Thèses sur le sujet « Suivi de réactions chimiques »
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Lewiner, France. « Application de la spectroscopie IRTF-ATR in situ au suivi en ligne de cristallisations discontinues ». Lyon 1, 2000. http://www.theses.fr/2000LYO10270.
Texte intégralBaumgarten, Guilherme. « Développement et caractérisation d’une sonde RMN portable appliquée au suivi de la qualité de l’eau et à l’étude de la cinétique des réactions chimiques ». Electronic Thesis or Diss., Strasbourg, 2024. http://www.theses.fr/2024STRAD014.
Texte intégralNuclear Magnetic Reaction (NMR) spectroscopy is a widely employed technique in the detection and quantification of chemical compounds, with a wide range of applications. In this manuscript, the focus is put on two of them: the detection of pollutants in drinking water and the monitoring of chemical reactions. While laboratory NMR equipment presents highly reliable analysis results, portable miniaturized NMR is an evolving research field with multiple technological and application-related challenges. Such emerging devices present however a clear advantage when compared to the classic, stablished ones: it can be used in the field, therefore saving time and limiting staff and consumables costs. In order to design NMR spectrometers to attain the desired portability and miniaturization, one has to compromise, however being able to understand what is at stake, so that the final product still meets the demands. For that, we propose a complete NMR simulation toolchain capable of generating diverse outcomes corresponding to a real NMR spectrometer. Furthermore, we develop a proof of concept for an electronic control and acquisition unit based on commercial-off-the-shelf components and validate it on a portable NMR spectrometer prototype. Finally, we use this prototype to assess the potential of portable miniaturized NMR for the targeted applications cited above. This study allowed us to identify the limits of our current prototypical device and to provide directions for its further improvement
Malangi, Gajendramurthy Chunchesh. « Vers la conception d'une sonde RMN immersible pour le suivi des réactions en solution ». Electronic Thesis or Diss., Strasbourg, 2024. http://www.theses.fr/2024STRAF007.
Texte intégralThis endeavour represents a pioneering effort to design and develop a cost-effective low-field Dip-NMR or Immersible NMR system dedicated to monitoring reaction mixtures at the closest possible source of information. While we have successfully designed and optimized the first version of prototype capable of acquiring single scanned NMR spectra of pure samples, further focused study and research are highly warranted to develop and integrate prototype into an immersible probe unit capable of multi-channel acquisition to realize the proposed Dip-NMR system. The NMR spectra obtained from Dip-NMR system were notably broad and necessitated dedicated chemometric methods for quantification and kinetic data extraction. Known reactions were monitored on a high-field high-resolution NMR spectrometer, with the kinetic data from this instrument serving as benchmark data for comparison and evaluation against the data obtained from Dip-NMR system. Various chemometric methods were explored and tested on the mimicked spectra for quantification and kinetic data extraction, with the results subsequently compared with the benchmark data. In parallel with the project’s goal, hydrosilylation reactions involving organic substrates such as nitriles, cyclic amides, and esters were catalyzed using an Ir(III) catalyst and monitored on a high-field high-resolution NMR spectrometer. These investigations have successfully yielded valuable insights into the reactions, contributing to a deeper understanding of the processes involved and laid important reference kinetic data for future testing of an advanced Dip-NMR probe prototype
Zuber, Emmanuel. « Approche biométrique de la dynamique de réactions antigène-anticorps : cas de deux systèmes automatisés de suivi en temps réel des cinétiques ». Lyon 1, 1997. http://www.theses.fr/1997LYO1T113.
Texte intégralGracia, Nadège. « Oxydation des lubrifiants moteurs suivie par spectroscopie infarouge et analyse chimiométrique ». Caen, 2010. http://www.theses.fr/2010CAEN2071.
Texte intégralMaintaining the quality of lubricants is essential because of their key role in machine duration and performance. Oxidation is one of the main causes of oil degradation. To prevent and reduce the consequences of this phenomena in the best possible way, mechanisms must be determined and well understood. An experimental system was built to reproduce, at the lab-scale and in an accelerated mode, the oxidation process of lubricating base oils under temperature close to those existing under working conditions. Mid-infrared spectroscopy has been chosen for on-line monitoring of the chemical changes happening along the process. To understand the oxidation evolution, the spectroscopic data recorded have been analysed with factorization techniques such as Principal Component Analysis (PCA), which has shown the action of iron as catalyst. The use of Multivariate Curve Resolution – Alternating Least Squares (MCR-ALS) method allowed to extract chemical information about the evolution of a substituted diphenylamine antioxidant during the induction period
Guenet-Attia, Frédérique. « Obtention rapide de modèles thermo-cinétiques de réactions en chimie fine par le couplage de la calorimétrie réactionnelle et du suivi analytique par spectroscopie infra-rouge ». Toulouse, INPT, 1998. http://www.theses.fr/1998INPT013G.
Texte intégralLaforge, Sébastien. « Transformation des xylènes sur zéolithe H-MWW : localisation des réactions dans les divers systèmes poreux ». Poitiers, 2003. http://www.theses.fr/2003POIT2283.
Texte intégralThe aim of this work was to determine precisely the role played by each of the three pore systems of the MCM-22 zeolite during xylenes transformation at 350ʿC. In the large supercages, the reactant can isomerise but also disproportionate, giving toluene and trimethylbenzenes. The latter, trapped inside the cages, undergo several secondary transformations, leading to the complete deactivation of this pore system after 24 hours of reaction. The role played by the external cups has been determined after poisoning with 2,4-dimethylquinoline. The relative significance of this pore system depend largely on the nature of the reactant but also on the physicochemical properties of the catalyst, and can be responsible for more than 30 % of the initial activity of MCM-22 zeolite. Finally, in the sinusoidal channels, only isomerization between m-xylene and p-xylene can occur, due to the small diameter of these channels
Lakraa, Mohammed. « Etude du fonctionnement d'un lit circulant pour la réaction catalytique d'oxydéshydrogénation de l'acide isobutyrique en acide méthacrylique ». Lille 1, 1994. http://www.theses.fr/1994LIL10189.
