Physical Sciences and Mathematics Commons^™

Characteristics And Stability Of Oxide Films On Plutonium Surfaces, Harry Guillermo García Flores

Department of Chemistry: Dissertations, Theses, and Student Research

The oxidation of plutonium (Pu) metal continues to be an area of considerable activity. The reaction characteristics have significant implications for production use, storage, and disposition of this radiological material. Developing an accurate physical model of the structures, oxidation states, and oxygen concentration gradients present during oxidation are essential to understanding this process. Traditionally, the stable oxides of Pu have been thought to be plutonium sesquioxide (Pu₂O₃, O/Pu = 1.5, Pu³⁺) and plutonium dioxide (PuO₂, O/Pu = 2.0, Pu⁴⁺), existing in a layered structure on Pu metal. Many of the …

Low Temperature Photo-Oxidation Of Chloroperoxidase Compound Ii, Xinting Yuan, Xin Sheng, John A. Horner, Brian Bennett, Leslie W. -M. Fung, Martin Newcomb

Physics Faculty Research and Publications

Oxidation of the heme-thiolate enzyme chloroperoxidase (CPO) from Caldariomyces fumago with peroxynitrite (PN) gave the Compound II intermediate, which was photo-oxidized with 365 nm light to give a reactive oxidizing species. Cryo-solvents at pH ≈ 6 were employed, and reactions were conducted at temperatures as low as − 50 °C. The activity of CPO as evaluated by the chlorodimedone assay was unaltered by treatment with PN or by production of the oxidizing transient and subsequent reaction with styrene. EPR spectra at 77 K gave the amount of ferric protein at each stage in the reaction sequence. The PN oxidation step …

Effects Of Open And Closed System Oxidation On Texture And Magnetic Response Of Remelted Basaltic Glass, Katherine Burgess, Reid F. Cooper, Julie A. Bowles, Jeffrey S. Gee, Daniele J. Cherniak

Geosciences Faculty Articles

As part of an experimental and observational study of the magnetic response of submarine basaltic glass (SBG), we have examined, using ion backscattering spectrometry (RBS), transmission and scanning electron microscopy, energy dispersive X-ray spectrometry, and surface X-ray diffraction, the textures wrought by the controlled, open and closed system oxidation of glasses prepared by the controlled environment remelting and quenching of natural SBG. Initial compositions with ~9 wt % FeO* were melted at 1430°C with the oxygen fugacity buffered at fayalite-magnetite-quartz; melts were cooled at a rate of 200°C min⁻¹ near the glass transition (T_g = 680°C). In open …

Ion-Molecule Reactions Of O,S-Dimethyl Methylphosphonothioate: Evidence For Intramolecular Sulfur Oxidation During Vx Perhydrolysis, Jilliarne Williams, Martin Paine, Stephen J. Blanksby, Michael L. Rogers, Andrew M. Mcanoy

Stephen Blanksby

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO- with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic …

Synthesis, Kinetic And Photocatalytic Studies Of Porphyrin-Ruthenium-Oxo Complexes, Yan Huang

Masters Theses & Specialist Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in Nature, namely the cytochrome P450 enzymes. Ruthenium porphyrin complexes have been the center of the research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes. This study focuses on kinetic and photocatalytic studies of oxidation reactions with wellcharacterized high-valent ruthenium-oxo porphyrin complexes.
The trans-dioxoruthenium(VI) porphyrins have been among the best characterized metal-oxo intermediates and their involvement as …

Molecular Characterization Of The Soluble Fraction Of Atmospheric Particulate Matter Obtained By Chemical Oxidation With Nitric Acid, Amanda Susan Priest

Chemistry & Biochemistry Theses & Dissertations

The availability of information regarding the composition of ambient atmospheric particulate matter and the transformations that these compounds may undergo upon atmospheric transit is surprisingly absent. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is used in this study to rapidly evaluate the composition of the water-soluble organic fraction of standard and collected atmospheric particulate matter samples, and the changes that these mixtures undergo upon oxidation with nitric acid. The standard samples include representative particulate matter collected over the course of a year in Washington, D.C. and particulate matter from the exhaust of a diesel-powered engine. The collected sample …

Oxidation Of Dibenzothiophene To Dibenzothiophene Using Metal Nanoparticles Supported On Silica, Karina Castillo

Open Access Theses & Dissertations

Silica and nanoparticles of Pt, Au, and Ag supported on silica were tested for the ability to oxidize dibenzothiophene (DBT) to sulfone. High performance liquid chromatography was used to study the removal of DBT from solution. In addition, X- ray diffraction, infrared spectroscopy and Raman Spectroscopy were used to characterize the product of the oxidation reaction. Further studies involved the use X-ray absorption spectroscopy to characterize the nanoparticle catalysts before and after the oxidation reaction.

