La synthèse et caractérisation de deux nouveaux liquides ioniques à base de cholinium nommés N-(2-hydroxyethyl)-N, N-dimethyl-N-octylammonium bis(trifluoromethanesulfonyl)imide [C8linChol]+[NTf2]- et N-(2-hydroxyethyl)-N-(2-ethylhexyl)-N, N-dimethyl ammonium bis(trifluoromethanesulfonyl)imide [C8ramChol]+[NTf2]- ont été synthétisés et caractérisés par 1H NMR, 13C NMR, ATR-FTIR et ESI-MS. Les propriétés thermodynamiques comme l’énergie d’activation pour le flot visqueux, le volume molaire et l’entropie molaire ont été déduits de mesures de la masse volumique et de la viscosité. Ces calculs ont montré que les liquides ioniques possédant des chaînes alkyles ramifiées sont plus ordonnés que ceux qui ont des chaînes alkyles linéaires. L’étude des propriétés d’extraction du liquide ionique ramifié et du liquide ionique linéaire montre qu’ils sont capables d’extraire respectivement 98,6% et 40,5% d’Ag(I) à pH 5. L’extraction d’Ag(I) avec un liquide ionique dérivé du phosphonium (2,4,4 dimethyl(penthyl) phosphinate de trihexyl (tetradecyl) phosphonium a également été étudié. Cette étude montre en particulier que 80 à 85% de l’Ag(I) pet être extrait à un Ph 3 par ce liquide ionique dilué dans un kérosène modifié ou non par du decan-1-ol. La spectroscopie infrarouge montre que l’extraction provient probablement de l’anion protonné du liquide ionique. / Synthesis and characterization of two new cholinium-based ionic liquids, named N-(2-hidroxyethyl)-N,N-dimethyl-N-octylammonium bis(trifluoromethanesulfonyl)imide [C8linCol]+[NTf2]- and N-(2-hidroxyethyl)-N-(2-ethylhexyl)-N,N-dimethyl-ammonium bis(trifluoromethanesulfonyl)imide [C8ramCol]+[NTf2]- has been developed by 1H NMR, 13C NMR, ATR-FTIR y ESI-MS. Properties as the viscous flux activation energy, the volume or the molar entropy have been calculated from the experimental data on density and viscosity. Calculations showed that the ramified ionic liquid possess a higher degree of structural order when compared with the linear ionic liquid. Also, their capacity for the recovery of Ag (I) was determined and an extraction level of 98.6% for the linear and 40.5% for the ramified ionic liquid was found. Maximum extraction was found at pH 5.0 with an important selectivity on the extraction of Ag (I) and Cu (II) towards Fe (III). Ag (I) extraction with a phosphonium-based ionic liquid (2,4,4 dimethyl(penthyl) phosphinate de trihexyl(tetradecyl) phosphonium) was also tested. Extraction tests were developed at different concentration values when dissolved in kerosene or kerosene plus decan-1-ol. An extraction level of 80 to 85% was determined with the different mixtures at a maximum recovery pH of 3.0. Spectroscopic characterization (ATR-IR) showed the protonation of the anion in the ionic liquid forming the acid specie. This specie is probably the responsible for the extraction of silver. The formation of a dimeric specie was found in the 31P NMR and the value of the formation constant was calculated.

