Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization

Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization

Date: May 2013
Creator: Figg, Travis M.
Description: There is a high demand for the development of processes for the conversion of ubiquitous molecules into industrially useful commodities. Transition metal catalysts are often utilized for the activation and functionalization of small organic molecules due to their diverse nature and proven utility with a myriad of chemical transformations. The functionalization of methane (CH4) and dinitrogen (N2) to methanol (CH3OH) and ammonia (NH3) respectively is of particular interest; however, both methane and dinitrogen are essentially inert due to the inherit strength of their bonds. In this dissertation a series of computational studies is performed to better understand the fundamental chemistry behind the functionalization of methane and the activation of dinitrogen in a homogeneous environment. A catalytic cycle is proposed for the oxy-functionalization of methane to methanol. The cycle consists of two key steps: (1) C-H activation across a metal-alkoxide bond (M-OR), and (2) regeneration of the M-OR species through an oxy-insertion step utilizing external oxidants. The C-H activation step has been extensively studied; however, the latter step is not as well understood with limited examples. For this work, we focus on the oxy-insertion step starting with a class of compounds known to do C-H activation (i.e., Pt(II) systems). Computational studies ...
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Water-soluble Phosphors for Hypoxia Detection in Chemical and Biological Media

Water-soluble Phosphors for Hypoxia Detection in Chemical and Biological Media

Access: Use of this item is restricted to the UNT Community.
Date: December 2012
Creator: Satumtira, Nisa Tara
Description: Water-soluble Pt(II) phosphors exist predominantly for photophysical studies. However, fewer are known to be candidates for cisplatin derivatives. If such a molecule could exist, it would be efficient at not only destroying the cancerous cells which harm the body, but the destruction would also be traceable within the human body as it occurred. Herein, research accomplished in chemistry describes the photophysical properties of a water-soluble phosphor. Spectroscopically, this phosphor is unique in that it possesses a strong green emission at room temperature in aqueous media. Its emission is also sensitive to the gaseous environment. These properties have been expanded to both analytical and biological applications. Studies showing the potential use of the phosphor as a heavy metal remover from aqueous solutions have been accomplished. The removal of toxic heavy metals was indicated by the loss of emission as well as the appearance of a precipitate. The gaseous sensitivity was elicited to be used as a potential cancerous cell biomarker. In vivo studies were accomplished in a wide variety of species, including bacteria (E. coli), worms (C. elegans), small crustaceans (Artemia), and fish (D. rerio and S. ocellatus). The phosphor in question is detectable in all of the above. This fundamental ...
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A Comparative Study of Errors in Chemistry and English Found in Examination Papers of Freshman Chemistry

A Comparative Study of Errors in Chemistry and English Found in Examination Papers of Freshman Chemistry

Date: August 1938
Creator: Phillips, Annie
Description: This study attempts to discover what types of errors are commonly made by students in freshman chemistry classes. It considers the errors resulting from the students' lack of knowledge of the subject taught, and errors attributed to their failure to use correct English in their expression of ideas.
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Comparison of Homework Systems (Four Web-Based) used in First-Semester General Chemistry

Comparison of Homework Systems (Four Web-Based) used in First-Semester General Chemistry

Date: May 2009
Creator: Belland, Joshua
Description: Web-based homework systems are becoming more common in general chemistry as instructors face ever-increasing enrollment. Yet providing meaningful feedback on assignments remains of the utmost importance. Chemistry instructors consider completion of homework integral to students' success in chemistry, yet only a few studies have compared the use of Web-based systems to the traditional paper-and-pencil homework within general chemistry. This study compares the traditional homework system to four different Web-based systems. Data from eight, semester classes consisting of a diagnostic pre-test, final semester grades, and the number of successful and unsuccessful students are analyzed. Statistically significant results suggest a chemistry instructor should carefully consider options when selecting a homework system.
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Atmospheric pressure plasma cleaning of contamination surfaces. 1997 mid-year progress report