Texte intégralSuisse, Philippe. « Synthèse du malonate de dimethyle par méthoxycarbonylation du dichlorométhane en catalyse homogène : méthodes chimiques et électrochimiques ». Lille 1, 1994. http://www.theses.fr/1994LIL10156.
Texte intégralYindoula, Philippe-José. « Étude des réactions chimiques par diffusion de la lumière ». Bordeaux 1, 1988. http://www.theses.fr/1988BOR10559.
Texte intégralLuca, Aurélie de. « Espaces chimiques optimaux pour la recherche par similarité, la classification et la modélisation de réactions chimiques représentées par des graphes condensés de réactions ». Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF027.
Texte intégralThis thesis aims to develop an approach based on the Condensed Graph of Reaction (CGR) method able to (i) select an optimal descriptor space the best separating different reaction classes, and (ii) to prepare special descriptors to be used in obtaining predictive structure-reactivity models. This methodology has been applied to similarity search studies in a database containing 8 different reaction classes, and to visualization of its chemical space using Kohonen maps and Generative Topographic Mapping. Another part of the thesis concerns development of predictive models for pKa and for optimal conditions for different types of Michael reaction involving both CGR-based and Electronic Effect Descriptors
Ladeveze, Fabien. « Microréacteurs en synthèse chimique : rôle de l'hydrodynamique et effets de la miniaturisation ». Phd thesis, Toulouse, INPT, 2005. http://oatao.univ-toulouse.fr/7408/1/ladeveze.pdf.
Texte intégralBonnardot, Jérôme. « Modélisation cinétique des réactions d'hydrotraitement par regroupement en familles chimiques ». Lyon 1, 1998. http://www.theses.fr/1998LYO19006.
Texte intégralRietsch, Vincent. « Nouvelles réactions en cascade au départ d’ω-cétoesters acétyléniques : synthèse du squelette tricyclique présent dans le Mangicol ». Strasbourg, 2009. http://www.theses.fr/2009STRA6044.
Texte intégralThis thesis deals with new cascade reactions starting from acetylenic ω-ketoesters tethered to mono- or bicycloalkanones or aromatic rings. A convenient and versatile general procedure was developed to prepare the acetylenic ω-ketoester starting materials. The reactivity of these substrates was tested towards Lewis acids such as TBSOTf and TMSOTf and bases like t-BuOK and NaOEt. These intramolecular reactions provided a new route to spiro derivatives, tricyclic electrophilic allenes, silyl ketene acetals, specific diesters and polyfunctionalized tricyclic derivatives. These new methodologies were successfully applied to the preparation of natural bioactive compounds belonging to the Hamigeran and Mangicol families
Charonnet, Emmanuelle. « Nouvelles réactions de fonctionnalisation sélective de dérivés 1,3-dicarbonylés ». Aix-Marseille 3, 2001. http://www.theses.fr/2001AIX30018.
Texte intégralIn this work, we proposed new domino anionic transformations based on the reactivity of stabilized carbanions from 1,3-dicarbonyls. The study allowed the synthesis of fused polycyclic molecules which can be used in the formation of structures present in a large number of natural products. First, we have extended and generalized a new facile two-carbon ring expansion of cyclopentanones by a domino C-C-dialkylation/retro-Dieckmann for the flexible preparation of functionalized seven-membered rings. We have also developped a stereoselective C-O-cycloalkylation cascade leading to vinyl enol ethers which could be involved in a Claisen rearrangement to give highly functionalized bridged bicyclic systems. Both, the mechanism and the stereoselectivity have been studied by semiempirical calculations which are qualitatively in agreement with the experimental results. In a second time, we described a new γ-functionalization of β-ketoamides with aromatic, aliphatic and α,β-ethylenic aldehydes. Thus, we accedγeed to γ-arylidenes, γ-alkylidenes et γ-allylidenes β-ketoamides which constitute cyclic Nazarov analogues having a high synthetic value with their three consecutive reactive sites, both nucleophilic and electrophilic. .
Gimadiev, Timur. « Modèles prédictifs pour les paramètres cinétiques et thermodynamiques des réactions chimiques ». Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAF007/document.
Texte intégralThis work is devoted to QSPR modeling of kinetic and thermodynamic properties of chemical reactions using the Condensed Graph of Reaction (CGR) approach. CGR allows encoding structures of reactants and products into one sole molecular graph for which molecular descriptors can be generated. A comprehensive database containing some 11000 manually collected reactions has been developed then used in the modeling. Predictive models were built for rate constants of Diels-Alder, SN2 and E2 reaction as well as for equilibrium constants of tautomeric transformations. They are available for the users via WEB portal. A part of the thesis concerned quantum mechanics studies of reactions between sydnones and strained alkynes for which the size of the dataset was not sufficient to produce statistically meaningful models
Bulteel, David. « Quantification de la réaction alcali-silice : application à un silex du Nord de la France ». Lille 1, 2000. http://www.theses.fr/2000LIL10116.
Texte intégralTaggougui, Mohamed. « Etudes d'additifs susceptibles de sécuriser les electrolytes des batteries lithium-ion du point de vue : contrôle de charge, de l'effet retardateur de flammes et de la mouillabilité ». Tours, 2007. http://www.theses.fr/2007TOUR4035.
