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Sample records for water-gas shift reaction

  1. Zeolite Membrane Reactor for Water Gas Shift Reaction for Hydrogen Production

    SciTech Connect

    Lin, Jerry Y.S.

    2013-01-29

    Gasification of biomass or heavy feedstock to produce hydrogen fuel gas using current technology is costly and energy-intensive. The technology includes water gas shift reaction in two or more reactor stages with inter-cooling to maximize conversion for a given catalyst volume. This project is focused on developing a membrane reactor for efficient conversion of water gas shift reaction to produce a hydrogen stream as a fuel and a carbon dioxide stream suitable for sequestration. The project was focused on synthesizing stable, hydrogen perm-selective MFI zeolite membranes for high temperature hydrogen separation; fabricating tubular MFI zeolite membrane reactor and stable water gas shift catalyst for membrane reactor applications, and identifying experimental conditions for water gas shift reaction in the zeolite membrane reactor that will produce a high purity hydrogen stream. The project has improved understanding of zeolite membrane synthesis, high temperature gas diffusion and separation mechanisms for zeolite membranes, synthesis and properties of sulfur resistant catalysts, fabrication and structure optimization of membrane supports, and fundamentals of coupling reaction with separation in zeolite membrane reactor for water gas shift reaction. Through the fundamental study, the research teams have developed MFI zeolite membranes with good perm-selectivity for hydrogen over carbon dioxide, carbon monoxide and water vapor, and high stability for operation in syngas mixture containing 500 part per million hydrogen sulfide at high temperatures around 500°C. The research teams also developed a sulfur resistant catalyst for water gas shift reaction. Modeling and experimental studies on the zeolite membrane reactor for water gas shift reaction have demonstrated the effective use of the zeolite membrane reactor for production of high purity hydrogen stream.

  2. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction

    SciTech Connect

    Laine, R.M.; Wood, B.J.; Krishnan, G.N.

    1986-04-01

    The objective of this project is to identify, prepare, test, characterize, and evaluate a practical, homogeneous catalyst for a water-gas shift process. The project effort is divided into the following five tasks: (1) Update SRI's recent review of the literature on the catalysis of the water-gas shift reaction (WGSR) to include references after 1982 and those in the patent literature. Based on this review, SRI will choose ten candidate systems to be evaluated as to their abilities to catalyze the WGSR using syngas derived from gasified coal. (2) Develop a test plan designed to effectively evaluate both the catalysts and, to some extent, reactor configuration for WGSR catalysis. (3) Perform a series of experiments to identify the most effective and economical of the ten candidate catalysts and then further evaluate the reaction kinetics of at least one selected catalyst system to develop sufficient data to provide the basis for the work in Task 4. (4) Develop a mathematical model of the final candidate system that uses rate expressions to describe the catalytic process. (5) Perform a techno-economical evaluation of the catalyst in terms of a proposed plant design based on the reaction model, current costs, and standard chemical engineering practice and compare the proposed design with a conventional hydrogen plant.

  3. Minimization of steam requirements and enhancement of water-gas shift reaction with warm gas temperature CO2 removal

    DOEpatents

    Siriwardane, Ranjani V; Fisher, II, James C

    2013-12-31

    The disclosure utilizes a hydroxide sorbent for humidification and CO.sub.2 removal from a gaseous stream comprised of CO and CO.sub.2 prior to entry into a water-gas-shift reactor, in order to decrease CO.sub.2 concentration and increase H.sub.2O concentration and shift the water-gas shift reaction toward the forward reaction products CO.sub.2 and H.sub.2. The hydroxide sorbent may be utilized for absorbtion of CO.sub.2 exiting the water-gas shift reactor, producing an enriched H.sub.2 stream. The disclosure further provides for regeneration of the hydroxide sorbent at temperature approximating water-gas shift conditions, and for utilizing H.sub.2O product liberated as a result of the CO.sub.2 absorption.

  4. Water-gas shift reaction catalyzed by redox enzymes on conducting graphite platelets.

    PubMed

    Lazarus, Oliver; Woolerton, Thomas W; Parkin, Alison; Lukey, Michael J; Reisner, Erwin; Seravalli, Javier; Pierce, Elizabeth; Ragsdale, Stephen W; Sargent, Frank; Armstrong, Fraser A

    2009-10-14

    The water-gas shift (WGS) reaction (CO + H(2)O <==> CO(2) + H(2)) is of major industrial significance in the production of H(2) from hydrocarbon sources. High temperatures are required, typically in excess of 200 degrees C, using d-metal catalysts on oxide supports. In our study the WGS process is separated into two half-cell electrochemical reactions (H(+) reduction and CO oxidation), catalyzed by enzymes attached to a conducting particle. The H(+) reduction reaction is catalyzed by a hydrogenase, Hyd-2, from Escherichia coli, and CO oxidation is catalyzed by a carbon monoxide dehydrogenase (CODH I) from Carboxydothermus hydrogenoformans. This results in a highly efficient heterogeneous catalyst with a turnover frequency, at 30 degrees C, of at least 2.5 s(-1) per minimum functional unit (a CODH/Hyd-2 pair) which is comparable to conventional high-temperature catalysts. PMID:19807170

  5. Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions

    SciTech Connect

    Zhai, Y.; Pierre, D; Si, R; Deng, W; Ferrin, P; Nilekar, A; Peng, G; Herron, J; Bell, D; et. al.

    2010-01-01

    We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H{sub 2}O + CO {yields} H{sub 2} + CO{sub 2}) used for producing H{sub 2}. The alkali ion-associated surface OH groups are activated by CO at low temperatures ({approx}100 C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O{sub x}(OH){sub y} species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.

  6. Plasmon-enhanced reverse water gas shift reaction over oxide supported Au catalysts

    SciTech Connect

    Upadhye, AA; Ro, I; Zeng, X; Kim, HJ; Tejedor, I; Anderson, MA; Dumesic, JA; Huber, GW

    2015-01-01

    We show that localized surface plasmon resonance (LSPR) can enhance the catalytic activities of different oxide-supported Au catalysts for the reverse water gas shift (RWGS) reaction. Oxide-supported Au catalysts showed 30 to 1300% higher activity for RWGS under visible light compared to dark conditions. Au/TiO2 catalyst prepared by the deposition-precipitation (DP) method with 3.5 nm average Au particle size showed the highest activity for the RWGS reaction. Visible light is converted into chemical energy for this reaction with up to a 5% overall efficiency. A shift in the apparent activation energy (from 47 kJ mol(-1) in dark to 35 kJ mol(-1) in light) and apparent reaction order with respect to CO2 (from 0.5 in dark to 1.0 in light) occurs due to the LSPR. Our kinetic results indicate that the LSPR increases the rate of either the hydroxyl hydrogenation or carboxyl decomposition more than any other steps in the reaction network.

  7. Hydrodesulphurization of Light Gas Oil using hydrogen from the Water Gas Shift Reaction

    NASA Astrophysics Data System (ADS)

    Alghamdi, Abdulaziz

    2009-12-01

    The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391C for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas) molar ratio by varying CO to H2 ratio. It is also planned to use different catalysts promoters and compare them with the un-promoted Mo based catalysts to achieve the optimum reaction conditions for treating LGO. The results of this study showed that Ni and Co have a promoting effect over unpromoted Mo catalysts for both HDS and WGSR. Ni was found to be the best promoter for both reactions. Fe showed no significant effect for both WGSR and HDS. V and K have a good promoting effect in WGSR but they inhibited the HDS reaction. Potassium was found to be the strongest inhibitor for the HDS reaction since no sulfur was removed during the reaction. Keywords. LGO, HDS, in situ H2, WGSR, oil upgrading, syn-gas.

  8. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    SciTech Connect

    Pizarro, C.; Escudey, M.; Moya, S.A.; Fabris, J.D.

    2005-04-26

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124 deg. C to 500 deg. C. The room temperature Moessbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 deg. C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  9. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction

    SciTech Connect

    Laine, R.M.

    1986-01-20

    The purpose of this report is to update and reorganize our recent review on homogeneous catalysis of the water-gas shift reaction (WGSR) based on recent literature publications and patents. This updated version will serve as a means of selecting 10 candidate catalyst systems for use in developing effective, sulfur-tolerant, low temperature WGSR catalysts. This report discusses the variations possible in the basic chemistry associated with WGSR catalytic cycles, including basic, acidic, and neutral conditions. Then individual mechanism for specific WGSR catalyst systems are discussed. Finally, on the basis of the literature reports, a list is presented of candidate catalysts and basic systems we have chosen for study in Task 3.

  10. The effect of PdZn particle size on reverse-water-gas-shift reaction

    SciTech Connect

    Lebarbier, Vanessa MC; Dagle, Robert A.; Datye, A. K.; Wang, Yong

    2010-05-15

    The effect of PdZn particle size on the catalytic activity of Pd/ZnO catalysts for the reverse-water-gas-shift (RWGS) reaction was studied. The PdZn particle size was varied by adjusting Pd loading and reducing the catalysts at different temperatures. XRD and IR spectroscopy characterization confirmed the absence of metallic Pd on the catalyst surface. Consequently, the effect of PdZn alloy particle size on the RWGS reaction can be unambiguously studied without the complication of reactions catalyzed by metallic Pd. The results indicated that the turnover frequency increases as the PdZn crystallite size decreases. Interestingly, this structure relationship between PdZn particle size and RWGS activity is consistent with that previously observed for the steam reforming of methanol, i.e., higher CO selectivity on smaller PdZn particles. Thus, RWGS has been identified as a likely potential reaction pathway to undesired CO formation in methanol steam reforming on Pd/ZnO catalysts for hydrogen production.

  11. On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper

    SciTech Connect

    Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos

    2008-01-30

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Periodic, self-consistent density functional theory (DFT-GGA) calculations are used to investigate the water gas shift reaction (WGSR) mechanism on Cu(111). The thermochemistry and activation energy barriers for all the elementary steps of the commonly accepted redox mechanism, involving complete water activation to atomic oxygen, are presented. Through our calculations, we identify carboxyl, a new reactive intermediate, which plays a central role in WGSR on Cu(111). The thermochemistry and activation energy barriers of the elementary steps of a new reaction path, involving carboxyl, are studied. A detailed DFTbased microkinetic model of experimental reaction rates, accounting for both the previous and the new WGSR mechanism show that, under relevant experimental conditions, (1) the carboxyl-mediated route is the dominant path, and (2) the initial hydrogen abstraction from water is the rate-limiting step. Formate is a stable spectator species, formed predominantly through CO? hydrogenation. In addition, the microkinetic model allows for predictions of (i) surface coverage of intermediates, (ii) WGSR apparent activation energy, and (iii) reaction orders with respect to CO, H?O, CO?, and H?.

  12. Density Functional Theory and Reaction Kinetics Studies of the WaterGas Shift Reaction on PtRe Catalysts

    SciTech Connect

    Carrasquillo-Flores, Ronald; Gallo, Jean Marcel R.; Hahn, Konstanze; Dumesic, James A.; Mavrikakis, Manos

    2013-11-05

    Periodic, self-consistent density functional theory calculations (DFT-GGA-PW91) on Pt(111) and Pt3Re(111) surfaces, reaction kinetics measurements, and microkinetic modeling are employed to study the mechanism of the watergas shift (WGS) reaction over Pt and PtRe catalysts. The values of the reaction rates and reaction orders predicted by the model are in agreement with the ones experimentally determined; the calculated apparent activation energies are matched to within 6% of the experimental values. The primary reaction pathway is predicted to take place through adsorbed carboxyl (COOH) species, whereas formate (HCOO) is predicted to be a spectator species. We conclude that the clean Pt(111) is a good representation of the active site for the WGS reaction on Pt catalysts, whereas the active sites on the PtRe alloy catalyst likely contain partially oxidized metal ensembles.

  13. Gold catalysts for pure hydrogen production in the water-gas shift reaction: activity, structure and reaction mechanism.

    PubMed

    Burch, Robbie

    2006-12-21

    The production of hydrogen containing very low levels of carbon monoxide for use in polymer electrolyte fuel cells requires the development of catalysts that show very high activity at low temperatures where the equilibrium for the removal of carbon monoxide using the water-gas shift reaction is favourable. It has been claimed that oxide-supported gold catalysts have the required high activity but there is considerable uncertainty in the literature about the feasibility of using these catalysts under real conditions. By comparing the activity of gold catalysts with that of platinum catalysts it is shown that well-prepared gold catalysts are significantly more active than the corresponding platinum catalysts. However, the method of preparation and pre-treatment of the gold catalysts is critical and activity variations of several orders of magnitude can be observed depending on the methods chosen. It is shown that an intimate contact between gold and the oxide support is important and any preparative procedure that does not generate such an interaction, or any subsequent treatment that can destroy such an interaction, may result in catalysts with low activity. The oxidation state and structure of active gold catalysts for the water-gas shift reaction is shown to comprise gold primarily in a zerovalent metallic state but in intimate contact with the support. This close contact between small metallic gold particles and the support may result in the "atoms" at the point of contact having a net charge (most probably cationic) but the high activity is associated with the presence of metallic gold. Both in situ XPS and XANES appear unequivocal on this point and this conclusion is consistent with similar measurements on gold catalysts even when used for CO oxidation. In situ EXAFS measurements under water gas shift conditions show that the active form of gold is a small gold cluster in intimate contact with the oxide support. The importance of the gold/oxide interface is indicated but the possible role of special sites (e.g., edge sites) on the gold clusters cannot be excluded. These may be important for CO oxidation but the fact that water has to be activated in the water gas shift reaction may point towards a more dominant role for the interfacial sites. The mechanism of the water gas shift reaction on gold and other low temperature catalysts has been widely investigated but little agreement exists. However, it is shown that a single "universal" model is consistent with much of the experimental literature. In this, it is proposed that the dominant surface intermediate is a function of reaction conditions. For example, as the temperature is increased the dominant species changes from a carbonate or carboxylate species, to a formate species and eventually at high temperatures to a mechanism that is characteristic of a redox process. Similar changes in the dominant intermediate are observed with changes in the gas composition. Overall, it is shown that reported variations in the kinetics, structure and reaction mechanism for the water gas shift reaction on gold catalysts can now be understood and rationalised. PMID:17136264

  14. A highly active and stable Ni-Mg phyllosilicate nanotubular catalyst for ultrahigh temperature water-gas shift reaction.

    PubMed

    Bian, Zhoufeng; Li, Ziwei; Ashok, Jangam; Kawi, Sibudjing

    2015-11-25

    A Ni-Mg phyllosilcate (PS) nanotubular catalyst has been developed by introducing Mg into Ni phyllosilicate nanotubes (PSNTs). The thermal stability is improved significantly. Furthermore, this binary metal PS nanotubular catalyst exhibits excellent activity and stability for ultrahigh temperature water-gas shift (WGS) reaction. PMID:26399997

  15. Approach to equilibrium of the water-gas shift reaction on a Ni/zirconia anode under solid oxide fuel-cell conditions

    NASA Astrophysics Data System (ADS)

    Ahmed, K.; Fger, K.

    The reverse water-gas shift reaction is carried out in a solid oxide fuel-cell at a range of fuel utilization levels and the approach of this reaction to thermodynamic equilibrium is calculated from the experimental data. It is found that the water-gas shift reaction is close to equilibrium only at high levels of fuel utilization. This is an important finding for modeling and simulation of fuel-cells.

  16. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction. Task 2, Test plan

    SciTech Connect

    Laine, R.M.; Wood, B.J.; Krishnan, G.N.

    1986-04-01

    The objective of this project is to identify, prepare, test, characterize, and evaluate a practical, homogeneous catalyst for a water-gas shift process. The project effort is divided into the following five tasks: (1) Update SRI`s recent review of the literature on the catalysis of the water-gas shift reaction (WGSR) to include references after 1982 and those in the patent literature. Based on this review, SRI will choose ten candidate systems to be evaluated as to their abilities to catalyze the WGSR using syngas derived from gasified coal. (2) Develop a test plan designed to effectively evaluate both the catalysts and, to some extent, reactor configuration for WGSR catalysis. (3) Perform a series of experiments to identify the most effective and economical of the ten candidate catalysts and then further evaluate the reaction kinetics of at least one selected catalyst system to develop sufficient data to provide the basis for the work in Task 4. (4) Develop a mathematical model of the final candidate system that uses rate expressions to describe the catalytic process. (5) Perform a techno-economical evaluation of the catalyst in terms of a proposed plant design based on the reaction model, current costs, and standard chemical engineering practice and compare the proposed design with a conventional hydrogen plant.

  17. Heat Integration of the Water-Gas Shift Reaction System for Carbon Sequestration Ready IGCC Process with Chemical Looping

    SciTech Connect

    Juan M. Salazara; Stephen E. Zitney; Urmila M. Diwekara

    2010-01-01

    Integrated gasification combined cycle (IGCC) technology has been considered as an important alternative for efficient power systems that can reduce fuel consumption and CO2 emissions. One of the technological schemes combines water-gas shift reaction and chemical-looping combustion as post gasification techniques in order to produce sequestration-ready CO2 and potentially reduce the size of the gas turbine. However, these schemes have not been energetically integrated and process synthesis techniques can be applied to obtain an optimal flowsheet. This work studies the heat exchange network synthesis (HENS) for the water-gas shift reaction train employing a set of alternative designs provided by Aspen energy analyzer (AEA) and combined in a process superstructure that was simulated in Aspen Plus (AP). This approach allows a rigorous evaluation of the alternative designs and their combinations avoiding all the AEA simplifications (linearized models of heat exchangers). A CAPE-OPEN compliant capability which makes use of a MINLP algorithm for sequential modular simulators was employed to obtain a heat exchange network that provided a cost of energy that was 27% lower than the base case. Highly influential parameters for the pos gasification technologies (i.e. CO/steam ratio, gasifier temperature and pressure) were calculated to obtain the minimum cost of energy while chemical looping parameters (oxidation and reduction temperature) were ensured to be satisfied.

  18. Performance of Au/M(x)O(y)/TiO(2) Catalysts in Water-Gas Shift Reaction

    SciTech Connect

    Ma, Zhen; Dai, Sheng; Yin, Hongfeng

    2010-01-01

    Our group recently developed a series of Au/M{sub x}O{sub y}/TiO{sub 2} catalysts for CO oxidation, and demonstrated that some of these catalysts are still active after high-temperature treatment whereas Au/TiO{sub 2} deactivates significantly due to the sintering of gold nanoparticles at elevated temperatures (Ma Z, Overbury SH, Dai S (2007) J Mol Catal A 273:97). In the current work, the performance of Au/M{sub x}O{sub y}/TiO{sub 2} (M = Al, Ca, Fe, Zn, Ga, Y, Zr, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) catalysts in water-gas shift (WGS) reaction was evaluated. The influences of different metal oxide (M{sub x}O{sub y}) additives and pretreatment temperatures were investigated, and the catalyst stability as a function of reaction time on stream was tested. Some of these novel gold catalysts, with high activity and stability in water-gas shift, furnish new possibilities for further fundamental research and industrial development.

  19. Structure Sensitivity of the Low-temperature Water-gas Shift Reaction on Cu–CeO2 catalysts

    SciTech Connect

    Si, R.; Zhang, L.; Raitano, J.; Yi, N.; Chan, S.-W.; Flytzani-Stephanopoulos, M.

    2012-01-17

    We have investigated the structure sensitivity of the water-gas shift (WGS) reaction on Cu-CeO{sub 2} catalysts prepared at the nanoscale by different techniques. On the surface of ceria, different CuO{sub x} structures exist. We show here that only the strongly bound Cu-[O{sub x}]-Ce species, probably associated with the surface oxygen vacancies of ceria, are active for catalyzing the low-temperature WGS reaction. Weakly bound CuO{sub x} clusters and CuO nanoparticles are spectator species in the reaction. Isolated Cu{sup 2+} ions doping the ceria surface are not active themselves, but they are important in that they create oxygen vacancies and can be used as a reservoir of copper to replenish surface Cu removed by leaching or sintering. Accordingly, synthesis techniques such as coprecipitation that allow for extensive solubility of Cu in ceria should be preferred over impregnation, deposition-precipitation, ion exchange or another two-step method whereby the copper precursor is added to already made ceria nanocrystals. For the synthesis of different structures, we have used two methods: a homogeneous coprecipitation (CP), involving hexamethylenetetramine as the precipitating agent and the pH buffer; and a deposition-precipitation (DP) technique. In the latter case, the ceria supports were first synthesized at the nanoscale with different shapes (rods, cubes) to investigate any potential shape effect on the reaction. Cu-CeO{sub 2} catalysts with different copper contents up to ca. 20 at.% were prepared. An indirect shape effect of CeO{sub 2}, manifested by the propensity to form oxygen vacancies and strongly bind copper in the active form, was established; i.e. the water-gas shift reaction is not structure-sensitive. The apparent activation energy of the reaction on all samples was similar, 50 {+-} 10 kJ/mol, in a product-free (2% CO-10% H{sub 2}O) gas mixture.

  20. Carbon capture by sorption-enhanced water-gas shift reaction process using hydrotalcite-based material

    SciTech Connect

    van Selow, E.R.; Cobden, P.D.; Verbraeken, P.A.; Hufton, J.R.; van den Brink, R.W.

    2009-05-15

    A novel route for precombustion decarbonization is the sorption-enhanced water-gas shift (SEWGS) process. In this process carbon dioxide is removed from a synthesis gas at elevated temperature by adsorption. Simultaneously, carbon monoxide is converted to carbon dioxide by the water-gas shift reaction. The periodic adsorption and desorption of carbon dioxide is induced by a pressure swing cycle, and the cyclic capacity can be amplified by purging with steam. From previous studies is it known that for SEWGS applications, hydrotalcite-based materials are particularly attractive as sorbent, and commercial high-temperature shift catalysts can be used for the conversion of carbon monoxide. Tablets of a potassium promoted hydrotalcite-based material are characterized in both breakthrough and cyclic experiments in a 2 m tall fixed-bed reactor. When exposed to a mixture of carbon dioxide, steam, and nitrogen at 400{sup o}C, the material shows a breakthrough capacity of 1.4 mmol/g. In subsequent experiments the material was mixed with tablets of promoted iron-chromium shift catalyst and exposed to a mixture of carbon dioxide, carbon monoxide, steam, hydrogen, and nitrogen. It is demonstrated that carbon monoxide conversion can be enhanced to 100% in the presence of a carbon dioxide sorbent. At breakthrough, carbon monoxide and carbon dioxide simultaneously appear at the end of the bed. During more than 300 cycles of adsorption/reaction and desorption, the capture rate, and carbon monoxide conversion are confirmed to be stable. Two different cycle types are investigated: one cycle with a CO{sub 2} rinse step and one cycle with a steam rinse step. The performance of both SEWGS cycles are discussed.

  1. Atomically dispersed Au-(OH)x species bound on titania catalyze the low-temperature water-gas shift reaction.

    PubMed

    Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

    2013-03-13

    We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au-O-TiO(x) sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this "excess" gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites. PMID:23437858

  2. Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory

    SciTech Connect

    Liu, P.

    2010-11-28

    Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO{sub 2}/Cu(111), ZrO{sub 2}/Cu(111) < MoO{sub 3}/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.

  3. On the importance of steady-state isotopic techniques for the investigation of the mechanism of the reverse water-gas-shift reaction.

    PubMed

    Tibiletti, Daniele; Goguet, Alexandre; Meunier, Frederic C; Breen, John P; Burch, Robbie

    2004-07-21

    The formation and reactivity of surface intermediates in the reverse water-gas-shift reaction on a Pt/CeO2 catalyst are critically dependent on the reaction conditions so that conclusions regarding the reaction mechanism cannot be inferred using ex operando conditions. PMID:15263955

  4. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction. Task 1, Topical report No. 1

    SciTech Connect

    Laine, R.M.

    1986-01-20

    The purpose of this report is to update and reorganize our recent review on homogeneous catalysis of the water-gas shift reaction (WGSR) based on recent literature publications and patents. This updated version will serve as a means of selecting 10 candidate catalyst systems for use in developing effective, sulfur-tolerant, low temperature WGSR catalysts. This report discusses the variations possible in the basic chemistry associated with WGSR catalytic cycles, including basic, acidic, and neutral conditions. Then individual mechanism for specific WGSR catalyst systems are discussed. Finally, on the basis of the literature reports, a list is presented of candidate catalysts and basic systems we have chosen for study in Task 3.

  5. SIC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Paul K.T. Liu

    2003-12-01

    A hydrogen selective membrane as a membrane reactor (MR) can significantly improve the power generation efficiency with a reduced capital and operating cost for the waster-gas-shift reaction. Existing hydrogen selective ceramic membranes are not suitable for the proposed MR due to their poor hydrothermal stability. In this project we have focused on the development of innovative silicon carbide (SiC) based hydrogen selective membranes, which can potentially overcome this technical barrier. SiC macro-porous membranes have been successfully fabricated via extrusion of commercially available SiC powder. Also, an SiC hydrogen selective thin film was prepared via our CVD/I technique. This composite membrane demonstrated excellent hydrogen selectivity at high temperature ({approx}600 C). More importantly, this membrane also exhibited a much improved hydrothermal stability at 600 C with 50% steam (atmospheric pressure) for nearly 100 hours. In parallel, we have explored an alternative approach to develop a H{sub 2} selective SiC membrane via pyrolysis of selected pre-ceramic polymers and sol-gel techniques. Building upon the positive progress made in the membrane development study, we conducted an optimization study to develop an H{sub 2} selective SiC membrane with sufficient hydrothermal stability suitable for the WGS environment. In addition, mathematical simulation has been performed to compare the performance of the membrane reactor (MR) vs conventional packed bed reactor for WGS reaction. Our result demonstrates that >99.999% conversion can be accomplished via WGS-MR using the hydrogen selective membrane developed by us. Further, water/CO ratio can be reduced, and >97% hydrogen recovery and <200 ppm CO can be accomplished according to the mathematical simulation. Thus, we believe that the operating economics of WGS can be improved significantly based upon the proposed MR concept. In parallel, gas separations and hydrothermal and long-term-storage stability of the hydrogen selected membrane have been experimentally demonstrated using a pilot-scale tubular membrane under a simulated WGS environment.

  6. DFT study of the water gas shift reaction on Ni(111), Ni(100) and Ni(110) surfaces

    NASA Astrophysics Data System (ADS)

    Mohsenzadeh, Abas; Richards, Tobias; Bolton, Kim

    2016-02-01

    Density functional theory (DFT) calculations were used to study the water gas shift (WGS) reaction on Ni(111), Ni(100) and Ni(110) surfaces. The adsorption energy for ten species involved in the reaction together with activation barriers and reaction energies for the nine most important elementary steps were determined using the same model and DFT methods. The results reveal that these energies are sensitive to the surface structure. In spite of this, the WGS reaction occurs mainly via the direct (also referred to as redox) pathway with the CO + O → CO2 reaction as the rate determining step on all three surfaces. The activation barrier obtained for this rate limiting step decreases in the order Ni(110) > Ni(111) > Ni(100). Therefore, if O species are present on the surfaces then the WGS reaction is fastest on the Ni(100) surface. However, the barrier for desorption of H2O (which is the source of the O species) is lower than its dissociation reaction on the Ni(111) and Ni(100) surfaces, but not on the Ni(110) surface. Hence, at low H2O(g) pressures, the direct pathway on the Ni(110) surface will dominate and will be the rate limiting step. The calculations also show that the reason that the WGS reaction does not primarily occur via the formate pathway is that this species is a stable intermediate on all surfaces. The reactions studied here support the Brønsted-Evans-Polanyi (BEP) principles with an R2 value of 0.99.

  7. Effect of cesium on alcohol synthesis, water-gas shift reaction, and ester hydrogenolysis over copper-zinc oxide catalysts

    SciTech Connect

    Young, C.W.

    1987-01-01

    This study comprises three subjects: (1) the effects of cesium doping and water concentration in the synthesis gas on methanol synthesis rate and the water-gas shift (WGS) reaction; (2) the hydrogenolysis of alkyl esters; and (3) the effect of cesium on higher alcohol synthesis, as well as the investigation of the chain growth reaction in higher alcohol synthesis over the Cu/ZnO catalysts. A two-parameter kinetic model quantitatively demonstrated that the maximum rate of methanol synthesis is determined by the balance between the promotional effect of cesium and the retarding effect stemming from the blockage of hydrogen activing sites. Another six-parameter kinetic model, in which the methanol and WGS reactions were considered simultaneously, can account for methanol activity in the water dependence study. At higher water concentrations, the cesium-doped catalysts were more active than the undoped catalyst for methanol synthesis, which was quantitatively shown to be due to the promotion of the WGS reaction by the cesium doping. The inhibition effect that occurred at high water concentrations in methyl acetate hydrogenolysis is due to the blockage of hydrogen activating sites. In addition, the kinetics of hydrogenolysis of n-propyl acetate resulted in a -0.49 order with respect to n-propyl acetate and a +1.83 order to hydrogen, which are in fair agreement with those derived in terms of Langmuir-Hinshelwood type kinetics. The aldehydic species involved in the hydrogenolysis of esters was evidence by a isopropylamine trapping experiment.

  8. Activity and stability of nanostructured gold-cerium oxide catalysts for the water-gas shift reaction

    NASA Astrophysics Data System (ADS)

    Fu, Qi

    Advanced low-temperature water-gas shift (LTS) catalysts of high activity and stability are under development to produce essentially CO-free hydrogen to feed PEM fuel cells for power generation. Materials based on nanocrystalline cerium oxide (ceria) are among the most promising LTS catalysts. Understanding the structural properties relationship with the WGS activity is fundamentally important in order to rational design the catalysts. Various gold structures, such as metallic gold nanoparticles, cluster and cations were found in gold-ceria sample containing 4--8 at% gold. To discriminate between the various gold species, leaching of the gold-ceria in sodium cyanide was conducted. The metallic gold and all other gold species not in close association with ceria were removed by leaching. A small amount of gold remained in the leached samples. The exact content of non-leachable gold was a function of the parent catalyst properties. Similar data were collected from Pt-ceria samples. STEM or HRTEM, coupled with EDX showed no gold or platinum particles remaining; only what appeared to be very fine clusters or atomically dispersed gold or platinum. Cationic gold or platinum was identified in these samples by XPS. The unexpected finding was that the catalytic activity of the leached samples was similar or slightly better than that of the parent catalyst after removal of the metallic gold or platinum particles by cyanide leaching. Thus, metallic nanoparticles are not necessary; they are mere spectators in the water-gas shift reaction. Nonmetallic gold or platinum species strongly associated with surface cerium-oxygen groups are responsible for the activity, since the extra gold or platinum present in the parent material does not increase the reaction rate; nor does it change the activation energy of the reaction. The importance of the oxide support properties became clear by this work. The amount of gold or platinum retained in active form depends on the surface properties of ceria. Addition of certain metals and dopants significantly enhances the reducibility of ceria. Temperature-programmed reduction of metal-ceria samples performed with H2 or CO, identified that the surface oxygen of ceria is weakened by the presence of the metal. The reduction of oxygen of gold-ceria by CO begins at ambient temperatures, while the onset of surface reduction of the metal-free Ce(La)Ox is at 200--250C. The WGS activity and reducibility both depend on the preparation of ceria, the dispersion of the metal additive and ceria particle size. However, no dependence on the metal particle size was found. (Abstract shortened by UMI.)

  9. A theoretical study of surface-structural sensitivity of the reverse water-gas shift reaction over Cu( hkl) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Gui-Chang; Jiang, Ling; Pang, Xian-Yong; Cai, Zun-Sheng; Pan, Yin-Ming; Zhao, Xue-Zhuang; Morikawa, Yoshitada; Nakamura, Junji

    2003-10-01

    The surface-structural sensitivity of the reverse water-gas shift (RWGS) reaction (CO 2 + H 2 ? CO + H 2O) over the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces has been studied by first-principle density functional calculations together with the UBI-QEP approach. Cluster models of the surface have been employed to simulate the adsorption of CO 2, H 2, H, O, OH, CO, and H 2O on the Cu( hkl) surfaces at low coverage. This sensitivity is determined by the difference in the activation barriers. It can be noticed that the most likely rate-determining step in RWGS reaction is the CO 2 dissociative adsorption, namely CO 2,g ? CO s + O s. The trend in the calculated activation barriers for the reaction of CO 2 dissociative adsorption follows the order of Cu(1 1 0) < Cu(1 0 0) < Cu(1 1 1), suggesting that the most efficient crystal surface for catalyzing RWGS reaction by copper is Cu(1 1 0), and the more densely packed Cu(1 1 1) surface is the least active among the Cu( hkl) surfaces studied here. As expected, the activation barriers for the recombinative reactions over Cu( hkl) are in the order of Cu(1 1 0) > Cu(1 0 0) > Cu(1 1 1), just opposite to the dissociative reactions. The interesting thing is that there is a good correlation between the adsorption bond length and the adsorption energy: The preferred adsorption site is the one with the shortest adsorption bond length. The present calculations are in good agreement with experimental observations.

  10. An improved microkinetic model for the water gas shift reaction on copper

    NASA Astrophysics Data System (ADS)

    Callaghan, Caitlin; Fishtik, Ilie; Datta, Ravindra; Carpenter, Michael; Chmielewski, Matthew; Lugo, Anibal

    2003-09-01

    A previously developed 13 elementary step microkinetic mechanism for the WGSR on Cu(1 1 1) [Surf. Sci. 512 (2002) 229] is extended by including four new elementary steps. Employing a systematic reaction route analysis, the microkinetic model is further analyzed, simplified and reduced. It is shown that from the total of 70 possible overall reaction routes (RRs), the kinetics of the WGS reaction on Cu is still dominated by only three RRs. Two of them, namely, the formate and associative RRs, are dominant at lower temperatures. The third one, referred to as a modified redox RR, is dominant at higher temperatures. Utilizing the quasi-equilibrium and steady-state assumptions, the microkinetic model is further reduced to a two-step mechanism similar to that of Temkin. The corresponding explicit rate expression with all parameters predicted a priori provides excellent agreement with the complete microkinetic model as well as with new experimental data provided here.

  11. Reaction mechanism of the reverse water-gas shift reaction using first-row middle transition metal catalysts L'M (M = Fe, Mn, Co): a computational study.

    PubMed

    Liu, Cong; Cundari, Thomas R; Wilson, Angela K

    2011-09-19

    The mechanism of the reverse water-gas shift reaction (CO(2) + H(2) ? CO + H(2)O) was investigated using the 3d transition metal complexes L'M (M = Fe, Mn, and Co, L' = parent ?-diketiminate). The thermodynamics and reaction barriers of the elementary reaction pathways were studied with the B3LYP density functional and two different basis sets: 6-311+G(d) and aug-cc-pVTZ. Plausible reactants, intermediates, transition states, and products were modeled, with different conformers and multiplicities for each identified. Different reaction pathways and side reactions were also considered. Reaction Gibbs free energies and activation energies for all steps were determined for each transition metal. Calculations indicate that the most desirable mechanism involves mostly monometallic complexes. Among the three catalysts modeled, the Mn complex shows the most favorable catalytic properties. Considering the individual reaction barriers, the Fe complex shows the lowest barrier for activation of CO(2). PMID:21838224

  12. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K. T. Liu

    2004-02-19

    Two process schemes have been investigated by us for the use of hydrotalcites we prepared as CO{sub 2} adsorbents to enhance water gas shift (WGS) reaction: Case I involves the adsorption enhanced WGS packed bed reactor and Case II involves the adsorption enhanced WGS membrane reactor. Both cases will achieve the same objective as the hydrotalcite membrane reactor: i.e., improving the WGS reactor efficiency via the concomitant removal of CO{sub 2} for sequestration. In this report a detailed investigation of the design characteristics and performance of Case II, termed the Hybrid Adsorbent-Membrane Reactor (HAMR), is presented. The HAMR system includes a packed-bed catalytic membrane reactor (hydrogen selective) coupling the WGS reaction (in a porous hydrogen selective membrane) with CO{sub 2} removal with an adsorbent in the permeate side. The reactor characteristics have been investigated for a range of permeance and selectivity relevant to the aforementioned application. The HAMR system shows enhanced CO conversion, hydrogen yield, and product purity, and provides good promise for reducing the hostile operating conditions of conventional WGS reactors, and for meeting the CO{sub 2} sequestration objective. In the next quarterly report we will present the simulation result for Case I as well as the progress on hydrotalcite membrane synthesis.

  13. Water-Gas Shift and CO Methanation Reactions over Ni-CeO2(111) Catalysts

    SciTech Connect

    S Senanayake; J Evans; S Agnoli; L Barrio; T Chen; J Hrbek; J Rodriguez

    2011-12-31

    X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO{sub 2}(111) surfaces. Upon adsorption on CeO{sub 2}(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500-800 K) leads to partial reduction of the ceria substrate with the formation of Ni{sup 2+} species that exists as NiO and/or Ce{sub 1-x}Ni{sub x}O{sub 2-y}. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO{sub 2}(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce{sup +3} cations, CO dissociates on the surface at 300 K forming NiC{sub x} compounds that may be involved in the formation of CH{sub 4} at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO{sub 2}(111) surfaces are able to catalyze the production of methane from CO and H{sub 2}, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO{sub 2}(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water-gas shift reaction.

  14. Water-Gas Shift and CO Methanation Reactions over Ni-CeO2(111) Catalysts

    SciTech Connect

    Senanayake, Sanjaya D; Evans, Jaime; Agnoli, Stefano; Barrio, Laura; Chen, Tsung-Liang; Hrbek, Jan; Radriguez, Jose

    2011-01-01

    X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO2(111) surfaces. Upon adsorption on CeO2(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500 800 K) leads to partial reduction of the ceria substrate with the formation of Ni2? species that exists as NiO and/or Ce1-xNixO2-y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO2(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce?3 cations, CO dissociates on the surface at 300 K forming NiCx compounds that may be involved in the formation of CH4 at higher temperatures. At medium and large Ni coverages ([0.3 ML), the Ni/CeO2(111) surfaces are able to catalyze the production of methane from CO and H2, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (\\0.3 ML), the Ni/CeO2(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water gas shift reaction.

  15. Probing the Reaction Intermediates for the Watergas Shift over Inverse CeOx / Au(1 1 1) Catalysts

    SciTech Connect

    Senanayake, S.; Stacchiola, D; Evans, J; Estrella, M; Barrio, L; Perez, M; Hrbek, J; Rodriguez, J

    2010-01-01

    The water-gas shift (WGS) is an important reaction for the production of molecular H{sub 2} from CO and H{sub 2}O. An inverse CeO{sub x}/Au(1 1 1) catalyst exhibits a very good WGS activity, better than that of copper surfaces or Cu nanoparticles dispersed on a ZnO(0 0 0 {bar 1}) substrate which model current WGS industrial catalysts. In this work we report on intermediates likely to arise during the CO + H{sub 2}O reaction over CeO{sub x}/Au(1 1 1) using soft X-ray photoemission (sXPS) and near-edge X-ray absorption fine structure (NEXAFS). Several potential intermediates including formates (HCOO), carbonates (CO{sub 3}) and carboxylates (HOCO) are considered. Adsorption of HCOOH and CO{sub 2} is used to create both HCOO and CO{sub 3} on the CeO{sub x}/Au(1 1 1) surface, respectively. HCOO appears to have greater stability with desorption temperatures up to 600 K while CO{sub 3} only survives on the surface up to 300 K. On the CeO{sub x}/Au(1 1 1) catalysts, the presence of Ce{sup 3+} leads to the dissociation of H{sub 2}O to give OH groups. We demonstrate experimentally that the OH species are stable on the surface up to 600 K and interact with CO to yield weakly bound intermediates. When there is an abundance of Ce{sup 4+}, the OH concentration is diminished and the likely intermediates are carbonates. As the surface defects are increased and the Ce{sup 3+}/Ce{sup 4+} ratio grows, the OH concentration also grows and both carbonate and formate species are observed on the surface after dosing CO to H{sub 2}O/CeO{sub x}/Au(1 1 1). The addition of ceria nanoparticles to Au(1 1 1) is essential to generate an active WGS catalyst and to increase the production and stability of key reaction intermediates (OH, HCOO and CO{sub 3}).

  16. Probing the Reaction Intermediates for the Water-Gas Shift over Inverse CeOx/Au(111) Catalysts

    SciTech Connect

    Rodriguez, J.A.; Senanayake, S.D.; Stacchiola, D.; Evans, J.; Estrella, M.; Barrio-Pliego, L.; Prez, M.; Hrbek, J.

    2010-05-04

    The water-gas shift (WGS) is an important reaction for the production of molecular H{sub 2} from CO and H{sub 2}O. An inverse CeO{sub x}/Au(1 1 1) catalyst exhibits a very good WGS activity, better than that of copper surfaces or Cu nanoparticles dispersed on a ZnO(0 0 0 {bar 1}) substrate which model current WGS industrial catalysts. In this work we report on intermediates likely to arise during the CO + H{sub 2}O reaction over CeO{sub x}/Au(1 1 1) using soft X-ray photoemission (sXPS) and near-edge X-ray absorption fine structure (NEXAFS). Several potential intermediates including formates (HCOO), carbonates (CO{sub 3}) and carboxylates (HOCO) are considered. Adsorption of HCOOH and CO{sub 2} is used to create both HCOO and CO{sub 3} on the CeO{sub x}/Au(1 1 1) surface, respectively. HCOO appears to have greater stability with desorption temperatures up to 600 K while CO{sub 3} only survives on the surface up to 300 K. On the CeO{sub x}/Au(1 1 1) catalysts, the presence of Ce{sup 3+} leads to the dissociation of H{sub 2}O to give OH groups. We demonstrate experimentally that the OH species are stable on the surface up to 600 K and interact with CO to yield weakly bound intermediates. When there is an abundance of Ce{sup 4+}, the OH concentration is diminished and the likely intermediates are carbonates. As the surface defects are increased and the Ce{sup 3+}/Ce{sup 4+} ratio grows, the OH concentration also grows and both carbonate and formate species are observed on the surface after dosing CO to H{sub 2}O/CeO{sub x}/Au(1 1 1). The addition of ceria nanoparticles to Au(1 1 1) is essential to generate an active WGS catalyst and to increase the production and stability of key reaction intermediates (OH, HCOO and CO{sub 3}).

  17. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS-SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2005-07-15

    A high temperature membrane reactor (MR) has been developed to enhance the water-gas-shift (WGS) reaction efficiency with concomitant CO{sub 2} removal for sequestration. This improved WGS-MR with CO{sub 2} recovery capability is ideally suitable for integration into the Integrated Gasification Combined-Cycle (IGCC) power generation system. Two different CO{sub 2}-affinity materials were selected in this study. The Mg-Al-CO{sub 3}-layered double hydroxide (LDH) was investigated as an adsorbent or a membrane for CO{sub 2} separation. The adsorption isotherm and intraparticle diffusivity for the LDH-based adsorbent were experimentally determined, and suitable for low temperature shift (LTS) of WGS. The LDH-based membranes were synthesized using our commercial ceramic membranes as substrate. These experimental membranes were characterized comprehensively in terms of their morphology, and CO{sub 2} permeance and selectivity to demonstrate the technical feasibility. In parallel, an alternative material-base membrane, carbonaceous membrane developed by us, was characterized, which also demonstrated enhanced CO{sub 2} selectivity at the LTS-WGS condition. With optimization on membrane defect reduction, these two types of membrane could be used commercially as CO{sub 2}-affinity membranes for the proposed application. Based upon the unique CO{sub 2} affinity of the LDHs at the LTS/WGS environment, we developed an innovative membrane reactor, Hybrid Adsorption and Membrane Reactor (HAMR), to achieve {approx}100% CO conversion, produce a high purity hydrogen product and deliver a concentrated CO{sub 2} stream for disposal. A mathematical model was developed to simulate this unique one -step process. Finally a benchtop reactor was employed to generate experimental data, which were consistent with the prediction from the HAMR mathematical model. In summary, the project objective, enhancing WGS efficiency for hydrogen production with concomitant CO{sub 2} removal for sequestration, has been theoretically and experimentally demonstrated via the developed one-step reactor, HAMR. Future development on reactor scale up and field testing is recommended.

  18. Microwave irradiation assisted rapid synthesis of Fe-Ru bimetallic nanoparticles and their catalytic properties in water-gas shift reaction

    SciTech Connect

    Du Jianquan; Zhang Yong; Tian Tian; Yan Shancheng; Wang Haitao

    2009-06-03

    Fe-Ru bimetallic nanoparticles were prepared by a microwave irradiation assisted glycol reduction method using poly-N-vinyl-2-pyrrolidone (PVP) as protective agent. The structure and morphology of the nanoparticles were characterized by X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDXA) and high-resolution transmission electron microscopy (HRTEM). EDXA and XRD analysis confirmed the presence of Fe and Ru. The bimetallic nanoparticles were subsequently loaded onto an MgAl{sub 2}O{sub 4} supporter with K{sub 2}O as promoters and used as catalyst for water-gas shift reaction. The results indicated that the FeRu bimetallic nanoparticles exhibit high catalytic activity for water-gas shift reaction due to the synergistic effect between iron and ruthenium. Potassium oxide can enhance the CO selectivity of the catalyst significantly besides increasing the catalyst activity.

  19. Supported Copper, Nickel and Copper-Nickel Nanoparticle Catalysts for Low Temperature Water-Gas-Shift Reaction

    NASA Astrophysics Data System (ADS)

    Lin, Jiann-Horng

    Hydrogen is being considered worldwide as a future replacement for gasoline, diesel fuel, natural gas in both the transportation and non-transportation sectors. Hydrogen is a versatile energy carrier that can be produced from a variety of widely available primary energy sources, including coal, natural gas, biomass, solar, wind, and nuclear power. Coal, the most abundant fossil fuel on the planet, is being looked at as the possible future major source of H2, due to the development of the integrated gasification combined cycle (IGCC) and integrated gasification fuel cell technologies (IGFC). The gasification of coal produces syngas consisting of predominately carbon monoxide and hydrogen with some remaining hydrocarbons, carbon dioxide and water. Then, the water-gas shift reaction is used to convert CO to CO2 and additional hydrogen. The present work describes the synthesis of model Cu, Ni and Cu-Ni catalysts prepared from metal colloids, and compares their behavior in the WGS reaction to that of traditional impregnation catalysts. Initially, we systematically explored the performance of traditional Cu, Ni and Cu-Ni WGS catalysts made by impregnation methods. Various bimetallic Cu-Ni catalysts were prepared by supported impregnation and compared to monometallic Cu and Ni catalysts. The presence of Cu in bimetallic catalysts suppressed undesirable methanation side reaction, while the Ni component was important for high WGS activity. Colloidal Cu, Ni and Cu-Ni alloy nanoparticles obtained by chemical reduction were deposited onto alumina to prepare supported catalysts. The resulting Cu and Ni nanoparticle catalysts were found to be 2.5 times more active in the WGS reaction per unit mass of active metal as compared to catalysts prepared by the conventional impregnation technique. The powder XRD and HAADF-STEM provided evidence supporting the formation of Cu-Ni particles containing the Cu core and Cu-Ni alloy shell. The XPS data indicated surface segregation of Cu in the bimetallic Cu-Ni catalysts after reduction. The colloidal Cu5Ni5 alloy catalyst exhibited the WGS reaction rate that was higher than that observed over colloidal Cu and Ni catalysts indicating for the very first time a favorable bimetallic effect for the Cu-Ni system. The presence of Cu in these bimetallic catalysts induced favorable structural and electronic effects not only for enhancing the WGS activity, but also for suppressing methane yield. Bimetallic Cu-Ni catalysts possessing a core-shell structure were synthesized that provided important insights into their structure-activity relationships in the WGS reaction. We employed a successive reduction route to synthesize Cu Ni and Ni Cu core-shell nanoparticles and deposited them onto alumina support to obtain supported bimetallic catalysts. The powder XRD patterns, CO chemisorption data, and UV-vis spectra indicated the formation of core-shell structures in the bimetallic Cu-Ni nanoparticles. Cu Ni catalysts showed similar WGS activities to supported Ni catalysts but lower methanation activity. Suppressed methanation activity observed for Cu Ni nanoparticles may be due to Cu segregation to the surface. Supported Ni Cu catalysts displayed WGS activity comparable to supported Cu catalysts. Therefore, these findings strongly suggested that supported Cu, Ni and Cu-Ni alloy nanoparticle catalysts prepared from metal colloids are very promising as highly active WGS catalysts.

  20. The role of copper in catalytic performance of a Fe-Cu-Al-O catalyst for water gas shift reaction.

    PubMed

    Ye, Yingchun; Wang, Lei; Zhang, Shiran; Zhu, Yuan; Shan, Junjun; Tao, Franklin Feng

    2013-05-14

    A Fe-Cu-Al-O water gas shift catalyst with a Fe : Cu atomic ratio of 4 : 1 upon pretreatment at 350 C in H2 exhibits a conversion higher than a physical mixture of Fe-Al-O and Cu-Al-O by ~40% over a temperature range of 300 C-450 C. In situ ambient pressure X-ray photoelectron spectroscopy studies suggest that the surface region of Fe-Cu-Al-O was restructured into a double-layer structure consisting of a surface layer of Fe3O4 and a metallic Cu layer below it upon pretreatment at 350 C. The strong metal (Cu)-oxide (Fe3O4) interface effect of this double layer structure enhances the catalytic activity of Fe3O4 in WGS. PMID:23323268

  1. The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)

    NASA Astrophysics Data System (ADS)

    Nakamura, I.; Fujitani, T.; Uchijima, T.; Nakamura, J.

    1998-03-01

    The catalytic activity of Zn vapor-deposited Cu(100) and Cu(110) surfaces for methanol synthesis by the hydrogenation of CO 2 and the reverse water-gas shift reaction were studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). At a reaction temperature of 523 K, no promotional effect of Zn was observed for the methanol synthesis on both Zn/Cu(100) and Zn/Cu(110). The results were quite different from those for Zn/Cu(111), on which a significant promotion of methanol synthesis activity appeared to be due to the deposition of Zn, indicating that the promotional effect of Zn was sensitive to the surface structure of Cu. However, hysteresis was observed in the catalytic activity for methanol synthesis over the Zn/Cu(110) surface upon heating above 543 K in the reaction mixture. The activity became twice that measured before heating, which was close to the methanol synthesis activity of Zn/Cu(111) at the same Zn coverage. On the other hand, no such hysteresis was observed for the reverse water-gas shift reaction on Zn/Cu(110), indicating that the active site for methanol synthesis was not identical to that for the reverse water-gas shift reaction. In the post-reaction surface analysis, formate species was detected on both Zn/Cu(100) and Zn/Cu(110), whose coverage increased with increasing Zn coverage at 0< ΘZn<0.2. No correlation between the formate coverage and the methanol synthesis activity was obtained, which was in contrast to the results for Zn/Cu(111). Thus, the structure sensitivity observed in the catalytic activity of methanol synthesis over Zn-deposited Cu surfaces is ascribed to the significant difference in the reactivity of the formate intermediate.

  2. Theoretical study of gas-phase reactions of Fe(CO){sub 5} with OH{sup {minus}} and their relevance for the water gas shift reaction

    SciTech Connect

    Torrent, M.; Sola, M.; Frenking, G.

    1999-07-19

    Revision of the homogeneously Fe(CO){sub 5}-catalyzed water gas shift reaction in the gas phase has been performed by means of quantum chemical calculations using gradient-corrected density functional theory (B3LYP) and ab initio methods at the CCSD(T) level. The classically assumed reaction path has been scrutinized step by step, and enlarged with novel mechanistic proposals. The calculations lend additional credit to some of the previously accepted steps in the catalytic cycle, such as the initial attack of OH{sup {minus}} to Fe(CO){sub 5} and also to the recently accepted decarboxylation of (CO){sub 4}FeCOOH{sup {minus}} (via a concerted mechanism involving a four-centered transition state), as well as to the acidification of the metal hydride (CO){sub 4}Fe{sub 4}H{sub {minus}} with water to yield the dihydride (CO){sub 4}FeH{sub 2}. The present investigation also examines in terms of energies and activation barriers the existence/participation of new intermediates (in particular, a metalloformate species, a water-hydride adduct, and a dihydrogen complex), not mentioned in prior studies. Finally, a transition-metal-containing S{sub N}2-type reaction is explored for the last stages of this chemical process as a mechanistic alternative to regenerate the starting catalyst.

  3. Advanced Water-Gas Shift Membrane Reactor

    SciTech Connect

    Sean Emerson; Thomas Vanderspurt; Susanne Opalka; Rakesh Radhakrishnan; Rhonda Willigan

    2009-01-07

    The overall objectives for this project were: (1) to identify a suitable PdCu tri-metallic alloy membrane with high stability and commercially relevant hydrogen permeation in the presence of trace amounts of carbon monoxide and sulfur; and (2) to identify and synthesize a water gas shift catalyst with a high operating life that is sulfur and chlorine tolerant at low concentrations of these impurities. This work successfully achieved the first project objective to identify a suitable PdCu tri-metallic alloy membrane composition, Pd{sub 0.47}Cu{sub 0.52}G5{sub 0.01}, that was selected based on atomistic and thermodynamic modeling alone. The second objective was partially successful in that catalysts were identified and evaluated that can withstand sulfur in high concentrations and at high pressures, but a long operating life was not achieved at the end of the project. From the limited durability testing it appears that the best catalyst, Pt-Re/Ce{sub 0.333}Zr{sub 0.333}E4{sub 0.333}O{sub 2}, is unable to maintain a long operating life at space velocities of 200,000 h{sup -1}. The reasons for the low durability do not appear to be related to the high concentrations of H{sub 2}S, but rather due to the high operating pressure and the influence the pressure has on the WGS reaction at this space velocity.

  4. Activity of CeOx and TiOx nanoparticles grown on Au(111) in the water-gas shift reaction.

    PubMed

    Rodriguez, J A; Ma, S; Liu, P; Hrbek, J; Evans, J; Prez, M

    2007-12-14

    The high performance of Au-CeO2 and Au-TiO2 catalysts in the water-gas shift (WGS) reaction (H2O + CO-->H2 + CO2) relies heavily on the direct participation of the oxide in the catalytic process. Although clean Au(111) is not catalytically active for the WGS, gold surfaces that are 20 to 30% covered by ceria or titania nanoparticles have activities comparable to those of good WGS catalysts such as Cu(111) or Cu(100). In TiO(2-x)/Au(111) and CeO(2-x)/Au(111), water dissociates on O vacancies of the oxide nanoparticles, CO adsorbs on Au sites located nearby, and subsequent reaction steps take place at the metal-oxide interface. In these inverse catalysts, the moderate chemical activity of bulk gold is coupled to that of a more reactive oxide. PMID:18079397

  5. Pulse studies to decipher the role of surface morphology in CuO/CeO? nanocatalysts for the water gas shift reaction

    SciTech Connect

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H?O ? CO?) was studied over CuO/CeO? catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO? (ns) exhibited a substantially better activity than CuO/CeO? (nc). The higher activity was associated with the unique properties of CuO/CeO? (ns), such as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce? in CeO? (ns).

