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The investigation of CO oxidation with supported noble metal catalysts to develop a fundamental understanding of the nature of the active sites, adsorbate-surface interactions, surface reaction pathways and the role of promoters is of prime importance for development of highly active and selective catalyst formulations for low temperature oxidation of carbon monoxide. Low temperature CO oxidation catalysts find applications in monitoring and elimination of CO in chemical process exhaust gases, in on-board control and diagnostics devices, automobile exhaust gas treatment systems for the development of zero-emission vehicles and, in closed-cycle CO2 lasers for remote sensing. Moreover, the investigation of the interaction of CO with noble metals and noble metals catalyzed oxidation of CO have important outcomes for upstream fuel processing systems and for the development of more CO tolerant anode materials for hydrogen fuel cell. Palladized tin dioxide is a well-known and highly active catalyst for CO oxidation which possesses the potential to satisfy the need for CO oxidation catalysts in the abovementioned areas however, research on this material is concentrated mostly around empirical studies which focus solely on CO sensing applications. This current research is undertaken to investigate both the mechanism of CO oxidation with Pd/SnO2 at the molecular scale and the possibility of promoting the CO activity of this catalyst by the application alkali-metal modifiers. Alkali-metal modified PdO/SnO2 catalysts were characterized by XPS, XRD and SEM and, tested with regard to their oxidation/reduction and CO oxidation behavior by in-situ dynamic methods such as, temperature-programmed reaction/reduction/desorption and impulse techniques. Modification of PdO/SnO2 by alkali-metals, namely Li, Na and K, resulted in catalyst formulations with different surface characteristics and reduction/oxidation behaviors that lead to superior activity in low temperature CO oxidation and selectivity towards CO in the presence of hydrogen. Studies have shown that these catalysts are potential candidates for CO oxidation catalysts in a wide range of areas.

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<p>The production of chlorate, chlorine and sodium hydroxiderelies heavily on electrical energy, so that savings in thisarea are always a pertinent issue. This can be brought aboutthrough increased mass transfer of reacting species to therespective electrodes, and through increased catalytic activityand uniformity of current density distribution at theseelectrodes. This thesis will present studies involvingmathematical modelling and experimental investigations of theseprocesses. They will show the effect that hydrodynamicbehaviour has on the total current density and cell voltages,along with the effects on current density distributions andindividual overpotentials atthe respective electrodes.</p><p>Primary, secondary and psuedo-tertiary current densitydistribution models of a chlor-alkali anode are presented anddiscussed. It is shown that the secondary model presentsresults rather similar to the pseudo-tertiary model, when thecurrent density distribution is investigated, although thepotential distribution differs rather markedly. Furthermore, itis seen that an adequate description of the hydrodynamicsaround the anode is required if the potential distribution, andthereby the prevalence of side-reactions, is to be reasonablepredicted.</p><p>A rigorous tertiary current density distribution model ofthe chlorate cell is also presented, which takes into accountthe developing hydrodynamic behaviour along the height of thecell. This shows that an increased flowrate gives more uniformcurrent density distributions. This is due to the fact that theincreased vertical flowrate of electrolyte replenishes ioncontent at the electrode surfaces, thus reducing concentrationoverpotentials. Furthermore, results from the model lead to theconclusion that it is the hypochlorite ion that partakes in themajor oxygen producing side-reaction.</p><p>A real-scale cross-section of a segmented anode-cathode pairfrom a chlorate cell was designed and built in order to studythe current density distribution in industrial conditions.These experiments showed that increased flowrate brought aboutmore even current density distributions, reduced cell voltageand increased the total current density. An investigation ofthe hydrodynamic effects on the respective electrodeoverpotentials shows the anode reactions being more favoured byincreased flowrate. This leads to the conclusion that theuniform current density distribution, caused by increasedflowrate, occurs primarily through decreasing the concentrationoverpotential at the anode rather than by decreasing thebubble-induced ohmic drop at the cathode.</p><p>Finally, results from experiments investigating thebubble-induced free convection from a small electrochemicalcell are presented. These experiments show that Laser DopplerVelocimetry is the most effective instrument for investigatingthe velocity profiles in bubble-containing electrochemicalsystems. The results also show that the flow can transform fromlaminar to turbulent behaviour on both the vertical andhorizontal planes, in electrochemical systems where bubbles areevolved.</p>