Texte intégralThis work aims at improving the security linked to the use of Li-batteries electrolytes. First, we tested the use of redox shuttles as an electrochemical system of internal protection against overcharge. We studied the possibility of employing ionic liquids as electrolytes for Li-ion accumulator. Finally, we tested two fluoro-alkylcarbonates as flame-retardant additives. Three classes of molecules were studied as redox shuttles : metallic complexes, aromatic and radical systems. Only a few molecules of the radical system allow an efficient protection against overcharge of the cell Li4Ti5O12 / (EC/DEC) + LiPF6 / LiFePO4. These molecules are the TEMPO (tetramethylpiperidinyl-1-oxy) and the Cyano-TEMPO, they limit the recharge voltage to 3. 5-3. 7 V vs. Li+/Li. We chose two ionic liquids whose anion is the bis(trifluoromethanesulfonyl)imide (TFSI-) ion and the cation N-trimethyl-N-hexylammonium (HTMA+) or N-trimethyl-N-propylammonium (PTMA+). Two electrolytes have been optimized regarding their transport properties and their thermal stability : HTMA+TFSI-/(EC:DEC) [ = 0. 3] + LiTFSI 1 mol. L-1 and PTMA+TFSI-/(EC:DEC) [ = 0. 25] + LiTFSI 1 mol. L-1 ( with the weight fraction of the ionic liquid in the mix). The electrochemical study shows that the electrolyte cannot be cycled on the graphite electrode. Cyclic voltammetry performed on the negative electrode demonstrates the absence of formation of the SEI and reveals the intercalation of ammonium cations into the graphene layers. The analysis of the electrode, after cycling, by X-Ray Diffraction (XRD) and NMR spectroscopy, confirms the insertion of the ammonium cations. To improve the cycling results, we replaced the EC by the Cl-EC (chloro-ethylene carbonate). Cl-EC allows the formation of the passivation layer that protects graphite against exfoliation, but does not prevent the intercalation of the ammonium cations. The cycling tests on the negative electrode Li4Ti5O12 and the positive LixCoO2 were conducted successfully. In order to improve the ininflamability of the electrolyte (EC/DMC/DEC + LiPF6 1 mol. L-1), we tested the use of two fluoro-alkylcarbonates as flame-retardant additives : the 2,2,3,3,4,4,4-hepatafluorobutyl methyl carbonate (FC2) and the 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl methyl carbonate (FC1). These two additives were synthetized at the laboratory. The electrochemical study demonstrates that the FC1 compound does not modify the cyclability of the positive electrode LixCoO2. Nevertheless, it generates an important loss of capacity of the graphite electrode. The cycling tests conducted on the LixCoO2 cathode and the graphite anode show the good performances of the FC2 additive
Tjollyn, Sophie. « Les anticorps, un outil au service de la chimie : applications à la cyclisation de l'époxysqualène ainsi qu'aux dosages de l'ergostérool et de l'acide 2,4-dichlorophénoxyacétique ». Aix-Marseille 3, 1997. http://www.theses.fr/1997AIX30106.
Texte intégralSqualli, Houssaini Ali. « Contribution à l'étude des réactions chimiques par analyse thermobarométrique isochore : application aux gels et coacervats de polyphosphates ». Lille 1, 1992. http://www.theses.fr/1992LIL10079.
Texte intégralPujol, Jean Gabriel. « Nouvelles synthèses stéréosélectives des flavanols-3 cis et trans ». Mulhouse, 1990. http://www.theses.fr/1990MULH0142.
Texte intégralAhr, Mathieu. « Réactions d'homocouplage de composés organomagnésiens aromatiques en présence de sels de fer ». Cergy-Pontoise, 2004. http://www.theses.fr/2004CERG0207.
Texte intégralA new homocoupling reaction of aryl Grignard reagents was developed. It takes place in the presence of iron salts and a organic halide which is used as an oxidant. A mechanism was proposed and discussed. Using 1,2-dihalogenoethanes as oxidant reagents, the homocoupling reaction of para-, meta- and ortho- subtitued by various functionalysed aryl Grignard reagents leads the corresponding biphenyls in good yields. 3,3'-bipyridine and 2,2'-difluoro-3,3'-dicarbethoxy-4,4'-bipyridine were also prepared. This reaction was used to perform intramolecular coupling reactions to create rings of 5, 6 and 8 atoms. At last, the total synthesis of N-methylcrinasiadine was completed using the intramolecular coupling reaction as the key step
Pasquier, Christian. « Etude de la réactivité de dérivés du 5-nitrouracile dans des réactions de transfert monoélectronique. Application à la synthèse de nouveaux agents d'intérêt pharmacologique ». Aix-Marseille 3, 1998. http://www.theses.fr/1998AIX30073.
Texte intégralJacob, Olivier. « Etude théorique du rôle du zinc dans les réactions d'hydratation de la fonction carbonyleApplication à l'étude du mécanisme catalytique de l'anhydrase carbonique ». Université Louis Pasteur (Strasbourg) (1971-2008), 1990. http://www.theses.fr/1990STR13128.
Texte intégralHany, Cindy. « Développement de méthodes thermiques pour la caractérisation de réactions chimiques en microfluidique ». Thesis, Bordeaux 1, 2009. http://www.theses.fr/2009BOR13936/document.
