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Die vorliegende Arbeit befasst sich mit der Verallgemeinerung von Reaktions-Diffusions-Systemen auf Subdiffusion. Die subdiffusive Dynamik auf mesoskopischer Skala wurde mittels Continuous-Time Random Walks mit breiten Wartezeitverteilungen modelliert. Die Reaktion findet auf mikroskopischer Skala, d.h. während der Wartezeiten, statt und unterliegt dem Massenwirkungsgesetz. Die resultierenden Integro-Differentialgleichungen weisen im Integralkern des Transportterms eine Abhängigkeit von der Reaktion auf. Im Falle der Degradation A->0 wurde ein allgemeiner Ausdruck für die Lösungen beliebiger Dirichlet-Randwertprobleme hergeleitet. Die Annahme, dass die Reaktion dem Massenwirkungsgesetz unterliegt, ist eine entscheidende Voraussetzung für die Existenz stationärer Profile unter Subdiffusion. Eine nichtlineare Reaktion stellt die irreversible autokatalytische Reaktion A+B->2A unter Subdiffusion dar. Es wurde ein Analogon zur Fisher-Kolmogorov-Petrovskii-Piscounov-Gleichung (FKPP) aufgestellt und die resultierenden propagierenden Fronten untersucht. Numerische Simulationen legten die Existenz zweier Regimes nahe, die sowohl mittels eines Crossover-Argumentes als auch durch analytische Berechnungen untersucht wurden. Das erste Regime ist charakterisiert durch eine Front, deren Breite und Geschwindigkeit sich mit der Zeit verringert. Das zweite, fluktuationsdominierte Regime liegt nicht im Geltungsbereich der kontinuierlichen Gleichung und weist eine stärkere Abnahme der Frontgeschwindigkeit sowie eine atomar scharf definierte Front auf. Ein anderes Szenario, bei dem eine Spezies A in ein mit immobilen B-Partikeln besetztes Medium hineindiffundiert und gemäß dem Schema A+B->(inert) reagiert, wurde ebenfalls betrachtet. Diese Anordnung wurde näherungsweise als ein Randwertproblem mit einem beweglichen Rand (Stefan-Problem) formuliert. Die analytisch gewonnenen Ergebnisse bzgl. der Position des beweglichen Randes wurden durch numerische Simulationen untermauert. / The present work studies the generalization of reaction-diffusion schemes to subdiffusion. The subdiffusive dynamics was modelled by means of continuous-time random walks on a mesoscopic scale with a heavy-tailed waiting time pdf lacking the first moment. The reaction was assumed to take place on a microscopic scale, i.e. during the waiting times, obeying the mass action law. The resultant equations are of integro-differential form, and the reaction explicitly affects the transport term. The long ranged memory of the subdiffusion kernel is modified by a factor accounting for the reaction of particles during the waiting times. The degradation A->0 was considered and a general expression for the solution to arbitrary Dirichlet Boundary Value Problems was derived. For stationary solutions to exist in reaction-subdiffusion, the assumption of reactions according to classical rate kinetics is essential. As an example for a nonlinear reaction-subdiffusion system, the irreversible autocatalytic reaction A+B->2A under subdiffusion is considered. A subdiffusive analogue of the classical Fisher-Kolmogorov-Petrovskii-Piscounov (FKPP) equation was derived and the resultant propagating fronts were studied. Two different regimes were detected in numerical simulations, and were discussed using both crossover arguments and analytic calculations. The first regime is characterized by a decaying front velocity and width. The fluctuation dominated regime is not within the scope of the continuous description. The velocity of the front decays faster in time than in the continuous regime, and the front is atomically sharp. Another setup where reactants A penetrate a medium initially filled with immobile reactants B and react according to the scheme A+B->(inert) was also considered. This problem was approximately described in terms of a moving boundary problem (Stefan-problem). The theoretical predictions concerning the moving boundary were corroborated by numerical simulations.

