Chemistry Commons^™

Final Report: Nevada System Of Higher Education Quality Assurance Program, Nevada System Of Higher Education

Publications (YM)

The principal purpose of the cooperative agreement was to develop and continue providing the public and the Office of Repository Development (ORD) of the U.S. Department of Energy’s (DOE) Office of Civilian Radioactive Waste Management (OCRWM) with an independently derived, unbiased body of scientific and engineering data concerning the study of Yucca Mountain as a potential high-level radioactive waste repository. Under this agreement, the Nevada System of Higher Education (NSHE), formerly the University and Community CollegeSystem of Nevada (UCCSN), performed scientific and engineering research, and maintained and fostered collaborative working relationships between government and academic researchers. In performing these activities, …

Equation Of State Of Gallium Oxide To 70 Gpa: Comparison Of Quasihydrostatic And Nonhydrostatic Compression, Kristina E. Lipinska-Kalita, Patricia Kalita, Oliver Hemmers, Thomas Hartmann

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond-anvil cell techniques were used to characterize pressure induced structural modifications in gallium oxide. Gallium oxide was studied on compression up to 70 GPa and on the following decompression. The effect of the pressure-transmitting medium on the structural transformations was investigated in two sets of compression and decompression runs, one with nitrogen as a quasihydrostatic pressure-transmitting medium and the other in nonhydrostatic pressure conditions. The x-ray diffraction data showed gradual phase transition from a low-density, monoclinic β-Ga₂O₃ to a high-density, rhombohedral α-Ga₂O₃. With the use of nitrogen as a …

Evaluation Of Cs/Sr Waste Form For Long Term Storage And Disposal, Gary Cerefice

Waste Forms Campaign (TRP)

The goal of this project is to examine the potential long term performance of the proposed aluminosilicate waste/storage form for the isolation and eventual direct disposal of the cesium and strontium separated from recycled nuclear fuel. In the first phase of this work, researchers will investigate the sintering procedure to prepare the drum-like aluminosilicate waste/storage form from the as-received aluminosilicate powder, and then examine the basic physical properties, phase structure and microstructure of the sintered aluminosilicate with /without mixing solution with several ppm Cs/Sr. In the second phase, researchers will evaluate the interaction of the proposed waste form with structural …

Photofragmentation Of Sif4 Upon Si 2p And F 1s Core Excitation: Cation And Anion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Renaud Guillemin, A. Wolska, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We have studied the fragmentation dynamics of core-excited SiF₄ by means of soft-x-ray photoexcitation and partial positive and negative ion yield measurements around the Si L_2,3-shell and F K-shell ionization thresholds. All detectable ionic fragments are reported and we observe significant differences between the various partial ion yields near the Si 2p threshold. The differences are similar to our previous results from CH₃Cl showing more extended fragmentation in correspondence to transitions to Rydberg states. At variance with smaller systems, we observe negative ion production in the shape resonance region. This can be related …

University Of Nevada, Las Vegas Transmutation Research Program Annual Progress Report Academic Year 2007-2008, Anthony Hechanova, Rebecca Paulson

Transmutation Research Program Reports (TRP)

It is my pleasure to present the UNLV Transmutation Research Program’s seventh annual report that highlights the academic year 2007-2008. Supporting this document are the many technical reports and theses that have been generated over the past seven years.

In the seventh year of our program, we continued to see growth in the Radiochemistry Ph.D. program with a total of 20 students in the fourth year of the program (we anticipated twelve in the program proposal). Since our inception, the program has sponsored to their conclusion 48 M.S. and 6 Ph.D. degrees. The program supported 53 graduate students, 11 undergraduates, …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

Observations related to the oxidation of iodide to iodine (I₂) or hypoiodic acid (HIO) by MnO₂ were continued. The formation of triiodide presumable involves the adsorption of iodide onto the MnO₂ surface (perhaps displacing a surface hydroxyl group). The iodide should be subsequently oxidized and released back into solution as IOH or I₂, which rapidly forms I₃ ^-. The kinetic data has been modeled as a first order process. First order rate constants have been obtained for the formation of iodine in the presence of MnO₂. The increase in iodide …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process (FLEX). The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the actinides …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective was to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solutions, and use this data to effectively separate species with very similar chemical properties.

In consultation with a DOE collaborator, electrochemical methods and materials were evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project, in its third year, successfully completed phases 1, 2. Phase 3 was partially completed. The project expanded to include phase 4.

The following were specific goals for 2007-2008:

• To …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU; includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership (GNEP). In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in …

F-Element Electrochemistry In Rtil Solutions: Electrochemical Separation Of Lanthanides And Actinides, David W. Hatchett

Separations Campaign (TRP)

Electrochemical methods can be used to effectively separate actinide and lanthanide species from complex mixtures. This is based on the unique electrochemical properties of each specific target species. In studies it has been found that, with the exception of Ce, aqueous solutions provide unsuitable electrochemical windows to effectively evaluate the thermodynamic properties that are useful for chemical separations. Therefore, a more novel approach was examined which eliminated the aqueous solution with a room temperature ionic liquid (RTIL) solution. RTIL solutions do not suffer from the side reactions that are prominent in aqueous environments. In addition, the potential window is much …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …

Separation Of Technetium From Uranium And Waste Form Synthesis, Kenneth Czerwinski

Waste Forms Campaign (TRP)

In this project, systematic investigations on the Tc-Zr binary metal system will be evaluated for the first time. The synthesis of metallic Tc as well as its alloys with Zr will be evaluated. In order to provide valuable data to AFC R&D, the thermodynamic equilibrium phases, as well as their performance under repository conditions, will be examined.

