Chemistry Commons^™

Nickelocene Adsorption On Single-Crystal Surfaces, D. L. Pugmire, C. M. Woodbridge, S. Root, Marjorie Langell

Marjorie A. Langell Publications

Nickelocene adsorption onto Ag(100), Ni(100), and NiO(100)/Ni(100) surfaces was studied with x-ray photoelectron spectroscopy and high-resolution electron energy loss spectroscopy at 135 K for monolayer and multilayer coverages of NiCp₂. On the relatively inert Ag(100) surface, nickelocene physisorbs molecularly, with its molecular axis perpendicular to the surface plane. Exposure to the reactive Ni(100) surface results in the decomposition of nickelocene into acetylene and acetylene-like fragments and, when this surface is warmed to 273 K, carbide contamination is observed. There is evidence for double-bond carbon on nickelocene-exposed NiO(100), and vinyl and propenyl fragments are the most likely decomposition products …

Zinc Speculation And Ligand Fluxes In Chesapeake Bay And Elizabeth River Pore Waters, Duncan Glover Byers

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on the vertical concentrations, complexation, speciation, and fluxes of total dissolved zinc and zinc complexing ligands, and zinc speciation in sediment pore waters in the Chesapeake Bay and Elizabeth River, Virginia.

Sediment pore waters were collected in mid and southern Chesapeake Bay in November 1997 and in the Elizabeth River (Pinner's Point) in March, April, and July 1998. Flux experiments were conducted in Elizabeth River sediment cores in April and July 1998. [TDZn] and zinc complexation were determined using differential pulse anodic stripping voltammetry at a hanging mercury drop electrode (DPASV-HMDE).

[TDZn] in the …

Intermediate Species Possessing Bent Dna Are Present Along The Pathway To Formation Of A Final Tbp-Tata Complex, Kay M. Parkhurst, Robyn M. Richards, Michael Brenowitz, Lawrence J. Parkhurst

Lawrence Parkhurst Publications

Binding of the TATA-binding protein (TBP) to the “TATA” sequences present in the promoters of eukaryotic class II genes is the first step in the sequential assembly of transcription pre-initiation complexes. Myriad structural changes, including severe bending of the DNA, accompany TBP-TATA complex formation. A detailed kinetic study has been conducted to elucidate the mechanistic details of TBP binding and DNA bending. The binding of Saccharomyces cerevisiae TBP to the adenovirus major late promoter (AdMLP) was followed in real-time through a range of temperatures and TBP concentrations using fluorescence resonance energy transfer (FRET) and stopped-flow mixing. The results of association …

High-Performance Liquid Chromatographic Separation Of Novel Atropic Α,Α-Disubstituted-Β-Amino Acids, Either On Different Β-Cyclodextrin-Bonded Phases Or As Their 1-Fluoro-2,4-Dinitrophenyl-5-L-Alanine Amide Derivatives, Gabriella Török, Antal Péter, Anne Gaucher, Michel Wakselman, Jean Paul Mazaleyrat, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

The high-performance liquid chromatographic enantioresolution of free and N- and/or C-protected derivatives of (R, S)-2',1':1,2;1',2':3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6 -carboxylic acid (β2-Bin) by direct and indirect methods is reported. The direct separation was carried out on native and different derivatized β -cyclodextrin-bonded phases. The indirect resolution was achieved by applying pre-column derivatization with 1-fluoro-2,4-dinitrophenyl-5-L-alanine amide. The effects of different parameters such as the mobile phase composition and the structures of the compounds on the enantiomeric resolution are discussed.

Methylene-Only Subspectra In 13C Cpmas Using A New Double Quantum Filtering Sequence, Paola Rossi, Raju Subramanian, Gerard S. Harbison

Gerard S. Harbison Publications

Methodology for the assignment of ¹³C CPMAS spectra is still in its infancy. Previous methods of CPMAS spectral editing have utilized differences in the strength of the ¹³C–¹H dipolar interaction or the rate and spin thermodynamics of crosspolarization from protons to carbon, to differentiate between quaternary, tertiary, and methylene carbons. We introduce a different approach, which is based on the fact that double-quantum coherence develops between the protons of a methylene group considerably faster than between most other proton spin pairs in an organic solid. We generate this coherence, filter it, convert it back to single …

Photochemistry And Pinhole Photography: An Interdisciplinary Experiment, Angeliki A. Rigos, Kevin Salemme

Visual & Performing Arts Faculty Publications

This interdisciplinary activity combines chemistry and art through the construction and use of a pinhole camera. We focused on the chemistry of the black and white photographic process as the science component of this activity. The reactions involved are good examples of photochemistry and multiphase chemical reactions, since the light sensitive materials (silver halides) are in the form of a gelatin emulsion of microscopic crystals.