  6. Atomically Dispersed Au-(OH)x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction

    SciTech Connect

    Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

    2013-03-27

    We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au–O–TiOx sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this “excess” gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

  7. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    DOE PAGESBeta

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), suchmore » as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).« less

  8. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    SciTech Connect

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), such as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).

  9. On the Importance of the Associative Carboxyl Mechanism for the Water-Gas Shift Reaction at Pt/CeO2 Interface Sites

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-03-06

    Periodic density functional theory calculations and microkinetic modeling are used to investigate the associative carboxyl pathways of the water-gas shift (WGS) reaction at the Pt/CeO2 (111) interface. Analysis of a microkinetic model based on parameters obtained from first principles suggests that the turnover frequencies for the CO-assisted associative carboxyl mechanism are comparable to experimental results. However, this microkinetic model containing various associative carboxyl pathways at interface sites cannot explain the experimentally observed activation barriers and reaction orders of Pt/CeO2 catalysts. Considering furthermore that a model of an associative carboxyl mechanism with redox regeneration, also derived from first principles and recently published by us, accurately predicts all kinetic parameters while displaying a 2 orders of magnitude higher turnover frequency, we conclude that at Pt/CeO2 interface sites, the WGS reaction follows a bifunctional Mars-van Krevelen mechanism in which support oxygen vacancies facilitate water dissociation.

  10. Development of Ni-Mo/Al2O3 catalyst for reverse water gas shift (RWGS) reaction.

    PubMed

    Kharaji, Abolfazl Gharibi; Shariati, Ahmad; Ostadi, Mohammad

    2014-09-01

    In the present study, Mo/Al2O3 catalyst was prepared using impregnation method. Then it was promoted with Ni ions to produce Ni-Mo/Al2O3 catalyst. The structures of the catalysts were studied using X-ray diffraction (XRD), Energy dispersive X-ray (EDAX), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), CO chemisorption, temperature programmed reduction of hydrogen (H2-TPR) and scanning electron microscope (SEM) techniques. Catalytic performances of the two catalysts were investigated in a fixed-bed reactor for RWGS reaction. The results indicated that addition of nickel promoter to Mo/Al2O3 catalyst enhances its activity. It is reasonable for the electron deficient state of the Ni species and existence of NiMoO4 phase to possess high activity in RWGS reaction. Stability test of Ni-Mo/Al2O3 catalyst was carried out in a fixed bed reactor and a high CO2 conversion for 60 h time on stream was demonstrated. This study introduces a new catalyst, Ni-Mo/Al2O3, with high activity and stability for RWGS reaction. PMID:25924339

  11. Gold(III)-CO and gold(III)-CO2 complexes and their role in the water-gas shift reaction

    PubMed Central

    Roşca, Dragoş-Adrian; Fernandez-Cestau, Julio; Morris, James; Wright, Joseph A.; Bochmann, Manfred

    2015-01-01

    The water-gas shift (WGS) reaction is an important process for the generation of hydrogen. Heterogeneous gold catalysts exhibit good WGS activity, but the nature of the active site, the oxidation state, and competing reaction mechanisms are very much matters of debate. Homogeneous gold WGS systems that could shed light on the mechanism are conspicuous by their absence: gold(I)–CO is inactive and gold(III)–CO complexes were unknown. We report the synthesis of the first example of an isolable CO complex of Au(III). Its reactivity demonstrates fundamental differences between the CO adducts of the neighboring d8 ions Pt(II) and Au(III): whereas Pt(II)-CO is stable to moisture, Au(III)–CO compounds are extremely susceptible to nucleophilic attack and show WGS reactivity at low temperature. The key to understanding these dramatic differences is the donation/back-donation ratio of the M–CO bond: gold-CO shows substantially less back-bonding than Pt-CO, irrespective of closely similar ν(CO) frequencies. Key WGS intermediates include the gold-CO2 complex [(C^N^C)Au]2(μ-CO2), which reductively eliminates CO2. The species identified here are in accord with Au(III) as active species and a carboxylate WGS mechanism. PMID:26601313

  12. Genesis and Evolution of Surface Species during Pt Atomic Layer Deposition on Oxide Supports Characterized by in Situ XAFS Analysis and Water-Gas Shift Reaction

    SciTech Connect

    Setthapun, Worajit; Williams, W. Damion; Kim, Seung Min; Feng, Hao; Elam, Jeffrey W.; Rabuffetti, Federico A.; Poeppelmeier, Kenneth R.; Stair, Peter C.; Stach, Eric A.; Ribeiro, Fabio H.; Miller, Jeffrey T.; Marshall, Christopher L.

    2010-06-03

    Platinum atomic layer deposition (ALD) using MeCpPtMe? was employed to prepare high loadings of uniform-sized, 1-2 nm Pt nanoparticles on high surface area Al?O?, TiO?, and SrTiO? supports. X-ray absorption fine structure was utilized to monitor the changes in the Pt species during each step of the synthesis. The temperature, precursor exposure time, treatment gas, and number of ALD cycles were found to affect the Pt particle size and density. Lower-temperature MeCpPtMe? adsorption yielded smaller particles due to reduced thermal decomposition. A 300 C air treatment of the adsorbed MeCpPtMe? leads to PtO. In subsequent ALD cycles, the MeCpPtMe? reduces the PtO to metallic Pt in the ratio of one precursor molecule per PtO. A 200 C H? treatment of the adsorbed MeCpPtMe? leads to the formation of 1-2 nm, metallic Pt nanoparticles. During subsequent ALD cycles, MeCpPtMe? adsorbs on the support, which, upon reduction, yields additional Pt nanoparticles with a minimal increase in size of the previously formed nanoparticles. The catalysts produced by ALD had identical water-gas shift reaction rates and reaction kinetics to those of Pt catalysts prepared by standard solution methods. ALD synthesis of catalytic nanoparticles is an attractive method for preparing novel model and practical catalysts.

  13. Theoretical studies on the catalysis of the reverse water-gas shift reaction using first-row transition metal beta-diketiminato complexes.

    PubMed

    Liu, Cong; Munjanja, Lloyd; Cundari, Thomas R; Wilson, Angela K

    2010-06-01

    The reverse water-gas shift reaction CO(2) + H(2) --> H(2)O + CO has been investigated using a set of homogeneous catalyst models L'M(I) (L' = beta-diketiminate, C(3)N(2)H(5)(-); M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). The thermodynamics of prototypical reaction pathways were simulated at two levels of theory: B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ. The modeled catalytic reaction has been considered in the following steps: coordination of CO(2) by the catalyst to generate a carbon dioxide complex, L'M(CO(2)); scission of L'M(CO(2)) to yield L'M(CO) and L'M(O); L'M(O) hydrogenation to form L'M(H(2)O). The final products, H(2)O and CO, were obtained from the dissociation of L'M(H(2)O) and L'M(CO). All of the reactants, intermediates, and products were modeled, where different possible conformers and multiplicities were identified and considered as potential minima. The reaction enthalpy DeltaH, of all steps for each catalyst as a function of transition metal have been determined. The Mn and Fe catalysts show more thermodynamically accessible pathways than the other catalyst models studied. The overall reaction enthalpy has been determined not only by B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ but also via a more rigorous ab initio electron-correlation-based approach, the correlation consistent Composite Approach (ccCA). PMID:20462216

  14. Interaction of CO with OH on Au(111): HCOO, CO3, and HOCO as Key Intermediates in the Water-Gas Shift Reaction

    SciTech Connect

    Senanayake, S.; Stacchiola, D; Liu, P; Mullins, C; Hrbek, J; Rodriguez, J

    2009-01-01

    We have investigated the role of formate (HCOO), carbonate (CO{sub 3}), and carboxyl (HOCO) species as possible intermediates in the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction on Au(111) using synchrotron-based core level photoemission, near-edge X-ray absorption fine structure (NEXAFS), and infrared absorption spectroscopy (IR). Adsorbed HCOO, CO{sub 3}, and OH species were prepared by adsorbing formic acid, carbon dioxide, and water on a Au(111) surface precovered with 0.2 ML of atomic oxygen, respectively. HCOOH interacts weakly with Au(111), but on O/Au(111) it dissociates its acidic H to yield adsorbed formate. The results of NEXAFS, IR, and density-functional calculations indicate that the formate adopts a bidentate configuration on Au(111). Since the HCOO groups are stable on Au(111) up to temperatures near 350 K, it is not likely that formate is a key intermediate for the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction at low temperatures. In fact, the formation of this species could lead eventually to surface poisoning. When compared to a formate species, a carbonate species formed by the reaction of CO{sub 2} with O/Au(111) has low stability, decomposing at temperatures between 100 and 125 K, and should not poison the gold surface. Neither HCOO nor CO{sub 3} was detected during the reaction of CO with OH on Au(111) at 90-120 K. The results of photoemission and IR spectroscopy point to HO {leftrightarrow} CO interactions, consistent with the formation of an unstable HOCO intermediate which has a very short lifetime on the gold surface. The possible mechanism for the low-temperature water-gas shift on gold catalysts is discussed in light of these results.

  15. On the Importance of MetalOxide Interface Sites for the WaterGas Shift Reaction Over Pt/CeO2 Catalysts

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-01-01

    The mechanism of watergas shift reaction at the three-phase boundary of Pt/CeO2 catalysts has been investigated using density functional theory and microkinetic modeling to better understand the importance of metaloxide interface sites in heterogeneous catalysis. Analysis of a microkinetic model based on parameters obtained from first principles suggests that both the Redox pathway and the Associative carboxyl pathway with redox regeneration could operate on Pt/CeO2 catalysts. Although (1) only few interfacial Pt atoms are found to be catalytically active at low temperatures due to strong adsorption of CO and (2) interfacial OH bond breakage is difficult due to the high reducibility of ceria, interface sites are 23 orders of magnitude more active than Pt (1 1 1) and stepped Pt surface sites and therefore effectively determine the overall activity of Pt/CeO2. The high activity of Pt/CeO2 interface sites originates from a significantly enhanced water activation and dissociation at interfacial oxygen vacancies.

  16. CO{sub 2} SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS-SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO{sub 2}

    SciTech Connect

    Paul K. T. Liu

    2005-01-31

    Our CO{sub 2}-affinity material synthesis activities thus far have offered two base materials suitable for hydrogen production via low temperature water gas shift reaction (LTS-WGS) with concomitant removal of CO{sub 2} for sequestration. They include (i) a nanoporous CO{sub 2}-affinity membrane and (ii) a hydrotalcite based CO-affinity adsorbent. These two materials offer a commercially viable opportunity for implementing an innovative process concept termed the hybrid adsorbent-membrane reactor (HAMR) for LTS-WGS, proposed by us in a previous quarterly report. A complete mathematical model has been developed in this quarter to describe the HAMR system, which offers process flexibility to incorporate both catalysts and adsorbents in the reactor as well as permeate sides. In comparison with the preliminary mathematical model we reported previously, this improved model incorporates ''time'' as an independent variable to realistically simulate the unsteady state nature of the adsorptive portion of the process. In the next quarterly report, we will complete the simulation to demonstrate the potential benefit of the proposed process based upon the performance parameters experimentally obtained from the CO{sub 2}-affinity adsorbent and membrane developed from this project.

  17. Genesis and evolution of surface species during Pt atomic layer deposition on oxide supports characterized by in-situ XAFS analysis and water-gas shift reaction.

    SciTech Connect

    Setthapun, W.; Williams, W.; Kim, S.; Feng, H.; Elam, J.; Rabuffetti, F.; Poeppelmeier, K.; Stair, P.; Stach, E.; Ribeiro, F.; Miller, J.; Marshall, C.; Northwestern Univ.; Purdue Univ.

    2010-06-03

    Platinum atomic layer deposition (ALD) using MeCpPtMe{sub 3} was employed to prepare high loadings of uniform-sized, 1-2 nm Pt nanoparticles on high surface area Al{sub 2}O{sub 3}, TiO{sub 2}, and SrTiO{sub 3} supports. X-ray absorption fine structure was utilized to monitor the changes in the Pt species during each step of the synthesis. The temperature, precursor exposure time, treatment gas, and number of ALD cycles were found to affect the Pt particle size and density. Lower-temperature MeCpPtMe{sub 3} adsorption yielded smaller particles due to reduced thermal decomposition. A 300 C air treatment of the adsorbed MeCpPtMe{sub 3} leads to PtO. In subsequent ALD cycles, the MeCpPtMe{sub 3} reduces the PtO to metallic Pt in the ratio of one precursor molecule per PtO. A 200 C H{sub 2} treatment of the adsorbed MeCpPtMe{sub 3} leads to the formation of 1-2 nm, metallic Pt nanoparticles. During subsequent ALD cycles, MeCpPtMe{sub 3} adsorbs on the support, which, upon reduction, yields additional Pt nanoparticles with a minimal increase in size of the previously formed nanoparticles. The catalysts produced by ALD had identical water-gas shift reaction rates and reaction kinetics to those of Pt catalysts prepared by standard solution methods. ALD synthesis of catalytic nanoparticles is an attractive method for preparing novel model and practical catalysts.

  18. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    SciTech Connect

    Barrio, L.; Kubacka, A; Zhou, G; Estrella, M; Martinez-Arias, A; Hanson, J; Fernandez-Garcia, M; Rodriguez, J

    2010-01-01

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni-O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate-carbonate route is operative for the production of hydrogen.

  19. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    SciTech Connect

    Rodriguez, J.A.; Barrio, L.; Kubacka, A.; Zhou, G.; Estrella, M.; Martı nez-Arias, A.; Hanson, J.C.; Fernandez-Garcı a, M.

    2010-07-29

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni?O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate?carbonate route is operative for the production of hydrogen.

  20. Process Intensification with Integrated Water-Gas-Shift Membrane Reactor

    SciTech Connect

    2009-11-01

    This factsheet describes a research project whose objective is to develop hydrogen-selective membranes for an innovative gas-separation process based on a water-gas-shift membrane reactor (WGS-MR) for the production of hydrogen.

  1. High-Temperature Water-Gas Shift Membrane Reactor Study

    SciTech Connect

    Ciocco, M.V.; Iyoha, O.; Enick, R.M.; Killmeyer, R.P.

    2007-06-01

    NETLs Office of Research and Development is exploring the integration of membrane reactors into coal gasification plants as a way of increasing efficiency and reducing costs. Water-Gas Shift Reaction experiments were conducted in membrane reactors at conditions similar to those encountered at the outlet of a coal gasifier. The changes in reactant conversion and product selectivity due to the removal of hydrogen via the membrane reactor were quantified. Research was conducted to determine the influence of residence time and H2S on CO conversion in both Pd and Pd80wt%Cu membrane reactors. Effects of the hydrogen sulfide-to-hydrogen ratio on palladium and a palladium-copper alloy at high-temperature were also investigated. These results were compared to thermodynamic calculations for the stability of palladium sulfides.

  2. Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

    PubMed

    Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

    2013-08-20

    Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and reactivity of novel materials and reactions in the future. PMID:23286528

  3. Comparison of the Activity of Au/CeO2 and Au/Fe2O3 Catalysts for the CO Oxidation and the Water-gas Shift Reactions

    SciTech Connect

    Deng,W.; Carpenter, C.; Yi, N.; Flytzani-Stephanopoulos, M.

    2007-01-01

    We compare the activity and relevant gold species of nanostructured gold-cerium oxide and gold-iron oxide catalysts for the CO oxidation by dioxygen and water. Well dispersed gold nanoparticles in reduced form provide the active sites for the CO oxidation reaction on both oxide supports. On the other hand, oxidized gold species, strongly bound on the support catalyze the water-gas shift reaction. Gold species weakly bound to ceria (doped with lanthana) or iron oxide can be removed by sodium cyanide at pH {>=}12. Both parent and leached catalysts were investigated. The activity of the leached gold-iron oxide catalyst in CO oxidation is approximately two orders of magnitude lower than that of the parent material. However, after exposure to H{sub 2} up to 400 C gold diffuses out and is in reduced form on the surface, a process accompanied by a dramatic enhancement of the CO oxidation activity. Similar results were found with the gold-ceria catalysts. On the other hand, pre-reduction of the calcined leached catalyst samples did not promote their water-gas shift activity. UV-Vis, XANES and XPS were used to probe the oxidation state of the catalysts after various treatments.

  4. Cr-free Fe-based metal oxide catalysts for high temperature water gas shift reaction of fuel processor using LPG

    SciTech Connect

    lee, Joon Y.; Lee, Dae-Won; Lee, Kwan Young; Wang, Yong

    2009-08-15

    The goal of this study was to identify the most suitable chromium-free iron-based catalysts for the HTS (high temperature shift) reaction of a fuel processor using LPG. Hexavalent chromium (Cr6+) in the commercial HTS catalyst has been regarded as hazardous material. We selected Ni and Co as the substitution for chromium in the Fe-based HTS catalyst and investigated the HTS activities of these Crfree catalysts at LPG reformate condition. Cr-free Fe-based catalysts which contain Ni, Zn, or Co instead of Cr were prepared by coprecipitation method and the performance of the catalysts in HTS was evaluated under gas mixture conditions (42% H2, 10% CO, 37% H2O, 8% CO2, and 3% CH4; R (reduction factor): about 1.2) similar to the gases from steam reforming of LPG (100% conversion at steam/carbon ratio = 3), which is higher than R (under 1) of typically studied LNG reformate condition. Among the prepared Cr-free Febased catalysts, the 5 wt%-Co/Fe/20 wt%-Ni and 5 wt%-Zn/Fe/20 wt%-Ni catalysts showed good catalytic activity under this reaction condition simulating LPG reformate gas.

  5. Unraveling the Active Site in Copper-ceria Systems for the Water Gas Shift Reaction: In-situ Characterization of an Inverse Powder CeO2-x/CuO-Cu Catalyst

    SciTech Connect

    Rodriguez, J.A.; Barrio, L.; Estrella, M.; Zhou, G.; Wen, W.; Hanson, J.C.; Hungra, A.B.; Horns, A.; Fernndez-Garca, M.; Arturo Martnez-Arias, A.

    2010-03-04

    An inverse powder system composed of CeO{sub 2} nanoparticles dispersed over a CuO-Cu matrix is proposed as a novel catalyst for the water-gas shift reaction. This inverse CeO{sub 2}/CuO-Cu catalyst exhibits a higher activity than standard Cu/CeO{sub 2} catalysts. In situ synchrotron characterization techniques were employed to follow the structural changes of CeO{sub 2}/CuO-Cu under reaction conditions. Time-resolved X-ray diffraction experiments showed the transformation of CuO to metallic Cu via a Cu{sub 2}O intermediate. Short-order structural changes were followed by pair distribution function analysis and corroborated the results obtained by diffraction. Moreover, X-ray absorption spectroscopy also revealed oxidation state changes from Cu{sup 2+} to Cu{sup 0} and the partial reduction of CeOx nanoparticles. The activity data obtained by mass spectrometry revealed that hydrogen production starts once the copper has been fully reduced. The strong interaction of ceria and copper boosted the catalytic performance of the sample. The inverse catalyst was active at low temperatures, stable to several reaction runs and to redox cycles. These characteristics are highly valuable for mobile fuel cell applications. The active phases of the inverse CeO{sub 2}/CuO-Cu catalyst are partially reduced ceria nanoparticles strongly interacting with metallic copper. The nature and structure of the ceria nanoparticles are of critical importance because they are involved in processes related to water dissociation over the catalyst surface.

  6. Unraveling the Active Site in Copper-Ceria Systems for the Water-Gas Shift Reaction: In Situ Characterization of an Inverse Powder CeO2-x/CuO-Cu Catalyst

    SciTech Connect

    Barrio, L.; Estrella, M; Zhou, G; Wen, W; Hanson, J; Hungria, A; Hornes, A; Fernandez-Garcia, M; Martinez-Arias, A; Rodriguez, J

    2010-01-01

    An inverse powder system composed of CeO{sub 2} nanoparticles dispersed over a CuO-Cu matrix is proposed as a novel catalyst for the water-gas shift reaction. This inverse CeO{sub 2}/CuO-Cu catalyst exhibits a higher activity than standard Cu/CeO{sub 2} catalysts. In situ synchrotron characterization techniques were employed to follow the structural changes of CeO{sub 2}/CuO-Cu under reaction conditions. Time-resolved X-ray diffraction experiments showed the transformation of CuO to metallic Cu via a Cu{sub 2}O intermediate. Short-order structural changes were followed by pair distribution function analysis and corroborated the results obtained by diffraction. Moreover, X-ray absorption spectroscopy also revealed oxidation state changes from Cu{sup 2+} to Cu{sup 0} and the partial reduction of CeO{sub x} nanoparticles. The activity data obtained by mass spectrometry revealed that hydrogen production starts once the copper has been fully reduced. The strong interaction of ceria and copper boosted the catalytic performance of the sample. The inverse catalyst was active at low temperatures, stable to several reaction runs and to redox cycles. These characteristics are highly valuable for mobile fuel cell applications. The active phases of the inverse CeO{sub 2}/CuO-Cu catalyst are partially reduced ceria nanoparticles strongly interacting with metallic copper. The nature and structure of the ceria nanoparticles are of critical importance because they are involved in processes related to water dissociation over the catalyst surface.

  7. Development of Novel Water-Gas Shift Membrane Reactor

    SciTech Connect

    Ho, W. S. Winston

    2004-12-29

    This report summarizes the objectives, technical barrier, approach, and accomplishments for the development of a novel water-gas-shift (WGS) membrane reactor for hydrogen enhancement and CO reduction. We have synthesized novel CO{sub 2}-selective membranes with high CO{sub 2} permeabilities and high CO{sub 2}/H{sub 2} and CO{sub 2}/CO selectivities by incorporating amino groups in polymer networks. We have also developed a one-dimensional non-isothermal model for the countercurrent WGS membrane reactor. The modeling results have shown that H{sub 2} enhancement (>99.6% H{sub 2} for the steam reforming of methane and >54% H{sub 2} for the autothermal reforming of gasoline with air on a dry basis) via CO{sub 2} removal and CO reduction to 10 ppm or lower are achievable for synthesis gases. With this model, we have elucidated the effects of system parameters, including CO{sub 2}/H{sub 2} selectivity, CO{sub 2} permeability, sweep/feed flow rate ratio, feed temperature, sweep temperature, feed pressure, catalyst activity, and feed CO concentration, on the membrane reactor performance. Based on the modeling study using the membrane data obtained, we showed the feasibility of achieving H{sub 2} enhancement via CO{sub 2} removal, CO reduction to {le} 10 ppm, and high H{sub 2} recovery. Using the membrane synthesized, we have obtained <10 ppm CO in the H{sub 2} product in WGS membrane reactor experiments. From the experiments, we verified the model developed. In addition, we removed CO{sub 2} from a syngas containing 17% CO{sub 2} to about 30 ppm. The CO{sub 2} removal data agreed well with the model developed. The syngas with about 0.1% CO{sub 2} and 1% CO was processed to convert the carbon oxides to methane via methanation to obtain <5 ppm CO in the H{sub 2} product.

  8. Development of an advanced water-gas shift conversion system. Final report

    SciTech Connect

    Sealock, L.J. Jr.; Elliott, D.C.; Butner, R.S.

    1985-04-01

    Pacific Northwest Laboratory has completed initial exploratory research to investigate the chemistry and use of a pressurized aqueous catalyst system for conducting the water-gas shift reaction. The research was done under sponsorship of the USDOE Morgantown Energy Technology Center. A 1.0 liter continuous bench scale reactor system was built and operated to investigate water-gas shift chemistry at high pressure. Details regarding the chemistry of the aqueous, base-catalyzed system in both batch and continuous reactors are presented for a temperature range of 200 to 350/sup 0/C and pressures from 500 to 3000 psig. The catalyst choice is sodium carbonate at a concentration of 6% in water, but any material which can generate hydroxide ions at the process conditions will effectively catalyze the reaction. This report summarizes the results of the bench-scale research on the concept and presents a discussion of optimum operating conditions, pressure effects and limitations, kinetic data, effects of gas flow rates, catalyst type, and preliminary concept evaluation. 16 refs., 29 figs., 8 tabs.

  9. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS

    SciTech Connect

    Carl R.F. Lund

    2002-08-02

    The kinetics of water-gas shift were studied over ferrochrome catalysts under conditions with high carbon dioxide partial pressures, such as would be expected in a membrane reactor. The catalyst activity is inhibited by increasing carbon dioxide partial pressure. A microkinetic model of the reaction kinetics was developed. The model indicated that catalyst performance could be improved by decreasing the strength of surface oxygen bonds. Literature data indicated that adding either ceria or copper to the catalyst as a promoter might impart this desired effect. Ceria-promoted ferrochrome catalysts did not perform any better than unpromoted catalyst at the conditions tested, but copper-promoted ferrochrome catalysts did offer an improvement over the base ferrochrome material. A different class of water-gas shift catalyst, sulfided CoMo/Al{sub 2}O{sub 3} is not affected by carbon dioxide and may be a good alternative to the ferrochrome system, provided other constraints, notably the requisite sulfur level and maximum temperature, are not too limiting. A model was developed for an adiabatic, high-temperature water-gas shift membrane reactor. Simulation results indicate that an excess of steam in the feed (three moles of water per mole of CO) is beneficial even in a membrane reactor as it reduces the rate of adiabatic temperature rise. The simulations also indicate that much greater improvement can be attained by improving the catalyst as opposed to improving the membrane. Further, eliminating the inhibition by carbon dioxide will have a greater impact than will increasing the catalyst activity (assuming inhibition is still operative). Follow-up research into the use of sulfide catalysts with continued kinetic and reactor modeling is suggested.

  10. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-01-01

    A Co/MgO/SiO[sub 2] Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al[sub 2]O[sub 3] water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240[degrees]C, a pressure of 0.79 MPa, and a 1.1 H[sub 2]/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO[sub 2] catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO[sub 2] operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts's operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  11. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

    PubMed Central

    2015-01-01

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

  12. The Integration of a Structural Water Gas Shift Catalyst with a Vanadium Alloy Hydrogen Transport Device

    SciTech Connect

    Barton, Thomas; Argyle, Morris; Popa, Tiberiu

    2009-06-30

    This project is in response to a requirement for a system that combines water gas shift technology with separation technology for coal derived synthesis gas. The justification of such a system would be improved efficiency for the overall hydrogen production. By removing hydrogen from the synthesis gas stream, the water gas shift equilibrium would force more carbon monoxide to carbon dioxide and maximize the total hydrogen produced. Additional benefit would derive from the reduction in capital cost of plant by the removal of one step in the process by integrating water gas shift with the membrane separation device. The answer turns out to be that the integration of hydrogen separation and water gas shift catalysis is possible and desirable. There are no significant roadblocks to that combination of technologies. The problem becomes one of design and selection of materials to optimize, or at least maximize performance of the two integrated steps. A goal of the project was to investigate the effects of alloying elements on the performance of vanadium membranes with respect to hydrogen flux and fabricability. Vanadium was chosen as a compromise between performance and cost. It is clear that the vanadium alloys for this application can be produced, but the approach is not simple and the results inconsistent. For any future contracts, large single batches of alloy would be obtained and rolled with larger facilities to produce the most consistent thin foils possible. Brazing was identified as a very likely choice for sealing the membranes to structural components. As alloying was beneficial to hydrogen transport, it became important to identify where those alloying elements might be detrimental to brazing. Cataloging positive and negative alloying effects was a significant portion of the initial project work on vanadium alloying. A water gas shift catalyst with ceramic like structural characteristics was the second large goal of the project. Alumina was added as a component of conventional high temperature water gas shift iron oxide based catalysts. The catalysts contained Fe-Al-Cr-Cu-O and were synthesized by co-precipitation. A series of catalysts were prepared with 5 to 50 wt% Al2O3, with 8 wt% Cr2O3, 4 wt% CuO, and the balance Fe2O3. All of the catalysts were compared to a reference WGS catalyst (88 wt% FeOx, 8 wt% Cr2O3, and 4 wt% CuO) with no alumina. Alumina addition to conventional high temperature water gas shift catalysts at concentrations of approximately 15 wt% increased CO conversion rates and increase thermal stability. A series of high temperature water gas shift catalysts containing iron, chromia, and copper oxides were prepared with small amounts of added ceria in the system Fe-Cr-Cu-Ce-O. The catalysts were also tested kinetically under WGS conditions. 2-4 wt% ceria addition (at the expense of the iron oxide content) resulted in increased reaction rates (from 22-32% higher) compared to the reference catalyst. The project goal of a 10,000 liter per day WGS-membrane reactor was achieved by a device operating on coal derived syngas containing significant amounts of carbon monoxide and hydrogen sulfide. The membrane flux was equivalent to 52 scfh/ft2 based on a 600 psi syngas inlet pressure and corresponded to membranes costing $191 per square foot. Over 40 hours of iv exposure time to syngas has been achieved for a double membrane reactor. Two modules of the Chart reactor were tested under coal syngas for over 75 hours with a single module tested for 50 hours. The permeance values for the Chart membranes were similar to the REB reactor though total flux was reduced due to significantly thicker membranes. Overall testing of membrane reactors on coal derived syngas was over 115 hours for all reactors tested. Testing of the REB double membrane device exceeded 40 hours. Performance of the double membrane reactor has been similar to the results for the single reactor with good maintenance of flux even after these long exposures to hydrogen sulfide. Of special interest is that the flux is highest at the start of each experiment as predicted, but unusually, the flux returns to higher values after exposures to air as short as 20 seconds. The assumption from these findings is that absorbed carbon monoxide, sulfur, or both are removed by exposure of the membranes to oxygen at 400ºC. This is a good sign that indicates that membranes affected by absorbed species can be recovered, and will require some thought to process design to allow for recovery steps during scaled operations of hydrogen production. An important characteristic in the data is the return to a higher flux level after each new exposure to air at temperature. This indicates that the membrane reactor may be subject to refreshment of the surface during operation.

  13. A new generation of water gas shift catalysts for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Ruettinger, Wolfgang; Ilinich, Oleg; Farrauto, Robert J.

    The generation of high-purity hydrogen from hydrocarbon fuels for fuel cell applications is essential for efficient operation of the solid polymer electrolyte (PEM) fuel cell. In general, most feasible strategies to generate hydrogen from hydrocarbon fuels consist of a reforming step to generate a mixture of H 2, CO, CO 2 and H 2O (steam) followed by water gas shift (WGS) and CO clean-up steps. The WGS reaction is industrially carried out using two particulate catalystsFeCr and CuZnat temperatures between 350-500 and 180-250 C, respectively. Both catalysts are pyrophoric: they spontaneously generate heat to dangerously high temperatures when exposed to air after activation. In addition, CuZn needs to be carefully activated before use. We have developed a base metal non-pyrophoric alternative to commercial CuZn. The catalyst, referred to as Selectra Shift, activates in process gas, has stable activity under a wide variety of process conditions and is safer if accidentally exposed to air. It therefore represents a safer alternative to the commercial CuZn for fuel cell applications. In addition, Engelhard has developed base metal and precious metal monolith WGS catalysts for applications where the catalyst must be optimized for small reactor volumes, lower pressure drop and mechanical integrity. Inhibitors are added to the precious metal catalyst to suppress the undesirable methanation side reaction.

  14. Operation, Modeling and Analysis of the Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2001-01-01

    The Reverse Water Gas Shift process is a candidate technology for water and oxygen production on Mars under the In-Situ Propellant Production project. This report focuses on the operation and analysis of the Reverse Water Gas Shift (RWGS) process, which has been constructed at Kennedy Space Center. A summary of results from the initial operation of the RWGS, process along with an analysis of these results is included in this report. In addition an evaluation of a material balance model developed from the work performed previously under the summer program is included along with recommendations for further experimental work.

  15. A Cu/Pt Near-Surface Alloy for Water-Gas Shift Catalysis.

    SciTech Connect

    Knudsen, Jan; Nilekar, Anand U.; Vang, Ronnie T.; Schnadt, Joachim; Kunkes, Edward L.; Dumesic, James A.; Mavrikakis, Manos; Besenbacher, Fleming

    2007-05-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The primary route to hydrogen production from fossil fuels involves the water-gas shift (WGS) reaction, and an improvement in the efficiency of WGS catalysts could therefore lead to a major leap forward in the realization of hydrogen economy. On the basis of a combination of high-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, we suggest the existence of a new thermodynamically stable Cu/Pt near-surface alloy (NSA). Temperature-programmed desorption and DFT reveal that this Cu/Pt NSA binds CO significantly more weakly than does Pt alone, thereby implying a considerable reduction in the potential for CO poisoning of the Cu/Pt NSA surface as compared to that of pure Pt. In addition, DFT calculations show that this Cu/Pt NSA is able to activate H2O easily, which is the rate-determining step for the WGS on several metal surfaces, and, at the same time, to bind the products of that reaction and formate intermediates rather weakly, thus avoiding possible poisoning of the catalyst surface. The Cu/Pt NSA is thus a promising candidate for an improved WGS catalyst.

  16. Water-Gas Shift Activity of Cu Surfaces and Cu Nanoparticles Supported on Metal Oxides

    SciTech Connect

    Rodriguez, J.; Liu, P; Wang, X; Wen, W; Hanson, J; Hrbek, J; Perez, M; Evans, J

    2009-01-01

    Oxide supported Cu catalysts show significant activity for the water-gas shift reaction (WGS, CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) but their performance is not fully understood and is highly dependent on the synthesis conditions or the nature of the oxide support. This article describes a series of new studies examining the water-gas shift activity of Cu/MgO(1 0 0) surfaces and compares it to the activities found for pure copper systems, Cu nanoparticles in contact with well-defined surfaces of TiO{sub 2}, ZnO, MoO{sub 2} and CeO{sub 2}, and Cu cations present in mixed-metal oxides. Catalytic tests performed over CuFe{sub 2}O{sub 4}, Ce{sub 1-x}Cu{sub x}O{sub 2} or CuMoO{sub 4} show significant WGS activity only when the Cu cations in the mixed-metal oxide are reduced to metallic copper. Thus, Cu nanoparticles were deposited on different oxide surfaces and their WGS activity was measured in a batch reactor (P{sub CO} = 20 Torr; P{sub H{sub 2}O} = 10 Torr; T = 575-650 K). The WGS activity of the Cu nanoparticles supported on MgO(1 0 0) was 2-3 times larger than that of Cu(1 0 0). Even better WGS catalysts were obtained when Cu was deposited on CeO{sub 2}(1 1 1) or TiO{sub 2}(1 1 0). An apparent activation energy of 13.8 kcal/mol was found for the WGS on Cu/MgO(1 0 0). This is smaller than the value of 15.2 kcal/mol observed on Cu(1 0 0), and substantially larger than the values of 7-9 kcal/mol seen for the apparent activation energies of the Cu/CeO2(1 1 1) and Cu/TiO2(1 1 0) catalysts. Post-reaction surface characterization pointed to the lack of O vacancies in the Cu/MgO(1 0 0) catalysts. This is in contrast to results found for Cu/CeO{sub 2}(1 1 1) and Cu/TiO{sub 2}(1 1 0), where the oxide support exhibits a significant concentration of O vacancies as a consequence of the WGS reaction. The oxygen vacancies present in Cu/CeO{sub 2}(1 1 1) and Cu/TiO{sub 2}(1 1 0) help in the dissociation of the water molecule and reduce the apparent activation energy for the WGS process. Such a phenomenon cannot occur on the Cu/MgO(0 0 1) catalysts, and the main steps of the WGS probably take place on the Cu nanoparticles.

  17. Microkinetics of water-gas shift over sulfided Mo/Al{sub 2}O{sub 3} catalysts

    SciTech Connect

    Lund, C.R.F.

    1996-08-01

    A microkinetic model was developed to explain the catalysis of the water-gas shift reaction by sulfided, alumina-supported molybdenum. IN this model, the reaction takes place through a regenerative (reduction-oxidation) scheme wherein the catalyst surface is alternately oxidized by water and then reduced by carbon monoxide. The surface of the catalyst is equilibrated with gas-phase H{sub 2}S under all reaction conditions studied. Coverages predicted by the model are consistent with the adsorption behavior of molybdenum sulfide catalysts. Simulations indicate that the effects of steam and H{sub 2}S levels are closely related. A maximum in CO conversion with increasing steam level may only occur at certain H{sub 2}S levels, and the ordering of CO conversion with increasing H{sub 2}S levels may invert as the steam level is changed.

  18. Integrated Water Gas Shift Membrane Reactors Utilizing Novel, Non Precious Metal Mixed Matrix Membrane

    SciTech Connect

    Ferraris, John

    2013-09-30

    Nanoparticles of zeolitic imidazolate frameworks and other related hybrid materials were prepared by modifying published synthesis procedures by introducing bases, changing stoichiometric ratios, or adjusting reaction conditions. These materials were stable at temperatures >300 °C and were compatible with the polymer matrices used to prepare mixed- matrix membranes (MMMs). MMMs tested at 300 °C exhibited a >30 fold increase in permeability, compared to those measured at 35 °C, while maintaining H{sub 2}/CO{sub 2} selectivity. Measurements at high pressure (up to 30 atm) and high temperature (up to 300 °C) resulted in an increase in gas flux across the membrane with retention of selectivity. No variations in permeability were observed at high pressures at either 35 or 300 °C. CO{sub 2}-induced plasticization was not observed for Matrimid®, VTEC, and PBI polymers or their MMMs at 30 atm and 300 °C. Membrane surface modification by cross-linking with ethanol diamine resulted in an increase in H{sub 2}/CO{sub 2} selectivity at 35 °C. Spectrometric analysis showed that the cross-linking was effective to temperatures <150 °C. At higher temperatures, the cross-linked membranes exhibit a H{sub 2}/CO{sub 2} selectivity similar to the uncross-linked polymer. Performance of the polybenzimidazole (PBI) hollow fibers prepared at Santa Fe Science and Technology (SFST, Inc.) showed increased flux o to a flat PBI membrane. A water-gas shift reactor has been built and currently being optimized for testing under DOE conditions.

  19. Catalytic and surface properties of nanocrystalline gold water gas shift catalysts

    NASA Astrophysics Data System (ADS)

    Kim, Chang Hwan

    A series of CeO2 supported gold catalysts were prepared and found to possess a high activities for the water gas shift reaction (WGS), a critical step in the production of H2 for use in petroleum refining, chemicals synthesis, and proton exchange membrane fuel cells. The deposition-precipitation method was employed in synthesizing these highly active, nanocrystalline gold catalysts. X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and dynamic sorption analyses were performed to characterize the gold catalysts. While some of these catalysts were initially four times more active than a commercial Cu-based catalyst, they were susceptible to deactivation. Characterization using techniques including temperature programmed oxidation, XPS, and FT-IR indicated that the deactivation was caused primarily by blockage of the active sites by carbonates and/or formates. Formation of these carbonaceous species appeared to be facilitated by oxygen deficient sites on the ceria surface and may have been associated with hydroxyl groups formed on the nanocrystalline gold particles under the H2 rich conditions. The deactivation could be managed by conditioning the CeO2 surface or adding constituents to minimize oxygen deficiency. The catalytic activity was fully recovered by calcining the deactivated materials in flowing air at elevated temperatures. The gold catalyst was washcoated onto microporous Fe-Al alloy foams for use in a micro-channel WGS reactor. The performance of these coated foams was inferior to that of the powder catalyst; however, a two stage micro-channel WGS reactor employing the gold catalyst was sufficient for a 100 W fuel processor system.

  20. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-01-01

    A cobalt Fischer-Tropsch catalyst (CO/MgO/silica) was reduced and slurried in combination with reduced Cu/ZnO/Al[sub 2]0[sub 3] water-gas-shift catalyst. Combined catalyst system was run at fixed process conditions for more than 400 hours. The system showed stable selectivity. The Cu/ZnO/Al[sub 2]0[sub 3] water-gas-shift catalyst remained reasonably active in the presence of the cobalt catalyst. Hydrocarbon selectivity of the cobalt and Cu/ZnO/Al[sub 2]0[sub 3] catalyst system compared favorably to selectivity of iron-based catalysts. Methane selectivity was slightly higher for the cobalt-based system, but C[sub 5][sup +] selectivity was essentially the same. The hydrocarbon product distribution appeared to exhibit a double-a behavior. a[sub 1] was near 0.80 which is higher than that of iron catalysts, while a[sub 2] was calculated to be 0.86 which is somewhat lower than would be typical for an iron-based catalyst.

  1. Iron-ceria Aerogels Doped with Palladium as Water-gas Shift Catalysts for the Production of Hydrogen

    SciTech Connect

    Bali, S.; Huggins, F; Ernst, R; Pugmire, R; Huffman, G; Eyring, E

    2010-01-01

    Mixed 4.5% iron oxide-95.5% cerium oxide aerogels doped with 1% and 2% palladium (Pd) by weight have been synthesized, and their activities for the catalysis of water-gas shift (WGS) reaction have been determined. The aerogels were synthesized using propylene oxide as the proton scavenger for the initiation of hydrolysis and polycondensation of a homogeneous alcoholic solution of cerium(III) chloride heptahydrate and iron(III) chloride hexahydrate precursor. Palladium was doped onto some of these materials by gas-phase incorporation (GPI) using ({eta}{sup 3}-allyl)({eta}{sup 5}-cyclopentadienyl)palladium as the volatile Pd precursor. Water-gas shift catalytic activities were evaluated in a six-channel fixed-bed reactor at atmospheric pressure and reaction temperatures ranging from 150 to 350 C. Both 1% and 2% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels showed WGS activities that increased significantly from 150 to 350 C. The activities of 1% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels were also compared with that of the 1% Pd-doped ceria aerogel without iron. The WGS activity of 1% Pd on 4.5% iron oxide-95.5% cerium oxide aerogels is substantially higher (5 times) than the activity of 1% Pd-doped ceria aerogel without iron. The gas-phase incorporation results in a better Pd dispersion. Ceria aerogel provides a nonrigid structure wherein iron is not significantly incorporated inside the matrix, thereby resulting in better contact between the Fe and Pd and thus enhancing the WGS activity. Further, neither Fe nor Pd is reduced during the ceria-aerogel-catalyzed WGS reaction. This behavior contrasts with that noted for other Fe-based WGS catalysts, in which the original ferric oxide is typically reduced to a nonstoichiometric magnetite form.

  2. A Comparative Study of the Water Gas Shift Reaction Over Platinum Catalysts Supported on CeO2, TiO2 and Ce-Modified TiO2

    SciTech Connect

    Gonzalez, I.; Navarro, R; Wen, W; Marinkovic, N; Rodriguez, J; Rosa, F; Fierro, J

    2010-01-01

    WGS reaction has been investigated on catalysts based on platinum supported over CeO{sub 2}, TiO{sub 2} and Ce-modified TiO{sub 2}. XPS and XANES analyses performed on calcined catalysts revealed a close contact between Pt precursors and cerium species on CeO{sub 2} and Ce-modified TiO{sub 2} supports. TPR results corroborate the intimate contact between Pt and cerium entities in the Pt/Ce-TiO{sub 2} catalyst that facilitates the reducibility of the support at low temperatures while the Ce-O-Ti surface interactions established in the Ce-modified TiO{sub 2} support decreases the reduction of TiO{sub 2} at high temperature. The changes in the support reducibility leads to significant differences in the WGS activity of the studied catalysts. Pt supported on Ce-modified TiO{sub 2} support exhibits better activity than those corresponding to individual CeO{sub 2} and TiO{sub 2}-supported catalysts. Additionally, the Ce-TiO{sub 2}-supported catalyst displays better stability at reaction temperatures higher than 573 K that observed on pure TiO{sub 2}-supported counterpart. Activity measurements, when coupled with the physicochemical characterization of catalysts suggest that the modifications in the surface reducibility of the support play an essential role in the enhancement of activity and stability observed when Pt is supported on the Ce-modified TiO{sub 2} substrate.

  3. An innovative catalyst system for slurry-phase Fischer-Tropsch synthesis: Cobalt plus a water-gas-shift catalyst

    SciTech Connect

    Satterfield, C.N.; Yates, I.C.; Chanenchuk, C.

    1991-07-01

    The feasibility of using a mechanical mixture of a Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst and a Cu-ZnO/Al{sub 2}O{sub 3} water-gas-shift (WGS) catalyst for hydrocarbon synthesis in a slurry reactor has been established. Such a mixture can combine the superior product distribution from cobalt with the high activity for the WGS reaction characteristic of iron. Weight ratios of Co/MgO/SiO{sub 2} to Cu-ZnO/Al{sub 2}O{sub 3} of 0.27 and 0.51 for the two catalysts were studied at 240{degrees}C, 0.79 MPa, and in situ H{sub 2}/CO ratios between 0.8 and 3.0. Each catalyst mixture showed stable Fischer-Tropsch activity for about 400 hours-on-stream at a level comparable to the cobalt catalyst operating alone. The Cu-ZnO/Al{sub 2}O{sub 3} catalyst exhibited a very slow loss of activity under these conditions, but when operated alone it was stable in a slurry reactor at 200--220{degrees}C, 0.79--1.48 MPa, and H{sub 2}/CO in situ ratios between 1.0 and 2.0. The presence of the water-gas-shift catalyst did not affect the long-term stability of the primary Fischer-Tropsch selectivity, but did increase the extent of secondary reactions, such as l-alkene hydrogenation and isomerization.

  4. An Investigation of the Reverse Water Gas Shift Process and Operating Alternatives

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2002-01-01

    The Reverse Water Gas Shift (RWGS) process can produce water and ultimately oxygen through electrolysis. This technology is being investigated for possible use in the exploration of Mars as well as a potential process to aid in the regeneration of oxygen from carbon dioxide. The initial part of this report summarizes the results obtained from operation of the RWGS process at Kennedy Space Center during May and June of this year. It has been demonstrated that close to complete conversion can be achieved with the RWGS process under certain operating conditions. The report also presents results obtained through simulation for an alternative staged configuration for RWGS which eliminates the recycle compressor. This configuration looks promising and hence seems worthy of experimental investigation.

  5. Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts.

    PubMed

    Ding, Kunlun; Gulec, Ahmet; Johnson, Alexis M; Schweitzer, Neil M; Stucky, Galen D; Marks, Laurence D; Stair, Peter C

    2015-10-01

    Identification and characterization of catalytic active sites are the prerequisites for an atomic-level understanding of the catalytic mechanism and rational design of high-performance heterogeneous catalysts. Indirect evidence in recent reports suggests that platinum (Pt) single atoms are exceptionally active catalytic sites. We demonstrate that infrared spectroscopy can be a fast and convenient characterization method with which to directly distinguish and quantify Pt single atoms from nanoparticles. In addition, we directly observe that only Pt nanoparticles show activity for carbon monoxide (CO) oxidation and water-gas shift at low temperatures, whereas Pt single atoms behave as spectators. The lack of catalytic activity of Pt single atoms can be partly attributed to the strong binding of CO molecules. PMID:26338796

  6. Activity and durability of water-gas shift catalysts used for the steam reforming of methanol

    NASA Astrophysics Data System (ADS)

    Lffler, D. G.; McDermott, S. D.; Renn, C. N.

    Commercially available water-gas shift catalysts were tested for methanol steam reforming in small-scale packed bed reactors at atmospheric pressure. The results showed that while the initial activity of chromia or zinc oxide catalysts was lower than that of copper-based catalysts, the durability of the chromia preparations was far superior to that of the copper-based samples at the temperatures investigated. Kinetic modeling suggested that copper and zinc oxide catalysts have deactivated by sintering of the metal phase; instead, the deactivation of chromia catalysts is consistent with feed poisoning. A zinc oxide/chromia catalyst was among the most active, and it certainly was the most stable, catalyst tested.

  7. In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

    PubMed

    Rodriguez, Jos A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

    2013-08-01

    In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O ? H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually work. PMID:23660768

  8. Design of water gas shift catalysts for hydrogen production in fuel processors.

    PubMed

    Opalka, S M; Vanderspurt, T H; Radhakrishnan, R; She, Y; Willigan, R R

    2008-02-13

    Low sulfur hydrocarbon fuels can be converted to fuel cell grade H(2) using a compact fuel processor architecture. The necessary high volumetric activity water gas shift (WGS) Pt on ceria-zirconia catalysts reacts CO-rich reformate with steam to yield H(2) and CO(2). Such highly selective, non-pyrophoric noble metal/Ce([1-(x+y)])Zr(x)Dp(y)O(2) catalysts were developed through coordinated atomic modeling, syntheses, structural characterization, kinetic performance tests, and micro-kinetic analyses. Density functional simulations made with the VASP code suggested that the undoped catalyst WGS activity would be limited by the strong binding of CO intermediates, blocking the reoxidation of the reduced oxide by water. These predictions were confirmed by in situ cylindrical internal reflection-Fourier transform infrared spectroscopy and by micro-kinetic analyses of the micro-reactor results. Atomic simulations were used to evaluate the impact transition metal dopants had on the surface chemistry of cubic ceria-zirconia. VASP predicted that acidic transition metal dopants such as Nb, Mo, Ta, and W would increase the oxide surface affinity for water and thus increase the turnover rate of the catalyst. The efficacy of Mo-doped ceria-zirconia compositions was confirmed at lower temperatures in replicated catalyst synthesis-reactor studies. PMID:21693898

  9. LYAPUNOV-Based Sensor Failure Detection and Recovery for the Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Haralambous, Michael G.

    2002-01-01

    Livingstone, a model-based AI software system, is planned for use in the autonomous fault diagnosis, reconfiguration, and control of the oxygen-producing reverse water gas shift (RWGS) process test-bed located in the Applied Chemistry Laboratory at KSC. In this report the RWGS process is first briefly described and an overview of Livingstone is given. Next, a Lyapunov-based approach for detecting and recovering from sensor failures, differing significantly from that used by Livingstone, is presented. In this new method, models used are in t e m of the defining differential equations of system components, thus differing from the qualitative, static models used by Livingstone. An easily computed scalar inequality constraint, expressed in terms of sensed system variables, is used to determine the existence of sensor failures. In the event of sensor failure, an observer/estimator is used for determining which sensors have failed. The theory underlying the new approach is developed. Finally, a recommendation is made to use the Lyapunov-based approach to complement the capability of Livingstone and to use this combination in the RWGS process.

  10. Lyapunov-Based Sensor Failure Detection And Recovery For The Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Haralambous, Michael G.

    2001-01-01

    Livingstone, a model-based AI software system, is planned for use in the autonomous fault diagnosis, reconfiguration, and control of the oxygen-producing reverse water gas shift (RWGS) process test-bed located in the Applied Chemistry Laboratory at KSC. In this report the RWGS process is first briefly described and an overview of Livingstone is given. Next, a Lyapunov-based approach for detecting and recovering from sensor failures, differing significantly from that used by Livingstone, is presented. In this new method, models used are in terms of the defining differential equations of system components, thus differing from the qualitative, static models used by Livingstone. An easily computed scalar inequality constraint, expressed in terms of sensed system variables, is used to determine the existence of sensor failures. In the event of sensor failure, an observer/estimator is used for determining which sensors have failed. The theory underlying the new approach is developed. Finally, a recommendation is made to use the Lyapunov-based approach to complement the capability of Livingstone and to use this combination in the RWGS process.

  11. Design of water gas shift catalysts for hydrogen production in fuel processors

    NASA Astrophysics Data System (ADS)

    Opalka, S. M.; Vanderspurt, T. H.; Radhakrishnan, R.; She, Y.; Willigan, R. R.

    2008-02-01

    Low sulfur hydrocarbon fuels can be converted to fuel cell grade H2 using a compact fuel processor architecture. The necessary high volumetric activity water gas shift (WGS) Pt on ceria-zirconia catalysts reacts CO-rich reformate with steam to yield H2 and CO2. Such highly selective, non-pyrophoric noble metal/Ce[1-(x+y)]ZrxDpyO2 catalysts were developed through coordinated atomic modeling, syntheses, structural characterization, kinetic performance tests, and micro-kinetic analyses. Density functional simulations made with the VASP code suggested that the undoped catalyst WGS activity would be limited by the strong binding of CO intermediates, blocking the reoxidation of the reduced oxide by water. These predictions were confirmed by in situ cylindrical internal reflection-Fourier transform infrared spectroscopy and by micro-kinetic analyses of the micro-reactor results. Atomic simulations were used to evaluate the impact transition metal dopants had on the surface chemistry of cubic ceria-zirconia. VASP predicted that acidic transition metal dopants such as Nb, Mo, Ta, and W would increase the oxide surface affinity for water and thus increase the turnover rate of the catalyst. The efficacy of Mo-doped ceria-zirconia compositions was confirmed at lower temperatures in replicated catalyst synthesis-reactor studies.

