Dissertations / Theses on the topic 'Autocatalytic reaction'

Soai’s discovery of chiral amplification in the autocatalytic alkylation of pyrimidine-5-carbaldehyde with diisopropylzinc is one of the most noteworthy findings of the last decade of the 20th century. This is the first experimental confirmation of an early theoretical rationalisation of autocatalysis as a mechanism for the evolution of biological homochirality from a racemic environment (Frank, 1953). This thesis describes kinetic and spectroscopic investigations that were conducted with the aim of better understanding the mechanism under which chiral amplification is achieved in the Soai system. The methodology used to perform the kinetic studies that are presented in this thesis focuses on the use of reaction calorimetry as in-situ tool coupled with the appropriate analytical technique for enantiomeric excess measurements. Observations of an unusual temperature effect on the reaction rate and a profound induction period are reported together with extensive kinetic investigations. Kinetic experiments were designed and carried out following Reaction Progress Kinetic Analysis methodology, which is described in detail. These experiments were carried out in order to ascertain the concentration dependence of the substrates and the reaction product, and revealed a 1.6 order in pyrimidyl aldehyde, a zero order in diisopropylzinc and a first order in the reaction product. Meticulous NMR studies of the alkoxide product at low temperature demonstrated its tendency to form tetrameric complexes, which could be either directly involved in the autocatalysis or be the precursors of the active catalytic species. Possible mechanisms that involve tetramers formation are proposed and supported by simulations carried out using COPASI simulation software. This thesis also includes a separate Chapter on the MIB mediated alkylation of benzaldehyde with diethylzinc, a system characterised by a marked nonlinear effect. Kinetic studies demonstrate how the high degree of chiral amplification comes at the expense of the reaction rate.

For life to arise from non-life, a metabolism must emerge and maintain itself, distinct from its environment. One line of research seeking to understand this emergence has focused on models of autocatalytic reaction networks (ARNs) and the conditions that allow them to approximate metabolic behavior. These models have identified reaction parameters from which a proto-metabolism might emerge given an adequate matter-energy flow through the system. This dissertation extends that research by answering the question: can dynamically structured interactions with the environment promote the emergence of ARNs? This question was inspired by theories that place the origin of life in contexts such as diurnal or tidal cycles. To answer it, an artificial chemistry system with ARN potential was implemented in the dissipative particle dynamics (DPD) modeling paradigm. Unlike differential equation (DE) models favored in prior ARN research, the DPD model is able to simulate environmental dynamics interacting with discrete particles, spatial heterogeneity, and rare events. This dissertation first presents a comparison of the DPD model to published DE results, showing qualitative similarity with some interesting differences. Multiple examples are then provided of dynamically changing flows from the environment that promote emergent ARNs more than constant flows. These include specific cycles of energy and mass flux that consistently increase metrics for ARN concentration and mass focusing. The results also demonstrate interesting nonlinear interactions between the system and cycle amplitude and period. These findings demonstrate the relevance that environmental dynamics has to ARN research and the potential for broader application as well.

This thesis studies the traveling wavefront created by the autocatalytic cubic chemical reaction A + 2B → 3B involving two chemical species A and B, where A is the reactant and B is the auto-catalyst. The diffusion coefficients for A and B are given by and . These coefficients differ as a result of the chemical species having different size and/or weight. Theoretical results show there exist bounds, and , depending on , where for speeds , a traveling wave solution exists, while for speeds , a solution does not exist. Moreover, if , and are similar to one another and in the order of when it is small. On the other hand, when there exists a minimum speed vmin, such that there is a traveling wave solution if the speed v > vmin. The determination of vmin is very important in determining the dynamics of general solutions. To fill in the gap of the theoretical study, we use numerical methods to determine vmin for various cases. The numerical algorithm used is the fourth-order Runge-Kutta method (RK4).
M.S.
Department of Mathematics
Sciences
Mathematical Science MS