To better understand the reaction, silica was synthesized at different pHs using three different acids. The acids used to synthesize the silica were HCl, HNO3, …

Oxidation Of Reduced Sulfur Compounds: A Triple-Oxygen-Isotope Perspective, Issaku E. Kohl

LSU Doctoral Dissertations

The Earth’s geochemical evolution is recorded in the rocks that compose its lithosphere. Specifically, sulfate minerals have been identified as being repositories of information concerning the past hydrosphere, atmosphere and biosphere. This is due to the non-labile nature of SO42- and its ability to store a record of the oxidative reactions and oxygen sources involved in its formation. Microbial dissimilatory sulfate reduction (MDSR) and sulfide oxidation cause oxygen from H2O and O2 to be trapped to varying degrees in ambient, dissolved SO42-. In order to better interpret the H2O and O2 signals in SO42-, we must deepen our understanding of …

Kinetic Studies Of The Sulfoxidation Of Aryl Methyl Sulfides By Trans-Dioxoruthenium(Vi) Porphyrin Complexes, Chris Abebrese

Masters Theses & Specialist Projects

The development of an efficient, catalytically active, biomimetic model for cytochrome P-450 enzymes has been an area of intense research activity. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes, the epoxidation of alkenes and aromatic rings, and the N-oxidation of amines, among others. In this project, the kinetics of two-electron sulfoxidation of para-substituted phenyl methyl sulfides to the corresponding sulfoxides with well-characterized trans-dioxoruthenium(VI) porphyrin complexes were studied by rapid stopped-flow spectroscopy. The substituent effect in sulfides and in dioxoruthenium(VI) complexes were …

Enhanced [Ru(Bpy)_3]~(2+)-Mediated Oxidation Of Guanine Prompted By Dhp, Bao-Lian Zhang, Wei Hong, Bao-Yi Lu, Hong Li

Journal of Electrochemistry

The effects of dihexadecyl phosphate(DHP) and multi-walled carbon nanotubes(MWNTs) on the oxidation of guanine mediated by[Ru(bpy)3]2+ on the ITO electrode have been investigated by cyclic voltammetry and differential pulse voltammetry.The results showed that [Ru(bpy)3]2+ can mediate the oxidation.In the range from 0.01 to 0.15 mmol·L-1,peak currents for guanine oxidation mediated by [Ru(bpy)3]2+ increased with the rise of DHP concentrations.On the contrary,cationic surfactant HTAC has the ability to weaken the mediated oxidation of guanine.In addition,the oxidative mechanism of guanine mediated by [Ru(bpy)3]2+ with the participation of DHP is discussed.

New Generation Of Catalytic Technologies For Environmental Protection On The Base Of Fiber-Glass Catalysts, Bair S. Balzhinimaev, Andrey N. Zagoruiko

Andrey N Zagoruiko

Novel glass-fiber based catalysts containing extra-low amounts of noble metals (0.01-0.02% mass of Pt or Pd) demonstrate unique performance in many catalytic reactions, resulted from the ability of the glass fibers to stabilize the transient metals in the glass bulk in a highly-dispersed form. Moreover, specific heat/mass transfer properties, original geometry, high flexibility and high mechanical strength of such catalysts give the way to develop really new catalytic processes and novel reactor designs. The paper is dedicated to the successful research and development (from fundamental research issues to pilot and semi-industrial tests) of different catalytic oxidation processes based on application …

Martian Life Detection With Amino Acid Enantiomers, Ali Jamil, Gaosen Zhang, Henry J. Sun

Undergraduate Research Opportunities Program (UROP)

The Viking mission showed that Martian soil can degrade a heterotrophic medium to carbon dioxide as if live microorganisms were present. The result is considered inconclusive, however, because abiotic oxidants, such as superoxides, may also exist on Mars and would explain the Viking result. One way to resolve this ambiguity is to repeat the Viking experiment with a isomerically pure medium. The consumption of one isomer, either D or L, would indicate biological activity. Indiscriminate destruction of both isomers would indicate abiotic redox processes. This idea was validated for glucose by REU research last summer (Sun et al. 2009). The …

Researching Nitrite Oxidation At High Temperatures, Dolores A. Huang, Jeremy A. Dodsworth, Brian P. Hedlund

Undergraduate Research Opportunities Program (UROP)

