Physical Chemistry Commons^™

Development On Hydriding/Dehydriding Kinetics Of Mg Nano-Materials For Hydrogen Storage, Wei Mo, Hong-Liang Sun, Hai-Chang Zhang, Hua-Bin Yang, Zuo-Xiang Zhou

Journal of Electrochemistry

The development of Mg nano-materials for hydrogen storage in the recent decade has been reviewed in this paper.It was shown the Mg nano-powders prepared by high-energy ball milling showed promising hydriding and dehydriding performance with the transition metal oxides and other types of hydrogen storage alloys(ABx)as the catalysts.

Special Photoelectrochemical Response Of Nano-Crystalline Tio2 Electrode, Bi-Bo Lan, Jian-Zhang Zhou, Yan-Yan Xi, Hong-Xiang Chen, Guang-Hua Yao, Zhong-Hua Lin

Journal of Electrochemistry

The nano-crystalline TiO₂ electrodes were prepared by spread method,electrodeposition and sol-gel method.The experimental results show that the nano-crystalline TiO₂ electrodes have special photoelectrochemical response-the photocrrent-potential curves appear peaks.The special photoelectrochemical behaviors of nano-(crystalline) TiO₂  electrodes are ascribed to nano-structure as well as special light induced redox reaction mechanism of nano-crystalline semiconductor electrodes.

Electrocatalytic Oxidation Of Glucose On Nano Pt/C Electrode, Cui-Lian Chen, Xiao-Lan Wei, Pei Kang Shen

Journal of Electrochemistry

Nano Pt/C electrocatalysts were prepared by intermittent microwave heating method.The electrooxidation of glucose on smooth Pt and～Pt/C electrodes has been studied and compared.The results showed that the electrochemical properties on nano Pt/C were improved due to the reduction of the overpotential and the increase in the kinetic rate.The surface area would be significantly increased when the particle size of the catalyst was reduced to nano-scale,resulting in the increase in the activity.The enhancement in the resistance to poisoning could be explained that the oxygen-containing species are easier to react with poisoning species on nano Pt/C and re-active the electrode.

Effects Of Sulfide Ions On The Inhibiting Efficiency Of Eda As A Copper Corrosion Inhibitor In Dilute Hcl Solution, Wen-Juan Qu, Rong-Gui Du, Chang-Jian Lin

Journal of Electrochemistry

The anticorrosion action of EDA on copper in dilute HCl solution and the effect of sulfide ions on the inhibiting efficiency were studied by the Tafel plot method.The corrosion potential of Cu shifted to more positive value and the corrosion current density decreased after the addition of Na₂S to the solution.The results indicated that sulphide ions could increase the inhibiting efficiency of EDA because of the synergistic inhibition effect between EDA and Na₂S,resulting from the adsorption of HS^- on the surface of Cu,facilitated the adsorption of EDA to form a highly protective adsorbed layer which …

The Complex Of Pasp And Tungstate As Inhibitors Of Cupronickel B10′S Corrosion In 3% Nacl Solution, Qun-Jie Xu, Guo-Ding Zhou, Hui-Feng Wang, Wen-Bin Cai

Journal of Electrochemistry

AC impedance and polarization curve measurements were conducted to study the effects of environ-ment-friendly inhibitors PASP,Na₂WO₄ and their complexes on the corrosion of cupronickel B10 in 3%NaCl solution.The results indicate that PASP or Na₂WO₄ alone does inhibit the corrosion of B10,and most effectiveconcentrations are 40 mg/L and 60 mg/L for PASP and Na₂WO₄,respectively.With the total concentration of 40mg/L for the complex inhibitors,the optimum complex ratio of PASP to Na₂WO₄ was 3:1.The complex of such a combination showed a significantly synergetic inhibition effect on the corrosion of B10.

