Physical Chemistry Commons^™

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

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. During the first two years of this program we have examined the potential of Fullerene Containing Carbon compounds (FCC) developed by KRI, and natural organic matter (NOM) as sorbents for iodine released during the reprocessing of nuclear fuel. This work involved the development of bench-scale testing of the FCC and NOM material in a simulated process off-gas environment.

Research Objectives and Goals

• Develop bench-scale experimental set-up and procedures for simulating PUREX head-end vapor phase; Develop experimental procedures …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report August-September 2004, Spencer M. Steinberg

Separations Campaign (TRP)

During first year of the project we were able to demonstrate iodine sorption by a sphagnum peat and Ca(OH)2 mixture. We decided to explore varying the ratio of Ca(OH)2 to sphagnum on the retention of iodine in both the iodine generator experiments and the fuel rod simulator experiments.

We also constructed a device for simulating the dissolution of fuel rods. Early experiments were impacted by sorption of iodine onto various components of the sorption train. We have eliminated or minimized iodine sorption by the system components. We retested both FCC and the sphagnum using this device. In these experiments a …

Probing Cation Antisite Disorder In Gd2ti2o7 Pyrochlore By Site-Specific Nexafs And Xps, Ponnusamy Nachimuthu, S. Thevuthasan, Mark H. Engelhard, W. J. Weber, D. K. Shuh, N. M. Hamdan, B. S. Mun, E. M. Adams, D. E. Mccready, V. Shutthanandan, Dennis W. Lindle, G. Balakrishnan, R. C. Ewing

Chemistry and Biochemistry Faculty Research

Disorder in Gd₂Ti₂O₇ is investigated by near-edge x-ray-absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS). NEXAFS shows Ti⁴⁺ ions occupy octahedral sites with a tetragonal distortion induced by vacant oxygen sites. O 1s XPS spectra obtained with a charge neutralization system from Gd₂Ti₂O₇(100) and the Gd₂Ti₂O₇ pyrochlore used by Chen et al. [Phys. Rev. Lett. 88, 105901 (2002)], both yielded a single peak, unlike the previous result on the latter that found two peaks. The current results give no evidence for …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report April-June 2004, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Study On Reduction Process Of Electrolyic Manganese Dioxide In Situ By Ultraviolet-Visible Absorption Spectroscopy, Li-Cai Zhu, Zhong-Zhi Yuan, Wei-Shan Li

Journal of Electrochemistry

The concentrationsof soluble Mn(Ⅲ) species, during the reduction ofelectrolytic MnO₂ (EMD) in alkaline solution,have been monitored in situ by UV-visible spectroscopy. The concentration of Mn(Ⅲ) ion in solution changes with discharge time. The first electron discharge process of EMD can be described by three different steps: 1) the reduction of Mn⁴⁺ ions on the surface of EMD particles and the structural defect regions within the EMD, 2) the reduction of Mn⁴⁺ ions in ramsdellite, 3)the reduction of Mn⁴⁺ ions in pyrolusite. During the second electron discharge of EMD, the soluble Mn(Ⅲ) is reduced to Mn(Ⅱ) , …

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

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBP-dodecane-nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30% TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number of different …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. During the first two years of this program the use of Fullerene Containing Carbon (FCC) compounds and Natural Organic Matter (NOM) as potential sorbents for iodine release from the reprocessing of nuclear fuel was examined. This work also included the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC and NOM materials in a simulated process off-gas environment. In the final year of the project we will complete studies of FCC and NOM …

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium.

Data collection and analysis of the Ce³⁺/Ce⁴⁺ redox couple in various supporting electrolytes has continued. All electrolyte systems were investigated at Pt, Au, and Glassy Carbon working electrodes. Analysis of these data was accomplished by performing appropriate background subtractions to reveal net peaks due to Ce redox behavior. Successful identification of the Ce redox couple was achieved with all electrolyte/electrode systems, although a decline in peak resolution was observed with increasing acid concentration. Optimal conditions in this experiment were …

Study On The Electrochemical Impedance Spectroscopy (Eis) Of Al-Bronze At Different Anodic Potentials, Hui Yu, Sa-Ying Dong, Hai-Bo Xu, Ming-Xian Sun

Journal of Electrochemistry

The corrosion dissolution mechanism of Al-bronze has been investigated by Electrochemical Impedance Spectroscopy (EIS) at different anodic potentials. In the active region, the corrosion products are complex compounds of cupreous chloride and the diffusion of CuCl_2^- is the control process of electrochemical reaction. In the transition region, there exhibits two capacitance loops on EIS because CuCl and cupreous oxides films deposit on the electrode surface. In the limiting current region, an inductance loop appears on the EIS because the breakdown of the oxides film leads to serious pit corrosion.

