This thesis has investigated several complex situations that may be encountered in electrochemical studies. Three main situations have been examined, they include the formation of polymer films on electrode surfaces during measurements, a novel nanocatalyst modified electrode surfaces, and organised carbon nanotube (CNT) structures on electrode surfaces. These have been utilised for different electrochemical applications owing to their dissimilar properties. Voltammetric techniques of cyclic voltammetry (CV), square wave voltammetry (SWV) and Fourier transformed large amplitude ac voltammetry (FTACV) have been utilised to examine these reactions. Chapter 3 reports the investigation of catechol oxidation and subsequent polymerisation through crosslinking with D-glucosamine or chitosan. Hydrogel can be formed on the electrode surface during the process, which changes the viscosity of the solution and thus affects the diffusion of chemical species. This process has been examined by several voltammetric techniques. A further examination of the chemical system has also been conducted using FTACV for the first time. Chapter 4 describes the preparation of carbon microsphere supported molybdenum disulfide. The material has been utilised as electrocatalysts for hydrogen evolution reaction (HER) in acidic media, and the performance tested by traditional linear sweep voltammetry (LSV) and advanced FTACV techniques. The FTACV technique has been used for the first time for HER processes. In addition, the synthesised particles have also been used for thermal catalytic decomposition of hydrogen sulfide, which shows a significant improvement in the conversion rate over conventional examples. Chapter 5 demonstrates the direct growth of vertically aligned CNT forests on a gold electrode. The electrochemical response of the fabricated electrode has also been examined with ferrocyanide as the redox species. Furthermore, the immobilisation of anthraquinone onto CNT forest has been attempted. The fabricated electrode was utilised as a pH sensor via CV and SWV, and both indicates a well correlated pH-potential relationship in the pH range of 2 to 12. The sensor has also been assessed by the FTACV technique.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / by Gerald Frank Zamiski. / M.S.

This thesis describes optical microscopical and spectroscopical studies of 2D materials, including graphite/graphene and multilayer/single layer MoS2, under strong charge transfer doping. Under this conceptually unifying umbrella lie many aspects of materials behaviors unique to each of the systems. The strong chemical doping results from intercalation and surface adsorption, and changes the electronic properties of the host 2D materials drastically. Associated with the significant electronic change, aspects such as mass transport, surface reaction, and phase transformation are covered in the following chapters. The first chapter introduces representative members of the 2D materials family, graphene and molybdenum disulphide (MoS2). It briefly reviews the history, discovery and unique properties of each materials class. The other part of the introduction focuses on the main methods utilized in the study of these materials. A concise survey of Raman spectroscopy and optical reflectance contrast spectroscopy will be presented. The second chapter investigates the intercalation process of Li into bulk graphite. This is a revisit of an extensively studied subject, with a new set of experiments and theories. Here we show that the daunting technical difficulties of disentangling complex electrochemical systems can be cleanly addressed with optical methods with well defined samples. Measuring and understanding the intrinsic transport of Li in graphite electrodes has been a difficult task. The challenge is well recognized to stem from a multitude of simultaneous electrochemical processes as well as systematic heterogeneities in the sample. We distinguish the Li intercalation process in graphite from all other processes, combining optical reflectance microscopy and Raman spectroscopy. The heterogeneity problem is circumvented by using lithography to tailor a single crystal into a defined geometry. We apply two levels of theoretical models