  12. Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Akatay, Mehmed Cem

    Water-gas shift (WGS), CO + H2O ? CO2 + H2 (DeltaH = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

  13. Kinetic and spectroscopic study of catalysts for water-gas shift and nitrogen oxide removal

    NASA Astrophysics Data System (ADS)

    Kispersky, Vincent Frederick

    Nitrogen oxides (NOx) are formed in high temperature combustion processes such as in power generation and motor vehicles. Increasingly stringent regulation of these harmful emissions continues to drive interest in developing, understanding and studying new catalytic formulations for exhaust aftertreatment. For mobile sources, predominantly heavy duty diesel engines, selective catalytic reduction (SCR) with NH3 has become the principal means of NO x abatement. An alternative technology developed, but now surpassed by SCR, is NOx Storage Reduction (NSR) catalysis. Both technologies have been studied in our laboratory and are the basis for this dissertation. We studied seven different lean NOx trap (LNT) monolith formulations for NSR ranging from 0.6 to 6.2 wt.% Pt and 4 to 20 wt.% Ba loadings on γ-Al 2O3. The noble metal component of a LNT oxidizes NO to NO 2 aiding in the storage of NO2 on the alkaline earth component. Before the storage component saturates, a reductant such as H2 is introduced into the vehicular exhaust and the stored NOx is released and reduced to N2. Once the storage component is free of NOx, reductant flow is ceased and storage is begun anew. Our research focused on understanding the effects that CO2 and H2O have on the storage capacity of the LNT over short as well as extended periods of time. We found that for high Ba loadings, CO 2 had a consistently detrimental effect on the fast NOx storage capacity (NSC), defined as the amount of NOx the catalyst can store before 1% of the inlet NOx is measured in the reactor outlet. Over long NOx storage periods, CO2 continued to inhibit storage compared to the same catalyst in CO2 free conditions. On low loadings of Ba, however, the inhibition of CO2 was significantly reduced. We found that the loading dependent characteristics of the Ba phase affected the way in which CO2 adsorbed on the storage component, which greatly affected the stability of the species on lower Ba loadings. The less stable adsorbed CO2 proved less competitive for NOx sorption sites, explaining the weak reduction of NSC by CO2 on low Ba loadings. Contrary to CO2, H2O exhibited both beneficial and inhibitory effects on the NSC. Over long periods of time, and at high Ba loadings, the addition of H2O in the feed increased the NSC, attributed to enhanced O2 spillover on the hydroxylated Ba surface allowing greater access to available NOx storage sites. When the Ba loading was reduced, the interaction sphere of Pt particles with the Ba storage component required for O2 to spillover to assist in NOx storage was reduced. Thus, despite the enhanced spillover capacity of oxygen on the hydroxylated storage component other NSC decreasing effects of H2O addition, such as Ba agglomeration, became more dominant and reduced the NSC. Recent developments in selective catalytic reduction have shown Cu and Fe/chabazite (CHA) based zeolites to be particularly well suited to sustaining high catalytic rates without degradation in the harsh environment of diesel engine exhaust. Little has been published about these catalysts as the academic community has just recently learned about the materials and their commercial implementation. Using operando X-ray absorption spectroscopy, combined with first-principles thermodynamics simulations and kinetic analysis, we have studied the nature of the Cu active site on Cu/SSZ-13, Cu/SAPO-34 and Cu/ZSM-5. Examining the catalysts under operando standard SCR conditions (300 ppm NO, 300 ppm NH3, 5% O2, 5% H2O and 5% CO2) showed the catalyst to be in a mixed Cu(I)-Cu(II) oxidation state. Neither the amount of Cu(I) nor Cu(II) individually correlated with the different rates measured on the various zeolite catalysts, and so we proposed that the SCR reaction progresses via a redox mechanism requiring both Cu(I) and Cu(II). First principles thermodynamic calculations found that the redox couple of Cu(I)H2O and Cu(II)(OH)2 were the most thermodynamically stable species of any of the OxHy variants modeled on Cu. The redox nature of the Cu active site was further investigated in a follow up study isolating the reducing portion of the SCR by removing O 2 from the reaction feed. Cutting off O2 drove the catalyst into a highly reduced state dominated by Cu(I) while removing a reductant drove the Cu into the fully oxidized state. Our research shows that not only is redox a vital part of the SCR reaction on Cu/zeolites, but that the oxidation state of the active site is highly sensitive to the gas environment. The water-gas shift (WGS) reaction is an industrially important step in H2 generation from steam reforming. I have had the opportunity to contribute to a number of studies in WGS by studying the catalysts in FTIR. We studied numerous catalytic formulations including Fe promoted Pd/Al 2O3 and Au/TiO2. We found that the Fe promoted the WGS rate of the catalyst by a factor of 160 compared to the Fe free Pd/Al 2O3. The reduced Fe promoter efficiently split H2O, typically the role performed by reducible supports, and the nearby noble metal particles provided spillover H2 to maintain the reduced Fe phase necessary to split H2O. Our study of Au/TiO2 involved the development of a modified operando transmission IR cell with ultra-low dead volume allowing for fast switching isotope experiments over the catalyst. The isotope switching experiments showed that only CO adsorbed on Au0 sites was an active surface intermediate at 120°C. Counting the amount of active surface Au atoms for the reaction ruled out the Au particle surface and perimeter atoms as the dominant active sites and confirmed our previous finding that the active site was composed mostly of low coordinated corner Au atoms.

  14. Kinetics of oxygen-enhanced water gas shift on bimetallic catalysts and the roles of metals and support

    NASA Astrophysics Data System (ADS)

    Kugai, Junichiro

    The post-processing of reformate is an important step in producing hydrogen (H2) with low carbon monoxide (CO) for low temperature fuel cells from syn-gas. However, the conventional process consists of three steps, i.e. two steps of water gas shift (WGS) and preferential oxidation (PROX) of CO, and it is not suitable for mobile applications due to the large volume of water gas shift (WGS) catalysts and conditioning and/or regeneration necessary for these catalysts. Aiming at replacing those three steps by a simple one-step process, small amount of oxygen was added to WGS (the reaction called oxygen-enhanced water gas shift or OWGS) to promote the reaction kinetics and low pyrophoric ceria-supported bimetallic catalysts were employed for stable performance in this reaction. Not only CO conversion, but also H2 yield was found to increase by the O2 addition on CeO2-supported catalysts. The characteristics of OWGS, high H2 production rate at 200 to 300C at short contact time where unreacted O2 exists, evidenced the impact of O2 addition on surface species on the catalyst. Around 1.5 of reaction order in CO for various CeO2-supported metal catalysts for OWGS compared to reaction orders in CO ranging from -0.1 to 0.6 depending on metal species for WGS shows O2 addition decreases CO coverage to free up the active sites for co-reactant (H2O) adsorption and activation. Among the monometallic and bimetallic catalysts, Pt-Cu and Pd-Cu bimetallic catalysts were superior to monometallic catalysts in OWGS. These bimetallic components were found to form alloys where noble metal is surrounded mainly by Cu to have strong interaction between noble metal and copper resulting in high OWGS activity and low pyrophoric property. The metal loadings were optimized for CeO2-supported Pd-Cu bimetallic system and 2 wt% Pd with 5 -- 10 wt% Cu were found to be the optimum for the present OWGS condition. In the kinetic study, Pd in Pd-Cu was shown to increase the active sites for H2O dissociation and/or the subsequent reaction with chemisorbed CO as well as Pd keeps Cu in reduced state. Cu was found to keep Pd dispersed, suppress H2 activation on Pd, and facilitate CO 2 desorption from catalyst surface. While composition and structure of metal have large impacts on OWGS performance, CeO2 was shown to create new sites for H2O activation at metal-ceria interfacial region in concert with metal. These new sites strongly activate H2O to drive OWGS and WGS compared to the pure metallic sites which are present in majority on Al2O3-supported catalyst. The observed two regimes of turnover rate, the one dependent on catalyst surface area and the other independent of surface area, strongly suggested bifunctional reaction pathway where the reaction rate is determined by activation of H2O and by association of chemisorbed CO and H 2O. The associative route was also evidenced by pulse response study where the reaction occurs only when CO and H2O pulses are supplied together, and thus pre-adsorbed species such as formate and carbonate identified by FT-IR are proven to be spectators. No correlation between WGS rate and isotopic exchange rate of molecularly adsorbed D2O with H 2 showed H2O dissociation is necessary for WGS to occur. Long duration tests revealed CeO2-supported Pd-Cu, Pt-Cu and Cu catalysts are stable in OWGS condition compared to Pt, Pd, and Al 2O3-supported Pd-Cu catalysts which exhibited continuous deactivation during about 70 hours of test. The addition of Cu prevents agglomeration of monometallic Pd and carbonate formation on monometallic Pt during the reaction. The better activity and stability of Pd-Cu and Pt-Cu bimetallic catalysts in the realistic OWGS condition were ascribed to the unique active sites consisting of highly dispersed Pd in Cu or Pt in Cu on CeO2, which are good for H2O activation with low reaction inhibition by the product gases. Pt monometallic catalyst showed and highest activity in OWGS in the absence of product gases, but this was found vulnerable in the presence of product gases due to strong adsorption of H2 and CO2 on t

  15. Pilot Scale Water Gas Shift - Membrane Device for Hydrogen from Coal

    SciTech Connect

    Barton, Tom

    2013-06-30

    The objectives of the project were to build pilot scale hydrogen separation systems for use in a gasification product stream. This device would demonstrate fabrication and manufacturing techniques for producing commercially ready facilities. The design was a 2 lb/day hydrogen device which included composite hydrogen separation membranes, a water gas shift monolith catalyst, and stainless steel structural components. Synkera Technologies was to prepare hydrogen separation membranes with metallic rims, and to adjust the alloy composition in their membranes to a palladium-gold composition which is sulfur resistant. Chart was to confirm their brazing technology for bonding the metallic rims of the composite membranes to their structural components and design and build the 2 lbs/day device incorporating membranes and catalysts. WRI prepared the catalysts and completed the testing of the membranes and devices on coal derived syngas. The reactor incorporated eighteen 2'' by 7'' composite palladium alloy membranes. These membranes were assembled with three stacks of three paired membranes. Initial vacuum testing and visual inspection indicated that some membranes were cracked, either in transportation or in testing. During replacement of the failed membranes, while pulling a vacuum on the back side of the membranes, folds were formed in the flexible composite membranes. In some instances these folds led to cracks, primarily at the interface between the alumina and the aluminum rim. The design of the 2 lb/day device was compromised by the lack of any membrane isolation. A leak in any membrane failed the entire device. A large number of tests were undertaken to bring the full 2 lb per day hydrogen capacity on line, but no single test lasted more than 48 hours. Subsequent tests to replace the mechanical seals with brazing have been promising, but the technology remains promising but not proven.

  16. Parametric Gasification of Oak and Pine Feedstocks Using the TCPDU and Slipstream Water-Gas Shift Catalysis

    SciTech Connect

    Hrdlicka, J.; Feik, C.; Carpenter, D.; Pomeroy, M.

    2008-12-01

    With oak and pine feedstocks, the Gasification of Biomass to Hydrogen project maximizes hydrogen production using the Full Stream Reformer during water-gas shift fixed-bed reactor testing. Results indicate that higher steam-to-biomass ratio and higher thermal cracker temperature yield higher hydrogen concentration. NREL's techno-economic models and analyses indicate hydrogen production from biomass may be viable at an estimated cost of $1.77/kg (current) and $1.47/kg (advanced in 2015). To verify these estimates, NREL used the Thermochemical Process Development Unit (TCPDU), an integrated system of unit operations that investigates biomass thermochemical conversion to gaseous and liquid fuels and chemicals.

  17. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, July 1, 1990--September 30, 1990

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-12-31

    A Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al{sub 2}O{sub 3} water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240{degrees}C, a pressure of 0.79 MPa, and a 1.1 H{sub 2}/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO{sub 2} catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO{sub 2} operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts`s operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  18. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Final technical progress report, September 12, 1991--December 11, 1994

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.; Richards-Babb, M.; Carr, T.

    1995-07-01

    The objective of this research was to investigate sulfur-resistant catalysts for the conversion of synthesis gas having H{sub 2}/CO {le} 1 into C{sub 1}--C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway, while also promoting the water gas shift reaction (WGSR). The catalysts chosen are bifunctional, base-hydrogenation, sulfur-tolerant transition metal sulfides with heavy alkali, e.g. Cs{sup +}, promoter dispersed on their surfaces. The modes of activation of H{sub 2} and CO on MoS{sub 2} and alkali-doped MoS{sub 2} were considered, and computational analyses of the thermodynamic stability of transition metal sulfides and of the electronic structure of these sulfide catalysts were carried out. In the preparation of the cesium-promoted MoS{sub 2} catalysts, a variety of preparation methods using CsOOCH were examined. In all cases, doping with CsOOCH led to a lost of surface area. The undoped molybdenum disulfide catalyst only produced hydrocarbons. Cs-doped MoS{sub 2} catalysts all produced linear alcohols, along with smaller amounts of hydrocarbons. With a 20 wt% CsOOCH/MoS{sub 2} catalyst, temperature, pressure, and flow rate dependences of the synthesis reactions were investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 synthesis gas during short term testing experiments. It was shown that with a carefully prepared 10 wt% CsOOCH/MoS{sub 2} catalyst, reproducible and high alcohol synthesis activity could be obtained. For example, at 295 C with H{sub 2}/CO = 1 synthesis gas at 8.3 MPa and with GHSV = 7,760 l/kg cat/hr, the total alcohol space time yield was ca 300 g/kg cat/hr (accompanied with a hydrocarbon space time yield of ca 60 g/kg cat/hr). Over a testing period of ca 130 hr, no net deactivation of the catalyst was observed. 90 refs., 82 figs., 14 tabs.

  19. An innovative catalyst system for slurry-phase Fischer-Tropsch synthesis: Cobalt plus a water-gas-shift catalyst. Final technical report

    SciTech Connect

    Satterfield, C.N.; Yates, I.C.; Chanenchuk, C.

    1991-07-01

    The feasibility of using a mechanical mixture of a Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst and a Cu-ZnO/Al{sub 2}O{sub 3} water-gas-shift (WGS) catalyst for hydrocarbon synthesis in a slurry reactor has been established. Such a mixture can combine the superior product distribution from cobalt with the high activity for the WGS reaction characteristic of iron. Weight ratios of Co/MgO/SiO{sub 2} to Cu-ZnO/Al{sub 2}O{sub 3} of 0.27 and 0.51 for the two catalysts were studied at 240{degrees}C, 0.79 MPa, and in situ H{sub 2}/CO ratios between 0.8 and 3.0. Each catalyst mixture showed stable Fischer-Tropsch activity for about 400 hours-on-stream at a level comparable to the cobalt catalyst operating alone. The Cu-ZnO/Al{sub 2}O{sub 3} catalyst exhibited a very slow loss of activity under these conditions, but when operated alone it was stable in a slurry reactor at 200--220{degrees}C, 0.79--1.48 MPa, and H{sub 2}/CO in situ ratios between 1.0 and 2.0. The presence of the water-gas-shift catalyst did not affect the long-term stability of the primary Fischer-Tropsch selectivity, but did increase the extent of secondary reactions, such as l-alkene hydrogenation and isomerization.

  20. Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

    DOEpatents

    Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

    2003-09-23

    Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

  1. Robust Low-Cost Water-Gas Shift Membrane Reactor for High-Purity Hydrogen Production form Coal-Derived Syngas

    SciTech Connect

    James Torkelson; Neng Ye; Zhijiang Li; Decio Coutinho; Mark Fokema

    2008-05-31

    This report details work performed in an effort to develop a low-cost, robust water gas shift membrane reactor to convert coal-derived syngas into high purity hydrogen. A sulfur- and halide-tolerant water gas shift catalyst and a sulfur-tolerant dense metallic hydrogen-permeable membrane were developed. The materials were integrated into a water gas shift membrane reactor in order to demonstrate the production of >99.97% pure hydrogen from a simulated coal-derived syngas stream containing 2000 ppm hydrogen sulfide. The objectives of the program were to (1) develop a contaminant-tolerant water gas shift catalyst that is able to achieve equilibrium carbon monoxide conversion at high space velocity and low steam to carbon monoxide ratio, (2) develop a contaminant-tolerant hydrogen-permeable membrane with a higher permeability than palladium, (3) demonstrate 1 L/h purified hydrogen production from coal-derived syngas in an integrated catalytic membrane reactor, and (4) conduct a cost analysis of the developed technology.

  2. Water-Gas-Shift Membrane Reactor for High-Pressure Hydrogen Production. A comprehensive project report (FY2010 - FY2012)

    SciTech Connect

    Klaehn, John; Peterson, Eric; Orme, Christopher; Bhandari, Dhaval; Miller, Scott; Ku, Anthony; Polishchuk, Kimberly; Narang, Kristi; Singh, Surinder; Wei, Wei; Shisler, Roger; Wickersham, Paul; McEvoy, Kevin; Alberts, William; Howson, Paul; Barton, Thomas; Sethi, Vijay

    2013-01-01

    Idaho National Laboratory (INL), GE Global Research (GEGR), and Western Research Institute (WRI) have successfully produced hydrogen-selective membranes for water-gas-shift (WGS) modules that enable high-pressure hydrogen product streams. Several high performance (HP) polymer membranes were investigated for their gas separation performance under simulated (mixed gas) and actual syngas conditions. To enable optimal module performance, membranes with high hydrogen (H2) selectivity, permeance, and stability under WGS conditions are required. The team determined that the VTEC PI 80-051 and VTEC PI 1388 (polyimide from Richard Blaine International, Inc.) are prime candidates for the H2 gas separations at operating temperatures (~200C). VTEC PI 80-051 was thoroughly analyzed for its H2 separations under syngas processing conditions using more-complex membrane configurations, such as tube modules and hollow fibers. These membrane formats have demonstrated that the selected VTEC membrane is capable of providing highly selective H2/CO2 separation (? = 7-9) and H2/CO separation (? = 40-80) in humidified syngas streams. In addition, the VTEC polymer membranes are resilient within the syngas environment (WRI coal gasification) at 200C for over 1000 hours. The information within this report conveys current developments of VTEC PI 80-051 as an effective H2 gas separations membrane for high-temperature syngas streams.

  3. Do Ni/Cu and Cu/Ni alloys have different catalytic performances towards water-gas shift? A density functional theory investigation.

    PubMed

    Huang, Yu Cheng; Zhou, Tao; Liu, Hai; Ling, ChongYi; Wang, SuFan; Du, Jin Yan

    2014-08-25

    Density functional calculations were preformed to investigate whether adding Ni into a Cu surface (denoted as Cu/Ni) or adding Cu into a Ni surface (Ni/Cu) is more efficient for catalyzing the water-gas shift (WGS)? The reactions of water dissociation and monoxide dissociation were selected to assess the activity and selectivity towards WGS, respectively. Our results show that Ni-atom modification of surfaces is thermodynamically favorable for both reactions. Kinetically, compared with pure Cu, water dissociation is greatly facilitated on Ni-modified surfaces, and the activity is insensitive to the Ni concentration; however, monoxide dissociation is not well-promoted on one Ni-atom-modified surfaces, but two Ni-atom modification can notably decrease the dissociation barriers. Overall, on the basis of these results, we conclude that 1) the catalytic performance of bimetallic metals is superior to monometallic ones; 2) at the same Ni concentration on the surface, Cu/Ni and Ni/Cu alloys have almost the same performance towards WGS; and 3) to acquire high WGS performance, the surface Ni atoms should either be low in concentration or highly dispersed. PMID:25044560

  4. Sorption-Enhanced Synthetic Natural Gas (SNG) Production from Syngas. A Novel Process Combining CO Methanation, Water-Gas Shift, and CO2 Capture

    SciTech Connect

    Lebarbier, Vanessa M.C.; Dagle, Robert A.; Kovarik, Libor; Albrecht, Karl O.; Li, Xiaohong S.; Li, Liyu; Taylor, Charles E.; Bao, Xinhe; Wang, Yong

    2013-07-08

    Synthetic natural gas (SNG) production from syngas is under investigation again due to the desire for less dependency from imports and the opportunity for increasing coal utilization and reducing green house gas emission. CO methanation is highly exothermic and substantial heat is liberated which can lead to process thermal imbalance and deactivation of the catalyst. As a result, conversion per pass is limited and substantial syngas recycle is employed in conventional processes. Furthermore, the conversion of syngas to SNG is typically performed at moderate temperatures (275 to 325°C) to ensure high CH4 yields since this reaction is thermodynamically limited. In this study, the effectiveness of a novel integrated process for the SNG production from syngas at high temperature (i.e. 600°C) was investigated. This integrated process consists of combining a CO methanation nickel-based catalyst with a high temperature CO2 capture sorbent in a single reactor. Integration with CO2 separation eliminates the reverse-water-gas shift and the requirement for a separate water-gas shift (WGS) unit. Easing of thermodynamic constraint offers the opportunity of enhancing yield to CH4 at higher operating temperature (500-700ºC) which also favors methanation kinetics and improves the overall process efficiency due to exploitation of reaction heat at higher temperatures. Furthermore, simultaneous CO2 capture eliminates green house gas emission. In this work, sorption-enhanced CO methanation was demonstrated using a mixture of a 68% CaO/32% MgAl2O4 sorbent and a CO methanation catalyst (Ni/Al2O3, Ni/MgAl2O4, or Ni/SiC) utilizing a syngas ratio (H2/CO) of 1, gas-hour-space velocity (GHSV) of 22 000 hr-1, pressure of 1 bar and a temperature of 600°C. These conditions resulted in ~90% yield to methane, which was maintained until the sorbent became saturated with CO2. By contrast, without the use of sorbent, equilibrium yield to methane is only 22%. Cyclic stability of the methanation catalyst and durability of the sorbent were also studied in the multiple carbonation-decarbonation cycle studies proving the potential of this integrated process in a practical application.

  5. Redox cycle stability of mixed oxides used for hydrogen generation in the cyclic water gas shift process

    SciTech Connect

    Datta, Pradyot

    2013-10-15

    Graphical abstract: - Highlights: • Fe{sub 2}O{sub 3} modified with CaO, SiO{sub 2} and Al{sub 2}O{sub 3} was studied in cyclic water gas shift reactor. • For the first time stability of such oxides were tested for 100 redox cycles. • Optimally added oxides significantly improved the activity and the stability of Fe{sub 2}O{sub 3}. • Increased stability was attributed to the impediment of neck formation. - Abstract: Repeated cycles of the reduction of Fe{sub 3}O{sub 4} with reductive gas, e.g. hydrogen and subsequent oxidation of the reduced iron material with water vapor can be harnessed as a process for the production of pure hydrogen. The redox behavior of iron oxide modified with various amounts of SiO{sub 2}, CaO and Al{sub 2}O{sub 3} was investigated in the present study. The total amount of the additional metal oxides was always below 15 wt%. The samples were prepared by co-precipitation using urea hydrolysis method. The influence of various metal oxides on the hydrogen production capacity and the material stability was studied in detail in terms of temperature-programmed reduction (TPR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. Furthermore, the activity and the stability of the samples were tested in repeated reduction with diluted H{sub 2} and re-oxidation cycles with H{sub 2}O. The results indicate that combination of several oxides as promoter increases the stability of the iron oxide material by mitigating the sintering process. The positive influence of the oxides in stabilizing the iron oxide material is attributed to the impediment of neck formation responsible for sintering.

  6. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts; Technical progress report, June 1992--August 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.

    1992-09-01

    During this quarter, high pressure (up to 100 atm = 10.3 MPa), high temperature (up to 350{degrees}C) catalyst testing was carried out with the 20 Wt% CS/MoS{sub 2} catalyst that was prepared. It was verified that this is an active catalyst for the synthesis of linear C{sub l}-C{sub 4} alcohols and that the yield increases with increasing temperature. However, the product selectivity is shifted toward enhanced hydrocarbon production, principally of methane. Temperature, pressure, and flow rate dependences of the synthesis reactions were also investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 Synthesis gas during short term testing experiments. The temperature seemed to produce the largest effect on alcohol yield and on the hydrocarbon selectivity, with both increasing with increasing temperature. The presence of 45.5 ppM H{sub 2}S in the synthesis gas did increase the C{sub 2}{sup +} alcohol/methanol molar ratio at 285{degrees}C, but this effect was not noticeable at higher temperatures under the reaction conditions that were employed. On the other hand, the presence of H{sub 2}S decreased the yield of methane at high temperatures (340--350{degrees}C), but this effect was not noticeable at the lower temperatures that were utilized. At high temperature and pressure (350{degrees}C and 10.3 MPa) with 45.5 ppM H{sub 2}S in the synthesis gas, it was shown that increasing the gas hourly space velocity of the synthesis gas reactant significantly decreased the yield of methane, while affecting the yield of alcohols to a much lesser extent.

  7. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1988--December 31, 1988

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-12-31

    A cobalt Fischer-Tropsch catalyst (CO/MgO/silica) was reduced and slurried in combination with reduced Cu/ZnO/Al{sub 2}0{sub 3} water-gas-shift catalyst. Combined catalyst system was run at fixed process conditions for more than 400 hours. The system showed stable selectivity. The Cu/ZnO/Al{sub 2}0{sub 3} water-gas-shift catalyst remained reasonably active in the presence of the cobalt catalyst. Hydrocarbon selectivity of the cobalt and Cu/ZnO/Al{sub 2}0{sub 3} catalyst system compared favorably to selectivity of iron-based catalysts. Methane selectivity was slightly higher for the cobalt-based system, but C{sub 5}{sup +} selectivity was essentially the same. The hydrocarbon product distribution appeared to exhibit a double-a behavior. a{sub 1} was near 0.80 which is higher than that of iron catalysts, while a{sub 2} was calculated to be 0.86 which is somewhat lower than would be typical for an iron-based catalyst.

  8. Water Gas Shift Reaction with A Single Stage Low Temperature Membrane Reactor

    SciTech Connect

    Ciora, Richard J; Liu, Paul KT

    2013-12-31

    Palladium membrane and Palladium membrane reactor were developed under this project for hydrogen separation and purification for fuel cell applications. A full-scale membrane reactor was designed, constructed and evaluated for the reformate produced from a commercial scale methanol reformer. In addition, the Pd membrane and module developed from this project was successfully evaluated in the field for hydrogen purification for commercial fuel cell applications.

  9. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, June 30, 1988--September 30, 1988

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-12-31

    This report details experiments performed on three different copper-based catalysts: Cu/Cr{sub 2}O{sub 3}, Cu/MnO/Cr{sub 2}O{sub 3} and Cu/ZnO/Al{sub 2}O{sub 3}. Of these three catalysts, the Cu/ZnO/Al{sub 2}O{sub 3} exhibits the greatest stability when slurried in octacosane. More than 1000 hours-on-stream indicate that the catalyst activity is not detrimentally affected by high pressure, high H{sub 2}/CO ratio, or the presence of alkenes. All of these are necessary stability characteristics for the water-gas shift catalyst, if it is to be used in combination with a cobalt Fischer-Tropsch catalyst. A review of documented reduction procedures for cobalt-based Fischer-Tropsch catalysts is presented.

  10. Determination of the Effect of Coal/Biomass-Derived Syngas Contaminants on the Performance of Fischer-Tropsch and Water-Gas-Shift Catalysts

    SciTech Connect

    Trembly, Jason; Cooper, Matthew; Farmer, Justin; Turk, Brian; Gupta, Raghubir

    2010-12-31

    Today, nearly all liquid fuels and commodity chemicals are produced from non-renewable resources such as crude oil and natural gas. Because of increasing scrutiny of carbon dioxide (CO{sub 2}) emissions produced using traditional fossil-fuel resources, the utilization of alternative feedstocks for the production of power, hydrogen, value-added chemicals, and high-quality hydrocarbon fuels such as diesel and substitute natural gas (SNG) is critical to meeting the rapidly growing energy needs of modern society. Coal and biomass are particularly attractive as alternative feedstocks because of the abundant reserves of these resources worldwide. The strategy of co-gasification of coal/biomass (CB) mixtures to produce syngas for synthesis of Fischer-Tropsch (FT) fuels offers distinct advantages over gasification of either coal or biomass alone. Co-feeding coal with biomass offers the opportunity to exploit economies of scale that are difficult to achieve in biomass gasification, while the addition of biomass to the coal gasifier feed leverages proven coal gasification technology and allows CO{sub 2} credit benefits. Syngas generated from CB mixtures will have a unique contaminant composition because coal and biomass possess different concentrations and types of contaminants, and the final syngas composition is also strongly influenced by the gasification technology used. Syngas cleanup for gasification of CB mixtures will need to address this unique contaminant composition to support downstream processing and equipment. To investigate the impact of CB gasification on the production of transportation fuels by FT synthesis, RTI International conducted thermodynamic studies to identify trace contaminants that will react with water-gas-shift and FT catalysts and built several automated microreactor systems to investigate the effect of single components and the synergistic effects of multiple contaminants on water-gas-shift and FT catalyst performance. The contaminants investigated were sodium chloride (NaCl), potassium chloride (KCl), hydrogen sulfide (H{sub 2}S), carbonyl sulfide (COS), ammonia (NH{sub 3}), and combinations thereof. This report details the thermodynamic studies and the individual and multi-contaminant results from this testing program.

  11. Effect of adding Co to MoS{sub 2}/Al{sub 2}O{sub 3} upon the kinetics of the water-gas shift

    SciTech Connect

    Lund, C.R.F.

    1996-09-01

    A microkinetic model for the kinetics of the water-gas shift over sulfided CoMo/Al{sub 2}O{sub 3} catalysts was developed starting from a similar model for unpromoted sulfided Mo/Al{sub 2}O{sub 3} catalysts. Co was found to promote the catalyst`s activity only at low CO/H{sub 2}O ratios; at high ratios the Mo catalyst was marginally more active than the CoMo catalyst. The most important different between the two models was the strength of interactions between the surface and hydroxyl groups. The addition of Co increased the stability of hydroxyl groups relative to sulfhydryl groups, and at higher H{sub 2}O concentrations this allowed oxidized surface sites to more readily participate in both steam adsorption and hydrogen desorption steps. The results are most easily reconciled in terms of a promotional model where the Co and Mo are in close proximity and the active sites are similar to sites on unpromoted Mo catalysts.

  12. Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

    SciTech Connect

    Alptekin, Gokhan

    2013-02-15

    Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H2S, NH3, HCN, AsH3, PH3, HCl, NaCl, KCl, AS3, NH4NO3, NH4OH, KNO3, HBr, HF, and HNO3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

  13. Role of metal components in Pd?Cu bimetallic catalysts supported on CeO2 for the oxygen-enhanced water gas shift

    SciTech Connect

    Kugai, J.; Miller, J. T.; Guo, N.; Song, C.

    2011-06-01

    Catalytic hydrogen production and CO removal in a post-reforming process are critical for low-temperature fuel cell applications. The present study aims at clarifying the role of metal components in bimetallic catalysts for oxygen-enhanced water gas shift (OWGS), wherein a small amount of O{sub 2} is added to H{sub 2}-rich reformate gas to enhance CO shift. Among CeO{sub 2}-supported bimetallic catalysts, Pd-Cu and Pt-Cu combinations were found to show strong synergetic promoting effect in OWGS, which leads to much higher CO conversion and higher H{sub 2} yield than WGS at low temperature around 250 C. Temperature programmed reduction (TPR) showed strong interaction between Pd and Cu in Pd-Cu/CeO{sub 2} by a single reduction peak in contrast to multiple peaks on monometallic Cu/CeO{sub 2}. Extended X-ray absorption fine structure (EXAFS) analysis revealed that such bimetallic Pd-Cu and Pt-Cu form alloy nanoparticles, where noble metal is mainly surrounded by Cu atoms. Oxygen storage capacity (OSC) measurements point to higher resistance of Pd-Cu to oxidation indicating that Pd keeps Cu in reduced state in air pulse condition. From kinetic study, Pd in Pd-Cu was found to promote CO shift, rather than CO oxidation by increasing the number of active sites and by suppressing H{sub 2} activation (that is inherent to monometallic Pd), which minimizes both the inhibition effect of H{sub 2} and the loss of H{sub 2} by oxidation in OWGS. Transient response technique revealed that Cu in Pd-Cu enhances desorption of strongly chemisorbed CO{sub 2} on catalyst surface in contrast to very slow CO{sub 2} desorption from surface of monometallic Pd. Thus, the excellent OWGS activity of Pd-Cu catalyst has been attributed to the complementary roles of the two metals for enhancing CO shift, which is realized by its alloy structure and the accompanying strong interaction between metal components.

  14. Gold, Copper, and Platinum Nanoparticles Dispersed on CeOx/TiO2(110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level

    SciTech Connect

    Park, J.; Graciani, J; Evans, J; Stacchiola, D; Senanayake, S; Barrio, L; Liu, P; Fdez. Sanz, J; Hrbek, J; Rodriguez, J

    2010-01-01

    At small coverages of ceria on TiO{sub 2}(110), the CeO{sub x} nanoparticles have an unusual coordination mode. Scanning tunneling microscopy and density-functional calculations point to the presence of Ce{sub 2}O{sub 3} dimers, which form diagonal arrays that have specific orientations of 0, 24, and 42{sup o} with respect to the [1 -1 0] direction of the titania substrate. At high coverages of ceria on TiO{sub 2}(110), the surface exhibits two types of terraces. In one type, the morphology is not very different from that observed at low ceria coverage. However, in the second type of terrace, there is a compact array of ceria particles with structures that do not match the structures of CeO{sub 2}(111) or CeO{sub 2}(110). The titania substrate imposes on the ceria nanoparticles nontypical coordination modes, enhancing their chemical reactivity. This phenomenon leads to a larger dispersion of supported metal nanoparticles (M = Au, Cu, Pt) and makes possible the direct participation of the oxide in catalytic reactions. The M/CeO{sub x}/TiO{sub 2}(110) surfaces display an extremely high catalytic activity for the water-gas shift reaction that follows the sequence Au/CeO{sub x}/TiO{sub 2}(110) < Cu/CeO{sub x}/TiO{sub 2}(110) < Pt/CeO{sub x}/TiO{sub 2}(110). For low coverages of Cu and CeO{sub x}, Cu/CeO{sub x}/TiO{sub 2}(110) is 8-12 times more active than Cu(111) or Cu/ZnO industrial catalysts. In the M/CeO{sub x}/TiO{sub 2}(110) systems, there is a strong coupling of the chemical properties of the admetal and the mixed-metal oxide: The adsorption and dissociation of water probably take place on the oxide, CO adsorbs on the admetal nanoparticles, and all subsequent reaction steps occur at the oxide-admetal interface. The high catalytic activity of the M/CeO{sub x}/TiO{sub 2}(110) surfaces reflects the unique properties of the mixed-metal oxide at the nanometer level.

  15. Gold, Copper and Platinum Nanoparticles Dispersed on CeOx/TiO2(110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level

    SciTech Connect

    Rodriguez, J.A.; Park, J.B.; Graciani, J.; Evans, J.; Stacchiola, D.; Senanayake, S.D.; Barrio, L.; Liu, P.; Sanz, J.F.; Hrbek, J.

    2010-01-13

    At small coverages of ceria on TiO{sub 2}(110), the CeO{sub x} nanoparticles have an unusual coordination mode. Scanning tunneling microscopy and density-functional calculations point to the presence of Ce{sub 2}O{sub 3} dimers, which form diagonal arrays that have specific orientations of 0, 24, and 42{sup o} with respect to the [1 -1 0] direction of the titania substrate. At high coverages of ceria on TiO{sub 2}(110), the surface exhibits two types of terraces. In one type, the morphology is not very different from that observed at low ceria coverage. However, in the second type of terrace, there is a compact array of ceria particles with structures that do not match the structures of CeO{sub 2}(111) or CeO{sub 2}(110). The titania substrate imposes on the ceria nanoparticles nontypical coordination modes, enhancing their chemical reactivity. This phenomenon leads to a larger dispersion of supported metal nanoparticles (M = Au, Cu, Pt) and makes possible the direct participation of the oxide in catalytic reactions. The M/CeO{sub x}/TiO{sub 2}(110) surfaces display an extremely high catalytic activity for the water-gas shift reaction that follows the sequence Au/CeO{sub x}/TiO{sub 2}(110) < Cu/CeO{sub x}/TiO{sub 2}(110) < Pt/CeO{sub x}/TiO{sub 2}(110). For low coverages of Cu and CeO{sub x}, Cu/CeO{sub x}/TiO{sub 2}(110) is 8-12 times more active than Cu(111) or Cu/ZnO industrial catalysts. In the M/CeO{sub x}/TiO{sub 2}(110) systems, there is a strong coupling of the chemical properties of the admetal and the mixed-metal oxide: The adsorption and dissociation of water probably take place on the oxide, CO adsorbs on the admetal nanoparticles, and all subsequent reaction steps occur at the oxide-admetal interface. The high catalytic activity of the M/CeO{sub x}/TiO{sub 2}(110) surfaces reflects the unique properties of the mixed-metal oxide at the nanometer level.

  16. Water gas furnace

    SciTech Connect

    Gallaro, C.

    1985-12-03

    A water gas furnace comprising an outer container to provide a housing in which coke is placed into its lower part. A water container is placed within the housing. The coke is ignited and heats the water in the container converting it into steam. The steam is ejected into the coke, which together with air, produces water gas. Preferably, pumice stones are placed above the coke. The water gas is accepted into the pores of the pumice stones, where the heated pumice stones ignite the water gas, producing heat. The heat is extracted by a heat exchanger provided about the housing.

  17. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2002-03-01

    To become a viable CO{sub 2} transport membrane, a reversible interaction between CO{sub 2} and the membrane material at the operating condition is a must. In the past quarter, we have conducted a comprehensive reversibility study using TGA and MS at {approx}200 C for both adsorption and desorption. This quarterly report summarizes the results. Evidently, CO{sub 2} can be reversible adsorbed and desorbed on the hydrotalcite surface via a pressure swing operation (i.e., between 1 bar and vacuum). About 2wt% working capacity was obtained. Even in the presence of water, the reversibility still holds. In the next quarter, we will focus on the reversibility under other operating conditions and the kinetic aspect of the reversibility study.

  18. Investigation of the Reverse Water Gas Shift Reaction for Production of Oxygen From Mars Atmospheric Carbon Dioxide

    NASA Technical Reports Server (NTRS)

    Meyer, Tom; Zubrin, Robert

    1997-01-01

    The first phase of the research includes a comprehensive analytical study examining the potential applications for engineering subsystems and mission strategies made possible by such RWGS based subsystems, and will include an actual experimental demonstration and performance characterization of a full-scale brassboard RWGS working unit. By the time of this presentation the laboratory demonstration unit will not yet be operational but we will present the results of our analytical studies to date and plans for the ongoing work.

  19. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2002-08-01

    As part of our optimization effort, we have conducted a comprehensive study to investigate the morphology and crystal growth kinetics of hydrotalcite powder formation. Based upon the information obtained from this study, we resumed the membrane optimization activities. Although the selectivity of the membrane remains in the Knudsen regime, the permeance decreases along with the number of impregnation. Thus, the permeance could be reduced to a minimum through repeated impregnation. Then, the membrane can be sealed with chemical vapor deposition technique. More characterization results on the membranes prepared will be available in the next quarterly report.

  20. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2003-05-20

    Hydrotalcite material properties, specifically its CO{sub 2} reversibility, are critical to the performance of the proposed hydrotalcite-based membrane. In this report, we summarize the fundamental study we have performed using TGA, TGA/MS, and DRIFTS to quantify the degree of CO{sub 2} reversibility for the temperature range from 200 to 300 C. Results from these three separate studies consistently exhibit the CO{sub 2} reversibility. In addition, water effect appears negligible. Finally a high-pressure experimental study was performed to determine the reversibility under the actual operating condition. The results from this high-pressure (CO{sub 2}) study also demonstrate the CO{sub 2} reversibility. In the next quarter, we will continue the high-pressure experiment in the presence of high-pressure steam to quantify its effect under the actual WGS environment. The quantitative information obtained from this study will then be incorporated in a mathematical model describing the CO{sub 2} permeance as a function of the membrane layer thickness.

  1. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Dennis Sparks; Khalid Azzam; Janet Chakkamadathil Mohandas; Wilson Shafer; Venkat Ramana Rao Pendyala

    2011-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities at different concentration levels of added contaminant.

  2. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Janet ChakkamadathilMohandas; Wilson Shafer

    2009-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.

  3. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burtron Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Dennis Sparks; Wilson Shafer

    2010-09-30

    The successful adaptation of conventional cobalt and iron-based Fischer-Tropsch synthesis catalysts for use in converting biomass-derived syngas hinges in part on understanding their susceptibility to byproducts produced during the biomass gasification process. With the possibility that oil production will peak in the near future, and due to concerns in maintaining energy security, the conversion of biomass-derived syngas and syngas derived from coal/biomass blends to Fischer-Tropsch synthesis products to liquid fuels may provide a sustainable path forward, especially considering if carbon sequestration can be successfully demonstrated. However, one current drawback is that it is unknown whether conventional catalysts based on iron and cobalt will be suitable without proper development because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using an entrained-flow oxygen-blown gasifier) than solely from coal, other byproducts may be present in higher concentrations. The current project examines the impact of a number of potential byproducts of concern from the gasification of biomass process, including compounds containing alkali chemicals like the chlorides of sodium and potassium. In the second year, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities.

  4. Influence of Rotating Shift Work on Visual Reaction Time and Visual Evoked Potential

    PubMed Central

    N, Krishnamurthy; A, Saravanan

    2014-01-01

    Background: The present day life style is changing the circadian rhythm of the body especially in rotating night shift workers. The impact of this prolongs their reaction time. Night shift also interferes with the circadian variation of pupil size which may affect the visual evoked potential. Aim: To compare the visual reaction time, visual evoked potential (VEP) in rotating night shift workers & day workers and also to correlate the changes in visual reaction time with visual evoked potential. Materials and Methods: Forty healthy male security guards & staff (25 35 y) who did rotating night shifts at least for six months & 40 d workers (25 35 y) who did not do night shift in last two years were involved in the study. Visual reaction time and the latency & amplitude of VEP were recorded. Result: Kolmogorov- Smirnov test for normalcy showed the latencies & amplitude of VEP to be normally distributed. Students unpaired t test showed significant difference (p<0.05) in the visual time and in the latencies of VEP between night shift & day workers. There was no significant difference in the amplitude of VEP. Conclusion: Night shift workers who are prone to circadian rhythm alteration will have prolonged visual reaction time & visual evoked potential abnormalities. Implementation of Bright Light Therapy would be beneficial to the night shift worker. PMID:25478332

  5. Acceptance on the move: public reaction to shifting vaccination realities.

    PubMed

    Velan, Baruch

    2011-12-01

    This review examines four events related to vaccination that have occurred in recent years: (a) the ongoing recovery from the MMR/Autism scare in the UK, (b) the upgrading of the Varicella vaccine to a universal childhood vaccine, (c) the major effort of authorities to provide a vaccine for A/H1N1 influenza and its rejection by the public, and, d) the current attempts to change the HPV vaccine target from girls only to boys and girls. All of these changes have been met with shifts in the public acceptance of the relevant vaccine. These shifts are characterized not only by the number of people willing to be vaccinated, but also by the attitudes and the motives related to acceptance. Examination of the interrelationship between changes in vaccination realities, and changes in acceptance patterns suggests that today, the public has a better understanding of vaccination, is acting in a more reflexive way, and is capable of changing attitudes and behavior. All together, changes in vaccination enhance debates and dialogues about vaccines, and lead to higher awareness and more conscious acceptance. PMID:22108039

  6. Theoretical Investigation of Intramolecular Hydrogen Shift Reactions in 3-Methyltetrahydrofuran (3-MTHF) Oxidation.

    PubMed

    Parab, Prajakta R; Sakade, Naoki; Sakai, Yasuyuki; Fernandes, Ravi; Heufer, K Alexander

    2015-11-01

    3-Methyltetrahydrofuran (3-MTHF) is proposed to be a promising fuel component among the cyclic oxygenated species. To have detailed insight of its combustion kinetics, intramolecular hydrogen shift reactions for the ROO to QOOH reaction class are studied for eight ROO isomers of 3-MTHF. Rate constants of all possible reaction paths that involve formation of cyclic transition states are computed by employing the CBS-QB3 composite method. A Pitzer-Gwinn-like approximation has been applied for the internal rotations in reactants, products, and transition states for the accurate treatment of hindered rotors. Calculated relative barrier heights highlight that the most favorable reaction channel proceeds via a six membered transition state, which is consistent with the computed rate constants. Comparing total rate constants in ROO isomers of 3-MTHF with the corresponding isomers of methylcyclopentane depicts faster kinetics in 3-MTHF than methylcyclopentane reflecting the effect of ring oxygen on the intramolecular hydrogen shift reactions. PMID:26444499

  7. Evaluation of C-14 as a natural tracer for injected fluids at theAidlin sector of The Geysers geothermal system through modeling ofmineral-water-gas Reactions

    SciTech Connect

    Dobson, Patrick; Sonnenthal, Eric; Lewicki, Jennifer; Kennedy, Mack

    2006-06-01

    A reactive-transport model for 14C was developed to test its applicability to the Aidlin geothermal system. Using TOUGHREACT, we developed a 1-D grid to evaluate the effects of water injection and subsequent water-rock-gas interaction on the compositions of the produced fluids. A dual-permeability model of the fracture-matrix system was used to describe reaction-transport processes in which the permeability of the fractures is many orders of magnitude higher than that of the rock matrix. The geochemical system included the principal minerals (K-feldspar, plagioclase, calcite, silica polymorphs) of the metagraywackes that comprise the geothermal reservoir rocks. Initial simulation results predict that the gas-phase CO2 in the reservoir will become more enriched in 14C as air-equilibrated injectate water (with a modern carbon signature) is incorporated into the system, and that these changes will precede accompanying decreases in reservoir temperature. The effects of injection on 14C in the rock matrix will be lessened somewhat because of the dissolution of matrix calcite with ''dead'' carbon.

  8. Electronic shift register memory based on molecular electron-transfer reactions

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

    1989-01-01

    The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

  9. The posterior shift anticipatory postural adjustment in choice reaction step initiation.

    PubMed

    Sun, Ruopeng; Guerra, Richard; Shea, John B

    2015-05-01

    The ability to step quickly in response to a perturbation has been shown to be critical for prevention of falls. The cognitive processing, weight shifting, and locomotion must be well timed to execute a successful step. The purpose of this study was to compare the response preparation and response execution processes between a simple (SRST) and a choice reaction stepping task (CRST). Nine healthy young subjects were recruited to participate in this study. Subjects were required to stand on a forceplate and maintain their balance, and step forward on a second forceplate with either the left or right foot after hearing an auditory tone. The center of pressure (COP) was analyzed to determine the types of anticipatory postural adjustment (APA) prior to a step. The APA phase and stepping phase timing was calculated based on the COP trajectory. Findings showed that reaction time (RT), APA phase and overall stepping latency were slower for CRST than for SRST. We also identified an intermediate type of APA response (posterior shift APA) in addition to the correct and error APA response, and found the posterior shift APA response had the fastest execution time for CRST, and may be beneficial for falls prevention. PMID:25863873

  10. High-throughput electrophoretic mobility shift assays for quantitative analysis of molecular binding reactions.

    PubMed

    Pan, Yuchen; Duncombe, Todd A; Kellenberger, Colleen A; Hammond, Ming C; Herr, Amy E

    2014-10-21

    We describe a platform for high-throughput electrophoretic mobility shift assays (EMSAs) for identification and characterization of molecular binding reactions. A photopatterned free-standing polyacrylamide gel array comprised of 8 mm-scale polyacrylamide gel strips acts as a chassis for 96 concurrent EMSAs. The high-throughput EMSAs was employed to assess binding of the Vc2 cyclic-di-GMP riboswitch to its ligand. In optimizing the riboswitch EMSAs on the free-standing polyacrylamide gel array, three design considerations were made: minimizing sample injection dispersion, mitigating evaporation from the open free-standing polyacrylamide gel structures during electrophoresis, and controlling unit-to-unit variation across the large-format free-standing polyacrylamide gel array. Optimized electrophoretic mobility shift conditions allowed for 10% difference in mobility shift baseline resolution within 3 min. The powerful 96-plex EMSAs increased the throughput to ?10 data/min, notably more efficient than either conventional slab EMSAs (?0.01 data/min) or even microchannel based microfluidic EMSAs (?0.3 data/min). The free-standing polyacrylamide gel EMSAs yielded reliable quantification of molecular binding and associated mobility shifts for a riboswitch-ligand interaction, thus demonstrating a screening assay platform suitable for riboswitches and potentially a wide range of RNA and other macromolecular targets. PMID:25233437

  11. High-Throughput Electrophoretic Mobility Shift Assays for Quantitative Analysis of Molecular Binding Reactions

    PubMed Central

    2015-01-01

    We describe a platform for high-throughput electrophoretic mobility shift assays (EMSAs) for identification and characterization of molecular binding reactions. A photopatterned free-standing polyacrylamide gel array comprised of 8 mm-scale polyacrylamide gel strips acts as a chassis for 96 concurrent EMSAs. The high-throughput EMSAs was employed to assess binding of the Vc2 cyclic-di-GMP riboswitch to its ligand. In optimizing the riboswitch EMSAs on the free-standing polyacrylamide gel array, three design considerations were made: minimizing sample injection dispersion, mitigating evaporation from the open free-standing polyacrylamide gel structures during electrophoresis, and controlling unit-to-unit variation across the large-format free-standing polyacrylamide gel array. Optimized electrophoretic mobility shift conditions allowed for 10% difference in mobility shift baseline resolution within 3 min. The powerful 96-plex EMSAs increased the throughput to ?10 data/min, notably more efficient than either conventional slab EMSAs (?0.01 data/min) or even microchannel based microfluidic EMSAs (?0.3 data/min). The free-standing polyacrylamide gel EMSAs yielded reliable quantification of molecular binding and associated mobility shifts for a riboswitchligand interaction, thus demonstrating a screening assay platform suitable for riboswitches and potentially a wide range of RNA and other macromolecular targets. PMID:25233437

  12. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.

    1992-03-01

    The objective of the proposed research is to investigate and develop a novel catalytic process for the conversion of coal-derived synthesis gas into high octane C{sub 1}-C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway. (VC)

  13. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.; Kieke, M.

    1991-12-01

    The objective of the proposed research is to investigate and develop a novel catalytic process for the conversion of coal-derived synthesis gas into high octane C{sub 1}{minus}C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway.

  14. Lamb shift in radical-ion pairs produces a singlet-triplet energy splitting in photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Vitalis, K. M.; Kominis, I. K.

    2014-09-01

    Radical-ion pairs, fundamental for understanding photosynthesis and the avian magnetic compass, were recently shown to be biological open quantum systems. We here show that the coupling of the radical-pair spin degrees of freedom to its decohering vibrational reservoir leads to a shift of the radical-pair magnetic energy levels. The Lamb shift Hamiltonian is diagonal in the singlet-triplet basis, and results in a singlet-triplet energy splitting physically indistinguishable from an exchange interaction. This could have significant implications for understanding the energy level structure and the dynamics of photosynthetic reaction centers.

  15. Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

    SciTech Connect

    Turov, A.V.; Khilya, V.P.

    1994-10-01

    The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

  16. Kinetic analysis of the phenyl-shift reaction in $\\beta$-O-4 lignin model compounds: A computational study.

    SciTech Connect

    Beste, Ariana; Buchanan III, A C

    2011-01-01

    The phenyl-shift reaction in $\\beta$-phenethyl phenyl ether ($\\beta - \\rm PhCH_2CH_2OPh$, $\\beta$-PPE) is an integral step in the pyrolysis of PPE, which is a model compound for the $\\beta$-O-4 linkage in lignin. We investigated the influence of natural occurring substituents (hydroxy, methoxy) on the reaction rate by calculating relative rate constant using density functional theory in combination with transition state theory, including anharmonic correction for low-frequency modes. The phenyl-shift reaction proceeds through an intermediate and the overall rate constants were computed invoking the steady-state approximation (its validity was confirmed). Substituents on the phenethyl group have only little influence on the rate constants. If a methoxy substituent is located in para position of the phenyl ring adjacent to the ether oxygen, the energies of the intermediate and second transition state are lowered, but the overall rate constant is not significantly altered. This is a consequence of the dominating first transition from pre-complex to intermediate in the overall rate constant. {\\it O}- and di-{\\it o}-methoxy substituents accelerate the phenyl-migration rate compared to $\\beta$-PPE.

  17. Nanoconfined nitrogen hydrogenation on Ru(0001): Prediction of entropy related shifts in the reaction equilibria

    NASA Astrophysics Data System (ADS)

    Polak, Micha; Rubinovich, Leonid

    2015-11-01

    Remarkable variations in NHx (x = 1,2,3) equilibrium molecular fractions are revealed by statistical-mechanical computations for a system composed of only few reactant atoms that are confined to nanoscale Ru(0001) surface. Using one of two sets of reported DFT-based reaction energetics as input, NH formation on the flat surface is enhanced up to ~ 50% compared to the thermodynamic limit (TL) of the macroscopic system. This nanoconfinement entropic effect on chemical equilibrium (NCECE), introduced and demonstrated by us before for some hypothetical reactions, originates from mixing entropy reduction in the small-system that increases the product molecular fraction in exothermic reactions, as is fully elucidated here for the case of NH. The other input set gives an opposite effect due to the reaction endothermicity on both flat and stepped surfaces. For concurrent ND and NH formation, including H - D exchange, the temperature and coverage dependent superposition of the three NCECE contributions have a significant effect on two of the three equilibrium constants of the coupled reactions, and increase/decrease the ND/NH fractions. The computed TL low fractions of NH2 and NH3 in the coupled three hydrogenation steps are further diminished by the NCECE, suggesting that from this aspect ammonia synthesis on smaller particles is expected to be less effective.

  18. Side feeding patterns and nuclear lifetime determinations by the Doppler shift attenuation method in ({alpha},n{gamma}) reactions

    SciTech Connect

    Mihai, C.; Filipescu, D.; Ivascu, M.; Bucurescu, D.; Cata-Danil, G.; Cata-Danil, I.; Deleanu, D.; Ghita, D.; Glodariu, T.; Marginean, N.; Marginean, R.; Negret, A.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.; Pasternak, A. A.; Lobach, Yu. N.

    2010-03-15

    {gamma} rays were measured at several angles in both singles and coincidence mode in the {sup 119}Sn({alpha},n{gamma}){sup 122}Te reaction at 15 MeV on a thick target. Lifetimes of excited states in {sup 122}Te were determined from a Monte Carlo Doppler shift attenuation method (DSAM) analysis of the Doppler broadened lines shapes of {gamma} rays de-exciting the levels. A comparison of several deduced lifetimes with recent results obtained with the (n,n{sup '}) reaction allowed us to validate the choice of a parameter used to calculate the contribution of the side feeding times. The ingredients of the DSAM line-shape analysis (stopping power, description of instrumental line shapes, and side feeding evaluation) are presented in some detail. It is concluded that with proper treatment of side feeding, a DSAM line-shape analysis of peaks in singles or coincidence spectra obtained following the ({alpha},n{gamma}) reaction is able to provide rather accurate values for the lifetimes of levels with low and medium spins.

  19. Synthesis of peptide thioesters via an N-S acyl shift reaction under mild acidic conditions on an N-4,5-dimethoxy-2-mercaptobenzyl auxiliary group.

    PubMed

    Nakamura, Ken'ichiroh; Kanao, Tomoki; Uesugi, Tomoya; Hara, Toshiaki; Sato, Takeshi; Kawakami, Toru; Aimoto, Saburo

    2009-11-01

    An efficient method of peptide thioester synthesis is described. The reaction is based on an N-4,5-dimethoxy-2-mercaptobenzyl (Dmmb) auxiliary-assisted N-S acyl shift reaction after assembling a peptide chain by Fmoc-solid phase peptide synthesis. The Dmmb-assisted N-S acyl shift reaction proceeded efficiently under mildly acidic conditions, and the peptide thioester was obtained by treating the resulting S-peptide with sodium 2-mercaptoethanesulfonate. No detectable epimerization of the amino acid residue adjacent to the thioester moiety in the case of Leu was found. The reactions were also amenable to the on-resin preparation of peptide thioesters. The utility was demonstrated by the synthesis of a 41-mer peptide thioester, a phosphorylated peptide thioester and a 33-mer peptide thioester containing a trimethylated lysine residue. PMID:19735084

  20. A multidimensional approach to the analysis of chemical shift titration experiments in the frame of a multiple reaction scheme.