Neptunium, with its rich redox chemistry, has a special position in the chemistry of actinides. With a decades-long history of development of aqueous separation methods for used nuclear fuel (UNF), management of neptunium remains an unresolved issue because of its not clearly defined redox speciation. Neptunium is present in two, pentavalent (V) and hexavalent (VI) oxidation states, both in their dioxocation O=Np=O neptunyl form, which differ greatly in their solvent extraction behavior. While the neptunium(VI) dioxocation is being very well extracted, the dioxocation of pentavalent neptunium is practically non-extractable by an organic solvent. As a result, neptunium is not well separated and remains distributed in both organic and aqueous extraction phases. The aim of this study was to develop or enhance the understanding of several key topics governing the redox behavior of neptunium in nitric acid medium, which are of vital importance for the engineering design of industrial-scale liquid-liquid separation systems. In this work, reactions of neptunium(V) and (VI) with vanadium(V) and acetohydroxamic acid - two redox agents envisioned for adjusting the neptunium oxidation state in aqueous separations ��� were studied in order to determine their kinetic characteristics, rate laws and rate constants, as a function of temperature and nitric acid concentration. Further were analyzed the interactions of neptunium(V) and (VI) with nitrous acid, which is formed as a product of radiolytic degradation of nitric acid caused by high levels of radioactivity present in such systems. Once HNO��� is distributed between both the aqueous solutions and organic solvent, nitrous acid is also formed in both phases and has a key influence on redox speciation of neptunium; therefore, the effects of gamma-radiation on the redox speciation of neptunium were investigated. The work also includes the results of examination of scavenging of nitrous acid by hydrogen peroxide, which is generated along with nitrous acid during radiolysis of aqueous solutions of nitric acid, and also by chemical reactions with added scavenging agents (methylurea, acetohydroxamic acid). / Graduation date: 2013

Car exhaust catalysts were introduced in the early 1980’s, to limit the release of pollutants such as hydrocarbons, carbon monoxide and nitrogen oxides. These catalysts contain noble metals such as palladium (Pd), platinum (Pt) and rhodium (Rh) and are able to simultaneously abate all three of the above-mentioned pollutants, hence the name three-way catalyst (TWC). The exposure to high temperatures (800-1000 °C) during operation and the presence of additives in gasoline and lubricants will, after a certain time, lower the activity of the TWC. High temperatures reduce the active area by causing the noble metals to agglomerate and sinter, whereas the additives alter the activity either by fouling the pores of the support material or by interacting with the metals. The main objective of this work was to develop a method which allows for the removal of contaminants (additives) from the washcoat and enables the redispersion of the active sites (noble metals), in an effort to recover lost catalyst activity. For this purpose, regeneration experiments were carried out on a wide spectrum of different commercial car exhaust catalysts. The influence of a thermal treatment in a controlled gas atmosphere, such as oxygen or hydrogen, and a redispersing agent, e.g. chlorine, on the activity of TWC was investigated by means of laboratory-scale activity measurements. Several complementary characterization methods such as SEM/TEM, XRD, BET, LA, XPS and TPR were employed to verify the effects of the regeneration treatments on the catalyst morphology (Papers I, II). The results show that partial regeneration of catalyst activity and noble metal dispersion was achieved after thermal treatment in an oxygen-chlorine rich atmosphere at temperatures below 500 °C. A wet-chemical regeneration treatment with dilute oxalic and citric acid solutions is evaluated in Paper III. These acidic solutions are able to dissolve and remove contaminants from the washcoat, thus partly restoring the catalyst activity. An investigation of the effects of an oxy-chlorine thermal treatment for regeneration of a ‘full-scale’ commercial automotive three-way catalyst was carried out (Paper IV). Improved catalyst activity for a high mileage catalyst could be observed, with emissions lowered by approximately 30 to 40 vol.% over the EC2000 driving cycle. The properties of fresh, aged and regenerated catalysts were then studied by means of labscale experiments, on a local as well as a global level using a mathematical model (Paper V). The model allows for comparison of the intrinsic properties of the active surface by deriving and tuning parameters of a fresh catalyst and verifying the activity of a regenerated or aged catalyst. / QC 20100812

One the most daunting technical challenges in the realization of biosensors is functionalizing transducing surfaces for the detection of biomolecules. Functionalization is defined as the formation of a bio-compatible interface on the transducing surfaces of bio-chemical sensors for immobilizing and subsequent sensing of biomolecules. The kinetics of functionalization reactions is a particularly important issue, since conventional functionalization protocols are associated with lengthy process times, from hours to days. The objective of this thesis is the improvement of the functionalization protocols and their kinetics for biosensing applications. This objective is realized via modeling and experimental verification of novel functionalization techniques in microfluidic environments. The improved functionalization protocols using microfluidic environments enable in-situ functionalization, which reduces the processing times and the amount of reagents consumed, compared to conventional methods. The functionalization is performed using self-assembled monolayers (SAMs) of thiols. The thiols are organic compounds with a sulphur group that assists in the chemisorption of the thiol to the surface of metals like gold. The two reactions in