Abstract This study concentrates on the preparation and characterization of some ionic liquids and their use in dimerization reaction of 2-methylpropene. Ionic liquids consist of cations and anions, and are commonly understood as green solvents. By definition their melting points should be lower than 100 °C. Prepared ionic liquids were used as catalytic solvents in dimerizations of 2-methylpropene to a high octane compound, isooctene. The monograph consists of two parts: the literature survey and the practical work. The literature survey reviews the preparation and characterization of ionic liquids as well as their environmental aspects, such as toxicity, biodegradability and recyclability. In addition, the acid catalyzed dimerization of butenes is discussed together with the dimerizations of light olefins carried out in ionic liquids. The practical work consists of three entities: The environmentally benign preparation of 1-alkyl-3-methylimidazolium-based ionic liquids under microwave activation, the characterization of ionic liquids and the use of the ionic liquids in the dimerization reaction. Ionic liquids absorb efficiently microwave irradiation and the most beneficial aspect in the microwave-assisted preparations was the considerably shortened reaction time compared to the conventional methods. In addition to the microwave-assisted preparations, [Cnmim][InCl4] ionic liquids were prepared successfully without microwave irradiation. A special attention was paid to the characterization of ionic liquids since impurities are known to affect on the properties of the ionic liquids. Ionic liquids were analysed with the following methods: 1H and 13C NMR, MS(ESI+ and ESI-), GC and elemental analysis. Characterization of ionic liquids was done by determining the thermal stability, the melting point and the crystal structure of each solid ionic liquid. The determination of the liquid range of ionic liquid is necessary in order to know the temperature limits for each ionic liquid. Novel InCl3-based ionic liquids revealed to be the more efficient than Brønsted acidic ILs as a catalytic reaction media in the dimerization of 2-methylpropene. It was preferable to apply [C6mim]Cl/InCl3 (x(InCl3) = 0.55) as a catalytic IL since then the conversion of 2-methylpropene and the product distribution revealed to be good. In order to maximize the production and the separation of dimers reaction should be carried out continuously at temperature high enough, such as 160 °C. Neutral InCl3-based ionic liquid did not catalyze reaction of 2-methylpropene, but it had to be acidic x(InCl3) > 0.5. Excess of InCl3 did not leach out from the IL and the recycling of IL was possible.

Au cours de cette thèse, des dispositifs électrochromes à base de polymères conducteurs électroniques ont été développés pour obtenir des systèmes pouvant passer d’un état coloré cyan, magenta ou jaune à un état incolore. Les polymères électrochromes sont des dérivés du poly(3,4-propylènedioxythiophène) (PProDOT) et du poly(3,4-éthylènedioxythiophène) (PEDOT). Un réseau de polyéthylène glycol incorporant un liquide ionique 1-éthyl-3-méthylimidazolium bis(trifluorométhylsulfonylimide) (EMITFSI) a été utilisé en tant que gel d’électrolyte. Dans un premier temps, les polymères cyan, magenta et jaunes ont été étudiés. La relation entre structure et propriétés colorimétriques des polymères cyan et jaunes a été étudiés par des calculs théoriques avec la théorie de fonctionnelle de densité, la spectroscopie UV/Vis et la colorimétrie. Ces deux dernières techniques ont également été utilisées pour l’étude des polymères magenta. Les polymères présentant les meilleures propriétés optiques ont ensuite été intégrés dans des dispositifs à deux électrodes. Ceux-ci ont été étudiées par des mesures électrochimiques pour évaluer les effets sur le fonctionnement du système et sa durée de vie. Grâce aux données obtenues, nous avons pu montrer que la stabilité des dispositifs était liée à l’efficacité coulombique des polymères cyan, magenta ou jaunes. Pour contourner l’effet de l’efficacité coulombique sur les systèmes en 2 électrodes, nous avons développé des dispositifs intégrant une pseudo-référence. L’application de ces systèmes à 3 électrodes avec un polymère cyan permet de multiplier la gamme de stabilité par 7. Finalement des démonstrateurs ont été produits avec plusieurs dispositifs de chaque couleur. / During the course of this work, electrochromic devices integrating electronically conductive polymers have been developed to obtain systems that could switch from a cyan, magenta or yellow color to an almost colorless one. The electrochromic polymers are derivatives of poly(3,4-propylenedioxythiophene) (PProDOT) and poly(3,4-ethylenedioxythiphene) (PEDOT). A network of polyethyleneglycol swollen with an ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) (EMITFSI) was used as a gel polymer electrolyte. As a first step, the cyan, magenta and yellow polymers were studied. The relationship between structure and colorimetric properties of the cyan and yellow polymers have been studied with theoretical calculation using the density functional theory, UV/Vis spectroscopy and colorimetry. These last two techniques have also been used to study the magenta polymers. The polymers with the best optical properties have then been integrated inside two electrode devices. They have been characterized with electrochemical measurement to evaluate the effects on the system and its lifetime. The data showed that the stability of the devices was linked to the reversibility of the cyan magenta or yellow polymers. As a workaround to the coulombic efficiency limitation on the 2 electrode systems, we have developed devices with a pseudo-reference. The application of those 3 electrode systems with a cyan polymer leads to a 7 fold increase of the device lifetime. Finally demonstrators have been produced with several devices of each color.