Texte intégralThis work deals with the development of new measurement methods in order to characterize high exothermic chemical reactions in safe conditions. Thus, we combine thermal analysis with microfluidic technology. The use of microfluidics allows to manipulate a very small amount of product safely. First, we have developed a microcalorimeter to measure the global heat flux produced in co-flow or droplet-flow configurations. Several parameters can be determined: reaction and mixing enthalpy, concentrations by calorimetric titration and kinetics. The second method uses an InfraRed camera to measure the temperature field of the isoperibolic millireactor. Then, the local evolution of the reaction is estimated by thermal processing. From such inverse methods, the thermokinetic parameters can be determined
Bezagu, Marine. « Réactions chimiques et mélanges locaux induits par ultrasons : vers une chimiothérapie ciblée ». Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066492/document.
Texte intégralDevelopment of targeted drug-delivery methods has become an increasingly important research field in cancer therapy. In this context, perfluorocarbon (PFC) microdroplets can be combined with ultrasound. The latter can remotely trigger the vaporization of the PFC phase, thus opening the microdroplets and releasing their content in a spatially controlled manner. In this work, we were able to establish that these PFC droplets could be used to control both temporally and spatially a spontaneous chemical reaction such as the non-catalyzed azide-alkyne cycloaddition. This « in situ chemistry » strategy was also successfully applied to the in vitro localized release of either a doxorubicin or a monomethylauristatin E prodrug and their subsequent activation by a specific enzyme, the β glucuronidase. We believe that such strategy could lead to drug synthesis directly into the tumors. A new microfluidic mixing method was also developed. Flows are typically laminar in microfluidic systems, which impedes an efficient and fast mixing between fluids. In order to design fully functionnal « labs on chips », mixing methods need to be implemented. In this context, we showed that the vaporization of a PFC phase under the focus of an ultrasound transducer could be used to achieve fast and efficient mixing in a microfluidic channel
Kribii, Abderahim. « Etude structurale des kérogènes par des réactions chimiques sélectives (transalkylation, hydrolyse, oxydation) ». Poitiers, 1994. http://www.theses.fr/1994POIT2365.
Texte intégralContamine, François. « Analyse d'un réacteur sonochimique : puissance, transfert de matière liquide-solide et réactions chimiques ». Toulouse, INPT, 1993. http://www.theses.fr/1993INPT024G.
Texte intégralCarpentier, Olivier. « Auscultation de sites miniers par méthodes thermiques, suivi des réactions de combustion ». Artois, 2006. http://www.theses.fr/2006ARTO0203.
Texte intégralThe second half of the XXs century was the decline of the mining industry in Western Europe. The transfer of patrimony to district planning authority impose an evaluation of the risks on the behavior of coal tips. The North of France counts above 300 coal tips. Built in cone, coal tips offer hillsides to the limit of the break, the stability of the building being questionned. We consider at 50% the proportion of the entered of coal tips, or which will enter, in combustion in Nord-Pas-de-Calais. The administrators are brought to assure a monitoring of coal tips in reaction. In the majority of the cases it is the infrared thermography which is used. Until now this technique limited itself to air interventions. The cost of the measure, the constraints practical and administrative limit the frequency of the interventions. The objective of the thesis was to work out an additional method of thermographical investigation on ground which allows a monitoring of the reaction a more supply way, less expensive and authorizing more regular interventions. Based on a coupled approach (topography, thermic, meteorology), campaigns of measure consist in realizing a 3D reconstruction of the site and its thermic cartography in differents times with the aim of a comparative study of the subsurface activity. This work articulates, on one hand, around a theoritical study of phenomenons of combustions in the massifs and transfers of heat at the solid-fluid interface, and, on the other hand, of a study experimental diligently on site to validate our numerical approach and to supply a methodology as for the follow-up of the reaction of combustion
Bechara, Rafeh. « L'ion Cu+ dans différentes matrices : aspects physico-chimiques et catalytiques ». Lille 1, 1986. http://www.theses.fr/1986LIL10037.
Texte intégralDargham, Khadigé. « Valorisation chimique et photochimique de l'acide isocyanurique ». Toulouse, INPT, 1988. http://www.theses.fr/1988INPT008G.
Texte intégralLaugier, André. « Représentation de la réaction chimique dans les registres macroscopique et microscopique : contribution au repérage des obstacles épistémologiques. Une étude en classe de seconde ». Pau, 1998. http://www.theses.fr/1998PAUU3008.
Texte intégralLi, Xin. « Diffusion and diffusion-based chemical and biological assays inside and outside microfluidic channels ». Paris 6, 2011. http://www.theses.fr/2011PA066340.
Texte intégralPempo, Delphine. « Synthèse totale de phéromones de fourmis ». Aix-Marseille 3, 1998. http://www.theses.fr/1998AIX30064.
Texte intégralBigan, Erwan. « Minimal conditions for protocell growth ». Palaiseau, Ecole polytechnique, 2015. http://www.theses.fr/2015EPXX0080.
Texte intégralFakih, Houssam. « Élaboration de revêtements de Ti3SiC2 sur SiC par RCVD ». Lyon 1, 2008. http://www.theses.fr/2008LYO10013.