Prionen sind das infektiöse Agens transmissibler spongiformer Enzephalopathien von Tieren und Menschen. Prionen bestehen hauptsächlich aus einer abnormal gefalteten und aggregierten Isoform des zellulären Prionproteins (PrP). Die Replikation von Prionen findet mutmaßlich durch keiminduzierte Polymerisation des Prionproteins statt. Es existieren verschiedene Prionstämme, die unterschiedliche Eigenschaften aufweisen, aber vom selben zellulären Prionprotein abstammen können. Neben PrP scheinen Kofaktormoleküle an der Prionreplikation beteiligt zu sein. Weiterhin wird angenommen, dass Kofaktoren bei der Definition von Stammeigenschaften beteiligt sind, sowie ein Einfluss auf die Infektiosität von Prionen besteht. In dieser Arbeit wurden die Auswirkungen verschiedener Kofaktoren auf die Replikation von vier Hamster-adaptierten Prionstämmen in vitro mittels der Methode der „Protein Misfolding Cyclic Amplification“ (PMCA) untersucht. Es wurden stammabhängige Unterschiede bezüglich der Anforderungen an die Replikationsbedingungen in der PMCA, sowie Kofaktor-Selektivitäten festgestellt. Der Einfluss von Kofaktoren wurde durch den Vergleich ausgewählter biologischer, biochemischer und biophysikalischer Eigenschaften von in vitro erzeugten PMCA Produkten (PrPres) mit denen nativer Prionkeime untersucht. Es zeigte sich, dass Kofaktoren Stammeigenschaften, wie die biologische Keimaktivität in primären Gliazellkulturen und biochemische Eigenschaften, wie die Migration in SDS-Gelen, beeinflussen können. Um festzustellen, ob unterschiedliche Kofaktorbedingungen während der PMCA messbare Veränderungen der Proteinkonformation hervorrufen, wurde PMCA generiertes PrPres mittels FT-IR Spektroskopie in einer Pilotstudie charakterisiert. Erste Befunde zeigten spektrale Unterschiede zwischen den Proteinkeimen und deren PMCA Produkten bei allen Stämmen, unabhängig von den Kofaktorbedingungen.
Prions are the causative agent of transmissible spongiform encephalopathies in animals and humans such as scrapie, bovine spongiform encephalopathy (BSE) and Creutzfeldt-Jakob disease (CJD). Prions are thought to be composed essentially of a misfolded and aberrantly aggregated isoform of the cellular prion protein (PrP) and to replicate by seeded PrP polymerization. Prions may exist in the form of distinct strains that differ in their phenotypic characteristics although they are derived from the same cellular prion protein. Cofactor molecules other than PrP may be involved in prion replication and may be a determinant of strain properties. Furthermore, cofactors may also be required for conveying infectivity. The present study examined the effects of different cofactor molecules on the replication efficacy of four hamster adapted prion agents using the method of serial protein misfolding cyclic amplification (PMCA) as in vitro assay for PrP misfolding and aggregation. The study revealed strain dependent differences of PMCA conditions and cofactors required for efficient in vitro replication. The impact of cofactors was assessed by comparative analyses of selected biological, biochemical and biophysical properties of PMCA products (PrPres) and native prion seeds. The biological seeding activity as monitored in a primary hamster glial cell assay, and biochemical properties such as electrophoretic migration in SDS-gels, were affected differently by different cofactors. In order to define the impact of putative cofactors on the molecular conversion of PrP in more detail, changes in the spatial structure associated with different cofactor molecule conditions during amplification of PrPres in PMCA was monitored by Fourier transform-infrared (FT-IR) spectroscopic analysis. Largely preliminary data revealed spectral differences between native prion seeds and progeny PMCA generated PrPres for all prion strains, but no variations due to different cofactor conditions.

Doctor of Philosophy
A detailed theoretical and numerical investigation of the behaviour of reactive systems under the influence of chaotic stirring is presented. These systems exhibit stationary solutions arising from the balance between chaotic advection and diffusion. Excessive stirring of such systems results in the termination of the reaction via a saddle-node bifurcation. The solution behaviour of these systems is analytically described using a recently developed nonperturbative, non-asymptotic variational method. This method involves fitting appropriate parameterised test functions to the solution, and also allows us to describe the bifurcations of these systems. This method is tested against numerical results obtained using a reduced one-dimensional reaction-advection-diffusion model. Four one- and two-component reactive systems with multiple homogeneous steady-states are analysed, namely autocatalytic, bistable, excitable and combustion systems. In addition to the generic stirring-induced saddle-node bifurcation, a rich and complex bifurcation scenario is observed in the excitable system. This includes a previously unreported region of bistability characterised by a hysteresis loop, a supercritical Hopf bifurcation and a saddle-node bifurcation arising from propagation failure. Results obtained with the nonperturbative method provide a good description of the bifurcations and solution behaviour in the various regimes of these chaotically stirred reaction-diffusion systems.