4-Methoxybenzaldehyde Pentafluorophenyl-Methylidenehydrazone, Michael A. Lewis, Charles Leslie Barnes, Bruce A. Hathaway, Rainer Glaser

Chemistry Faculty Research & Creative Works

The crystal structure of the mixed azine C₁₅H₉F₅N₂O is described. The molecule has a high degree of planarity. The two phenyl rings deviate from perfect planarity by less than 2° and the dihedral angles between the ipso-C atoms and the azine bridge also show a minute deviation from planarity of less than 2°. The only dihedral angle that indicates any significant twisting is the dihedral angle about the azine bridge [C1-N1-N2-C8 174.8 (6)°], and even this one is relatively small. Face-to-face arene-arene contacts are the dominant intermolecular interactions. There are double …

Spectroscopic And Kinetic Investigation Of Carbocation Reactivity In Supercritical Carbon Dioxide, Hongshu Jin

Masters Theses

Recent interest in the use of supercritical CO₂ as an environmentally benign reaction medium has included the development of solvent systems that may support polar and ionic chemistry. Carbocations are key intermediate in a variety of synthetically important reactions and characterization of their reactivity is the focus of this work. UV-visible absorption, and steady-state and time-resolved fluorescence spectroscopy has been used to identify and monitor the reaction kinetics of 9- phenylxanthenium carbocation. The arylcarbocation is conveniently generated from 9- phenylxanthen-9-ol in supercritical CO₂ under mildly acidic conditions. Under these conditions 9-phenylxanthenium ion is extremely stable and persists for …

Overview: Nonlinear Dynamics Related To Polymeric Systems, Irving R. Epstein, John A. Pojman

Faculty Publications

No abstract provided.

Period-Doubling Behavior In Frontal Polymerization Of Multifunctional Acrylates, Jonathan Masere, Felicia Stewart, Timothy Meehan, John A. Pojman

Faculty Publications

Front dynamics in the frontal polymerization of two multifunctional acrylate monomers, 1,6-hexanediol diacrylate (HDDA) and trimethylolpropane ethoxylate triacrylate (TMPTA), with Lupersol 231 [1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane] as the initiator, are studied. In most frontal polymerization systems, the dynamics are associated with a planar front propagating through the sample. However, in some cases, front behavior can be altered: the front becomes nonplanar characterized by complex patterns like spin modes and pulsations. To determine how these periodic and aperiodic modes arise, reactant solutions consisting of HDDA diluted with diethyl phthalate (DEP) and TMPTA diluted with dimethyl sulfoxide (DMSO) were used in the study. …

Media Coverage Of Epa's Draft Dioxin Reassessment Report, Sharon M. Friedman, Megan A. Fitzpatrick, Brenda P. Egolf

RISK: Health, Safety & Environment (1990-2002)

Using content analysis, the authors examine the utility of news media in democratic decision making.

Cross-Linking Of Polystyrene By Friedel–Crafts Chemistry To Improve Thermal Stability, Zhitao Wang, David D. Jiang, Michael A. Mckinney, Charles Wilkie

Chemistry Faculty Research and Publications

Copolymers which contain either alcohol or chloride functionalized polystyrene units have been prepared and they participate in Friedel–Crafts chemistry to give cross-linked polymers by the evolution of either hydrogen chloride or water. Proof of cross-linking comes from the identification of the evolved gas, the insolubility of the product, and the thermal resistance of the newly formed polymer. The onset temperature for the degradation is raised by about 100°C relative to that of polystyrene and the fraction which is not volatile at 800°C ranges from 10% for the alcohol copolymers to 20% for the chloride copolymers.