to interpret the intrinsic information revealed in our data. Concentration dependent diffusion coefficients are measured, in agreement with theoretical results. The effects of sample geometry and electrode reaction kinetics on the overall intercalation are elucidated. The third chapter presents the study of lithiation on single and few layer graphene. Raman spectroscopy reveals a high doping level similar in strength to that of the bulk intercalated compound. The optical reflectance imaging, however, shows a different observation from the bulk case. We directly visualize the surface film formation and associated strong doping. The lithiation in single and few layer graphene progresses differently from the bulk graphite, since certain stages of the intercalation compound cannot be sustained by a single or few layer sample. The realization of strong charge transfer doping in lithiated single and few layer graphene could lead to discoveries of interesting physics. The direct visualization of surface film formation could have important implications in the design of electrochemical energy storage systems. The fourth chapter explores the structural effect of strong charge transfer doping in bulk and multilayer MoS2 with optical methods. MoS2, as a representative material of the transition metal dichalcogenide family, possesses different structural polymorphs. Strong charge transfer doping induces a structural phase change, which goes from the usual thermodynamically stable semiconducting 2H phase into the metallic 1T/1T' phase. The metallic 1T/1T' structure can remain a metastable phase without the stabilization of intercalants. We optically induce the 1T/1T' to 2H phase change and measure the temperature dependent kinetics of the structural phase transformation with in situ Raman spectroscopy. We demonstrate a photolithography technique, which efficiently patterns in-plane coherent heterojunctions between 1T/1T' and 2H MoS2. The fifth and final chapter describes the study of the structural change in single layer MoS2. More spectroscopic methods are employed for characterization, such as photoluminescence spectroscopy and second harmonic generation. The results indicate that the structural change occurs in single layer MoS2 after reaction with n-butyl lithium. The structural change can be reversed by thermal and laser annealing, similar to the case of bulk and multilayer MoS2. The annealed MoS2 exhibits reduced crystallinity. Future directions to further this work are outlined in the last section.

In this thesis, the adsorption of single-wall carbon nanotubes (SWCNTs) at the liquid/liquid interface, and the subsequent electrochemical investigation of the electrical properties of the adsorbed nanotubes have been studied. Prior to the adsorption of the nanotube, the stability of dispersion of SWCNTs in non-aqueous solvents was assessed by determining the onset of aggregation of the SWCNTs when organic electrolyte was introduced. It was found that electrostatic repulsion between the SWCNTs contributes significantly to the stability of the SWCNTs in non-aqueous solvents. Similar result was also found when the aggregation kinetics of molybdenum disulphide (MoS2) dispersion in non-aqueous media was studied using the same organic electrolyte. The formation of nanomaterial-polymer composites by deliberate electrochemical oxidation of pyrrole and the sonochemical polymerisation of the organic solvent was also studied. Electrolyte addition was shown to be a promising way to separate the 2D material from the sonopolymer.

This work aims to define the modes of action of a series of metal extraction ligands with particular focus on how these depend on the formation of supramolecular assemblies. Though solvent extraction processes are well established industrially often the understanding, particularly of the metal coordination chemistry, is less so. A greater understanding of a variety of solvent extraction systems can lead to the development of stronger and more specific extractants. Chapter 2 examines the role of inter-ligand interactions in the extraction of copper by phenolic oximes and pyrazoles. Computational methods are used to understand the importance of inter-ligand outer-sphere interactions in