Texte intégralThis thesis deals with the growth of C-Si-Ti coatings in general and Ti3SiC2 phase MAX in particular on a ceramic substrate. The method consists in depositing a first SiC sub-layer by chemical vapour deposition (CVD) under low pressure from H2/CH3SiCl3. The growth of Ti-Si-C coatings was obtained by reactive CVD (RCVD) from a H2/TiCl4 gaseous mixture still under low pressure reacting on each SiC solid sub-layer that was previously deposited. The effect of temperature (from 1000°C to 1200°C) and the deposition time (from 3 minutes to 3 hours) were studied. On the basis of a thermodynamic study, the H2/TiCl4 ratio was chosen sufficiently high to favour the formation of the ternary Ti3SiC2 against other phases of the system C-Si-Ti. At 1100°C, the growth of a thin continuous layer pure Ti3SiC2 is first observed, in accordance with thermodynamic study. In that case, the basal crystallographic planes are oriented perpendicular to the substrate. The growth of the Ti3SiC2 by RCVD involves partial or total SiC consumption by solid-gas reaction and solid-state diffusion. But for longer deposition times, the simultaneous growth of an additional Ti5Si3Cx sub-layer on surface Ti3SiC2 and a TiC sub-layer on the other side of SiC was then observed. A way to get Ti3SiC2 thicker sublayers without TiC and Ti5Si3Cx is to alternate short SiC deposition and RCVD treatment sequences as many times as necessary. Another method to obtain thinner sub-layers Ti3SiC2 was the use of pressure-pulsed CVD method. In addition, the pressure-pulsed method allowed the preferential orientation to be prevented in the Ti3SiC2 coating
Koubachi, Jamal. « Développement et application des réactions d'arylations et d'alcénylations directes pallado-catalysées pour la synthèse d'imidazo[1,2-a]pyridines diversement substituées ». Orléans, 2008. http://www.theses.fr/2008ORLE2021.
Texte intégralQuinton, Julia. « Développement et utilisation de dosages immunométriques pour la recherche de nouvelles réactions chimiques ». Paris 11, 2010. http://www.theses.fr/2010PA112218.
Texte intégralThe main goal of this project is the discovery of new ligation reactions by sandwich immunoassays. These sandwich test are usually used for the detection of macromolecules (proteins, virus or bacteria) for applications in diagnostic and they are poorly described for the detection of small compounds. Firstly, the development of the "sandwich test" has been carried out by evaluating the minimum size of the compounds which could be detected through the simultaneous binding oftwo antibodies. This study showed that a ternary complex could be formed even if the spacer separating two epitopes is constituted by only 5 carbon atoms. The screening by "sandwich test" has been first validated on known reactions: the Huisgen cycloaddition and Sonogashira reactions. Secondly, the screening by "sandwich test" has been realised in order to find new reactions. 2688 reactions have been realised on 96 well plates in different experimental conditions and then screened by "sandwich test". 67 hits have been observed and resulted from the formation of cross coupled products. However, among these 67 hits, 13 products resulted from known reaction and 54 hits resulted from new ones. Only 2 reactions have been optimised and reproduced at bigger scale. This screening led to the discovery of a new desulfuration reaction catalysed by copper that allowed the straighfoward formation of iso-urea in presence of phenols. This reaction was very efficient in an intramolecular way and led to the formation of benzoxazoles from aminophenols. Then, this screening permitted the disco very of a second new reaction: an innovative reaction of cyclisation in the presence of N-hydroxythiourea, alcynes and copper salts
Hoonakker, Frank. « Graphes condensés de réactions, applications à la recherche par similarité, la classification et la modélisation ». Université Louis Pasteur (Strasbourg) (1971-2008), 2008. https://publication-theses.unistra.fr/restreint/theses_doctorat/2008/HOONAKKER_Frank_2008.pdf.
Texte intégralThis work is devoted to the developpement of new methods of mining of chemical reactions based on the Condensed Graph of Reaction (CGR) approach. A CGR integrates an information about all reactants and products of a given chemical reaction into one 2D molecular graph. Due to the application of both conventional (simple, double, etc. ) and dynamical (single to double, broken single, etc. ) bond types, a CGR ”condenses” a reaction (involving many molecules) into one pseudo-molecule. This formally allows one to apply to CGRs the chemoinformatics approaches earlier developed for individual compounds. Three possible applications of CGRs were considered: – unsupervised classification of reactions based on clustering algorithms; – reactions similarity search, and – Quantitative Structure Reactivity Relationships (QSRR). Model calculations performed on four databases containing from 1 000 to 200 000 reactions demonstrated high efficiency of the developed approaches and software tools. An system for optimizing reactions condition has been designed, and patented in the USA
Airiau, Etienne. « Synthèse d'hétérocycles azotés par réactions multicomposantes et domino basées sur l'hydroformylation ». Strasbourg, 2009. https://publication-theses.unistra.fr/public/theses_doctorat/2009/AIRIAU_Etienne_2009.pdf.
Texte intégralThe objective of this thesis was the development of new synthetic routes towards nitrogen heterocycles within the concept of atom economy. Our method is based on hydroformylation, a fundamental reaction in homogeneous catalysis, which was used to triggered domino reactions. The hydroformylation allows the introduction of an aldehyde onto an olefin in the presence of a catalyst, hydrogen and carbon monoxide. Firstly, a multi-component reaction, the aza-Sakurai-Hosomi, allowed the one-pot synthesis of homoallylamines which have been subjected to a sequence hydroformylation / reduction to lead to mono or disubstituted piperidine rings. Coniine, anabasine, dihydropinidine and 4-propyloctahydro-1H-quinolizine are thus obtained in few steps. With the same strategy, (±)-allosédamine and (±)-allo-Lobéline ware also obtained. Then, regioselective hydroformylation of vinylacetamide enabled in-situ formation of Nacyliminiums ions that can be trapped by various nucleophiles in a diastereoselective manner. A multicomponent domino reaction has also been developed. The use of allylsilanes as nucleophiles led to a domino cyclohydrocarbonylation/aza-Sakurai-Hosomi/ hydroformylation reaction. This strategy was then applied to the synthesis of epilupinine, a quinolizidine alkaloid. Domino reactions triggered by hydroformylation allows an efficient access to various nitrogen heterocycles
Berrah, Yacine. « Etude de différentes stratégies de modélisation de réactions complexes dans un réacteur fermé en synthèse organique : application à la réaction de cyanoéthylation du malonate de diméthyle ». Lyon 1, 1991. http://www.theses.fr/1991LYO10216.