the functionalization process examined in this thesis are the SAM formation and the SAM/probe molecule conjugation. SAM/probe molecule conjugation is the chemical treatment of the SAM followed by the binding of the probe molecule to the SAM. In general, the probe molecule is selective in binding with a given biomolecule, called the target molecule. Within this thesis, the probe molecule is an antibody and the target molecule is an antigen. The kinetics of the reaction between the probe (antibody) and the target biomolecule (antigen) is also studied. The reaction between an antigen and its antibody is called the immunoreaction. The biosensing technique that utilizes the immunoreaction is immunoassay. A numerical model is constructed using the finite element method (FEM), and is used to study the kinetics of the functionalization reactions. The aim of the kinetic studies is to achieve both minimal process times and reagents consumption. The impact of several important parameters on the kinetics of the reactions is investigated, and the trends observed are explained using kinetic descriptive dimensionless numbers, such as the Damköhler number and the Peclet number. Careful numerical modeling of the reactions contributes to a number of findings. A considerably faster than conventional SAM formation protocol is predicted. This fast-SAM protocol is capable of reducing the process times from the conventional 24-hours to 15 minutes. The numerical simulations also predict that conventional conjugation protocols result in the overexposure of the SAM and the probe molecule to the conjugation reagents. This overexposure consequently lowers conjugation efficiencies. The immunoreaction kinetics of a 70 kilo-Dalton heat shock protein (HSP70) with its antibody in a hypothetical microchannel is also investigated through the FEM simulations. Optimal reaction conditions are determined, including the flow velocity and the surface concentration of the immobilized probes (antibodies). Based on the numerical results and a series of experimental studies, the fast-SAM protocol application is successfully confirmed. Moreover, the optimum reagent concentration for a given one- hour conjugation process time is determined. This functionalization protocol is successfully applied to immobilize the HSP70 antibody on gold surfaces. The use of the fast-SAM protocol and the predicted optimum conjugation conditions result in binding of the HSP70 antibody on gold, with the same or superior immobilization quality, compared to the conventional protocols. Upon implementation of a 70 μm.s^(-1) flow velocity, the reaction is observed to complete in around 30-35 minutes, which is close to the numerically predicted 30 minutes and 16 seconds. This immunoreaction time is considerably less than conventional 4-12 hour processes. The modified in-situ functionalization techniques achieved here are promising for substantially reducing the preparation times and improving the performance of biosensors, in general, and immunoassays, in particular.

Chemical modification is an important way to improve the properties of existing polymers, and one of the important examples is the hydrogenation of nitrile butadiene rubber (NBR) in organic solvent by homogeneous catalysis in order to extend its application. This process has been industrialized for many years to provide high performance elastomers (HNBR) for the automotive industry, especially those used to produce components in engine compartments. In the current commercial process, a batch reactor is employed for the hydrogenation step, which is labor intensive and not suitable for large volume of production. Thus, novel hydrogenation devices such as a continuous process are being developed in our research group to overcome these drawbacks. In order to make the process more practical for industrial application, high concentration polymer solutions should be targeted for the continuous hydrogenation. However, many problems are encountered due to the viscosity of the high concentration polymer solution, which increases tremendously as the reaction goes on, resulting in severe mass transfer and heat transfer problems. So, hydrogenation kinetics in high concentration NBR solution, as well as the rheological properties of this viscous solution are very essential and fundamental for the design of novel hydrogenation processes and reactor scale up. In the present work, hydrogenation of NBR in high concentration solution was carried out in a batch reactor. A commercial rhodium catalyst, Wilkinson’s catalyst, was used with triphenylphosphine as the co-catalyst and chlorobenzene as the solvent. The reactor was modified and a PID controller was tuned to fit this strong exothermic reaction. It was observed that when NBR solution is in a high concentration the kinetic behavior was greatly affected by mass transfer processes, especially the gas-liquid mass transfer. Reactor internals were designed and various agitators were investigated to improve the mechanical mixing. Experimental results show that the turbine-anchor combined agitator could provide superior mixing for this viscous reaction system. The kinetic behavior of NBR hydrogenation under low catalyst concentration was also studied. It was observed that the hydrogenation degree of the polymer could not reach 95% if less than 0.1%wt catalyst (based on polymer mass) was used, deviating from the behavior under a normal catalyst concentration. The viscosity of the NBR-MCB solutions was measured in a rotational rheometer that has a cylinder sensor under both room conditions and reaction conditions. Parameters that might affect the viscosity of the solutions were studied, especially the hydrogenation degree of polymer. Rheological properties of NBR-MEK solutions, as well as NBR melts were also studied for relevant information. It is concluded that the hydrogenation kinetics deviates from that reported by Parent et al. [6] when polymer is in high concentration and/or catalyst is in low concentration; and that the reaction solution (HNBR/NBR-MCB solution) deviates from Newtonian behavior when polymer concentration and hydrogenation degree are high.