The research objectives of this project are as follows:

• Evaluate anion exchange methods for achieving the separation of Tc from U.

• Synthesize metallic Tc from the separated product.

• Synthesize and characterize Tc alloys.

• Investigate Tc-corrosion and Tc-leaching of binary …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic and microscopic methods, intermediate chemical phases at the interface, intermixing/diffusion behavior, and the electronic interface structure for different coating materials and metals are examined.

In detail, the project studies the interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon. Using SiC single crystals and highly-ordered pyrolytic carbon (HOPG) as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert fuels containing ZrO₂ and MgO as the inert matrix. Ceramics with this inert matrix, Ce, U and eventually Pu will be synthesized and examined. While the Advanced Fuel Cycle Initiative focus is on inert fuels with Pu as the fissile component, this task will perform initial laboratory experiments with Ce and U. The initial work with Ce will be performed early in the project with results used as a basis for U studies. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf. …

Impact Of The Synthesis Process On Structure Properties For Afci Fuel Candidates, Kenneth Czerwinski

Fuels Campaign (TRP)

The research objectives are:

• To explore a low-temperature fluoride route to synthesize actinide nitrides. • To characterize actinide nitrides structurally and thermally.

• To use high resolution TEM techniques to explore the microstructure of the radioactive samples.

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Tyler A. Sullens

Fuels Campaign (TRP)

One of the original synthetic routes devised for the synthesis of U (III)N involved the entire reaction taking place in liquid ammonia. Several experimental reactions were conducted in an attempt to synthesize the UI₃(NH₃)_x and U(NH₂)₃(NH₃)_x precursors of U(III) N. Each attempt involved cleaning of the uranium metal to remove the oxide coating of the metal reagent with 3 washes of concentrated nitric acid, each followed by a rinse with liquid ammonia. Success of this cleaning procedure was varied, with a majority of cleaned metal oxidizing rapidly once …

Gnep Quarterly Input – Unlv July 1 Through September 30, 2007, Harry Reid Center For Environmental Studies. Nuclear Science And Technology Division

Transmutation Research Program Reports (TRP)

Quarterly report highlighting research projects, activities and objectives of the Transmutation Research Program at the Nuclear Science & Technology Division, Harry Reid Research Center.

The University of Nevada, Las Vegas supports the Global Nuclear Energy Partnership (GNEP) through research and development of technologies for economic and environmentally sound refinement of spent nuclear fuel. The UNLV program has four components: infrastructure, international collaboration, student-based research, and management and program support.

Fundamental Studies Of Hydrogen Storage And Catalysis, Balakrishnan Naduvalath

UNLV Renewable Energy Symposium

This inaugural event is dedicated to showcasing the renewable/sustainable energy projects of UNLV faculty, staff, students, and collaborators, as well as other external projects underway statewide and nationally. The development and utilization of new technologies to protect the environment, achieve energy independence, and strengthen the economy will be explored. Speakers and poster-session presenters will provide further insight to many ongoing projects and innovative research ideas.

Organized by UNLV’s Office of Strategic Energy Programs, the event offers participants the opportunity to learn about energy projects and will encourage networking and collaboration. This symposium is intended for researchers, educators, students, policy makers, …

Afci Quarterly Input – Unlv April 1 Through June 30, 2007, Harry Reid Center For Environmental Studies. Nuclear Science And Technology Division

Transmutation Research Program Reports (TRP)

Quarterly report highlighting research projects, activities and objectives of the Transmutation Research Program at the Nuclear Science & Technology Division, Harry Reid Research Center.

The University of Nevada, Las Vegas supports the AFCI through research and development of technologies for economic and environmentally sound refinement of spent nuclear fuel. The UNLV program has four components: infrastructure, international collaboration, student-based research, and management and program support.

Direct Analysis Of Solid Corrosion Products By Laser Ablation Icp-Ms: Method Development And The Interaction Of Aqueous Uranium, Gadolinium And Neodymium With Iron Shot And Iron (Iii) Oxide, James Cizdziel, Klaus J. Stetzenbach, Amy J. Smiecinski

Publications (YM)

The purpose of this report is to summarize the work and present conclusions of Project Activity Task ORD-RF-03 conducted under cooperative agreement number DE-FC28-04RW12237 between the U.S. Department of Energy and the Nevada System of Higher Education (NSHE). The work was conducted in the Harry Reid Center for Environmental Studies of the University of Nevada Las Vegas from October 1, 2004 to September 30, 2006. The purpose of the study was to develop a method using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the direct analysis of iron corrosion products, to evaluate its capabilities, advantages, and limitations, and …

