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At least 19 records

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Huang, C. J.↗

Optimizing Surfactant Templating of Yttria-Stabilized Zirconia Aerogels for High-Temperature Applications: Effect of Anionic and Nonionic Surfactant

Aerogels, mesoporous materials with extreme material properties including high specific surface area, low density, and low thermal conductivity, can be useful for applications including catalysis, sorption media, and drug delivery. The low thermal conductivity and high surface area of aerogels makes them advantageous as thermal management systems, specifically for aerospace or aeronautics applications. However, the pore collapse and subsequent surface area decrease of aerogels following exposure to high temperatures must be mitigated to allow aerogels to be effectively used in thermal management applications. This work investigates the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant Pluronic® P-123 as surfactant templates in yttria-stabilized zirconia (YSZ) aerogels. By utilizing surfactant templates, known to influence pore structure, it is anticipated that sintering and densification of the aerogels following high-temperature exposure will be mitigated. It was determined that the addition of SDS and P-123 increased the surface area and pore volume of as-dried aerogels and suppressed crystallite growth at high temperatures. However, the impact of surfactant templates on the surface area and pore volume of heat-treated aerogels was negligible, potentially due to low concentrations of surfactant and the removal of the surfactant following high-temperature exposure.

Yttria-stabilized zirconia aerogels↗

Optimizing Surfactant Templating of Yttria-stabilized Zirconia Aerogels for High-temperature Applications: Effect of Anionic & Nonionic Surfactant

Aerogels are useful thermal insulators due to low density, low thermal conductivity, and a tortuous path for solid conduction. However, the formulation must be optimized to increase thermal stability as drastic densification and surface area decrease is often exhibited after high-temperature exposure. Current research investigates yttria-stabilized zirconia (YSZ) aerogels for expected use between 600°C and 1000°C. We anticipate that new sol-gel chemistries will yield YSZ aerogels with retained mesoporous structure, increased surface area, and minimized shrinkage upon high-temperature exposure. This work investigates the anionic surfactant, sodium dodecyl sulfate (SDS), and the nonionic surfactant, Pluronic® P-123, as templating agents to prevent the collapse of the aerogel pore structure upon gelation and drying. To determine the effect of surfactant, characterization techniques such as nitrogen physisorption, x-ray diffraction, and scanning electron microscopy are used. By optimizing surfactant concentration, the thermal stability of YSZ aerogels can be enhanced, producing more efficient thermal insulators.

Rebecca C. Walker↗

The effects of cations and anions on hydrogen chemisorption at Pt

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Huang, J. C.↗

Effect of polynucleotides on the dimerization of glycine

Results from experiments to determine the effect of polynucleotides on abiological formation of peptide bonds are reported. The reaction between glycine molecules in an aqueous phase in the presence of a condensing agent was chosen as a model, with polyphosphates being selected as the condensing agent for biologically relevant peptide formation. Four types of polynucleotides were used: polygluanic acid (G), polyuridic acid (U), polyadenylic acid (A), and polycytidylic acid (C); the effects of small anions, acetate, chloride, and phosphate, were also studied. Procedures are given, including concentrations, pH, and incubation time, and the type of amino acid analyzer. The diglycine yields were, in order of most to least: G, C, A, U, and are diagrammed as a function of time; rate of formation followed the same order of magnitude as the final yields. Anion presence displayed no discernible effect. The results are taken to indicate that polynucleotides do have an effect on the formation of peptide bonds, an effect significant in the understanding of chemical evolution.

Mizutani, H.↗

Effect of KOH concentration and anions on the performance of Ni-H2 battery positive plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galavanostatic charging; and discharging in a flooded electrolyte cell. Three different concentrations of KOH (40 percent, 31 percent, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate or silicate were investigated. The end of charge voltage at C/10 charge and at 10 C showed the following order: 40 percent KOH is greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOE. The middischarge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without the added contaminants and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH where the capacity declined after 1000 cycles at 80 percent DOD. At the end of cycling the plate tested in the presence of sulfate and silicate experienced measurable weight loss as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the second oxidation peak that corresponds to the formation of a different phase of oxidized Ni has a lower peak current at -5 C compared to 25 C and oxygen evolution occurs a higher potential at -5 C. The reduction peak (discharge reaction) is more polarized at 25 C compared to -5 C. The presence of silicate alters the potentials only marginally. The implications of these results in plate treatment and low temperature operation are discussed.