Dans les réacteurs industriels ou dans la nature, l'écoulement de fluides peut être couplé à des réactions chimiques. Dans de nombreux cas, il en résulte l'apparition de structures complexes dont les propriétés dépendent entre autres de la géométrie du système.

Dans ce contexte, le but de notre thèse a été d'étudier de manière théorique et sur des modèles réaction-diffusion-convection simples les propriétés de dynamiques spatio-temporelles résultant du couplage chimie-hydrodynamique.

Nous nous sommes focalisés sur les instabilités hydrodynamiques de digitation visqueuse et de densité qui apparaissent respectivement lorsqu'un fluide dense est placé au-dessus d'un fluide moins dense dans le champ de gravité et lorsqu'un fluide visqueux est déplacé par un fluide moins visqueux dans un milieu poreux.

En particulier, nous avons étudié les problèmes suivants:

- L'influence d'une réaction chimique de type A + B → C sur la digitation visqueuse. Nous avons montré que les structures formées lors de cette instabilité varient selon que le réactif A est injecté dans le réactif B ou vice-versa si ces réactifs n'ont pas un coefficient de diffusion ou une concentration initiale identiques.

- Le rôle de pertes de chaleur par les parois du réacteur dans le cadre de la digitation de densité de fronts autocatalytiques exothermiques. Nous avons caractérisé les conditions de stabilité de fronts en fonction des pertes de chaleur et expliqué l'apparition de zones anormalement chaudes lors de cette instabilité.

- L'influence de l'inhomogénéité du milieu sur la digitation de densité de solutions réactives ou non. Nous avons montré que les variations spatiales de perméabilité d'un milieu poreux peuvent figer ou faire osciller la structure de digitation dans certaines conditions.

- L'influence d'un champ électrique transverse sur l'instabilité diffusive et la digitation de densité de fronts autocatalytiques. Il a été montré que cette interaction peut donner lieu à des nouvelles structures et changer les propriétés du front.

En conclusion, nous avons montré que le couplage entre réactions chimiques et mouvements hydrodynamiques est capable de générer de nouvelles structures spatio-temporelles dont les propriétés dépendent entre autres des conditions imposées au système.

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In industrial reactors or in nature, fluid flows can be coupled to chemical reactions. In many cases, the result is the emergence of complex structures whose properties depend among others on the geometry of the system.

In this context, the purpose of our thesis was to study theoretically using simple models of reaction-diffusion-convection, the properties of dynamics resulting from the coupling between chemistry and hydrodynamics.

We focused on the hydrodynamic instabilities of viscous and density fingering that occur respectively when a dense fluid is placed above a less dense one in the gravity field and when a viscous fluid is displaced by a less viscous fluid in a porous medium.

In particular, we studied the following issues:

- The influence of a chemical reaction type A + B → C on viscous fingering. We have shown that the fingering patterns observed during this instability depends on whether the reactant A is injected into the reactant B or vice versa if they do not have identical diffusion coefficients or initial concentrations.

- The role of heat losses through the reactor walls on the density fingering of exothermic autocatalytic fronts. We have characterized the conditions of stability of fronts depending on heat losses and explained the appearance of unusually hot areas during this instability.

- The influence of the inhomogeneity of the medium on the density fingering of reactive solutions or not. We have shown that spatial variations of permeability of a porous medium may freeze or generate oscillating fingering pattern under certain conditions.

- The influence of a transverse electric field on the Rayleigh-Taylor and diffusive instabilities of autocatalytic fronts. It was shown that this interaction may lead to new structures and may change the properties of the front.

