Chemistry Commons^™

A New Cell Structure For Proton Exchange Membrane Fuel Cell, Ming Han, Hong-Feng Xu, Bao-Lian Yi

Journal of Electrochemistry

Separating the functions of current collection and gas flow distribution and then to design two separate elements to achieve the desired performance characteristics, a nonconventional cell structure for proton exchange membrane fuel cells bave been developed. The current collector is achieved using a thin stain steel sheet, the gas flow distribution is achieved using a carbon paper that has the desired chemical durabiliy when in contact with the proton exchange membrane. Combining these two separate elements into a single divice yields a bifunctional device that performs as a bipolar separator plate. The advantages of this alternative appproach to making biplar …

Study Of Electrochemistry Of Tetrasulphonated Phthalocyanine Zinc In Aqueous And Nonaqueous Solvents, Er-Sheng Liu, Yi-Qun Wu, Jian-Hui Yang, Li-Ying Huang, Jun-Dong Wang, Su-Ling Yang, Nai-Sheng Chen, Jin-Ling Huang

Journal of Electrochemistry

The voltammetry of Tetra-sulphonated phthalocyanine Zn(TSPcZn)in DMSO and DMF solution has been examined and compared with those obtained in aqueous solution. The results showed that three pairs of redox peaks were appear in non-aqueous solvents, exhibiting three quasi-reversible phthalocyanine ligand based one-electron transfers, while in aqueous solution did no quasi-reversible behaviour was observed. The photoelectrochemical effect of light on TSPcZn redox reactions were also discussed.

Oxidation Mechanism Of Hypophosphite, Dong-Bai Sun, Ying Jin, Hong-Ying Yu, De-Jun Yang

Journal of Electrochemistry

There exist two oxidation current peaks on the anodic polarization curve between -0.7 V and 0 V (SCE) in Na-hypophosphite solution. Peak Ⅰ (-0.55 V, SCE) , which represents the oxidation process from H₂PO₂^- to H₂PO₃^-, has been studied previously. Peak Ⅱ, which is located at the potential about -0.4 V (SCE), is investigated emphatically in this paper. The results show that, peak Ⅰ and Ⅱ are corresponding to two successive steps in oxidation process of H₂PO₂^-, i.e. peak Ⅱ corresponds to the oxidation process of …

Synthesis And Application Of Polymeric Corrosion Inhibitor For Reinforced Concrete, Wei-Wei Lin, Sheng-Xian Wang, Jian-Qing Zhang, Jun Yuan, Zhen-Guo Ji

Journal of Electrochemistry

A new polymer E-T was synthesized and used as a corrosion inhibitor for reinforced concrete. The inhibitive behavior and mechanism were studied with linear polarization, Tafel polarization, EIS and XPS method in simulated pore solution system with concrete samples. The result showed that the polymer was a mixing type inhibitor. A 1% dosage was sufficient to imhibit the corrosion of steel in simulated pore solution system. The salt endurance was enhanced from 0.02 mol/L to 0.10 mol/L. The result also showed the good synergetic effect of NaNO₂, especially in low NaNO₂ concentration. The EIS showed that E-T …

Study On The Mechanism Of Ni/Zro2 Composite Electrodeposition, Qun-Jia Peng, Dao-Bin Mu, Ju-Sheng Ma, Xiang-Yun Tang

Journal of Electrochemistry

The effects of cathodic current density and amount of particle dispersion in solution on the codeposition of Ni/ZrO₂ composite in Watts bath were studied, and the machanism of the composite electrodeposition was investigated. The study shows that the composite electrodeposition is controlled by the transfer of particles to the cathode when the dispersion amount is small, causing the decrease of the codeposition with the increase of current density. With large amount dispersion, the composite electrodeposition is first controlled by the strong adsorption of particles on the cathode at low current density, resulting in the increase of the codeposition with …

Electrodeposition Of Neodymium-Iron Group Alloy Films In (P-Ch3C6H4So3)3Nd System, Peng Liu, Ye-Xiang Tong, Qi-Qin Yang, Yan-Sheng Yang