    PubMed

    D'Alo, Anthony; Dumont, Elise; Maury, Olivier; Giraud, Nicolas

    2013-10-01

    We present a method for fitting curves acquired by chemical shift titration experiments, in the frame of a three-step complexation mechanism. To that end, we have implemented a fitting procedure, based on a nonlinear least squares fitting method, that determines the best fitting curve using a "coarse grid search" approach and provides distributions for the different parameters of the complexation model that are compatible with the experimental precision. The resulting analysis protocol is first described and validated on a theoretical data set. We show its ability to converge to the true parameter values of the simulated reaction scheme and to evaluate complexation constants together with multidimensional uncertainties. Then, we apply this protocol to the study of the supramolecular interactions, in aqueous solution, between a lanthanide complex and three different model molecules, using NMR titration experiments. We show that within the uncertainty that can be evaluated from the parameter distributions generated during our analysis, the affinities between the lanthanide derivative and each model molecule can be discriminated, and we propose values for the corresponding thermodynamic constants. PMID:23955873

  1. Lifetime measurements by the Doppler-shift attenuation method in the {sup 115}Sn({alpha},n{gamma}){sup 118}Te reaction

    SciTech Connect

    Mihai, C.; Pasternak, A. A.; Pascu, S.; Filipescu, D.; Ivascu, M.; Bucurescu, D.; Cata-Danil, I.; Deleanu, D.; Ghita, D. G.; Glodariu, T.; Marginean, N.; Marginean, R.; Negret, A.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.; Cata-Danil, G.

    2011-05-15

    {gamma} rays were measured at several angles in both singles and coincidence modes in the {sup 115}Sn({alpha},n{gamma}){sup 118}Te reaction at 15 MeV on a thick target. Multipolarities and mixing ratios were determined from the {gamma}-ray angular distribution analysis. Lifetimes of 11 low- and medium-spin excited states in {sup 118}Te were determined from a Monte Carlo Doppler-shift attenuation method analysis of the Doppler broadened line shapes of {gamma} rays deexciting the levels. The results are discussed in comparison with the predictions of the interacting boson model.

  2. Circuit-dependent striatal PKA and ERK signaling underlies rapid behavioral shift in mating reaction of male mice

    PubMed Central

    Goto, Akihiro; Nakahara, Ichiro; Yamaguchi, Takashi; Kamioka, Yuji; Sumiyama, Kenta; Matsuda, Michiyuki; Nakanishi, Shigetada; Funabiki, Kazuo

    2015-01-01

    The selection of reward-seeking and aversive behaviors is controlled by two distinct D1 and D2 receptor-expressing striatal medium spiny neurons, namely the direct pathway MSNs (dMSNs) and the indirect pathway MSNs (iMSNs), but the dynamic modulation of signaling cascades of dMSNs and iMSNs in behaving animals remains largely elusive. We developed an in vivo methodology to monitor Frster resonance energy transfer (FRET) of the activities of PKA and ERK in either dMSNs or iMSNs by microendoscopy in freely moving mice. PKA and ERK were coordinately but oppositely regulated between dMSNs and iMSNs by rewarding cocaine administration and aversive electric shocks. Notably, the activities of PKA and ERK rapidly shifted when male mice became active or indifferent toward female mice during mating behavior. Importantly, manipulation of PKA cascades by the Designer Receptor recapitulated active and indifferent mating behaviors, indicating a causal linkage of a dynamic activity shift of PKA and ERK between dMSNs and iMSNs in action selection. PMID:25964359

  3. High-pressure catalytic reactions over single-crystal metal surfaces

    NASA Astrophysics Data System (ADS)

    Rodriguez, JosA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  4. Zinc causes a shift toward citrate at equilibrium of the m-aconitase reaction of prostate mitochondria.

    PubMed

    Costello, L C; Franklin, R B; Liu, Y; Kennedy, M C

    2000-01-30

    Prostate secretory epithelial cells have the unique function and capability of accumulating and secreting extraordinarily high levels of citrate. To achieve this, these cells possess a uniquely limiting mitochondrial (m)-aconitase activity that minimizes the oxidation of citrate via the Krebs cycle. The steady-state citrate/isocitrate ratio of mammalian tissues is generally maintained at about 10-11/l, independent of the concentration of citrate, which is the result of the chemical equilibrium reached in the presence of m-aconitase. In contrast, the citrate/isocitrate ratio of prostate tissue is about 30-40/l. Zinc, which is also accumulated in prostate cells at much higher levels than in other cells, inhibits m-aconitase activity thereby minimizing citrate oxidation. This current report is concerned with an effect of zinc on the equilibrium of the reaction catalyzed by m-aconitase. Studies were conducted with mitochondrial extract preparations from rat ventral prostate epithelial cells. With citrate as the initial substrate, the addition of zinc (7-10 microM) to the prostate mitochondrial preparation resulted in a change in the citrate/isocitrate ratio at equilibrium from an average of 10.5/l to 13.5/l. In contrast, the identical treatment of kidney mitochondrial preparations resulted in no zinc-induced change in the citrate/isocitrate ratio. When either cis-aconitate or isocitrate was employed as the initial substrate, the addition of zinc did not alter the citrate/isocitrate ratio of prostate or kidney preparations. Partial purification of the prostate preparation revealed that the prostate mitochondrial extract contained a putative protein (which we have designated as 'citrate factor protein') that is required for the zinc-induced increase in the citrate/isocitrate ratio. This novel effect of zinc provides another mechanism by which it is assured that the accumulation of citrate is maximized in citrate-producing prostate epithelial cells. PMID:10766339

  5. Preparation of neuroprotective condensed 1,4-benzoxazepines by regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction

    PubMed Central

    Tóth, László; Fu, Yan; Zhang, Hai Yan; Mándi, Attila; Kövér, Katalin E; Illyés, Tünde-Zita; Kiss-Szikszai, Attila; Balogh, Balázs; Kurtán, Tibor

    2014-01-01

    Summary Condensed O,N-heterocycles containing tetrahydro-1,4-benzoxazepine and tetrahydroquinoline moieties were prepared by a regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction of a 4-aryl-2-phenyl-1,4-benzoxazepine derivative obtained from flavanone. The relative configuration of products were determined by the correlation of 3 J H,H coupling data with the geometry of major conformers accessed by DFT conformational analysis. Separated enantiomers of the products were characterized by HPLC-ECD data, which allowed their configurational assignment on the basis of TDDFT-ECD calculation of the solution conformers. Two compounds showed neuroprotective activities against hydrogen peroxide (H2O2) or β-amyloid25–35 (Aβ25–35)-induced cellular injuries in human neuroblastoma SH-SY5Y cells in the range of those of positive controls. PMID:25550721

  6. Computational Chemistry-Based Identification of Ultra-Low Temperature Water-Gas-Shift Catalysts

    SciTech Connect

    Manos Mavrikakis

    2008-08-31

    The current work seeks to identify novel, catalytically-active, stable, poison-resistant LWGS catalysts that retain the superior activity typical of conventional Cu catalysts but can be operated at similar or lower temperatures. A database for the Binding Energies (BEs) of the LWGS relevant species, namely CO, O and OH on the most-stable, close-packed facets of a set of 17 catalytically relevant transition metals was established. This BE data and a database of previously established segregation energies was utilized to predict the stability of bimetallic NSAs that could be synthesized by combinations of the 17 parent transition metals. NSAs that were potentially stable both in vacuo and under the influence of strong-binding WGS intermediates were then selected for adsorption studies. A set of 40 NSAs were identified that satisfied all three screener criteria and the binding energies of CO, O and OH were calculated on a set of 66, 43 and 79 NSA candidates respectively. Several NSAs were found that bound intermediates weaker than the monometallic catalysts and were thus potentially poison-resistant. Finally, kinetic studies were performed and resulted in the discovery of a specific NSA-based bimetallic catalyst Cu/Pt that is potentially a promising LWGS catalyst. This stable Cu/Pt subsurface alloy is expected to provide facile H{sub 2}O activation and remain relatively resistant from the poisoning by CO, S and formate intermediates.

  7. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1989-01-01

    The rate of synthesis gas consumption over a cobalt FischerTropsch catalyst was measured in a well-mixed, continuous-flow, slurry reactor at 220 to 240[degrees]C, 0.5 to 1.5 MPa, H[sub 2]/CO feed ratios of 1.5 to 3.5 and conversions of 7 to 68% of hydrogen and 11 to 73% of carbon monoxide. The inhibiting effect of carbon monoxide was determined quantitatively and a Langmuir-Hinshelwood-type equation of the following form was found to best represent the results: -R[sub H[sub 2+Co

  8. Shift of reaction pathway by added chloride ions in the oxidation of aromatic ketones by dichloroisocyanuric acid—A kinetic study

    NASA Astrophysics Data System (ADS)

    Kumar, Y. Lakshman; Nadh, R. Venkata; Radhakrishnamurti, P. S.

    2016-03-01

    Role of added chloride ions on the shift of reaction pathway of oxidation of aromatic ketones (acetophenone, desoxybenzoin) by dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid—perchloric acid medium. Participation of enolic and protonated forms of ketones in the rate determining steps is manifested from zero and first orders with respect to the oxidant in absence and presence of added chloride ions, respectively. Positive and negative effects of acid and dielectric constant on the reaction rate were observed. The observations deduce plausible mechanisms involving (i) rate-determining formation of enol from the conjugate acid of the ketone (SH+) in the absence of added chloride ions and (ii) rapid formation of molecular chlorine species from HOCl (hydrolytic species of DCICA) in the presence of added chloride ions, which then interacts with SH+ in a rate-determining step prior to the rapid steps of product formation. The order of Arrhenius parameters substantiate the proposed plausible mechanisms based on order of reactants both in presence and absence of added chloride ions.

  9. SurfKin: an ab initio kinetic code for modeling surface reactions.

    PubMed

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-01

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. PMID:25111729

  10. Shifting Attention

    ERIC Educational Resources Information Center

    Ingram, Jenni

    2014-01-01

    This article examines the shifts in attention and focus as one teacher introduces and explains an image that represents the processes involved in a numeric problem that his students have been working on. This paper takes a micro-analytic approach to examine how the focus of attention shifts through what the teacher and students do and say in the…

  11. Shifting Attention

    ERIC Educational Resources Information Center

    Ingram, Jenni

    2014-01-01

    This article examines the shifts in attention and focus as one teacher introduces and explains an image that represents the processes involved in a numeric problem that his students have been working on. This paper takes a micro-analytic approach to examine how the focus of attention shifts through what the teacher and students do and say in the

  12. Assessing Deep Water Gas Hydrate Systems and Seafloor Stability

    NASA Astrophysics Data System (ADS)

    Hardage, B. A.; Roberts, H. H.

    2005-05-01

    We demonstrate how four-component ocean-bottom-cable (4-C OBC) seismic data acquired in deep water can be used to study near-seafloor strata and the geologic characteristics of fluid and gas expulsion systems that extend to the seafloor and become thermogenic sources of gas hydrates. We document the importance of the converted-shear (P-SV) mode extracted from 4-C OBC data. We show that P-SV data provide a spatial resolution of deep-water, near-seafloor strata that is an order of magnitude better than the resolution of the compressional (P-P) mode. Shear wave velocities less than 100 m/s in unconsolidated near-seafloor sediments produce scattered SV wavelengths of meter scale even when long-range surface-based air guns illuminate the seafloor with frequencies that do not exceed 100 Hz. These short wavelengths allow the P-SV mode to define geologic detail that cannot be detected with P-P scattered data. The geomechanical properties of the seafloor strata are determined by transforming seismic measurements of compressional and shear velocities into estimates of compressional and shear moduli. Current 4-C OBC technology available from major seismic contractors allows deep-water gas hydrate systems and seafloor stability to now be studied over large areas of many hundreds of square kilometers.

  13. The Effect of Rain on Air-Water Gas Exchange

    NASA Technical Reports Server (NTRS)

    Ho, David T.; Bliven, Larry F.; Wanninkhof, Rik; Schlosser, Peter

    1997-01-01

    The relationship between gas transfer velocity and rain rate was investigated at NASA's Rain-Sea Interaction Facility (RSIF) using several SF, evasion experiments. During each experiment, a water tank below the rain simulator was supersaturated with SF6, a synthetic gas, and the gas transfer velocities were calculated from the measured decrease in SF6 concentration with time. The results from experiments with IS different rain rates (7 to 10 mm/h) and 1 of 2 drop sizes (2.8 or 4.2 mm diameter) confirm a significant and systematic enhancement of air-water gas exchange by rainfall. The gas transfer velocities derived from our experiment were related to the kinetic energy flux calculated from the rain rate and drop size. The relationship obtained for mono-dropsize rain at the RSIF was extrapolated to natural rain using the kinetic energy flux of natural rain calculated from the Marshall-Palmer raindrop size distribution. Results of laboratory experiments at RSIF were compared to field observations made during a tropical rainstorm in Miami, Florida and show good agreement between laboratory and field data.

  14. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, Michael B.; Hargens, Alan R.; Dulchavsky, Scott A.; Ebert, Douglas J.; Lee, Stuart M. C.; Laurie, Steven S.; Garcia, Kathleen M.; Sargsyan, Ashot E.; Martin, David S.; Liu, John; Macias, Brandon R.; Arbeille, Philippe; Danielson, Richard; Chang, Douglas; Gunga, Hanns-Christian; Johnston, Smith L.; Westby, Christian M.; Ploutz-Snyder, Robert J.; Smith, Scott M.

    2016-01-01

    We hypothesize that microgravity-induced cephalad fluid shifts elevate intracranial pressure (ICP) and contribute to VIIP. We will test this hypothesis and a possible countermeasure in ISS astronauts.

  15. Experimental and Theoretical Study of an Intramolecular CF3-Group Shift in the Reactions of ?-Bromoenones with 1,2-Diamines.

    PubMed

    Muzalevskiy, Vasily M; Ustynyuk, Yury A; Gloriozov, Igor P; Chertkov, Vyacheslav A; Rulev, Alexander Yu; Kondrashov, Evgeniy V; Ushakov, Igor A; Romanov, Alexey R; Nenajdenko, Valentine G

    2015-11-16

    The reactions of trifluoromethylated 2-bromoenones and N,N'-dialkyl-1,2-diamines have been studied. Depending on the structures of the starting compounds, the formation of 2-trifluoroacetylpiperazine or 3-trifluoromethylpiperazine-2-ones was observed. The mechanism of the reaction is discussed in terms of multistep processes involving sequential substitution of bromine in the starting ?-bromoenones and intramolecular cyclization of the captodative aminoenones as key intermediates to form the target heterocycles. The results of theoretical calculations are in perfect agreement with the experimental data. The unique role of the trifluoromethyl group in this reaction is demonstrated. PMID:26440451

  16. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M. B.; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Laurie, S.; Garcia, K.; Sargsyan, A.; Martin, D.; Lui, J.; Macias, B.; Arbeille, P.; Danielson, R.; Chang, D.; Gunga, H.; Johnston, S.; Westby, C.; Ribeiro, L.; Ploutz-Snyder, R.; Smith, S.

    2015-01-01

    INTRODUCTION: Mechanisms responsible for the ocular structural and functional changes that characterize the visual impairment and intracranial pressure (ICP) syndrome (VIIP) are unclear, but hypothesized to be secondary to the cephalad fluid shift experienced in spaceflight. This study will relate the fluid distribution and compartmentalization associated with long-duration spaceflight with VIIP symptoms. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as the VIIP-related effects of those shifts, can be predicted preflight with acute hemodynamic manipulations, and also if lower body negative pressure (LBNP) can reverse the VIIP effects. METHODS: Physiologic variables will be examined pre-, in- and post-flight in 10 International Space Station crewmembers including: fluid compartmentalization (D2O and NaBr dilution); interstitial tissue thickness (ultrasound); vascular dimensions and dynamics (ultrasound and MRI (including cerebrospinal fluid pulsatility)); ocular measures (optical coherence tomography, intraocular pressure, ultrasound); and ICP measures (tympanic membrane displacement, otoacoustic emissions). Pre- and post-flight measures will be assessed while upright, supine and during 15 deg head-down tilt (HDT). In-flight measures will occur early and late during 6 or 12 month missions. LBNP will be evaluated as a countermeasure during HDT and during spaceflight. RESULTS: The first two crewmembers are in the preflight testing phase. Preliminary results characterize the acute fluid shifts experienced from upright, to supine and HDT postures (increased stroke volume, jugular dimensions and measures of ICP) which are reversed with 25 millimeters Hg LBNP. DISCUSSION: Initial results indicate that acute cephalad fluid shifts may be related to VIIP symptoms, but also may be reversible by LBNP. The effect of a chronic fluid shift has yet to be evaluated. Learning Objectives: Current spaceflight VIIP research is described, including novel hardware and countermeasures.

  17. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M.; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Lauriie, S.; Garcia, K.; Sargsyan, A.; Martin, D.; Ribeiro, L.; Lui, J.; Macias, B.; Arbeille, P.; Danielson, R.; Chang, D.; Johnston, S.; Ploutz-Snyder, R.; Smith, S.

    2016-01-01

    NASA is focusing on long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low-Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but more than 50% of ISS astronauts experienced more profound, chronic changes with objective structural and functional findings such as papilledema and choroidal folds. Globe flattening, optic nerve sheath dilation, and optic nerve tortuosity also are apparent. This pattern is referred to as the visual impairment and intracranial pressure (VIIP) syndrome. VIIP signs and symptoms, as well as postflight lumbar puncture data, suggest that elevated intracranial pressure (ICP) may be associated with the spaceflight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration spaceflight, and to correlate these findings with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as the VIIP-related effects of those shifts, is predicted by the crewmember's preflight conditions and responses to acute hemodynamic manipulations (such as head-down tilt). Lastly, we will evaluate the patterns of fluid distribution in ISS astronauts during acute reversal of fluid shifts through application of lower body negative pressure (LBNP) interventions to characterize and explain general and individual responses. METHODS: We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the Figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, calcaneus tissue thickness (by ultrasound); (3) vascular dimensions by ultrasound (jugular veins, cerebral and carotid arteries, vertebral arteries and veins, portal vein); (4) vascular dynamics by MRI (head/neck blood flow, cerebrospinal fluid pulsatility); (5) ocular measures (optical coherence tomography, intraocular pressure, 2-dimensional ultrasound including optic nerve sheath diameter, globe flattening, and retina-choroid thickness, Doppler ultrasound of ophthalmic and retinal arteries, and veins); (6) cardiac variables by ultrasound (inferior vena cava, tricuspid flow and tissue Doppler, pulmonic valve, stroke volume, right heart dimensions and function, four-chamber views); and (7) ICP measures (tympanic membrane displacement, distortion-product otoacoustic emissions, and ICP calculated by MRI). On the ground, acute head-down tilt will induce cephalad fluid shifts, whereas LBNP will oppose these shifts. Controlled Mueller maneuvers will manipulate cardiovascular variables. Through interventions applied before, during, and after flight, we intend to fully evaluate the relationship between fluid shifts and the VIIP syndrome.

  18. Bridging silyl groups in sigma-bond metathesis and [1, 2] shifts. An experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3

    SciTech Connect

    Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Andersen, Richard

    2010-04-21

    The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference in energy required to form a pentacoordinate silicon or carbon atom in the transition state. This difference clearly distinguishes a silyl from an alkyl group as shown in the study of"Pyrolysis of Tetramethylsilane Yielding Free d-orbitals by Seyferth and Pudvin in ChemTech 1981, 11, 230-233".

  19. KINETIC UNDERSTANDING OF THE SYNGAS-TO-DME REACTION SYSTEM AND ITS IMPLICATIONS TO PROCESS AND ECONOMICS

    SciTech Connect

    Xiang-Dong Peng

    2002-12-01

    In a single-step synthesis gas-to-dimethyl ether process, synthesis gas (or syngas, a mixture of H{sub 2} and CO) is converted into dimethyl ether (DME) in a single reactor. The three reactions involved in this process, methanol synthesis, methanol dehydration and water gas shift, form an interesting reaction network. The interplay among these three reactions results in excellent syngas conversion or reactor productivity. A fundamental understanding of this interplay helps to explain many experimental and simulation observations, to identify optimal reaction conditions, and to provide guidelines for process development. The higher syngas conversion or reactor productivity in the syngas-to-DME reaction system, compared to that in the syngas-to-methanol reaction system, is referred to as chemical synergy. This synergy exhibits a strong dependence on the composition of the reactor feed. To demonstrate the extent of this dependence, simulations with adjusted activity for each reaction were performed to reveal the relative rate of each reaction. The results show that the water gas shift reaction is the most rapid, being practically controlled by the equilibrium. Both methanol synthesis and methanol dehydration reactions are kinetically controlled. The kinetics of the dehydration reactions is greater than that of the methanol synthesis reaction in the CO-rich regime. However, the rates of these two reactions come closer as the H{sub 2} concentration in the reactor feed increases. The role of the dehydration reaction is to remove the equilibrium barrier for the methanol synthesis reaction. The role of the water gas shift reaction is more complex; it helps the kinetics of methanol dehydration by keeping the water concentration low, which in turn enhances methanol synthesis. It also readjusts the H{sub 2}:CO ratio in the reactor as the reactions proceed. In the CO-rich regime, the water gas shift reaction supplements the limiting reactant, H{sub 2}, by reacting water with CO. This enhances both the kinetics and thermodynamic driving force of the methanol synthesis reaction. In the H{sub 2}-rich regime, water gas shift consumes the limiting reactant, CO, which harms both the kinetics and thermodynamics of methanol synthesis. An understanding of these complex roles of the methanol dehydration and water gas shift reactions and of their dependence on the syngas composition explains why the synergy is high in the CO-rich regime, but decreases with increasing H{sub 2} or CO{sub 2} content in the reactor feed. The methanol equivalent productivity of the syngas-to-DME reactor is also a strong function of the reactor feed. A mathematical approach was developed to understand this dependence. The approach divides a power law type of rate equation into two terms, the kinetic term (the rate of the forward reaction) and the thermodynamics or driving force term (1- approach to equilibrium). The equations for the best feed composition for each term were derived. The approach was developed for the single reaction system, and then extended to the syngas-to-DME reaction system. The equations provide insights into why and how the methanol synthesis in the syngasto-DME system depends on the other two reactions. They can also be used to calculate the best feed composition for a given conversion. The analysis shows that for typical commercial syngas conversion, the optimal H{sub 2}:CO ratio for the LPDME{trademark} reactor is around 1-to-1, in good agreement with the results from the simulation. While the 1-to-1 feed provides a good foundation for some process configurations, it does not match the composition of natural gas-derived syngas, which typically has a H{sub 2}:CO ratio of 2:1 or greater. The process would also produce one CO{sub 2} molecule for every DME product, both a materials utilization and an environmental problem. However, recycling CO{sub 2} to the syngas generation unit can solve all of these problems. Integration schemes with different syngas generation technologies (dry reforming, steam methane reforming and partial oxidation) were developed. The feasibility of these schemes was illustrated by simulations using realistic kinetics, thermodynamics, and commercial conditions. Finally, this report discusses the implications of the kinetic understanding and the resulting process schemes to the process economics. It was recognized that, for the overall process, the cost saving in the synthesis loop due to the reaction synergy is counteracted by the cost addition due to CO{sub 2} formation and the resulting costly separation.

  20. Polychlorinated dibenzo-p-dioxin and furan (PCDD/F) formation from chlorophenols: Consequences of different reaction orders and phase shifts for control

    SciTech Connect

    Altwicker, E.R.

    1996-12-31

    This paper reviews laboratory rates of formation of PCDD from chlorophenols over fly ash and de novo rates. Corrected to chlorophenol concentrations expected in incinerators conditions should exist that would favor r{sub dn} > r{sub p}, especially at lower temperatures (< 300 C), though this leaves potentially rapid formation unexplained. However, a correction on the basis of available carbon can lead to the reverse conclusion. At higher temperatures over sand (585--675 C) chlorobenzenes and chlorophenols rapidly form both PCDD/PCDF, with PCDD/PCDF-ratios always less than one. Quartz, however, is largely inert. Reaction orders in chlorophenols over fly ash have been reported as zero and one; the gas phase reaction order is two. Depending on which type of kinetics prevail this could strongly influence chlorophenol control strategies. Another variable for which only scant information is available is the phase distribution of PCDD/F leaving the stack.

  1. A novel reaction-based colorimetric and ratiometric fluorescent sensor for cyanide anion with a large emission shift and high selectivity.

    PubMed

    Wang, Shaodan; Fei, Xiaoliang; Guo, Jing; Yang, Qingbiao; Li, Yaoxian; Song, Yan

    2016-02-01

    A hybrid carbazole-hemicyanine dye (Cac) has been developed as a novel colorimetric and ratiometric fluorescent sensor for cyanide detection. Upon treatment with cyanide, Cac displayed a remarkable fluorescence ratiometric response, with the emission wavelength displaying a very large emission shift (214nm). The detection of cyanide was performed via the nucleophilic addition of cyanide anion to the indolium group of the sensor, which resulted in the blocking of the intramolecular charge transfer (ICT) process in the sensor, inducing a ratiometric fluorescence change and simultaneously an obvious color change. Furthermore, competitive anions did not showed any significant changes both in color and emission intensity ratio (I381/I595), indicating the high selectivity of the sensor to CN(-). PMID:26653444

  2. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, Michael; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Sargsyan, A.; Martin, D.; Lui, J.; Macias, B.; Arbeille, P.; Platts, S.

    2014-01-01

    NASA is focusing on long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but more than 30% of ISS astronauts experience more profound, chronic changes with objective structural and functional findings such as papilledema and choroidal folds. Globe flattening, optic nerve sheath dilation, and optic nerve tortuosity also are apparent. This pattern is referred to as the visual impairment and intracranial pressure (VIIP) syndrome. VIIP signs and symptoms, as well as postflight lumbar puncture data, suggest that elevated intracranial pressure (ICP) may be associated with the space flight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration space flight, and to correlate these findings with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during space flight, as well as the VIIP-related effects of those shifts, is predicted by the crewmember's pre-flight condition and responses to acute hemodynamic manipulations (such as head-down tilt). Lastly, we will evaluate the patterns of fluid distribution in ISS astronauts during acute reversal of fluid shifts through application of lower body negative pressure (LBNP) interventions to characterize and explain general and individual responses. We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the Figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, calcaneus tissue thickness (by ultrasound); (3) vascular dimensions by ultrasound (jugular veins, cerebral and carotid arteries, vertebral arteries and veins, portal vein); (4) vascular dynamics by MRI (head/neck blood flow, cerebrospinal fluid pulsatility); (5) ocular measures (optical coherence tomography, intraocular pressure, 2-dimensional ultrasound including optic nerve sheath diameter, globe flattening, and retina-choroid thickness, Doppler ultrasound of ophthalmic and retinal arteries, and veins); (6) cardiac variables by ultrasound (inferior vena cava, tricuspid flow and tissue Doppler, pulmonic valve, stroke volume, right heart dimensions and function, four-chamber views); and (7) ICP measures (tympanic membrane displacement, distortion-product otoacoustic emissions, and ICP calculated by MRI). On the ground, acute head-down tilt will induce cephalad fluid shifts, whereas LBNP will oppose these shifts. Controlled Mueller maneuvers will manipulate cardiovascular variables. Through interventions applied before, during, and after flight, we intend to fully evaluate the relationship between fluid shifts and the VIIP syndrome. This study has been selected for flight implementation and is one of the candidate investigations being considered for the one year mission.

  3. Rate equations of solid-catalyzed reactions

    SciTech Connect

    Mezaki, R.; Inoue, H.

    1991-01-01

    Rate Equations of Solid-Catalyzed Reactions, edited by Mezaki and Inoue, contains a comprehensive compilation of kinetic rate expressions for a large number of relevant catalytic reaction systems. Mezaki and Inoue should be commended for their effort. For the practicing catalytic engineer the book should serve as a quick reference guide for assessing the functional dependence of rate on various operating conditions for a catalytic reaction system of interest. Even in this age of computer-aid literature searches this book should reduce the typically large activation barrier and search time associated with locating kinetic rate expressions for a particular reaction system. It is a recommended reference book for all whom are involved in the business of catalytic reactions. However, its format is not amenable for teaching. The book is structured according to the reaction system type. Chapter (1) focuses on synthesis (e.g., of sulfur trioxide, ammonia, methanol), (2) on hydrogenations (e.g., of carbon monoxide, carbon dioxide, ethylene, cyclohexene), (3) on hydrogenolysis (of low molecular weight alkanes such as ethane and/or pentane), (4) on hydrocracking (of higher molecular weight components such as n-hexane and n-dodecane), (5) on dehydrogenation (e.g., of ethanol, ethane, cyclohexane), (6) on complete oxidation (e.g., of hydrogen, carbon monoxide, alkanes, and olefins), (7) on partial oxidation (e.g., of methanol, ethylene, xylenes, and ammonia), (8) on isomerization (e.g., of methane, ethane, and cyclohexane), (10) on decomposition of ammonia and nitric oxide, (11) on dehydration of various alcohols, (12) on cumene cracking, and (13) on other key reactions such as water-gas shift and nitric oxide reduction.

  4. The reaction of European lobster larvae (Homarus gammarus) to different quality food: effects of ontogenetic shifts and pre-feeding history.

    PubMed

    Schoo, Katherina L; Aberle, Nicole; Malzahn, Arne M; Schmalenbach, Isabel; Boersma, Maarten

    2014-02-01

    Young larval stages of many organisms represent bottlenecks in the life-history of many species. The high mortality commonly observed in, for example, decapod larvae has often been linked to poor nutrition, with most studies focussing on food quantity. Here, we focus instead on the effects of quality and have investigated its effects on the nutritional condition of lobster larvae. We established a tri-trophic food chain consisting of the cryptophyte Rhodomonas salina, the calanoid copepod Acartia tonsa and larvae of the European lobster Homarus gammarus. In a set of experiments, we manipulated the C:N:P stoichiometry of the primary producers, and accordingly those of the primary consumer. In a first experiment, R. salina was grown under N- and P-limitation and the nutrient content of the algae was manipulated by addition of the limiting nutrient to create a food quality gradient. In a second experiment, the effect on lobster larvae of long- and short-term exposure to food of varying quality during ontogenetic development was investigated. The condition of the lobster larvae was negatively affected even by subtle N- and P-nutrient limitations of the algae. Furthermore, younger lobster larvae were more vulnerable to nutrient limitation than older ones, suggesting an ontogenetic shift in the capacity of lobster larvae to cope with low quality food. The results presented here might have substantial consequences for the survival of lobster larvae in the field, as, in the light of future climate change and re-oligotrophication of the North Sea, lobster larvae might face marked changes in temperature and nutrient conditions, thus significantly altering their condition and growth. PMID:24072442

  5. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, December 1991--February 1992

    SciTech Connect

    Klier, K.; Herman, R.G.

    1992-03-01

    The objective of the proposed research is to investigate and develop a novel catalytic process for the conversion of coal-derived synthesis gas into high octane C{sub 1}-C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway. (VC)

  6. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, September--November 1991

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.; Kieke, M.

    1991-12-01

    The objective of the proposed research is to investigate and develop a novel catalytic process for the conversion of coal-derived synthesis gas into high octane C{sub 1}{minus}C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway.

  7. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, June 1993--August 1993

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.; Carr, T.

    1993-09-01

    Various preparation methods of synthesizing molybdenum disulfide and various alkali doping procedures were studied to determine if various preparation paramenters affected catalyst activity. Testing was performed on an undoped molybdenum disulfide sample with H{sub 2}/CO = 1 synthesis gas at 8.1 MPa and at temperatures of 245, 255, 265, 275, 280, 300, 320, and 295C, and only hydrocarbons were formed. A methanol injection experiment with undoped catalyst showed that homologation of methanol did not occur over the undoped MOS{sub 2}. Catalytic testing on a cesium formate doped molybdenum disulfide catalyst corresponding to 9 wt% Cs/MoS{sub 2} at 8.1 MPa and temperatures of 245, 255, 265, 275, 285, and 295C, mostly linear alcohols. The CS/MOS{sub 2} sample was protected from air exposure during preparation and testiag. As with the other recently tested alkali-promoted MOS{sub 2} catalysts, this cataylst was not as active as previous CS/MOS{sub 2} catalysts [1], and some deactivation during these systematic studies was observed. X-Ray powder diffraction and BET surface area measurements are being used to characterize the catalysts, and electron microscopy analyses are being carried out.

  8. CHLORIDE POISONING OF WATER GAS SHIFT ACTIVITY ON NICKEL CATALYSTS DURING STEAM REFORMING. (R826694C633)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  9. CHLORIDE POISONING OF WATER GAS SHIFT ACTIVITY ON NICKEL CATALYSTS DURING STEAM REFORMING. (R822721C633)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, C.E.; Robinson, P.R.

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  11. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, Carlos E.; Robinson, Paul R.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  12. Associate reactions of dihydridobis(trimethylphosphine)platinum(II). Molecular structures of (diphenylacetylene)bis(trimethylphosphine)platinum and hydridotris(trimethylphosphine)platinum(II) tetraphenylborate

    SciTech Connect

    Packett, D.L.; Syed, A.; Trogler, W.C.

    1988-01-01

    In recent years sterically unhindered platinum dihydrides PtH/sub 2/L/sub 2/ (L = PMe/sub 3/, PEt/sub 3/) have been isolated and found to be much more reactive than related compounds containing bulky phosphine ligands. Such compounds may be involved as intermediates int he catalysis of alkene hydrogenation, nitrile and olefin hydration, alcoholysis, hydrosilation, and the water gas shift reaction. Oxidative addition and reductive elimination of H/sub 2/ from sterically unhindered dihydrides has been the subject of experimental and theoretical studies, since these reactions model the behavior of hydrogen on platinum surfaces. This paper examines reactions of the PMe/sub 3/ derivative in detail to define its reactivity. In particular the authors were interested in the competition between H/sub 2/ dissociation to generate Pt(PMe/sub 3/)/sub 2/ vs associative attack at platinum in the substitution and oxidative addition reactions of these complexes.

  13. Shifting sugars and shifting paradigms.

    PubMed

    Siegal, Mark L

    2015-02-01

    No organism lives in a constant environment. Based on classical studies in molecular biology, many have viewed microbes as following strict rules for shifting their metabolic activities when prevailing conditions change. For example, students learn that the bacterium Escherichia coli makes proteins for digesting lactose only when lactose is available and glucose, a better sugar, is not. However, recent studies, including three PLOS Biology papers examining sugar utilization in the budding yeast Saccharomyces cerevisiae, show that considerable heterogeneity in response to complex environments exists within and between populations. These results join similar recent results in other organisms that suggest that microbial populations anticipate predictable environmental changes and hedge their bets against unpredictable ones. The classical view therefore represents but one special case in a range of evolutionary adaptations to environmental changes that all organisms face. PMID:25688600

  14. Shifting Sugars and Shifting Paradigms

    PubMed Central

    Siegal, Mark L.

    2015-01-01

    No organism lives in a constant environment. Based on classical studies in molecular biology, many have viewed microbes as following strict rules for shifting their metabolic activities when prevailing conditions change. For example, students learn that the bacterium Escherichia coli makes proteins for digesting lactose only when lactose is available and glucose, a better sugar, is not. However, recent studies, including three PLOS Biology papers examining sugar utilization in the budding yeast Saccharomyces cerevisiae, show that considerable heterogeneity in response to complex environments exists within and between populations. These results join similar recent results in other organisms that suggest that microbial populations anticipate predictable environmental changes and hedge their bets against unpredictable ones. The classical view therefore represents but one special case in a range of evolutionary adaptations to environmental changes that all organisms face. PMID:25688600

  15. Oxygen-regulated mRNAs for light-harvesting and reaction center complexes and for bacteriochlorophyll and carotenoid biosynthesis in Rhodobacter capsulatus during the shift from anaerobic to aerobic growth.

    PubMed Central

    Zhu, Y S; Cook, D N; Leach, F; Armstrong, G A; Alberti, M; Hearst, J E

    1986-01-01

    The stability and regulation by oxygen of mRNAs for the photosynthetic apparatus in Rhodobacter capsulatus have been studied by using proflavin to inhibit transcription and by shifting cells from anaerobic to aerobic conditions. The results from the inhibition experiments show that the mRNA for the light-harvesting LH-II polypeptides (beta, alpha) is more stable than that for the light-harvesting LH-I polypeptides (beta, alpha) during anaerobic growth, whereas the mRNAs for the reaction center polypeptides L (RC-L), M (RC-M), and H (RC-H) are less stable than both the LH-I and LH-II mRNAs. When photosynthetic cells are shifted from anaerobic to aerobic conditions, an immediate decrease in the levels of mRNA for the LH-I, LH-II, RC-L, RC-M, and RC-H proteins was observed. The level of mRNA for the LH-II proteins, however, is more sensitive to oxygen and is reduced faster than the level of mRNA for the LH-I proteins. These results suggest that oxygen represses the expression of genes coding for the light-harvesting antenna and reaction center complexes and may selectively accelerate the degradation of mRNA for the LH-II proteins. The mRNAs for several enzymes in the bacteriochlorophyll biosynthetic pathway are regulated by oxygen in a similar manner. The mRNAs for carotenoid biosynthetic enzymes, however, are regulated by oxygen in a different way. We have found that the amounts of mRNAs for carotenoid biosynthetic enzyme, relative to the amounts of mRNAs for LH and RC, increased during the shift from anaerobic to aerobic conditions. We have particularly shown that although the expression of most photosynthetic genes in R. capsulatus is repressed by oxygen, the crtA gene, located in the BamHI H fragment of the R' plasmid pRPS404 and responsible for the oxidation of spheroidene to spheroidenone, responds to oxygen in an opposite fashion. This exzymatic oxidation may protect the photosynthetic apparatus from photooxidative damage. Images PMID:2430948

  16. Acetic Acid Reforming over Rh Supported on La2O3/CeO2-ZrO2: Catalytic Performance and Reaction Pathway Analysis

    SciTech Connect

    Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

    2013-07-11

    Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C, steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.

  17. Reaction pathways and catalyst requirements in the synthesis of isobutanol from CO and H{sub 2}

    SciTech Connect

    Xu, M.; Stephens, B.L.; Gines, M.J.L.; Iglesia, E.

    1996-12-31

    The synthesis of isobutanol and methanol from CO/H{sub 2} on K-Cu-Mg-CeO{sub x} catalysts is inhibited by CO{sub 2}, one of the reaction products. Alcohol coupling reactions show that CO{sub 2} decreases the rates of both alcohol dehydrogenation and base-catalyzed chain growth condensation reactions. Basic site density and reactivity were determined using a {sup 12}CO{sub 2}/{sup 13}CO{sub 2} isotopic transient technique. Addition of K to Cu-Mg-CeO{sub x} increases both basic site density and strength, but influences weakly the rate of base-catalyzed alcohol coupling reactions. Cu enhances the rates of alcohol dehydrogenation, and Ce increases Cu dispersion and stabilizes high surface area MgO. The cross-coupling reactions of acetaldehyde and {sup 13}C-labeled methanol produce singly-labeled propionaldehyde, suggesting that it forms by the condensation of acetaldehyde and a reactive intermediate derived from methanol. Isobutyraldehyde, a precursor to isobutanol, forms via the condensation of propionaldehyde and reactive C{sub 1} species resulting from methanol. Temperature-programmed surface reaction studies of preadsorbed ethanol have shown that CO decreases the rate of base-catalyzed self-condensation reactions of ethanol to acetone, possibly due to the poisoning of basic and metal sites by the CO{sub 2} formed from CO by water-gas shift or Boudouard reactions.

  18. Fe/MCM-41 sylilated catalyst: structural changes determination during the Fischer-Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Bengoa, J. F.; Fellenz, N. A.; Cagnoli, M. V.; Cano, L. A.; Gallegos, N. G.; Alvarez, A. M.; Marchetti, S. G.

    2010-01-01

    Two Fe/MCM-41 systems, one of them sylilated, were obtained to be used as catalysts in Fischer-Tropsch reaction. They have more than 90% of the iron species located inside the support channels, leading to a narrow crystal size distribution accessible to reactive gases. The samples were characterized by X-ray diffraction, atomic absorption spectroscopy, N2 adsorption, Mössbauer spectroscopy and Fourier transformer infrared spectroscopy. Mössbauer spectroscopy allowed us to demonstrate that the catalytic active species were the same in both catalysts. The only difference between them was the surface hydrophobicity, which decreases the “water gas shift reaction” in the sylilated catalyst. Besides, this solid is more active for hydrocarbon production, with a lower methane yield.

  19. Integrated reformer and shift reactor

    DOEpatents

    Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

    2006-06-27

    A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

  20. The adsorption behavior of octafluoropropane at the water/gas interface

    SciTech Connect

    Giebel, Friederike; Paulus, Michael; Nase, Julia Bieder, Steffen; Kiesel, Irena; Tolan, Metin

    2014-12-14

    We studied the adsorption behavior of the gas octafluoropropane at the water/gas interface as a function of different pressures. In a custom-made measurement cell, the gas pressure was varied in a range between 1 bar and close to the condensation pressure of octafluoropropane. The electron density profiles of the adsorption layers show that the layer thickness increases with pressure. The evolution of the layer electron density indicates that the bulk electron density is reached if a layer consisting of more than one monolayer of octafluoropropane is adsorbed on the water surface.

  1. Corrosion of API 5L B and X52 in crude oil/water/gas mixtures

    SciTech Connect

    Perdomo, J.J.; Gonzalez, J.J.; Viloria, A.; De Veer, H.; De Abreu, Y.

    2000-02-01

    Laboratory and field tests were conducted to evaluate the corrosion behavior of API 5L grade B and X52 steels using Furrial's crude oil in the presence of water and gas containing carbon dioxide (CO{sub 2}) and hydrogen sulfide (H{sub 2}S). The results suggest that the corrosiveness of this crude oil/water/gas mixture is not detrimental to either steel. However, pitting corrosion was observed. The low general corrosion rates measured were attributed to the natural inhibiting properties of the crude oil.

  2. The effects of oil viscosity on sweet corrosion in multiphase oil/water/gas horizontal pipelines

    SciTech Connect

    Jepson, W.P.; Menezes, R.

    1995-10-01

    Experiments were carried out in a 10 cm I.D., three phase oil/water/gas horizontal Plexiglass pipeline. Mixtures of salt water with oils of viscosities 2 cp and 96 cp ranging from 0% to 100% off were used for the liquid phase with carbon dioxide as the gas phase. Results indicate that, for both full pipe flow and slug flow, at each water percentage up to approximately 60%, the corrosion rate increased with off viscosity at each flow condition. Above 60% water, the corrosion rate decreased rapidly to negligible values. In slug flow, the corrosion rate increased with increase in Froude number. This may be attributed to presence of gas at the bottom of the pipe and the higher pressure drops across the slug front at each Froude number.

  3. Theoretical study on the reaction mechanism of the gas-phase H2/CO2/Ni(3D) system.

    PubMed

    Qin, Song; Hu, Changwei; Yang, Huaqing; Su, Zhishan

    2005-07-28

    The ground-state potential energy surface (PES) in the gas-phase H2/CO2/Ni(3D) system is investigated at the CCSD(T)//B3LYP/6-311+G(2d,2p) levels in order to explore the possible reaction mechanism of the reverse water gas shift reaction catalyzed by Ni(3D). The calculations predict that the C-O bond cleavage of CO2 assisted by co-interacted H2 is prior to the dissociation of the H2, and the most feasible reaction path for Ni(3D) + H2 + CO2 --> Ni(3D) + H2O + CO is endothermic by 12.5 kJ mol(-1) with an energy barrier of 103.9 kJ mol(-1). The rate-determining step for the overall reaction is predicted to be the hydrogen migration with water formation. The promotion effect of H2 on the cleavage of C-O bond in CO2 is also discussed and compared with the analogous reaction of Ni(3D) + CO2 --> NiO + CO, and the difference between triplet and singlet H2/CO2/Ni systems is also discussed. PMID:16833994

  4. Molecular implementation of molecular shift register memories

    NASA Technical Reports Server (NTRS)

    Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

    1991-01-01

    An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

  5. Characterization of Ni and W co-loaded SBA-15 catalyst and its hydrogen production catalytic ability on ethanol steam reforming reaction

    NASA Astrophysics Data System (ADS)

    Kim, Dongjin; Kwak, Byeong Sub; Min, Bong-Ki; Kang, Misook

    2015-03-01

    This study evaluated the application of advanced bimetallic catalytic species of Ni and W to effectively produce hydrogen gases from ethanol steam reforming. The highest reactivity was achieved using the Ni0.95W0.05/SBA-15 catalyst. The maximum H2 production and ethanol conversion of 90% and 85%, respectively, were obtained for 0.4 g catalyst at 600 C after 10 h with a EtOH:H2O ratio of 1:3 and a gas hourly space velocity of 6000 h-1. This highlights a synergy between the Ni and W loading on SBA-15 during ethanol steam reforming that occurs through the inhibition of Ni particle agglomeration and consequent decrease in catalytic deactivation. Additionally, the supplied W ingredients promoted CO2 selectivity, which was generated from the CO-water gas shift reaction.

  6. Making Shifts toward Proficiency

    ERIC Educational Resources Information Center

    McGatha, Maggie B.; Bay-Williams, Jennifer M.

    2013-01-01

    The Leading for Mathematical Proficiency (LMP) Framework (Bay-Williams et al.) has three components: (1) The Standards for Mathematical Practice; (2) Shifts in classroom practice; and (3) Teaching skills. This article briefly describes each component of the LMP framework and then focuses more in depth on the second component, the shifts in

  7. Making Shifts toward Proficiency

    ERIC Educational Resources Information Center

    McGatha, Maggie B.; Bay-Williams, Jennifer M.

    2013-01-01

    The Leading for Mathematical Proficiency (LMP) Framework (Bay-Williams et al.) has three components: (1) The Standards for Mathematical Practice; (2) Shifts in classroom practice; and (3) Teaching skills. This article briefly describes each component of the LMP framework and then focuses more in depth on the second component, the shifts in…

  8. Style Shift in Translation

    ERIC Educational Resources Information Center

    Al-Qinai, Jamal

    2009-01-01

    The phenomenon of style shift in translated texts is ascribed mainly to textual incompatibility in terms of rhetorical asymmetry and divergence at the formality level. Mandatory shifts result from a systematic dissimilarity between the source language and the target language in terms of the underlying system of syntax, semantics and rhetorical…

  9. Shifting scintillator neutron detector

    DOEpatents

    Clonts, Lloyd G; Cooper, Ronald G; Crow, Jr., Morris Lowell; Hannah, Bruce W; Hodges, Jason P; Richards, John D; Riedel, Richard A

    2014-03-04

    Provided are sensors and methods for detecting thermal neutrons. Provided is an apparatus having a scintillator for absorbing a neutron, the scintillator having a back side for discharging a scintillation light of a first wavelength in response to the absorbed neutron, an array of wavelength-shifting fibers proximate to the back side of the scintillator for shifting the scintillation light of the first wavelength to light of a second wavelength, the wavelength-shifting fibers being disposed in a two-dimensional pattern and defining a plurality of scattering plane pixels where the wavelength-shifting fibers overlap, a plurality of photomultiplier tubes, in coded optical communication with the wavelength-shifting fibers, for converting the light of the second wavelength to an electronic signal, and a processor for processing the electronic signal to identify one of the plurality of scattering plane pixels as indicative of a position within the scintillator where the neutron was absorbed.

  10. Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qinghe; Chen, Jingguang G.

    2012-09-01

    Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their "Pt-like" properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O2, H2O, CO and CO2) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.

  11. Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qinghe; Chen, Jingguang G.

    2012-09-01

    Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their Pt-like properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O2, H2O, CO and CO2) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.

  12. In-water gas combustion in linear and annular gas bubbles

    NASA Astrophysics Data System (ADS)

    Teslenko, V. S.; Drozhzhin, A. P.; Medvedev, R. N.; Batraev, I. S.

    2014-08-01

    A new pulsed-cyclic method of in-water gas combustion was developed with separate feed of fuel gas and oxygen with the focus on development of new technologies for heat generators and submerged propellers. The results of calorimetric and hydrodynamic measurements are presented. In-water combustion of acetylene, hydrogen, and propane was tested with the operation frequency of 2-2.5 Hz and with a linear injector. The combustion dynamics of combustion of stoichiometric mixture with propane (C3H8+5O2) was studied for a bubble near a solid wall; the produced gas bubble continues expansion and oscillations (for the case of linear and annular bubbles). It was demonstrated that gas combustion in annular bubbles produces two same-magnitude pulses of force acting on the wall. The first pulse is produced due to expansion of combustion products, and the second pulse is produced due to axial cumulative processes after bubble collapse. This process shapes an annular vortex which facilitates high-speed convective processes between combustion products and liquid; and this convection produces small-size bubbles.

  13. Air-water gas exchange of organochlorine compounds in Lake Baikal, Russia

    SciTech Connect

    McConnell, L.L.; Kucklick, J.R.; Bidleman, T.F.; Ivanov, G.P.; Chernyak, S.M.

    1996-10-01

    Air and surface water samples were collected at Lake Baikal, Russia, during June 1991 to determine concentrations of organochlorine pesticides and polychlorinated biphenyl (PCB) congeners. These data were combined with Henry`s law constants to estimate the gas flux rate across the air-water interface of each compound class. Air samples were collected at Lake Baikal and from nearby Irkutsk. Water samples were collected from three mid-lake stations and at the mouth of two major tributaries. Average air concentrations of chlorinated bornanes (14 pg m{sup -3}), chlordanes (4.9 pg m{sup -3}), and hexachlorobenzene (HCB) (194 pg m{sup -3}) were similar to global backgound of Arctic levels. However, air concentrations of hexachlorocyclohexanes (HCHs), DDTs, and PCBs were closer to those observed in the Great Lakes region. Significantly higher levels of these three compound classes in air over Irkutsk suggests that regional atmospheric transport and deposition may be an important source of these persistent compounds to Lake Baikal. Air-water gas exchange calculations resulted in net depositional flux values for {alpha}-HCH, {gamma}-HCH, DDTs, and chlorinated bornanes at 112, 23, 3.6, and 2.4 ng m{sup -2} d{sup -1}, respectively. The total net flux of 22 PCB congeners, chlordanes, and HCB was from water to air (volatilization) at 47, 1.8, and 32 ng m{sup -2} d{sup -1}, respectively. 50 refs., 7 figs., 5 tabs.

  14. Shape-Shifting Plastic

    SciTech Connect

    2015-05-20

    A new plastic developed by ORNL and Washington State University transforms from its original shape through a series of temporary shapes and returns to its initial form. The shape-shifting process is controlled through changes in temperature

  15. Molecular Electronic Shift Registers

    NASA Technical Reports Server (NTRS)

    Beratan, David N.; Onuchic, Jose N.

    1990-01-01

    Molecular-scale shift registers eventually constructed as parts of high-density integrated memory circuits. In principle, variety of organic molecules makes possible large number of different configurations and modes of operation for such shift-register devices. Several classes of devices and implementations in some specific types of molecules proposed. All based on transfer of electrons or holes along chains of repeating molecular units.

  16. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1989--December 31, 1989

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1989-12-31

    The rate of synthesis gas consumption over a cobalt FischerTropsch catalyst was measured in a well-mixed, continuous-flow, slurry reactor at 220 to 240{degrees}C, 0.5 to 1.5 MPa, H{sub 2}/CO feed ratios of 1.5 to 3.5 and conversions of 7 to 68% of hydrogen and 11 to 73% of carbon monoxide. The inhibiting effect of carbon monoxide was determined quantitatively and a Langmuir-Hinshelwood-type equation of the following form was found to best represent the results: -R{sub H{sub 2+Co}} = (a P{sub CO}P{sub H{sub 2}})/(1 + b P{sub CO}){sup 2}. The apparent activation energy was 93 to 95 kJ/mol. Data from previous studies on cobalt-based Fischer-Tropsch catalysts are also well correlated with this rate expression.

  17. AUDITORY-VISUAL PERCEPTUAL SHIFTING IN SPEECH HANDICAPPED CHILDREN.

    ERIC Educational Resources Information Center

    FLOWERS, ARTHUR

    INTERACTION BETWEEN VISION AND HEARING WERE STUDIED IN 35 SPEECH HANDICAPPED FIRST-GRADE CHILDREN. THE ABILITY TO SHIFT ATTENTION FROM ONE SENSORY MODALITY TO ANOTHER WAS LABELED AS "PERCEPTUAL SHIFTING." A DEVICE DEVELOPED BY EXPERIMENTAL PSYCHOLOGISTS PRESENTED VARIOUS STIMULI TO EACH SUBJECT AND RECORDED THE SUBJECT'S REACTION TIME. STIMULI…

  18. Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

    NASA Technical Reports Server (NTRS)

    Beratan, D.

    1993-01-01

    A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

  19. Hot compressed watera suitable and sustainable solvent and reaction medium?

    NASA Astrophysics Data System (ADS)

    Dinjus, E.; Kruse, A.

    2004-04-01

    Hot compressed water in the sub- and supercritical state exhibits exciting physical and chemical properties, which can be varied continuously from gas-like to liquid-like behaviour. Correspondingly, the solvent properties can change from non-polar behaviour as present, for example, in organic solvents to highly ionic characteristics like in salt melts. This opens up several promising opportunities for separation processes and chemical reactions. Under supercritical conditions, substantial amounts of gases and organic substances can homogeneously be mixed with water, which then can be separated by adjusting the subcritical conditions by forming additional phases. This can beneficially be combined with chemical reactions occurring in the homogeneous state leading to integrated processes, which are more effective and competitive. Three approaches to the technical application of hot compressed water are presented to show and discuss the technology, potential, technical hurdles and future research demand in this area of research and development. In supercritical water oxidation (SCWO) water is used as a medium in which organic pollutants are completely degraded under the addition of oxygen, which is completely miscible with water under the process conditions of up to 650 C and pressures around 25 MPa. Thus, high space-time yields in compact reactor designs can be realized. Hydrogen is produced from biomass by hydrothermal gasification. Here, in an excess of water, the reaction at temperatures up to 700 C and pressures around 30 MPa directly leads to valuable hydrogen instead of synthetic gas, as in conventional gasification processes, or methane at subcritical conditions in water. After reaction, pressurized hydrogen is obtained and can easily be enriched due to the different partition coefficients of hydrogen and carbon dioxide between the aqueous and gas phase. Even homogeneous catalysis is possible in supercritical water. This has been demonstrated with the cobalt-catalysed cyclotrimerization of acetylenes to form benzene derivatives or hydroformylation to produce aldehydes from olefins. There, only the addition of CO is necessary, the H2 required being formed by the equilibrium of the water-gas-shift reaction. After a homogeneous reaction in the supercritical state, the reaction mixture can be separated at subcritical conditions. In support of the chemical and technical developments and to principally understand the experimental findings fundamental aspects have to be investigated as well. Intensive studies have been devoted to chemical kinetics including the modelling with elementary reaction steps, e.g. to separate ionic and radical reaction pathways. Depending on the reaction conditions, ionic or radical reaction pathways can be favoured or suppressed, allowing for control selectivity. Furthermore, corrosion of relevant reactor materials has been investigated.