In conclusion, we showed that the coupling between chemical reactions and hydrodynamic motions can generate new space-time structures whose properties depend among others, on the conditions imposed on the system.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished

La propagation d'un front de réaction-diffusion est étudiée expérimentalement dans un écoulement cellulaire multiéchelle. Le front est produit par réaction autocatalytique en solution. L'écoulement est réalisé en géométrie de Hele-Shaw par électroconvection, son caractère multiéchelle étant réalisé par l'action combinée de deux nappes d'aimants d'échelles différentes. La géométrie du front et sa vitesse moyenne de propagation sont déterminées pour une large gamme d'intensité des vortex de chaque échelle. Elles sont confortées par une simulation numérique de l'avancée du domaine brulé dans le domaine frais. L'effet de la nature multiéchelle de l'écoulement sur la vitesse moyenne du front est compris par une méthode de renormalisation dont la validation est fournie par l'obtention d'un courbe maitresse pour l'ensemble des données
The propagation of a reaction-diffusion front is experimentally studied in a multi-scale cellular flow. The front is produced by an autocatalytic chemical reaction in an aqueous solution. The flow is generated by electroconvection and its multi-scale nature is induced by overlaying magnets of different scales. This enables an independent tune of the flow intensity at each scale. The geometry and the mean velocity of the front have been determined over a large range of scale intensities. These features are confirmed by a numerical simulation based on a burnt and fresh domain dynamics, the burnt domain expanding across the fresh one. The effect of the multi-scale nature of the flow on the mean front velocity is recovered by a renormalisation method validated by a collapse of the data onto a single curve

Motivated by the existence of complex behaviors arising from interactions between chemistry and fluid dynamics in numerous research problems and every-day life situations, we theoretically investigate the dynamics resulting from the interplay between chemistry, diffusion, and fluid motions in a reactive aqueous solution. As a chemical reaction induces changes in the temperature and in the composition of the reactive medium, such a reaction can modify the properties of the solution (density, viscosity, surface tension,…) and thereby trigger convective motions, which in turn affect the reaction. Two classes of convective flows are commonly occurring in solutions open to air, namely Marangoni flows arising from surface tension gradients and buoyancy flows driven by density gradients. As both flows can be induced by compositional changes as well as thermal changes and in turn modify them, the resulting experimental dynamics are often complex. The purpose of our thesis is to gain insight into these intricate dynamics thanks to the theoretical analysis of model systems where only one type of convective flow is present. In particular, we numerically study the spatio-temporal evolution of model chemical fronts resulting from the coupling between reactions, diffusion, and convection. Such fronts correspond to self-organized interfaces between the products and the reactants, which typically have different density and surface tension. Fluid motions are therefore spontaneously induced due to these differences across the front.

In this context, we first address the propagation of a model autocatalytic front in a horizontal solution layer, in the presence of pure Marangoni convection on the one hand and of pure buoyancy convection on the other hand. We evidence that, in both cases, the system attains an asymptotic dynamics characterized by a steady fluid vortex traveling with the front at a constant speed. The presence of convection results in a deformation and acceleration of the chemical front compared to the reaction-diffusion situation. However we note important differences between the Marangoni and buoyancy cases that could help differentiate experimentally between the influence of each hydrodynamic effect arising in solutions open to the air. We also consider how the kinetics and the exothermicity of the reaction influence the dynamics of the system. The propagation of an isothermal front occurring when two diffusive reactants are initially separated and react according to a simple bimolecular reaction is next studied in the presence of chemically-induced buoyancy convection. We show that the reaction-diffusion predictions established for convection-free systems are modified in the presence of fluid motions and propose a new way to classify the various possible reaction-diffusion-convection dynamics./En induisant des changements de composition et de température, une réaction chimique peut modifier les propriétés physiques (densité, viscosité, tension superficielle,…) de la solution dans laquelle elle se déroule et ainsi générer des mouvements de convection qui, à leur tour, peuvent affecter la réaction. Les deux sources de convection les plus courantes en solution ouverte à l’air sont les gradients de tension superficielle, ou effets Marangoni, et les gradients de densité. Comme ces deux sources sont en compétition et peuvent toutes deux résulter de différences de concentration ou de température, les dynamiques observées expérimentalement sont souvent complexes. Le but de notre thèse est de contribuer à la compréhension de telles dynamiques par une étude théorique analysant des modèles réaction-diffusion-convection simples. En particulier, nous étudions numériquement l’évolution spatio-temporelle de fronts chimiques résultant du couplage entre chimie non-linéaire, diffusion et hydrodynamique. Ces fronts constituent l’interface auto-organisée entre les produits et les réactifs qui typiquement ont des densités et tensions superficielles différentes. Des mouvements du fluide peuvent dès lors être spontanément initiés dus à ces différences au travers du front.

