Inorganic Chemistry Commons^™

Dissolution And Electrochemical Recovery Of Uo2, Uo3, And U3o8 In Ionic Liquids, Katherine Iolani Thornock Luebke

UNLV Theses, Dissertations, Professional Papers, and Capstones

This research explores a novel method of increasing the solubility of uranium oxides and other actinide oxides in room temperature ionic liquids (IL) using direct dissolution. The goal is to further expand our knowledge of actinide dissolution and possible nuclear fuel cycle material applications using ionic liquids. The novelty of the methods is focused on the use of oxidizing gas generated using air passed through an ozone generator. While examples of dissolution exist in IL using acidic functionalized ionic liquids, the solubility of all possible oxide species was not demonstrated. Also, the addition of aqueous acid to IL containing actinide …

Crystallographic Exploration Of Fundamental Technetium Species At Nonambient Conditions, Daniel S. Mast

UNLV Theses, Dissertations, Professional Papers, and Capstones

The study of mater under extreme conditions has yielded fascinating insight into the physical and chemical nature of materials that under more modest conditions are considered mundane but have quite unusual properties when under pressure. Examples of this are the lightest of elements found in the first two rows and in the heaviest elements of the lanthanide and actinide series. Pure elements, though the simplest possible chemical systems, have proven to be among the most complex and interesting. Technetium metal is a simple HCP transition metal that, due to its half-filled d-shell, has a rich chemistry and an important place …

Covalency Is Frustrating: La2sn2o7 And The Nature Of Bonding In Pyrochlores Under High Pressure–Temperature Conditions, Christian Childs, Keith V. Lawler, Andrew L. Hector, Sylvain Petitgirard, Ori Noked, Jesse S. Smith, Dominik Daisenberger, Lucile Bezacier, Marek Jura, Chris J. Pickard, Ashkan Salamat

Chemistry and Biochemistry Faculty Research

Natural specimens of the pyrochlore (A2B2O7) compounds have been found to retain foreign actinide impurities within their parent framework, undergoing metamictization to a fully amorphous state. The response to radionuclide decay identifies pyrochlore systems with having high radiation tolerance and tailored use in radioactive waste applications and radionuclide sequestration. High pressure is a powerful pathway to high density states and amorphization with parallels to radiation-induced processes. Here, La2Sn2O7 is evaluated under extreme conditions via the combination of laser heating in a diamond anvil cell with X-ray diffraction and Raman spectroscopy. The measurements are supported by ab initio random structure searching …

The Electrochemical Deposition Of Samarium And Europium Dissolved In Ionic Liquid Solvent, Bea Martinez

UNLV Theses, Dissertations, Professional Papers, and Capstones

Rare-earth elements include the lanthanide series in the periodic table with the addition of scandium and yttrium. China produces approximately 95% of the world’s rare-earths supply and is the largest consumer of the world’s rare earth supply. Domestic production of rare-earth metals is a priority in the US. The domestic demand for rare-earth elements is largely based on their use in electronic devices, catalytic converters, and more importantly defense applications. Therefore, China’s monopoly of rare-earth elements is viewed as a threat to national security. Although capital investments have resulted in an increase in domestic mining and refining of rare-earth materials, …

Synthesis And Electrochemical Characterization Of Pani/Ni And Pani/Au/Ni Composites, Morgan Emily Pacini

UNLV Theses, Dissertations, Professional Papers, and Capstones

The purpose of this research is to show that the electrochemically controlled formation of monometallic and bimetallic catalysts in polyaniline (PANI) can directly influence the efficiency and reproducibility of the catalytic oxidation of methanol. PANI is a conductive polymer that provides a three-dimensional template for the metallic catalysts deposition at nitrogen sites. The controlled deposition of metallic species can be achieved using the normal oxidation/reduction cycles of PANI. The deposition of metallic species relies on anion precursors that are electrostatically bound by the polymer during the oxidation cycle. The precursor is reduced directly at the nitrogen sites in the polymer …