  20. Eluding catastrophic shifts

    PubMed Central

    Villa Martín, Paula; Bonachela, Juan A.; Levin, Simon A.; Muñoz, Miguel A.

    2015-01-01

    Transitions between regimes with radically different properties are ubiquitous in nature. Such transitions can occur either smoothly or in an abrupt and catastrophic fashion. Important examples of the latter can be found in ecology, climate sciences, and economics, to name a few, where regime shifts have catastrophic consequences that are mostly irreversible (e.g., desertification, coral reef collapses, and market crashes). Predicting and preventing these abrupt transitions remains a challenging and important task. Usually, simple deterministic equations are used to model and rationalize these complex situations. However, stochastic effects might have a profound effect. Here we use 1D and 2D spatially explicit models to show that intrinsic (demographic) stochasticity can alter deterministic predictions dramatically, especially in the presence of other realistic features such as limited mobility or spatial heterogeneity. In particular, these ingredients can alter the possibility of catastrophic shifts by giving rise to much smoother and easily reversible continuous ones. The ideas presented here can help further understand catastrophic shifts and contribute to the discussion about the possibility of preventing such shifts to minimize their disruptive ecological, economic, and societal consequences. PMID:25825772

  1. Eluding catastrophic shifts.

    PubMed

    Villa Martn, Paula; Bonachela, Juan A; Levin, Simon A; Muoz, Miguel A

    2015-04-14

    Transitions between regimes with radically different properties are ubiquitous in nature. Such transitions can occur either smoothly or in an abrupt and catastrophic fashion. Important examples of the latter can be found in ecology, climate sciences, and economics, to name a few, where regime shifts have catastrophic consequences that are mostly irreversible (e.g., desertification, coral reef collapses, and market crashes). Predicting and preventing these abrupt transitions remains a challenging and important task. Usually, simple deterministic equations are used to model and rationalize these complex situations. However, stochastic effects might have a profound effect. Here we use 1D and 2D spatially explicit models to show that intrinsic (demographic) stochasticity can alter deterministic predictions dramatically, especially in the presence of other realistic features such as limited mobility or spatial heterogeneity. In particular, these ingredients can alter the possibility of catastrophic shifts by giving rise to much smoother and easily reversible continuous ones. The ideas presented here can help further understand catastrophic shifts and contribute to the discussion about the possibility of preventing such shifts to minimize their disruptive ecological, economic, and societal consequences. PMID:25825772

  2. Trophic shift, not collapse

    USGS Publications Warehouse

    Madenjian, Charles P.; Rutherford, Edward S.; Stow, Craig A.; Roseman, Edward F.; He, Ji X.

    2013-01-01

    scientists who are closely monitoring Lake Hurons food web, we believe that the ongoing changes are more accurately characterized as a trophic shift in which benthic pathways have become more prominent. While decreases in abundance have occurred for some species, others are experiencing improved reproduction resulting in the restoration of several important native species.

  3. Shifts that divide population

    NASA Astrophysics Data System (ADS)

    Muneepeerakul, Rachata; Qubbaj, Murad; Aggarwal, Rimjhim; Anderies, John M.; Janssen, Marco

    2014-05-01

    How does a population of organisms in an ecosystem or of people in a society respond to rapid shifts in the environment? Answers to this question are critical to our ability to anticipate and cope with a changing ecohydrological system. We have developed a generic model of adaptation mechanisms, based on replicator dynamics, in which we derive a simple and insightful threshold condition that separates two important types of responses: 'cohesive transition' in which the whole population changes gradually together, and 'population-dividing transition' in which the population splits into two groups with one eventually dominating the other. The threshold depends on the magnitude of the shift and the shape of the fitness landscape. Division in populations can fundamentally alter the functioning of and induce subsequent feedbacks within the system; knowing the condition that gives rise to such division is thus fundamentally important.

  4. Electrophoretic Mobility Shift Assays.

    PubMed

    Rowe, Sarah E; O'Gara, James P

    2016-01-01

    Experimental demonstration of regulatory protein interactions with the sequences upstream of potential target genes is an important element in gene expression studies. These experiments termed electrophoretic mobility shift assays (EMSAs) provide valuable insight into the mechanism of action of transcription factors. EMSAs combined with downstream applications such as transcriptional analysis help uncover precisely how regulatory proteins control target gene expression. This chapter comprises a guideline for expression and purification of recombinant transcription factor proteins followed by a detailed protocol for EMSAs. PMID:26194709

  5. The shifting beverage landscape.

    PubMed

    Storey, Maureen

    2010-04-26

    STOREY, M.L. The shifting beverage landscape. PHYSIOL BEHAV, 2010. - Simultaneous lifestyle changes have occurred in the last few decades, creating an imbalance in energy intake and energy expenditure that has led to overweight and obesity. Trends in the food supply show that total daily calories available per capita increased 28% since 1970. Total energy intake among men and women has also increased dramatically since that time. Some have suggested that intake of beverages has had a disproportional impact on obesity. Data collected by the Beverage Marketing Corporation between 1988-2008 demonstrate that, in reality, fewer calories per ounce are being produced by the beverage industry. Moreover, data from the National Cancer Institute show that soft drink intake represents 5.5% of daily calories. Data from NHANES 1999-2003 vs. 2003-06 may demonstrate a shift in beverage consumption for age/gender groups, ages 6 to>60years. The beverages provided in schools have significantly changed since 2006 when the beverage industry implemented School Beverage Guidelines. This voluntary action has removed full-calorie soft drinks from participating schools across the country. This shift to lower-calorie and smaller-portion beverages in school has led to a significant decrease in total beverage calories in schools. These data support the concept that to prevent and treat obesity, public health efforts should focus on energy balance and that a narrow focus on sweetened beverages is unlikely to have any meaningful impact on this complex problem. PMID:20188750

  6. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic compounds is critical for understanding deep subsurface ecosystems and the origin of organic compounds on Mars and other planets.

  7. Catastrophic shifts in ecosystems

    NASA Astrophysics Data System (ADS)

    Scheffer, Marten; Carpenter, Steve; Foley, Jonathan A.; Folke, Carl; Walker, Brian

    2001-10-01

    All ecosystems are exposed to gradual changes in climate, nutrient loading, habitat fragmentation or biotic exploitation. Nature is usually assumed to respond to gradual change in a smooth way. However, studies on lakes, coral reefs, oceans, forests and arid lands have shown that smooth change can be interrupted by sudden drastic switches to a contrasting state. Although diverse events can trigger such shifts, recent studies show that a loss of resilience usually paves the way for a switch to an alternative state. This suggests that strategies for sustainable management of such ecosystems should focus on maintaining resilience.

  8. Simplified power shift transmission

    SciTech Connect

    Michael, R.A.

    1987-04-21

    A multi-speed transmission is described for transferring power between a first shaft and a second shaft, the transmission comprising: a compound planetary assembly including a sun gear, a ring gear concentric with the sun gear, a reaction gear concentric with the ring gear, a planetary gear carrier rotatably supporting first and second sets of planet gears, the first planet gear set intermeshing with the ring gear. The sun gear and the second planet gear set intermesh with the first planet gear set and the reaction gear, means for selectively coupling the first shaft with the sun gear and the reaction gear, and means for selectively preventing rotation of the ring gear, and reaction gear and the planetary carrier; a simple planetary assembly comprising a sun gear component concentric with the sun gear of the compound planetary assembly, a ring gear component concentric with both of the sun gears, and a planetary gear carrier component rotatably supporting a set of planet gears, the planet gear set meshing with the sun gear and the ring gear of the simple planetary.

  9. Shift of meaning and students' alternative concepts

    NASA Astrophysics Data System (ADS)

    Schmidt, Hans-Jrgen; Volke, Dagmar

    2003-11-01

    The purpose of the study was to establish a relationship between the shift of meaning of the concept oxidation that has taken place during the historical development, and students' alternative concepts. First Examination Board papers were examined. The result enabled us to specify the research question. In the main part of the study, multiple-choice items were given to 3074 senior high school students. They were asked to select the correct answer and to justify their choices. Additional illustrative material was collected in four interviews with senior high school students. The analysis of the data revealed the mechanism that some students used to interpret the reactions from NO3m to NO and from CO32m to CO2. Students' interpretations were based on the concept of a transfer of oxide ions. The mechanism explains some correct and incorrect answers to the problems. The interview study also revealed that students were reluctant to accept water as a Brnsted base. It is suggested to use students' alternative concepts about oxidation reactions in class, helping them to better understand the half-reaction method. Students should also understand that the meaning of the concept oxidation has shifted in the course of time. In the area of acid-base reactions, further research is needed.

  10. Shifted nondiffractive Bessel beams

    NASA Astrophysics Data System (ADS)

    Kovalev, Alexey A.; Kotlyar, Victor V.; Porfirev, Alexey A.

    2015-05-01

    Nondiffractive Bessel beams are well known to have infinite energy and infinite orbital angular momentum (OAM). However, when normalized to unity of energy, their OAM is finite. In this work, we derive an analytical relationship for calculating the normalized OAM of the superposition of off-axis Bessel beams characterized by the same topological charge. We show that if the constituent beams of the superposition have real-valued weight coefficients, the total OAM of the superposition of the Bessel beams equals that of an individual nonshifted Bessel beam. This property enables generating nondiffractive beams with different intensity distributions but identical OAM. The superposition of a set of identical Bessel beams centered on an arbitrary-radius circle is shown to be equivalent to an individual constituent Bessel beam put in the circle center. As a result of a complex shift of the Bessel beam, the transverse intensity distribution and OAM of the beam are also shown to change. We show that, in the superposition of two or more complex-shifted Bessel beams, the OAM may remain unchanged, while the intensity distribution is changed. Numerical simulation is in good agreement with theory.

  11. 2DCOR-GC: an application of the generalized two-dimensional correlation analysis as a route to optimization of continuous flow supercritical fluid reactions.

    PubMed

    Hyde, Jason R; Bourne, Richard A; Noda, Isao; Stephenson, Phil; Poliakoff, Martyn

    2004-11-01

    A new approach for optimization and monitoring of continuous reactions has been developed using 2D correlation methods for the analysis of GC data (2DCOR-GC). 2DCOR-GC maps are obtained following perturbation of the system that allow the effect of changing reaction parameters such as time, temperature, pressure, or concentration to be both monitored and sequenced with regard to changes in the raw GC data. In this paper, we describe the application of the 2DCOR-GC technique to monitoring the reverse water-gas shift reaction in scCO(2). 2DCOR-GC is combined with FT-IR data to validate the methodology. We also report the application of 2DCOR-GC to probe the mechanism of the alkylation of m-cresol with isopropyl alcohol in scCO(2) using Nafion SAC-13 as the catalyst. These results identify coeluting peaks that could easily be missed without exhaustive method development. PMID:15516110

  12. Phase shifting diffraction interferometer

    DOEpatents

    Sommargren, Gary E. (Santa Cruz, CA)

    1996-01-01

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of .lambda./1000 where .lambda. is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about .lambda./50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms.

  13. Phase shifting interferometer

    DOEpatents

    Sommargren, G.E.

    1999-08-03

    An interferometer is disclosed which has the capability of measuring optical elements and systems with an accuracy of {lambda}/1000 where {lambda} is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about {lambda}/50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. Whereas current interferometers illuminate the optic to be tested with an aberrated wavefront which also limits the accuracy of the measurement, this interferometer uses an essentially perfect spherical measurement wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms. 11 figs.

  14. Phase shifting diffraction interferometer

    DOEpatents

    Sommargren, G.E.

    1996-08-29

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of {lambda}/1000 where {lambda} is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about {lambda}/50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms. 8 figs.

  15. Phase shifting interferometer

    DOEpatents

    Sommargren, Gary E. (Santa Cruz, CA)

    1999-01-01

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of .lambda./1000 where .lambda. is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about .lambda./50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. Whereas current interferometers illuminate the optic to be tested with an aberrated wavefront which also limits the accuracy of the measurement, this interferometer uses an essentially perfect spherical measurement wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms.

  16. 20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean.

    PubMed

    Jantunen, Liisa M; Wong, Fiona; Gawor, Anya; Kylin, Henrik; Helm, Paul A; Stern, Gary A; Strachan, William M J; Burniston, Deborah A; Bidleman, Terry F

    2015-12-01

    The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (?CHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ?CHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals. PMID:26196214

  17. The Modality Shift Experiment in Adults and Children with High Functioning Autism

    ERIC Educational Resources Information Center

    Williams, Diane L.; Goldstein, Gerald; Minshew, Nancy J.

    2013-01-01

    This study used the modality shift experiment, a relatively simple reaction time measure to visual and auditory stimuli, to examine attentional shifting within and across modalities in 33 children and 42 adults with high-functioning autism as compared to matched numbers of age- and ability-matched typical controls. An exaggerated "modality shift

  18. Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions.

    PubMed

    Li, Shuirong; Gong, Jinlong

    2014-11-01

    Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal-support interaction were discussed. A second approach-the promotion in the mobility of the surface oxygen-is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design of other types of heterogeneous base-metal catalysts for high temperature processes including methanation, dry reforming, and hydrocarbon combustion. PMID:25182070

  19. Hydraulically actuated well shifting tool

    SciTech Connect

    Roth, B.A.

    1992-10-20

    This patent describes a hydraulically actuated shifting tool for actuating a sliding member in a well tool. It comprises: a housing having a hydraulic fluid bore therein; shifting dog means positioned on the housing for movement away and toward the housing; locking dog means positioned on the housing for movement away and toward the body; shifting dog hydraulic actuating means in fluid communication with the bore for causing engagement of the shifting dogs with the sliding member; locking dog hydraulic actuating means in communication with the bore for causing engagement of the locking dogs with the locking means; and hydraulic shifting means in communication with the bore for causing relative movement between the shifting dog means and the locking dog means for shifting the sliding sleeve.

  20. Reaction of silicon ion (/sup 2/P) with silane (SiH/sub 4/, SiD/sub 4/). Heats of formation of SiH/sub n/, SiH/sub n//sup +/ (n = 1, 2, 3), and SiH/sub n//sup +/ (n = 0, 1, 2, 3). Remarkable isotope exchange reaction involving four hydrogen shifts

    SciTech Connect

    Boo, B.H.; Armentrout, P.B.

    1987-06-10

    The reaction of ground-state silicon ion with silane is investigated by using a guided ion beam tandem mass spectrometer. Reaction cross sections of all possible fragments, Si/sub m/H/sub n//sup +/ (m = 1, 2; n = 0, 1, 2, 3), as a function of relative kinetic energy are determined. All thermal energies, the major product is Si/sub 2/H/sub 2//sup +/. One remarkable reaction, the interchange of the projectile silicon ion with the target silicon atom, is observed at near zero kinetic energy. Labeling experiments employing /sup 30/Si/sup +/ for the beam or SiD/sub 4/ for the reactant indicate the intermediacy of the disilicon hydrides for the formation of the observed products. From the endothermicities of several reactions, the 298 K heats of formation for several ionic and neutral silicon hydrides are derived: ..delta..H/sub f//sup 0/(SiH) = 90.0 +/- 1.7, ..delta..H/sub f//sup 0/(SiH/sub 2/) = 69.0 +/- 2, ..delta..H/sub f//sup 0/(SiH/sub 3/) = 48.5 +/- 1.6, ..delta..H/sub f//sup 0/(SiH/sub 2//sup +/) = 276.1 +/- 1.7, ..delta..H/sub f//sup 0/(SiH/sub 3//sup +/) = 237.1 +/- 2, ..delta..H/sub f//sup 0/(Si/sub 2//sup +/) less than or equal to 328.0 +/- 2, ..delta..H/sub f//sup 0/(Si/sub 2/H/sup +/) less than or equal to 304.4 +/- 1.6, ..delta..H/sub f//sup 0/(Si/sub 2/H/sub 2/) less than or equal to 268.0 +/- 2.6, ..delta..H/sub f//sup 0/(Si/sub 2/H/sub 3//sup +/) = 266 +/- 2, all in kcal/mol. From an evaluation of these and other experiments, values of ..delta..H/sub f//sup 0/(SiH/sub 2//sup +/) and ..delta..H/sub f//sup 0/(SiH/sub 2/) of 278.0 +/- 1.4 and 68.5 +/- 1.5 kcal/mol, respectively, are recommended.

  1. Transmission shift mechanism

    SciTech Connect

    Smith, R.R.

    1989-06-20

    This patent describes a mechanism for selecting the gear of an automatic transmission in a vehicle. The mechanism consists of: a pressure source; a gear selection valve having an inlet means for receiving fluid from the pressure source, first outlet ports, and second outlet ports; a manual override means for opening and blocking communication between the pressure source and the first ports and for simultaneously opening and blocking communication between the pressure source and the second outlet ports; a port selector means within the valve for controlling flow through the second ports, the port selector means being movable to a plurality of positions, each position permitting a selected second outlet port to open; a selector control mans for moving the port selector means from one position to another, the selector control means including a planetary gear set connected by an input shaft to the transmission and connected to a vehicle load by an output shaft, the planetary gear set having a ring gear whose angular position is a function of reaction torque imposed by the load on the output shaft, the selector control means further including an arm assembly connected between the ring gear and the port selector means so that the position of the port selector means is a function of the reaction torque on the output shaft.

  2. Emission spectroscopy of a microhollow cathode discharge plasma in helium-water gas mixtures

    SciTech Connect

    Namba, S.; Yamasaki, T.; Hane, Y.; Fukuhara, D.; Kozue, K.; Takiyama, K.

    2011-10-01

    A dc microhollow cathode discharge (MHCD) plasma was generated inflowing helium gas containing water vapor. The cathode hole diameters were 0.3, 0.7, 1.0, and 2.0 mm, each with a length of 2.0 mm. Emission spectroscopy was carried out to investigate the discharge mode and to determine the plasma parameters. For the 0.3-mm cathode, stable MHCDs in an abnormal glow mode existed at pressures up to 100 kPa, whereas for larger diameters, a plasma was not generated at atmospheric pressure. An analysis of the lineshapes relevant to He at 667.8 nm and to H{alpha} at 656.3 nm implied an electron density and gas temperature of 2 x 10{sup 14} cm{sup -3} and 1100 K, respectively, for a 100-kPa discharge in the negative glow region. The dependence of the OH band, and H{alpha} intensities on the discharge current exhibited different behaviors. Specifically, the OH spectrum had a maximum intensity at a certain current, while the H atom intensity kept increasing with the discharge current. This observation implies that a high concentration of OH radicals results in quenching, leading to the production of H atoms via the reaction OH + e{sup -}{yields} O + H + e{sup -}.

  3. Antiretroviral therapy: Shifting sands.

    PubMed

    Sashindran, V K; Chauhan, Rajeev

    2016-01-01

    HIV/AIDS has been an extremely difficult pandemic to control. However, with the advent of antiretroviral therapy (ART), HIV has now been transformed into a chronic illness in patients who have continued treatment access and excellent long-term adherence. Existing indications for ART initiation in asymptomatic patients were based on CD4 levels; however, recent evidence has broken the shackles of CD4 levels. Early initiation of ART in HIV patients irrespective of CD4 counts can have profound positive impact on morbidity and mortality. Early initiation of ART has been found not only beneficial for patients but also to community as it reduces the risk of transmission. There have been few financial concerns about providing ART to all HIV-positive people but various studies have proven that early initiation of ART not only proves to be cost-effective but also contributes to economic and social growth of community. A novel multidisciplinary approach with early initiation and availability of ART at its heart can turn the tide in our favor in future. Effective preexposure prophylaxis and postexposure prophylaxis can also lower transmission risk of HIV in community. New understanding of HIV pathogenesis is opening new vistas to cure and prevention. Various promising candidate vaccines and drugs are undergoing aggressive clinical trials, raising optimism for an ever-elusive cure for HIV. This review describes various facets of tectonic shift in management of HIV. PMID:26900224

  4. Lamb shift for static atoms outside a Schwarzschild black hole

    SciTech Connect

    Zhou Wenting; Yu Hongwei

    2010-11-15

    We study, by separately calculating the contributions of vacuum fluctuations and radiation reaction to the atomic energy level shift, the Lamb shift of a static two-level atom interacting with real massless scalar fields in the Boulware, Unruh, and Hartle-Hawking vacuums outside a Schwarzschild black hole. We find that in the Boulware vacuum, the Lamb shift gets a correction arising as a result of the backscattering of vacuum field modes off the space-time curvature, which is reminiscent of the correction to the Lamb shift induced by the presence of cavities. However, when the Unruh and Hartle-Hawking vacua are concerned, our results show that the Lamb shift behaves as if the atom were irradiated by a thermal radiation or immersed in a thermal bath at the Hawking temperature, depending on whether the scalar field is in the Unruh or the Hartle-Hawking vacuum. Remarkably, the thermal radiation is always backscattered by the space-time geometry.

  5. Portable shift register

    SciTech Connect

    Halbig, J.K.; Bourret, S.C.; Hansen, W.J.; Hicks, D.V.; Klosterbuer, S.F.; Krick, M.S.

    1994-01-01

    An electronics package for a small, battery-operated, self-contained, neutron coincidence counter based on a portable shift-register (PSR) has been developed. The counter was developed for applications not adequately addressed by commercial packages, including in-plant measurements to demonstrate compliance with regulations (domestic and international), in-plant process control, and in-field measurements (environmental monitoring or safeguards). Our package's features, which address these applications, include the following: Small size for portability and ease of installation;battery or mains operation; a built-in battery to power the unit and a typical detector such as a small sample counter, for over 6 h if power lines are bad or noisy, if there is a temporary absence of power, or if portability is desired; complete support, including bias, for standard neutron detectors; a powerful communications package to easily facilitate robust external control over a serial port; and a C-library to simplify creating external control programs in computers or other controllers. Whereas the PSR specifically addresses the applications mentioned above, it also performs all the measurements made by previous electronics packages for neutron coincidence counters developed at Los Alamos and commercialized. The PSR electronics package, exclusive of carrying handle, is 8 by 10 by 20 cm; it contains the circuit boards, battery, and bias supply and weighs less than 2 kg. This instrument package is the second in an emerging family of portable measurement instruments being developed; the first was the Miniature and Modular Multichannel Analyzer (M[sup 3]CA). The PSR makes extensive use of hardware and software developed for the M[sup 3]CA; like the M[sup 3]CA, it is intended primarily for use with an external controller interfaced over a serial channel.

  6. Thermochromic shifts in supercritical fluids

    SciTech Connect

    Yonker, C.R.; Smith, R.D. )

    1989-02-23

    Thermochromic shifts of organic solute molecules in supercritical CO{sub 2} under conditions of both constant pressure and density are compared to previous studies of solvatochromic shifts at isothermal conditions. Similar solvatochromic and thermochromic shifts are seen as a function of density for supercritical CO{sub 2}. At constant density a small thermochromic shift ({approx}400 cm{sup {minus}1}) for supercritical CO{sub 2} was seen for both 2-nitroanisole and 4-ethylnitrobenzene. The excited-state dipole moments for 2-nitroanisole, as calculated from the thermochromic and solvatochromic data, were in agreement.

  7. Quantized beam shifts in graphene

    SciTech Connect

    de Melo Kort-Kamp, Wilton Junior; Sinitsyn, Nikolai; Dalvit, Diego Alejandro Roberto

    2015-10-08

    We predict the existence of quantized Imbert-Fedorov, Goos-Hanchen, and photonic spin Hall shifts for light beams impinging on a graphene-on-substrate system in an external magnetic field. In the quantum Hall regime the Imbert-Fedorov and photonic spin Hall shifts are quantized in integer multiples of the fine structure constant α, while the Goos-Hanchen ones in multiples of α2. We investigate the influence on these shifts of magnetic field, temperature, and material dispersion and dissipation. An experimental demonstration of quantized beam shifts could be achieved at terahertz frequencies for moderate values of the magnetic field.

  8. [Shifting path of industrial pollution gravity centers and its driving mechanism in Pan-Yangtze River Delta].

    PubMed

    Zhao, Hai-Xia; Jiang, Xiao-Wei; Cui, Jian-Xin

    2014-11-01

    Shifting path of industrial pollution gravity centers is the response of environmental special formation during the industry transfer process, in order to prove the responding of industrial pollution gravity centers to industry transfer in economically developed areas, this paper calculates the gravity centers of industrial wastewater, gas and solid patterns and reveals the shifting path and its driving mechanism, using the data of industrial pollution in the Pan-Yangtze River Delta from 2000 to 2010. The results show that the gravity center of the industrial waste in Pan-Yangtze River Delta shifts for sure in the last 10 years, and gravity center of solid waste shifts the maximum distance within the three wastes, which was 180.18 km, and shifting distances for waste gas and waste water were 109.51 km and 85.92 km respectively. Moreover, the gravity center of the industrial waste in Pan-Yangtze River Delta shifts westwards, and gravity centers of waste water, gas and solid shift for 0.40 degrees, 0.17 degrees and 0.03 degrees respectively. The shifting of industrial pollution gravity centers is driven by many factors. The rapid development of the heavy industry in Anhui and Jiangxi provinces results in the westward shifting of the pollutions. The optimization and adjustment of industrial structures in Yangtze River Delta region benefit to alleviating industrial pollution, and high-polluting industries shifted to Anhui and Jiangxi provinces promotes pollution gravity center shifting to west. While the development of massive clean enterprise, strong environmental management efforts and better environmental monitoring system slow the shifting trend of industrial pollution to the east in Yangtze River Delta. The study of industrial pollution gravity shift and its driving mechanism provides a new angle of view to analyze the relationship between economic development and environmental pollution, and also provides academic basis for synthetical management and control of environmental pollution in Pan-Yangtze River Delta, especially in the transition period. PMID:25639121

  9. Shifts in fisheries management: adapting to regime shifts

    PubMed Central

    King, Jacquelynne R.; McFarlane, Gordon A.; Punt, André E.

    2015-01-01

    For many years, fisheries management was based on optimizing yield and maintaining a target biomass, with little regard given to low-frequency environmental forcing. However, this policy was often unsuccessful. In the last two to three decades, fisheries science and management have undergone a shift towards balancing sustainable yield with conservation, with the goal of including ecosystem considerations in decision-making frameworks. Scientific understanding of low-frequency climate–ocean variability, which is manifested as ecosystem regime shifts and states, has led to attempts to incorporate these shifts and states into fisheries assessment and management. To date, operationalizing these attempts to provide tactical advice has met with limited success. We review efforts to incorporate regime shifts and states into the assessment and management of fisheries resources, propose directions for future investigation and outline a potential framework to include regime shifts and changes in ecosystem states into fisheries management.

  10. Wind driven vertical transport in a vegetated, wetland water column with air-water gas exchange

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2010-12-01

    Flow around arrays of cylinders at low and intermediate Reynolds numbers has been studied numerically, analytically and experimentally. Early results demonstrated that at flow around randomly oriented cylinders exhibits reduced turbulent length scales and reduced diffusivity when compared to similarly forced, unimpeded flows (Nepf 1999). While horizontal dispersion in flows through cylinder arrays has received considerable research attention, the case of vertical dispersion of reactive constituents has not. This case is relevant to the vertical transfer of dissolved gases in wetlands with emergent vegetation. We present results showing that the presence of vegetation can significantly enhance vertical transport, including gas transfer across the air-water interface. Specifically, we study a wind-sheared air-water interface in which randomly arrayed cylinders represent emergent vegetation. Wind is one of several processes that may govern physical dispersion of dissolved gases in wetlands. Wind represents the dominant force for gas transfer across the air-water interface in the ocean. Empirical relationships between wind and the gas transfer coefficient, k, have been used to estimate spatial variability of CO2 exchange across the worlds’ oceans. Because wetlands with emergent vegetation are different from oceans, different model of wind effects is needed. We investigated the vertical transport of dissolved oxygen in a scaled wetland model built inside a laboratory tank equipped with an open-ended wind tunnel. Plastic tubing immersed in water to a depth of approximately 40 cm represented emergent vegetation of cylindrical form such as hard-stem bulrush (Schoenoplectus acutus). After partially removing the oxygen from the tank water via reaction with sodium sulfite, we used an optical probe to measure dissolved oxygen at mid-depth as the tank water re-equilibrated with the air above. We used dissolved oxygen time-series for a range of mean wind speeds to estimate the gas transfer coefficient, k, for both a vegetated condition and a control condition (no cylinders). The presence of cylinders in the tank substantially increased the rate of the gas transfer. For the highest wind speed, the gas transfer coefficient was several times higher when cylinders were present compared to when they were not. The gas transfer coefficient for the vegetated condition also proved sensitive to wind speed, increasing markedly with increasing mean wind speeds. Profiles of dissolved oxygen revealed well-mixed conditions in the bulk water column following prolonged air-flow above the water surface, suggesting application of the thin-film model is appropriate. The enhanced gas exchange observed might be explained by increased turbulent kinetic energy within the water column and the anisotropy of the cylinder array, which constrains horizontal motions more than vertical motions. Improved understanding of gas exchange in vegetated water columns may be of particularly use to investigations of carbon fluxes and soil accretion in wetlands. Reference: Nepf, H. (1999), Drag, turbulence, and diffusion in flow through emergent vegetation, Water Resour. Res., 35(2), 479-489.

  11. Reaction theory

    NASA Astrophysics Data System (ADS)

    Typel, Stefan

    2016-01-01

    Reactions with atomic nuclei play a pivotal role in the experimental study of nuclei. They are a tool in order to obtain crucial information on nuclear structure of nuclei, in particular for unstable nuclei far off the valley of stability. Besides the investigation of nuclear properties, nuclear reactions can be used as indirect methods to extract cross sections of astrophysical interest that cannot be measured directly in the laboratory. After an overview over the variety of nuclear reactions and their major characteristics, the basic formalism of reaction theory is introduced and essential concepts are presented in order to describe direct reactions. The main challenges in the future development of reaction theory are addressed.

  12. In-Cylinder Reaction Chemistry and Kinetics During Negative Valve Overlap Fuel Injection Under Low-Oxygen Conditions

    SciTech Connect

    Kalaskar, Vickey B; Szybist, James P; Splitter, Derek A; Pihl, Josh A; Gao, Zhiming; Daw, C Stuart

    2013-01-01

    Fuel injection into the negative valve overlap (NVO) period is a common method for controlling combustion phasing in homogeneous charge compression ignition (HCCI) as well as other forms of advanced combustion. During this event, at least a portion of the fuel hydrocarbons can be converted to products containing significant levels of H2 and CO, as well as other short chain hydrocarbons by means of thermal cracking, water-gas shift, and partial oxidation reactions, depending on the availability of oxygen and the time-temperature-pressure history. The resulting products alter the autoignition properties of the combined fuel mixture for HCCI. Fuel-rich chemistry in a partial oxidation environment is also relevant to other high efficiency engine concepts (e.g., the dedicated EGR (D-EGR) concept from SWRI). In this study, we used a unique 6-stroke engine cycle to experimentally investigate the chemistry of a range of fuels injected during NVO under low oxygen conditions. Fuels investigated included iso-octane, iso-butanol, ethanol, and methanol. Products from NVO chemistry were highly dependent on fuel type and injection timing, with iso-octane producing less than 1.5% hydrogen and methanol producing more than 8%. We compare the experimental trends with CHEMKIN (single zone, 0-D model) predictions using multiple kinetic mechanisms available in the current literature. Our primary conclusion is that the kinetic mechanisms investigated are unable to accurately predict the magnitude and trends of major species we observed.

  13. Equilibria That Shift Left upon Addition of More Reactant

    ERIC Educational Resources Information Center

    Lacy, Jeffrey E.

    2005-01-01

    The presentations that will enable students to perform a side-by-side comparison of two conditions and gain better understanding of reactions at equilibrium are illustrated. A novel stoichiometric criterion for identifying equilibria that shift left upon addition of reactant is derived.

  14. Dynamic phase-shifting photoelasticity.

    PubMed

    Asundi, A; Tong, L; Boay, C G

    2001-08-01

    The application of phase-shifting photoelasticity to a real-time dynamic event involves simultaneous recording of the four phase-shifted images. Here an instrument, believed to be novel, is developed and described for this purpose. Use of a Multispec Imager is introduced into digital photoelasticity for the first time to our knowledge. This device enables splitting the optical energy of an object into four identical paths, thus permitting recording of the required four phase-shifted images. Experimental demonstration is provided for validation. PMID:18360395

  15. Biological conversion of synthesis gas culture development

    SciTech Connect

    Klasson, K.T.; Basu, R.; Johnson, E.R.; Clausen, E.C.; Gaddy, J.L.

    1992-03-01

    Research continues on the conversion of synthesis by shift reactions involving bacteria. Topics discussed here include: biological water gas shift, sulfur gas utilization, experimental screening procedures, water gas shift studies, H{sub 2}S removal studies, COS degradation by selected CO-utilizing bacteria, and indirect COS utilization by Chlorobia. (VC)

  16. Marine biological shifts and climate.

    PubMed

    Beaugrand, Grégory; Goberville, Eric; Luczak, Christophe; Kirby, Richard R

    2014-05-22

    Phenological, biogeographic and community shifts are among the reported responses of marine ecosystems and their species to climate change. However, despite both the profound consequences for ecosystem functioning and services, our understanding of the root causes underlying these biological changes remains rudimentary. Here, we show that a significant proportion of the responses of species and communities to climate change are deterministic at some emergent spatio-temporal scales, enabling testable predictions and more accurate projections of future changes. We propose a theory based on the concept of the ecological niche to connect phenological, biogeographic and long-term community shifts. The theory explains approximately 70% of the phenological and biogeographic shifts of a key zooplankton Calanus finmarchicus in the North Atlantic and approximately 56% of the long-term shifts in copepods observed in the North Sea during the period 1958-2009. PMID:24718760

  17. Refining the shifted topological vertex

    SciTech Connect

    Drissi, L. B.; Jehjouh, H.; Saidi, E. H.

    2009-01-15

    We study aspects of the refining and shifting properties of the 3d MacMahon function C{sub 3}(q) used in topological string theory and BKP hierarchy. We derive the explicit expressions of the shifted topological vertex S{sub {lambda}}{sub {mu}}{sub {nu}}(q) and its refined version T{sub {lambda}}{sub {mu}}{sub {nu}}(q,t). These vertices complete results in literature.

  18. On the coefficients of small eddy and surface divergence models for the air-water gas transfer velocity

    NASA Astrophysics Data System (ADS)

    Wang, Binbin; Liao, Qian; Fillingham, Joseph H.; Bootsma, Harvey A.

    2015-03-01

    Recent studies suggested that under low to moderate wind conditions without bubble entraining wave breaking, the air-water gas transfer velocity k+ can be mechanistically parameterized by the near-surface turbulence, following the small eddy model (SEM). Field measurements have supported this model in a variety of environmental forcing systems. Alternatively, surface divergence model (SDM) has also been shown to predict the gas transfer velocity across the air-water interface in laboratory settings. However, the empirically determined model coefficients (α in SEM and c1 in SDM) scattered over a wide range. Here we present the first field measurement of the near-surface turbulence with a novel floating PIV system on Lake Michigan, which allows us to evaluate the SEM and SDM in situ in the natural environment. k+ was derived from the CO2 flux that was measured simultaneously with a floating gas chamber. Measured results indicate that α and c1 are not universal constants. Regression analysis showed that α˜log>(ɛ>) while the near-surface turbulence dissipation rate ɛ is approximately greater than 10-6 m2 s-3 according to data measured for this study as well as from other published results measured in similar environments or in laboratory settings. It also showed that α scales linearly with the turbulent Reynolds number. Similarly, coefficient c1 in the SDM was found to linearly scale with the Reynolds number. These findings suggest that larger eddies are also important parameters, and the dissipation rate in the SEM or the surface divergence β' in the SDM alone may not be adequate to determine k+ completely.

  19. Nonlocality in deuteron stripping reactions.

    PubMed

    Timofeyuk, N K; Johnson, R C

    2013-03-15

    We propose a new method for the analysis of deuteron stripping reactions, A(d,p)B, in which the nonlocality of nucleon-nucleus interactions and three-body degrees of freedom are accounted for in a consistent way. The model deals with equivalent local nucleon potentials taken at an energy shifted by ∼40  MeV from the "E(d)/2" value frequently used in the analysis of experimental data, where E(d) is the incident deuteron energy. The "E(d)/2" rule lies at the heart of all three-body analyses of (d, p) reactions performed so far with the aim of obtaining nuclear structure properties such as spectroscopic factors and asymptotic normalization coefficients that are crucial for our understanding of nuclear shell evolution in neutron- and proton-rich regions of the nuclear periodic table and for predicting the cross sections of stellar reactions. The large predicted shift arises from the large relative kinetic energy of the neutron and proton in the incident deuteron in those components of the n+p+A wave function that dominate the (d, p) reaction amplitude. The large shift reduces the effective d-A potentials and leads to a change in predicted (d, p) cross sections, thus affecting the interpretation of these reactions in terms of nuclear structure. PMID:25166525

  20. Schedule shifts, cancer and longevity

    PubMed Central

    Cornlissen, Germaine; Halberg, Julia; Halberg, Franz; de la Pena, Salvador Sanchez; Nelson, Walter; Schwartzkopff, Othild; Stoynev, Alexander; Haus, Erhard

    2008-01-01

    Prompted by a recent report of the possible carcinogenic effect of shiftwork focusing on the disruption of circadian rhythms, we review studies involving shifts in schedule implemented at varying intervals in unicells, insects and mammals, including humans. Results indicate the desirability to account for a broader-than-circadian view. They also suggest the possibility of optimizing schedule shifts by selecting intervals between consecutive shifts associated with potential side-effects such as an increase in cancer risk. Toward this goal, marker rhythmometry is most desirable. The monitoring of blood pressure and heart rate present the added benefit of assessing cardiovascular disease risks resulting not only from an elevated blood pressure but also from abnormal variability in blood pressure and/or heart rate of normotensive as well as hypertensive subjects. PMID:19227006

  1. Engineering the nonlinear phase shift.

    PubMed

    Chen, Yan; Pasrija, Geeta; Farhang-Boroujeny, Behrouz; Blair, Steve

    2003-10-15

    We treat the nonlinear phase shift response in the weak perturbation limit as a linear digital filter that can be synthesized into the values of its poles and zeros and mapped onto an optical architecture. This procedure results in a significant enhancement in the nonlinear sensitivity with a response that is robust to frequency changes within the filter passband. A precompensation technique can be used to reduce distortions under strongly driven nonlinear operation to achieve a larger phase shift. We also show that nonlinear sensitivity improves with increasing filter group delay and can be increased within constant linear bandwidth by use of higher-order filters. PMID:14587784

  2. Considerations Based on Reaction Rate on Char Gasification Behavior in Two-stage Gasifier for Biomass

    NASA Astrophysics Data System (ADS)

    Taniguchi, Miki; Nishiyama, Akio; Sasauchi, Kenichi; Ito, Yusuke; Akamatsu, Fumiteru

    In order to develop a small-scale gasifier in which biomass can be converted to energy with high efficiency, we planned a gasification process that consists of two parts: pyrolysis part (rotary kiln) and gasification part (downdraft gasifier). We performed fundamental experiments on gasification part and discussed the appropriate conditions such as air supply location, air ratio, air temperature and hearth load. We considered the results by calculating reaction rates of representative reactions on char gasification part and found that water gas reaction is dominant in the reduction area and its behavior gives important information to decide the adequate length of the char layer.

  3. Information storage at the molecular level - The design of a molecular shift register memory

    NASA Technical Reports Server (NTRS)

    Beratan, David N.; Onuchic, Jose Nelson; Hopfield, J. J.

    1989-01-01

    The control of electron transfer rates is discussed and a molecular shift register memory at the molecular level is described. The memory elements are made up of molecules which can exist in either an oxidized or reduced state and the bits can be shifted between the cells with photoinduced electron transfer reactions. The device integrates designed molecules onto a VLSI substrate. A control structure to modify the flow of information along a shift register is indicated schematically.

  4. Decrease in carbonyl sulfide in the feed to Claus converters by shift catalysts

    SciTech Connect

    Gens, T.A. )

    1994-07-01

    The principal reaction in the burner in a Claus plant is the combustion of part of the hydrogen sulfide to form sulfur dioxide, which can react with more hydrogen sulfide to form sulfur. Alumina or commercial shift catalysts were used downstream of a Claus burner to shift carbon monoxide to carbon dioxide before it could react to form carbonyl sulfide. The shift catalysts were effective in preventing formation of carbonyl sulfide, thereby decreasing sulfur losses.

  5. A molecular shift register based on electron transfer

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Josenelson; Beratan, David N.

    1988-01-01

    An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a 'molecular electronic device' that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density.

  6. The Modality Shift Experiment in Adults and Children with High Functioning Autism

    ERIC Educational Resources Information Center

    Williams, Diane L.; Goldstein, Gerald; Minshew, Nancy J.

    2013-01-01

    This study used the modality shift experiment, a relatively simple reaction time measure to visual and auditory stimuli, to examine attentional shifting within and across modalities in 33 children and 42 adults with high-functioning autism as compared to matched numbers of age- and ability-matched typical controls. An exaggerated "modality shift…

  7. Leadership Shifts in Changing Field

    ERIC Educational Resources Information Center

    Zubrzycki, Jaclyn

    2013-01-01

    As groups representing local and state education players struggle to remain relevant in a policy conversation often dominated by foundations, think tanks, new advocacy groups, and political and business figures, a shift in leadership has been under way at major associations. Most of the changes have come as part of the natural churn; former…

  8. Flexible shift scheduling of physicians.

    PubMed

    Brunner, Jens O; Bard, Jonathan F; Kolisch, Rainer

    2009-09-01

    This research addresses a shift scheduling problem in which physicians at a German university hospital are assigned to demand periods over a planning horizon that can extend up to several weeks. When performing the scheduling it is necessary to take into account a variety of legal and institutional constraints that are imposed by a national labor agreement, which governs all physicians in German university hospitals. Currently, most medical departments develop their staff schedules manually at great cost and time. To solve the problem, a new modeling approach is developed that requires shifts to be generated implicitly. Rather than beginning with a predetermined number of shift types and start times, shifts are allowed to start at every pre-defined period in the planning horizon and extend up to 13 h with an hour-long break included. The objective is to find an assignment such that the total hours that have to be paid out as overtime are minimal under the restrictions given by the labor agreement. The problem is formulated as a mixed-integer program and solved with CPLEX. During the solution process individual lines-of-work are constructed for each physician. Using data from an anesthesia department, computational results indicate that high quality schedules can be obtained much more quickly than by current practice. PMID:19739361

  9. Technology Counts 2012: Virtual Shift

    ERIC Educational Resources Information Center

    Education Week, 2012

    2012-01-01

    Virtual education is moving into that intersection where rising popularity meets calls for greater accountability. How the virtual education movement responds to those calls will have a significant impact on how it evolves in K-12 over the next five to 10 years. This report tackles this shift in the virtual education landscape. It examines the…

  10. Digital Phase-Shift Standard

    NASA Technical Reports Server (NTRS)

    Cramp, J. A.

    1983-01-01

    Digital phase-shift standard used in combination with oscillator to calibrate other phase standards and phase-angle voltmeters. Phase-shifter circuit provides two square-wave outputs, A and B, with phase difference between them selectable in 30 degrees increments. Circuit is used with input signals as low as 1 volt rms, in almost any waveform.

  11. Technology Counts 2012: Virtual Shift

    ERIC Educational Resources Information Center

    Education Week, 2012

    2012-01-01

    Virtual education is moving into that intersection where rising popularity meets calls for greater accountability. How the virtual education movement responds to those calls will have a significant impact on how it evolves in K-12 over the next five to 10 years. This report tackles this shift in the virtual education landscape. It examines the

  12. Lamb shift in muonic hydrogen

    SciTech Connect

    Borie, E.

    2005-03-01

    The Lamb shift in muonic hydrogen continues to be a subject of experimental and theoretical investigation. Here my older work on the subject is updated to provide a complementary calculation of the energies of the 2p-2s transitions in muonic hydrogen.

  13. The Shift Needed for Sustainability

    ERIC Educational Resources Information Center

    Smith, Peter A. C.; Sharicz, Carol

    2011-01-01

    Purpose: The purpose of this action research is to begin to assess to what extent organizations have in practice begun to make the shift towards triple bottom line (TBL) sustainability. Design/methodology/approach: A definition of TBL sustainability is provided, and key elements of TBL sustainability considered necessary to success are identified

  14. The Shift Needed for Sustainability

    ERIC Educational Resources Information Center

    Smith, Peter A. C.; Sharicz, Carol

    2011-01-01

    Purpose: The purpose of this action research is to begin to assess to what extent organizations have in practice begun to make the shift towards triple bottom line (TBL) sustainability. Design/methodology/approach: A definition of TBL sustainability is provided, and key elements of TBL sustainability considered necessary to success are identified…

  15. Illinois Shifting Gears Policy Evaluation

    ERIC Educational Resources Information Center

    Weitzel, Peter C.

    2009-01-01

    Illinois Shifting Gears is a multilevel initiative that has simultaneously created bridge programs in the field and altered state policy to facilitate the creation of more programs in the future. These efforts have informed each other, giving policymakers the opportunity to interact with practitioners, troubleshoot bridge programs, and make

  16. Proton Chemical-Shift Spectra

    NASA Astrophysics Data System (ADS)

    Simova, Svetlana; Sengstschmid, Helmut; Freeman, Ray

    1997-01-01

    Three related methods are explored for obtaining high-resolution proton spectra without spin-spin splittings, termed "chemical-shift spectra." They are based on two-dimensionalJspectroscopy, where theF1dimension is derived by Fourier transformation of spin-echo modulation. The first technique superimposes theJspectrum on its reflection in theF1= 0 axis, creating multiplet patterns in the form of a St. Andrew's cross. The other two techniques purge certain antiphase product-operator terms, either by dispersal in an inhomogeneous effective radiofrequency field oriented at the magic angle (54.7°) or by means of azfilter. In all three cases, the two-dimensional multiplets are separated by means of a symmetry filter and their centers are taken as a measure of the respective chemical shifts. The 400 MHz proton chemical-shift spectrum of 4-androsten-3,17-dione is presented as an illustrative example. Good separation is achieved, even for interpenetrating spin multiplets with near degeneracies in their chemical shifts. Complications due to strong-coupling effects are discussed.

  17. Leadership Shifts in Changing Field

    ERIC Educational Resources Information Center

    Zubrzycki, Jaclyn

    2013-01-01

    As groups representing local and state education players struggle to remain relevant in a policy conversation often dominated by foundations, think tanks, new advocacy groups, and political and business figures, a shift in leadership has been under way at major associations. Most of the changes have come as part of the natural churn; former

  18. Drug Reactions

    MedlinePLUS

    Most of the time, medicines make our lives better. They reduce aches and pains, fight infections, and control problems such as high blood pressure or diabetes. But medicines can also cause unwanted reactions. One problem is ...

  19. In situ Characterization of Pt Catalysts Supported on Ceria Modified TiO(2) for the WGS reaction: Influence of Ceria Loading

    SciTech Connect

    Rodriguez J. A.; Barrio, L.; Zhou, G.; Gonzalez, I.D.; Estrella, M.; Hanson, J.; Navarro, R.M.; Fierro, J.L.G.

    2012-01-01

    This work analyzes the influence of cerium content (6-15 wt%) on a TiO{sub 2} support over the structure and water gas shift (WGS) activity of Pt catalysts. The structural properties of these Pt/Ce-TiO{sub 2} catalysts were characterized by XRD, TEM and XANES. Physicochemical characterization of the catalysts showed differences in the structure and dispersion of Ce entities on the support with Ce loading. For the samples with low ceria content (6 wt%), cerium is deposited on the support in the form of CeO{sub x} clusters in a highly dispersed state in close interaction with the Ti atoms. The formation of CeO{sub x} clusters at low Ce-loading on the support facilitates the dispersion of small particles of Pt and improves the reducibility of ceria component at low temperatures. The changes in platinum dispersion and support reducibility with Ce-loading on the TiO{sub 2} support lead to significant differences in the WGS activity. Pt supported on the sample with lower Ce content (6 wt%) shows better activity than those corresponding to catalysts with higher Ce content (15 wt%). Activity measurements coupled with catalysts characterization suggest that the improvement in the reducibility of the support with lower Ce content was associated with the presence of CeO{sub x} clusters of high reducibility that improve the chemical activity of the oxide-metal interfaces at which the WGS reaction takes place.

  20. The influence of nano-architectured CeOx supports in RhPd/CeO? for the catalytic ethanol steam reforming reaction

    SciTech Connect

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO? cubes and CeO? rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO?-cubes > RhPd/CeO? -rods > RhPd/CeO?- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO?-cubes and RhPd/CeO? -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

  1. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    DOE PAGESBeta

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

  2. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    SciTech Connect

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

  3. Exclusive Reactions

    NASA Astrophysics Data System (ADS)

    Mueller, A. H.

    1997-02-01

    After some introductory remarks a brief review of the status of exclusive reactions and of color transparency is given. Special emphasis is given to the ?y transition form factor, which appears to be the first exclusive reaction where the hard scattering perturbative QCD picture seems to work well. Deeply virtual Compton scattering, which may become an exciting source of new information on partonic spin and angular momentum structure, is also briefly reviewed.

  4. Combined shift and methanation in a fluidized-bed reactor. Final report, 25 September 1979-31 December 1980

    SciTech Connect

    Streeter, R.C.

    1981-02-01

    The objective of this program was to demonstrate the feasibility of employing a gas-phase, catalytic, fluidized-bed reactor to carry out the water-gas shift and methanation reactions simultaneously, without product gas recycle. The major portion of the experimental work involved PEDU-scale tests in a 6-inch ID reactor, operating at 1000 psig and temperatures in the range of 900 to 1000/sup 0/F, with a nominal catalyst charge of one cubic foot. These tests included operation for extended time periods (35 to 40 hours) with feed H/sub 2/:CO ratios of 2:1 in the absence of steam, and 1:1 using steam:gas ratios of 0.1:1 to 0.2:1. Five different catalysts were evaluated. Bench-scale tests, each of approximately 10 days' duration, were also conducted. At H/sub 2/:CO = 2:1 (without steam), no significant carbon deposition occurred at temperatures of 800 and 950/sup 0/F. At 1100/sup 0/F, however, considerable carbon formation did occur, possibly due to the onset of CH/sub 4/ pyrolysis. At H/sub 2/:CO = 1:1 and 950/sup 0/F, carbon deposition took place readily in the absence of steam. Small amounts of steam in the feed (e.g., steam:gas ratio = 0.1:1) were effective in inhibiting carbon formation, although larger amounts (steam:gas ratio = 0.5:1) resulted in deactivation and loss of metal surface area through sintering. Results of auxiliary studies at Brigham Young University (BYU) on rates of carbon formation and removal are also presented. As to the relative tendencies of the various catalysts to undergo carbon deposition, results of the BYU studies generally confirmed observations made during PEDU testing at BCR. Catalyst regeneration tests at BYU with 10 percent O/sub 2/ in N/sub 2/ showed that 80 to 96 percent of the original metal surface could be restored at temperatures of 572 to 662/sup 0/F.

  5. Billingsley dimension on shift spaces

    NASA Astrophysics Data System (ADS)

    Pfister, C.-E.; Sullivan, W. G.

    2003-03-01

    We consider a class of subshifts Sigma over a finite alphabet, including sofic shifts. For a large class of metrics we determine the Hausdorff dimension of sets of points of Sigma defined by their limit-point set under the empirical measure. Our approach to computing the Billingsley dimension of saturated sets is fundamentally different and applies to more general shift spaces and measures than the technique of Billingsley, which was significantly developed by Cajar and recently extended by others. One main feature of our approach is an algorithmic construction of a large (in the sense of dimension theory) subset of a saturated set. This generalizes similar constructions of subsets of normal or generic points.

  6. KVI Lamb-shift polarimeter

    SciTech Connect

    Beijers, J.P.M.; Kremers, H.R.; Kalantar-Nayestanaki, N.

    2006-03-15

    The design and operation of a Lamb-shift polarimeter is discussed. This polarimeter is used to measure the polarization of proton and deuteron beams extracted from the KVI polarized-ion source. The major components of the Lamb-shift polarimeter (LSP) are described in some detail. These include the deceleration lens system, cesium neutralization oven, spin filter, metastable-atom detection system, and the solenoid. Typical operating parameters of the LSP will be given together with some representative spin-polarization measurements. The design criterion of measuring the polarization of a H{sup +} or D{sup +} beam within 60 s and with a statistical uncertainty smaller than 2% has been met.

  7. Looping through the Lamb Shift

    SciTech Connect

    Hazi, A U

    2007-02-06

    Sometimes in science, a small measurement can have big ramifications. For a team of Livermore scientists, such was the case when they measured a small shift in the spectrum of extremely ionized atoms of uranium. The measurement involves the Lamb shift, a subtle change in the energy of an electron orbiting an atom's nucleus. The precision of the Livermore result was 10 times greater than that of existing measurements, making it the best measurement to date of a complicated correction to the simplest quantum description of how atoms behave. The measurement introduces a new realm in the search for deviations between the theory of quantum electrodynamics (QED), which is an extension of quantum mechanics, and the real world. Such deviations, if discovered, would have far-reaching consequences, indicating that QED is not a fundamental theory of nature.

  8. Lamb shift in muonic deuterium

    SciTech Connect

    Gorchtein, Mikhail; Vanderhaeghen, Marc; Carlson, Carl E.