No description available.

The attenuation mechanism of shock waves of arbitrary strength propagating in air has been reasonably well understood. On the other hand, very little is known about the precise mechanism of shock wave attenuation and energy dissipation in liquids. The equation of state for shock propagation in water is empirical in nature and considerable differences exist with reference to the exact value of various constants even in the cast of Tait’ s equation of state, which is popularly used by researchers to describe the shock wave propagating through water. In recent times, considerable attention is being focused by researchers on shock wave attenuation and associated features in liquid medium mainly in the backdrop of development of many innovative industrial applications of shock waves. The present study focuses on generating reliable experimental data on shock wave attenuation in liquids of different viscosity. Experiments have been performed in a conventional vertical shock tube and a modified diaphragmless shock tube to understand how shock wave of requisite strength attenuates in liquids. A new vertical shock tube was designed, fabricated and successfully tested in the laboratory as a part of this study. In this new facility shock loading experiments with liquids or any complex fluid medium can be carried out. In the present study five liquids (Water, Castor Oil, Sodium Chloride (10%NaCl aqueous solution), Kerosene and Glycerin) have been subjected to shock wave loading. Exhaustive static pressure measurements in the liquid medium have been carried out to understand the attenuation characteristics of shock waves. The validity of Taits equation state has been experimentally verified for water. Based on the experimental results modified Taits equation of state has been obtained for castor oil, sodium chloride, kerosene and glycerin. Illustrative theoretical study is also carried out to complement the experiments.

Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T13:08:08Z (GMT). No. of bitstreams: 1 Corilo_YuriEberlimde_M.pdf: 973329 bytes, checksum: 0e8a6362dd2a94d8ce4185376aa8bde3 (MD5) Previous issue date: 2009 / Resumo: A técnica de ionização a pressão atmosférica por electrospray (ESI) se tornou rapidamente a mais utilizada nas áreas de química e bioquímica, em estudos mecanísticos e em análises por ¿fingerprinting¿. ESI é versátil devido a sua alta sensibilidade e capacidade de transferir espécies iônicas da solução para a fase gasosa de forma branda, permitindo inclusive que espécies de alto peso molecular fracamente ligadas permaneçam intactas. Entre os líquidos iônicos (LI) já conhecidos, destacam-se os compostos heterocíclicos da classe dos cátions imidazólios. A espectrometria de massas não era capaz de detectar e analisar essa classe de compostos devido à baixa volatilidade que estes LI apresentam. Entretanto, com o desenvolvimento da técnica de ESI tornou-se possível à transferência desses compostos para a fase gasosa de uma forma bastante branda e eficaz. Estas espécies, podem ser detectadas por espectrometria de massas mesmo sofrendo modificações como fragmentações, rearranjos e reações, pelo fato de um ou dois anéis imidazóis funcionarem como uma ¿âncora¿ de carga, permitindo o estudo de propriedades intrínsecas destes compostos, como reatividade bimolecular. Através de experimentos com ESI em tandem (ESI-pseudo-MS, e ESIMS/ MS) utilizando a técnica de dissociação induzida por colisão (CID), foi possível formar, selecionar e identificar várias novas espécies de carbenos e radicais com sítios afastados de cargas múltiplas e arinos imidazólios / Abstract: The ionization technique, atmospheric pressure electrospray (ESI) has become rapidly the most used in the fields of chemistry and biochemistry, mechanistic studies and in analysis by fingerprint. ESI is versatile due to its high sensibility and capability to transfer ionic species from the solution to the gas phase in a soft way, allowing, inclusively, that species of high molecular weight weakly bonded remain intact. Among the ionic liquids (IL¿s) known, heterocyclic imidazolium cations stand out. Mass spectrometry was not able to detect and analyze this class of compounds due to the low volatility of these compounds. However, with the development