Vaidyanathan, H.↗

Effect of KOH Concentration and Anions on the Performance of a Ni-H2 Battery Positive Plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galvanostatic charging and discharging in a flooded electrolyte cell. Three different concentrations of potassium hydroxide (KOH) (40, 31, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate, or silicate were investigated. The end-of-charge voltage at C/10 charge and at 10 degrees C showed the following order: 40 percent KOH greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOH. The mid discharge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without added contaminants, and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH, where the capacity declined after 1,000 cycles at 80 percent depth of discharge (DOD). At the end of cycling, all the plates tested experienced a weight loss, except in the case of 31 percent KOH, as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the cathodic peak potentials are less polarized in the presence and absence of silicate at -5 degrees C compared to 25 degrees C indicating a slightly higher voltage during discharge in a Ni-H2 battery. Futhermore, the features of the current-potential profile were practically unchanged in the presence of silicate.

Vaidyanathan, Hari↗

Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

Nadarajah, Arunan↗

Anions in Cometary Comae

The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

Charnley, Steven B.↗

Catalysts for electrochemical generation of oxygen

An effort was made to study the effects of cation and anion additions on oxygen evolution kinetics on platinum and the inhibitive or catalytic nature of the additions. The kinetics and mechanism of oxygen evolution on planitum metal in hydrofluoric and sulfuric acids, including the effects of foreign anions, were examined. The LEED-Auger-thin layer electrochemical system was developed for the examination of electrocatalytic surfaces. Samples for electrocatalytic LEED-Auger studies were prepared and examined.

Ogrady, W. E.↗

Method of forming a relatively stable slip of silicon metal particles and yttrium containing particles

The method concerns forming a relatively stable slip of silicon metal particles and yttrium containing particles. In one embodiment, a casting slip of silicon metal particles is formed in water. Particles of a yttrium containing sintering aid are added to the casting slip. The yttrium containing sintering aid is a compound which has at least some solubility in water to form Y.sup.+3 ions which have a high potential for totally flocculating the silicon metal particles into a semiporous solid. A small amount of a fluoride salt is added to the casting slip which contains the yttrium containing sintering aid. The fluoride salt is one which will produce fluoride anions when dissolved in water. The small amount of the fluoride anions produced are effective to suppress the flocculation of the silicon metal particles by the Y.sup.+3 ions so that all particles remain in suspension in the casting slip and the casting slip has both an increased shelf life and can be used to cast articles having a relatively thick cross-section. The pH of the casting slip is maintained in a range from 7.5 to 9. Preferably, the fluoride salt used is one which is based on a monovalent cation such as sodium or ammonia. The steps of adding the yttrium containing sintering aid and the fluoride salt may be interchanged if desired, and the salt may be added to a solution containing the sintering aid prior to addition of the silicon metal particles.

Dickie, Ray A.↗

Grain boundary mobility in anion doped MgO

Certain anions OH(-), F(-) and Gl(-) are shown to enhance grain growth in MgO. The magnitude of their effect decreases in the order in which the anions are listed and depends on their location (solid-solution, second phase) in the MgO lattice. As most anions exhibit relatively high vapor pressures at sintering temperatures, they retard densification and invariably promote residual porosity. The role of anions on grain growth rates was studied in relation to their effect on pore mobility and pore removal; the atomic process controlling the actual rates was determined from observed kinetics in conjunction with the microstructural features. With respect to controlling mechanisms, the effects of all anions are not the same. OH(-) and F(-) control behavior through creation of a defect structure and a grain boundary liquid phase while Cl(-) promotes matter transport within pores by evaporation-condensation. Studies on an additional anion, S to the minus 2nd power gave results which were no different from undoped MgO, possibly because of evaporative losses during hot pressing. Hence, the effect of sulphur is negligible or undetermined.

Kapadia, C. M.↗

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

Lee, Timothy J.↗