As an important chemical raw material, alcohols can be used as fuels, solvents and chemical feedstocks to produce a variety of downstream products. With limited fossil fuel resources, alcohol synthesis from syngas reactions can be a potential alternative to the traditional petroleum based alcohol synthesis. Among many catalysts active for syngas to alcohol processes, alkali promoted Mo2C has shown promising performance. More interestingly, the alkali promoter was found to play an important role in shifting the reaction selectivity from hydrocarbons to alcohols. However, limited understanding of the mechanism of this alkali promoter effect is available due to the complexity of syngas reaction mechanism and low content of alkali added to the catalysts. In this thesis, we performed a comprehensive investigation of the alkali promoter effect with density functional theory (DFT) calculations as our primary tool. We first examine various Mo2C surfaces to determine a representative surface structure active to alkali adsorption. On this particular surface, we develop a syngas reaction network including relevant reaction mechanisms proposed in previous literature. With energetics derived from DFT calculations and a BEP relation, we predict the syngas reaction selectivity and find it to be in excellent agreement with experimental results. The dominant reaction mechanism and selectivity determining steps are determined from sensitivity analysis. We also propose a formation mechanism of alkali promoters on Mo2C catalysts that shows consistency between experimental IR and DFT computed vibrational frequencies. Finally, the effect of alkali promoters on the selectivity determining steps for syngas reactions are investigated from DFT calculations and charge analysis. We are able to rationalize the role of alkali promoters in shifting the reaction selectivity from hydrocarbons to alcohols on Mo2C catalysts.

The purpose of this study was to determine the cementitious parameters and placement temperature that impact internal sulfate attack in concrete. Concrete structures make up a large percentage of the infrastructure and multifamily housing. Durability is very important. Cements can be formulated to reduce the impact of external environmental exposure such as high salinity from marine environments or high sulfate levels from soils or surface waters. Concrete is also subject to internal attack such as alkali aggregate reaction, (AAR), and delayed ettringite formation, (DEF). This study focused on some of the cement chemistry issues that determine susceptibility of cement to DEF. Expansion due to DEF can weaken the concrete matrix resulting in microcracks that in some cases may progress to severe matrix cracking. The end result is loss of load carrying capacity and costly repairs. In this study, mortar bars were made with the as received cement chemistry and using additions of sulfate, and alkalis. The bars were then heat cured at various temperatures and stored in a saturated lime solution at room temperature. Measurements were made at predetermined time intervals. The series of mixes were made to determine the effect of varying sulfate levels, heat curing temperature, and alkali content in order to isolate the effect of these constituents. The cements were selected on the basis of tricalcium aluminate, alkali content, sulfate levels, C3S levels and fineness. The results indicate that a relationship exists between the rate and level of expansion experienced by the mortar bars and cementitious parameters, namely, alkali content, sulfate content, C3S levels and heat curing temperature.

Numerous cases of premature concrete deterioration due to alkali-silica reaction and/or delayed ettringite formation have developed within highway infrastructure in the state of Texas over the past two decades. Although experimental research and in-situ load testing on an international scale has indicated that moderate levels of deterioration are unlikely to pose a threat to structural safety, the discovery of reinforcing bar fracture in Japan due to ASR-related expansion has called into question the integrity of heavily damaged structures. A two-part experimental program was conducted at The University of Texas at Austin relating to ASR/DEF-induced reinforcing bar fracture. Work conducted under TxDOT Project 0-6491 included the fabrication and monitoring of four concrete specimens. Methods were employed to simulate a fracture of the transverse reinforcement within the time frame of the study and the applicability of various NDT monitoring techniques to detect bar fracture was evaluated. Furthermore, a number of reinforcing bar samples were tested and analyzed to investigate (1) the development of reinforcing bar cracking due to the bending operation and (2) the progression of cracks after application of an expansive opening force on bars with 90° bends. Research findings and conclusions form a preliminary assessment on the potential for reinforcing bar fracture within affected infrastructure in Texas. / text