A molecular-level understanding of a heterogeneous catalytic reaction is the key goal of heterogeneous catalysis. A surface science approach enables the realization of this goal. However, the working conditions (ultrahigh vacuum (UHV) conditions) of traditional surface science techniques restrict the investigations of heterogeneous catalysis system under industrial working conditions (atmospheric pressures). Polarization Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRAS) can be operated in both UHV and atmospheric pressure conditions with a wide temperature span while providing high resolution (4 cm-1 is used in this dissertation) spectra. In this dissertation, PM-IRAS has been employed as a major technique to: 1) obtain both electronic and chemical information of catalysts from UHV to elevated pressure conditions; 2) explore reaction mechanisms by in situ monitoring surface species with concurrent kinetic measurements. In this dissertation, NO adsorption and dissociation on Rh(111) have been studied. Our PM-IRAS spectra show a transition of NO adsorption on three-fold hollow sites to atop sites occurs at low temperatures (<275 K). NO dissociation is found to account for this transition. The results indicated the dissociation of NO occurs well below the temperature previously reported. Characterizations of highly catalytically active Au films have also been carried out. Electronic and chemical properties of (1 x 1)- and (1 x 3)-Au/TiOx/Mo(112) films are investigated by PM-IRAS using CO as a probe molecule. The Au overlayers are found to be electron-rich and to have significantly different electronic properties compared with bulk Au. The exceptionally high catalytic activity of the Au bilayer structure is related to its unique electronic properties. CO oxidation reactions on Rh, Pd, and Pt single crystals are explored from low CO pressures under steady-state conditions (less than 1 x 10-4 Torr) to high pressures (0.01-10 Torr) at various gaseous reactant compositions. Surface CO species are probed with in situ PM-IRAS to elucidate the surface phases under reaction conditions. These experimental results are used to correlate reaction kinetics and surface reactant species. It is evident that there is a continuum over the pressure range studied with respect to the reaction mechanism. The most active phase has been shown to be an oxygen-dominant surface. The formation of a subsurface oxygen layer is found to deactivate the reaction.

BaSIC, which stands for Bioclastic and Shape-preserving Inorganic Conversion, is shape-preserving chemical conversion process of biological (or man-made) silica structures for producing complex 3-D microscale structures. This dissertation reports the BaSIC reaction of halide gases (i.e., TiF4, ZrF4, and ZrCl4) with 3-D silica structures, (i.e., diatom frustules, silicified direct-write assembly scaffolds, and Stöber silica spheres) to produce titania and zirconia replicas of the original 3-D structures. The kinetics of reaction of silica with titanium tetrafluoride gas is analyzed by using a novel HTXRD reaction chamber, nitrogen adsorption, and transmission electron microscope (TEM). The crystal structure and the temperature-induced phase transformation (from the room temperature hexagonal R-3c structure to the higher temperature cubic Pm3m structure) of polycrystalline TiOF2 that was synthesized through metathetic reaction of silica with TiF4(g) is reported. Additionally, potential applications of the converted titania diatom frustules (i.e., as a fast micron-sized ethanol sensor, and as a pesticide hydrolyzing agent) are also demonstrated in this work.