Dans ce contexte, nous étudions la propagation d’un front chimique autocatalytique se propageant dans une solution aqueuse horizontale, d’une part en la seule présence d’effets Marangoni, et d’autre part en présence uniquement d’effets de densité. Nous avons montré que dans les deux cas, le système atteint une dynamique asymptotique caractérisée par la présence d’un rouleau de convection stationnaire se propageant à vitesse constante avec le front. Ce front est à la fois déformé et accéléré par les mouvements convectifs par rapport à la situation réaction-diffusion. Nous avons mis en évidence d’importantes différences entre les deux régimes hydrodynamiques qui pourraient aider les expérimentateurs à différencier les effets de tension superficielle de ceux de densité générés par la propagation de fronts chimiques en solution. Nous avons également considéré l’influence de la cinétique de réaction ainsi que de l’exothermicité sur la dynamique de ces fronts. Enfin, nous avons étudié la propagation en présence de convection d’un front de réaction impliquant deux espèces de densités différentes, initialement séparées et réagissant selon une cinétique bimoléculaire. Nous avons montré que la convection modifie les propriétés réaction-diffusion du système et nous proposons de nouveaux critères pour classifier les dynamiques réaction-diffusion-convection.

Doctorat en Sciences
info:eu-repo/semantics/nonPublished

Ce travail est dédié à la modélisation multi-échelle des phénomènes liés à la transition de spin dans des composés du Fe(II). Le développement d'un modèle macroscopique type réaction-diffusion pour la transition de phase à partir de l'Hamiltonien d'Ising a permis l'étude théorique des aspects spatio-temporels de la fraction haut-spin lors de la transition de phase du premier ordre dans des monocristaux commutables. La comparaison à l'expérience a conduit à de très bons accords pour le comportement du front de transition, ce qui a permis de mieux comprendre les mesures de microscopie optique. Ce travail a été étendu à l'étude des effets photo-thermiques qui causent l'échauffement du cristal par la lumière du microscope conduisant à un système d'équations différentielles couplées tenant compte du couplage thermique avec le bain.Ces équations prédisent des comportements non-linéaires du cristal dans son domaine bistable, tels que l’existence d’effets autocatalytiques, dont les conditions d'émergence ont été précisées. La dernière partie de la thèse est consacrée à une extension du modèle électro-élastique. Ici on démontre que la frustration élastique est à l'origine de la transition de spin en deux étapes et des transitions incomplètes. Ceci nous a amené aussi à prédire l'organisation de structures complexes de la fraction haut-spin dans les phases intermédiaires. Plusieurs types d'auto-organisation ont été révélés dont des structures modulées de la fraction haut-spin. Ce type de comportements a été observé expérimentalement très récemment dans les composés à transition de spin
This work is devoted to the multiscale modeling of the spin transition phenomena in Fe(II) spin crossover compounds. The development of a macroscopic reaction-diffusion-like model for the phase transition from the Ising-like Hamiltonian allowed the theoretical study of the spatio-temporal behavior of the high-spin fraction accompanying the first-order phase transition in switchable spin crossover single crystals. The comparison to experiments led to an excellent agreement for the dynamics of the high-spin/low-spin interface which improved the understanding of the optical microscopy measurements. Next, this work was extended to the study of photothermic effects due to the crystal heating by the light of the microscope leading to a coupled system of differential equations accounting for the thermal coupling with the bath temperature. These equations predict nonlinear behaviors for crystals in the bistable region, such as the autocatalytic effects, for which we established the conditions of their emergence. The last part of this thesis is devoted to an extension of the electro-elastic model. Here we prove that the elastic frustration is at the origin of the existence of two-step and of incomplete spin crossover transitions. Furthermore, this model allowed us to predict structures of complex patterns in high-spin fractions for intermediate phases. Several types of self-organisation were revealed such as the spatially-modulated structures of the high-spin fractions. Some of these behaviors have been experimentally observed, very recently, in spin crossover compounds