Alkali-silica reaction (ASR) and delayed ettringite formation (DEF) are expansive reactions that can lead to the premature deterioration of concrete structures. Both have been implicated in the deterioration of numerous structures around the world, including many transportation structures in Texas. As a result of considerable research advances, ASR and DEF are now avoidable in new construction, but evaluating and managing the existing stock of structures damaged by these mechanisms remains a challenge. While the published guidance for evaluating structures is very effective at diagnosing the presence of ASR and DEF, there remain significant weaknesses with respect to the evaluation of structural safety and serviceability and nondestructive testing (NDT) is a minor component of the evaluation process. The research described in this dissertation involved a wide range of tests on plain and reinforced concrete at multiple scales. This included small cylinders and prisms, larger plain and reinforced concrete specimens in outdoor exposure, full-scale reinforced concrete beams, and core samples from the outdoor exposure specimens and full-scale reinforced concrete beams. Nondestructive test methods were applied at all scales, and the full-scale beams were also tested in four-point flexure to determine the effects of ASR and DEF on flexural strength and serviceability. Severe expansions from ASR and DEF did not reduce the strength of the full-scale beams or result in excessive deflections under live loads, despite significant decreases in the compressive strength and elastic modulus measured from core samples. Most NDT methods were found to be effective at low expansions but had difficulty correlating to larger expansions. Two promising NDT methods have been identified for future research and development, and guidance regarding existing test methods is offered. / text

A limited number of laboratory studies and pilot programs have been reported in chemical Enhanced Oil Recovery (EOR) flooding of carbonate reservoirs (Adams & Schievelbein, 1987). Fewer still have involved surfactants in limestone reservoirs. No surfactant/polymer flood on a field wide basis of a carbonate reservoir has ever been documented in the literature (Manrique, Muci, & Gurfinkel, 2010). This void represents a colossal opportunity given that nearly a third of the 32 billion barrels of oil consumed in the world each year come from carbonate reservoirs (Sheng, 2011, pp. 1, 254). This thesis is based on experiments with a high hardness (~5,000 ppm divalent ions) carbonate field. Phase behavior, aqueous stability, and core flood experiments were performed using polymer and various surfactants and co-solvents. Both commercially available and laboratory synthesized surfactants were tested. The objective was to optimize the chemical injection design in order to lower interfacial tension between water and oil in the reservoir. Research was also done with alkali intended for use with hard brines. The main challenges when working with hard brine were poor solubilization and low aqueous stability limits. However, highly propoxylated and ethoxylated surfactants mixed with internal olefin sulfonates, hydrophilic sulfates, and sec-butanol were observed to have very high solubilization ratios, fast phase behavior equilibration times, negligible viscous macroemulsion effects, and excellent aqueous stability. Spinning drop interfacial tensiometer tests confirmed low IFT values were obtained for a range of acceptable salinities with hard brine. Three core floods were performed using one of the surfactant formulations developed. One flood was done with field core, brine, and crude oil and failed to meet expectations because of high levels of heterogeneity (vugs) within the core that lead to an elongated oil bank and low and slow oil recovery. The other floods were done with Estillades Limestone. The first Estillades flood used hard synthetic field brine and had better mobility but poor oil recovery. The last core flood had good mobility and recovered 90% of the residual oil to water flooding, but only after a total of 1.1 pore volumes of 1.0 wt% surfactant solution were injected. The results provided in this thesis constitute proof of concept that S/P flooding can be done in high salinity and hardness reservoirs. / text

In recent years, it has been discovered that some structural elements of the I-10 and I-35 corridor passing through San Antonio, Texas (San Antonio Y) are suffering from premature concrete deterioration related to alkali-silica reaction (ASR) and/or delayed ettringite formation (DEF). While there is considerable evidence of materials related distress, the degree of damage to structural capacity has not been quantified. In a comprehensive search of literature, very little research has been identified that quantifies the amount of structural damage caused by ASR and/or DEF on the load carrying capacity of structural piers. Due to the fact that this integral stretch of interstate highway sees a large volume of traffic, it is desirable to determine a method of assessing the degree of structural damage, and the necessity of taking remedial actions. The purpose of this thesis is to develop an assessment methodology which can be used by The Texas Department of Transportation (TxDOT) to evaluate the current and future integrity of structural elements in the San Antonio Y. The key steps included in the methodology are conducting a literature review on the effects of ASR and/or DEF on the structural properties of reinforced concrete, evaluating in-situ engineering properties of existing concrete, investigating the basis for the original design, and performing an experimental investigation to determine the effect of cracking on the load carrying capacity of typical SAY piers. This thesis presents the findings from this research. / text