square-planar copper complexes. It is shown that functionalisation at different positions on the phenol ring can either stabilise or destabilise the copper complex and it is possible to predict the strength of extractants from DFT calculations. Substitution ortho to the phenolic oxygen in the oximes and pyrazoles can have a major effect of enhancing the strength of extractants by “buttressing” the H-bonding between ligands. However, in the amino-methyl substituted oximes buttressing is so strong that is has an adverse effect on complex formation. Crystal structures are confirmed by both ENDOR EPR spectroscopy and DFT structures. A series of 6-X-4-methyl-2-(5-alkyl-1H-pyrazol-3-yl)- phenols (X = H, OMe, Br and NO2) was synthesised and characterised (X = H, OMe, Br and NO2) and the copper extractant found to be 6-nitro-4-methyl-2-(5-(1,3,5-tri-methyl-pentyl)- 1H-pyrazol-3-yl)-phenol extractants. Computational DFT studies in the gas phase were carried out to calculate the formation energies of analogous phenolic pyrazole copper complexes. The predicted order of these energies followed the same trend shown by experimental solvent extraction studies. Studies also showed that substitution can affect not only complex stability through inter-ligand interactions through hydrogen bonding in the outer-sphere but also the strength of metal-ligand bonds. Chapter 3 looks at synergistic solvent extraction systems: where more than one extractant works together to provide additional strength and selectivity. Combinations of neutral N and O donor ligands with carboxylic, phosphinic and sulfonic acids were studied by solvent extraction, crystallographic and computational methods. Crystal structures and DFT-optimised structures show that ligands and acid form pseudo-tridentate ligands where both the neutral ligand and the deprotonated acid are coordinated directly to the metal centre with inter-ligand hydrogen bonding allowing for a more flexible backbone than a classic tridentate system. Although synergistic extractions systems often utilise carboxylic acids many of the structures show the similarities with systems containing phosphinic acids and it was shown experimentally that some extraction systems show greater synergism with phosphinic than carboxylic acid in the recovery of nickel. Chapter 4 deals with the extraction of molybdenum with commercial phosphinic acid extractant Cyanex 600. The propensity for molybdenum to form oxo clusters in aqueous solutions and the influence pH in both the speciation of the Mo species and extraction conditions contributes to a complex extraction profile. The pH dependence of extraction shows that different mechanisms operate at low (pH < 0) and high (pH > 0) pH. The extraction curve shows a conventional S-curve between pH 0 and 1.5 and slope analysis within this pH range gives a value very close to two but identification of structures which match this profile is complex. Maximum pH extraction is see at ~ pH 1.5. ESMS studies identified very similar species in the organic phase despite the variation seen in the S-curve. A survey of the structures of metal complexes of phosphinate ligands suggests that molybdenum-phosphinate complexes can often form cubane-like structure and negative ion ESMS data supports the concept of cluster formation in the organic phase. A common feature of the spectra are tetra- tri- and bi-metal- oxo species and spectra show a large number of peaks. It is very probable that the extraction of molybdenum(VI) with phosphinic acids is a dynamic system as extraction is influenced by the molybdenum speciation in the aqueous phase which is in turn influenced by both the pH and the molybdenum concentration both of which change over the course of a conventional extraction.