Improved Partial Charge Models In Siliceous Zeolites For The Simulation Of Adsorption And Identification Of Catalytic Sites, Jarod J. Wolffis

UNLV Theses, Dissertations, Professional Papers, and Capstones

Utilization of computational modelling and simulation is expanding as computer processing power has increased and as new tools have been developed. This thesis focuses on efforts to improve the accuracy of simulations in aluminosilicate zeolites, an industrially important category of materials for catalysis and separations. For these sorbents, partial atomic charge represents a critical parameter in molecular mechanics simulations, determining the Coulombic non-bonding interaction. Partial charges may also be used as a measure of important physical parameters of the system such as the degree of covalency or the relative acidity of catalytic sites. We compare several common methods for predicting …

Assessing Different Zeolitic Adsorbents For Their Potential Use In Kr And Xe Separation, Breetha Alagappan

UNLV Theses, Dissertations, Professional Papers, and Capstones

Separation of Kr from Xe is an important problem in spent nuclear fuel fission gas management. The energy intensive and expensive cryogenic distillation method is currently used to separate these gases. In this thesis, we have carried out the research into appropriate sorbents for the separation of Kr and Xe using pressure swing adsorption. We have examined zeolites using gas adsorption studies as they have the potential to be more cost effective than other sorbents. Zeolites are microporous aluminosilicates and have ordered pore structures. The pores in zeolites have extra-framework cations are substantially free to move. The mobility of cations …

Elemental Contributions From Minor And Major Constituents Of Bone On The Separation Of Radiostrontium, Ashlee Rae Dailey

UNLV Theses, Dissertations, Professional Papers, and Capstones

While many methods exist to separate and analyze radionuclides from a variety of environmental matrices, the performance of all of these methods is often limited by other interfering constituents that are consistently found in most of these samples. The presence of such constituents can significantly reduce the recovery of the radioisotopes of interests and lead to incomplete separations.

Strontium has the same oxidation state and a similar atomic radius as calcium and is therefore readily able to substitute for calcium in lattice sites. This similarity in behavior leads to the preferential accumulation of strontium in newly formed bone. The study …

Molecular Forensic Science Analysis Of Nuclear Materials, Dallas Reilly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Concerns over the proliferation and instances of nuclear material in the environment have increased interest in the expansion of nuclear forensics analysis and attribution programs. A new related field, molecular forensic science (MFS) has helped meet this expansion by applying common scientific analyses to nuclear forensics scenarios. In this work, MFS was applied to three scenarios related to nuclear forensics analysis. In the first, uranium dioxide was synthesized and aged at four sets of static environmental conditions and studied for changes in chemical speciation. The second highlighted the importance of bulk versus particle characterizations by analyzing a heterogeneous industrially prepared …

Electrochemistry Of Pani/Metal Composites In Basic Solutions, Tamthinhan Quy

UNLV Theses, Dissertations, Professional Papers, and Capstones

Polyaniline (PANI) has been extensively investigated due to its unique conductivity, which is primarily dependent on the oxidation state of the material and the solution pH. PANI is an insulator when it is oxidized, and the solution pH exceeds four. Numerous attempts to extend PANI's conductivity to neutral and alkaline environments have been unsuccessful. However, our previous study has demonstrated that PANI/Pd composite is conductive and catalytically active in a basic solution, pH ∼ 12. Therefore, the conductivity and the electrochemical properties of PANI composites including PANI/Au, PANI/Pd and PANI/Pt were evaluated in basic solutions. The fundamental studies of PANI/metal …

Extraction Chromatographic Studies Of Rutherfordium And Dubnium Homologs, Megan E. Bennett

UNLV Theses, Dissertations, Professional Papers, and Capstones

Studying the chemistry of transactinide elements does not only allow for these elements to be properly placed in the Periodic Table, but it also permits for the extrapolation of the electronic structure based upon the position of the element in the Periodic Table. In addition it enable for the assessment of the role that relativistic effects play in the chemical behavior of the heaviest elements. An improved understanding of the role of relativistic effects in chemistry of the heaviest elements allows for a better understanding of the fundamentals principles that govern the Periodic Table. In order to investigate the chemistry …