To enable future environmentally friendly access to space by means of solid rocket propulsion a viable replacement to the hazardous ammonium perchlorate oxidizer is needed. Ammonium dinitramide (ADN) is one of few such compounds currently known. Unfortunately compatibility issues with many polymer binder systems and unexplained solid-state behavior have thus far hampered the development of ADN-based propellants. Chapters one, two and three offer a general introduction to the thesis, and into relevant aspects of quantum chemistry and polymer chemistry. Chapter four of this thesis presents extensive quantum chemical and spectroscopic studies that explain much of ADN’s anomalous reactivity, solid-state behavior and thermal stability. Polarization of surface dinitramide anions has been identified as the main reason for the decreased stability of solid ADN, and theoretical models have been developed to explain and predict the solid-state stability of general dinitramide salts. Experimental decomposition characteristics for ADN, such as activation energy and decomposition products, have been explained for different physical conditions. The reactivity of ADN towards many chemical groups is explained by ammonium-mediated conjugate addition reactions. It is predicted that ADN can be stabilized by changing the surface chemistry with additives, for example by using hydrogen bond donors, and by trapping radical intermediates using suitable amine-functionalities. Chapter five presents several conceptual green energetic materials (GEMs), including different pentazolate derivatives, which have been subjected to thorough theoretical studies. One of these, trinitramide (TNA), has been synthesized and characterized by vibrational and nuclear magnetic resonance spectroscopy. Finally, chapter six covers the synthesis of several polymeric materials based on polyoxetanes, which have been tested for compatibility with ADN. Successful formation of polymer matrices based on the ADN-compatible polyglycidyl azide polymer (GAP) has been demonstrated using a novel type of macromolecular curing agent. In light of these results further work towards ADN-propellants is strongly encouraged. / QC 20101103

Chemical modification is an important way to improve the properties of existing polymers, and one of the important examples is the hydrogenation of nitrile butadiene rubber (NBR) in organic solvent by homogeneous catalysis in order to extend its application. This process has been industrialized for many years to provide high performance elastomers (HNBR) for the automotive industry, especially those used to produce components in engine compartments. In the current commercial process, a batch reactor is employed for the hydrogenation step, which is labor intensive and not suitable for large volume of production. Thus, novel hydrogenation devices such as a continuous process are being developed in our research group to overcome these drawbacks. In order to make the process more practical for industrial application, high concentration polymer solutions should be targeted for the continuous hydrogenation. However, many problems are encountered due to the viscosity of the high concentration polymer solution, which increases tremendously as the reaction goes on, resulting in severe mass transfer and heat transfer problems. So, hydrogenation kinetics in high concentration NBR solution, as well as the rheological properties of this viscous solution are very essential and fundamental for the design of novel hydrogenation processes and reactor scale up. In the present work, hydrogenation of NBR in high concentration solution was carried out in a batch reactor. A commercial rhodium catalyst, Wilkinson’s catalyst, was used with triphenylphosphine as the co-catalyst and chlorobenzene as the solvent. The reactor was modified and a PID controller was tuned to fit this strong exothermic reaction. It was observed that when NBR solution is in a high concentration the kinetic behavior was greatly affected by mass transfer processes, especially the gas-liquid mass transfer. Reactor internals were designed and various agitators were investigated to improve the mechanical mixing. Experimental results show that the turbine-anchor combined agitator could provide superior mixing for this viscous reaction system. The kinetic behavior of NBR hydrogenation under low catalyst concentration was also studied. It was observed that the hydrogenation degree of the polymer could not reach 95% if less than 0.1%wt catalyst (based on polymer mass) was used, deviating from the behavior under a normal catalyst concentration. The viscosity of the NBR-MCB solutions was measured in a rotational rheometer that has a cylinder sensor under both room conditions and reaction conditions. Parameters that might affect the viscosity of the solutions were studied, especially the hydrogenation degree of polymer. Rheological properties of NBR-MEK solutions, as well as NBR melts were also studied for relevant information. It is concluded that the hydrogenation kinetics deviates from that reported by Parent et al. [6] when polymer is in high concentration and/or catalyst is in low concentration; and that the reaction solution (HNBR/NBR-MCB solution) deviates from Newtonian behavior when polymer concentration and hydrogenation degree are high.