Effect Of Applied Potentials On The Formation Of Self-Assembled Monolayers Of Alkanethiol, Peng Diao, Xiao-Ning Wang, Qun-Chao Hou, Min Guo, Min Xiang, Qi Zhang

Journal of Electrochemistry

The self-assembled monolayers(SAMs)of n-dodecanethiol were prepared on gold substrates under electrochemical conditions using potential step technique.Electrochemical impedance spectroscopy was employed to characterize the SAMs prepared under different substrate potentials.It is found that the potential applied to gold substrate has great influence on the formation of SAMs.Within potential regime-0.8 V to 1.2 V,the increase of applied potential firstly leads to the formation of SAMs with higher packing density,better ordering and less defects.However,after reaching the maximum at 0.4 V,the packing density and the ordering of SAMs begin to deteriorate when the substrate potential is further increased.This work provides solid experimental basis for …

The Effect Of Solution Concentration On Properties Of Ru-Ti-Ir Oxide Anode Coatings, Ke Wang, Yan Han, Jun-Tao Wang, Xiao-Ling Zhang, Yu-Pu Sun

Journal of Electrochemistry

The anode coatings of Ru-Ti-Ir oxide with various solution concentrations were prepared by thermal decomposition.The scanning electron microscope(SEM),energy dispersive X-ray detector(EDX),X-ray diffraction(XRD),accelerated life,polarization curve,cyclic voltammetry and electrochemical impedance.spectroscopy(EIS)tests were carried out.The results showed that there was an obvious effect of solution concentrations on the morphology of the coatings,but little effect on polarization of chlorine evolution.Voltammetric charges and double layer capacitances of anode coatings had a tendency to fall down firstly then increase afterwards as the solution concentration increased.

Electrochemical Reduction Behavior Of Benzaldehyde In The Ionic Liquids, Ning Zhao, Wen-Ju Dong, Qi-Zeng Shi

Journal of Electrochemistry

In this paper, the electrochemical reduction of benzaldehyde was investigated in C₄MIMBF₄, C₆MIMBF₄  and C₈MIMBF₄ ionic liquids by cyclic linear sweep voltammetry,cyclic square-wave voltammetry and chronocoulometry.Benzaldehyde exhibits two successive one-electron irreversible reduction(E_P1=-1.39 V, E_P2=1.69 V) with GC electrode in C₄MIMBF₄, the voltammetric data for benzaldehyde give diffusion coefficients of 1.5*10^-8cm²/s and 1.3*10⁸cm²/s. There is one current peak in C₆MIMBF₄  and C₈MIMBF₄ ionic liquids due to their stronger alkalinity …

Oxygen Enrichment Effect Of Ceo2 To The Cathode Performance Of Proton Exchange Membrane Fuel Cell, Xiang-Li Hou, Hong-Feng Xu, Jian-Hua Dong, Xin Sun

Journal of Electrochemistry

CeO₂ was added to Pt/C catalyst in the cathode of PEMFC by both sol and impregnation methods.The samples were evaluated by TEM,cyclic voltammogram techniques and proton exchange membrane fuel cell performance test.The addition of CeO₂ obviously improved the performance of PEMFC and represented a notable function of oxygen enrichment in the cathode side.But with the addition of CeO₂,part of the catalyst surface was covered and led to the performance drop of the PEMFC.The best content of CeO₂ is 1% when it is added by impregnation method and 3% when it is added by sol method.

Effects Of Srb Biofilm And Corrosion Product Films On Corrosion Behavior Of Carbon Steel, Jing Lin, Yong-Gui Yan, Guang-Zhang Chen, Guang-Zhou Liu, Qing-Fen Li

Journal of Electrochemistry

Electrochemical techniques and surface analysis techniques were applied to study corrosion characteristic of A₃ steel.The effects on corrosion behavior of A₃ steel by sulfate-reducing bacteria(SRB)(biotic media)and corrosion product(abiotic media)were studied.The results showed that biofilms and corrosion product films play different role during different stages.Biofilms were easier flaky with increasing of its thickness.Non-uniform biofilms reduced pitting corrosion of the specimens.The corrosion product films formed under abiotic conditions were more adherently to the surface of the metal than those formed in biogenic media.

In-Situ Detection Of The Effect Of Brighter In The Solution For Nickel And Phosphor Alloy, Jian Zheng, Ning Li, De-Yu Li, Guo-Feng Cui

Journal of Electrochemistry

In this work,the gold-plated mica was used for the substrate,the concentration of 5% of normal plating solution for the nickel was used as the mother solution,and the effect for the deposition by the brighter with ECSTM was in-situ detected.The solution for deposition without the brighter has no brightness,though the values of the roughness and the H_(A-V) have reduced in evidence after deposition;the solution for deposition with the complete brighter although has great brightness,the values of the roughness and the H_(A-V) have increased(after) deposition;the solution for deposition with the half brighter has a moderate effect on the H_(A-V) and (brightness).Hence,the brighter …

25th Ccs Congress (Notes Of The First Circular), Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.