of the ESI technique has become possible the transfer of these compounds to the gas phase. These species may be detected by mass spectrometry even when they suffer modifications such as fragmentations, rearrangements or other reactions, due to the fact that one or two imidazolium rings work as a charge ¿anchor¿, allowing the study of intrinsic proprieties of these compounds, such as bimolecular reactivity. Through tandem ESI experiments (ESI-psedo-MS, and ESI-MS/MS) using the collision induced dissociation (CID) technique, it was possible to form, select and identify several new species of multiply charged carbenes, radicals and arynes / Mestrado / Quimica Organica / Mestre em Química

Orientador: Marcos Nogueira Eberlin / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:25:38Z (GMT). No. of bitstreams: 1 Nachtigall_FabianeManke_D.pdf: 3920782 bytes, checksum: 88d49f1c9eaf6b17b3567019b6df9444 (MD5) Previous issue date: 2009 / Resumo: Com o objetivo de entender as propriedades intrínsecas dos líquidos iônicos imidazólios, foram desenvolvidos trabalhos de investigação dos mecanismos de dissociação e destilação, força intrínseca de ligações de hidrogênio e formação e caracterização de carbenos a partir destes compostos. Tais estudos foram realizados através da espectrometria de massas com técnicas API (Atmospheric Pressure Ionization) como ESI-MS(/MS) (Eletrospray Ionization Mass Spectrometry) e APCI-MS(/MS) (Atmospheric Pressure Chemical Ionization Mass Spectrometry) que são técincas de ionização branda que permitem a análise dos compostos por infusão direta da solução de interesse. Para estes estudos foram escolhidos cátions imidazólios com diferentes substituintes nas posições N-1, N-3 e C-2, além de diferentes ânions como contra-íons. O objetivo do trabalho foi testar como essas modificações na cadeia iriam afetar as porpriedades intrínsecas estudadas. A partir dos resultados obtidos nos trabalhos realizados foi possível propor mecanismos de fragmentação para uma vasta gama de líquidos iônicos imidazólios, e propor um mecanismo de destilação para alguns destes compostos. Foram realizadas medidas onde foi possível ordenar e medir a magnitude intrínseca das ligações de hidrogênio para diferentes cátions. Além disso foram obtidas informações a respeito da formação e caracterização de carbenos a partir de líquidos iônicos di, tri e tetraimidazólios. / Abstract: In order to understand the intrinsic properties of imidazolium ionic liquids, studies of dissociation and distillation mechanisms were developed. The intrinsic strength of hydrogen bonds and formation and characterization of carbenes from these compounds were also investigated. Such studies were conducted by API (Atmospheric Pressure Ionization) mass spectrometry techniques such as ESI-MS(/MS) (Electrospray Ionization Mass Spectrometry) and APCI-MS(/MS) (Atmospheric Pressure Chemical Ionization Mass Spectrometry) which are soft ionization techniques allowing the analysis of compounds by direct infusion of the solution of interest. For these studies, imidazolium cations with different substituent at positions N-1, N-3 and C-2 and different anions as counter ions were selected. The objective was to test how these changes in the chains would affect the intrinsic properties studied. From the results of the work fragmentation mechanisms for a wide range of imidazolium ionic liquids were proposed, as well as a mechanism for the distillation of some of these compounds. Measurements were made to order the intrinsic strength of hydrogen bonding for different cations. Further information was obtained about the formation and characterization of carbenes from di-, tri-and tetra-imidazolium ionic liquids. / Doutorado / Quimica Organica / Doutor em Ciências

