, except for the [Ni-Versatic 10] complex, which corresponds to a dehydrated complex. However, all organometallic complexes with cobalt are dehydrated complexes, that is, coordination sites are completely filled with extractant molecules.

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-08-03T14:41:11Z No. of bitstreams: 1 Josangela do Carmo Trezena de Araujo.pdf: 806488 bytes, checksum: 1d6f571b90a6d27e46e45f4b5581b53f (MD5) / Made available in DSpace on 2016-08-03T14:41:11Z (GMT). No. of bitstreams: 1 Josangela do Carmo Trezena de Araujo.pdf: 806488 bytes, checksum: 1d6f571b90a6d27e46e45f4b5581b53f (MD5) Previous issue date: 2009-03-10 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The silicon uptake by plants results in amelioration of metals phytotoxicity. Such outcome can enhance phytoextraction owing to increased plant tolerance to metals. The critical levels of Si in plants and soils, as well as the best extractant to be used in soil, are still matter of discussion. The work aimed at evaluating the effectiveness of methods for Si extraction from soil (calcium chloride, acetic acid, citric acid, and water). In addition, the biomass yield, concentration and content of Si in maize plants grown in a Pb-contaminated soil were also studied. Si was applied at the rates 0, 100, 250, 350, and 500 mg kg-1 in 5.5 dm-3 pots in which 65 days old plants were cultivated. The Si doses promoted biomass reduction but increased the Si concentration in roots and shoots. However, applying up to 100 mg kg-1 of Si enhanced biomass. Calcium chloride and acetic acid were the extractants best correlated with Si concentrations in plants. / A absorção de Si pelas plantas tem resultado em efeitos benéficos e amenizante da fitotoxicidade de metais pesados, o que pode melhorar a fitoextração de metais do solo devido ao aumento da tolerância das plantas ao metal. Os níveis críticos de Si no solo, em relação a algumas espécies de plantas, ainda estão sendo estabelecidos no Brasil. No entanto, ainda não está definido qual o melhor extrator a ser usado. O objetivo desse trabalho foi avaliar a eficiência dos métodos de extração de Si (cloreto de cálcio, ácido acético, ácido cítrico e água), além de determinar a produção de matéria seca, teor e conteúdo de silício em plantas de milho em solo contaminado por chumbo. As doses de 0, 100, 250, 350 e 500 mg kg-1 de Si, foram aplicadas em vasos de 5,5 dm-3, cultivados com plantas de milho por 65 dias. Com aplicação das doses de Si houve redução da produção de matéria seca de plantas de milho cultivadas no solo contaminado. A adição de doses crescentes de Si ao solo contaminado promoveu aumento dos teores de Si na parte aérea e raiz das plantas. A dose de 100 mg kg-1 de Si foi a mais eficiente no aumento de biomassa. O cloreto de cálcio e o ácido acético foram os extratores que mais se correlacionaram com os teores de Si extraídos pelas plantas.

The aim of this study was to develop a cost-effective process to produce a grape seed extract of high quality using only non-toxic extractants. When this study was started no grape seed extract was produced in South Africa. Large quantities were imported to supply the local demand in the human and animal herbal medicine industry. Grape seed extract is mainly used to boost the immune system of humans and animals based on its antioxidant activity. Initial work with different extractants established the polarity of the compounds with antioxidant activity. Antioxidant related activity was determined with five analysis techniques. Parameters such as the type, preparation and pre-treatment of grape seed, ratio of extractant to grape seed, composition of extractant, extraction time, extraction temperature, the interaction between temperature and time, drying temperature and subsequent treatment of extracts to remove compounds without antioxidant activity were evaluated. In all cases the cost implications of different methods used were kept in mind. Not only the quality but also the quantity extracted is important in establishing a viable extraction plant. According to the patent literature most techniques used to date produce yields of 0.5 to 2.5 %. The laboratory product went through five stages of development. The percentage extracted for our five laboratory products decreased from 12.0, 10.1, 6.0, 5.9 to 5.5 % whereas antioxidant activity for our product increased from 30, 55, 67 78 to 172 % compared to the best available commercial product. An important reason for the success of the procedure developed, is that we analyzed the different products developed with sophisticated procedures that gave information about the chemical composition of the extract. From this information procedures could be developed to increase the yield and activity. The procedure has been licensed to a private company that is in the process of establishing a factory for the large-scale production of grape seed extract. The detail regarding the procedure is confidential to protect the intellectual property and industrial exploitation of the process. / Dissertation (MSc)--University of Pretoria, 2004. / gm2014 / Paraclinical Sciences / unrestricted