Femtosecond Nuclear Motion Of Hcl Probed By Resonant X-Ray Raman Scattering In The Cl 1s Region, Marc Simon, Loic Journel, Stephane Carniato, Richard Taieb, I. Minkov, Faris Gel'mukhanov, P. Salek, H. Agren, Renaud Guillemin, Wayne C. Stolte, A. C. Hudson, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Femtosecond dynamics are observed by resonant x-ray Raman scattering (RXS) after excitation along the dissociative Cl 1s→6ơ* resonance of gas-phase HCl. The short core-hole lifetime results in a complete breakdown of the common nondispersive behavior of soft-x-ray transitions between parallel potentials. We evidence a general phenomenon of RXS in the hard-x-ray region: a complete quenching of vibrational broadening. This opens up a unique opportunity for superhigh resolution x-ray spectroscopy beyond vibrational and lifetime limitations.

Phase Change Enthalpies And Entropies Of Liquid Crystals, William Acree, James Chickos

Chemistry & Biochemistry Faculty Works

No abstract provided.

Spectroscopic And Thermodynamic Analysis Of Co Rebinding And Photodissociation From Fe (Ii) Lpo, Dustin Michael Lockney

Theses, Dissertations and Capstones

Lactoperoxidase (LPO) is a heme peroxidase found in tears, milk, saliva, and cervical fluids that has bactericidal activity. The bactericidal nature of LPO is due to its ability to oxidize halides and pseudohalides in the presence of H2O2. Full understanding of the catalytic cycle of LPO requires detailed characterization of the mechanism of ligand binding to the enzyme active site. This includes a dynamic and energetic description of conformational changes associated with heme-ligand interactions. Photoacoustic calorimetry is applied to determine the kinetics and magnitude of reaction volume and enthalpy changes for CO dissociation from CO-LPO. Time-resolved absorption spectroscopy was used …

Tunneling Through Weak Interactions:  Comparison Of Through-Space-, H-Bond-, And Through-Bond-Mediated Tunneling, Westin Kurlancheek '03, Robert J. Cave

All HMC Faculty Publications and Research

Results from ab initio electronic structure theory calculations on model systems allow for the detailed comparison of tunneling through covalently bonded contacts, hydrogen bonds, and van der Waals contacts. Considerable geometrical sensitivity as well as an exponential distance dependence of the tunneling is observed for tunneling through various nonbonded contacts. However, the fundamental result from the present study is that at most a modest difference is observed between tunneling mediated by H-bonds and tunneling mediated by van der Waals contacts at typical distances for each type of interaction. These results are considered in relation to the pathways model of Beratan …

Density Functional Studies Of The Structure And Bonding Of Nitrosyl Metalloporphyrin Complexes, John P. Graham, Robbie Davis

Journal of the Arkansas Academy of Science

Density functional calculations were used to determine optimized geometries fornitrosyl-metalloporphyrin complexes of Fe(II),Co(II)and Mn(II).The optimized structures were found to be consistent with experimental data and previous computational predictions using single point density functional calculations. Vibrational frequencies for the N-0stretching mode were also calculated and shown to be consistent with experimental data. The nature of the bonding between the metal center and nitrosyl ligand is discussed in relation to the structure of the M-N-0 linkage. The results were found to be consistent with previous descriptions derived from the Fenske-Hall approximate molecular orbital method. Other interesting structural features in the optimized geometries …

Electron Shock Waves, Mostafa Hemmati, Michael Weller, Taylor Duncan

Journal of the Arkansas Academy of Science

In this paper we describe numerical investigations of breakdown waves concentrating on antiforce waves. We employed one-dimensional electron fluid dynamical equations for a luminous pulse wave propagating into a neutral gas region and subjected to an applied electric field. We assumed that the electrons were the main element in the propagation of the wave and that the electron gas partial pressure provided the driving force. These waves are considered to be shock fronted and are composed of two regions: the thin sheath region behind the shock front and the thicker quasi-neutral region following the sheath region. Our set of equations, …

Development Of A Calix[4]Arene Sensor For Soft Metals Based On Nitrile Functionality, Benjamin Schazmann, Dermot Diamond

Articles

The current work is amongst the first to examine the potential usefulness of the nitrile functional group in potentiometric analytical sensors for soft metals. Nitrile functionality has hereby been incorporated into a calix[4]arene skeleton to give a series of new cation selective hosts. The analytical sensing behaviour of these hosts was examined by Ion Selective Electrode (ISE) based potentiometry. In all cases a preference for soft metals was observed, explained primarily in terms of soft–soft compatibility between calix[4]arene nitrile hosts and metal guests in combination with a classical ‘lock and key’ best fit mechanism. Hosts 2, 3 and 4 showed …

Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin

Chemistry Faculty Publications

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.

Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

We are presenting the preparation, characterization and density functional theory (DFT) studies {B3LYP/6-31+G(d)) of several reiated classes of N-nitrosocarbamates and N-nitrosoureas. The iong-range goal is the design and preparation of compounds, which would undergo photochemical or hydrolytic decomposition, to yield stabilized cyclic cations that can serve as alkylating agents at various nucleophilic centers, including DNA bases.

Perkin Reaction: Rapid And Efficient Process Optimization Through A Microwave/Design Of Experiments Couple, R. David Pace, Laura Mcwilliams

Journal of the Arkansas Academy of Science

Microwave chemistry and a Design of Experiments (DOE) protocol were employed together in order to rapidly and efficiently optimize a modified Perkin reaction. Microwave heating significantly reduced the reaction time, and the DOE provided a statistically significant understanding of underlying process relationships in a minimum number of experimental runs. In all, the reaction time was reduced from1hour to 2 minutes, factors important to yield were identified, an interesting cross-term interaction was discovered, and it was demonstrated that the more economical sodium acetate trihydrate catalyst was a viable alternative to the more costly anhydrous sodium acetate.

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)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of nuclear waste. Iodine-129, a long-lived fission product formed by both commercial nuclear power generation and nuclear weapons production, is released when reprocessing nuclear fuel. Since iodine can be concentrated in the human thyroid, any uncontrolled release of iodine may result in an increased rate of thyroid cancer in the exposed population. For this reason, recovery of iodine is important for implementing any nuclear transmutation strategy.

The stability of the association of iodine with FCC and NOM products are studied. Product …

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 …

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

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborators, electrochemical methods and materials will be 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 is in its third year and has successfully completed Phases 1 and 2.

The following were specific goals for this year:

• To develop a fundamental …

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

Separations Campaign (TRP)

The research objectives of this project are as follows:

• 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 (by the addition of NaNO₃), 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 Pu are evaluated as a function of AHA concentration, metal ion concentration, …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 1st Quarterly Report, 2006, Clemens Heske

Fuels Campaign (TRP)

This project is devoted to an in-depth study of the chemical and electronic impact of metal fission products on the coating layers in TRISO nuclear fuel. In particular, there is a focus on the investigation of Pd, Cs, and Ag and their interface formation with SiC and carbon-based substrates. A variety of surface and near-surface bulk sensitive probes that investigate the occupied and unoccupied electronic states of the substrate and the metal overlayer have been utilized. By a controlled and stepwise deposition of the metal overlayer, it is possible to gain substantial insight into the formation of interfaces and their …

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

Fuels Campaign (TRP)

In this project the chemical bonding and interface formation of metal fission products with the coating materials used in TRISO fuel particles is investigated. The interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon is studied in detail. Using the SiC single crystals and TRISO coating materials as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied with a photoelectron spectroscopy, Auger electron spectroscopy, Inverse Photoemission, X-ray emission spectroscopy, and X-ray absorption spectroscopy. Recent additions to the experimental approach include microscopic techniques (Transmission Electron Microscopy, Scanning Tunneling Microscopy, Atomic Force Microscopy) …

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

Fuels Campaign (TRP)

This project examines inert fuels containing ZrO₂ and MgO as the inert matrix, with the relative amount of MgO varied from 30% to 70% in ZrO₂. Reactor physics calculations are used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf with reactor grade Pu providing the fissile component, with up to 10% of ²³⁹Pu. Ceramics are synthesized and characterized based on the reactor physics results. The solubility of the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, are investigated in a manner to provide thermodynamic data necessary for …

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Thomas Hartmann

Fuels Campaign (TRP)

A wide variety of fuel concepts are considered for advanced reactor technology including metals, metal oxides or metal nitrides as solid solutions or composite materials. Nitride fuels have appropriate properties for advanced fuels including high thermal conductivity, thermal stability, solid-state solubility of actinides, fissile metal density, and suitable neutronic properties. A drawback of nitride fuels involves their synthesis. A key parameter for preparing oxide fuels is the precipitation step in the sol-gel process. For nitride fuels, the current synthetic route is carbothermic reduction from the oxide to the nitride. This process step is based on solid phase reactions and for …