Texte intégralHadj, Mebarek Ahmed. « Etude de l'apparition de phénomènes d'emballement lors de réactions entre métaux électropositifs et dérivés organiques hétérofonctionnels ». Mulhouse, 1999. http://www.theses.fr/1999MULH0555.
Texte intégralSchweitzer, Jean-Marc. « Modélisation cinétique des réactions catalytiques d'hydrocraquage par la théorie des événements constitutifs ». Lyon 1, 1998. http://www.theses.fr/1998LYO19005.
Texte intégralYuan, Ling-Zhi. « réactions inattendues de réduction régiosélectives de benziles et de arylalkyldicétones ». Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLS265.
Texte intégralIn this work, we have described that, for the first time the TMSCl - NaI association was used to regioselectively reduce a variety of alpha diketones as benzils in methylene chloride. Moreover, we showed that this association was able to reduce various arylalkylketones as well as alpha ketoesters, ketoacids and hydrazinoesters with total selectivity. The mechanism of action is probably due to radicals was fully studied with many experiments
Wylock, Christophe. « Contribution à l'étude des transferts de matière gaz-liquide en présence de réactions chimiques ». Doctoral thesis, Universite Libre de Bruxelles, 2009. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/210257.
Texte intégralDans ces colonnes, une phase gazeuse contenant un mélange d’air et dioxyde de carbone (CO2) est dispersée sous forme de bulles dans une solution aqueuse de carbonate et de bicarbonate de sodium (respectivement Na2CO3 et NaHCO3). Cette dispersion donne lieu à un transfert de CO2 des bulles vers la phase liquide. Au sein des colonnes, la phase gazeuse se répartit dans deux populations de bulles :des petites bulles (diamètre de quelques mm) et des grandes bulles (diamètre de quelques cm). Le transfert bulle-liquide de CO2 est couplé à des réactions chimiques prenant place en phase liquide, qui conduisent à la conversion du Na2CO3 en NaHCO3. Une fois la concentration de saturation dépassée le NaHCO3 précipite sous forme de cristaux et un mélange liquide-solide est recueilli à la sortie de ces colonnes.
Ce travail, réalisé en collaboration avec la société Solvay, porte sur l’étude et la modélisation mathématique des phénomènes de transfert de matière entre phases, couplés à des réactions chimiques, prenant place au sein d’une colonne BIR. L’association d’études sur des colonnes à bulles à l’échelle industrielle ou réduite (pilote) et d’études plus fondamentales sur des dispositifs de laboratoire permet de développer une meilleure compréhension du fonctionnement des colonnes BIR et d’en construire un modèle mathématique détaillé.
L’objectif appliqué de ce travail est la mise au point d’un modèle mathématique complet et opérationnel d’une colonne BIR. Cet objectif est supporté par trois blocs de travail, dans lesquels différents outils sont développés et exploités.
Le premier bloc est consacré à la modélisation mathématique du transfert bulle-liquide de CO2 dans une solution aqueuse de NaHCO3 et de Na2CO3. Ce transfert est couplé à des réactions chimiques en phase liquide qui influencent sa vitesse. Dans un premier temps, des modèles sont développés selon des approches unidimensionnelles classiquement rencontrées dans la littérature. Ces approches passent par une idéalisation de l’écoulement du liquide autour des bulles. Une expression simplifiée de la vitesse du transfert bulle-liquide de CO2, est également développée et validée pour le modèle de colonne BIR.
Dans un second temps, une modélisation complète des phénomènes de transport (convection et diffusion), couplés à des réactions chimiques, est réalisée en suivant une approche bidimensionnelle axisymétrique. L’influence de la vitesse de réactions sur la vitesse de transfert est étudiée et les résultats des deux approches sont également comparés.
Le deuxième bloc est consacré à l’étude expérimentale du transfert gaz-liquide de CO2 dans des solutions aqueuses de NaHCO3 et de Na2CO3. A cette fin, un dispositif expérimental est développé et présenté. Du CO2 est mis en contact avec des solutions aqueuses de NaHCO3 et de Na2CO3 dans une cellule transparente. Les phénomènes provoqués en phase liquide par le transfert de CO2 sont observés à l’aide d’un interféromètre de Mach-Zehnder.
Les résultats expérimentaux sont comparés à des résultats de simulation obtenus avec un des modèles unidimensionnels développés dans le premier bloc. De cette comparaison, il apparaît qu’une mauvaise estimation de la valeur de certains paramètres physico-chimiques apparaissant dans les équations de ce modèle conduit à des écarts significatifs entre les grandeurs observées expérimentalement et les grandeurs estimées par simulation des équations du modèle.
C’est pourquoi une méthode d’estimation paramétrique est également développée afin d’identifier les valeurs numériques de ces paramètres physico-chimiques sur base des résultats expérimentaux. Ces dernières sont également discutées.
Dans le troisième bloc, nous apportons une contribution à l’étude des cinétiques de précipitation du NaHCO3 dans un cristallisoir à cuve agitée. Cette partie du travail est réalisée en collaboration avec Vanessa Gutierrez (du service Matières et Matériaux de l’ULB).
Nous contribuons à cette étude par le développement de trois outils :une table de calcul Excel permettant de synthétiser les résultats expérimentaux, un ensemble de simulations de l’écoulement au sein du cristallisoir par mécanique des fluides numérique et une nouvelle méthode d’extraction des cinétiques de précipitation du NaHCO3 à partir des résultats expérimentaux. Ces trois outils sont également utilisés de façon combinée pour estimer les influences de la fraction massique de solide et de l’agitation sur la cinétique de germination secondaire du NaHCO3.