Diffusional Interactions At Dual Disk Microelectrodes: Comparison Of Experiment With Three-Dimensional Random Walk Simulations, John E. Baur, Perry N. Motsegood

Faculty Publications – Chemistry

Three dimensional random walk simulations were used to model the diffusional interactions between coplanar dual disk microelectrodes. Working curves for the dependence of shielding factor, collection efficiency, and amplification factor on the size of the gap between the electrodes were developed. The simulations showed that when the gap size was ≥22 radii, the electrodes could be considered as independent and diffusionally isolated. Empirical equations for determining the gap size from simple shielding and generator-collector experiments were established. The simulation was used to model the collector electrode response for square waves of various frequencies applied to the generator electrode. Simulation results …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Progress Reports 1-1 And 1-2, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

Immobilization of highly radioactive and long-lived isotope of ¹²⁹I, which is a fission product in spent nuclear fuel, requires development of new durable host-materials. Such materials should be characterized with the following principal features:

• High loading capacity to iodine incorporation
• Chemical durability and radiation resistance in order to prevent iodine release over long time (higher than 105 years) storage under conditions of underground repository of radioactive wastes
• Possibility to use iodine-doped material as a target for iodine transmutation.

Iodine is a very volatile chemical element, and even its chemically strong compounds such as AgI and CuI are not stable …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Progress Report 1-3, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

During previous reporting periods we studied properties of iodine doped FCC in comparison with activated carbon. An additional goal was to investigate the possibility to convert iodine doped FCC and activated carbon into ceramic-like material avoiding iodine loss. In order to obtain ceramic based on C_xN_y with fullerene structure we decided to carry out gamma irradiation of iodine doped samples in nitrogen atmosphere (0.7 atm. N₂). It was found that iodine doping and irradiation caused principal changes in composition of FCC such as substituting of fullerene C₆₀ and graphite (both formed by benzene-like carbon …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quaterly Report, Kenneth Czerwinski, Byron Bennett

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBP-dodecane- nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30 % TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number …

Performance Characteristics Of Beamline 6.3.1 From 200 Ev To 2000 Ev At The Advanced Light Source, Ponnusamy Nachimuthu, J. H. Underwood, C. D. Kemp, Eric M. Gullikson, Dennis W. Lindle, David K. Shuh, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

Bend magnet beamline 6.3.1 at the Advanced Light Source operates from 200 eV to 2000 eV, primarily used for x-ray absorption fine structure investigations. The beamline optics consist of a compact, entrance-slitless, Hettrick-Underwood type variable-line-spacing plane-grating monochromator and refocusing mirrors to provide a 25 μm × 500 μm spot at the focal point in the reflectometer end station. Wavelength is scanned by the simple rotation of the grating and illuminates a fixed exit slit. The LabView based beamline control and data acquisition computer code has been implemented to provide a convenient interface to the user. The dedicated end station is …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report September-December 2003, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Determination Of Cystine By Second Order Differential Simple Oscillographic Voltammetry, Fu-Fang Tao, Jian-Bin Zheng

Journal of Electrochemistry

In 0.2 mol/L NaOH, cystine can cause an sensitive incision at -0.5 V (vs.SCE) of cathodic branch of dE/dt-E curve or second order differential simple oscillogram. Based on the oscillographic charateristic, second order differential simple oscillographic voltammetry was applied to the determination of cystine in tablet. The linear range and the detection limit for determination of cystine were 2.5×10^-6～3.5×10^-5 mol/L and 1.0×10^-6 mol/L, respectively. The relative standard deviation for 2.000×10^-5 mol/L cystine was 1.8% (n=5).

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

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. During the first year of this program we have examined the potential of Fullerene Containing Carbon compounds (FCC) developed by KRI, and natural organic matter (NOM) as sorbents for iodine released during the reprocessing of nuclear fuel. This work involved the development of bench-scale testing of the FCC and NOM material in a simulated process off-gas environment.

During the first two quarters of this program we explored various analytical methods available for measurement of iodine, iodide, and iodate. …

Fabrication Of Scanning Micro Cl- Probe And In Situ Imaging Of Cl- At The Interface Of 2024 Al Aloy/Solution, Yu-Hua Lin, Min-Hua Shao, Rong-Gang Hu, Yan Li, Rong-Gui Du, Chang-Jian Lin

Journal of Electrochemistry

Micro combination Ag/AgCl electrode with a tip measuring tens micron in diameter was fabricated. The probe satisfied in situ imaging of Cl^- distribution at metal surface in chloride solution because of its excellent linearity between potential and Cl- concentration, rapid response, good stability and selectivity. With the aid of the home made Micro Electrode Scanning system and scanning Cl^- probe, the effect of the [Cl^-] at 2024-Al/solution interface on localized corrosion process was investigated. It was demonstated directly that Cl^- ion in solution immigrated toward, then adsorbed preferentially and accumulated at the junction between the …

Photofragmentation Dynamics Of Core-Excited Water By Anion-Yield Spectroscopy, Wayne C. Stolte, M. M. Sant'anna, Gunnar Ohrwall, Maria Novella Piancastelli, I. Dominguez-Lopez, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial-anion and- cation yields from H₂O are presented for photon energies near the oxygen K edge. The O^- yield exhibits a feature above threshold attributed to doubly excited states, in contrast to the H^- and cation yields, which are nearly featureless above threshold. Additionally, the lack of the OH^- fragment indicates radiative decay and provides a negligible amount of anion formation.