La dissolution du dioxyde d’uranium en milieu nitrique est une étape clef du traitement des combustibles nucléaires usés. Elle précède en effet le procédé PUREX, qui permet l’extraction liquide - liquide des radionucléides valorisables. Cette dissolution est triphasique et autocatalytique, ce qui fait que de nombreux phénomènes impactent la réaction. Une bonne compréhension de ces phénomènes, autant à l’échelle microscopique que macroscopique, est nécessaire pour pouvoir proposer un modèle de la vitesse de disparition du solide au sein des dissolveurs. Les paramètres cinétiques de la réaction de dissolution ont été déterminés, en intégrant son aspect autocatalytique. L’étude cinétique a été réalisée en suivant la dissolution par microscopie optique. Cette technique d’analyse permet une approche uni-particulaire, qui est nécessaire car elle permet de limiter l’accumulation de l’espèce autocatalytique à l’interface solide – liquide. De plus, la dissolution du dioxyde d’uranium produit des oxydes d’azote. Une réaction volumique entre ces gaz et le catalyseur a été mise en évidence. Les cinétiques de cette réaction ont été estimées à partir des résultats expérimentaux. L’importance de la prise en compte des échanges à l’interface gaz – liquide pour définir la concentration de catalyseur en solution a été démontrée. Un modèle a été réalisé sur Matlab pour permettre de discriminer l’influence de ces différents éléments. Ce modèle donne des résultats cohérents avec l’expérimental, aussi bien à l’échelle microscopique que macroscopique. Plusieurs nombres adimensionnels ont également été mis en évidence pour cerner les phénomènes dont l’impact est prépondérant, en fonction de la géométrie et de l’hydrodynamique du dissolveur. Ce modèle a permis de cerner quelques pistes d’optimisation de procédés mettant en jeux des réactions autocatalytiques. Notamment, le fait que pour ces réactions particulières, les échanges aux interfaces solide - liquide et liquide - gaz peuvent être utilisés comme leviers pour maitriser la vitesse de disparition du solide
Recycling of nuclear fuel is based on liquid – liquid extraction. The dissolution of uranium dioxide in nitric medium is hence a key step at the head - end of the entire process. This particular dissolution is triphasic and autocatalytic, which means that numerous phenomena must be taken into account. A complete understanding of these phenomena, at macroscopic and microscopic scale, is necessary in order to model the solid disappearance rate in dissolvers. The kinetical parameters of the reaction were determined for both the catalyzed and non-catalyzed reactions. The kinetic study was realized thanks to a single particle approach. The reaction rates were measured by optical microscopy. This analytical technic enables to limit the catalyst accumulation at the solid - liquid interface. Moreover, nitrous oxides are products of the uranium dioxide dissolution. Evidence of a volumic reaction between these gases and the catalyst were found, and the kinetics of this reaction was estimated from the experimental results. Gas – liquid exchanges were shown to have an important impact on the catalyst concentration in the reactor. A model was realized thanks to the software Matlab to simulate these different phenomena. It was shown to be in good agreement with experimental results, at the microscopic and macroscopic scale. Dimensionless numbers were highlighted to describe the impact of each phenomenon on the solid disappearance, including the influence of the geometry and hydrodynamics of the reactor. Finally, ways of process optimization for autocatalytic reactions were determined thanks to the model. For instance, gas – liquid and solid – liquid exchanges were shown to be an interesting lever to fix the catalyst concentration in the reactor and at the solid surface