    2013-11-07

    We consider the two-photon exchange contribution to the 2P-2S Lamb shift in muonic deuterium in the framework of forward dispersion relations. The dispersion integrals are evaluated with minimal model dependence using experimental data on elastic deuteron form factors and inelastic electron-deuteron scattering, both in the quasielastic and hadronic range. The subtraction constant that is required to ensure convergence of the dispersion relation for the forward Compton amplitude T{sub 1} (?,Q{sup 2}) is related to the deuteron magnetic polarizability ?(Q{sup 2}) and represents the main source of uncertainty in our analysis. We obtain for the Lamb shift ?E{sub 2P-2S} = 1.6200.190 meV and discuss ways to further reduce this uncertainty.

  9. Anthropometric changes and fluid shifts

    NASA Technical Reports Server (NTRS)

    Thornton, W. E.; Hoffler, G. W.; Rummel, J. A.

    1977-01-01

    In an effort to obtain the most comprehensive and coherent picture of changes under weightlessness, a set of measurements on Skylab 2 was initiated and at every opportunity, additional studies were added. All pertinent information from ancillary sources were gleaned and collated. On Skylab 2, the initial anthropometric studies were scheduled in conjunction with muscle study. A single set of facial photographs was made in-flight. Additional measurements were made on Skylab 3, with photographs and truncal and limb girth measurements in-flight. Prior to Skylab 4, it was felt there was considerable evidence for large and rapid fluid shifts, so a series of in-flight volume and center of mass measurements and infrared photographs were scheduled to be conducted in the Skylab 4 mission. A number of changes were properly documented for the first time, most important of which were the fluid shifts. The following description of Skylab anthropometrics address work done on Skylab 4 primarily.

  10. Shift Work and Endocrine Disorders

    PubMed Central

    Ulhôa, M. A.; Marqueze, E. C.; Burgos, L. G. A.; Moreno, C. R. C.

    2015-01-01

    The objective of this review was to investigate the impact of shift and night work on metabolic processes and the role of alterations in the sleep-wake cycle and feeding times and environmental changes in the occurrence of metabolic disorders. The literature review was performed by searching three electronic databases for relevant studies published in the last 10 years. The methodological quality of each study was assessed, and best-evidence synthesis was applied to draw conclusions. The literature has shown changes in concentrations of melatonin, cortisol, ghrelin, and leptin among shift workers. Melatonin has been implicated for its role in the synthesis and action of insulin. The action of this hormone also regulates the expression of transporter glucose type 4 or triggers phosphorylation of the insulin receptor. Therefore, a reduction in melatonin can be associated with an increase in insulin resistance and a propensity for the development of diabetes. Moreover, shift work can negatively affect sleep and contribute to sedentarism, unhealthy eating habits, and stress. Recent studies on metabolic processes have increasingly revealed their complexity. Physiological changes induced in workers who invert their activity-rest cycle to fulfill work hours include disruptions in metabolic processes. PMID:25892993

  11. Frequency shifts in gravitational resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Baeler, S.; Nesvizhevsky, V. V.; Pignol, G.; Protasov, K. V.; Rebreyend, D.; Kupriyanova, E. A.; Voronin, A. Yu.

    2015-02-01

    Quantum states of ultracold neutrons in a gravitational field are characterized through gravitational resonance spectroscopy. This paper discusses systematic effects that appear in the spectroscopic measurements. The discussed frequency shiftswhich we call the Stern-Gerlach shift, interference shift, and spectator-state shiftappear in conceivable measurement schemes and have general importance. These shifts have to be taken into account in precision experiments.

  12. Paradigm shifts in corneal transplantation.

    PubMed

    Tan, Donald T H; Anshu, Arundhati; Mehta, Jodhbir S

    2009-04-01

    Conventional corneal transplantation, in the form of penetrating keratoplasty (PK), involves full-thickness replacement of the cornea, and is a highly successful procedure. However, the cornea is anatomically a multi-layered structure. Pathology may only affect individual layers of the cornea, hence selective lamellar surgical replacement of only the diseased corneal layers whilst retaining unaffected layers represents a new paradigm shift in the field. Recent advancements in surgical techniques and instrumentation have resulted in several forms of manual, microkeratome and femto-second laser-assisted lamellar transplantation procedures. Anterior lamellar keratoplasty (ALK) aims at replacing only diseased or scarred corneal stroma, whilst retaining the unaffected corneal endothelial layer, thus obviating the risk of endothelial allograft rejection. Posterior lamellar keratoplasty/endothelial keratoplasty (PLK/EK) involves the replacement of the dysfunctional endothelial cell layer only. Whilst significant technical and surgical challenges are involved in performing lamellar micro-dissection of a tissue which is only 0.5 mm thick, the benefits of a more controlled surgical procedure and improved graft survival rates have resulted in a shift away from conventional PK. This review details the current advances in emerging lamellar corneal surgical procedures and highlights the main advantages and disadvantages of these new lamellar corneal procedures. PMID:19434336

  13. Sectoral shifts and aggregate unemployment

    SciTech Connect

    Loungani, P.

    1986-01-01

    Some recent research has taken the view that sectoral or industry-specific shocks significantly affect aggregate unemployment by increasing the amount of inter-industry labor reallocation required. The empirical evidence for this view rests on the finding that during the 1950s - and again during the 1970s - there was a positive correlation between aggregate unemployment and the dispersion of employment growth rates. This thesis demonstrates that this correlation arises largely because oil price shocks affect both unemployment and the dispersion of employment growth. Once the dispersion due to oil shocks is accounted for, the residual dispersion in employment has very low explanatory power for unemployment. Since the dispersion index does not measure pure sectoral shifts, an alternate measure of dispersion is developed that serves as a better proxy for the amount of inter-industry labor reallocation required each period. Estimates using this measure suggest that, during the 1950s, temporary increases in the relative price of oil were responsible for generating the observed correlation. On the other hand, sectoral shifts were important during the 1970s; in particular, the 1973 oil price increase has had significant reallocative effects on the economy. This contention is subjected to further tests by looking at the time-series behavior of employment in durable-goods industries and also by following the inter-industry movements of workers over time through the use of panel data.

  14. Protein chemical shift analysis: a practical guide.

    PubMed

    Wishart, D S; Nip, A M

    1998-01-01

    Proper protein chemical shift analysis requires careful experimental measurements and the implementation of standardized referencing procedures. In this article we outline the steps necessary to ensure proper chemical shift referencing and the selection criteria for choosing appropriate "random coil" amino acid chemical shift values for predicting, comparing, and assigning 1H, 13C, and 15N resonances in proteins. By making use of these standardized conditions we demonstrate how several recently developed methods, namely homologous assignment techniques and empirical chemical shift contour maps (or hypersurfaces), can significantly improve the accuracy of chemical shift prediction for 1H, 13C, and 15N nuclei. In addition to illustrating the potential utility of chemical shift prediction, we also outline procedures for identifying secondary structure elements through heteronuclear chemical shift analysis and further demonstrate how empirical shift contour maps can actually be used to refine, and more importantly generate, reasonably good three-dimensional protein structures. PMID:9923684

  15. Discrete radon transform with shift of coordinate

    SciTech Connect

    Wei, X.; Wu, L.

    1994-12-31

    This paper describes the Radon transform with shift of coordinates. The appropriate shift value of spatial coordinate gives less alias in the data reconstruction and the appropriate shift value of frequency coordinate makes the reconstruction stable. The method is suitable to signal processing of seismogram, an example of wave field separation to practical VSP data is shown in the paper.

  16. Balmer line shifts in quasars

    NASA Astrophysics Data System (ADS)

    Sulentic, J. W.; Marziani, P.; Del Olmo, A.; Zamfir, S.

    2016-02-01

    We offer a broad review of Balmer line phenomenology in type 1 active galactic nuclei, briefly summarising luminosity and radio loudness effects, and discussing interpretation in terms of nebular physics along the 4D eigenvector 1 sequence of quasars. We stress that relatively rare, peculiar Balmer line profiles (i.e., with large shifts with respect to the rest frame or double and multiple peaked) that start attracted attentions since the 1970s are still passable of multiple dynamical interpretation. More mainstream objects are still not fully understood as well, since competing dynamical models and geometries are possible. Further progress may come from inter-line comparison across the 4D Eigenvector 1 sequence.

  17. Shift of voltage reversal in stacked microbial fuel cells

    NASA Astrophysics Data System (ADS)

    An, Junyeong; Kim, Bongkyu; Chang, In Seop; Lee, Hyung-Sool

    2015-03-01

    We proved that sluggish kinetics on the cathode and the imbalance of cathode kinetics cause voltage reversal in a stacked microbial fuel cell (MFC) equipped with a non-Pt cathode. Catholyte aeration to a unit MFC against passive air diffusion to the cathode in the other unit MFC shifted voltage reversal between the two units, due to improved mass transport and O2 concentration effects in the aerated MFC. The shifted voltage reversal returned to an original status when catholyte aeration was stopped. A Pt-coated cathode increased the rate of oxygen reduction reaction (ORR) by a factor of ∼20, as compared to the non-Pt cathode. As a result, the anodic reaction rate that became slower than the rate on the Pt-cathode limited current density to overpotential in the stacked MFC equipped with the Pt-cathode. This work shows that dominant kinetic bottlenecks, which are the primary cause of voltage reversal, can be shifted between individual MFCs of stacked MFCs or electrodes depending on relative kinetics.

  18. Reverse shift mechanism for automotive manual transmission

    SciTech Connect

    Inui, M.; Ogawa, S.

    1987-03-03

    A reverse shift mechanism is described for an automotive manual transmission of a type having a reverse idler gear which is movable to selectively complete a reverse gear train, the reverse shift mechanism comprising: a reverse shift arm having a portion disposed adjacent the reverse idler gear and pivotally carried with respect to a transmission casing so that the portion rocks along a direction of axis of the reverse idler gear in response to shifting operation. The portion of the reverse shift arm is provided with a blind hole which is open at a first end toward the reverse idler gear and is closed at a second end away from the reverse idler gear; and a shift arm shoe carried by the portion of the reverse shift arm adjacent the reverse idler gear for pushing the reverse idler gear. The shift arm shoe has an end adapted to engage with a circumferential groove formed in the reverse idler gear and an opposing end shaped to fit in the blind hole of the reverse shift arm; whereby the shift arm shoe is prevented from coming off during assembly by virtue of a vacuum effect created by air confined in the blind hole by fitting engagement between the opposing end and the blind hole, and is held in place after assembly by being clamped between the groove of the reverse idler gear and the blind hole of the reverse shift arm.

  19. Recovery and detachment between shifts, and fatigue during a twelve-hour shift.

    PubMed

    Korunka, Christian; Kubicek, Bettina; Prem, Roman; Cvitan, Antonio

    2012-01-01

    The study investigated the role of recovery and detachment in the break period between two shifts for fatigue in the current shift. A time-based paper-and-pencil diary study was carried out observing sixty-four railway controllers over ten consecutive working shifts. The results demonstrated that fatigue in the current shift was not only affected by recovery and psychological detachment during break phases before a shift, but also by fatigue at shift onset and perceived workload during the shift. PMID:22317209

  20. Dealing with a Paradigm Shift

    PubMed Central

    Pack, Allan I.

    2015-01-01

    Recent changes in policies by insurance companies with respect to mandating home sleep apnea testing rather than in-laboratory studies have a large impact on the financial viability of clinical sleep centers. Coping with this disruptive change requires forward planning. First, it is important to be well positioned with respect to facilities so that these can be quickly downsized to control costs. There is also a need to develop, in advance, an accredited home sleep study program so that centers can respond to the rapidly changing environment. Following the change there is a need to control costs by rapidly downsizing the technology workforce. Technologists can be retrained for other essential roles. Centralizing the precertification process with knowledgeable, well-trained staff and a robust auditing process is an essential component. The approach taken at the University of Pennsylvania to this change is described as is how one can ensure continued financial viability of a comprehensive sleep center program in a major academic medical center. Citation: Pack AI. Dealing with a paradigm shift. J Clin Sleep Med 2015;11(8):925–929. PMID:26094918

  1. Bedside Shift-to-Shift Handoffs: A Systematic Review of the Literature.

    PubMed

    Mardis, Tyler; Mardis, Matt; Davis, Joshua; Justice, Ellen M; Riley Holdinsky, Stacie; Donnelly, John; Ragozine-Bush, Heather; Riesenberg, Lee Ann

    2016-01-01

    Multiple institutions identify communication and shift-to-shift handoffs as a source of clinical errors. Conducting handoffs at the bedside has been proposed as a potential solution to improve the quality of communication at change of shift. This article reports a systematic review of English-language research articles, published between January 1, 2008, and October 31, 2014, focused on bedside shift-to-shift handoffs. Forty-one articles were identified and analyzed in this systematic review. PMID:26192148

  2. Interpreting lateral dynamic weight shifts using a simple inverted pendulum model.

    PubMed

    Kennedy, Michael W; Bretl, Timothy; Schmiedeler, James P

    2014-01-01

    Seventy-five young, healthy adults completed a lateral weight-shifting activity in which each shifted his/her center of pressure (CoP) to visually displayed target locations with the aid of visual CoP feedback. Each subject's CoP data were modeled using a single-link inverted pendulum system with a spring-damper at the joint. This extends the simple inverted pendulum model of static balance in the sagittal plane to lateral weight-shifting balance. The model controlled pendulum angle using PD control and a ramp setpoint trajectory, and weight-shifting was characterized by both shift speed and a non-minimum phase (NMP) behavior metric. This NMP behavior metric examines the force magnitude at shift initiation and provides weight-shifting balance performance information that parallels the examination of peak ground reaction forces in gait analysis. Control parameters were optimized on a subject-by-subject basis to match balance metrics for modeled results to metric values calculated from experimental data. Overall, the model matches experimental data well (average percent error of 0.35% for shifting speed and 0.05% for NMP behavior). These results suggest that the single-link inverted pendulum model can be used effectively to capture lateral weight-shifting balance, as it has been shown to model static balance. PMID:24708905

  3. Calculation of image shift in panoramic photography

    NASA Astrophysics Data System (ADS)

    Miller, B. M.; Morskova, M. N.

    1985-03-01

    A method is suggested for calculating the image shift in a panoramic photograph applicable to panoramic aerial photographs, though this does not limit the general nature of its applicability. A program was written in FORTRAN for the BESM-6 computer to implement the algorithm. Continuous use of various systems for compensating image shift in panoramic apparatus is proposed for selection of solutions most acceptable for residual shift and design complexities.

  4. Jet Lag and Shift Work Disorder.

    PubMed

    Reid, Kathryn J; Abbott, Sabra M

    2015-12-01

    Jet lag and shift work disorder are circadian rhythm sleep-wake disorders resulting from behaviorally altering the sleep-wake schedule in relation to the external environment. Not everyone who experiences trans-meridian travel or performs shift work has a disorder. The prevalence of jet lag disorder is unclear, approximately 5%-10% of shift workers have shift work disorder. Treatment aims to realign the internal circadian clock with the external environment. Behavioral therapies include sleep hygiene and management of the light-dark and sleep schedule. Pharmacologic agents are used to treat insomnia and excessive sleepiness, and melatonin is used to facilitate sleep and circadian realignment. PMID:26568127

  5. The second-order gravitational red shift

    NASA Technical Reports Server (NTRS)

    Jaffe, J.

    1973-01-01

    The direct measurement of the nonlinear term of the gravitational field equations by using very stable clocks is discussed along with measuring the perhelion advance of a planet or satellite. These are considered measurements of the second-order gravitational red shift. The exact expression for the frequency shift of light in a gravitational field is derived. Other topics discussed include: The Doppler-cancelling technique; the second-order red shift in a spherically symmetric gravitational field; finite signal transit time; and the reality and interpretation of coordinates in the second-order red shift experiment.

  6. Goos-Haenchen shift in complex crystals

    SciTech Connect

    Longhi, Stefano; Della Valle, Giuseppe; Staliunas, Kestutis

    2011-10-15

    The Goos-Haenchen (GH) effect for wave scattering from complex PT-symmetric periodic potentials (complex crystals) is theoretically investigated, with specific reference to optical GH shift in photonic crystal slabs with a sinusoidal periodic modulation of both real and imaginary parts of the dielectric constant. The analysis highlights some distinct and rather unique features as compared to the GH shift found in ordinary crystals. In particular, as opposed to GH shift in ordinary crystals, which is large at the band gap edges, in complex crystals the GH shift can be large inside the reflection (amplification) band and becomes extremely large as the PT symmetry-breaking threshold is approached.

  7. Exercise, energy balance and the shift worker.

    PubMed

    Atkinson, Greg; Fullick, Sarah; Grindey, Charlotte; Maclaren, Don

    2008-01-01

    Shift work is now common in society and is not restricted to heavy industry or emergency services, but is increasingly found amongst 'white collar' occupations and the growing number of service industries. Participation in shift work is associated with increased body mass index, prevalence of obesity and other health problems. We review the behavioural and biological disturbances that occur during shift work and discuss their impact on leisure-time physical activity and energy balance. Shift work generally decreases opportunities for physical activity and participation in sports. For those shift workers who are able to exercise, subjective and biological responses can be altered if the exercise is taken at unusual times of day and/or if the shift worker is sleep deprived. These altered responses may in turn impact on the longer-term adherence to an exercise programme. The favourable effects of exercise on body mass control and sleep quality in shift workers have not been confirmed. Similarly, recent reports of relationships between sleep duration and obesity have not been examined in a shift work context. There is no evidence that exercise can mediate certain circadian rhythm characteristics (e.g. amplitude or timing) for improved tolerance to shift work. Total energy intake and meal composition do not seem to be affected by participation in shift work. Meal frequency is generally reduced but snacking is increased on the night shift. Unavailability of preferred foods in the workplace, a lack of time, and a reduced desire to eat at night explain these findings. 'Normal' eating habits with the family are also disrupted. The metabolic responses to food are also altered by shift work-mediated disruptions to sleep and circadian rhythms. Whether any interactions on human metabolism exist between timing or content of food intake and physical activity during shift work is not known at present. There are very few randomized controlled studies on the efficacy of physical activity or dietary interventions during shift work. Some favourable effects of such interventions on fatigue levels at work have been reported, but biological and behavioural outcomes relevant to long-term health and energy balance have not been studied adequately. In addition, recruitment and retention of research participants for randomized controlled trials of physical activity or dietary interventions have been very difficult. We present a model of the various behavioural and biological factors relevant to exercise and energy balance during shift work as a framework for future research. PMID:18620467

  8. In-line phase shift tomosynthesis

    SciTech Connect

    Hammonds, Jeffrey C.; Price, Ronald R.; Pickens, David R.; Donnelly, Edwin F.

    2013-08-15

    Purpose: The purpose of this work is to (1) demonstrate laboratory measurements of phase shift images derived from in-line phase-contrast radiographs using the attenuation-partition based algorithm (APBA) of Yan et al.[Opt. Express 18(15), 16074–16089 (2010)], (2) verify that the APBA reconstructed images obey the linearity principle, and (3) reconstruct tomosynthesis phase shift images from a collection of angularly sampled planar phase shift images.Methods: An unmodified, commercially available cabinet x-ray system (Faxitron LX-60) was used in this experiment. This system contains a tungsten anode x-ray tube with a nominal focal spot size of 10 μm. The digital detector uses CsI/CMOS with a pixel size of 50 × 50 μm. The phantoms used consisted of one acrylic plate, two polystyrene plates, and a habanero pepper. Tomosynthesis images were reconstructed from 51 images acquired over a ±25° arc. All phase shift images were reconstructed using the APBA.Results: Image contrast derived from the planar phase shift image of an acrylic plate of uniform thickness exceeded the contrast of the traditional attenuation image by an approximate factor of two. Comparison of the planar phase shift images from a single, uniform thickness polystyrene plate with two polystyrene plates demonstrated an approximate linearity of the estimated phase shift with plate thickness (−1600 rad vs −2970 rad). Tomographic phase shift images of the habanero pepper exhibited acceptable spatial resolution and contrast comparable to the corresponding attenuation image.Conclusions: This work demonstrated the feasibility of laboratory-based phase shift tomosynthesis and suggests that phase shift imaging could potentially provide a new imaging biomarker. Further investigation will be needed to determine if phase shift contrast will be able to provide new tissue contrast information or improved clinical performance.

  9. Lamb Shift in Nonrelativistic Quantum Electrodynamics.

    ERIC Educational Resources Information Center

    Grotch, Howard

    1981-01-01

    The bound electron self-energy or Lamb shift is calculated in nonrelativistic quantum electrodynamics. Retardation is retained and also an interaction previously dropped in other nonrelativistic approaches is kept. Results are finite without introducing a cutoff and lead to a Lamb shift in hydrogen of 1030.9 MHz. (Author/JN)

  10. A Short History of Three Chemical Shifts

    ERIC Educational Resources Information Center

    Nagaoka, Shin-ichi

    2007-01-01

    A short history of chemical shifts in nuclear magnetic resonance (NMR), electron spectroscopy for chemical analysis (ESCA) and Mossbauer spectroscopy, which are useful for chemical studies, is described. The term chemical shift is shown to have originated in the mistaken assumption that nuclei of a given element would all undergo resonance at the

  11. 29 CFR 102.165 - Cost shifting.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 2 2010-07-01 2010-07-01 false Cost shifting. 102.165 Section 102.165 Labor Regulations... by Administrative Offset 102.165 Cost shifting. Costs incurred by the Agency in connection with... offset. Such costs may include administrative costs and attorneys fees....

  12. 29 CFR 102.171 - Cost shifting.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 2 2010-07-01 2010-07-01 false Cost shifting. 102.171 Section 102.171 Labor Regulations... By Federal Income Tax Refund Offset 102.171 Cost shifting. Costs incurred by the Agency in... amount of the offset. Such costs may include administrative costs and attorneys fees....

  13. A Short History of Three Chemical Shifts

    ERIC Educational Resources Information Center

    Nagaoka, Shin-ichi

    2007-01-01

    A short history of chemical shifts in nuclear magnetic resonance (NMR), electron spectroscopy for chemical analysis (ESCA) and Mossbauer spectroscopy, which are useful for chemical studies, is described. The term chemical shift is shown to have originated in the mistaken assumption that nuclei of a given element would all undergo resonance at the…

  14. Four-phase differential phase shift resolver

    NASA Technical Reports Server (NTRS)

    Hopkins, P. M.; Wallingford, W. M.

    1973-01-01

    Two systems have been developed to resolve phase uncertainty without transmitting reference signals. In both methods signal is impressed on carrier as differential, rather than absolute, phase shift. At the receiver four-phase demodulation and logic process unambiguously resolves differential phase shift of input carrier.

  15. Two-color emissive probes for click reactions.

    PubMed

    Wirtz, Marcel; Grter, Andreas; Rebmann, Philipp; Dier, Tobias; Volmer, Dietrich A; Huch, Volker; Jung, Gregor

    2014-10-28

    Cu(I)-catalyzed azide-alkyne cyclization (CuAAC) is the paradigmatic click reaction of continuous interest. Especially fluorogenic and FRET probes have become indispensable tools for life sciences. Here, we present a fluorescent alkyne for monitoring CuAAC, which undergoes a bathochromic shift upon reaction. Application in single-molecule and catalysis research is foreseen. PMID:25200167

  16. Rainbow-shift mechanism behind discrete optical-potential ambiguities

    SciTech Connect

    Brandan, M.E. ); McVoy, K.W. )

    1991-03-01

    Some years ago, Drisko {ital et} {ital al}. suggested that the discrete ambiguity often encountered for elastic scattering optical potentials could be understood as being due to the interior or small-{ital l} {ital S}-matrix elements for two equivalent'' potentials differing in phase by 2{pi}, {ital l}-by-{ital l}. We point out that the {ital absence} of this phase change for peripheral partial waves is equally essential, and suggest that a deeper understanding of the ambiguity may be achieved by viewing it as a consequence of a farside interference between interior and peripheral partial waves. It is this interference which produces the broad Airy maxima'' of a nuclear rainbow, and we show that a Drisko-type phase-shift increment {delta}{sub {ital l}}{r arrow}({delta}{sub {ital l}}+{pi}) for low-{ital l} phases relative to the high-{ital l} ones is exactly what is needed to shift a farside rainbow pattern by one Airy maximum, thus providing an equivalent rainbow-shift'' interpretation of the discrete ambiguity. The physical importance of both interpretations lies in the fact that the existence of discrete ambiguities (as well as of nuclear rainbows) is explicit evidence for low-{ital l} transparency in nucleus-nucleus collisions. The essential role played by low partial waves explains why peripheral reactions have generally not proven helpful in resolving this ambiguity.

  17. Shaping the light/dark pattern for circadian adaptation to night shift work.

    PubMed

    Smith, Mark R; Cullnan, Erin E; Eastman, Charmane I

    2008-10-20

    This is the second in a series of simulated night shift studies designed to achieve and subsequently maintain a compromise circadian phase position between complete entrainment to the daytime sleep period and no phase shift at all. We predict that this compromise will yield improved night shift alertness and daytime sleep, while still permitting adequate late night sleep and daytime wakefulness on days off. Our goal is to delay the dim light melatonin onset (DLMO) from its baseline phase of approximately 21:00 to our target of approximately 3:00. Healthy young subjects (n=31) underwent three night shifts followed by two days off. Two experimental groups received intermittent bright light pulses during night shifts (total durations of 75 and 120 min per night shift), wore dark sunglasses when outside, slept in dark bedrooms at scheduled times after night shifts and on days off, and received outdoor light exposure upon awakening from sleep. A control group remained in dim room light during night shifts, wore lighter sunglasses, and had unrestricted sleep and outdoor light exposure. After the days off, the DLMO of the experimental groups was approximately 00:00-1:00, not quite at the target of 3:00, but in a good position to reach the target after subsequent night shifts with bright light. The DLMO of the control group changed little from baseline. Experimental subjects performed better than control subjects during night shifts on a reaction time task. Subsequent studies will reveal whether the target phase is achieved and maintained through more alternations of night shifts and days off. PMID:18675836

  18. Comment on the reference compound for chemical shift and Knight shift determination of (209)Bi nuclei.

    PubMed

    Nowak, Bogdan

    2015-01-01

    Several groups exploring the (209)Bi NMR in solids, including usual insulators, metallic and magnetic materials and recently diamagnetic topological materials, use different standards (usually old and invalid) for chemical shift (Knight shift) determination, ignoring IUPAC recommendations. As a consequence the published shift values exhibit considerable differences (up to 17,500 ppm). PMID:25534279

  19. U.S. Geological Survey Georgia Water Science Center and Albany Water, Gas, and Light Commission Cooperative Water Program-Summary of Activities, July 2005 through June 2006

    USGS Publications Warehouse

    Gordon, Debbie Warner

    2006-01-01

    The U.S. Geological Survey (USGS) has been working with the Albany Water, Gas, and Light Commission to monitor ground-water quality and availability since 1977. This report presents the findings for July 2005 through June 2006 and summarizes the ground-water and surface-water conditions for 2005. Water levels in 14 wells were continuously monitored in Dougherty County, Georgia. Water levels in 12 of those wells were above normal, one was normal, and one was below normal. Ground-water samples collected from the Upper Floridan aquifer indicate that nitrate levels have increased in 13 wells and decreased in two wells from a year earlier. A sample also was collected from the Flint River. A trilinear diagram showing the percent composition of selected major cations and anions indicates that the ground-water quality of the Upper Floridan aquifer at the Albany wellfield is distinctly different from the water quality of the Flint River. To improve the understanding of the ground-water flow system and nitrate movement in the Upper Floridan aquifer, the USGS is developing a ground-water flow model in the southwest Albany area, Georgia.

  20. Deblending Microlensing Events Using Astrometric Shifts

    NASA Astrophysics Data System (ADS)

    Goldberg, D. M.; Wozniak, P.; Paczynski, B.

    1997-12-01

    In this poster, we present the prospect that astrometric shifts can be used to identify blended microlensing events in crowded fields. Moreover, by measuring an astrometric shift, one can determine the position of the true lensed star with respect to the local field with very high precision. We first perform several simulations of microlensing searches in crowded fields and find that if we assume a dark lens, and that the lensed star obeys a power law luminosity function, n(L)~ L(-beta ) , over half the simulated events show a measurable astrometric shift. For simulations of 20000 stars on a 256x 256 Nyquist sampled CCD frame, we found that with beta =2, 58% of the events were significantly blended (F_{*}/Ftot <= 0.9), and of those, 73% had a large astrometric shift (>= 0.5 pixels). For beta =3, we found that 85% were significantly blended, and that 85% of those had a significant shift. Since we expect most blended events to show a significant shift, we look in the OGLE I database (Wozniak & Szymanski 1997), and find measurable and systematic shifts in over half the candidate microlensing events, including OGLE # 5, which was considered to be blended from photometric data.

  1. Computational Study of Hydrogen Shifts and Ring-Opening Mechanisms in ?-Pinene Ozonolysis Products.

    PubMed

    Kurtn, Theo; Rissanen, Matti P; Mackeprang, Kasper; Thornton, Joel A; Hyttinen, Noora; Jrgensen, Solvejg; Ehn, Mikael; Kjaergaard, Henrik G

    2015-11-19

    Autoxidation by sequential peroxy radical hydrogen shifts (H-shifts) and O2 additions has recently emerged as a promising mechanism for the rapid formation of highly oxidized, low-volatility organic compounds in the atmosphere. A key prerequisite for autoxidation is that the H-shifts of the initial peroxy radicals formed by, e.g., OH or O3 oxidation are fast enough to compete with bimolecular sink reactions. In most atmospheric conditions, these restrict the lifetime of peroxy radicals to be on the order of seconds. We have systematically investigated all potentially important (nonmethyl, sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of ?-pinene using density functional (?B97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler cyclohexene ozonolysis system, none of the calculated H-shifts have rate constants above 1 s(-1) at 298 K, and most are below 0.01 s(-1). The low rate constants are connected to the presence of the strained cyclobutyl ring in the ?-pinene-derived peroxy radicals, which hinders H-shifts both from and across the ring. For autoxidation to yield the experimentally observed highly oxidized products in the ?-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for opening the cyclobutyl ring in the ?-pinene ozonolysis system. PMID:26529548

  2. Visual sensitivities tuned by heterochronic shifts in opsin gene expression

    PubMed Central

    Carleton, Karen L; Spady, Tyrone C; Streelman, J Todd; Kidd, Michael R; McFarland, William N; Loew, Ellis R

    2008-01-01

    Background Cichlid fishes have radiated into hundreds of species in the Great Lakes of Africa. Brightly colored males display on leks and vie to be chosen by females as mates. Strong discrimination by females causes differential male mating success, rapid evolution of male color patterns and, possibly, speciation. In addition to differences in color pattern, Lake Malawi cichlids also show some of the largest known shifts in visual sensitivity among closely related species. These shifts result from modulated expression of seven cone opsin genes. However, the mechanisms for this modulated expression are unknown. Results In this work, we ask whether these differences might result from changes in developmental patterning of cone opsin genes. To test this, we compared the developmental pattern of cone opsin gene expression of the Nile tilapia, Oreochromis niloticus, with that of several cichlid species from Lake Malawi. In tilapia, quantitative polymerase chain reaction showed that opsin gene expression changes dynamically from a larval gene set through a juvenile set to a final adult set. In contrast, Lake Malawi species showed one of two developmental patterns. In some species, the expressed gene set changes slowly, either retaining the larval pattern or progressing only from larval to juvenile gene sets (neoteny). In the other species, the same genes are expressed in both larvae and adults but correspond to the tilapia adult genes (direct development). Conclusion Differences in visual sensitivities among species of Lake Malawi cichlids arise through heterochronic shifts relative to the ontogenetic pattern of the tilapia outgroup. Heterochrony has previously been shown to be a powerful mechanism for change in morphological evolution. We found that altering developmental expression patterns is also an important mechanism for altering sensory systems. These resulting sensory shifts will have major impacts on visual communication and could help drive cichlid speciation. PMID:18500997

  3. Shifting Mindsets: The Changing Work Roles of Vocational Education and Training Practitioners

    ERIC Educational Resources Information Center

    Harris, Roger; Simons, Michele; Clayton, Berwyn

    2005-01-01

    Reforms to Australia's vocational education and training (VET) sector have had a significant impact on practitioners' work in public and private providers. This study analyses practitioners' perceptions of, and reactions to, the changes. The scope of these changes has been substantial and has required shifts to practitioners' habits, norms, skills

  4. Deterministic convergence in iterative phase shifting

    SciTech Connect

    Luna, Esteban; Salas, Luis; Sohn, Erika; Ruiz, Elfego; Nunez, Juan M.; Herrera, Joel

    2009-03-10

    Previous implementations of the iterative phase shifting method, in which the phase of a test object is computed from measurements using a phase shifting interferometer with unknown positions of the reference, do not provide an accurate way of knowing when convergence has been attained. We present a new approach to this method that allows us to deterministically identify convergence. The method is tested with a home-built Fizeau interferometer that measures optical surfaces polished to {lambda}/100 using the Hydra tool. The intrinsic quality of the measurements is better than 0.5 nm. Other possible applications for this technique include fringe projection or any problem where phase shifting is involved.

  5. Theory of the Helium Isotope Shift

    SciTech Connect

    Pachucki, Krzysztof; Yerokhin, V. A.

    2015-09-15

    Theory of the isotope shift of the centroid energies of light few-electron atoms is reviewed. Numerical results are presented for the isotope shift of the 2{sup 3}P-2{sup 3}S and 2{sup 1}S-2{sup 3}S transition energies of {sup 3}He and {sup 4}He. By comparing theoretical predictions for the isotope shift with the experimental results, the difference of the squares of the nuclear charge radii of {sup 3}He and {sup 4}He, δR{sup 2}, is determined with high accuracy.

  6. Search for Higgs Shifts in White Dwarfs

    NASA Astrophysics Data System (ADS)

    Onofrio, Roberto; Wegner, Gary A.

    2014-08-01

    We report on a search for differential shifts between electronic and vibronic transitions in carbon-rich white dwarfs BPM 27606 and Procyon B. The absence of differential shifts within the spectral resolution and taking into account systematic effects such as space motion and pressure shifts allows us to set the first upper bound of astrophysical origin on the coupling between the Higgs field and the Kreschmann curvature invariant. Our analysis provides the basis for a more general methodology to derive bounds to the coupling of long-range scalar fields to curvature invariants in an astrophysical setting complementary to the ones available from high-energy physics or table-top experiments.

  7. Shifting media induced super-resolution imaging

    NASA Astrophysics Data System (ADS)

    Du, Yong; Zang, XiaoFei; Shi, Cheng; Ji, XueBin; Zhu, YiMing

    2015-02-01

    In this paper, we propose a novel method to achieve super-resolution imaging by utilizing shifting media based on the transformation optics theory. According to the effective medium theory, the homogenous but anisotropic shifting media can be simply replaced by only two kinds of homogenous and isotropic materials in an alternating layered structure. In addition, another scheme of the symmetrical trapezoidal shifting media shells with layered isotropic materials is proposed to realize the super-resolution imaging. Finite element simulations have been performed to prove these ideas.

  8. Search for Higgs shifts in white dwarfs

    SciTech Connect

    Onofrio, Roberto; Wegner, Gary A. E-mail: gary.a.wegner@dartmouth.edu

    2014-08-20

    We report on a search for differential shifts between electronic and vibronic transitions in carbon-rich white dwarfs BPM 27606 and Procyon B. The absence of differential shifts within the spectral resolution and taking into account systematic effects such as space motion and pressure shifts allows us to set the first upper bound of astrophysical origin on the coupling between the Higgs field and the Kreschmann curvature invariant. Our analysis provides the basis for a more general methodology to derive bounds to the coupling of long-range scalar fields to curvature invariants in an astrophysical setting complementary to the ones available from high-energy physics or table-top experiments.

  9. Cause of absorption band shift of disperse red-13 attached on silica spheres

    NASA Astrophysics Data System (ADS)

    Kim, Byoung-Ju; Kim, Hyung-Deok; Kim, Na-Rae; Bang, Byeong-Gyu; Park, Eun-Hye; Kang, Kwang-Sun

    2015-08-01

    A reversible color change and large absorption band shift have been observed for the disperse red-13 (DR-13) attached on the surface of the monodisperse silica spheres. Two step synthetic processes including urethane bond formation and hydrolysis-condensation reactions were used to attach the DR-13 on the surface of the silica spheres. After the reaction, the characteristic absorption peak at 2270 cm-1 representing the -N=C=O asymmetric stretching vibration disappeared, and the a new absorption peak at 1700 cm-1 corresponding the C=O stretching vibration appeared. A visual and reversible color change was observed before and after wetting in alcohol. Although the absorption peak of DR-13 in alcohol is at 510 nm, the absorption peak shifts to 788 nm when it is dried. The absorption peak shifts to 718 nm when it is wetted in alcohol. This result can be explained by the formation of intramolecular charge transfer band.

  10. Zero-Shift EUVE Science Payload Operations

    NASA Astrophysics Data System (ADS)

    Stroozas, B. A.; Ringrose, P.; Kaplan, G. C.; Biroscak, D.; Vallerga, J. V.; Malina, R. F.

    1996-05-01

    The Extreme Ultraviolet Explorer (EUVE ) Project at the Center for EUV Astrophysics (CEA) at the University of California, Berkeley, is now functioning in a ``zero-shift" science payload operations scenario. Whereas traditional satellite mission operations are conducted by human controllers working in three separate shifts on a 24 hour/day basis, zero-shift payload operations completely eliminate the need for human operators to support routine console activities. This poster discusses the transition from a single- to a zero-shift payload operations environment: its purpose, the goals and benefits, the instrument health and safety considerations, the multiphased implementation approach, and the lessons learned along the way. This work has been funded by NASA contract NAS5-29298.

  11. Stabilizing windings for tilting and shifting modes

    SciTech Connect

    Jardin, S.C.; Christensen, U.R.

    1982-02-26

    This invention provides simple, inexpensive, independent and passive, conducting loops for stabilizing a plasma ring having externally produced equilibrium fields on opposite sides of the plasma ring and internal plasma currents that interact to tilt and/or shift the plasma ring relative to the externally produced equilibrium field so as to produce unstable tilting and/or shifting modes in the plasma ring. More particularly this invention provides first and second passive conducting loops for containing first and second induced currents in first and second directions corresponding to the amplitude and directions of the unstable tilting and/or shifting modes in the plasma ring. To this end, the induced currents provide additional magnetic fields for producing restoring forces and/or restoring torques for counteracting the tilting and/or shifting modes when the conducting loops are held fixed in stationary positions relative to the externally produced equilibrium fields on opposite sides of the plasma ring.

  12. Prolonged Instability Prior to a Regime Shift

    PubMed Central

    Spanbauer, Trisha L.; Allen, Craig R.; Angeler, David G.; Eason, Tarsha; Fritz, Sherilyn C.; Garmestani, Ahjond S.; Nash, Kirsty L.; Stone, Jeffery R.

    2014-01-01

    Regime shifts are generally defined as the point of abrupt change in the state of a system. However, a seemingly abrupt transition can be the product of a system reorganization that has been ongoing much longer than is evident in statistical analysis of a single component of the system. Using both univariate and multivariate statistical methods, we tested a long-term high-resolution paleoecological dataset with a known change in species assemblage for a regime shift. Analysis of this dataset with Fisher Information and multivariate time series modeling showed that there was a?2000 year period of instability prior to the regime shift. This period of instability and the subsequent regime shift coincide with regional climate change, indicating that the system is undergoing extrinsic forcing. Paleoecological records offer a unique opportunity to test tools for the detection of thresholds and stable-states, and thus to examine the long-term stability of ecosystems over periods of multiple millennia. PMID:25280010

  13. Tracking a phase-shift-keyed signal

    NASA Technical Reports Server (NTRS)

    Villarreal, S.; Lenett, S. D.; Kobayashi, H. S.; Pawlowski, J. F.

    1977-01-01

    In detector, phase shifter is used to generate negative phase shift opposing detected phase angle. This produces converted series sideband and component carrier, with residual carrier signal and converted series sideband and component carrier added together to produce tracking signal.

  14. Shifting standards and stereotype-based judgments.

    PubMed

    Biernat, M; Manis, M

    1994-01-01

    Four studies tested a model of stereotype-based shifts in judgment standards developed by M. Biernat, M. Manis, and T. E. Nelson (1991). The model suggests that subjective judgments of target persons from different social groups may fail to reveal the stereotyped expectations of judges, because they invite the use of different evaluative standards; more "objective" or common rule indicators reduce such standard shifts. The stereotypes that men are more competent than women, women are more verbally able than men, Whites are more verbally able than Blacks, and Blacks are more athletic than Whites were successfully used to demonstrate the shifting standards phenomenon. Several individual-difference measures were also effective in predicting differential susceptibility to standard shifts, and direct evidence was provided that differing comparison standards account for substantial differences in target ratings. PMID:8126651

  15. Cognitive Set-Shifting in Anorexia Nervosa

    PubMed Central

    Shott, Megan E.; Filoteo, J. Vincent; Bhatnagar, Kelly A.C.; Peak, Nicole J.; Hagman, Jennifer O.; Rockwell, Roxanne; Kaye, Walter H.; Frank, Guido K.W.

    2013-01-01

    Objective Adult anorexia nervosa (AN) is associated with inefficient cognitive flexibility and set-shifting. Whether such inefficiencies also characterize adolescent AN is an important area of research. Method Adolescents with AN and matched controls were administered a computerized task that required initial learning of an explicit rule using corrective feedback and learning of a new rule after a set number of trials. Adult patients with AN and controls were also examined. Results Adolescents with AN did not differ from matched controls with respect to set-shifting cost (decrease in performance after rule change), whereas adults with AN had significantly greater set-shifting cost compared with controls. Discussion This study suggests that set-shifting inefficiencies may not be a vulnerability factor for AN development in adolescents with AN, but might become an important aspect of the disorder at later age, and could point towards developmental neurobiologic brain changes that could affect AN at different ages. PMID:22492553

  16. Red Shifts with Obliquely Approaching Light Sources.

    ERIC Educational Resources Information Center

    Head, C. E.; Moore-Head, M. E.

    1988-01-01

    Refutes the Doppler effect as the explanation of large red shifts in the spectra of distant galaxies and explains the relativistic effects in which the light sources approach the observer obliquely. Provides several diagrams and graphs. (YP)

  17. [Sleep disorders among physicians on shift work].

    PubMed

    Schlafer, O; Wenzel, V; Hgl, B

    2014-11-01

    Sleep disorders in physicians who perform shift work can result in increased risks of health problems that negatively impact performance and patient safety. Even those who cope well with shift work are likely to suffer from sleep disorders. The aim of this manuscript is to discuss possible causes, contributing factors and consequences of sleep disorders in physicians and to identify measures that can improve adaptation to shift work and treatment strategies for shift work-associated sleep disorders. The risk factors that influence the development of sleep disorders in physicians are numerous and include genetic factors (15 % of the population), age (> 50 years), undiagnosed sleep apnea,, alcohol abuse as well as multiple stress factors inherent in clinical duties (including shift work), research, teaching and family obligations. Several studies have reported an increased risk for medical errors in sleep-deprived physicians. Shift workers have an increased risk for psychiatric and cardiovascular diseases and shift work may also be a contributing factor to cancer. A relationship has been reported not only with sleep deprivation and changes in food intake but also with diabetes mellitus, obesity, hypertension and coronary heart disease. Nicotine and alcohol consumption are more frequent among shift workers. Increased sickness and accident rates among physicians when commuting (especially after night shifts) have a socioeconomic impact. In order to reduce fatigue and to improve performance, short naps during shiftwork or naps plus caffeine, have been proposed as coping strategies; however, napping during adverse circadian phases is less effective, if not impossible when unable to fall asleep. Bright and blue light supports alertness during a night shift. After shiftwork, direct sunlight exposure to the retina can be avoided by using dark sunglasses or glasses with orange lenses for commuting home. The home environment for daytime sleeping after a night shift should be very dark to allow endogenous melatonin secretion, which is a night signal and supports continuous sleep. Sleep disorders can be treated with timed light exposure, as well as behavioral and environmental strategies to compensate for sleep deprivation. Fatigue due to sleep deprivation can only be systematically treated with sleep. PMID:25213642

  18. Best focus shift mechanism for thick masks

    NASA Astrophysics Data System (ADS)

    Burkhardt, Martin; Raghunathan, Ananthan

    2015-03-01

    The best focus shift due to thick mask effects is well known, both in ArF, and more importantly in EUV, where the shorter wavelength is small compared to both mask openings and absorber height. While the effect is stronger in opaque features in clear field masks, the best focus shift is visible in dark field masks as well, and it becomes even more pronounced when scattering bars are added to non-dense features. This pattern dependent focus variation can be predicted in both exact EMF simulations and fast image calculations that are used for optical proximity correction (OPC). Even though this focus shift can be predicted and patterns can be corrected in OPC, we would like to understand the mechanism that causes this focus shift. This can help us understand if, in addition to best focus shift, the image quality is further deteriorated due to the thick mask effects. The best focus shift is found to be an interplay of the complex diffraction coefficient due to thick mask effects and the direction of the light that is incident on the mask, or coherence value ?. A change in focus adds a phase term to each of the complex diffraction coefficients, causing their rotation in a phasor diagram. Best focus is found when the phasors have an angle of 0 or 180 degrees to each other and depending on which diffracted orders are caught in the pupil and contribute to imaging. We investigate the effect of partial coherence, mask thickness, and assist feature placement on best focus shift. We observe a waveguide effect in the absorber gaps because of the reduced real index of refraction in the absorber layer, making vacuum the optically dense medium. We suggest ways to lessen the best focus shifts through assist feature placement or the use of alternative absorbers that are closer matched to the dielectric index of vacuum.

  19. Illuminating geographical patterns in species' range shifts.

    PubMed

    Grenouillet, Gaël; Comte, Lise

    2014-10-01

    Species' range shifts in response to ongoing climate change have been widely documented, but although complex spatial patterns in species' responses are expected to be common, comprehensive comparisons of species' ranges over time have undergone little investigation. Here, we outline a modeling framework based on historical and current species distribution records for disentangling different drivers (i.e. climatic vs. nonclimatic) and assessing distinct facets (i.e. colonization, extirpation, persistence, and lags) of species' range shifts. We used extensive monitoring data for stream fish assemblages throughout France to assess range shifts for 32 fish species between an initial period (1980-1992) and a contemporary one (2003-2009). Our results provide strong evidence that the responses of individual species varied considerably and exhibited complex mosaics of spatial rearrangements. By dissociating range shifts in climatically suitable and unsuitable habitats, we demonstrated that patterns in climate-driven colonization and extirpation were less marked than those attributed to nonclimatic drivers, although this situation could rapidly shift in the near future. We also found evidence that range shifts could be related to some species' traits and that the traits involved varied depending on the facet of range shift considered. The persistence of populations in climatically unsuitable areas was greater for short-lived species, whereas the extent of the lag behind climate change was greater for long-lived, restricted-range, and low-elevation species. We further demonstrated that nonclimatic extirpations were primarily related to the size of the species' range, whereas climate-driven extirpations were better explained by thermal tolerance. Thus, the proposed framework demonstrated its potential for markedly improving our understanding of the key processes involved in range shifting and also offers a template for informing management decisions. Conservation strategies would greatly benefit from identifying both the geographical patterns and the species' traits associated with complex modifications of species' distributions in response to global changes. PMID:24616088

  20. Cellular cooperation with shift updating and repulsion

    PubMed Central

    Pavlogiannis, Andreas; Chatterjee, Krishnendu; Adlam, Ben; Nowak, Martin A.

    2015-01-01

    Population structure can facilitate evolution of cooperation. In a structured population, cooperators can form clusters which resist exploitation by defectors. Recently, it was observed that a shift update rule is an extremely strong amplifier of cooperation in a one dimensional spatial model. For the shift update rule, an individual is chosen for reproduction proportional to fecundity; the offspring is placed next to the parent; a random individual dies. Subsequently, the population is rearranged (shifted) until all individual cells are again evenly spaced out. For large population size and a one dimensional population structure, the shift update rule favors cooperation for any benefit-to-cost ratio greater than one. But every attempt to generalize shift updating to higher dimensions while maintaining its strong effect has failed. The reason is that in two dimensions the clusters are fragmented by the movements caused by rearranging the cells. Here we introduce the natural phenomenon of a repulsive force between cells of different types. After a birth and death event, the cells are being rearranged minimizing the overall energy expenditure. If the repulsive force is sufficiently high, shift becomes a strong promoter of cooperation in two dimensions. PMID:26602306

  1. Sleep deprivation due to shift work.

    PubMed

    Costa, Giovanni

    2015-01-01

    Sleep deprivation due to shift work is related to perturbation of the sleep/wake cycle, associated with the modified activity/rest pattern. This may cause a significant disruption of circadian rhythms of biologic functions, driven by the body clock located in the suprachiasmatic nuclei of the hypothalamus. Shift and night workers have to change sleep times and strategies according to their duty periods; consequently, both sleep length and quality can be considerably affected depending on the variable start and finish times on different shifts. About 10% of night and rotating shift workers, aged between 18 and 65 years, have been estimated to have a diagnosable "shift-work sleep disorder," according to the International Classification of Sleep Disorders, version 2 (ICSD-2). In the long run, this may lead to persistent and severe disturbances of sleep, chronic fatigue and psychoneurotic syndromes, besides being a risk or aggravating factor for accidents, gastrointestinal, cardiovascular, and reproductive disorders, as well as, probably, for cancer. Preventive and corrective actions deal with the organization of shift schedules according to ergonomic criteria, careful health surveillance, appropriate education and training on effective countermeasures, in particular, sleep hygiene and napping. PMID:26563802

  2. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  3. Scalar Field Theories with Polynomial Shift Symmetries

    NASA Astrophysics Data System (ADS)

    Griffin, Tom; Grosvenor, Kevin T.; Hořava, Petr; Yan, Ziqi

    2015-12-01

    We continue our study of naturalness in nonrelativistic QFTs of the Lifshitz type, focusing on scalar fields that can play the role of Nambu-Goldstone (NG) modes associated with spontaneous symmetry breaking. Such systems allow for an extension of the constant shift symmetry to a shift by a polynomial of degree P in spatial coordinates. These "polynomial shift symmetries" in turn protect the technical naturalness of modes with a higher-order dispersion relation, and lead to a refinement of the proposed classification of infrared Gaussian fixed points available to describe NG modes in nonrelativistic theories. Generic interactions in such theories break the polynomial shift symmetry explicitly to the constant shift. It is thus natural to ask: Given a Gaussian fixed point with polynomial shift symmetry of degree P, what are the lowest-dimension operators that preserve this symmetry, and deform the theory into a self-interacting scalar field theory with the shift symmetry of degree P? To answer this (essentially cohomological) question, we develop a new graph-theoretical technique, and use it to prove several classification theorems. First, in the special case of P = 1 (essentially equivalent to Galileons), we reproduce the known Galileon N-point invariants, and find their novel interpretation in terms of graph theory, as an equal-weight sum over all labeled trees with N vertices. Then we extend the classification to P > 1 and find a whole host of new invariants, including those that represent the most relevant (or least irrelevant) deformations of the corresponding Gaussian fixed points, and we study their uniqueness.

  4. A holistic view of marine regime shifts

    PubMed Central

    Conversi, Alessandra; Dakos, Vasilis; Grdmark, Anna; Ling, Scott; Folke, Carl; Mumby, Peter J.; Greene, Charles; Edwards, Martin; Blenckner, Thorsten; Casini, Michele; Pershing, Andrew; Mllmann, Christian

    2015-01-01

    Understanding marine regime shifts is important not only for ecology but also for developing marine management that assures the provision of ecosystem services to humanity. While regime shift theory is well developed, there is still no common understanding on drivers, mechanisms and characteristic of abrupt changes in real marine ecosystems. Based on contributions to the present theme issue, we highlight some general issues that need to be overcome for developing a more comprehensive understanding of marine ecosystem regime shifts. We find a great divide between benthic reef and pelagic ocean systems in how regime shift theory is linked to observed abrupt changes. Furthermore, we suggest that the long-lasting discussion on the prevalence of top-down trophic or bottom-up physical drivers in inducing regime shifts may be overcome by taking into consideration the synergistic interactions of multiple stressors, and the special characteristics of different ecosystem types. We present a framework for the holistic investigation of marine regime shifts that considers multiple exogenous drivers that interact with endogenous mechanisms to cause abrupt, catastrophic change. This framework takes into account the time-delayed synergies of these stressors, which erode the resilience of the ecosystem and eventually enable the crossing of ecological thresholds. Finally, considering that increased pressures in the marine environment are predicted by the current climate change assessments, in order to avoid major losses of ecosystem services, we suggest that marine management approaches should incorporate knowledge on environmental thresholds and develop tools that consider regime shift dynamics and characteristics. This grand challenge can only be achieved through a holistic view of marine ecosystem dynamics as evidenced by this theme issue.

  5. [Comparison of shift work and night shifts: impacts on health and wellbeing among sanitary workers].