Manganese Oxide Mineral Phases Produced At Room Temperature Under Acidic Conditions Investigated With Xrd, Tem, Sem, Eds, And Bet, Nancy R. Birkner

UNLV Theses, Dissertations, Professional Papers, and Capstones

This thesis concerns characterization of synthetic manganese oxides belonging to mineral phases known as Birnessite and Cryptomelane. Presented here are the results of an experiment designed to examine the influence of sodium, potassium, chloride, and sulfate ions on the reduction of potassium permanganate under acidic conditions at room temperature to produce Birnessite and Cryptomelane. The experiments used KMnO4 as the source of Mn and the resulting Birnessite and Cryptomelane precipitates were washed with 18 Mn/cm NANOpure water at the end of syntheses. Several state-of-the-art solid state techniques were used to characterize the Mn-based oxide mineral phases. Based on the literature …

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 …

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.

Low-Energy Nondipole Effects In Molecular Nitrogen Valence-Shell Photoionization, Oliver Hemmers, Renaud Guillemin, D. Rolles, A. Wolska, Dennis W. Lindle, E. P. Kanter, B. Krassig, S. H. Southworth, R. Wehlitz, B. Zimmermann, V. Mckoy, P. W. Langhoff

Environmental Studies Faculty Publications

Observations are reported for the first time of significant nondipole effects in the photoionization of the outer-valence orbitals of diatomic molecules. Measured nondipole angular-distribution parameters for the 3σ_g, 1π_u, and 2σ_u shells of N₂ exhibit spectral variations with incident photon energies from thresholds to ∼200  eV which are attributed via concomitant calculations to particular final-state symmetry waves arising from (E1)⊗(M1,E2) radiation-matter interactions first-order in photon momentum. Comparisons with previously reported K-edge studies in N₂ verify linear scaling with photon momentum, accounting in part for the significantly enhanced nondipole behavior observed in inner-shell ionization …

Nondipole Effects In The Photoionization Of Xe 4d5/2 And 4d3/2: Evidence For Quadrupole Satellites, Oliver Hemmers, Renaud Guillemin, D. Rolles, A. Wolska, Dennis W. Lindle, K. T. Cheng, W. R. Johnson, H. L. Zhou, S. T. Manson

Environmental Studies Faculty Publications

Measurements of nondipole parameters in spin-orbit-resolved Xe 4d photoionization demonstrate dynamical differences arising from relativistic effects. The experimental data do not agree with relativistic random-phase approximation calculations of single ionization dipole and quadrupole channels. It is suggested that the discrepancy is due to the omission of multiple-excitation quadrupole channels, i.e., quadrupole satellite transitions.

Nearest-Neighbor-Atom Core-Hole Transfer In Isolated Molecules, Renaud Guillemin, Oliver Hemmers, D. Rolles, S. W. Yu, A. Wolska, I. Tran, A. C. Hudson, J. Baker, Dennis W. Lindle

Environmental Studies Faculty Publications

A new phenomenon sensitive only to next-door-neighbor atoms in isolated molecules is demonstrated using angle-resolved photoemission of site-selective core electrons. Evidence for this interatomic core-to-core electron interaction is observable only by measuring nondipolar angular distributions of photoelectrons. In essence, the phenomenon acts as a very fine atomic-scale sensor of nearest-neighbor elemental identity.

Dramatic Nondipole Effects In Low-Energy Photoionization: Experimental And Theoretical Study Of Xe 5s, Oliver Hemmers, Renaud Guillemin, E. P. Kanter, B. Krassig, Dennis W. Lindle, S. H. Southworth, R. Wehlitz, J. Baker, A. C. Hudson, M. Lotrakul, D. Rolles, Wayne C. Stolte, I. Tran, A. Wolska, S. Yu, M. Ya Amusia, K. T. Cheng, L. V. Chernysheva, W. R. Johnson, S. T. Manson

Environmental Studies Faculty Publications

The Xe 5s nondipole photoelectron parameter γ is obtained experimentally and theoretically from threshold to ∼200  eV photon energy. Significant nondipole effects are seen even in the threshold region of this valence shell photoionization. In addition, contrary to previous understanding, clear evidence of interchannel coupling among quadrupole photoionization channels is found.