Molecular recognition plays an essential role in the self-assembly and self-organisation of biological and chemical systems alike—allowing individual components to form complex interconnected networks. Within these systems, the nature of the recognition and reactive processes determines their functional and structural properties, and even small changes in their identity or orientation can exert a dramatic effect on the observed properties. The rapidly developing field of systems chemistry aims to move away from the established paradigm in which molecules are studied in isolation, towards the study of networks of molecules that interact and react with each other. Taking inspiration from complex natural systems, where recognition processes never operate in isolation, systems chemistry aims to study chemical networks with the view to examining the system-level properties that arise from the interactions and reactions between the components within these systems. The work presented in this thesis aims to advance the nascent field of systems chemistry by bringing together small organic molecules that can react and interact together to form interconnected networks, exhibiting complex behaviour, such as self-replication, as a result. Three simple building blocks are used to construct a network of two structurally similar replicators and their kinetic behaviour is probed through a comprehensive kinetic analysis. The selectivity for one of the recognition-mediated reactive processes over another is examined within the network in isolation as well as in a scenario where the network is embedded within a pool of exchanging components. The interconnected, two-replicator network is examined under far-from-equilibrium reaction-diffusion conditions, showing that chemical replicating networks can exhibit signs of selective replication—a complex phenomenon normally associated with biological systems. Finally, a design of a well-characterised replicator is exploited for the construction of a network integrating self-replication with a another recognition-directed process, leading to the formation of a mechanically-interlocked architecture—a [2]rotaxane.

Opération de tête des procédés hydrométallurgiques de recyclage des combustibles nucléaires usés, la dissolution est une étape importante : la mise en solution des éléments chimiques est indispensable avant la réalisation des étapes d’extraction liquide-liquide permettant de faire le tri entre matière valorisable et déchets ultimes. Cette étude a pour objectif de mieux appréhender les phénomènes chimiques, physico-chimiques et hydrodynamiques de la réaction de dissolution du dioxyde d’uranium en milieu nitrique. Elle s’inscrit dans une démarche de modélisation du procédé par l’expression des vitesses intrinsèques de réaction et la description des phénomènes physico-chimiques aux interfaces. Une approche par microscopie optique a permis de confirmer le caractère fortement autocatalytique de la réaction et de mesurer, pour la première fois, les vitesses « vraies » de la réaction chimique. L’attaque des massifs, obtenus par frittage, se fait par des sites préférentiels d’attaque et entraîne le développement de failles dans les massifs qui peuvent aller jusqu’à déliter le massif. Cette attaque non uniforme est rendue possible par l’établissement d’un bullage dans ces failles qui permet un renouvellement périodiquement des réactifs et entretient la réaction en leur sein. Ce point constitue un élément clef du mécanisme : un lien fort entre développement des failles, bullage dans les failles, et vitesses de dissolution globales est mis en évidence dans ce travail. Enfin, un modèle intégrant les bilans couplés de matière liés à l’évolution structurelle du solide et des compositions en phase liquide, et tenant compte du transport aux interfaces, est proposé. Les simulations fondées sur ce modèle sont proches des observations expérimentales, et permettent de reproduire pour la première fois l’effet de différents paramètres réactionnels, comme celui de la diminution des cinétiques lors d’une augmentation de la turbulence
Dissolution is a milestone of the head-end of hydrometallurgical processes used for recycling spent nuclear fuel. The solubilization of the chemical elements is essential before performing the liquid-liquid extraction steps to separate reusable material and final waste. This study aims at better understanding the chemical, physico-chemical and hydrodynamic phenomena of uranium dioxide dissolution reactions in nitric medium. This study is also part of a modeling approach aiming at expressing the intrinsic reaction rates and describing of the physico-chemical phenomena at interfaces. Optical microscopy confirmed the highly autocatalytic nature of the reaction and led to measurements, for the very first time, of "true" chemical kinetics of the reaction. The acid attack of sintering-manufactured solids occurs through preferential attack sites. It develops cracks in the solids that can lead to the cleavage of the solid. This inhomogeneous attack is made possible by the establishment of bubbling in the cracks which allows periodic renewal of the reagents and thus maintains the reaction within the cracks. This point is a key component of the mechanism: a strong link between the development of cracks, bubbling through the cracks, and overall dissolution kinetics is demonstrated in this work. Finally, a model coupling material balance to the structural evolution of the solid and liquid phase compositions, and taking into account the interfacial transport is proposed. The simulations based on this model are close to the experimental observations, and allow to reproduce for the very the first time the effect of various reaction parameters, such as the reduction of overall kinetics when turbulence increases