Enfin, la synthèse de l’ensemble des résultats de ces études est réalisée. Le résultat final est le développement d’un modèle mathématique complet et opérationnel des colonnes BIR. Ce modèle est développé en suivant l’approche de modélisation en compartiments, développée au cours du travail de Benoît Haut. Ce modèle synthétise les trois blocs d’études réalisées dans ce travail, ainsi que les travaux d’Aurélie Larcy (du service Transferts, Interfaces et Procédés de l’ULB) et de Vanessa Gutierrez. Les équations modélisant les différents phénomènes sont présentées, ainsi que la méthode utilisée pour résoudre ces équations. Des simulations des équations du modèle sont réalisées et discutées. Les résultats de simulation sont également comparés à des mesures effectuées sur une colonne BIR. Un accord raisonnable est observé.
A l’issue de ce travail, nous disposons donc d’un modèle opérationnel de colonne BIR. Bien que ce modèle doive encore être optimisé et validé, il peut déjà être utilisé pour étudier l’effet des caractéristiques géométriques des colonnes BIR et des conditions appliquées à ces colonnes sur le comportement des simulations des équations du modèle et pour identifier des tendances.
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The refined sodium bicarbonate is produced by the Solvay company using large size bubble columns, called the BIR columns.
In these columns, a gaseous phase containing an air-carbon dioxyde mixture (CO2) is dispersed under the form of bubbles in an aqueous solution of sodium carbonate and sodium bicarbonate (Na2CO3 and NaHCO3, respectively). This dispersion leads to a CO2 transfer from the bubbles to the liquid phase. Inside these columns, the gaseous phase is distributed in two bubbles populations :small bubbles (a few mm of diameter) and large bubbles (a few cm of diameter).
The bubble-liquid CO2 transfer is coupled with chemical reactions taking places in the liquid phase that leads to the conversion of Na2CO3 to NaHCO3. When the solution is supersaturated in NaHCO3, the NaHCO3 precipitates under the form of crystals and a liquid-solid mixture is extracted at the outlet of the BIR columns.
This work, realized in collaboration with Solvay, aims to study and to model mathematically the mass transport phenomena between the phases, coupled with chemical reactions, taking places inside a BIR column. Study of bubble columns at the industrial and the pilot scale is combined to a more fundamental study at laboratory scale to improve the understanding of the BIR columns functioning and to develop a detailed mathematical modeling.
The applied objective of this work is to develop a complete and operational mathematical modeling of a BIR column. This objective is supported by three blocks of work. In each block, several tools are developed and used.
The first block is devoted to the mathematical modeling of the bubble-liquid CO2 transfer in an NaHCO3 and Na2CO3 aqueous solution. This transfer is coupled with chemical reactions in liquid phase, which affect the transfer rate.
In a first time, mathematical models are developed following the classical one-dimensional approaches of the literature. These approaches idealize the liquid flow around the bubbles. A simplified expression of the bubble-liquid CO2 transfer rate is equally developed and validated for the BIR column model.
In a second time, a complete modeling of the transport phenomena (convection and diffusion) coupled with chemical reactions is developed, following an axisymmetrical twodimensional approach. The chemical reaction rate influence on the bubble-liquid transfer rate is studied and the results of the two approaches are then compared.
The second block is devoted to the experimental study of the gas-liquid CO2 transfer to NaHCO3 and Na2CO3 aqueous solutions. An experimental set-up is developed and presented. CO2 is put in contact with NaHCO3 and Na2CO3 aqueous solutions in a transparent cell. The phenomena induced in liquid phase by the CO2 transfer are observed using a Mach-Zehnder interferometer.
The experimental results are compared to simulation results that are obtained using one of the one-dimensional model developed in the first block. From this comparison, it appears that a wrong estimation of some physico-chemical parameter values leads to significative differences between the experimentally observed quantities and those estimated by simulation of the model equations. Therefore, a parametric estimation method is developed in order to estimate those parameters numerical values from the experimental results. The found values are then discussed.
In the third block is presented a contribution to the NaHCO3 precipitation kinetic study in a stirred-tank crystallizer. This part of the work is realized in collaboration with Vanessa Gutierrez (Chemicals and Materials Department of ULB).
Three tools are developed :tables in Excel sheet to synthetize the experimental results, a set of simulations of the flow inside the crystallizer by Computational Fluid Dynamic (CFD) and a new method to extract the NaHCO3 precipitation kinetics from the experimental measurements. These three tools are combined to estimate the influences of the solid mass fraction and the flow on the NaHCO3 secondary nucleation rate.
Finally, the synthesis of all these results is realized. The final result is the development of a complete and operational mathematical model of BIR columns. This model is developed following the compartmental modeling approach, developed in the PhD thesis of Benoît Haut. This model synthetizes the three block of study realized in this work and the studies of Aurélie Larcy (Transfers, Interfaces and Processes Department of ULB) and those of Vanessa Gutierrez. The equations modeling the phenomena taking place in a BIR column are presented as the used method to solve these equations. The equations of the model are simulated and the results are discussed. The results are equally compared to experimental measurement realized on a BIR column. A reasonable agreement is observed.
At the end of this work, an operational model of a BIR column is thus developed. Although this model have to be optimized and validated, it can already be used to study the influences of the geometrical characteristics of the BIR columns and of the conditions applied to these columns on the behaviour of the model equation simulations and to identity tendencies.
Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished
Munteanu, Sorin. « Micro électrochimie et optique couplées pour l'imagerie et l'étude de réactions chimiques de surface ». Phd thesis, Université Pierre et Marie Curie - Paris VI, 2012. http://pastel.archives-ouvertes.fr/pastel-00802004.