Sustainable Green Manufacturing Of Energetic Materials, Ted Alex Formeza

Theses

Pollution from manufacturing processes of the major energetic materials currently used in the U.S., 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7 tetraazacyclooctane (HMX) was briefly evaluated. It was found that acetic acid was a major pollutant. It appeared that the British Process could be controlled to reduce the polluting effluents better than the Bachmann Process used in the U.S. Most of the effort for producing the next generation of energetic materials is currently centered around the production of 1,3,3-trinitroazetidine (TNAZ). We evaluated five synthetic routes for producing TNAZ. We reduced the number of potential processes by carefully considering possible changes in the schemes that …

Catalyctic Reduction Of Nitric Oxide By Copper Catalyzed Granular Activated Carbon In The Presence Of Oxygen, Shan Xiao

Theses

The catalytic reduction of nitric oxides by solid carbonaceous material consisting primarily of granular activated carbon or (GAC) was studied in a fix bed catalytic reactor in order to develop the technology for removing NO and soot simultaneously from diesel engine exhaust. The catalytic activity and conversion of NO as a function of reaction temperature was evaluated as a function of space velocity. The results show that at lean condition and high gaseous hourly space velocity, vis., 50,000 ~ 80,000, Cu-ZSM-5 does not perform as well with CO and GAC as it does with gaseous hydrocarbons(HC). Plain GAC has low …

The Influential Factors On The Triboelectrochemical Behaviors Of The Passive Alloys, Dong-Bai Sun, Tao Li, Hong-Ying Yu, De-Jun Yang

Journal of Electrochemistry

The tribocorrosion process of Fe-Cr alloys with different Cr content in H₂SO₄ solution was investigated. The influence of applied load, friction velocity, Cr content and concentration of H₂SO₄ in solution on the triboelectrochemical behaviors of the alloys was analyzed. It is shown that applied load and friction velocity have singnificant influence on the tribocurrent density in passive region when friction process occurs on part of the surface of alloy. Increasing the corrosion resistance of alloys or decreasing the aggressive of the solution can reduce the alloy removal velocity.

A Study On The Cathode Protection Potential Against Pitting Corrosion, Chun-Chun Xu, You-Ping Liu, Xiao-Bo Zhang, Xu-Hui Zhao

Journal of Electrochemistry

The methods have been developed to determine the protection potential against pitting corrosion. They are based on the theory that the pitting protection potential (E_p) is actually the transition potential of the direction of current between the occluded cell and the external surface (E_T). E_T lasts from -220 mV to -440 mV (SCE), the lowest of which can be considered as cathode protection potential. The E_p values determined with cyclic potentiodynamic polarization method is included in the E_T with above methods.

The Adsorption Stability Of Interface Corrosion Inhibitor, Fu-Xing Gan, Di-Hua Wang, Jin-Yun Zou

Journal of Electrochemistry

Some new results on the adsorption stability of interface corrosion inhibitor are presented. The concept of adsorption stability and the factors influencing the adsorption stability were discussed. It is shown that the anodic desorption potential can be employed to evaluate the adsorption stability of the inhibitor as an empirical character in some conditions. Electrochemical oscillations phenomena were observed for the first time on a rotating iron electrode in H₂SO₄ solution containing organic inhibitor in the active potential region. These potentiostatic current oscillations can occur under cathodic polarization, as well as under anodic plarization. The oscillation period, amplitude, …

The Influence Of Heat On The Measurement Of Photocurrent At The Anodic Film Of Nickel Electrode, Hang Chen, Zhi-Yu Jiang

Journal of Electrochemistry

The influence of heat on the measurement of photocurrent for nickel electrode in 1 mol/L NaOH solution was investigated by using the photocurrent, photothermal and thermal current methods. It was found that the appearance of photocurrent in potential region of -0.75~0.20 V (vs. Hg/HgO electrode) was due to the p-type semiconductor properties of Ni(OH)₂ film in which is agree with the previous report. In the Ni(OH)₂/NiOOH redox potential region, the increase of temperature at the surface of working electrode during irradiation significantly promoted the electrochemical reaction strongly. The photocurrent observed in potential region 0.20~0.57 V is mainly …

Effects Of Nickel Content And Simulated Heat Affected Zone Of 2205 Duplex Stainless Steel On Pitting Corrosion, Horng-Yih Liou, Ju-Tung Lee, Wen-Ta Tsai, Rong-Iuan Hsieh, Yeongtsuen Pan