Com objetivo de avaliar a eficiência do uso de fertilizante (contendo macronutrientes - nitrogênio, fósforo e potássio - e micronutrientes - cobalto e molibdênio), associado a fungicida e a inoculante, no tratamento de sementes de soja (variedade cultivada FT-Abyara), foram realizados dois experimentos, em laboratório (2007) e em campo (safra agrícola de 2007/2008), no Departamento de Biologia da Universidade Federal de Santa Maria, em Santa Maria-RS. O experimento I constou de tratamentos de doses de macronutrientes e micronutrientes em mistura com os fungicidas Thiram e Carbendazim aplicados em Bradyrhizobium spp. em meio de cultura YMA. O experimento II foi realizado para avaliar o efeito do tratamento de sementes de soja com micronutrientes e fungicidas na sobrevivência de Bradyrhizobium spp. e sua influência no crescimento da planta. Com relação aos diferentes fertilizantes avaliados, verifica-se que o maior número de nódulos por planta e maior massa de matéria seca de nódulos foi obtido com os compostos que continham cobalto e molibdênio, resultado também observado em relação aos tratamentos com fungicidas. Os resultados experimentais permitem inferir que todos os tratamentos com fertilizantes aplicados via sementes aumentaram significativamente a altura de planta, o comprimento de raiz, e a massa de matéria seca da parte aérea e de raiz quando comparados à testemunha sem tratamento com fertilizante, fungicida e inoculante. Em função dos resultados obtidos neste trabalho com a cultura de soja, pode-se concluir que: (i) o tratamento de sementes com fungicidas diminui o número de células viáveis de Bradyrhizobium spp.; (ii) a utilização de cobalto e molibdênio no tratamento de sementes proporciona aumento na quantidade de células de Bradyrhizobium spp.; e (iii) o melhor parâmetro para avaliar a eficiência da inoculação no tratamento de sementes é o número de células viáveis de Bradyrhizobium spp. / With the purpose of evaluating the efficiency of fertilizers (with macronutrients - nitrogen, phosphorus and potassium - and micronutrients - cobalt e molybdenum), fungicides and inoculant utilization in the soybean (cultivar \'FT-Abyara\') seed treatment, two experiments were carried out, in laboratory (2007) and in field (season 2007/2008), at Biology Department of Federal University of Santa Maria, in Santa Maria, \'Rio Grande do Sul\' State, Brazil. The experiment I consisted of evaluating the macronutrients and micronutrients doses treatments mixed with fungicides (Thiram and Carbendazim) applied in the YMA culture medium of Bradyrhizobium spp. The experiment II consisted of evaluating the soybean seed treatment (with micronutrients and fungicides) effect on Bradyrhizobium spp. survival and its influence on the plant growth. In relation to different evaluated fertilizers, the higher number of nodules per plant and higher nodules dry mass were obtained with cobalt and molybdenum seed treatments. Similar results also were obtained with fungicides treatments. According to the results, all treatments with fertilizers increased the soybean plant height, root length, dry matter of canopy and roots when compared to the control (without fertilizers, fungicides and inoculant). According to the results, there are the following conclusions: (i) the seed treatment with fungicides decreases the viable cells number of Bradyrhizobium spp.; (ii) the utilization of cobalt and molybdenum in the seed treatment increases the Bradyrhizobium spp. cells number; and (iii) the best parameter to evaluate the seed treatment inoculation efficiency is the viable cells number of Bradyrhizobium spp.

Com o objetivo de avaliar a maneira como a aplicação foliar no estádio fenológico V5, do herbicida pós-emergente Lactofen em mistura com os micronutrientes Co e Mo, pode interferir com o crescimento e a produtividade da cultura da soja, cv. Conquista, o presente trabalho de pesquisa foi conduzido em duas áreas experimentais da Escola Superior de Agricultura \"Luiz de Queiroz\" (USP/ESALQ), em Piracicaba-SP: uma na Fazenda Areão, durante os anos agrícolas de 2003/04, 2004/05 e 2005/06 em solo LATOSSOLO VERMELHO Distrófico argiloso e outra na Estação Experimental de Anhembi, durante os anos agrícolas 2003/04 e 2005/06 em solo LATOSSOLO AMARELO Distrófico típico. Delineado experimentalmente sob blocos ao acaso com quatro repetições, os onze tratamentos constaram de diferentes formas de aplicação e interações entre os micronutrientes Co e Mo e o herbicida pós-emergente Lactofen: T1 = controle; T2 = tratamento de sementes com Co e Mo; T3 = tratamento de sementes com Co e Mo + aplicação de herbicida em V5; T4 = aplicação foliar de Co e Mo em V5; T5 = aplicação foliar de Co e Mo + herbicida em V5; T6 = aplicação de herbicida