Journal of Electrochemistry

Neodymium p-toluenesulfonate was prepared and applied to the electrodepositon of neodymium-iron group alloy films. This salt has high solubility in DMF and can be dehydrated easily. Cyclic voltammograms of Pt electrode in (p-CH₃C₆H₄SO₃) 3Nd + MCl₂(M=Fe,Co,Ni) + DMF indicated that the neodymiun-iron group alloys can be elcetrodeposited from this medium, the Nd-Fe, Nd-Co and Nd-Ni films were obtained by electrolysis at constant potential. The Nd-Fe, Nd-Co and Nd-Ni films are amorphous in which the rare earth contents are in the range of 15 at%～60 at% as analyzed by XRD and …

Study On Steel Corrosion In Simulated Biofilm Environment In Seawater, Qing-Fei Wang, Jing Sui, Run-Xi Su, De-Ying Kong, Shi-Zhe Song

Journal of Electrochemistry

Biofilm is one of the main factors that influence metal corrosion in seawater environment. According to the structure and property of biofilm, a natural biopolymeric gel, calcium alginate(an extracellular biopolymer containing carboxylate functional groups) can deposite on metal surfaces to form films. Corrosion behavior of alloyed steel E2, 10CrMoAl and 18-8 stainless steel were studied in simulated biofilm environment by various electrochemical methods ,including measurements of the corrosion potential, polarization curves,galvanic current and electrochemical impedance. The results show that such an approach is informative to reveal “how” and “to what extent” biofilm can influence the metal corrosion process.

Macrocyclic Antibiotics As Separation Agents, Daniel W. Amstrong

Chemistry Faculty Research & Creative Works

Macrocyclic antibiotics having ring structures with at least 10 members act as separation agents in crystallization, precipitation, filtration, electrophoresis and chromatography. The macrocyclic antibiotics include ansamacrolides, macrolides, marocyclic peptides, polyenes and derivatives thereof. The process has been found to be especially advantageous for separation of optical isomers by electrophoresis and chromatography.

Thermodynamic Expansion Of Nucleation Free-Energy Barrier And Size Of Critical Nucleus Near The Vapor-Liquid Coexistence, Kenichiro Koga, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Nucleation free-energy barrier height and size of the critical nucleus are expanded in powers of the chemical potential difference between the supersaturated vapor (or expanded liquid) in the metastable state and the saturated vapor-liquid system in the stable equilibrium state at the same temperature. The coefficients in the expansions are expressed in terms of the thermodynamic properties at the stable equilibrium state. Comparisons with the results obtained from the density-functional calculation for nucleation of the Lennard–Jones fluid show that systematic improvement in predicting properties of the critical nucleus, either liquid droplet or vapor cavity, is achieved by adding the higher …

[2,3:5,6]Dibenzo[2.2.2]Octa-2,5,7-Triene (C2/C) And [2,3:5,6]Dibenzo[2.2.2]Octa-2,5-Diene, Lary Burrows, John M. Masnovi, Ronald J. Baker

Chemistry Faculty Publications

Two barrelene homologs are reported. Strain in the bicyclic framework of [2,3:5,6]dibenzo[2.2.2]octa-2,5,7- triene, (I) (C16H12), which is manifest in the deviations from ideality of the bond angles in the central bicyclic ringoSyStem and compression of the double bond [1.312 (3)A], is reduced in the more saturated derivative, [2,3:5,6]dibenzo[2.2.2]octa-2,5-diene, (II) (CI6H14), with the corresponding single bond being 1.5380 (19)A. The formation of isomorphs of (I) in both chiral (C2) and achiral (C2/c) space groups has implications for asymmetric syntheses involving solid (I) which rely on a non-centrosymmetric space group.

Valence-Band Electronic Structure Of Co3O4 Epitaxy On Coo(100), Marjorie Langell, M.D. Anderson, G.A. Carson, L. Peng, S. Smith

Marjorie A. Langell Publications

Valence-band photoemission studies have been performed on a CoO(100) single crystal as it is slowly oxidized under 1×10^-4 Torr O₂ at 623 K, eventually forming a Co₃O₄ epitaxial film. The most significant changes occur in 3d-related features, with the peak located at the top of the valence band sharpening and shifting to lower binding energies as the spinel oxide forms. Constant initial-state measurements indicate that Co₃O₄ contains admixture from neighboring O 2p in its 3d band, as observed for CoO and other monoxide charge-transfer insulators. Unlike the rocksalt …