15N-nitrate (NO3 -) pool dilution experiments show that ammonia (NH3) is oxidized to nitrate in geothermal springs up to at least 85C; however, nitrite (NO2 -)- oxidizing microorganisms are only known to grow up to 66°C. We hypothesize that thermophilic microorganisms oxidize nitrite to nitrate at high temperatures. Alternatively, it is possible that nitrite is oxidized abiotically. We propose to test these hypotheses by setting up microbial enrichments designed to grow thermophilic nitrite oxidizing bacteria by varying incubation temperature (50, 65, 80°C), oxygen concentration (20% and 5%), and cultivation media. A negative control consisting of filtered spring water (0.1 μm) …

The Mechanism Of Electrochemical Testing Method Under Synergistic Effect Of Nacl And Water Vapor At 600℃, Li Liu, Ying Li, Fu-Hui Wang

Journal of Electrochemistry

The existence of electrochemical reaction during the corrosion process of pure Fe under a deposit of solid NaCl in water vapor at above 400 ℃ had been detected by measuring the corrosion current using double-layer electrode.In EIS measurement,only one capacitive loop was obtained on the pure metals and this gave the information of oxide layer on them.The electrochemical impedance spectroscopy(EIS) and scanning-electron microscopy(SEM) results testified that there is a good relationship between the resistance of oxide layer Rox and the corresion reaction rate for pure metals with different oxidation times.The electrochemical technique is an effective method for studying corrosion performance …

A Theoretical Study Of Methanol Oxidation Mechanisms By Methanol Dehydrogenase Enzymes For Fuel Cell Applications, Nagesh B. Idupulapati

Doctoral Dissertations

Enzymes are considered for electrochemical generation of power in fuel cells. Methanol dehydrogenase (MDH) is one such enzyme, which has been used as an anodic catalyst for a methanol-fed biofuel cell producing enough power for small electronic device applications. In practice, however, there are power output limitations associated with this MDH fuel cell, which may potentially be eliminated or reduced if the reactivity of this enzyme during the oxidation of methanol at the molecular level is clearly understood.

Two mechanisms for the methanol oxidation process by MDH have been proposed in the literature, Addition-Elimination (A-E) and Hydride Transfer (H-T), but …

Ion-Molecule Reactions Of O,S-Dimethyl Methylphosphonothioate: Evidence For Intramolecular Sulfur Oxidation During Vx Perhydrolysis, Jilliarne Williams, Martin Paine, Stephen J. Blanksby, Michael L. Rogers, Andrew M. Mcanoy

Faculty of Science - Papers (Archive)

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO- with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic …

Sulphur-Tagged Metal-Organic Frameworks And Their Post-Synthetic Oxidation, Andrew D. Burrows, Christopher G. Frost, Mary F. Mahon, Christopher Richardson

Faculty of Science - Papers (Archive)

No abstract provided.

Kinetics Of Co Oxidation Over Pt-Ceo_X Supported On Air-Oxidized Activated Carbon, Berri̇n Gülyüz, Şeyma Özkara Aydinoğlu, Ahmet Erhan Aksoylu, Zeynep İlsen Önsan

Turkish Journal of Chemistry

Kinetics of low-temperature CO oxidation was studied under atmospheric pressure at 383 K in the initial rates region over 1wt%Pt-1wt%CeO_x supported on air-oxidized activated carbon (AC2). Feed concentrations of 1-5 mol% CO and 1-2.5 mol% O_2 with balance He were used for CO oxidation in the absence of hydrogen. A simple power-function rate expression was obtained with reaction orders of -0.24 in CO and 0.98 in O_2, and a plausible LHHW expression compatible with mechanisms reported in the literature was proposed. Feed concentrations of 5 mol% CO and 2.5 mol% O_2 were used for investigating the effect of the presence …

A Bio-Inspired Molecular Water Oxidation Catalyst For Renewable Hydrogen Generation: An Examination Of Salt Effects, Robin Brimblecombe, Miriam Rotstein, Annette Koo, G Charles Dismukes, Gerhard F. Swiegers, Leone Spiccia

Faculty of Science - Papers (Archive)

Most transport fuels are derived from fossil fuels, generate greenhouse gases, and consume significant amounts of water in the extraction, purification, and/or burning processes. The generation of hydrogen using solar energy to split water, ideally from abundant water sources such as sea water or other non-potable sources, could potentially provide an unlimited, clean fuel for the future. Solar, electrochemical water splitting typically combines a photoanode at which water oxidation occurs, with a cathode for proton reduction to hydrogen. In recent work, we have found that a bioinspired tetra-manganese cluster catalyzes water oxidation at relatively low overpotentials (0.38 V) when doped …