em V5 + foliar de Co e Mo 3 a 5 dias após; T7 = aplicação foliar de Co e Mo em V5 + aplicação de herbicida 3 a 5 dias após; T8 = aplicação foliar de Co em V5; T9 = aplicação foliar de Co + herbicida em V5; T10 = aplicação foliar de Mo em V5; T11 = aplicação foliar de Mo + herbicida em V5; Os parâmetros avaliados foram: pH das soluções de Lactofen e de micronutrientes; avaliação da fitotoxicidade causada pelo herbicida Lactofen; análise do estado nutricional das plantas em N, Co e Mo; altura final de planta; altura de inserção da primeira vagem; número de ramificações; número de vagens e de grãos por planta; grau de acamamento; peso de 1000 grãos e produtividade agrícola. Concluiu-se que: a) fornecimento de cobalto e molibdênio para a soja, cultivar Conquista, via tratamento de sementes ou via foliar, a partir de sais desses micronutrientes, pode diminuir o peso de mil grãos e a produtividade agrícola da cultura; b) a aplicação foliar do herbicida Lactofen no estádio fenológico V5 da soja, cultivar Conquista, pode interferir negativamente com o crescimento vegetativo, resultando na redução da altura final de planta, do peso de mil grãos e da produtividade agrícola da cultura; c) a aplicação foliar do herbicida Lactofen no estádio fenológico V5 da cultura da soja causa fitotoxicidade às folhas, em grau variável de leve a médio. / The purpose of this work was to evaluate how foliar applications of the post-emergence herbicide Lactofen mixed with the micronutrients Co and Mo at V5 phenological stage influence the growth and productivity of soybean, cv. Conquista. The study was conducted in two experimental areas of Escola Superior de Agricultura \"Luiz de Queiroz\" (USP/ESALQ), Piracicaba-SP. One of them was located in the Areão Farm, in a clay Oxisol, during the crop years 2003/04, 2204/05 and 2005/06. The other was located in the Anhembi Experimental Station, in an Oxisol, during the crop years of 2003/04 and 2005/06. The eleven treatments tested involved different application procedures and interactions between the micronutrients Co and Mo and the post-emergence herbicide Lactofen in a randomized block design, with four replicates. Treatments were T1 = control; T2 = seeds treated with Co and Mo; T3 = seeds treated with Co and Mo + herbicide application at V5 stage; T4 = foliar-applied Co and Mo at V5 stage; T5 = foliar-applied Co and Mo + herbicide application at V5 stage; T6 = herbicide application at V5 stage + foliar-applied Co and Mo 3 to 5 days after herbicide application; T7 = foliar-applied Co and Mo at V5 stage + herbicide application 3 to 5 days after micronutrients application; T8 = foliar-applied Co at V5 stage; T9 = foliar-applied Co + herbicide application at V5 stage; T10 = foliar-applied Mo at V5 stage; T11 = foliar-applied Mo + herbicide application at V5 stage. The parameters evaluated were: pH of Lactofen and micronutrient solutions; phytotoxicity caused by Lactofen; analysis of plant nutritional state regarding N, Co and Mo; final plant height; insertion height of the first pod; number of branches per plant; number of pods and grains per plant; lodging level; mass of 1,000 grains and yield. It was concluded that: a) the application of Co and Mo salts to soybean, cv. Conquista, whether foliar applied or used in seed treatment, may reduce the mass of 1,000 grains and crop productivity; b) the foliar application of Lactofen to soybean, cv. Conquista, at V5 phenological stage may affect the vegetative growth negatively, reducing the plant final height, the mass of 1,000 grains and the yield; c) the foliar application of Lactofen to soybean at V5 V5 phenological stage leads to leaf phytotoxicity at mild to moderate levels.