Atmospheric pressure plasma cleaning of contamination surfaces. 1997 mid-year progress report

Date: June 1, 1997
Creator: Selwyn, G.S. & Hicks, R.
Description: 'Goals of the project are to (1) identify the key physics and chemistry underlying the use of high pressure plasmas for etching removal of actinides and actinide surrogates; and (2) identify key surface reactions and plasma physics necessary for optimization of the atmospheric pressure plasma jet. Technical description of the work decommissioning of transuranic waste (TRU) into low-level radioactive waste (LLW) represents the largest cleanup cost associated with the nuclear weapons complex. This work is directed towards developing a low-cost plasma technology capable of converting TRU into LLW, based upon highly selective plasma etching of plutonium and other actinides from contaminated surfaces. In this way, only the actinide material is removed, leaving the surface less contaminated. The plasma etches actinide material by producing a volatile halide compound, which may be efficiently trapped using filters. To achieve practical, low-cost operation of a plasma capable of etching actinide materials, the authors have developed a y-mode, resonant-cavity, atmospheric pressure plasma jet (APPJ). In contrast to conventional, low pressure plasmas, the APPJ produces a purely-chemical effluent free of ions, and so achieves very high selectivity and produces negligible damage to the surface. Since the jet operates outside a chamber, many nuclear wastes may be ...
Contributing Partner: UNT Libraries Government Documents Department
Micro electromechanical systems (MEMS) for mechanical engineers

Micro electromechanical systems (MEMS) for mechanical engineers

Date: November 18, 1996
Creator: Lee, A. P., LLNL
Description: The ongoing advances in Microelectromechanical Systems (MEMS) are providing man-kind the freedom to travel to dimensional spaces never before conceivable. Advances include new fabrication processes, new materials, tailored modeling tools, new fabrication machines, systems integration, and more detailed studies of physics and surface chemistry as applied to the micro scale. In the ten years since its inauguration, MEMS technology is penetrating industries of automobile, healthcare, biotechnology, sports/entertainment, measurement systems, data storage, photonics/optics, computer, aerospace, precision instruments/robotics, and environment monitoring. It is projected that by the turn of the century, MEMS will impact every individual in the industrial world, totaling sales up to $14 billion (source: System Planning Corp.). MEMS programs in major universities have spawned up all over the United States, preparing the brain-power and expertise for the next wave of MEMS breakthroughs. It should be pointed out that although MEMS has been initiated by electrical engineering researchers through the involvement of IC fabrication techniques, today it has evolved such that it requires a totally multi-disciplinary team to develop useful devices. Mechanical engineers are especially crucial to the success of MEMS development, since 90% of the physical realm involved is mechanical. Mechanical engineers are needed for the design of MEMS, ...
Contributing Partner: UNT Libraries Government Documents Department
Mechanism of pitting corrosion prevention by nitrite in carbon steel exposed to dilute salt solutions. 1998 annual progress report

Mechanism of pitting corrosion prevention by nitrite in carbon steel exposed to dilute salt solutions. 1998 annual progress report

Date: June 1, 1998
Creator: Zapp, P.E. & Zee, J. van
Description: 'The overall goal of this project is to develop a fundamental understanding of the role of nitrite in preventing the breakdown of protective oxide(s) on carbon steel and the onset of pitting. Pitting corrosion of carbon steel exposed to dilute alkaline salt solutions can be induced by nitrate, sulfate, and chloride ions and is prevented by sufficient concentration of nitrite. A significant example of this material/electrolyte system is the storage and processing of DOE''s high-level radioactive liquid waste in carbon steel tanks. Added nitrite in the waste has a considerable downstream impact on the immobilization of the waste in a stable glass form. Waste tank integrity and glass production efficiency may benefit from the fundamental understanding of nitrite''s role in preventing pitting. This report summarizes progress after approximately six months of effort in this three-year EMSP project. Initial experimental and theoretical work has focused on the electrochemical behavior of carbon steel in simplified non-radioactive solutions that simulate complex dilute radioactive waste solutions. These solutions contain corrosion-inducing species such as nitrate and chloride and the corrosion-inhibiting nitrite at moderately alkaline pHs. The electrochemical behavior of interest here is that of the open-circuit potential of the steel specimen at equilibrium in the ...
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Fundamental limits on NOx reduction by plasma