E1-E2 Interference In The Vuv Photoionization Of He, E. P. Kanter, B. Krassig, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, M. Ya Amusia, L. V. Chernysheva, N. L. S. Martin

Environmental Studies Faculty Publications

We have measured the forward-backward asymmetry of photoelectron angular distributions produced in the vacuum ultraviolet photoionization of helium. This asymmetry, a consequence of the breakdown of the dipole approximation, measures the real part of the ratio of the quadrupole and dipole matrix elements. In the autoionization region, the strong energy dependence of the asymmetry permits an experimental separation of the ratio of those magnitudes from their phase difference. We experimentally determined the Fano parameters of the 2p²¹D₂ quadrupole resonance, and report improved values of the width Γ and line profile parameter q from those previously available …

Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff

Environmental Studies Faculty Publications

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N₂. Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.

Photoexcitation Of A Dipole-Forbidden Resonance In Helium, B. Krassig, E. P. Kanter, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, N. L. S. Martin

Environmental Studies Faculty Publications

We have observed photoexcitation of the dipole-forbidden 1s²¹S₀→2p²¹D₂ resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2ℓ2ℓ^′ autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p¹P₁ and 2p²¹D₂ levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q₂ to be markedly different from theoretical expectations.

Large Nondipole Effects In The Angular Distributions Of K-Shell Photoelectrons From Molecular Nitrogen, Oliver Hemmers, H. Wang, P. Focke, I. A. Sellin, Dennis W. Lindle, J. C. Arce, J. A. Sheehy, P. W. Langhoff

Environmental Studies Faculty Publications

Measurements of angular distributions of K-shell electrons photoejected from molecular nitrogen are reported which reveal large deviations at relatively low photon energies ( ħω≤500eV) from emission patterns anticipated from the dipole approximation to interactions between radiation and matter. A concomitant theoretical analysis incorporating the effects of electromagnetic retardation attributes the observed large nondipole behaviors in N₂ to bond-length-dependent terms in the E1⊗(E2,M1) photoelectron emission amplitudes which are indicative of a potentially universal nondipole behavior in molecular photoionization.

Dynamical Relativistic Effects In Photoionization: Spin-Orbit-Resolved Angular Distributions Of Xenon 4d Photoelectrons Near The Cooper Minimum, H. Wang, G. Snell, Oliver Hemmers, M. M. Sant'anna, I. A. Sellin, N. Berrah, Dennis W. Lindle, P. C. Deshmukh, N. Haque, S. T. Manson

Environmental Studies Faculty Publications

Two decades ago, it was predicted [Y. S. Kim et al., Phys. Rev. Lett. 46, 1326 (1981)] that relativistic effects should alter the dynamics of the photoionization process in the vicinity of Cooper minima. The present experimental and theoretical study of the angular distributions of Xe 4d_3/2 and 4d_5/2 photoelectrons demonstrates this effect for the first time. The results clearly imply that relativistic effects are likely to be important for intermediate- Z atoms at most energies.

Relativistic Effects On Interchannel Coupling In Atomic Photoionization: The Photoelectron Angular Distribution Of Xe, Oliver Hemmers, S. T. Manson, M. M. Sant'anna, P. Focke, H. Wang, I. A. Sellin, Dennis W. Lindle

Environmental Studies Faculty Publications

Measurements of the photoelectron angular-distribution asymmetry parameter β for Xe 5s photoionization have been performed in the 80–200 eV photon-energy region. The results show a substantial deviation from the nonrelativistic value of β=2 and provide a clear signature of significant relativistic effects in interchannel coupling.