Groundwater Characterization At Yucca Mountain Task 2: Surface Complexation And Solid Phase Sorption, Kenneth Czerwinski, Anthony Hechanova, Amy J. Smiecinski

Publications (YM)

The purpose and scope of this report is to present an overview of the experiments, methods, results, and conclusions from research performed for the project “Groundwater Characterization at Yucca Mountain Task 2: Surface Complexation and Solid Phase Dissolution”. The impact of surface complexation, alteration phase formation, and solution competition with metal ions on the solubility and speciation of actinide elements (U, Pu, Np) will be examined. In particular the role of iron (as Fe2+ and Fe3+) and silicate (as SO3 2-) concentrations on speciation, solubility, sorption, and secondary phase formation of actinides will be investigated. While a large body of …

High Temperature Heat Exchanger Project: Quarterly Progress Report January 1, 2007 Through March 31, 2007, Anthony Hechanova

Publications (NSTD)

• The variation of sulfur dioxide production (throughput) of the baseline design of the Ceramatec sulfuric acid decomposer with total mass flow rate of reacting flow has been calculated. According to the calculations, the sulfur dioxide production increases as the total mass flow rate of reacting flow increases regardless of the fact that decomposition percentage of sulfuric trioxide decreases. A parametric study of the baseline design of the Ceramatec sulfuric acid decomposer was performed.

• The thermal performance using various channel geometries for the decomposer was studied. The baseline design (straight channels) has 89.5% thermal efficiency while the thermal efficiency …

Afci Quarterly Input – Unlv January 1 Through March 31, 2007, Harry Reid Center For Environmental Studies. Nuclear Science And Technology Division

Transmutation Research Program Reports (TRP)

Quarterly report highlighting research projects, activities and objectives of the Transmutation Research Program at the Nuclear Science & Technology Division, Harry Reid Research Center.

The University of Nevada, Las Vegas supports the AFCI through research and development of technologies for economic and environmentally sound refinement of spent nuclear fuel. The UNLV program has four components: infrastructure, international collaboration, student-based research, and management and program support.

Fragmentation Of Methyl Chloride Studied By Partial Positive And Negative Ion Yield Spectroscopy, D. Ceolin, Maria Novella Piancastelli, Renaud Guillemin, Wayne C. Stolte, S-W Yu, Oliver Hemmers, Dennis W. Lindle

Environmental Studies Faculty Publications

The authors present partial-ion-yield experiments on the methyl chloride molecule excited in the vicinity of the Cl2p and C1s inner shells. A large number of fragments, cations produced by dissociation or recombination processes, as well as anionic species, have been detected. Although the spectra exhibit different intensity distributions depending on the core-excited atom, general observations include strong site-selective fragmentation along the C–Cl bond axis and a strong intensity dependence of transitions involving Rydberg series on fragment size.

Basic Research Needs For Geosciences: Facilitating 21st Century Energy Systems, U.S. Department Of Energy, Office Of Basic Energy Sciences, Donald J. Depaolo, Franklin M. Orr Jr.

Publications (YM)

Executive Summary

Serious challenges must be faced in this century as the world seeks to meet global energy needs and at the same time reduce emissions of greenhouse gases to the atmosphere. Even with a growing energy supply from alternative sources, fossil carbon resources will remain in heavy use and will generate large volumes of carbon dioxide (CO₂). To reduce the atmospheric impact of this fossil energy use, it is necessary to capture and sequester a substantial fraction of the produced CO₂. Subsurface geologic formations offer a potential location for long-term storage of the requisite large …

Chemical Analyses In Support Of Yucca Mountain Studies, Harry Reid Center For Environmental Studies, University Of Nevada, Las Vegas

Publications (YM)

Research Objectives: Provide preparation of injectates, sorption studies and analyses for tracer tests Provide REE, trace metals, majors and field measurement data from wells of the Nye County Early Warning Drilling Program (NCEWDP)and Inyo County Other laboratory needs as they arise

Design And Performance Of A Curved-Crystal X-Ray Emission Spectrometer, A. C. Hudson, Wayne C. Stolte, Dennis W. Lindle, Renaud Guillemin

Chemistry and Biochemistry Faculty Research

A curved-crystal x-ray emission spectrometer has been designed and built to measure 2–5 keV x-ray fluorescence resulting from a core-level excitation of gas phase species. The spectrometer can rotate 180°, allowing detection of emitted x rays with variable polarization angles, and is capable of collecting spectra over a wide energy range (20 eV wide with 0.5 eV resolution at the Cl K edge) simultaneously. In addition, the entire experimental chamber can be rotated about the incident-radiation axis by nearly 360° while maintaining vacuum, permitting measurements of angular distributions of emitted x rays.

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert fuels containing ZrO₂ and MgO as the inert matrix. Ceramics with this inert matrix, Ce, U and eventually Pu will be synthesized and examined. While the Advanced Fuel Cycle Initiative focus is on inert fuels with Pu as the fissile component, this task will perform initial laboratory experiments with Ce and U. The initial work with Ce will be performed early in the project with results used as a basis for U studies. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf. …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process, or FLEX. The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the …