Journal of Electrochemistry

The effects of nickel content and Gleeble simulated heat affected zone (HAZ) of 2205 stainless steel on pitting corrosion were investigated in this paper. The results showed that nickel content, ranging from 4.5 wt% to 6.5 wt% in base metal, had only a minor effect on the electrochemical polarization curves, with all E_np's and E_pp's falling in the rang of 1100~1200 mV. Comparing with the base metal, the simulated HAZ microstructure caused an increase in the anodic current density, a distinct decrease in both E_np and E_pp , and a reduction in the passive …

Investigation Of Solution Chemistry In Crevice Of Carbon Steel And Its Anodic Polarization Behavior, Zhuo Chen, Cui-Wei Du, Bei Cao, Yin-Shun Wu, Hai Yang, Zheng-Rong Zhang

Journal of Electrochemistry

A self-made wedge-shaped simulated crevice apparatus was designed to investigate the solution chemistry in crevice of carbon steel and its anodic polarization behavior. For carbon steel with 3.5%(wt) NaCl, the change and the distribution of electrode potential, concentration of Cl^- and pH value of solution in the crevice, and the current density of metal in the crevice were measured respectively under various conditions of anodic polarization. The results showed that without polarization the metal about 2 cm away from the opening of the crevice was attacked preferentially because of its lowest free corrosion potential. The anodic polarization promoted the …

The Behaviors Of Capacity Loss Of Limn2O4 Cathodeat Elevated Temperatures, Xiao-Hong Hu, Han-Xi Yang, Xin-Ping Ai, Sheng-Xian Li, Xin-Lin Hong

Journal of Electrochemistry

The capacity loss of spinel LiMn₂O₄ cathode at elevated temperatures was evaluated by constant current charge-discharge methods and it was found that serious capacity loss and cycleability decrease occured at above 50, especially for the charged cells. The mechanisms for this phenomena were examined by atomic emission and infrared spectrometry of the electrolyte, XRD measurment of the cycled elecrode and microelectrode voltammetry of LiMn₂O₄ at room and elevated temperatures. The results showed that with increasing temperature, Mn and Li ions tended to redistribute partly in the spinel framework due to the disproportion of Mn …

Effect Of Inhibitor On Electrochemical Behavior Of 1cr18 Stainless Steel In Acidic Solution Under Friction, Jin-Ping Xiong

Journal of Electrochemistry

The electrochemical behavior of 1Cr18 stainless steel had been studied using a reciprocating triboelectrochemical equipment under friction in 0.2 mol/L H₂SO₄ solution with and without addition of thiourea, the frictionized surface of 1Cr18 stainless steel had been examined by the SEM, XPS and IR. The results showed that the loss rate of 1Cr18 stainless steel in the solution could be reduced by addition of thiourea. The adsorption of thiourea on the surface of 1Cr18 stainless steel prohibited the oxidization of Cr³⁺ to form Cr(Ⅵ) and formation of passive film consisting of CrO₄^2- or/and Cr(Ⅵ), …

Electrochemical Behavior Of Riboflavin On Glassy Carbon Electrode, Hong Li, Lin-Cai Jiang, Liang-Nian Ji

Journal of Electrochemistry

The electrochemical behavior of riboflavin(RF) on glassy carbon has been investigated by using potential sweep, rotating ring-disc electrode and the measurement of differential capacitance. It is shown that a single well-behaved oxidation-reduction wave corresponding to a reversible two-electrons reaction apears in medium of pH<6, and the adsorption of RFH₂ formed by electro-reduction is weak and hence its solubility is good. In medium of pH>6, there are two separating but overlapping partly oxidation-reduction waves corresponding to two-step one-electron reaction. The adsorptions of RFH and RFH₂ produced by reduction reactions in medium of 6

Study On The Microband Array Electrode-Based Glucose Microsensor, Neng-Qin Jia, Chui-Jue Sun, Lin Gao, Zong-Rang Zhang, Jian-Zhong Zhu, Guo-Xiong Zhang

Journal of Electrochemistry

The microband array electrode (MAE) consisting of 11 Pt microband of 5 m in wide, 2000 m long and 85 m gap was fabricated with a thin film techology. The MAE was characterized by means of cyclic voltammetry in a solution of K₃Fe(CN)₆ and H₂O₂. The results showed higher current density on MAE than on conventional Pt eletrode due to the strong edge effect of the former. A glucose microsensor was constructed with the substrate electrode of microband array. Microband array electrode was modified by Nafion followed by the immobilization of ferrocene onto …