Com o objetivo de avaliar a maneira como a aplicação foliar no estádio fenológico V5, do herbicida pós-emergente Lactofen em mistura com os micronutrientes Co e Mo, pode interferir com o crescimento e a produtividade da cultura da soja, cv. Conquista, o presente trabalho de pesquisa foi conduzido em duas áreas experimentais da Escola Superior de Agricultura \"Luiz de Queiroz\" (USP/ESALQ), em Piracicaba-SP: uma na Fazenda Areão, durante os anos agrícolas de 2003/04, 2004/05 e 2005/06 em solo LATOSSOLO VERMELHO Distrófico argiloso e outra na Estação Experimental de Anhembi, durante os anos agrícolas 2003/04 e 2005/06 em solo LATOSSOLO AMARELO Distrófico típico. Delineado experimentalmente sob blocos ao acaso com quatro repetições, os onze tratamentos constaram de diferentes formas de aplicação e interações entre os micronutrientes Co e Mo e o herbicida pós-emergente Lactofen: T1 = controle; T2 = tratamento de sementes com Co e Mo; T3 = tratamento de sementes com Co e Mo + aplicação de herbicida em V5; T4 = aplicação foliar de Co e Mo em V5; T5 = aplicação foliar de Co e Mo + herbicida em V5; T6 = aplicação de herbicida em V5 + foliar de Co e Mo 3 a 5 dias após; T7 = aplicação foliar de Co e Mo em V5 + aplicação de herbicida 3 a 5 dias após; T8 = aplicação foliar de Co em V5; T9 = aplicação foliar de Co + herbicida em V5; T10 = aplicação foliar de Mo em V5; T11 = aplicação foliar de Mo + herbicida em V5; Os parâmetros avaliados foram: pH das soluções de Lactofen e de micronutrientes; avaliação da fitotoxicidade causada pelo herbicida Lactofen; análise do estado nutricional das plantas em N, Co e Mo; altura final de planta; altura de inserção da primeira vagem; número de ramificações; número de vagens e de grãos por planta; grau de acamamento; peso de 1000 grãos e produtividade agrícola. Concluiu-se que: a) fornecimento de cobalto e molibdênio para a soja, cultivar Conquista, via tratamento de sementes ou via foliar, a partir de sais desses micronutrientes, pode diminuir o peso de mil grãos e a produtividade agrícola da cultura; b) a aplicação foliar do herbicida Lactofen no estádio fenológico V5 da soja, cultivar Conquista, pode interferir negativamente com o crescimento vegetativo, resultando na redução da altura final de planta, do peso de mil grãos e da produtividade agrícola da cultura; c) a aplicação foliar do herbicida Lactofen no estádio fenológico V5 da cultura da soja causa fitotoxicidade às folhas, em grau variável de leve a médio. / The purpose of this work was to evaluate how foliar applications of the post-emergence herbicide Lactofen mixed with the micronutrients Co and Mo at V5 phenological stage influence the growth and productivity of soybean, cv. Conquista. The study was conducted in two experimental areas of Escola Superior de Agricultura \"Luiz de Queiroz\" (USP/ESALQ), Piracicaba-SP. One of them was located in the Areão Farm, in a clay Oxisol, during the crop years 2003/04, 2204/05 and 2005/06. The other was located in the Anhembi Experimental Station, in an Oxisol, during the crop years of 2003/04 and 2005/06. The eleven treatments tested involved different application procedures and interactions between the micronutrients Co and Mo and the post-emergence herbicide Lactofen in a randomized block design, with four replicates. Treatments were T1 = control; T2 = seeds treated with Co and Mo; T3 = seeds treated with Co and Mo + herbicide application at V5 stage; T4 = foliar-applied Co and Mo at V5 stage; T5 = foliar-applied Co and Mo + herbicide application at V5 stage; T6 = herbicide application at V5 stage + foliar-applied Co and Mo 3 to 5 days after herbicide application; T7 = foliar-applied Co and Mo at V5 stage + herbicide application 3 to 5 days after micronutrients application; T8 = foliar-applied Co at V5 stage; T9 = foliar-applied Co + herbicide application at V5 stage; T10 = foliar-applied Mo at V5 stage; T11 = foliar-applied Mo + herbicide application at V5 stage. The parameters evaluated were: pH of Lactofen and micronutrient solutions; phytotoxicity caused by Lactofen; analysis of plant nutritional state regarding N, Co and Mo; final plant height; insertion height of the first pod; number of branches per plant; number of pods and grains per plant; lodging level; mass of 1,000 grains and yield. It was concluded that: a) the application of Co and Mo salts to soybean, cv. Conquista, whether foliar applied or used in seed treatment, may reduce the mass of 1,000 grains and crop productivity; b) the foliar application of Lactofen to soybean, cv. Conquista, at V5 phenological stage may affect the vegetative growth negatively, reducing the plant final height, the mass of 1,000 grains and the yield; c) the foliar application of Lactofen to soybean at V5 V5 phenological stage leads to leaf phytotoxicity at mild to moderate levels.