The syntheses and characterisation of di(cyclohexylmethyl), di(2-cyclohexylethyl), di(2-methylcyclohexyl) and di(4-methylcyclohexyl) phosphoric acids; cyclohexylmethyl phosphonic acid monocyclohexylmethyl ester, di(cyclohexylmethyl), di(4-methylcyclohexyl), di(4-tert- butylcyclohexyl), di(3-methylcyclohexyl), di(3,5-dimethylcyclohexy) and di(2-methylcyclohexyl) phosphinic acids are reported. Problems encountered and how they were resolved during the preparation of the above organophosphorus acids are reported and discussed in detail. These acids are then evaluated as potential hydrometallurgical extractants, for the separation of cobalt from nickel in acid leach liquors, and compared with two commercially available extractants, namely di(2-ethylhexyl)phosphoric acid (D2EHPA) and di(2,4-4- trimethylpentyl)phosphinic acid (Cyanex 272). The effects of variablest such as metal feed solution concentration, extractant concentration, diluent, modifier and temperature are examined experimentally in order to determine which factors are important for optimisation of an extraction system. The extraction characteristics for each acid as a function of pH are presented graphically and the pHO 5 values, distribution coefficients and separation factors are calculated. The dialkylphosphinic acids are found to exhibit much greater selectivity, for cobalt over nickel, than the dialkylphosphoric acids. It is postulated, that steric crowding of the phosphorus atom, by the hydrocarbon groups attached to the phosphorus, increases the selectivity of an extractant. This effect is particularly apparent in the dialkylphosphinic acids with di(2-methylcyclohexyl)phosphinic acid giving the best selectivity; much better than the commercially available Cyanex 272. Several of the dialkylphosphinic acids, evaluated as extractants in this thesis, are protected by a British Patent Application. / Science and Engineering Research Council

Dans le cadre de la séparation sélective pour le traitement et la valorisation des combustibles nucléaires usés, l’extraction liquide/liquide est largement utilisée au niveau industriel. Néanmoins, ce procédé est encore mal compris en ce qui concerne les phénomènes physico-chimiques qui se produisent à l’interface liquide/liquide. Ce travail porte sur la compréhension de la dynamique de l’interface liquide nanométrique durant le transfert d’une espèce entre une phase aqueuse et une phase organique. Deux techniques expérimentales ont principalement été utilisées: la mesure de tension interfaciale et l’optique non linéaire. Ce travail a également donné lieu au développement d’un modèle numérique de dynamique de transfert de phase prenant en compte à la fois des phénomènes de transport diffusif proche de l’interface et une cinétique chimique sur l’interface décrivant les processus d’adsorption/désorption. Des systèmes modèles constitués de molécules surfactantes et/ou chromophores et/ou complexantes ont été étudiés aux interfaces air/liquide et liquide/liquide. L’adsorption/désorption, l’agrégation en surface, la complexation d’ion à une interface liquide et la structuration des systèmes ont ainsi pu être étudiées tant d’un point de vue des états d’équilibre que de la dynamique. Enfin, ces études ont été appliquées à un système d’intérêt industriel utilisé dans le procédé de dépollution DIAMEX / Liquid-liquid extraction processes are widely used in the industrial fields of selective separation. Despites its numerous applications, the microscopic mechanisms which occur during a liquid liquid extraction processes are really unknown specially at the liquid/liquid interface. Thus, this work deals on the understanding of the phenomena which drive the mass transfer across a liquid/liquid interface. Two experimental techniques were used in this work: dynamic interfacial tension measurement and non-linear optical experiments. Along with the use of this experimental approach, a numerical model describing the mass transfer dynamic has been developed. This model works under the assumption that both diffusion and a chemical step describing adsorption and desorption processes contribute to the global transfer kinetics. Model systems of surfactant molecules, chromophore molecules and complexing molecule were investigated at liquid/liquid and air/liquid interface. Interfacial phenomena like adsorption, surface aggregation and ion complexing were studied. Finally, the methodology developed in this work was applied to studied an extractant molecule with potential industrial application