Interchannel Coupling In The Photoionization Of The M-Shell Of Kr Well Above Threshold: Experiment And Theory, H. S. Chakraborty, D. L. Hansen, Oliver Hemmers, P. C. Deshmukh, P. Focke, I. A. Sellin, Clemens Heske, Dennis W. Lindle, S. T. Manson

Environmental Studies Faculty Publications

Photoionization cross sections and asymmetry (β) parameters for Kr 3s, 3p, and 3d subshells have been measured and calculated in the 300–1300-eV photon energy range. Good agreement between experiment and theory is found for both cross-section branching ratios and β parameters. Interchannel coupling among the channels arising from 3s, 3p, and 3d subshells is found to be necessary for quantitative accuracy of the theory. This shows that the interchannel coupling phenomenology far above threshold, found previously for outer shells of Ne and Ar, is also operative for inner atomic shells.

Electric-Octupole And Pure-Electric-Quadrupole Effects In Soft X-Ray Photoemission, Andrei Derevianko, Oliver Hemmers, S. Oblad, P. Glans, H. Wang, S. B. Whitfield, R. Wehlitz, I. A. Sellin, W. R. Johnson, Dennis W. Lindle

Environmental Studies Faculty Publications

Second-order [O(k²), k = ω/c] nondipole effects in soft-x-ray photoemission are demonstrated via an experimental and a theoretical study of angular distributions of neon valence photoelectrons in the 100–1200 eV photon-energy range. A newly derived theoretical expression for nondipolar angular distributions characterizes the second-order effects using four new parameters with primary contributions from pure-quadrupole and octupole-dipole interference terms. Independent-particle calculations of these parameters account for a significant portion of the existing discrepancy between experiment and theory for Ne 2p first-order nondipole parameters.

Validity Of The Independent-Particle Approximation In X-Ray Photoemission: The Exception, Not The Rule, D. Hansen, Oliver Hemmers, H. Wang, Dennis W. Lindle, P. Focke, I. A. Sellin, Clemens Heske, H. S. Chakraborty, P. C. Deshmukh, S. T. Manson

Environmental Studies Faculty Publications

A combined experimental and theoretical study of argon valence photoionization illustrates the discovery of the broad lack of validity of the independent-particle approximation (IPA) for x-ray photoemission. In addition to previously known breakdowns of the IPA, which are limited to high photon energies and regions very near threshold, the observed breakdown in photoionization at intermediate energies demonstrates generally that the IPA is valid only in very restricted domains. These restrictions are expected to be relevant throughout the periodic table, with consequences for a wide variety of applications.

Development, Verification And Use Of Methods To Model Chemical And Thermal Processes For Lakes Mead And Powell, John Eric Edinger, Edward M. Buchak, Joseph S. Norton, Bureau Of Reclamation

Publications (WR)

Analysis and development of carbonate-bicarbonate chemical subroutine.

Lake Mead And Lake Powell Salinity Reports, Cathy Lee, Steve Gazafy

Publications (WR)

The enclosed reports were compiled for the Colorado River Water Quality Office based on salinity data for Lake Mead and Lake Powell. According to the regional director of the office, the reports are not considered "polished" documents for public distribution. However, he considers them to be "interesting, rough appraisals of general trends that may be very important In our understanding the hydro-salinity system in the Colorado River."

Water Chemistry Survey Of Boulder Basin, Lake Mead, P. R. Tramutt, Bureau Of Reclamation

Publications (WR)

The survey results indicate that the impoundment of water behind Hoover Dam has not adversely affected the dissolved oxygen (DO) content and that water quality and DO content were uniform regardless of depth. The study made in April-May 1964 will provide water quality data of Lake Mead prior to releases from Lake Powell as a basis for evaluating Lake Powell's effect on water quality and limnology of Lake Mead. The performance of a DO analyzer was tested and found unsatisfactory at depths below 150 ft. Parameters tested by standard chemical analyses of water samples in the Denver Laboratory and by …