O Brasil planeja construir uma planta de produção do 99Mo por fissão do 235U, devido à crescente utilização deste radioisótopo no setor de medicina nuclear. Neste trabalho buscou-se estimar as características físico-químicas e radiológicas dos rejeitos radioativos que serão gerados em tal instalação, além de fornecer subsídios teóricos a serem utilizados na definição do gerenciamento desses rejeitos. Estabelecidos dois cenários de produção para este projeto e utilizando-se o código Scale®, foram calculados os inventários radioisotópicos dos fluxos de rejeitos. Considerando-se o processamento químico dos alvos de urânio, foi possível caracterizar os rejeitos a partir de suas características químicas e radiológicas. Utilizando-se o software MicroShield®, determinou-se então as concentrações de atividade desses rejeitos em até 3 meses de produção. Este trabalho ainda apresenta o cálculo das taxas de dose variando-se tanto a espessura da blindagem, a ser utilizada numa embalagem para transporte in-site, quanto a quantidade de rejeito líquido retido em tal embalagem. Os radionuclídeos responsáveis pela maior parcela da dose de radiação foram identificados de forma a facilitar a determinação do método mais apropriado para o gerenciamento dos rejeitos após sua separação e antes de seu armazenamento. Os resultados aqui apresentados constituem uma compilação inicial do que é esperado em termos de rejeitos radioativos líquidos numa planta produtora de 99Mo e podem auxiliar no desenvolvimento do plano de gerenciamento de rejeitos de tal instalação. / Brazil intends to build a facility for the 99Mo production through 235U fission, once this radioisotope is largely used in nuclear medicine. This study aimed at estimating the physical, chemical and radiological characteristics of radioactive waste expected to be generated in that facility, and to provide theoretical subsides that can be used on the definition of a proper waste management system. Two production scenarios were established and the radioisotope inventories of the wastes were calculated by Scale®. From the chemical processing of the uranium targets the wastes were characterized on their chemical and radiological features. MicroShield® was used to determine the activity concentrations up to three months of 99Mo production. In addition, this work presents dose rate calculation for several sizes of shielding and different amount of wastes, collected in a proper package for in-site transportation. Radionuclides responsible for higher doses were identified in order to facilitate choosing the most appropriate method for managing the wastes after their chemical separation and before their storage. These results are part of what is expected on radioactive wastes at a 99Mo production facility and might help on the development of the waste management planning for that facility.

The syntheses of a new class of polycyclic TriAmino DiCarbenes (TADCs), based on 3,9-diazajulolidine, and their precursors and adducts are described. Starting with 2,6-dimethyl-nitrobenzene, 2,6-bis ((alkylamino)methyl)anilines (alkyl = isopropyl, mesityl, and tert-butyl) were synthesized in 40% yield over five steps. These triamines were then di-cyclized stepwise to diformamidinium dications or formamidinium/2-methoxyformaminals using oxonium salts and trialkyl orthoformates. A diformamidinium dication was characterized by single-crystal X-ray diffractometry. Treatment with various bases, particularly lithium hexamethyldisilylazide, led to the novel TADCs and monocarbenes, two of which were isolated and characterized by 1H and 13C NMR spectroscopies. In both cases, treatment with elemental sulfur trapped the TADCs as dithiobiurets. No TADC-transition metal complexes were successfully isolated from reactions of the diformamidinium dications or LiHMDS TADC complex with a number of transition metal complexes. With the exception of these two cases, all other TADCs were not isolated because they rapidly reacted to form dimers, trimers, and tetramers. One of these dimers was isolated and its structure determined using 1D and 2D NMR spectroscopies, along with high-resolution electrospray ionization mass spectrometry. This revealed that the TADC had dimerized to form an ene-triamine, likely via 1,3-shift of a benzylic proton. Novel N-heterocyclic Carbene (NHC) complexes of molybdenum were also synthesized and characterized. Reaction of Cp2Mo2(CO)4 (Cp = C5H5) with dimesityl-imidazol-2-ylidenes (IMes) or dimesityl-imidazolidin-2-ylidenes (SIMes) yielded the molybdoradicals CpMo(CO)2(NHC) (NHC = IMes or SIMes). The carbonyl infrared stretching frequencies and the relative metal-to-NHC π-backbonding for IMes and SIMes complexes are compared. Reaction of the less bulky dimethyl-imidazol-2-ylidene (IMe) with Cp2Mo2(CO)4 yielded the Mo-Mo triple bond complex Cp2Mo2(CO)3(IMe) by CO substitution. This is the first example of an NHC-ligated metal-metal multiply bonded complex. Single crystal X-ray diffractometry of these new organomolybdenum and organodimolybdenum complexes is discussed.