O cádmio (Cd) é um elemento potencialmente tóxico para as plantas, animais e homens. O Cd é particularmente perigoso devido à sua mobilidade relativamente alta em solos e transferência para as plantas. Além disso, plantas que crescem em solos contaminados podem acumular Cd nos tecidos comestíveis em grandes quantidades sem qualquer sintoma visível de toxicidade. O Cd tem recebido atenção especial por sua associação com diversos problemas na saúde humana. Devido à crescente preocupação com a ingestão de Cd por alimentos, os riscos de sua entrada na cadeia alimentar precisam ser cuidadosamente considerados. Neste contexto, objetivou-se, com este estudo, avaliar a disponibilidade de Cd no solo, sua transferência e toxicidade para as culturas de alface, arroz e feijão, por meio de experimentos desenvolvidos em Latossolos com atributos contrastantes, contaminados com doses de Cd. Os experimentos foram desenvolvidos em casa de vegetação em PiracicabaSP. Cultivaram-se plantas de alface, arroz e feijão em vasos de 3 dm3 preenchidos amostras de um Latossolo Vermelho Eutrófico e um Latossolo Vermelho-Amarelo Distrófico. Adotou-se o delineamento experimental em blocos ao acaso, em esquema fatorial 5x2, com três repetições. Os tratamentos corresponderam a: 0,0; 0,5; 1,3; 3,0 e 6,0 mg dm-3 de Cd, definidos com base nos valores orientadores de qualidade do solo para Cd estabelecidos pela Companhia de Tecnologia de Saneamento Ambiental CETESB, aplicados nos solos na forma de CdCl2.H2O. Os teores de Cd nos solos aumentaram linearmente em função das doses de Cd. Os extratores DTPA, Mehlich-1 e CaCl2 foram eficientes na avaliação dos teores disponíveis de Cd nos solos. O Cd esteve mais associado a frações menos estáveis (trocável e matéria orgânica). O aumento das doses de Cd promoveu diminuição da produção de biomassa e o aumento nos teores e nas quantidades acumuladas desse elemento nas partes vegetais estudadas. Contudo, não foram observados outros sintomas de toxicidade nas plantas. Os teores e acúmulos de P, Cu, Fe, Ni, Mn, Pb e Zn, nas raízes, parte aérea, folhas e grãos, foram diferentemente influenciados pelas doses de Cd. A distribuição de Cd nas partes das plantas variou em função da cultura: alface = folhas > raiz > caule; arroz = raiz > parte aérea > grãos, e feijão = parte aérea > raiz > vagem > grãos. O teor de Cd nos grãos de feijão está abaixo do limite máximo estabelecido para o consumo humano conforme a legislação brasileira. Entretanto, a concentração de Cd nas folhas de alface e nos grãos de arroz ultrapassa tal limite quando o teor de Cd no solo está acima do valor de referência de qualidade proposto pela CETESB. O valor da ingestão diária de Cd pelo consumo de alface e feijão está dentro do valor provisório de ingestão diária tolerável (PTDI) sugerido pela Organização das Nações Unidas para Alimentação e Agricultura FAO/WHO. No entanto, o valor da ingestão diária de Cd pelo consumo de arroz por adultos está acima do PTDI. Consequentemente, o consumo desse alimento poderá trazer riscos à saúde humana. / Cadmium (Cd) is potentially toxic element to plants, animals and humans. Cd is particularly dangerous due to its relatively high mobility in soils and transfer to plants. Moreover, plants growing in contaminated soils can accumulate Cd in edible tissues in large quantities without any visible signs. Cd has received considerable attention in view of its association with a number of human health problems. Due to increasing concern about the intake of Cd in foods, the risks of its potential entry in the food chain need to be carefully considered. The objective of this study was to evaluate the availability of Cd in soil, the uptake by plants and to estimate the daily intake of Cd from lettuce, rice and bean plants grown in Brazilian tropical soils. The experiment was carried out under greenhouse conditions in Piracicaba, state of São Paulo, Brazil. Lettuce, rice and bean plants were cultivated in pots filled with 3 dm3 of two Oxisols (Typic Hapludox and Rhodic Hapludox) using a randomized block design in a factorial scheme (5 x 2) with three replicates. The treatments consisted of: 0.0; 0.5; 1.3; 3.0 and 6.0 mg dm-3 rates of Cd (as CdCl2), based on the guideline established by the Environmental Agency of the State of Sao Paulo CETESB. Considering all the experiments it was found that the external loading of Cd linearly increased the concentration of Cd in both soils. DTPA, Mehlich-1 e CaCl2 were effective in predicting soil Cd availability. The Cd distributions in both soils were strongly associated with exchangeable and organic matter fractions, which are characterized by instable chemical bonds. The application Cd rates decreased the plant biomass. However, the crops did not display any other symptoms of Cd toxicity or of deficiency in other nutrients which might be caused by the presence of Cd in the soil. Loadings of Cd to soil linearly or quadratically increased the concentration and accumulation of Cd in different parts of the plants. The concentration and accumulation of P, Cu, Fe, Ni, Mn, Pb and Zn in the root, shoot, leaves and grain were influenced differentially by Cd treatments. Cadmium distribution in different parts of the plants varied depending on the crop: lettuce = leaves > root > stem, rice = root > shoot > grains, and bean = shoot > root > pod > grain. Cadmium concentration in bean remained below the threshold for human consumption established by Brazilian legislation. However, lettuce and rice Cd concentration in edible parts exceeded the acceptable limit when the soil Cd concentration is above the quality reference value proposed by CETESB. Daily intakes of Cd from lettuce and bean plants grown in both Oxisols are within the provisional tolerable daily intake (PTDI) of Cd determined by the Food and Agriculture Organization of the United Nations FAO/WHO. However, the daily intake of Cd from rice for adults is above the PTDI. Consequently, the consumption of this food can pose risks to human health.