Oxidation And Adsorption Of Deoxyribonucleic Acid At Highly Ordered Pyrolytic Graphite And Glass Carbon Electrode, Jian-Zhang Zhou, Ling-Ling Wu, Jin Luo, Zhong-Hua Lin

Journal of Electrochemistry

It is shown that calf thymus DNA (CT DNA) can be adsorbed at highly ordered pyrolytic graphite (HOPG) electrode and detected by differential pulse voltammetry (DPV) and electrochemical atomic force microscopy (ECAFM). It is found that controlled potential pre-polarization influences largely the adsorption of dsDNA while it has little influence on ssDNA. It is demonstrated that ECAFM is useful to exploit adsorption of DNA at HOPGE. The pattern of adsorption of DNA at HOPG electrode that fits best with the experimental data is proposed. The results aslo shows that UV/Vis reflection spectroscopy, which has not been used in studying electrochemical …

Some Electrochemical Studies On The Bionic Nereistoxin Pesticide-(Ch3)2Nhch(Ch2S2O3)2Na⋅H2O, Chang-Geng Zhang

Journal of Electrochemistry

A study of cyclic voltammetric behavior of the nereistoxin pesticide known as Shachongdan is reported. The effects of scan rate, electrolyte pH, and concentration are discussed.The study shows that this electrode process is an irreversible electrode reaction. The saturate adsorption of dihydronereistoxin on the electrode is also discussed with the saturate adsorption amount of 8.23×10^-10 mol/cm².

Study On The Hydrogen Permeation Through Zinc Electrodeposit, Jiang-Li Cao, Ji-Xun Wu, Yan-Ping Lu, Jie Shi

Journal of Electrochemistry

The electrochemical hydrogen-permeation technique was used to study hydrogen permeation through zinc electrodeposit with bilayer specimens of Fe substrate/zinc electrodeposit. The effect of coating thickness on hydrogen diffusion coefficient and hydrogen steady-state flux was studied. The results showed that hydrogen diffusion coefficient was approximately in the range of 10-11 cm²·s^-1 rank and zinc coating could retard hydrogen permeation. Accordingly, hydrogen steady-state flux and effective diffusion coefficient declined while the coating thickness increased.

In Situ Ftir Spectroelectrochemical Study Of Palladium Hexacyanoferrate Thin Film Deposited On Glassy Carbon Electrode, Ai-Li Bo, Xiang-Qin Lin

Journal of Electrochemistry

The electrochemically deposited Palladium hexacyanoferrate thin film on Glassy Carbon electrode (PdHCF|GC) has been studied in HCl, KCl and NaCl solutions by in-situ external reflection FTIR spectroelectrochemical technique. It is found that the behavior of the electroactive PdHCF film can be understood in terms of two states: Pd₂Fe(II)(CN)₆ formed in the inner layer and (M⁺)2Fe(II)(CN)₆ (M⁺: electrolyte cation) formed in the outer layer. The inner layer is oxidized at E_m=0.87 V in 1 mol/L KCl, while for the outer layer Em=0.77 V(vs. Ag/AgCl). In 1 mol/L NaCl or HCl solutions, …

Xyz-2 High-Performance Electrochemical Suppressor For Ion Chromatography, Wei-Ling Hu, Hua-Shui Lin

Journal of Electrochemistry

The packings of electrochemical suppressor on ion chromatography were studied. It was found that the best packing is the appropriately sulfonate globular resins uniform in size.Using these resins, suppression efficiency was improved to 99.98%,and sensitivity improves about 10%, the reproducibilities of both the height of ion peaks and retention time are very good (c.v<2).

Influence Of Ptfe And Nafion On The Utilization Efficiency Of Pt/C Catalyst In Pemfc, Xiao-Liang Cheng, Bao-Lian Yi, Jing-Xin Zhang, Ming Han, Ya-Guang Qiao

Journal of Electrochemistry

With cycling voltammetry curve(C-V), TEM and SEM photographs, the influence of PTFE and Nafion on the platinum utilization in catalyst layer of PEMFC was investigated. The results show that in gas diffusion electrode, the blocking effect of PTFE in the platinum utilization is not pronunced. In the thin-film catalyst layer, the electron conduct of the catalyst was blocked by the nafion solid and this caused the decrease of platinum utilization. With the increase of the nafion content in the catalyst layer, both platinum utilization and the electron conductivity decreased in the catalyst layer. Because the molecule size of nafion is …