Orientador: Carlos Roque Duarte Correia / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:22:36Z (GMT). No. of bitstreams: 1 Pastre_JulioCezar_D.pdf: 10159507 bytes, checksum: 4f4f32c2c414df354e1d53179d9ebe18 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho, efetuou-se um estudo da reação de Heck de acrilatos substituídos com sais de arenodiazônio. Um protocolo estereosseletivo para a preparação de acrilatos b,b-diarilssubstituidos foi desenvolvido, baseando-se na arilação Heck do cinamato de metila com sais de arenodiazônio, catalisada por Pd(OAc)2, em metanol. A diastereosseletivade da reação de Heck apresentou uma acentuada dependência com a natureza eletrônica do sal de arenodiazônio empregado. A metodologia ainda forneceu uma rota conveniente para 3-arilindanonas e 4-ariltetralonas, permitindo as sínteses formais totais da (±)-indatralina (4 etapas, 54 % de rendimento global) e da (±)-sertralina (7 etapas, 49 % de rendimento global). A extensão da metodologia para acrilatos mais substituídos (inclusive para acrilatos cíclicos) foi feita com sucesso para a maioria dos casos e os adutos de Heck foram obtidos em bons rendimentos e seletividades, independente do padrão de substituição do sal de arenodiazônio empregado. Esta metodologia foi aplicada à síntese total da (±)-paroxetina (8 etapas, 15 % de rendimento global) e da (±)-nocaína (6 etapas, 20 % de rendimento global). Verificou-se ainda que a reação de arilação de Heck empregando sais de arenodiazônio ocorre de maneira eficiente em meios reacionais alternativos, como PEG e líquidos iônicos. Uma série de líquidos iônicos quirais inéditos do tipo piridínio, imidazolínio e imidazólio foi preparada e testada, não revelando nenhuma incidência no curso estereoquímico da reação. Os resultados obtidos demonstram o enorme potencial sintético do emprego de sais de arenodiazônio em reações de Heck, constituindo uma metodologia bastante versatil em Síntese Orgânica. / Abstract: In this work, we present a study of the Heck reaction of substituted acrilates with arenediazonium salts. A stereoselective protocol for the preparation of b,b-disubstituted acrylates in good yields by means of a Heck-Matsuda reaction was accomplished. The method employs a base- and ligand-free Heck reaction of methyl cinnamate using arenediazonium salts as electrophiles. The Heck reaction displays a remarkable electronic dependence regarding the diastereoselectivity of the arylation process, which correlates with the electronic nature of the arenediazonium salts employed. The overall methodology provides a convenient route to 3-arylindanones and 4-aryltetralones allowing the concise formal total syntheses of the therapeutically important psychoactive compounds (±)-indatraline (4 steps, 54 % global yield) and (±)-sertraline (7 steps, 49 % global yield). The methodology was also successfully extended to more substituted acrylates and the Heck adducts were obtained in good to excellent yields, regardless of the substitution pattern of the arenediazonium salt employed. This methodology was applied to the total synthesis of (±)-paroxetine (8 steps, 15 % global yield) and (±)nocaine (6 steps, 20 % global yield). We also verified that the Heck reaction using arenediazonium salts occurs in an efficient way in alternative reaction media, like PEG and ionic liquids. A series of new chiral ionic liquids was prepared and evaluated in the Heck reaction. In spite the overall performance of the Heck reaction, in all the cases studied no asymmetric induction was detected. Our results demonstrate the enormous synthetic potential of the Heck reaction using arenediazonium salts, constituting a versatile methodology in Organic Synthesis. / Doutorado / Quimica Organica / Doutor em Ciências

Orientador: Maurice de Koning / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-27T17:09:46Z (GMT). No. of bitstreams: 1 Leite_RodolfoPaula_M.pdf: 4064445 bytes, checksum: 15e944e3607ec0d3b8cb66d00b6ea4f3 (MD5) Previous issue date: 2015 / Resumo: Neste trabalho, apresentamos um estudo a respeito do modelo de Uhlenbeck-Ford como um sistema de referencia para calculos de energia livre de sistemas na fase fluida, utilizando metodos de simulacao molecular. Este sistema artificial, que e caracterizado por um potencial puramente repulsivo e que diverge rapidamente, foi originalmente proposto como um modelo para o estudo teorico de gases imperfeitos. Este modelo foi motivado pelo fato de que todas as integrais de muitos corpos, envolvidas no calculo dos coeficientes viriais, podem ser facilmente calculadas analiticamente. Entretanto apenas oito coeficientes eram conhecidos. Dois novos coeficientes (..10 e ..11) foram determinados para o modelo neste trabalho, alem de uma expressao essencialmente exata para a equacao de estado e energia livre de Helmholtz em funcao