Fundamental limits on NOx reduction by plasma

Date: April 7, 1997
Creator: Penetrante, B. M., LLNL
Description: This paper discusses the gas-phase reaction mechanisms for removal of NO{sub x} in a plasma. The effect of oxygen content on the competition between the reduction and oxidation processes is discussed. The effect of the electron kinetic energy distribution on the radical production and subsequent chemistry is then discussed in order to predict the best performance that can be achieved for NO{sub x} reduction using the plasma alone. The fundamental limit on the minimum electrical energy consumption that will be required to implement NO{sub x} reduction in any type of plasma reactor is established.
Contributing Partner: UNT Libraries Government Documents Department
Direct investigations of the immobilization of radionuclides in the alteration phases of spent nuclear fuel. 1998 annual progress report

Direct investigations of the immobilization of radionuclides in the alteration phases of spent nuclear fuel. 1998 annual progress report

Date: June 1, 1998
Creator: Burns, P.C. & Finch, R.J.
Description: 'In an oxidizing environment, such as in the proposed repository at Yucca Mountain, rapid alteration rates are expected for spent nuclear fuel. Lab.-scale simulations have repeatedly shown that the dominant alteration products under repository conditions will be uranyl phases. There is an inadequate database that relates to the effects of the alteration products on the release of radionuclides, but this information is essential to provide a radionuclide release estimate. It is likely that many of the radionuclides contained in the fuel will be incorporated into the alteration products that form, potentially with a profound impact on the future mobility of radionuclides in the repository. The authors objective is to characterize the incorporation of radionuclides into alteration products by synthesis of uranyl phases doped with radionuclides, appropriate surrogate elements, or non-radioactive isotopes, followed by detailed phase characterization by diffraction and spectroscopic techniques. The research will permit a more realistic estimate of the release rates of the radionuclides from the near-field environment. This report summarizes work after 8 months of a 3-year project. The objective of investigating radionuclide incorporation in uranyl phases has required the development of synthesis techniques for various uranyl phases that are expected to form under repository conditions. The ...
Contributing Partner: UNT Libraries Government Documents Department
Investigation of novel electrode materials for electrochemically-based remediation of high- and low-level mixed wastes in the DOE complex. 1998 annual progress report

Investigation of novel electrode materials for electrochemically-based remediation of high- and low-level mixed wastes in the DOE complex. 1998 annual progress report

Date: June 1, 1998
Creator: Lewis, N.S.
Description: 'One of the key issues that must be solved to achieve a successful remediation of the high level liquid wastes (HLW) at the Hanford and at Savannah River sites is the removal of the significant quantities of nitrate and nitrite in the existing liquid waste streams that are presently on these sites in the DOE complex. One method of waste stream remediation is electrochemical oxidation, which is an in-situ method that has been well-documented to have significant advantages in many areas with respect to pump-and-treat approaches to waste remediation. There are, however, significant aspects of the electrochemical oxidation process that need to be addressed from a basic research viewpoint. The research to be performed under this proposal will investigate new materials, initially based on degenerately-doped titanias, for use in the electrochemical degradation of organics and nitrogen-containing compounds in sites of concern to the DOE remediation effort. This report summarizes work after 1.5 years of a 3-year project. Progress has been made in two main areas of work. First, significant effort has been made in synthesis and characterization of new anode materials for electrochemical remediation purposes. Secondly, these materials have also been characterized as photoanodes for photoelectrochemical activity and remediation applications. ...
Contributing Partner: UNT Libraries Government Documents Department
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