Texte intégralSoorkia, Satchin. « Spectroscopie et dynamique de réactions chimiques préparées dans des complexes de van der Waals ». Phd thesis, Université Paris Sud - Paris XI, 2008. http://tel.archives-ouvertes.fr/tel-00343531.
Texte intégralDans ces complexes, l'une des réactions qui nous intéresse conduit à la formation de $\ce {ZrF}$. La spectroscopie électronique de $\ce {ZrF}$ dans ses bandes principales entre 400~-~470~nm est extrêmement riche et surprenante pour une molécule diatomique. Cette étude a permis d'identifier l'état fondamental de $\ce {ZrF}$ ($\rm X^2\Delta$) à travers la simulation des structures rotationnelles des bandes observées et d'obtenir des informations essentielles sur sa structure électronique. Ces résultats expérimentaux sont en accord avec les calculs \emph{ab initio}.
Les états excités du complexe $\ce {Zr\bond{...}F\bond{-}CH3}$ ont été étudiés avec une méthode de dépopulation. Le domaine spectral 615~-~700~nm est particulièrement intéressant car il révèle un groupe diffus de bandes déplacées vers les plus faibles longueurs d'onde et élargies par rapport à la transition $\rm z^3F$~$\leftarrow$~$\rm a^3F$ dans le métal. Cette transition est interdite à partir de l'état fondamental $\rm a^3F_2$ du zirconium mais permise à partir de l'état $\rm a^3F_4$. La complexation par $\ce {CH3F}$ permet un couplage entre ces deux composantes et assure la ransition optique depuis l'état fondamental du complexe.
Mertz, Helene. « Modélisation des réactions chimiques dans un code de simulation par la méthode Monte Carlo ». Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLV012/document.
Texte intégralDirect Simulation Monte Carlo (DSMC) methods are used in Ariane group to compute aerodynamic forces and moments and heat fluxes on space objects for hypersonic flows in rarefied regimes.To caracterise the dislocation of the stages and the debris footprints, a precise modelisation of the mechanism that contribute to the heat flux is necessary. The contribution of the chemical reactions is important for the determination of the heat flux. The purpose of this thesis is to develop the in house IEMC tool using the DSMC method so that it can compute reactive flows.The different steps of the developments are presented in this work. The first step is the presentation, implementation and verification of two different chemistry models. They are validated for simulations on real test cases. Different models are tested in order to evaluate their effect. Chemical models implemented in the code depend on new input parameters, whose numerical data are uncertain. Using a uncertainty quantification study, it is shown that the output data of the reactive simulation, especially the heat flux, is weakly impacted by the tested uncertain parameters
Soorkia, Satchin. « Spectroscopie et dynamique de réactions chimiques préparées dans les complexes de Van der Waals ». Paris 11, 2008. http://www.theses.fr/2008PA112106.
Texte intégralTransition metal elements have d valence electrons and are characterized by a great variety of electronic configurations responsible for their specific reactivity. The elements of the second row in particular have 4d and 5s atomic orbitals of similar size and energy which can be both involved in chemical processes. We have been interested in the reactivity of a transition metal element, zirconium, combined with a simple organic functionalized molecule in a van der Waals complex formed in a supersonic molecular beam in the model reaction Zr + CH3F. In this context, one of the chemicals reactions that we are interested in leads to the formation of ZrF. The electronic spectroscopy of ZrF in the spectral domain 400 – 470 nm is extremely rich and surprising for a diatomic molecule. With this study, we have been able to identify the ground state of ZrF (X2) by simulating the observed rotational structures and obtain essential information on the electronic structure. These experimental results are in agreement with ab initio calculations. The excited states of the complex Zr. . . F-CH3 have been studied with a depopulation method. The spectral domain 615 – 700 nm is particularly interesting because it reveals a group of diffuse bands red-shifted and broadened with respect to the transition z3F←a3F in the metal. This transition is forbidden from the ground state a3F2 of zirconium but allowed from the a3F4 state. Complexation of the metal atom with a CH3F molecule allows coupling of these two states to occur which ensures the optical transition from the ground state of the complex
Sun, Yuemei. « Simulation de réactions chimiques en catalyse hétérogène : l'hydrogène sur la surface (111) du palladium ». Thesis, Lyon, École normale supérieure, 2014. http://www.theses.fr/2014ENSL0923.
Texte intégralIn this thesis, we studied dissociative adsorption of hydrogen on Pd(111) with particular attention paid to the surface coverage effect and the diffusion of a hydrogen adatom on Pd(111). With the help of DFT calculations, we carried out a systematic investigation of the effect of H-adatoms on the dissociation energetics of H2 on H-covered Pd(111) surfaces at various coverages. A quite surprising finding is that the H-adatoms do not only have a poisoning effect but can also promote H2 dissociation when they are adsorbed on sites which are sufficiently far from the dissociating H2 molecule. The macroscopic diffusion coefficient of an H-adatom on Pd(111) is determined from molecular dynamics simulations with the help of Einstein formula for different surface temperatures, i.e., Ts=500K, 300K and 250K. An accelerated molecular dynamics method was developed in order to study the diffusion at low surface temperatures. In our approach, the acceleration is achieved by increasing the kinetic energy of the diffusing atom according to the Maxwell-Boltzmann distribution at a higher temperature and correcting the time scale in a consistent way. For testing the validity of our method, we performed simulations for the diffusion of H adatom on Pd(111) surface at T=300K and T=100K. The diffusion coefficient obtained from the accelerated MD method is in agreement with that obtained from the direct MD and TST methods. And the physical time scale can be extended to the order of microseconds