    PubMed

    Della Betta, F; Martinellit, R; Del Re, C; Tarquini, M; Fantasia, D; Paoletti, A

    2011-01-01

    The generally agreed view is that there is no ideal shift system, and that most systems will have both advantages and disadvantages. As such, attention has been placed on trying to identify good and bad features of shift systems, with a view to minimising the possible ill health as a consequence of shiftwork. The present study focuses on the quality of the shift and looks at the implications for individual health and wellbeing, during the wellbeing, during the shift. Three groups of sanitary workers, one working in the morning, one working two shifts, and the other working three, took part. All completed a version of the standard shiftwork index (SSI), a set of self reported questionnaires related to health and wellbeing. The three groups differed on many outcome measures, although the differences that did exist didn't suggested advantages for one shift system over the others. PMID:23393869

  6. HASH: a program to accurately predict protein H? shifts from neighboring backbone shifts.

    PubMed

    Zeng, Jianyang; Zhou, Pei; Donald, Bruce Randall

    2013-01-01

    Chemical shifts provide not only peak identities for analyzing nuclear magnetic resonance (NMR) data, but also an important source of conformational information for studying protein structures. Current structural studies requiring H(?) chemical shifts suffer from the following limitations. (1) For large proteins, the H(?) chemical shifts can be difficult to assign using conventional NMR triple-resonance experiments, mainly due to the fast transverse relaxation rate of C(?) that restricts the signal sensitivity. (2) Previous chemical shift prediction approaches either require homologous models with high sequence similarity or rely heavily on accurate backbone and side-chain structural coordinates. When neither sequence homologues nor structural coordinates are available, we must resort to other information to predict H(?) chemical shifts. Predicting accurate H(?) chemical shifts using other obtainable information, such as the chemical shifts of nearby backbone atoms (i.e., adjacent atoms in the sequence), can remedy the above dilemmas, and hence advance NMR-based structural studies of proteins. By specifically exploiting the dependencies on chemical shifts of nearby backbone atoms, we propose a novel machine learning algorithm, called HASH, to predict H(?) chemical shifts. HASH combines a new fragment-based chemical shift search approach with a non-parametric regression model, called the generalized additive model, to effectively solve the prediction problem. We demonstrate that the chemical shifts of nearby backbone atoms provide a reliable source of information for predicting accurate H(?) chemical shifts. Our testing results on different possible combinations of input data indicate that HASH has a wide rage of potential NMR applications in structural and biological studies of proteins. PMID:23242797

  7. Personality factors related to shift work tolerance in two- and three-shift workers.

    PubMed

    Natvik, Sylvia; Bjorvatn, Bjrn; Moen, Bente Elisabeth; Magery, Nils; Sivertsen, Brge; Pallesen, Stle

    2011-07-01

    This study aimed to investigate whether different personality variables were associated with shift work tolerance, and whether these potential associations were moderated by various types of shift work. The sample comprised 1505 nurses who worked either two or three rotating shifts. Personality traits were measured in terms of morningness, flexibility, languidity and hardiness. Morningness reflects the tendency to be alert relatively early in the morning and sleepy relatively early in the evening. Flexibility denotes the ability to both work and sleep at odd times of the day, while languidity concerns the tendency to become tired/sleepy when cutting down on sleep. Hardiness relates to resilience to stressful life events. The dependent variables in this study comprised of measures of insomnia, sleepiness, depression and anxiety. Hierarchical regression analyses, which controlled for demographic variables and work load, revealed that Morningness was significantly and negatively related to insomnia. The Morningness by Shift type interaction was overall significant for depressive symptoms. Morningness was near significantly associated with lower levels of depressive symptoms in three-shift workers, but unrelated to depressive symptoms in two-shift workers. Flexibility was associated with higher levels of depressive symptoms. Flexibility by Shift type interaction was significant for insomnia, indicating that flexibility was negatively associated with insomnia for three-shift workers and unrelated with insomnia for two-shift workers. Languidity was associated with higher levels of sleepiness, depressive and anxiety symptoms. Hardiness was associated with lower levels of all four dependent variables. PMID:21172694

  8. Phase shifting interferometry from two normalized interferograms with random tilt phase-shift.

    PubMed

    Liu, Fengwei; Wu, Yongqian; Wu, Fan

    2015-07-27

    We propose a novel phase shifting interferometry from two normalized interferograms with random tilt phase-shift. The determination of tilt phase-shift is performed by extracting the tilted phase-shift plane from the phase difference of two normalized interferograms, and with the calculated tilt phase-shift value the phase distribution can be retrieved from the two normalized frames. By analyzing the distribution of phase difference and utilizing special points fitting method, the tilted phase-shift plane is extracted in three different cases, which relate to different magnitudes of tilts. Proposed method has been applied to simulations and experiments successfully and the satisfactory results manifest that proposed method is of high accuracy and high speed compared with the three step iterative method. Additionally, both open and closed fringe can be analyzed with proposed method. What's more, it cannot only eliminate the small tilt-shift error caused by slight vibration in phase-shifting interferometry, but also detect the large tilt phase-shift in phase-tilting interferometry. Thus, it will relaxes the requirements on the accuracy of phase shifter, and the costly phase shifter may even be useless by applying proposed method in high amplitude vibrated circumstance to achieve high-precision analysis. PMID:26367653

  9. Nozzle Aerodynamic Stability During a Throat Shift

    NASA Technical Reports Server (NTRS)

    Kawecki, Edwin J.; Ribeiro, Gregg L.

    2005-01-01

    An experimental investigation was conducted on the internal aerodynamic stability of a family of two-dimensional (2-D) High Speed Civil Transport (HSCT) nozzle concepts. These nozzles function during takeoff as mixer-ejectors to meet acoustic requirements, and then convert to conventional high-performance convergent-divergent (CD) nozzles at cruise. The transition between takeoff mode and cruise mode results in the aerodynamic throat and the minimum cross-sectional area that controls the engine backpressure shifting location within the nozzle. The stability and steadiness of the nozzle aerodynamics during this so called throat shift process can directly affect the engine aerodynamic stability, and the mechanical design of the nozzle. The objective of the study was to determine if pressure spikes or other perturbations occurred during the throat shift process and, if so, identify the caused mechanisms for the perturbations. The two nozzle concepts modeled in the test program were the fixed chute (FC) and downstream mixer (DSM). These 2-D nozzles differ principally in that the FC has a large over-area between the forward throat and aft throat locations, while the DSM has an over-area of only about 10 percent. The conclusions were that engine mass flow and backpressure can be held constant simultaneously during nozzle throat shifts on this class of nozzles, and mode shifts can be accomplished at a constant mass flow and engine backpressure without upstream pressure perturbations.

  10. Leprosy type 1 reaction (formerly reversal reaction).

    PubMed

    Naafs, Bernard; van Hees, Colette L M

    2016-01-01

    Nerve damage leading to impairment and permanent disability is the major problem in the course of a leprosy infection. Most of the damage occurs during two types of leprosy reactions, type 1 reaction (T1R) and type 2 reaction (T2R). Timely and adequate treatment may prevent this damage. Particular T1R reactions, however, are often diagnosed too late and are even missed. Clinical symptoms and warning signs are therefore covered, as are the immunology and pathophysiology of nerve damage. The differences between upgrading and downgrading, old terms but still relevant, are explained. Methods to detect reactions and to monitor their treatment are given. Triggering factors, the mechanisms of the reactions, including autoimmunity, and the presence of physical compression are discussed. Treatment over the years is placed in its context, and based on this information a treatment schedule is recommended. PMID:26773622

  11. The Glyoxal Clock Reaction

    ERIC Educational Resources Information Center

    Ealy, Julie B.; Negron, Alexandra Rodriguez; Stephens, Jessica; Stauffer, Rebecca; Furrow, Stanley D.

    2007-01-01

    Research on the glyoxal clock reaction has led to adaptation of the clock reaction to a general chemistry experiment. This particular reaction is just one of many that used formaldehyde in the past. The kinetics of the glyoxal clock makes the reaction suitable as a general chemistry lab using a Calculator Based Laboratory (CBL) or a LabPro. The…

  12. The Glyoxal Clock Reaction

    ERIC Educational Resources Information Center

    Ealy, Julie B.; Negron, Alexandra Rodriguez; Stephens, Jessica; Stauffer, Rebecca; Furrow, Stanley D.

    2007-01-01

    Research on the glyoxal clock reaction has led to adaptation of the clock reaction to a general chemistry experiment. This particular reaction is just one of many that used formaldehyde in the past. The kinetics of the glyoxal clock makes the reaction suitable as a general chemistry lab using a Calculator Based Laboratory (CBL) or a LabPro. The

  13. Shift symmetry and inflation in supergravity

    SciTech Connect

    Brax, Philippe; Martin, Jerome

    2005-07-15

    We consider models of inflation in supergravity with a shift symmetry. We focus on models with one modulus and one inflaton field. The presence of this symmetry guarantees the existence of a flat direction for the inflaton field. Mildly breaking the shift symmetry using a superpotential which depends not only on the modulus, but also on the inflaton field allows one to lift the inflaton flat direction. Along the inflaton direction, the {eta} problem is alleviated. Combining the KKLT mechanism for modulus stabilization and a shift symmetry breaking superpotential of the chaotic inflation type, we find models reminiscent of 'mutated hybrid inflation' where the inflationary trajectory is curved in the modulus-inflaton plane. We analyze the phenomenology of these models and stress their differences with both chaotic and hybrid inflation.

  14. Measurements of isotope shift in Eu II

    NASA Astrophysics Data System (ADS)

    Broström, Lars; Mannervik, Sven; Royen, Peder; Wännström, Anders

    1995-03-01

    The isotope shift between singly-charged 151Eu and 153Eu in the 4f7(8So)6s 9So4 - 4f7(8So)6p1/2 J = 4 transition at 4129 Å has been measured using fast ion beam-laser technique. This Eu line has attracted interest in connection with efforts of obtaining a cosmochronometer based on observed Th/Eu abundance ratios. Knowledge of the isotope shift is of importance in order to check that contaminations from line blends do not contribute to the line intensity of Eu II. The measured value of the isotope shift -0.1527 (2) cm-1 is consistent with the old spectroscopic value of Krebs and Winkler (-0.1503 (25)cm-1) using a Fabry-Perot interferometer, while the accuracy is improved substantially.

  15. The affective shift model of work engagement.

    PubMed

    Bledow, Ronald; Schmitt, Antje; Frese, Michael; Kühnel, Jana

    2011-11-01

    On the basis of self-regulation theories, the authors develop an affective shift model of work engagement according to which work engagement emerges from the dynamic interplay of positive and negative affect. The affective shift model posits that negative affect is positively related to work engagement if negative affect is followed by positive affect. The authors applied experience sampling methodology to test the model. Data on affective events, mood, and work engagement was collected twice a day over 9 working days among 55 software developers. In support of the affective shift model, negative mood and negative events experienced in the morning of a working day were positively related to work engagement in the afternoon if positive mood in the time interval between morning and afternoon was high. Individual differences in positive affectivity moderated within-person relationships. The authors discuss how work engagement can be fostered through affect regulation. PMID:21766997

  16. Energy shift due to anisotropic blackbody radiation

    NASA Astrophysics Data System (ADS)

    Flambaum, V. V.; Porsev, S. G.; Safronova, M. S.

    2016-02-01

    In many applications a source of the blackbody radiation (BBR) can be highly anisotropic. This leads to the BBR shift that depends on tensor polarizability and on the projection of the total angular momentum of ions and atoms in a trap. We derived a formula for the anisotropic BBR shift and performed numerical calculations of this effect for Ca+and Yb+ transitions of experimental interest. These ions were used for a design of high-precision atomic clocks, fundamental physics tests such as the search for the Lorentz invariance violation and space-time variation of the fundamental constants, and quantum information. Anisotropic BBR shift may be one of the major systematic effects in these experiments.

  17. Shift work in a security environment

    SciTech Connect

    Longhouser, G.A. Jr.

    1993-12-31

    Human beings are diurnal species, normally active by day and asleep by night. Yet over thirty million Americans struggle with work schedules that include an off-normal work effort. The railroads, law enforcement, health services, Department of Defense, factory workers, chemical plants and public services, communications and utility workers must provide some form of around-the-clock effort. Shift work has been around since the advent of recorded history. There has always been a need for some type of off-normal service and assistance. The impact of shift work is replete with tales and factual evidence of an increased personnel error rate; disorders, both personal and family, and of course, increased accident events. In recent memory, the Three Mile Island Nuclear Plant incident, Union Carbide`s explosion in Bhopal, and the Chernobyl Nuclear Plant catastrophe all occurred during off-normal working hours. Yet management overall has done little to correct the production-driven twelve hour, seven day week shift mentality of the nineteenth century. Most schedules in use today are nothing more than cosmetic variations of the old production schedules. This could be driven by a management consideration of the worker`s response to change coupled with a reluctant buy-in of responsibility for the effects of change. Florida Power Corporation has developed for its nuclear security force, a unique work schedule which attempts to employ the sound principles of circadian rhythms coupled with a comprehensive training program to counter the problems associated with shift work. The results over the last four years have seen a marked reduction in the generic problems of personnel errors, absenteeism, unscheduled overtime and turnover rates. Utilization and understanding of this scheduling process for rotational shift work needs to be assessed to determine if the benefits are site specific or provide an expected response to the problems of shift work.

  18. Understanding and diagnosing shift work disorder.

    PubMed

    Thorpy, Michael

    2011-09-01

    A significant proportion of the workforce in industrialized countries (16%) are employed as shift workers. These workers may be susceptible to shift work disorder (SWD), a circadian rhythm sleep disorder, particularly those who work at night or on early-morning shifts. Shift work disorder remains an underdiagnosed and undertreated problem among this population. Patients with SWD have difficulty initiating sleep and waking up. Often, these patients have excessive sleepiness during their work shift. Shift work disorder has been associated with decreased productivity, impaired safety, diminished quality of life, and adverse effects on health. Several tools have been validated to assess excessive daytime sleepiness and are often used to assess excessive nighttime sleepiness, such as that experienced in patients with SWD, including the Epworth Sleepiness Scale and the Multiple Sleep Latency Test. The criteria for diagnosing SWD as established by the American Academy of Sleep Medicine (AASM) and published in the International Classification of Sleep Disorders-Second Edition (ICSD-2) were most recently updated in 2005 and thus do not contain newer agents approved for use in patients with SWD. The symptoms of SWD can be treated using behavioral, prescription, and nonprescription therapies. Current treatment guidelines suggest nonpharmacologic interventions, such as exercise and exposure to light. In addition, medications that contain melatonin or caffeine may have clinical benefits in some patients with SWD. However, modafinil and armodafinil are approved by the US Food and Drug Administration to improve wakefulness in patients with excessive sleepiness associated with SWD, and recent data suggest a clinical benefit. The use of these therapies can significantly improve sleep, performance, and quality of life for patients with SWD. PMID:21904091

  19. Gear shift controller for automatic transmission

    SciTech Connect

    Nishikawa, M.; Sakai, S.; Sakurai, T.

    1987-01-20

    A gear shift controller is described for an automatic transmission having a gear shift, comprising: a hydraulic torque converter; a gear change group, having a plurality of gears, each gear providing a different transmission ratio for the transmission of power from the hydraulic torque converter to the output of the transmission, each of the gears comprising a gear train; a one-way clutch interposed in at least one of the gear trains; a plurality of clutch means operatively connected with the gear trains for actuating each of the gear trains selectively; a gear change determination circuit operatively connected with the clutch means to control the operation of each of the clutch means according to a predetermined gear shifting program for engaging a gear train selected by the program; a coasting detection circuit for detecting a car in the coasting state; a gear shift limiting circuit, operatively connected with the gear change determination circuit and with the coasting detection circuit. The circuit is for actuating only the gear train in which the one-way clutch is interposed immediately, regardless of the selected gear train and of the operation of the gear change determination circuit, when the coasting detection circuit has determined the car to be coasting; and an operation transfer control system including a brake operation detecting means and a mode selector switch means for transferring the operation of the gear shift limiting circuit. The operation transfer control system is adapted to stop, upon detection of one of the brake operation and a reset state of the mode selector switch, the operation of the gear shift limiting circuit and to place the plurality of clutch means under the control of the gear change determination circuit.

  20. Shift-and-add for astronomical imaging

    NASA Technical Reports Server (NTRS)

    Ribak, Erez; Hege, E. Keith; Strobel, Nicolas V.; Christou, Julian C.

    1989-01-01

    Diffraction-limited astronomical images have been obtained utilizing a variant of the shift-and-add method. It is shown that the matched filter approach for extending the weighted shift-and-add method reduces specklegrams from extended objects and from an object dominated by photon noise. The method is aberration-insensitive and yields very high dynamic range results. The iterative method for arriving at the matched filter does not automatically converge in the case of photon-noisy specklegrams for objects with more than one maximum.

  1. Phase-shift binary digital holography.

    PubMed

    Horisaki, Ryoichi; Tahara, Tatsuki

    2014-11-15

    We propose phase-shift digital holography (DH) with a one-bit image sensor. In this method, the propagating complex field from an object is binarized by a one-bit sensor using a phase-shifter. The complex field on the hologram plane is then calculated with the one-bit image data. The object field is recovered via Fresnel back-propagation of the calculated hologram and filtering to suppress some artifacts caused by the binarization. The concept was demonstrated in preliminary experiments by using a synthetically binarized hologram with single-shot and multi-shot phase-shift DH. PMID:25490472

  2. Model-based phase shifting interferometry.

    PubMed

    Deck, Leslie L

    2014-07-20

    A general method of surface profiling with phase-shifting interferometry techniques uses iterative linear regression to fit the sequence of interferograms to a physical model of the cavity. The physical model incorporates all important cavity influences, including environmentally induced rigid-body motion, phase shifter miscalibrations, multiple interference, geometry-induced spatial phase-shift variations, and their cross-couplings. By incorporating an initial estimate of the surface profile and iteratively solving for space- and time-dependent variables separately, convergence is robust and rapid. The technique has no restriction on surface shape or departure. PMID:25090197

  3. Doppler frequency shift of sound apparatus

    NASA Astrophysics Data System (ADS)

    Schier, Walter

    2011-04-01

    A large 1-m diameter rotary table with a semicircular waveguide along its periphery is the basis of the Doppler frequency shift of sound apparatus. A "button" speaker is attached to the outer edge of the rotary table and a microphone pickup is positioned on the wall of the waveguide at its midpoint. At approximate speeds of 25 mph (11 m/s), the velocity measured from the frequency shift between the approaching and receding speaker compared to the velocity measured from the repeat sound pattern agree to within 1%. The microphone output is fed successively to our 10 computer stations.

  4. Lamb shift in the muonic deuterium atom

    SciTech Connect

    Krutov, A. A.; Martynenko, A. P.

    2011-11-15

    We present an investigation of the Lamb shift (2P{sub 1/2}-2S{sub 1/2}) in the muonic deuterium ({mu}D) atom using the three-dimensional quasipotential method in quantum electrodynamics. The vacuum polarization, nuclear-structure, and recoil effects are calculated with the account of contributions of orders {alpha}{sup 3}, {alpha}{sup 4}, {alpha}{sup 5}, and {alpha}{sup 6}. The results are compared with earlier performed calculations. The obtained numerical value of the Lamb shift at 202.4139 meV can be considered a reliable estimate for comparison with forthcoming experimental data.

  5. Lamb shift in the muonic helium ion

    SciTech Connect

    Martynenko, A. P.

    2007-07-15

    The Lamb shift (2P{sub 1/2}-2S{sub 1/2}) in the muonic helium ion ({mu}-{sub 2}{sup 4}He){sup +} is calculated with the account of contributions of orders {alpha}{sup 3}, {alpha}{sup 4}, {alpha}{sup 5}, and {alpha}{sup 6}. Special attention is given to corrections of the electron vacuum polarization, the nuclear structure, and recoil effects. The obtained numerical value of the Lamb shift 1381.72 meV can be considered as a reliable estimate for the comparison with experimental data.

  6. Shift-symmetries at higher order

    NASA Astrophysics Data System (ADS)

    Abel, Steven; Stewart, Richard J.

    2016-02-01

    The fate of shift-symmetries in effective string models is considered beyond tree-level. Such symmetries have been proposed in the past as a way to maintain a hierarchically small Higgs mass and also play a role in schemes of cosmological relaxation. It is argued that on general grounds one expects shift-symmetries to be restored in the limit of certain asymmetric compactifications, to all orders in perturbation theory. This behaviour is verified by explicit computation of the Kähler potential to one-loop order.

  7. Thermometry via light shifts in optical lattices.

    PubMed

    McDonald, M; McGuyer, B H; Iwata, G Z; Zelevinsky, T

    2015-01-16

    For atoms or molecules in optical lattices, conventional thermometry methods are often unsuitable due to low particle numbers or a lack of cycling transitions. However, a differential spectroscopic light shift can map temperature onto the line shape with a low sensitivity to trap anharmonicity. We study narrow molecular transitions to demonstrate precise frequency-based lattice thermometry, as well as carrier cooling. This approach should be applicable down to nanokelvin temperatures. We also discuss how the thermal light shift can affect the accuracy of optical lattice clocks. PMID:25635543

  8. Change from slowly rotating 8-hour shifts to rapidly rotating 8-hour and 12-hour shifts using participative shift roster design.

    TOXLINE Toxicology Bibliographic Information

    Smith PA; Wright BM; Mackey RW; Milsop HW; Yates SC

    1998-01-01

    OBJECTIVES: The study examined the impact of change, from slowly rotating continuous 8-hour shifts to more rapidly rotating continuous 8-hour and 12-hour shifts, on the health and quality of life of shift workers.METHODS: Self-report survey data were collected from 72 shift workers at 3 sewage treatment plants before and several months after roster change. After the change 1 plant first worked a rapidly rotating, 8-hour shift roster and then worked a 12-hour shift roster, and the other 2 plants worked continuous 12-hour shift rosters.RESULTS: After the change the shift workers at each plant reported increased satisfaction with roster design, a decrease in physical and psychological circadian malaise associated with shift work, improved day sleep quality, less tiredness, and improvements in the quality of home, social and work life. A between-plant comparison of the rapidly rotating 8-hour and 12-hour shift rosters showed greater improvements had been obtained with the 12-hour shift roster, and no significant differences in tiredness or sleep quality between the redesigned 8- and 12-hour shift rosters. However, a within-plant matched-pairs comparison at the 1st plant of the rapidly rotating 8-hour shift roster and the 12-hour shift roster showed no significant differences.CONCLUSIONS: The results show that the prior level of support for change may best explain the impact of roster redesign on individual well-being. They lend further support to shift worker participation in roster design.

  9. Computational studies of dielectric permittivity effects on chemical shifts of alanine dipeptide

    NASA Astrophysics Data System (ADS)

    Sahakyan, Aleksandr B.

    2012-09-01

    Dielectric permittivity effect on chemical shifts of alanine dipeptide is studied using hybrid density functional theory. The dependence is shown to be highly sensitive to conformation, and, a reasonable explanation is outlined based on the solvent reaction field model. The danger of the observed shape of dependence for the chemical shift evaluations at low dielectric constant environment, as in the case of protein interior, is emphasized. The nuclear shielding sensitivity towards the dielectric permittivity is examined over different ?/? combinations. Comparison with the experimental data from protein backbone suggests an effective dielectric constant of ?4-5 for protein interior.

  10. A paradigm shift in patient satisfaction assessment.

    PubMed

    Otani, Koichiro; Harris, Lisa E; Tierney, William M

    2003-09-01

    The authors investigated the relationships between patients' reactions to health care attributes and their overall satisfaction with primary care. The study found the following: (1) patients' overall satisfaction levels are disproportionately influenced by low levels of their reactions (less satisfied) to the primary care attribute, rather than simply averaged out among attribute reactions. This is a noncompensatory relationship. (2) The marginal impact of primary care attributes on overall satisfaction decreases at higher levels of patients' reactions (more satisfied) to primary care attributes, indicating a nonlinear relationship. Patients combine their reactions to the health care attributes by means of noncompensatory and nonlinear models to form their overall satisfaction. Decision makers should selectively concentrate training resources on those areas of attributes showing high dissatisfaction rather than attempt to improve an attribute that showed the largest parameter estimate. This approach would not only save resources but result in better outcomes of patient satisfaction. PMID:12971233

  11. Water in low-mass star-forming regions with Herschel. The link between water gas and ice in protostellar envelopes

    NASA Astrophysics Data System (ADS)

    Schmalzl, M.; Visser, R.; Walsh, C.; Albertsson, T.; van Dishoeck, E. F.; Kristensen, L. E.; Mottram, J. C.

    2014-12-01

    Aims: Our aim is to determine the critical parameters in water chemistry and the contribution of water to the oxygen budget by observing and modelling water gas and ice for a sample of eleven low-mass protostars, for which both forms of water have been observed. Methods: A simplified chemistry network, which is benchmarked against more sophisticated chemical networks, is developed that includes the necessary ingredients to determine the water vapour and ice abundance profiles in the cold, outer envelope in which the temperature increases towards the protostar. Comparing the results from this chemical network to observations of water emission lines and previously published water ice column densities, allows us to probe the influence of various agents (e.g., far-ultraviolet (FUV) field, initial abundances, timescales, and kinematics). Results: The observed water ice abundances with respect to hydrogen nuclei in our sample are 30-80 ppm, and therefore contain only 10-30% of the volatile oxygen budget of 320 ppm. The keys to reproduce this result are a low initial water ice abundance after the pre-collapse phase together with the fact that atomic oxygen cannot freeze-out and form water ice in regions with Tdust ? 15 K. This requires short prestellar core lifetimes ?0.1 Myr. The water vapour profile is shaped through the interplay of FUV photodesorption, photodissociation, and freeze-out. The water vapour line profiles are an invaluable tracer for the FUV photon flux and envelope kinematics. Conclusions: The finding that only a fraction of the oxygen budget is locked in water ice can be explained either by a short pre-collapse time of ?0.1 Myr at densities of nH ~ 104 cm-3, or by some other process that resets the initial water ice abundance for the post-collapse phase. A key for the understanding of the water ice abundance is the binding energy of atomic oxygen on ice. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

  12. The hydroarylation reaction--scope and limitations.

    PubMed

    Namyslo, Jan C; Storsberg, Jrg; Klinge, Jens; Grtner, Christian; Yao, Min-Liang; Ocal, Nuket; Kaufmann, Dieter Eckhard

    2010-05-01

    The synthetic potential of stereoselective, palladium-catalyzed hydro(het)arylation reactions of bi-, tri- and tetracyclic (hetero)alkenes in the presence of phospines and arsines as highly efficient ligands was studied. The mechanism of this reductive Heck reaction becomes more complex in the case of benzonorbornenes. Hydroarylation of diazabicyclo-[2.2.1]heptenes provides a stereoselective access to aryldiaminocyclopentanes. Electron-deficient arylpalladium complexes shift the reaction towards the product of a formal 1,2-hydrazidoarylation reaction of 1,3-cyclopentadiene by a stereoselective C-N cleavage. Due to steric reasons, rigid bicyclo[2.2.2]octenes react slower in hydroarylation reactions than the corresponding bicyclo[2.2.1]heptenes. The more flexible bicyclo[4.2.2]decene system already tends to undergo domino-Heck reactions, even under reductive conditions. When a tetracyclic cis-allylcyclopropane is carbopalladated in the presence of formates, the neighboring cyclopropane ring is attacked in the first reported example of a pi,sigma domino-Heck reaction. PMID:20657489

  13. Work shift duration: a review comparing eight hour and 12 hour shift systems

    PubMed Central

    Smith, L.; Folkard, S.; Tucker, P.; Macdonald, I.

    1998-01-01

    OBJECTIVES: Shiftwork is now a major feature of working life across a broad range of industries. The features of the shift systems operated can impact on the wellbeing, performance, and sleep of shiftworkers. This paper reviews the current state of knowledge on one major characteristic of shift rotas-namely, shift duration. Evidence comparing the relative effects of eight hour and 12 hour shifts on fatigue and job performance, safety, sleep, and physical and psychological health are considered. At the organisational level, factors such as the mode of system implementation, attitudes towards shift rotas, sickness absence and turnover, overtime, and moonlighting are discussed. METHODS: Manual and electronic searches of the shiftwork research literature were conducted to obtain information on comparisons between eight hour and 12 hour shifts. RESULTS: The research findings are largely equivocal. The bulk of the evidence suggests few differences between eight and 12 hour shifts in the way they affect people. There may even be advantages to 12 hour shifts in terms of lower stress levels, better physical and psychological wellbeing, improved durations and quality of off duty sleep as well as improvements in family relations. On the negative side, the main concerns are fatigue and safety. It is noted that a 12 hour shift does not equate with being active for only 12 hours. CONCLUSIONS: There can be considerable extension of the person's time awake either side of the shift. However, the effects of longer term exposure to extended work days have been relatively uncharted in any systematic way. Longitudinal comparative research into the chronic impact of the compressed working week is needed. PMID:9624275

  14. Helping Administrators Identify Shifts in Enrollment Patterns.

    ERIC Educational Resources Information Center

    Salley, Charles D.

    The spiraling cost of higher education has led to questions of accountability and cost effectiveness and called more attention to budgetary and financial structures. This shift in decision-making responsibilities is closely tied to recent changes in enrollment growth that has reached a static or declining stage. In view of this trend,

  15. A Tectonic Shift in Global Higher Education

    ERIC Educational Resources Information Center

    Daniel, John; Kanwar, Asha; Uvalic-Trumbic, Stamenka

    2006-01-01

    Europeans lament that their universities are lagging behind those in the United States, while Americans worry that their academic leadership is threatened by complacency. Both groups, however, are missing the tectonic shift that will transform the map of higher education worldwide--the growth of universities in the developing world. Spreading

  16. Implications of Shifting Technology in Education

    ERIC Educational Resources Information Center

    Holland, Janet; Holland, John

    2014-01-01

    This article examines the implications of shifting technology trends by looking at what we've lost or are losing, where we are, and where we need to go for making the needed transitions in knowledge and skills. Areas of growth within new media and the tech industry are good indicators of our growing interests in mobility, improved quality,…

  17. Majors' Shift to Natural Gas, The

    EIA Publications

    2001-01-01

    The Majors' Shift to Natural Gas investigates the factors that have guided the United States' major energy producers' growth in U.S. natural gas production relative to oil production. The analysis draws heavily on financial and operating data from the Energy Information Administration's Financial Reporting System (FRS)

  18. NMR crystallography: the use of chemical shifts

    NASA Astrophysics Data System (ADS)

    Harris, Robin K.

    2004-10-01

    Measurements of chemical shifts obtained from magic-angle spinning NMR spectra (together with quantum mechanical computations of shielding) can provide valuable information on crystallography. Examples are given of the determination of crystallographic asymmetric units, of molecular symmetry in the solid-state environment, and of crystallographic space group assignment. Measurements of full tensor components for 199Hg have given additional coordination information. The nature of intermolecular hydrogen bonding in cortisone acetate polymorphs and solvates is obtained from chemical shift information, also involving measurement of the full tensor parameters. The resulting data have been used as restraints, built into the computation algorithm, in the analysis of powder diffraction patterns to give full crystal structures. A combination of quantum mechanical computation of shielding and measurement of proton chemical shifts (obtained by high-speed MAS) leads to the determination of the position of a proton in an intermolecular hydrogen bond. A recently-developed computer program specifically based on crystallographic repetition has been shown to give acceptable results. Moreover, NMR chemical shifts can distinguish between static and dynamic disorder in crystalline materials and can be used to determine modes and rates of molecular exchange motion.

  19. The Phase Shift in the Jumping Ring

    ERIC Educational Resources Information Center

    Jeffery, Rondo N.; Amiri, Farhang

    2008-01-01

    The popular physics demonstration experiment known as Thomson's Jumping Ring (JR) has been variously explained as a simple example of Lenz's law, or as the result of a phase shift of the ring current relative to the induced emf. The failure of the first-quadrant Lenz's law explanation is shown by the time the ring takes to jump and by levitation.

  20. RQL Fuel Shifting Sector Rig Test

    NASA Technical Reports Server (NTRS)

    Holdeman, James D. (Technical Monitor); Haid, Daniel A.; Koopman, Frederick S.; Peschke, William O. T.; Siskind, Kenneth S.

    2004-01-01

    The low emissions potential of a Rich-Quench-Lean (RQL) combustor for use in the HIgh Speed Civil transport (HSCT) application was evaluated as part of the NASA Critical Propulsion Components (CPC) Program. Fuel shifting as an approach to combustor control was evaluated in a multiple bank RQL combustor, utilizing reduced scale quench technology implemented in a convoluted linear with quench plate concept.

  1. Survey Detects Shifting Priorities of School Boards

    ERIC Educational Resources Information Center

    Samuels, Christina A.

    2011-01-01

    The author reports the results of a nationwide survey of school board members which show a shift in focus toward student achievement and away from district-management issues known as the "killer B's": buses, buildings, books, budgets, and bonds. But today's school board members appear not to be as interested in issues that many policy observers

  2. Written Language Shift among Norwegian Youth

    ERIC Educational Resources Information Center

    zerk, Kamil; Todal, Jon

    2013-01-01

    In Norway there are two written Norwegian languages, Bokml and Nynorsk. Of these two written languages Bokml is being used by the majority of the people, and Bokml has the highest prestige in the society. This article is about the shift of written language from Nynorsk to Bokml among young people in a traditional Nynorsk district in the

  3. Hispanics Find Jobs that Shift Migration

    ERIC Educational Resources Information Center

    Gilroy, Marilyn

    2007-01-01

    Economic opportunity, the force that has driven population shifts for years, is changing the face of migration as Hispanics move into parts of the nation beyond border states and traditional ports of entry. North Carolina, Tennessee, Georgia, and Indiana are experiencing a steady growth in Hispanic population. In addition, West Virginia, Ohio, and

  4. Paradigmatic Shift or Tinkering at the Edges?

    ERIC Educational Resources Information Center

    Sutherland, Margaret

    2012-01-01

    In their target paper, "Towards a systemic theory of gifted education," A. Ziegler and S. N. Phillipson present a long awaited call for a paradigmatic shift in thinking within the field of gifted education. The paper considers how educators and researchers within the field could bring about such a change. They challenge the prevailing

  5. Effectiveness of the Twelve-Hour Shift.

    ERIC Educational Resources Information Center

    Brinton, Robert D.

    1983-01-01

    Although labor unions traditionally have fought for shorter working hours, there have been recent reversals in this trend. The Pulp and Paperboard Division of Temple-Eastex Incorporated converted to a 12-hour shift and found that safety improved, productivity increased, and overtime decreased. (JOW)

  6. Scientists detect shift in Arctic Ocean system

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2011-12-01

    The Arctic Ocean system has shifted to a “new normal” since 2006, and there are now a sufficient number of years of data to indicate this shift, according to a new Arctic Report Card. The report card, issued on 1 December by the U.S. National Oceanic and Atmospheric Administration (NOAA) along with the U.S. Army Corps of Engineers, other agencies, and an international team of researchers, indicates that 2011 saw significant changes to the Arctic atmosphere, sea ice and ocean, and hydrology and terrestrial cryosphere, as well as some changes to Arctic marine and terrestrial ecosystems, and this shift has widespread environmental and social implications. The report refers to 2006 because precursors that year led to dramatic sea ice loss in 2007. “The shift is characterized by the persistent decline in the thickness and summer extent of the sea ice cover and a warmer, fresher upper ocean,” according to the report, which also indicates a repeated occurrence of 2010 Arctic winter wind patterns this year that are different from the norm, among other concerns. “The 2011 report card shows that record-setting changes are occurring throughout the Arctic environmental system. Given the projection of continued global warming, it is very likely that major Arctic changes will continue in years to come, with increasing climatic, biological, and social impacts,” the report indicates.

  7. Phase shift of stepwise reflectivity profile mirrors.

    PubMed

    Giuri, C; Perrone, M R; Flori, D; Piegari, A; Scaglione, S

    1997-04-20

    The effects of phase shifts in laser beams transmitted by output couplers with a stepwise reflectivity profile have been experimentally investigated with a XeCl laser. It is shown that the phase distortions of the cavity output coupler affect significantly the propagation properties of the output laser beam but do not affect the output beam energy and pulse width. PMID:18253234

  8. The Phase Shift in the Jumping Ring

    ERIC Educational Resources Information Center

    Jeffery, Rondo N.; Amiri, Farhang

    2008-01-01

    The popular physics demonstration experiment known as Thomson's Jumping Ring (JR) has been variously explained as a simple example of Lenz's law, or as the result of a phase shift of the ring current relative to the induced emf. The failure of the first-quadrant Lenz's law explanation is shown by the time the ring takes to jump and by levitation.…

  9. Student life - Be clever on training shifts.

    PubMed

    O'Reilly-Foley, Georgina

    2015-12-16

    Welcome to the most exciting journey of your working life. During your nurse training, you may feel every emotion under the sun and will gain insight into a whole new world of knowledge, experience and people. Here are some survival tips to get you ready for your first shift. PMID:26669412

  10. Differential phase shift keyed communication system

    NASA Technical Reports Server (NTRS)

    Hopkins, P. M.; Wallingford, W. M. (inventors)

    1974-01-01

    A communication system using differential phase-shift-keying (DPSK) transmits and receives binary data without requiring timing or phase reference signals. The system encodes and modulates the data at the transmitter, and decodes and demodulates the data at the receiver, without ambiguity as to the data content.

  11. Heart-rate pulse-shift detector

    NASA Technical Reports Server (NTRS)

    Anderson, M.

    1974-01-01

    Detector circuit accurately separates and counts phase-shift pulses over wide range of basic pulse-rate frequency, and also provides reasonable representation of full repetitive EKG waveform. Single telemeter implanted in small animal monitors not only body temperature but also animal movement and heart rate.

  12. Using LEADS to shift to high performance.

    PubMed

    Fenwick, Shauna; Hagge, Erna

    2016-03-01

    Health systems across Canada are tasked to measure results of all their strategic initiatives. Included in most strategic plans is leadership development. How to measure leadership effectiveness in relation to organizational objectives is key in determining organizational effectiveness. The following findings offer considerations for a 21(st)-century approach to shifting to high-performance systems. PMID:26872796

  13. Study Predicts Dramatic Shifts in Enrollments.

    ERIC Educational Resources Information Center

    Evangelauf, Jean

    1991-01-01

    A new study detailing demographic shifts in the college-age population predicts growth in minority high school graduates and shrinkage or maintenance of White graduation rates. The report is the first to provide state-by-state figures on actual and projected graduates from 1986 through 1995 by racial and ethnic group. (MSE)

  14. A Paradigm Shift to Improve Academic Performance

    ERIC Educational Resources Information Center

    Rulloda, Rudolfo B.

    2009-01-01

    A shift to computer skills for improving academic performances was investigated. The No Child Left Behind Act of 2001 increased the amount of high school dropouts after the Act was enacted. At-risk students were included in this research study. Several models described using teachers for core subjects and mentors to built citizenship skills, along…

  15. Implications of Shifting Technology in Education

    ERIC Educational Resources Information Center

    Holland, Janet; Holland, John

    2014-01-01

    This article examines the implications of shifting technology trends by looking at what we've lost or are losing, where we are, and where we need to go for making the needed transitions in knowledge and skills. Areas of growth within new media and the tech industry are good indicators of our growing interests in mobility, improved quality,

  16. Work Shifts and Disability: A National View.

    ERIC Educational Resources Information Center

    Presser, Harriet B.; Altman, Barbara

    2002-01-01

    More than one-fifth of employed persons with disabilities work late or rotating shifts, about the same as nondisabled workers. Day workers with disabilities receive lower hourly wages than nondisabled workers. Except for men, nonday workers with disabilities receive wages similar to their nondisabled counterparts. (Contains 27 references.)

  17. Prescription of Physical Activity: A Paradigm Shift.

    ERIC Educational Resources Information Center

    Morgan, William P.

    2001-01-01

    Proposes a paradigm shift in physical activity prescription which involves: an idiographic approach; preferred exertion rather than a given percent of maximum in the prescription of exercise intensity; and purposeful physical activity. A summary of 10 cases is presented, revealing adherence figures ranging from 5 to 79 years. Adherence of 100…

  18. Tilting and shifting modes in a spheromak

    SciTech Connect

    Jardin, S.C.; Chance, M.S.; Dewar, R.L.; Grimm, R.C.; Monticello, D.A.

    1981-04-01

    In the absence of a conducting wall, typical spheromak plasmas are unstable to tilting and/or shifting modes. The effects of the cross-sectional shape, aspect ratio, and the location of a conducting wall on the stability of these modes are investigated.

  19. Deindustrialization and the Shift to Services.

    ERIC Educational Resources Information Center

    Kutscher, Ronald E.; Personick, Valerie A.

    1986-01-01

    Bureau of Labor Statistics data show the industrial sector as a whole in healthy shape, but a few manufacturing industries in deep trouble. These industries include tobacco manufacturers, iron and steel foundries, leather products, and steel manufacturers. Also examines shifts in employment and output, job quality, and outlook for the future. (CT)

  20. Survey Detects Shifting Priorities of School Boards

    ERIC Educational Resources Information Center

    Samuels, Christina A.

    2011-01-01

    The author reports the results of a nationwide survey of school board members which show a shift in focus toward student achievement and away from district-management issues known as the "killer B's": buses, buildings, books, budgets, and bonds. But today's school board members appear not to be as interested in issues that many policy observers…

  1. Shifting Paradigms: From Flexner to Competencies.

    ERIC Educational Resources Information Center

    Carraccio, Carol; Wolfsthal, Susan D.; Englander, Robert; Ferentz, Kevin; Martin, Christine

    2002-01-01

    Reviewed the literature on competency-based medical education to: (1) understand the evolution of this educational paradigm; (2) assess the evidence to date of the efficacy of competency-based education; and (3) provide practical insights into how to accomplish full implementation and evaluation of the paradigm shift. (EV)

  2. Attention-Shifting in Frederick Douglass.

    ERIC Educational Resources Information Center

    Leroux, Neil R.

    A study explored rhetorical strategies and dynamics within a single speech delivered by Frederick Douglass on July 5, l852 in Rochester, New York, which was considered by speaker and audience to be an Independence Day speech. An examination of the text suggests that Douglass embarked on a strategy of attention-shifting--turning the attention of…

  3. Has the Education Paradigm Begun to Shift?

    ERIC Educational Resources Information Center

    Chadwick, Clifton B.

    2014-01-01

    The author reviews various elements of what may be considered as evidence that the long-awaited shift in the education paradigm is actually happening. Concepts like student-centered learning, attainment-based evaluation, knowledge-based constructivism, and effort-based intelligence are growing, are being more widely recognized as important, and

  4. Solvent stark effects and spectral shifts. II

    SciTech Connect

    Nicol, M; Swain, J; Shum, Y Y; Merin, R; Chen, R H.H.

    1981-03-01

    Solvent shifts of the energies of the lowest /sup 1/L/sub a/ bands of the electronic absorption spectra of anthracene, chrysene, phenanthrene, and tetracene and of the lowest /sup 1/L/sub b/ bands of the electronic absorption spectra of naphthalene, phenanthrene, chrysene, and picene are reported. The origins of these shifts are analyzed in terms of theories developed by Baur and Nicol and by Abe. Satisfactory fits of the experimental data are obtained for theoretical expressions derived from both theories, but discrepancies are observed between the relative magnitudes assigned to the various contributions to the shifts by the two theories. The magnitudes of the parameters of the Baur and Nicol theory, relating solvent shifts to the dielectric constant and refractive index of the solvent, are found to be the same within experimental precision for the /sup 1/L/sub a/ transitions in all of the molecules studied; a similar regularity of the parameters for the /sup 1/L/sub b/ transitions also is observed.

  5. Blackbody radiation shifts in optical atomic clocks.

    PubMed

    Safronova, Marianna; Kozlov, Mikhail; Clark, Charles

    2012-03-01

    A review of recent theoretical calculations of blackbody radiation (BBR) shifts in optical atomic clocks is presented. We summarize previous results for monovalent ions that were obtained by a relativistic all-order single-double method, where all single and double excitations of the Dirac- Fock wave function are included to all orders of perturbation theory. A recently developed method for accurate calculations of BBR shifts in divalent atoms is then presented. This approach combines the relativistic all-order method and the configuration interaction method, which provides for accurate treatment of correlation corrections in atoms with two valence electrons. Calculations of the BBR shifts in B+, Al+, and In+ have enabled us to reduce the present fractional uncertainties in the frequencies of their clock transitions as measured at room temperature: to 4 10-19 for Al+ and 10-18 for B+ and In+. These uncertainties approach recent estimates of the limits of precision of currently proposed optical atomic clocks. We discuss directions of future theoretical developments for reducing clock uncertainties resulting from blackbody radiation shifts. PMID:22481777

  6. Exploring Insight: Focus on Shifts of Attention

    ERIC Educational Resources Information Center

    Palatnik, Alik; Koichu, Boris

    2015-01-01

    The paper presents and analyses a sequence of events that preceded an insight solution to a challenging problem in the context of numerical sequences. A threeweek long solution process by a pair of ninth-grade students is analysed by means of the theory of shifts of attention. The goal for this article is to reveal the potential of this theory

  7. The extramolecular contributions to the photoelectron and soft x-ray photon chemical shift in solid and liquid benzene

    NASA Astrophysics Data System (ADS)

    gren, Hans; Karlstrm, Gunnar

    1983-07-01

    The origin of the phase transition shifts (PTS) in photoelectron and x-ray photon energies in solid and liquid benzene is investigated from a sudden, time-independent standpoint. Supermolecular dimer and perturbational induction energy calculations are undertaken. The role of localization of ionization, of reaction field due to intramolecular relaxation, and of partitioning the extramolecular polarizabilities into local bond and atom components are explored. The structure dependence of the phase transition shift is investigated and it is found that the structure of liquid benzene is sufficiently different from that of the solid to predict a significant shift in the photoelectron spectrum.

  8. Rate limiting processes in the bohr shift in human red cells

    PubMed Central

    Forster, R. E.; Steen, J. B.

    1968-01-01

    1. The rates of the Bohr shift of human red cells and some of its constituent reactions have been studied with a modified Hartridge—Roughton rapid reaction apparatus using an oxygen electrode to measure the progress of the reaction. 2. The rate of the Bohr shift was compatible with the hypothesis that the transfer of H+ across the membrane by means of CO2 exchange and reaction with buffers is generally the rate-limiting step. (a) When the Bohr off-reaction was produced by a marked increase in PCO2 around the cells, the half-time at 37° C was 0·12 sec. In this case CO2 was available initially to diffuse into the cells, the process being predominantly limited by the rate of intracellular CO2 hydration. (b) When the Bohr off-shift was produced by an increase of [H+] outside the cell, PCO2 being low and equal within and outside the cells, the half time became 0·31 sec. In this case, even at the start, the H2CO3 formed by the almost instantaneous neutralization reaction of H+ and HCO3- had to dehydrate to form CO2 and this in turn had to diffuse into and react within the red cell before the [HbO2] could change. When a carbonic anhydrase inhibitor was added to slow the CO2 reaction inside the cell, the half-time rose to 10 sec. (c) The Bohr off-shift in a haemolysed cell suspension produced by an increase in PCO2 appeared to be limited by the rate at which the CO2 could hydrate to form H+. 3. The Bohr off-shift has an average Q10 of 2·5 between 42·5 and 28° C with an activation energy of 8000 cal. 4. The pronounced importance of the CO2-bicarbonate system for rapid intracellular pH changes is discussed in connexion with some physiological situations. PMID:5664232

  9. Sleep Loss and Fatigue in Shift Work and Shift Work Disorder

    PubMed Central

    kerstedt, Torbjrn; Wright, Kenneth P.

    2010-01-01

    Shift work is highly prevalent in industrialized societies (>20%) but, when it includes night work, it has pronounced negative effects on sleep, subjective and physiological sleepiness, performance, accident risk, as well as on health outcomes such as cardiovascular disease and certain forms of cancer. The reason is the conflict between the day oriented circadian physiology and the requirement for work and sleep at the wrong biological time of day. Other factors that negatively impact work shift sleepiness and accident risk include long duration shifts greater than 12 hours and individual vulnerability for phase intolerance that may lead to a diagnosis of shift work disorder; i.e., those shift workers with the greatest sleepiness and performance impairment during the biological night and insomnia during the biological day. Whereas some countermeasures may be used to ameliorate the negative impact of shift work on nighttime sleepiness and daytime insomnia (combined countermeasures may be the best available), there seems at present to be no way to eliminate most of the negative effects of shift work on human physiology and cognition. PMID:20640236

  10. Classical toy models for the monopole shift and the quadrupole shift.

    PubMed

    Rose, Katrin; Cottenier, Stefaan

    2012-08-28

    The penetration of s- and p(1/2)-electrons into the atomic nucleus leads to a variety of observable effects. The presence of s-electrons inside the nucleus gives rise to the isotope shift in atomic spectroscopy, and to the isomer shift in Mssbauer spectroscopy. Both well-known phenomena are manifestations of the more general monopole shift. In a recent paper (Koch et al., Phys. Rev. A, 2010, 81, 032507), we discussed the existence of the formally analogous quadrupole shift: a tensor correction to the electric quadrupole interaction due to the penetration of relativistic p(1/2)-electrons into the nucleus. The quadrupole shift is predicted to be observable by high-accuracy molecular spectroscopy on a set of 4 molecules (the quadrupole anomaly). The simple physics behind all these related phenomena is easily obscured by an elaborate mathematical formalism that is required for their derivation: a multipole expansion in combination with perturbation theory, invoking quantum physics and ideally relativity. In the present paper, we take a totally different approach. We consider three classical 'toy models' that can be solved by elementary calculus, and that nevertheless contain all essential physics of the monopole and quadrupole shifts. We hope that this intuitive (yet exact) analysis will increase the understanding about multipole shift phenomena in a broader community. PMID:22782015

  11. Mechanisms and origins of the switchable regioselectivity of FeBr3-catalyzed [1,2]-aryl and [1,2]-alkyl shifts of ?-aryl aldehydes.

    PubMed

    Liu, Congcong; Liu, Yuxia; Tang, Yanan; Liang, Haosheng; Bi, Siwei

    2016-02-16

    With the aid of DFT calculations, the FeBr3-catalyzed skeletal rearrangements of 2-cyclohexanal,2-p-C6H4OMe-propylaldehyde () and 2-phenyl,2-p-C6H4OMe-propylaldehyde () were investigated theoretically. As compared to mono-FeBr3 as a catalyst, the bis-FeBr3 serving as a catalyst is found to be not only enhancing the catalytic efficiency but also improving the product selectivity. For the reaction starting from , the [1,2]-group shift (first step) is rate-determining, and why the Cy shift is the most favored is rationalized in comparison with the p-C6H4OMe and Me shifts. For the reaction starting from , the [1,2]-H shift (second step) is rate-determining although the [1,2]-p-C6H4OMe shift is favored over the [1,2]-phenyl shift. In contrast to the experimental proposal, the newly established H2O/Br(-) joint-assisted H-shift mechanism explains the partial ?-H source of the [1,2]-Cy shift product. In addition, we discussed the inherent mechanism that explains why both the [1,2]-p-C6H4OMe and [1,2]-p-C6H4CF3 shifts are more facile than the [1,2]-phenyl shift although the substituents -OMe and -CF3 have opposite electronic behaviors. PMID:26822257

  12. Iterative phase-shifting algorithm immune to random phase shifts and tilts.

    PubMed

    Chen, Yi-Chun; Lin, Po-Chih; Lee, Chung-Min; Liang, Chao-Wen

    2013-05-10

    An iterative phase-shifting algorithm based on the least-squares principle is developed to overcome the random piston and tilt wavefront errors generated from the phase shifter. The algorithm iteratively calculates the phase distribution and the phase-shifting map to minimize the sum of squared errors in the interferograms. The performance of the algorithm is evaluated via computer simulations and validated by the Fizeau interferometer measurements. The results show that the proposed algorithm has a fast convergence rate and satisfactory phase-estimation accuracy, improving the measurement precision of the phase-shifting interferometers with significant phase-shifter errors. PMID:23669854

  13. Hospital pricing: cost shifting and competition.

    PubMed

    Morrisey, M A

    1993-05-01

    The issue of cost shifting has taken on enormous policy implications. It is estimated that unsponsored and undercompensated hospital costs--one measure of cost shifting--has totaled $21.5 billion in 1991. The health services research literature indicates that hospitals set different prices for different payers. However, the empirical evidence on hospitals' ability to raise prices to one payer to make up for unsponsored care or lower payments by other payers is mixed at best. No study has concluded that hospitals have raised prices to fully adjust for such actions. The extent of cost shifting is limited by the market. When a hospital has market power, it is able to set prices above marginal costs. However, when a buyer has enough patient/subscribers and a willingness to direct them to particular providers based on price considerations, hospitals have less flexibility in raising prices above costs. Thus, the extent of cost shifting is limited by the market. Cost shifting is not as easy as it may have been in the past because the nature of hospital and insurer competition has changed radically in the last decade. While hospital quality, services, and amenities still matter, some buyers are increasingly concerned about the price they pay. Evidence from studies of PPO and HMO negotiations with hospitals suggests that hospitals' market power is eroding, at least in some areas. In areas with relatively few hospital competitors and little PPO or HMO activity, Medicaid and Medicare price reductions and uncompensated care burdens will be partially absorbed by higher prices paid by private payers. In more price sensitive markets and in markets in which prices to private payers have risen to those commensurate with the market power of local hospitals, such cost shifting will not occur. A market-based approach in hospital pricing requires an explicit policy for the uninsured. In a competitive market, a hospital that traditionally cared for the uninsured by spending some of its profits on them will be unable to do so, at least to the same extent as it did in the past. Increased competition in health care without consideration of the uninsured will decrease the uninsured's access to care. PMID:10129621

  14. Transitional Bubble in Periodic Flow Phase Shift

    NASA Technical Reports Server (NTRS)

    Talan, M.; Hourmouziadis, Jean

    2004-01-01

    One particular characteristic observed in unsteady shear layers is the phase shift relative to the main flow. In attached boundary layers this will have an effect both on the instantaneous skin friction and heat transfer. In separation bubbles the contribution to the drag is dominated by the pressure distribution. However, the most significant effect appears to be the phase shift on the transition process. Unsteady transition behaviour may determine the bursting of the bubble resulting in an un-recoverable full separation. An early analysis of the phase shift was performed by Stokes for the incompressible boundary layer of an oscillating wall and an oscillating main flow. An amplitude overshoot within the shear layer as well as a phase shift were observed that can be attributed to the relatively slow diffusion of viscous stresses compared to the fast change of pressure. Experiments in a low speed facility with the boundary layer of a flat plate were evaluated in respect to phase shift. A pressure distribution similar to that on the suction surface of a turbomachinery aerofoil was superimposed generating a typical transitional separation bubble. A periodically unsteady main flow in the suction type wind tunnel was introduced via a rotating flap downstream of the test section. The experiments covered a range of the three similarity parameters of momentum-loss-thickness Reynolds-number of 92 to 226 and Strouhal-number (reduced frequency) of 0.0001 to 0.0004 at the separation point, and an amplitude range up to 19 %. The free stream turbulence level was less than 1% .Upstream of the separation point the phase shift in the laminar boundary layer does not appear to be affected significantly bay either of the three parameters. The trend perpendicular to the wall is similar to the Stokes analysis. The problem scales well with the wave velocity introduced by Stokes, however, the lag of the main flow near the wall is less than indicated analytically. The separation point comes closest to the Stokes analysis but the phase is still 20 degrees lower at the wall.

  15. The center of ground reaction force during lifting.

    PubMed

    Tsuang, Y H; Cheng, C K; Wang, C L; Chen, P Q; Hang, Y S; Liu, T K

    1995-01-01

    The center locations of the ground reaction force were estimated when subjects assumed upright and bending postures as well as when they lifted at low and high speeds. Ten subjects participated in this study and were instructed to assume two postures and to perform two liftings sequentially in a random order. The center locations of the ground reaction force were calculated using a Computerized Dyno Graphic system (INFOTRONIC). The center of the ground reaction force in the full bending posture had a more anterior location than it did in the upright standing posture. When measured during the lifting activity, the center of the ground reaction force shifted forward and then backward during the whole activity. The center location shifted to a more anterior location during high-speed lifting than it did during low-speed lifting. PMID:7770552

  16. Microfluidic chemical reaction circuits

    SciTech Connect

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  17. Microscale Thermite Reactions.