碩士
淡江大學
化學工程學系
88
The cure of a commercial cyanate ester monomer(PT30 resin),which reacts to form a polycyanurate network, has been investigated by using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). We have determined the conversions reached at several isothermal temperatures (513~553K) and the reaction rates. The experimental data, showing an autocatalytic behavior, conforms to the model proposed by Kamal, which includes two reaction orders, m and n, two rate constants, k1 and k2. The model gives a good description of cure kinetics up to the onset of gelation. The values of the parameters m, n and rate constants k1, k2 for each curing tempurate have been obtained from Kenny’s graphic-analytical teachnique. The autocatalytic model predictions are in good agreement with the experimental data at high curing temperatures. At low curing temperature, the autocatalytic model predictions are deviating from the experimental data after gelation occuring. The activation energies for the rate constants k1 and k2 are 80.9kJ/mole and 82.3 kJ/mole. The overall reaction order is about 1.99(m=0.99,n=1.0). The present model satisfactorily describes the experimental data at both of low and high curing temperatures. It was possible to predict the cure kinetics over the whole range of conversion. The activation energies for the rate constants k1 and k2 are 86.4kJ/mole and 80.2kJ/mole. The overall reaction order is about 1.94(m=0.95,n=0.99).

In the U.S. Chemical Safety and Hazard Investigation Board (CSB) report, Improving Reactive Hazard Management, there are 37 out of 167 accidents, which occurred in a storage tank or a storage area. This fact demonstrates that thermal runaway problems in chemical storage processes have not been give enough attention. Hydroxylamine Nitrate (HAN) is an important member of the hydroxylamine compound family and its diluted aqueous solution is widely used in the nuclear industry for equipment decontamination. It is also used as a solid or aqueous propellant. Due to its instability and autocatalytic behavior, it has been involved in several incidents at the Hanford and Savannah River Sites (SRS). Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work focuses on extracting its autocatalytic kinetics mechanism and studying its critical behavior from adiabatic calorimetry measurements. The lumped autocatalytic kinetics model, the associated model parameters and HAN critical condition are determined for the first time. The contamination effect of iron ions and nitric acid on diluted hydroxylamine nitrate solution is also studied. This work also identified the safe storage conditions for a small quantity HAN diluted solution with thermal explosion theory. Computational Fluid Dynamics (CFD) was used to further study the influence of natural convection and system scale on the critical behavior for a large quantity of chemical and thus proposed the practical storage guidelines for industrial practice.

During the last 30 years considerable attention was paid to open systems far from thermal equilibrium. Under certain conditions these dissipative systems show a qualitatively new behavior on macroscopic length scales, which are known as spatiotemporal structures. These new structures arise as a feature of collective behavior of a many-body systems. One particular example of dissipative systems considered in the present Thesis is the systems with reactant birth and death. Such systems arise, e.g., in description of the population growth or the kinetics of chemical reactions. To describe the systems with a large number of particles, one has to impose some restrictions. So, it is assumed that individual properties of particles are not important, only their interaction and interaction result (reaction) are taken into account. A number of rules, which describe the behavior of particles on the microscopic level, are known as a mathematical model. There exist two methods to analyze properties of a mathematical model. The first is analysis based on the master equation. In general, this method fails to describe the properties of spatiotemporal structures. There are no analytical approximations taking into account the effect of long-range particle correlation, which is important for description of the changes on a macroscopic range. The second approach are Monte Carlo (MC) computer simulations, which actually is alternative to experiments. The MC method takes into account long-range reactant correlations. They arise as a result of microscopical model. MC has disadvantages typical for all numerical methods, e.g., a large simulation time. In the present Thesis the Lotka-type and the A+B->0 models are considered in detail. These reactions are commonly found as one of a component in many chemical reactions. The emphasis is made on understanding the basic properties of these models. Further, several physically important modifications of the Lotka-type and the A+B->0 models are made. Firstly, in Chapter 1. the Lotka-type model is extended to investigate the resonance properties. Secondly, the effect of reactant diffusion and interaction is incorporated into Lotka-type model in Chapter 2. Thirdly, the standard A+B->0 reaction is extended to the case of surface reconstruction in Chapter 3. General conclusion is presented at the end of the Thesis, which is ended by four Appendices.