Molecular Water Oxidation Catalysts For Photoelectrochemical Cells, Robin Brimblecombe, Charles Dismukes, Gerhard F. Swiegers, Leone Spiccia

Faculty of Science - Papers (Archive)

Photoelectrochemical cells that efficiently split water into oxygen and hydrogen, "the fuel of the future", need to combine robust water oxidation catalysts at the anode (2H(2)O -> O-2 + 4H(+) + 4e(-)) with hydrogen reduction catalysts at the cathode (2H(+) + 2e(-) -> H-2). Both sets of catalysts will, ideally, operate at low overpotentials and employ light-driven or light-assisted processes. In this Perspective article, we focus on significant efforts to develop solid state materials and molecular coordination complexes as catalyst for water oxidation. We briefly review the field with emphasis on the various molecular catalysts that have been developed and …

A Bio-Inspired Molecular Catalyst That Selectively Catalyzes Water Oxidation In Seawater, Without Significant Chlorine Formation, Robin Brimblecombe, G. Charles Dismukes, Gerhard F. Swiegers, Leone Spiccia

Faculty of Science - Papers (Archive)

Most transport fuels are derived from fossil fuels, generate greenhouse gases, and consume significant amounts of water in the extraction, purification, and/or burning processes. The generation of hydrogen using solar energy to split water, ideally from sea water or other non-potable sources, could potentially provide an unlimited, clean fuel for the future. Solar, electrochemical water splitting typically combines a photoanode at which water oxidation occurs, with a cathode for proton reduction to hydrogen. In recent work we have found that a bioinspired tetra-manganese cluster catalyzes water oxidation at relatively low overpotentials (0.38 V) when doped into a Nafion proton conduction …

A Lab To Stemulate Undergraduate Students Into Science, Technology, Engineering And Mathematics Majors, Nicole Lynn Speelman

Browse all Theses and Dissertations

The central focus is the development and implementation of a research/lab module for first year chemistry courses. Electrochemical techniques are utilized to study oxidation and reduction reactions of neurotransmitters with a poly(2,2'-Bithiophene) modified electrode. The goal is to excite students about chemistry and encourage them to continue studies in Science, Technology, Engineering, and Mathematics (STEM) during their undergraduate education. The lab module was created for Project REEL (Research Experiences to Enhance Learning) and will be illustrated with results typically obtained by students. The experiment is inquiry-based, which includes challenging questions students have to do collaboration and research to answer, as …

Study Of Corrosion Of Materials In The Sulfur-Iodine Hydrogen Production Cycle, Thao Trung Ho

UNLV Theses, Dissertations, Professional Papers, and Capstones

Hydrogen is of great interest since the availability of traditional fossil fuels is in decline. Strictly speaking, hydrogen is not a primary source of energy but is an energy carrier, since energy typically must be used from another source (electricity, natural gas, coal, etc.) to produce it. Of hydrogen production techniques, the Sulfur-Iodine thermochemical water splitting process (S-I cycle), which was proposed by General Atomics (GA), is promising with its simplicity and high efficiency. Most of the chemicals are recycled except water. However, the S-I cycle operates in a harsh, corrosive environment in the presence of a mixture of iodine …

Comparison Of The Electrochemical Properties Of Ethanol In Perchloric Acid And Ionic Liquids, Sandra Felix-Balderrama

Browse all Theses and Dissertations

1-Ethyl-3-Methylimidazolium Tetrafluroborate (EMImBF₄) and 1-Ethyl-3-Methylimidazlium Bis(trifluoromethanesulfonyl)imide (EMImTFSI) ionic liquids were synthesized and characterized in order to study the electrochemical oxidation of ethanol in these ionic liquids on a platinum surface electrode.

It was found that pure EMImBF₄ exhibits an electrochemical window of 4.4 V,while EMImTFSI exhibits an electrochemical window of 5.0 V.

Electrochemical study of ethanol in perchloric acid showed that the oxidation of ethanol strongly depends on the concentration of ethanol and on the temperature of the solution. The poisoning of the platinum electrode only depends on the concentration of ethanol. At a low concentration of …

Synthesis And First X-Ray Structures Of Cobalt(Ii) And Cobalt(Iii) Complexes Bearing 2,4-Dioxo-Alkanoic Acid Dialkylamide Ligands, Brian Pagenkopf, Jian Wang, Nicholas A. Morra, Hongda Zhao, Vincent Lynch, Robert Mcdonald, John F. Reichwein

Chemistry Publications

The aerobic oxidation of 5-hydroxy pentenes to trans-tetrahydrofurans (THFs), the Mukaiyama oxidation, has in recent years emerged as a powerful tool in synthetic chemistry. In this report we describe the first crystal structures of 2,4-dioxo-alkanoic acid dialkylamide complexes for both Co(II) and Co(III) salts. The Co(II) structures show an unprecedented arrangement of atoms, with a central Co(II)(H₂O)₆ flanked by two Co(II) atoms each coordinated with three anionic chelating ligands. The dimeric Co(III) structures show two anionic chelating ligands and bridging hydroxyl groups.