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report April-June 2003, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Study Of Marine Biocorrosion Using Afm And Molecular Techniques, Herbert H.P.Fang, Lichong Xu, Tong Zhang

Journal of Electrochemistry

Biofilm is ubiquitous in nature.However,corrosin caused by biofilm is still by and large overlooked. This presentation is to demonstrate the applications of several newly developed analytical techniques in chemisrty and microbiology for the study of marine biocorrosion on steel. AFM(atomic force microscopy) was applied to investigate the initial formation mechanism of biofilm and the degree of corrosion of steel in polluted seawater. DNA/RNA-related molecular techniques were used to analyze the microbial composition corrosive biofilm. Results showed that microbial corrosion began within six days, and the corroded volume in the increased as a power function of time with an index 2.83. …

Perfluorinated Sulfonic Acid Lithium Conductivity Humidity Sensor, Hong-Feng Xu, Jing Liu, Li Wan

Journal of Electrochemistry

Treat carbon paper with 3% PTFE solution and dried in 340 ℃ for 40 minutes to enhance its intension, and level off the surface of the carbon paper with a mixture of XC-72 carbon black and PTFE solution. With those treated carbon paper as electrodes, recast Nafion thin film from 5% Nafion solution as humidity sensitive material, a solid polymer electrolyte humidity sensor was prepared on a thin PET film. Take the relative humidity data from several saturated salt solutions, the relationship between conductivity response and relative humidity was studied at different relative humidies .The results showed: when the polymer …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorbtion materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report January-March 2003, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

In Situ Measurements Of Solution Conductivity In Microwave Field, Yong-Qing Su, Chun-Peng Liu

Journal of Electrochemistry

The curves of the conductivity as a function of temperature for 24 kinds of solutions have been in situ measured both in the microwave field and in absence of microwave field. The results indicated that the relationship between the conductivity in microwave field (L_w) and temperature (T) can be expressed by an equation L_w=a′+b′T+c′T² , similar to the one that is valid in absence of the microwave field L_n=a+bT+cT². Conductivity in the absence and presence of microwave field can be linked by the equation lnL_w=A+BL_n+CL²_{n …}

Simulation Of Dynamic Electrochemical Processes, John Cassidy

Articles

This work is designed to introduce electrochemists in a tutorial manner to the basics of modeling of electrochemical systems based primarily on diffusion equations. There is an introduction to analytical and numerical methods with examples taken from typical electrochemical experiments. The Laplace transform is used to derive the Cottrell equation and chronopotentiometry. The response of an electrode to a Gaussian concentration profile is detailed. Laplace’s equation is solved for a simple cell to determine the potential distribution. Discrete methods are employed to calculate the current time behavior following a potential step using the explicit finite difference method. Cyclic voltammetry is …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report September-December 2002, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorbtion materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Fragmentation Processes Following Core Excitation In Acetylene And Ethylene By Partial Ion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Gunnar Ohrwall, S-W Yu, D. Bull, K. Lantz, Alfred S. Schlachter, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial ion yield spectroscopy provides a very detailed picture of fragmentation processes following core excitation in isolated molecules. We exploit this potential in the analysis of decay processes following C1s→π and C1s→Rydberg excitations in ethylene and acetylene. We show that the relative intensity of spectral features related to the excitation to empty molecular orbitals or to Rydberg states is a function of the time variation of the fragmentation process. Namely, we see an intensity increase in the Rydberg states compared to the molecular orbitals as the fragmentation process becomes more extensive, a result attributable to the diffuse nature of the …

Creating Nanocavities Of Tunable Sizes: Hollow Helices, Bing Gong, Huaqiang Zeng, Jin Zhu, Lihua Yuan, Yaohua Han, Shizhi Cheng, Mako Furukawa, Ruben D. Parra, Audrey Y. Kovalevsky, Jeffrey L. Mills, Ewa Skrzypczak-Jankun, Suzana Martinovic, Richard D. Smith, Chong Zheng, Thomas Szyperski, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A general strategy for creating nanocavities with tunable sizes based on the folding of unnatural oligomers is presented. The backbones of these oligomers are rigidified by localized, threecenter intramolecular hydrogen bonds, which lead to well-defined hollow helical conformations. Changing the curvature of the oligomer backbone leads to the adjustment of the interior cavity size. Helices with interior cavities of 10 Å to >30 Å across, the largest thus far formed by the folding of unnatural foldamers, are generated. Cavities of these sizes are usually seen at the tertiary and quaternary structural levels of proteins. The ability to tune molecular dimensions …

Holographic Analysis Of Diffraction Structure Factors, S. Marchesini, N. Mannella, C. S. Fadley, M. A. Van Hove, J. J. Bucher, D. K. Shuh, L. Fabris, M. J. Press, M. W. West, Wayne C. Stolte, Z. Hussain

Chemistry and Biochemistry Faculty Research

We combine the theory of inside-source/inside-detector x-ray fluorescence holography and Kossel lines/x ray standing waves in kinematic approximation to directly obtain the phases of the diffraction structure factors. The influence of Kossel lines and standing waves on holography is also discussed. We obtain partial phase determination from experimental data obtaining the sign of the real part of the structure factor for several reciprocal lattice vectors of a vanadium crystal.