de um parametro adimensional. Este nos permitira reunir todas as informacoes a respeito da energia livre do sistema em uma unica expressao, independentemente da escolha de parametros do potencial. Por fim, exploraremos a aplicabilidade deste modelo como um sistema de referencia para calculos de energia livre de sistemas na fase fluida, usando tecnicas de simulacao molecular a partir de processos fora de equilibrio. Nossos resultados para o fluido de Lennard-Jones e para o silicio liquido, descrito pelo potencial de Stillinger-Weber, demonstraram que o modelo de Uhlenbeck-Ford servira como um sistema de referencia para o calculo de energia livre de sistemas na fase fluida / Abstract: In this work, we present a study of the Uhlenbeck-Ford model as a reference system for freeenergy calculations of fluid-phase systems by molecular simulation methods. This artificial system, which is characterized by a rapidly-decaying purely repulsive potential, was originally proposed as a model for the theoretical study of imperfect gases, enabled by the fact that all the many-center integrals involved in the virial coefficients can be easily computed analytically. Although only eight coefficients were known. Two new coefficients (..10 e ..11) were determined for the model in this work, in addition to an essentially accurate expression to the equation of state and Helmholtz free-energy as a function of a dimensionless parameter. This will allow us to gather all information regarding the system of free-energy in a single expression, regardless of the choice of potential parameters. In the end, we explore the applicability of this model as a reference system for free-energy calculations of fluid-phase systems, using non equilibrium process with molecular simulation techniques. Our results for thevLennard-Jones fluid and liquid silicon, described by Stillinger-Weber potential, demonstrate that the Uhlenbeck-Ford model can be used as a reference system for free-energy calculations of fluid-phase systems / Mestrado / Física / Mestre em Física

Orientador: Alex Antonelli / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T22:57:05Z (GMT). No. of bitstreams: 1 AlvarezDonado_ReneAlberto_M.pdf: 4171490 bytes, checksum: e9cef25e59956ed4e6201f408c88c61c (MD5) Previous issue date: 2016 / Resumo: Através de simulações de dinâmica molecular (MD) estudou-se o comportamento da viscosidade como função da temperatura para a liga Cu46Zr47Al7 que apresenta uma transição dinâmica frágil - forte. A interação entre as partículas foi modelada pelo potencial Modified Embeddded Atom Method (MEAM). As simulações de dinâmica molecular foram feitas usando as equações de Nosé-Hover e a viscosidade foi calculada pela fórmula de Green-Kubo. Observou-se que para uma temperatura reduzida (Tg/T ) de 0.8, o comportamento da viscosidade muda de frágil para forte. Usando a equação de Vogel-Fulcher-Tammann (VFT) em nossos resultados da simulação, observou-se que os valores da viscosidade calculados acima de 0.8 não são bem descritos por este ajuste, o que pode ser entendido como uma mudança no comportamento da viscosidade depois de atingir essa temperatura. A regressão feita usando a equação do VFT deu um valor limitante inferior para a temperatura de transição vítrea de 650K, o qual é um valor próximo da temperatura de transição vítrea reportada para estas ligas / Abstract: By means of molecular dynamic simulation (MD) we studied the behavior of the viscosity of a Cu46Zr47Al7 alloy, as a function of temperature, which displays a fragile - strong transition. Interactions between particles are modeled using the Modified Embedded Atom Method (MEAM). For the molecular simulations, we used the Nosé-Hoover equations, while the Green-Kubo formula gave us the viscosity. It was observed that, for a reduced temperature (Tg/T ) of 0.8, the behavior of the viscosity changes from fragile to strong. Using the Vogel-Fulcher-Tammann (VFT) equation in our results from the simulation, we noticed that the viscosity values above of 0.8 reaching this temperature. The regression achieved by VFT equation gave us a lowerbound value of 650K for the glass transition, which is very close to the glass transition temperature reported for this kind of alloys / Mestrado / Física / Mestre em Física / 1370420/2014 / CAPES