Peroxynitrite Chemistry: Formation, Decomposition And Possible Deactivation Mechanisms By Thiols, Olufunke Modupe Olagunju

Dissertations and Theses

Kinetics of formation and decomposition of peroxynitrite was studied in acidic and buffer solutions. Peroxynitrous acid was formed in acidic media by the reaction of H₂O₂ with HNO^₂ and NO +. Bimolecular rate constant for reaction of H²O² with HNO^₂ at 25°C was determined to be 3.7 × 10 3 M-¹ s-¹. Peroxynitrous acid formed is highly unstable with half life of approximately 1 second. Decomposition of peroxynitrite is highly pH-dependent. In acidic media, peroxynitrous acid decomposes to nitrate while at neutral to slightly basic media, products of decomposition …

Mass Spectrometry-Based High Throughput Approach For Identification Of Molecular Modification Of Oxidative Process In Respiratory Diseases, Wei Song

ETD Archive

Eosinophil peroxidase (EPO) and myeloperoxidase (MPO) have been implicated in generating reactive species and promoting oxidative modifications in numerous diseases. The detection and identification of potential pathways has been proven extremely challenge due to evanescence nature of these reactive species. An alternative approach to study the involvement of oxidative modification is to detect and quantify the stable molecular fingerprints, like oxidized tyrosine species, in biological matrices. Previously reported analytical methods for quantifying oxidized amino acids have typically been limited by: low sensitivity, specificity and the failure of detection potential oxidation products generated during sample handling. Using GC/MS in combination with …

Reactivity Of (2-Alkenyl-3-Pentene-1,5-Diyl)Iron Complexes: Preparation Of Functionalized Vinylcyclopropanes And Cycloheptadienes, Rajesh K. Pandey, Lizhu Wang, Nathaniel J Wallock, Sergey Lindeman, William Donaldson

Chemistry Faculty Research and Publications

The reactivity of (2-alkenyl-3-pentene-1,5-diyl)iron complexes toward olefin metathesis, cycloaddition, and mild oxidations (MnO₂ or mCPBA) was examined. Cycloaddition reactions were observed to occur with modest diastereoselectivity (33−63% de). Decomplexation of the (3-pentenediyl) ligand may be accomplished by oxidation with either CAN or alkaline hydrogen peroxide to afford vinylcyclopropanecarboxylates or divinylcyclopropanecarboxylates. Reduction of the latter, followed by Cope rearrangement generates cycloheptadienylmethanols. These studies demonstrate that (2-alkenyl-3-pentene-1,5-diyl)iron complexes can serve as organometallic scaffolds for the preparation of a wide variety of structural motifs containing up to 5 contiguous stereocenters.

Physical And Oxidative Removal Of Organics During Fenton Treatment Of Mature Municipal Landfill Leachate, Yang Deng

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Municipal landfill leachate, especially mature leachate, may disrupt the performance of moderately-sized municipal activated sludge wastewater treatment plants, and likewise tend to be recalcitrant to biological pretreatment. Recently, Fenton methods have been investigated for chemical treatment or pre-treatment of mature leachate. In this paper, the results of laboratory tests to determine the roles of oxidation and coagulation in reducing the organic content of mature leachate during Fenton treatment are presented. The efficiencies of chemical oxygen demand (COD) oxidation and coagulation were tested, and the ratio of COD removal by oxidation to that by coagulation was assessed, under various operating conditions. …

Kinetics And Mechanism Of Oxygen Delignification, Yun Ji

Electronic Theses and Dissertations

Considerable research has been conducted into the kinetics and selectivity of the oxygen delignification process to overcome limitation in its use. However most studies were performed in a batch reactor whereby the hydroxide and dissolved oxygen concentrations are changing during the reaction time in an effort to simulate tower performance in pulp mills. This makes it difficult to determine the reaction order of the different reactants in the rate expressions. Also the lignin content and cellulose degradation of the pulp are only established at the end of the experiment when the sample is removed from the batch reactor. To overcome …