Effect Of Uniform Electric Field On Homogeneous Vapor–Liquid Nucleation And Phase Equilibria. Ii. Extended Simple Point Charge Model Water, G.T. Gao, K.J. Oh, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The effects of a uniform electric field on homogeneous vapor–liquid nucleation of the extended simple point charge (SPC/E) model water have been simulated. A grand canonical Monte Carlo simulation approach [I. Kusaka et al., J. Chem. Phys. 108, 3416 (1998)], which directly gives the equilibrium distribution of physical clusters, is employed to calculate the formation free energy of the SPC/E water cluster. The results show that the formation free energy is lowered in a uniform field if the chemical potential of the supersaturated vapor is fixed; in this case, the field enhances the rate of nucleation. However, if the vapor …

Langmuir Monolayers As Disordered Solids: Strain-Tilt-Backbone Coupling And Natural Order Parameters For The Swiveling Transitions, Tadeusz Luty, David R. Swanson, Craig J. Eckhardt

Craig J. Eckhardt Publications

Multistability of Langmuir monolayers, in particular those composed of fatty acids, is reflected by a very rich and complicated phase diagram. We argue that strain-tilt-backbone coupling determines the behavior described by that diagram. Following the solid state approach, we show that a natural order parameter set is defined by thermal averages of spherical harmonics and strain tensor components. In addition, we show that the backbone order parameter can be conveniently represented by an elastic dipole tensor. Treating Langmuir monolayers as disordered solids, we have derived an orientational entropy contribution to the free energy. The swiveling transition between L₂ ( …

Role Of Zeta Potential In Micro-Carrier Process, Pallavi Mehta

Theses

The micro-carrier process recently developed at NJIT is a new high rate settling technology for water and wastewater treatment. This process utilizes the micro-cater as a flocculating enhancement agent to achieve rapid removal of colloidal particles. This thesis consist of two parts, namely, 1) A review of the flocculation process utilized in water and wastewater treatment, and 2) An experimental program to evaluate the role of zeta potential in the flocculation process.

The results of this study indicated that the DLVO theory (Darjaguin, Landau, Overbeek, Verwey theory) is applicable to micro-cater process in the absence of polyelectrolytes. The best flocculation …

Enantiomeric Composition Of Nornicotine, Anatabine, And Anabasine In Tobacco, Daniel W. Armstrong, Xiande Wang, Jauh Tzuoh Lee, Yan Song Liu

Chemistry Faculty Research & Creative Works

Literature reports on the optical purity of the minor alkaloids in tobacco leaf and its products often contradict one another. The enantiomeric compositions of nornicotine, anatabine, and anabasine were measured using gas chromatography/mass spectrometry (GC/MS) (with a chiral stationary phase) in three types of tobacco leaf (Burley, Turkish, and Virginia); three types of smokeless tobacco (loose-leaf, dry snuff, and moist snuff); and four types of cigarettes. Regardless of the tobacco type or product, anabasine always had the highest relative percentage of the minor (R)-(+)-enantiomeric component (between 40 and 46% vs. 54-60% of the (S)-(-)-enantiomer). Of the four common tobacco alkaloids, …

Role Of Reactive Oxygen Species In Mercapto-Methylimidazole-Induced Gastric Acid Secretion And Stress-Induced Gastric Ulceration, Uday Bandyopadhyay, Dipak Das, Debasish Bandyopadhyay, Mrinalini Bhattacharjee, Ranajit K. Banerjee

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The objective of the present study is to delineate the role of reactive oxygen species in drug-induced gastric hyperacidity and stress-induced gastric ulceration. We reported earlier that mercaptomethylimidazole (MMI), an antithyroid drug, induces gastric acid (HCl) secretion partially through H2receptor activation of the parietal cell by histamine release and partially through an intracellular mechanism. While studying the latter, MMI-induced acid secretion was found to correlate well with the inactivation of the peroxidase, an important H2O2metabolizing enzyme of the mucosa. MMI activates the isolated parietal cell for acid secretion, which is sensitive to omeprazole. Peroxidase and catalase activity of the isolated …

Relationship Between Udp-Glucose 4-Epimerase Activity And Oligoglucose Glycoforms In Two Strains Of Neisseria Meningitidis, F K. Lee, B W. Gibson, William Melaugh, A Zaleski, M A. Apicella

Chemistry Faculty Publications

Sodium dodecyl sulfate-polyacrylamide gel analysis of lipooligosaccharide (LOS) from Neisseria meningitidis has demonstrated considerable microheterogeneity in the variable region of LOS due to the presence of novel glycoforms. As a step toward understanding the basis for the expression of these novel glycoforms, we have examined the LOS structures and UDP-glucose 4-epimerase (epimerase) activity levels in two strains (NMB and MA-1) and their respective galE mutants. Strain NMB was found to have low epimerase activity and to contain multiple glycoforms, some of which appear to contain only glucose sugars. The galE mutant had only the oligoglucose glycoforms. Strain MA-1 had higher …

Experimental And Theoretical Investigations Of The Structure And The Stability Of The Bnsi Molecule, Giovanni Meloni, R Viswanathan

Chemistry Faculty Publications

Theoretical computations were carried out to determine the structure and molecular parameters of the BNSi molecule. The most stable isomer is found to have a BNSi linear geometry. Thermal functions as derived from the theoretical computed molecular parameters were used in the evaluation of the thermodynamic properties of BNSi from high-temperature Knudsen effusion mass spectrometric equilibrium data. From the reactions analyzed by the second-law and third-law methods, the enthalpy of formation,ΔfHo0, and of atomization, ΔaHo0, in kJ mol⁻¹, for BNSi, were obtained as 398±16 and 1078±17, respectively.

Thermodynamic Investigation Of The Ainc And Aicn Isomers By Knudsen Cell Mass Spectrometry, Giovanni Meloni, Karl A. Gingerich

Chemistry Faculty Publications

Equilibria involving the isomers AlNC and AlCN above a mixture of aluminum nitride, graphite, and gold contained in a graphite Knudsen cell were investigated with a mass spectrometer. The enthalpies of formation,ΔfHo0, and of atomization, ΔaHo0, in kJ mol⁻¹, for AlNC and AlCN, were derived as 281.3±14 and 303.8±14, and as 1228.1±15 and 1205.6±15, respectively.

Adjacent-Dim-Isoelectronic Molecules And Chemical Similarity Ii, Myla Thomas

Capstone Research Projects

No abstract provided.

Application Of Geometric Probability Techniques To The Evaluation Of Interaction Energies Arising From A General Radial Potential, David Schleef, Michelle Parry, Shu-Ju Tu, Brian Woodahl, Ephraim Fischbach

Chemistry & Physics Faculty Publications

A formalism is developed for using geometric probability techniques to evaluate interaction energies arising from a general radial potential V(r₁₂), where r₁₂ = ∣r₂−r₁∣. The integrals that arise in calculating these energies can be separated into a radial piece that depends on r₁₂ and a nonradial piece that describes the geometry of the system, including the density distribution. We show that all geometric information can be encoded into a “radial density function” G(r₁₂;ρ₁,ρ₂), which depends on r_{12 …}

Iron-Induced Oxidative Stress In Erythrocyte Membranes Of Non-Insulin-Dependent Diabetic Nigerians, Gbolahan W. Okunade, Odutayo O. Odunuge, Olufunso O. Olorunsogo

Faculty Publications

The presence of higher level of endogenous free radical reaction products in the erythrocyte ghost membrane (EGM) of Non-insulin-dependent diabetes mellitus (NIDDM) subjects compared with that of normal healthy controls has been demonstrated. The EGMs of NIDDM subjects were also shown to be more susceptible to exogenously generated oxidative stress than those of normal healthy individuals. The decreased level of reactive thiol groups in the EGM of NIDDM individuals supported this observation. We propose that the presence of significant levels of non-heme iron in the EGM of NIDDM subjects is an indication of the potential for iron-catalysed production of hydroxy …

Reversal Of Sodium Arsenite Inhibition Of Rat Liver Microsomal Ca2+ Pumping Atpase By Vitamin C, Odutayo O. Odunuge, Gbolahan W. Okunade, Olufunso O. Olorunsogo

Faculty Publications

Sodium arsenite (NaAsO2), at 10% of its median lethal dose, was administered to rats with and without vitamin C pretreatment. Liver microsomal fraction was isolated and the activity of Ca2+-ATPase was assayed. Sodium arsenite was found to inhibit the activity of the liver microsomal Ca2+-ATPase to 50% to that of control rats. The specific activity of the enzyme in rats administered sodium arsenite with vitamin C pretreatment was not significantly different from that of control rats.

The Effect Of Carrier Gas Pressure On Vapor Phase Nucleation Experiments Using A Thermal Diffusion Cloud Chamber, D. Kane, S. P. Fisenko, M. Rusyniak, M. S. El-Shall

Chemistry Publications

Recent measurements of critical supersaturations for the vapor phase homogeneous nucleation of several substances using a diffusion cloud chamber technique exhibit a dependence on the pressure of the carrier gas used in the experiments. A model of droplet growth and motion in a diffusion cloud chamber, combined with the density and temperature profiles of the chamber is presented to explain the pressure dependent results. The model demonstrates that at higher carrier gas pressures the growth of the droplets is retarded and the optical scattering signal from the particles is reduced. It is concluded that the observed effect may not result …

A Theoretical Study Of The Electronic Coupling Element For Electron Transfer In Water, Newt E. Miller '99, Matthew C. Wander '97, Robert J. Cave

All HMC Faculty Publications and Research

The electronic coupling element for electron transfer between a donor and acceptor in water is examined using simulations combining molecular dynamics and semiempirical quantum mechanics. In the first phase of the simulations a model donor and acceptor are solvated in water, using realistic potentials. Following equilbration, molecular dynamics simulations are performed with the donor, acceptor, and water at approximately 300 K, under periodic boundary conditions. In the second phase of the simulation, the electronic coupling element between the donor and acceptor is calculated for a number of time slices, in the presence of the intervening water molecules (those having a …

Classification Of Explosives Transformation Products In Plant Tissue, Steven L. Larson, Robert P. Jones, Lynn Escalon, Don Parker

United States Army Corps of Engineers, Omaha District

Explosives contamination in surface or groundwater used for the irrigation of food crops and phytoremediation of explosives-contaminated soil or water using plant-assisted biodegradation have brought about concerns as to the fate of explosives in plants. Liquid scintillation counting, high-performance liquid chromatography, and gel permeation chromatography were utilized to characterize explosives (hexahydro-1,3,5-trinitro-1,3,5-triazine and trinitrotoluene) and their metabolites in plant tissues obtained from three separate studies. Analyzing tissues of yellow nutsedge (Cyperus esculentus), corn (Zea mays), lettuce (Lacuta sativa), tomato (Lyopersicum esculentum), radish (Raphanus sativus), and parrot feather (Myriophyllum aquaticum) …

Comparison Of Methods For Calculating The Properties Of Intramolecular Hydrogen Bonds. Excited State Proton Transfer, T. Kar, Steve Scheiner, M. Cuma

Chemistry and Biochemistry Faculty Publications

A series of molecules related to malonaldehyde, containing an intramolecular H-bond, are used as the testbed for a variety of levels of ab initio calculation. Of particular interest are the excitation energies of the first set of valence excited states, nπ^∗ and ππ^∗, both singlet and triplet, as well as the energetics of proton transfer in each state. Taking coupled cluster results as a point of reference, configuration interaction-singles–second-order Møller–Plesset (CIS–MP2) excitation energies are too large, as are CIS to a lesser extent, although these approaches successfully reproduce the order of the various states. The …

The Hofmann Rearrangement Using Household Bleach: Synthesis Of 3-Nitroaniline, Ram Mohan, Keith Monk

Scholarship

No abstract provided.

Oxidation Of Benzoins To Benzils Using Bismuth(Iii) Nitrate-Copper(Ii) Acetate, Ram Mohan, Steven Tymonko, Bryce Nattier

Scholarship

Benzoins are oxidized to benzils in excellent yields by 0.4 equivalents of Bi(NO₃)3.5H₂0 and 4 mol% of Cu(OAc)₂₃)₃.5H₂0 is a stable, inexpensive, commercially available solid. The relatively low cost and low toxicity of bismuth(Ill) nitrate makes this procedure a particularly attractive method for oxidation of benzoins.

Co Photolysis Of Cytochrome Oxidase Investigated By Ps Resonance Raman Spectroscopy, Johannes Schelvis, Constantinos Varotsis, Geurt Deinum, Gerald T. Babcock

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Low-power picosecond resonance Raman spectroscopy was used to investigate the identity of the axial ligand of heme a3 and relaxation processes in the heme a3 pocket of cytochrome oxidase after CO photolysis. Our results show that the proximal histidine remains ligated to heme a3 after CO photolysis excluding the transient ligation of a photolabile, endogenous ligand. Furthermore, the relaxation of the heme a3 macrocycle modes occurs on the sub ps time scale, while relaxation of the heme pocket to its equilibrium conformation takes place on the μs time scale.