    ERIC Educational Resources Information Center

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana

    1998-01-01

    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  18. Anaphylaxis-Like Reactions

    MedlinePLUS

    ... Clinical Immunology View full profile Anaphylaxis: Anaphylaxis-Like Reactions When exposed to a foreign substance, some people ... the same as for anaphylaxis. More Anaphylaxis-Like Reactions Information Back to Anaphylaxis Reviewed on 7/12 ...

  19. Allergic reactions (image)

    MedlinePLUS

    Allergic reaction is a sensitivity to a specific substance, called an allergen, that is contacted through the skin, inhaled into the lungs, swallowed or injected. The body's reaction to an allergen can be mild, such as ...

  20. Classification of clock reactions.

    PubMed

    Horvth, Attila K; Nagypl, Istvn

    2015-02-23

    Autocatalytic systems are sometimes designated as clock reactions or reactions that exhibit clock behavior. To resolve the recent dispute over the term clock reaction, we describe a new approach to classify systems featuring clock behavior into three distinct groups: substrate-depletive clock reactions, autocatalysis-driven clock reactions, and systems that have pseudo clock behavior. Many of the well-known classical and recently discovered reactions can conveniently be put into these categories. We also provide a convincing argument for classifying some autocatalytic processes as clock reactions, but it does not necessarily mean that all autocatalytic processes should be classified as autocatalysis-driven clock reactions. This classification can be conveniently performed if the kinetic nature of the given system has been completely elucidated and understood. PMID:25425415

  1. Moving attention - Evidence for time-invariant shifts of visual selective attention

    NASA Technical Reports Server (NTRS)

    Remington, R.; Pierce, L.

    1984-01-01

    Two experiments measured the time to shift spatial selective attention across the visual field to targets 2 or 10 deg from central fixation. A central arrow cued the most likely target location. The direction of attention was inferred from reaction times to expected, unexpected, and neutral locations. The development of a spatial attentional set with time was examined by presenting target probes at varying times after the cue. There were no effects of distance on the time course of the attentional set. Reaction times for far locations were slower than for near, but the effects of attention were evident by 150 msec in both cases. Spatial attention does not shift with a characteristic, fixed velocity. Rather, velocity is proportional to distance, resulting in a movement time that is invariant over the distances tested.

  2. Infrared phase-shifting digital interferometer

    NASA Astrophysics Data System (ADS)

    Chen, Jinbang; Chen, Lei; Huang, Shenwang; Jin, Guoyou

    1996-10-01

    This paper describes theory and performance of a self- developed IR phase-shifting digital interferometer which uses a CO2 laser as light source, this instrument comprises of a Fizeau interferometer whose aperture reaches (Phi) 250mm with accuracy better than (lambda) /50, and a Twyman spherical interferometer. Using piezoelectric transducer to shift reference mirror, phase measurement interferometry can be carried out as well as the temperature modulation of PEV target. A series of software packages used as wavefront fitting, image quality evaluation, are incorporated into the instrument. With the help of microcomputer, this interferometric system can measure refractive-index homogeneity of IR transmitting materials, wavefront error of IR optical system and surface quality of rough surface etc., which can all be shown by detailed data of optical path difference, vivid 2D contour and 3D surface.

  3. Is the Lamb shift chemically significant?

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.; Bauschlicher, Charles W., Jr.; Schwenke, David W.; Pyykko, Pekka; Arnold, James (Technical Monitor)

    2001-01-01

    The contribution of the Lamb shift to the atomization energies of some prototype molecules, BF3, AlF3, and GaF3, is estimated by a perturbation procedure. It is found to be in the range of 3-5% of the one-electron scalar relativistic contribution to the atomization energy. The maximum absolute value is 0.2 kcal/mol for GaF3. These sample calculations indicate that the Lamb shift is probably small enough to be neglected for energetics of molecules containing light atoms if the target accuracy is 1 kcal/mol, but for higher accuracy calculations and for molecules containing heavy elements it must be considered.

  4. Evolutionary shift dynamics on a cycle

    PubMed Central

    Allen, Benjamin; Nowak, Martin A.

    2012-01-01

    We present a new model of evolutionary dynamics in one-dimensional space. Individuals are arranged on a cycle. When a new offspring is born, another individual dies and the rest shift around the cycle to make room. This rule, which is inspired by spatial evolution in somatic tissue and microbial colonies, has the remarkable property that, in the limit of large population size, evolution acts to maximize the payoff of the whole population. Therefore, social dilemmas, in which some individuals benefit at the expense of others, are resolved. We demonstrate this principle for both discrete and continuous games. We also discuss extensions of our model to other one-dimensional spatial configurations. We conclude that shift dynamics in one dimension is an unusually strong promoter of cooperative behavior. PMID:22814475

  5. Geometric phase shifts in biological oscillators.

    PubMed

    Tourigny, David S

    2014-08-21

    Many intracellular processes continue to oscillate during the cell cycle. Although it is not well-understood how they are affected by discontinuities in the cellular environment, the general assumption is that oscillations remain robust provided the period of cell divisions is much larger than the period of the oscillator. Here, I will show that under these conditions a cell will in fact have to correct for an additional quantity added to the phase of oscillation upon every repetition of the cell cycle. The resulting phase shift is an analogue of the geometric phase, a curious entity first discovered in quantum mechanics. In this letter, I will discuss the theory of the geometric phase shift and demonstrate its relevance to biological oscillations. PMID:24769251

  6. Phase-Shifting Zernike Interferometer Wavefront Sensor

    NASA Technical Reports Server (NTRS)

    Wallace, J. Kent; Rao, Shanti; Jensen-Clemb, Rebecca M.; Serabyn, Gene

    2011-01-01

    The canonical Zernike phase-contrast technique1,2,3,4 transforms a phase object in one plane into an intensity object in the conjugate plane. This is done by applying a static pi/2 phase shift to the central core (approx. lambda/D) of the PSF which is intermediate between the input and output planes. Here we present a new architecture for this sensor. First, the optical system is simple and all reflective. Second, the phase shift in the central core of the PSF is dynamic and or arbitrary size. This common-path, all-reflective design makes it minimally sensitive to vibration, polarization and wavelength. We review the theory of operation, describe the optical system, summarize numerical simulations and sensitivities and review results from a laboratory demonstration of this novel instrument

  7. Phase-Shifting Zernike Interferometer Wavefront Sensor

    NASA Technical Reports Server (NTRS)

    Wallace, J. Kent; Rao, Shanti; Jensen-Clem, Rebecca M.

    2011-01-01

    The canonical Zernike phase-contrast technique transforms a phase object in one plane into an intensity object in the conjugate plane. This is done by applying a static pi/2 phase shift to the central core (approx. lambda/diameter) of the PSF which is intermediate between the input and output plane. Here we present a new architecture for this sensor. First, the optical system is simple and all reflective, and second the phase shift in the central core of the PSF is dynamic and can be made arbitrarily large. This common-path, all-reflective design makes it minimally sensitive to vibration, polarization and wavelength. We review the theory of operation, describe the optical system, summarize numerical simulations and sensitivities and review results from a laboratory demonstration of this novel instrument.

  8. Stabilizing windings for tilting and shifting modes

    DOEpatents

    Jardin, Stephen C. (Princeton, NJ); Christensen, Uffe R. (Princeton, NJ)

    1984-01-01

    This invention relates to passive conducting loops for stabilizing a plasma ring against unstable tilting and/or shifting modes. To this end, for example, plasma ring in a spheromak is stabilized by a set of four figure-8 shaped loops having one pair on one side of the plasma and one pair on the other side with each pair comprising two loops whose axes are transverse to each other.

  9. Phase shift of stepwise reflectivity profile mirrors

    SciTech Connect

    Perrone, M.R.,; Flori, D.; Piegari, A.; Scaglione, S.,

    1997-04-01

    The effects of phase shifts in laser beams transmitted by output couplers with a stepwise reflectivity profile have been experimentally investigated with a XeCl laser. It is shown that the phase distortions of the cavity output coupler affect significantly the propagation properties of the output laser beam but do not affect the output beam energy and pulse width. {copyright} 1997 Optical Society of America

  10. Exploring Insight: Focus on Shifts of Attention

    ERIC Educational Resources Information Center

    Palatnik, Alik; Koichu, Boris

    2015-01-01

    The paper presents and analyses a sequence of events that preceded an insight solution to a challenging problem in the context of numerical sequences. A three­week long solution process by a pair of ninth­-grade students is analysed by means of the theory of shifts of attention. The goal for this article is to reveal the potential of this theory…

  11. Frontal sinus fractures: a conservative shift.

    PubMed

    Weathers, William M; Wolfswinkel, Erik M; Hatef, Daniel A; Lee, Edward I; Brown, Rodger H; Hollier, Larry H

    2013-09-01

    This article reflects on the changing management of frontal sinus fractures. Severity of these injuries has decreased tremendously since the universal adoption of seat belts and air bags. Recently, there has been a shift from aggressive surgical management to more conservative management strategies, some forgoing surgery all together. New technologies, such as bioabsorbable plates and endoscopic sinus surgery, are leading the way in improved surgical management strategies and offer promising alternatives to the more traditional approaches. PMID:24436753

  12. Collisionally induced atomic clock shifts and correlations

    SciTech Connect

    Band, Y. B.; Osherov, I.

    2011-07-15

    We develop a formalism to incorporate exchange symmetry considerations into the calculation of collisional frequency shifts for atomic clocks using a density-matrix formalism. The formalism is developed for both fermionic and bosonic atomic clocks. Numerical results for a finite-temperature {sup 87}Sr {sup 1}S{sub 0} (F=9/2) atomic clock in a magic wavelength optical lattice are presented.

  13. Real-time phase shift interference microscopy.

    PubMed

    Safrani, Avner; Abdulhalim, Ibrahim

    2014-09-01

    A real-time phase shift interference microscopy system is presented using a polarization-based Linnik interferometer operating with three synchronized, phase-masked, parallel detectors. Using this method, several important applications that require high speed and accuracy, such as dynamic focusing control, tilt measurement, submicrometer roughness measurement, and 3D profiling of fine structures, are demonstrated in 50 volumes per second and with 2 nm height repeatability. PMID:25166114

  14. All fiber interferometric Bragg peak shift demodulation

    NASA Astrophysics Data System (ADS)

    Stepien, Karol; J?wik, Michalina; Tenderenda, Tadeusz; Nasilowski, Tomasz

    2015-12-01

    In this paper we present the idea and test results of an all-fiber unbalanced Mach-Zehnder interferometer for fiber Bragg grating shift demodulation. The interferometer design allows to monitor Bragg wavelength changes (caused by temperature or strain variations) as changes of intensity on the output detector. Furthermore the construction is cost-effective and based on simple optoelectronic components, which makes the solution attractive for application as a low cost fiber Bragg grating interrogator.

  15. Nuclear waste vitrification efficiency: cold cap reactions

    SciTech Connect

    Hrma, Pavel R.; Kruger, Albert A.; Pokorny, Richard

    2012-12-15

    The cost and schedule of nuclear waste treatment and immobilization are greatly affected by the rate of glass production. Various factors influence the performance of a waste-glass melter. One of the most significant, and also one of the least understood, is the process of batch melting. Studies are being conducted to gain fundamental understanding of the batch reactions, particularly those that influence the rate of melting, and models are being developed to link batch makeup and melter operation to the melting rate. Batch melting takes place within the cold cap, i.e., a batch layer floating on the surface of molten glass. The conversion of batch to glass consists of various chemical reactions, phase transitions, and diffusion-controlled processes. These include water evaporation (slurry feed contains as high as 60% water), gas evolution, the melting of salts, the formation of borate melt, reactions of borate melt with molten salts and with amorphous oxides (Fe2O3 and Al2O3), the formation of intermediate crystalline phases, the formation of a continuous glass-forming melt, the growth and collapse of primary foam, and the dissolution of residual solids. To this list we also need to add the formation of secondary foam that originates from molten glass but accumulates on the bottom of the cold cap. This study presents relevant data obtained for a high-level-waste melter feed and introduces a one-dimensional (1D) mathematical model of the cold cap as a step toward an advanced three-dimensional (3D) version for a complete model of the waste glass melter. The 1D model describes the batch-to-glass conversion within the cold cap as it progresses in a vertical direction. With constitutive equations and key parameters based on measured data, and simplified boundary conditions on the cold-cap interfaces with the glass melt and the plenum space of the melter, the model provides sensitivity analysis of the response of the cold cap to the batch makeup and melter conditions. The model demonstrates that batch foaming has a decisive influence on the rate of melting. Understanding the dynamics of the foam layer at the bottom of the cold cap and the heat transfer through it appears crucial for a reliable prediction of the rate of melting as a function of the melter-feed makeup and melter operation parameters. Although the study is focused on a batch for waste vitrification, the authors expect that the outcome will also be relevant for commercial glass melting.

  16. NUCLEAR WASTE VITRIFICATION EFFICIENCY COLD CAP REACTIONS

    SciTech Connect

    KRUGER AA; HRMA PR; POKORNY R

    2011-07-29

    The cost and schedule of nuclear waste treatment and immobilization are greatly affected by the rate of glass production. Various factors influence the performance of a waste-glass melter. One of the most significant, and also one of the least understood, is the process of batch melting. Studies are being conducted to gain fundamental understanding of the batch reactions, particularly those that influence the rate of melting, and models are being developed to link batch makeup and melter operation to the melting rate. Batch melting takes place within the cold cap, i.e., a batch layer floating on the surface of molten glass. The conversion of batch to glass consists of various chemical reactions, phase transitions, and diffusion-controlled processes. These include water evaporation (slurry feed contains as high as 60% water), gas evolution, the melting of salts, the formation of borate melt, reactions of borate melt with molten salts and with amorphous oxides (Fe{sub 2}O{sub 3} and Al{sub 2}O{sub 3}), the formation of intermediate crystalline phases, the formation of a continuous glass-forming melt, the growth and collapse of primary foam, and the dissolution of residual solids. To this list we also need to add the formation of secondary foam that originates from molten glass but accumulates on the bottom of the cold cap. This study presents relevant data obtained for a high-level-waste melter feed and introduces a one-dimensional (1D) mathematical model of the cold cap as a step toward an advanced three-dimensional (3D) version for a complete model of the waste glass melter. The 1D model describes the batch-to-glass conversion within the cold cap as it progresses in a vertical direction. With constitutive equations and key parameters based on measured data, and simplified boundary conditions on the cold-cap interfaces with the glass melt and the plenum space of the melter, the model provides sensitivity analysis of the response of the cold cap to the batch makeup and melter conditions. The model demonstrates that batch foaming has a decisive influence on the rate of melting. Understanding the dynamics of the foam layer at the bottom of the cold cap and the heat transfer through it appears crucial for a reliable prediction of the rate of melting as a function of the melter-feed makeup and melter operation parameters. Although the study is focused on a batch for waste vitrification, the authors expect that the outcome will also be relevant for commercial glass melting.

  17. Theoretical isotope shifts in neutral barium

    NASA Astrophysics Data System (ADS)

    Naz, C.; Li, J. G.; Godefroid, M.

    2015-03-01

    The present work deals with a set of problems in isotope shifts of neutral barium spectral lines. Some well-known transitions (6 s2 1S0-6 s 6 p 1,3P1o and 6 s2 1S0-6 p2 3P0) are investigated. Values of the changes in the nuclear mean-square charge radius are deduced from the available experimental isotope shifts using our ab initio electronic factors. The three sets {? A ,A'} obtained from these lines are consistent with each other. The combination of the available nuclear mean-square radii with our electronic factors for the 6 s 5 d 3D1 ,2-6 s 6 p 1P1o transitions produces isotope shift values in conflict with the laser spectroscopy measurements of U. Dammalapati et al. [Eur. Phys. J. D 53, 1 (2009), 10.1140/epjd/e2009-00076-x].

  18. Leaf morphology shift linked to climate change.

    PubMed

    Guerin, Greg R; Wen, Haixia; Lowe, Andrew J

    2012-10-23

    Climate change is driving adaptive shifts within species, but research on plants has been focused on phenology. Leaf morphology has demonstrated links with climate and varies within species along climate gradients. We predicted that, given within-species variation along a climate gradient, a morphological shift should have occurred over time due to climate change. We tested this prediction, taking advantage of latitudinal and altitudinal variations within the Adelaide Geosyncline region, South Australia, historical herbarium specimens (n = 255) and field sampling (n = 274). Leaf width in the study taxon, Dodonaea viscosa subsp. angustissima, was negatively correlated with latitude regionally, and leaf area was negatively correlated with altitude locally. Analysis of herbarium specimens revealed a 2 mm decrease in leaf width (total range 1-9 mm) over 127 years across the region. The results are consistent with a morphological response to contemporary climate change. We conclude that leaf width is linked to maximum temperature regionally (latitude gradient) and leaf area to minimum temperature locally (altitude gradient). These data indicate a morphological shift consistent with a direct response to climate change and could inform provenance selection for restoration with further investigation of the genetic basis and adaptive significance of observed variation. PMID:22764114

  19. Microscopic Theory of the Knight Shift

    NASA Astrophysics Data System (ADS)

    Hall, Bianca

    2015-03-01

    The Knight shift has been used for detecting possible parallel spin states, such as Sr2RuO4. However an improved theory of the Knight shift is needed to explain anomalies that have been found in a variety of superconductors below the superconducting transition temperature. The standard model includes the Zeeman and hyperfine interactions of the magnetic field and the electron-electron pairing interaction necessary for superconductivity. The new model now includes a term based on the Anderson model of local moments in metals. The local electron states in the original Anderson model now correspond to local atomic electron orbitals. When these orbital energies are singly occupied and close to the Fermi energy, the spins of the electrons can interact with the nuclear spins and the spins of the electrons in the conducting bands. Additionally, the paths of the electrons in the conduction bands depend on the direction and magnitude of the magnetic induction. With these new terms included, this model has the potential to describe the anomalous behavior seen in Knight shift measurements on unconventional superconductors.

  20. Aircraft noise-induced temporary threshold shift.

    PubMed

    Wu, Y X; Liu, X L; Wang, B G; Wang, X Y

    1989-03-01

    Audiograms were taken on 20 young men before and immediately after exposure to Fighter-6 ground running-up noise, and their course of recovery was followed. The sound levels at the engine hatch were 117-128 dB(A). The noise-induced temporary threshold shift was more than 13 dB. The maximum threshold shift occurred at 4 kHz. The shift in the low and speech frequencies recovers more rapidly and is completed in 30 min, whereas that in the high-frequency range recovers much more slowly, not returning to normal until 24 h later. High-frequency hearing loss is at risk in groundcrew. In order to prevent hearing damage, they ought to wear ear-protectors. We discovered that the V-shaped depression was not at 4 kHz but at 6 kHz. The former view concerning the pathogenesis of "4 kHz depression", therefore, is open to question. This interesting subject warrants further study. PMID:2712804

  1. Projecting the risk of future climate shifts

    NASA Astrophysics Data System (ADS)

    Enfield, David B.; Cid-Serrano, Luis

    2006-06-01

    Recent research has shown that decadal-to-multidecadal (D2M) climate variability is associated with environmental changes that have important consequences for human activities, such as public health, water availability, frequency of hurricanes, and so forth. As scientists, how do we convert these relationships into decision support products useful to water managers, insurance actuaries, and others, whose principal interest lies in knowing when future climate regime shifts will likely occur that affect long-horizon decisions? Unfortunately, numerical models are far from being able to make deterministic predictions for future D2M climate shifts. However, the recent development of paleoclimate reconstructions of the Atlantic Multidecadal Oscillation (AMO) (Gray et al., [2004]) and Pacific Decadal Oscillation (PDO); (MacDonald and Case, [2005]) give us a viable alternative: to estimate probability distribution functions from long climate index series that allow us to calculate the probability of future D2M regime shifts. In this paper, we show how probabilistic projections can be developed for a specific climate mode - the AMO as represented by the Gray et al. ([2004]) tree-ring reconstruction. The methods are robust and can be applied to any D2M climate mode for which a sufficiently long index series exists, as well as to the growing body of paleo-proxy reconstructions that have become available. The target index need not be a paleo-proxy calibrated against a climate index; it may profitably be calibrated against a specific resource of interest, such as stream flow or lake levels.

  2. Set Shifting Training with Categorization Tasks

    PubMed Central

    Soveri, Anna; Waris, Otto; Laine, Matti

    2013-01-01

    The very few cognitive training studies targeting an important executive function, set shifting, have reported performance improvements that also generalized to untrained tasks. The present randomized controlled trial extends set shifting training research by comparing previously used cued training with uncued training. A computerized adaptation of the Wisconsin Card Sorting Test was utilized as the training task in a pretest-posttest experimental design involving three groups of university students. One group received uncued training (n?=?14), another received cued training (n?=?14) and the control group (n?=?14) only participated in pre- and posttests. The uncued training group showed posttraining performance increases on their training task, but neither training group showed statistically significant transfer effects. Nevertheless, comparison of effect sizes for transfer effects indicated that our results did not differ significantly from the previous studies. Our results suggest that the cognitive effects of computerized set shifting training are mostly task-specific, and would preclude any robust generalization effects with this training. PMID:24324717

  3. Is there a shift to active nanostructures?

    PubMed Central

    Youtie, Jan; Porter, Alan L.; Shapira, Philip

    2009-01-01

    It has been suggested that an important transition in the long-run trajectory of nanotechnology development is a shift from passive to active nanostructures. Such a shift could present different or increased societal impacts and require new approaches for risk assessment. An active nanostructure changes or evolves its state during its operation, according to the National Science Foundations (2006) Active Nanostructures and Nanosystems grant solicitation. Active nanostructure examples include nanoelectromechanical systems (NEMS), nanomachines, self-healing materials, targeted drugs and chemicals, energy storage devices, and sensors. This article considers two questions: (a) Is there a shift to active nanostructures? (b) How can we characterize the prototypical areas into which active nanostructures may emerge? We build upon the NSF definition of active nanostructures to develop a research publication search strategy, with a particular intent to distinguish between passive and active nanotechnologies. We perform bibliometric analyses and describe the main publication trends from 1995 to 2008. We then describe the prototypes of research that emerge based on reading the abstracts and review papers encountered in our search. Preliminary results suggest that there is a sharp rise in active nanostructures publications in 2006, and this rise is maintained in 2007 and through to early 2008. We present a typology that can be used to describe the kind of active nanostructures that may be commercialized and regulated in the future. PMID:21170117

  4. Atomic clocks with suppressed blackbody radiation shift.

    PubMed

    Yudin, V I; Taichenachev, A V; Okhapkin, M V; Bagayev, S N; Tamm, Chr; Peik, E; Huntemann, N; Mehlstubler, T E; Riehle, F

    2011-07-15

    We develop a concept of atomic clocks where the blackbody radiation shift and its fluctuations can be suppressed by 1-3 orders of magnitude independent of the environmental temperature. The suppression is based on the fact that in a system with two accessible clock transitions (with frequencies ?1 and ?2) which are exposed to the same thermal environment, there exists a "synthetic" frequency ?(syn) ? (?1 - ?12?2) largely immune to the blackbody radiation shift. For example, in the case of 171Yb+ it is possible to create a synthetic-frequency-based clock in which the fractional blackbody radiation shift can be suppressed to the level of 10(-18) in a broad interval near room temperature (30015??K). We also propose a realization of our method with the use of an optical frequency comb generator stabilized to both frequencies ?1 and ?2, where the frequency ?(syn) is generated as one of the components of the comb spectrum. PMID:21838344

  5. Experience with the shift technical advisor position

    SciTech Connect

    Melber, B.D.; Olson, J.; Schreiber, R.E.; Winges, L.

    1984-03-01

    The provision of engineering expertise on shift at commercial nuclear power plants has mainly taken the form of the Shift Technical Advisor (STA). This person, acting in a capacity that is part engineer and part operator, is expected to advise the operations crew in the event of an emergency and review plant operating experience during normal circumstances. The position was mandated by the Nuclear Regulatory Commission following the incident at Three Mile Island. This report expands on a growing body of knowledge regarding the effectiveness of the STA. The new data presented here come from interviews with plant personnel and utility officials from nine sites. Researchers from the Pacific Northwest Laboratory (PNL) interviewed plant personnel, including the STA and immediate management, the shift supervisor and management, the training department, and ancillary staff, all of whom affect the intended performance of the STA. The conclusions of the report are that the design of the STA position results in limited contribution during emergencies; more comprehensive ways should be sought to provide the variety and specificity of engineering expertise needed during such times.

  6. Diamagnetic shifts in atomic hyperfine structure

    SciTech Connect

    Lipson, S.J.

    1986-01-01

    A series of precision measurements of the hyperfine structure of the 5/sup 2/S/sub 1/2/ ground state of two isotopes of atomic rubidium in magnetic fields of up to 8 T was made using a laser optical-pumping technique. Observed departures from the predictions of the Breit-Rabi formula include the first measurement of a magnetically induced quadrupole hyperfine shift. A field dependence of the effective value of the nuclear-to-electronic g-factor ratio g/sub I//g/sub J/ was revealed, and the previous observation of a diamagnetic shift in dipole hyperfine structure in /sup 85/Rb was confirmed and extended to /sup 87/Rb. In order to distinguish among these effects, all of the ..delta..m/sub I/ = +/- 1 nuclear Zeeman transitions in both /sup 85/Rb and /sup 87/Rb were measured at each field. Four evacuated, wax-coated sample cells were used, containing natural isotopic abundance rubidium vapor. Perturbation theory is used to examine the effects of an external magnetic field on the ground-state hyperfine structure of an alkali atom. A Hamiltonian is developed and evaluated to yield a modified Breit-Rabi formula which provides an excellent fit to the experimental data. Approximate calculations performed using this model are in good agreement with the dipole and quadruple results. The shift in the g-factor ratio, on the other hand, is much larger than predicted.

  7. Two-stage coal liquefaction without gas-phase hydrogen

    DOEpatents

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  8. Regime shifts in the anthropocene: drivers, risks, and resilience.

    PubMed

    Rocha, Juan Carlos; Peterson, Garry D; Biggs, Reinette

    2015-01-01

    Many ecosystems can experience regime shifts: surprising, large and persistent changes in the function and structure of ecosystems. Assessing whether continued global change will lead to further regime shifts, or has the potential to trigger cascading regime shifts has been a central question in global change policy. Addressing this issue has, however, been hampered by the focus of regime shift research on specific cases and types of regime shifts. To systematically assess the global risk of regime shifts we conducted a comparative analysis of 25 generic types of regime shifts across marine, terrestrial and polar systems; identifying their drivers, and impacts on ecosystem services. Our results show that the drivers of regime shifts are diverse and co-occur strongly, which suggests that continued global change can be expected to synchronously increase the risk of multiple regime shifts. Furthermore, many regime shift drivers are related to climate change and food production, whose links to the continued expansion of human activities makes them difficult to limit. Because many regime shifts can amplify the drivers of other regime shifts, continued global change can also be expected to increase the risk of cascading regime shifts. Nevertheless, the variety of scales at which regime shift drivers operate provides opportunities for reducing the risk of many types of regime shifts by addressing local or regional drivers, even in the absence of rapid reduction of global drivers. PMID:26267896

  9. Regime Shifts in the Anthropocene: Drivers, Risks, and Resilience

    PubMed Central

    Rocha, Juan Carlos; Peterson, Garry D.; Biggs, Reinette

    2015-01-01

    Many ecosystems can experience regime shifts: surprising, large and persistent changes in the function and structure of ecosystems. Assessing whether continued global change will lead to further regime shifts, or has the potential to trigger cascading regime shifts has been a central question in global change policy. Addressing this issue has, however, been hampered by the focus of regime shift research on specific cases and types of regime shifts. To systematically assess the global risk of regime shifts we conducted a comparative analysis of 25 generic types of regime shifts across marine, terrestrial and polar systems; identifying their drivers, and impacts on ecosystem services. Our results show that the drivers of regime shifts are diverse and co-occur strongly, which suggests that continued global change can be expected to synchronously increase the risk of multiple regime shifts. Furthermore, many regime shift drivers are related to climate change and food production, whose links to the continued expansion of human activities makes them difficult to limit. Because many regime shifts can amplify the drivers of other regime shifts, continued global change can also be expected to increase the risk of cascading regime shifts. Nevertheless, the variety of scales at which regime shift drivers operate provides opportunities for reducing the risk of many types of regime shifts by addressing local or regional drivers, even in the absence of rapid reduction of global drivers. PMID:26267896

  10. Pterandra pyroidea: a case of pollination shift within Neotropical Malpighiaceae

    PubMed Central

    Cappellari, Simone C.; Haleem, Muhammad A.; Marsaioli, Anita J.; Tidon, Rosana; Simpson, Beryl B.

    2011-01-01

    Background and Aims Most Neotropical species of Malpighiaceae produce floral fatty oils in calyx glands to attract pollinating oil-collecting bees, which depend on this resource for reproduction. This specialized type of pollination system tends to be lost in members of the family that occur outside the geographic distribution (e.g. Africa) of Neotropical oil-collecting bees. This study focused on the pollination ecology, chemical ecology and reproductive biology of an oil flower species, Pterandra pyroidea (Malpighiaceae) from the Brazilian Cerrado. Populations of this species consist of plants with oil-secreting (glandular) flowers, plants with non-oil-secreting flowers (eglandular) or a mix of both plant types. This study specifically aims to clarify the role of eglandular morphs in this species. Methods Data on pollinators were recorded by in situ observations. Breeding system experiments were conducted by isolating inflorescences and by enzymatic reactions. Floral resources, pollen and floral oils offered by this species were analysed by staining and a combination of various spectroscopic methods. Key Results Eglandular flowers of P. pyroidea do not act as mimics of their oil-producing conspecifics to attract pollinators. Instead, both oil-producing and oil-free flowers depend on pollen-collecting bees for reproduction, and their main pollinators are bumble-bees. Floral oils produced by glandular flowers are less complex than those described in closely related genera. Conclusions Eglandular flowers represent a shift in the pollination system in which oil is being lost and pollen is becoming the main reward of P. pyroidea flowers. Pollination shifts of this kind have hitherto not been demonstrated empirically within Neotropical Malpighiaceae and this species exhibits an unusual transition from a specialized towards a generalized pollination system in an area considered the hotspot of oil-collecting bee diversity in the Neotropics. Transitions of this type provide an opportunity to study ongoing evolutionary mechanisms that promote the persistence of species previously involved in specialized mutualistic relationships. PMID:21610210

  11. Pressure Shift and Gravitational RedShift of Balmer Lines in White Dwarfs: Rediscussion

    NASA Astrophysics Data System (ADS)

    Halenka, Jacek; Olchawa, Wieslaw; Madej, Jerzy; Grabowski, Boleslaw

    2015-08-01

    The Stark-induced shift and asymmetry, the so-called pressure shift (PS) of H? and H? Balmer lines in spectra of DA white dwarfs (WDs), have been examined in detail as masking effects in measurements of the gravitational redshift in WDs. The results are compared with our earlier ones from a quarter of a century ago. In these earlier papers, the standard, symmetrical Stark line profiles, as a dominant constituent of the Balmer line profiles but shifted as a whole by the PS effect, were applied to all spectrally active layers of the WD atmosphere. At present, in each of the WD layers, the Stark line profiles (especially of H?) are inherently asymmetrical and shifted due to the effects of strong inhomogeneity of the perturbing fields in plasma. To calculate the Stark line profiles in successive layers of the WD atmosphere we used the modified Full Computer Simulation Method, able to take adequately into account the complexity of local elementary quantum processes in plasma. In the case of the H? line, the present value of Stark-induced shift of the synthetic H? line profile is about half the previous one and it is negligible in comparison with the gravitational redshift. In the case of the H? line, the present value of Stark-induced shift of the synthetic H? line profile is about twice the previous one. The source of this extra shift is the asymmetry of H? peaks. In memory of Jan Jerzy Kubikowski (1927-1968)one of the pioneers of plasma in astrophysics.

  12. Eye gaze triggers reflexive attention shifts: evidence from lateralised ERPs.

    PubMed

    Feng, Qing; Zhang, Xuemin

    2014-11-17

    Social cues, such as another individual?s eye gaze, provide valuable information regarding the actions and intentions of others. Previous studies have suggested that seeing another?s gaze automatically orients one?s attention in the gaze direction. In this event-related potential (ERP) study, a spatial cuing paradigm was combined with a visual search task in which targets were defined by feature conjunctions in order to eliminate effects of target/distractor salience. Participants viewed centrally presented faces with neutral expressions in which eyes looked to the left or right. The participants? task was to identify a target object (with or without gap) defined by a combination of shape and orientation, which appeared in either the same (cued) or the opposite (uncued) location as the direction of the eye gaze. There was behavioural evidence of a gaze congruency effect, as reaction times (RTs) were faster when the eyes looked towards the target rather than away from the location of the target. The ERP data indicated the presence of significant gaze-congruent early directing attention negativity (EDAN) and anterior directing attention negativity (ADAN), reflecting attention shifts to the cued location in advance of the target presentation. ERP data did not show evidence of later orienting of attention triggered by gaze cues in the late attention-directing attention positivity (LDAP) at posterior sites. The results disclosed the neural response during reflexive attention shifting triggered by gazes and ascertained the relationship among EDAN, ADAN, LDAP and gaze-elicited attention shifts. After the presentation of the target array without salient stimuli, the presence of the N2-posterior-contralateral (N2pc) in the cued trials and the absence in the uncued trials further supported that attention had been directed to the possible target location prior to the target onset. The ERPs in response to the target array also extend our understanding of the neural response that orients spatial attention by providing valuable information about the temporal dynamics without the influence of salience. PMID:25241361

  13. Green binary and phase shifting mask

    NASA Astrophysics Data System (ADS)

    Shy, S. L.; Hong, Chao-Sin; Wu, Cheng-San; Chen, S. J.; Wu, Hung-Yu; Ting, Yung-Chiang

    2009-12-01

    SixNy/Ni thin film green mask blanks were developed , and are now going to be used to replace general chromium film used for binary mask as well as to replace molydium silicide embedded material for AttPSM for I-line (365 nm), KrF (248 nm), ArF (193 nm) and Contact/Proximity lithography. A bilayer structure of a 1 nm thick opaque, conductive nickel layer and a SixNy layer is proposed for binary and phase-shifting mask. With the good controlling of plasma CVD of SixNy under silane (50 sccm), ammonia (5 sccm) and nitrogen (100 sccm), the pressure is 250 mTorr. and RF frequency 13.56 MHz and power 50 W. SixNy has enough deposition latitude to meet the requirements as an embedded layer for required phase shift 180 degree, and the T% in 193, 248 and 365 nm can be adjusted between 2% to 20% for binary and phase shifting mask usage. Ni can be deposited by E-gun, its sheet resistance Rs is less than 1.435 k?/square. Jeol e-beam system and I-line stepper are used to evaluate these thin film green mask blanks, feature size less than 200 nm half pitch pattern and 0.558 ?m pitch contact hole can be printed. Transmission spectrums of various thickness of SixNy film are inspected by using UV spectrometer and FTIR. Optical constants of the SixNy film are measured by n & k meter and surface roughness is inspected by using Atomic Force Microscope (AFM).

  14. Thermotolerance of apple tree leaves probed by chlorophyll a fluorescence and modulated 820nm reflection during seasonal shift.

    PubMed

    Duan, Ying; Zhang, Mengxia; Gao, Jin; Li, Pengmin; Goltsev, Vasilij; Ma, Fengwang

    2015-11-01

    During the seasonal shift from June to August, air temperatures increase. To explore how apple trees improve their thermotolerance during this shift, we examined the photochemical reaction capacity of apple tree leaves by simultaneous measurement of prompt chlorophyll fluorescence, delayed chlorophyll fluorescence, and modulated 820nm reflection at varying temperatures. It was found that the reaction centers and antennae of photosystem II (PSII) and photosystem I (PSI), the donor side of PSII, the electron transfer capacity from QA to QB, and the reoxidation capacity of plastoquinol were all sensitive to heat stress, particularly in June. As the season shifted, apple tree leaves improved in thermotolerance. Interestingly, the acclimation to seasonal shift enhanced the thermotolerance of PSII and PSI reaction centers more than that of their antennae, and the activity of PSII more than that of PSI. This may be a strategy for plant adaptation to changes in environmental temperatures. In addition, results from prompt and delayed fluorescence, as well as modulated 820nm reflection corroborate each other. We suggest that the simultaneous measurement of the three independent signals may provide more information on thermal acclimation mechanisms of photochemical reactions in plant leaves. PMID:26298695

  15. Polarization phase shifting dispersed fringe sensor.

    PubMed

    Olczak, Gene

    2012-02-13

    The dispersed fringe sensor (DFS) has been demonstrated as an effective means of measuring mirror segment piston error for telescopes with primary mirror apertures below 10 meters. With larger proposed telescopes such as The Thirty Meter Telescope (TMT) and The European Large Telescope (ELT) including ever more segments, there is a need for improvement in the co-phasing capability for segmented primary mirrors. In this paper a novel DFS that employs polarization phase shifting technology is introduced. This novel technology provides system designers and engineers with a new tool to extend the dynamic range of a DFS. PMID:22418128

  16. Light shift reduction in atomic clocks

    NASA Astrophysics Data System (ADS)

    Affolderbach, C.; Andreeva, Ch.; Cartaleva, Stefka S.; Karaulanov, Todor S.; Mileti, Gaetano; Slavov, Dimitar G.

    2004-06-01

    In this paper we present a detailed description of a method for reduction of the light shift in laser-pumped gas-cell atomic clocks. The method consists in using a multi-frequency optical pumping obtained through frequency modulation of the laser spectrum with precisely controllable parameters. Experimental evidence of a strong reduction of the frequency dependence of the LS in an optical pumping Rb gas-cell clock is demonstrated in a large frequency interval, which is in a very good agreement with the numerical estimations reported.

  17. A tentative explanation of cosmological red shift

    NASA Technical Reports Server (NTRS)

    Chang, T.; Torr, D. G.

    1990-01-01

    The authors suggest a possible alternative explanation of cosmological red shift. They consider that there exists a background field in the universe, and that light (the photon) has an extremely weak interaction with this background, and as result, experiences an energy loss. By analogy with damped oscillations, the authors introduce a dumping term with the first derivative with respect to time in the wave equation. The solution yields a linearly reduced frequency of the light with travel distance. The purpose of this exercise is to demonstrate how a simple alternative interpretation of the Hubble relation can be generated.

  18. Pendulum Shifts, Context, Error, and Personal Accountability

    SciTech Connect

    Harold Blackman; Oren Hester

    2011-09-01

    This paper describes a series of tools that were developed to achieve a balance in under-standing LOWs and the human component of events (including accountability) as the INL continues its shift to a learning culture where people report, are accountable and interested in making a positive difference - and want to report because information is handled correctly and the result benefits both the reporting individual and the organization. We present our model for understanding these interrelationships; the initiatives that were undertaken to improve overall performance.

  19. Resonance-shifting luminescent solar concentrators

    DOEpatents

    Giebink, Noel Christopher; Wiederrecht, Gary P; Wasielewski, Michael R

    2014-09-23

    An optical system and method to overcome luminescent solar concentrator inefficiencies by resonance-shifting, in which sharply directed emission from a bi-layer cavity into a glass substrate returns to interact with the cavity off-resonance at each subsequent reflection, significantly reducing reabsorption loss en route to the edges. In one embodiment, the system comprises a luminescent solar concentrator comprising a transparent substrate, a luminescent film having a variable thickness; and a low refractive index layer disposed between the transparent substrate and the luminescent film.

  20. Suprachiasmatic stimulation phase shifts rodent circadian rhythms.

    PubMed

    Rusak, B; Groos, G

    1982-03-12

    The integrity of the suprachiasmatic nuclei (SCN) of the hypothalamus is essential to the expression of normal circadian rhythms in rodents. Electrical stimulation of the SCN caused phase shifts and period changes in the freerunning feeding rhythms of rats and activity rhythms of hamsters. The phase response curve for SCN stimulation appears to parallel that for light pulses. These findings strengthen the hypothesis derived from lesion studies that the SCN are the dominant light-entrained oscillators in the rodent circadian system. PMID:7063851

  1. Auroral Substorms: Paradigm Shifts in Research

    NASA Astrophysics Data System (ADS)

    Akasofu, Syun-Ichi

    2010-08-01

    The study of scientific advancement is the study of evolving thought. Disciplines progress as old prevailing theoretical ideas are toppled by new ones, one after another. Provided that new ideas can be independently verified, scientists at any level can greatly contribute to their field. Though space weather is a young field, it has been riddled with such paradigm shifts. As a scientist who has worked on auroral and magnetospheric substorm research during several of these moments, I have witnessed firsthand how diligence, patience, and creativity combine to advance science.

  2. Solar Doppler shifts - Sources of continuous spectra

    NASA Technical Reports Server (NTRS)

    Duvall, T. L., Jr.; Harvey, J. W.

    1986-01-01

    Oscillation observations can be used to study nonoscillatory solar phenomena that exhibit Doppler shifts. The paper discusses several effects of these phenomena and their associated temporal and spatial power spectra: (1) they limit the signal-to-noise ratio and sometimes detectability of oscillation modes; (2) there is the potential for better understanding and/or detection of solar phenomena; (3) large-scale convection may spatially modulate oscillation modes, leading to a continuous background spectrum; and (4) in regions of the spectrum where the resolution to separate modes is lacking one can determine upper limits for the integrated effects of modes.

  3. Ambiguity produces attention shifts in category learning.

    PubMed

    Vadillo, Miguel A; Orgaz, Cristina; Luque, David; Nelson, James Byron

    2016-04-01

    It has been suggested that people and nonhuman animals protect their knowledge from interference by shifting attention toward the context when presented with information that contradicts their previous beliefs. Despite that suggestion, no studies have directly measured changes in attention while participants are exposed to an interference treatment. In the present experiments, we adapted a dot-probe task to track participants' attention to cues and contexts while they were completing a simple category learning task. The results support the hypothesis that interference produces a change in the allocation of attention to cues and contexts. PMID:26980780

  4. NMR characterization of cellulose acetate: chemical shift assignments, substituent effects, and chemical shift additivity.

    PubMed

    Kono, Hiroyuki; Hashimoto, Hisaho; Shimizu, Yuuichi

    2015-03-15

    A series of cellulose acetates (CA) with degrees of substitution (DS) ranging from 2.92-0.92 dissolved in dimethylsulfoxide (DMSO)-d6 and cellulose dissolved in tetrabutylammonium fluoride (TBAF)/DMSO-d6 were investigated by two-dimensional NMR spectroscopy. The NMR spectroscopic analysis allowed the determination of the (1)H and (13)C NMR chemical shifts of the eight anhydroglucose units (AGUs) that contain CA: 2,3,6-tri-, 2,3-di-, 2,6-di-, 3,6-di-, 2-mono-, 3-mono-, 6-mono-, and unacetylated AGUs. A comparative analysis of the chemical shift data revealed the substituent effect of acetyl groups at the 2-, 3-, and 6-positions on the (1)H and (13)C nuclei in the same AGU. In addition, chemical shift additivity could be applied to the (1)H and (13)C chemical shifts of CA because the chemical shifts of the diacetylated and triacetylated AGUs could be almost completely explained by the acetyl substituent effects at the 2-, 3-, and 6-positions. PMID:25542112

  5. Wideband Doppler frequency shift measurement and direction ambiguity resolution using optical frequency shift and optical heterodyning.

    PubMed

    Lu, Bing; Pan, Wei; Zou, Xihua; Yan, Xianglei; Yan, Lianshan; Luo, Bin

    2015-05-15

    A photonic approach for both wideband Doppler frequency shift (DFS) measurement and direction ambiguity resolution is proposed and experimentally demonstrated. In the proposed approach, a light wave from a laser diode is split into two paths. In one path, the DFS information is converted into an optical sideband close to the optical carrier by using two cascaded electro-optic modulators, while in the other path, the optical carrier is up-shifted by a specific value (e.g., from several MHz to hundreds of MHz) using an optical-frequency shift module. Then the optical signals from the two paths are combined and detected by a low-speed photodetector (PD), generating a low-frequency electronic signal. Through a subtraction between the specific optical frequency shift and the measured frequency of the low-frequency signal, the value of DFS is estimated from the derived absolute value, and the direction ambiguity is resolved from the derived sign (i.e., + or -). In the proof-of-concept experiments, DFSs from -90 to 90 kHz are successfully estimated for microwave signals at 10, 15, and 20 GHz, where the estimation errors are lower than 60??Hz. The estimation errors can be further reduced via the use of a more stable optical frequency shift module. PMID:26393729

  6. Automatic Detection of Attention Shifts in Infancy: Eye Tracking in the Fixation Shift Paradigm

    PubMed Central

    Kulke, Louisa; Atkinson, Janette; Braddick, Oliver

    2015-01-01

    This study measured changes in switches of attention between 1 and 9 months of age in 67 typically developing infants. Remote eye-tracking (Tobii X120) was used to measure saccadic latencies, related to switches of fixation, as a measure of shifts of attention, from a central stimulus to a peripheral visual target, measured in the Fixation Shift Paradigm. Fixation shifts occur later if the central fixation stimulus stays visible when the peripheral target appears (competition condition), than if the central stimulus disappears as the peripheral target appears (non-competition condition). This difference decreases with age. Our results show significantly faster disengagement in infants over 4 months than in the younger group, and provide more precise measures of fixation shifts, than behavioural observation with the same paradigm. Reduced saccadic latencies in the course of a test session indicate a novel learning effect. The Fixation Shift Paradigm combined with remote eye-tracking measures showed improved temporal and spatial accuracy compared to direct observation by a trained observer, and allowed an increased number of trials in a short testing time. This makes it an infant-friendly non-invasive procedure, involving minimal observational training, suitable for use in future studies of clinical populations to detect early attentional abnormalities in the first few months of life. PMID:26625161

  7. Application of the generalized shift operator to the Hankel transform.

    PubMed

    Baddour, Natalie

    2014-01-01

    It is well known that the Hankel transform possesses neither a shift-modulation nor a convolution-multiplication rule, both of which have found many uses when used with other integral transforms. In this paper, the generalized shift operator, as defined by Levitan, is applied to the Hankel transform. It is shown that under this generalized definition of shift, both convolution and shift theorems now apply to the Hankel transform. The operation of a generalized shift is compared to that of a simple shift via example. PMID:24877034

  8. Cost-shifting in the current medical environment

    NASA Astrophysics Data System (ADS)

    Gruber, William H.

    1994-12-01

    `Cost shifting' occurs when there is not a fair or accurate match of the payment and use of medical services. A common `cost shifting' occurs when an insured patient is charged more to cover free services provided to an uninsured patient. This paper documents the multiple negative consequences of the many categories of cost shifting, reviews forces which are leading both to an increase and decrease in the magnitude of cost shifting, and evaluates the consequences of cost shifting on the goals of U.S. health care reform and investment in medical technology. Policy to minimize the negative consequences of cost shifting is recommended.

  9. Goos-Hnchen shifts in harmonic generation from metals.

    PubMed

    Yallapragada, V J; Gopal, Achanta Venu; Agarwal, G S

    2013-05-01

    We present the first calculation of the Goos-Hnchen shifts in the context of the nonlinear generation of fields. We specifically concentrate on shifts of second harmonic generated at metallic surfaces. At metallic surfaces the second harmonic primarily arises from discontinuities of the field at surfaces which not only result in large harmonic generation but also in significant Goos-Hnchen shifts of the generated second harmonic. Our results can be extended to other shifts like angular shifts and Fedorov-Imbert shifts. PMID:23669944

  10. Inhomogeneity in laboratory plasma discharges and Stark shift measurement

    NASA Astrophysics Data System (ADS)

    Obradovi?, B. M.; Ivkovi?, M.; Ivkovi?, S. S.; Cvetanovi?, N.; Sretenovi?, G. B.; Kova?evi?, V. V.; Krsti?, I. B.; Kuraica, M. M.

    2016-01-01

    Several examples of Stark spectral line shifts from different laboratory plasma experiments are presented. The difference is outlined between the Stark shift caused by the micro field of charged particles on one side and the Stark shift caused by macroscopic electric field occurring in plasma sheaths on the other. In the first case the shift is used for testing of the Stark shifting theory and/or measurement of density of electrons while in the second it is used for measurement of macroscopic electric field strength. It is shown that inhomogeneity of the plasma can be used to provide the reference nonshifted lines for exact evaluation of the shift magnitude.

  11. The polymorphic phototest reaction

    SciTech Connect

    Jansen, C.

    1982-09-01

    One hundred tem patients with polymorphic light eruption (PMLE) and 58 control subjects were tested with an overdose of erythemogenic radiation. A morphologically abnormal phototest reaction was demonstrable in 72% of the patients with PMLE and in 9% of the control subjects. On the average, a dose of 3.8 times the patient's minimal erythemal dose was needed to produce the reaction. The most common findings in positive phototest reaction sites were edema and itching. A medium-pressure mercury lamp was shown to be as effective as a xenon arc lamp in producing the phototest reaction. The time of the reaction varied considerably in different patients, and frequent inspections of test sites were necessary to detect positive phototest reactions. When properly performed and interpreted, phototesting is a valuable diagnostic procedure for PMLE.

  12. Radical reactions of borohydrides.

    PubMed

    Kawamoto, Takuji; Ryu, Ilhyong

    2014-12-28

    Borohydrides are an important class of reagents in both organic and inorganic chemistry. Though popular as hydride-transfer reagents for reduction, since earlier work from the 1970s, borohydride reagents have also been known to serve as hydrogen-transfer reagents. In pursuit of greener tin hydride substitutes, recent progress has been made to mediate radical C-C bond forming reactions, including Giese reactions, radical carbonylation and addition to HCHO reactions, with borohydride reagents. This review article focuses on state-of-the-art borohydride based radical reactions, also covering earlier work, kinetics and some DFT calculations with respect to the hydrogen transfer mechanism. PMID:25349957

  13. Sleeve reaction chamber system

    DOEpatents

    Northrup, M. Allen (Berkeley, CA); Beeman, Barton V. (San Mateo, CA); Benett, William J. (Livermore, CA); Hadley, Dean R. (Manteca, CA); Landre, Phoebe (Livermore, CA); Lehew, Stacy L. (Livermore, CA); Krulevitch, Peter A. (Pleasanton, CA)

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  14. Tissue Reaction and Biomechanics.

    PubMed

    Melsen, Birte

    2016-01-01

    Tissue reaction to orthodontic force has been a subject of research with the purpose of providing the orthodontists with information necessary for the application of a force system that can generate a maximum of tooth movement and modeling of the alveolar process with a minimum of damage. Traditionally, the studies of bone biological reactions have been distinguishable from those performed by bone biologists. This has led to a controversy regarding both the terminology and perception of the reaction to mechanical perturbation. The present chapter, with its basis in bone biology, surveys the attempts by orthodontists to optimize the tissue reaction and shorten treatment time. PMID:26599116

  15. Damage detection using frequency shift path

    NASA Astrophysics Data System (ADS)

    Wang, Longqi; Lie, Seng Tjhen; Zhang, Yao

    2016-01-01

    This paper introduces a novel concept called FREquency Shift (FRESH) path to describe the dynamic behavior of structures with auxiliary mass. FRESH path combines the effects of frequency shifting and amplitude changing into one space curve, providing a tool for analyzing structure health status and properties. A damage index called FRESH curvature is then proposed to detect local stiffness reduction. FRESH curvature can be easily adapted for a particular problem since the sensitivity of the index can be adjusted by changing auxiliary mass or excitation power. An algorithm is proposed to adjust automatically the contribution from frequency and amplitude in the method. Because the extraction of FRESH path requires highly accurate frequency and amplitude estimators; therefore, a procedure based on discrete time Fourier transform is introduced to extract accurate frequency and amplitude with the time complexity of O (n log n), which is verified by simulation signals. Moreover, numerical examples with different damage sizes, severities and damping are presented to demonstrate the validity of the proposed damage index. In addition, applications of FRESH path on two steel beams with different damages are presented and the results show that the proposed method is valid and computational efficient.

  16. Saturated Dispersive Extinction Theory of Red Shift

    NASA Astrophysics Data System (ADS)

    Wang, Ling Jun

    2012-03-01

    The Dispersive Extinction Theory (DET) proposed by WangfootnotetextWang, Ling Jun, Physics Essays, 18, No. 2, (2005). offers an alternative to the Big Bang. According to DET, the cosmic red shift is caused by the dispersive extinction of the star light during the propagation from the stars to the earth, instead of being caused by the Doppler shift due to the expansion of the universe.footnotetextHubble, E., Astrophys. J. 64, 321 (1926).^,footnotetextHubble, E., The Realm of the Nebulae, (Yale University Press, New Haven, 1936). DET allows an infinite, stable, non expanding universe, and is immune of the fundamental problems inherent to the Big Bang such as the horizon problem, the extreme violation of the conservation of mass, energy and charge, and the geocentric nature which violates the principle of relativity.footnotetextWang, Ling Jun, Physics Essays, 20, No. 2, (2007). The scenario dealt with in Reference (1) is a one in which the extinction by the space medium is not saturated. This work deals with a different scenario when the extinction is saturated. The saturated extinction causes limited energy loss, and the star light can travel a much greater distance than in the unsaturated scenario.

  17. Robust shift and add approach to superresolution

    NASA Astrophysics Data System (ADS)

    Farsiu, Sina; Robinson, Dirk; Elad, Michael; Milanfar, Peyman

    2003-11-01

    In the last two decades, many papers have been published, proposing a variety of methods for multi-frame resolution enhancement. These methods, which have a wide range of complexity, memory and time requirements, are usually very sensitive to their assumed model of data and noise, often limiting their utility. Different implementations of the non-iterative Shift and Add concept have been proposed as very fast and effective super-resolution algorithms. The paper of Elad & Hel-Or 2001 provided an adequate mathematical justification for the Shift and Add method for the simple case of an additive Gaussian noise model. In this paper we prove that additive Gaussian distribution is not a proper model for super-resolution noise. Specifically, we show that Lp norm minimization (1<=p<=2) results in a pixelwise weighted mean algorithm which requires the least possible amount of computation time and memory and produces a maximum likelihood solution. We also justify the use of a robust prior information term based on bilateral filter idea. Finally, for the underdetermined case, where the number of non-redundant low-resolution frames are less than square of the resolution enhancement factor, we propose a method for detection and removal of outlier pixels. Our experiments using commercialdigital cameras show that our proposed super-resolution method provides significant improvements in both accuracy and efficiency.

  18. The Underlying Social Dynamics of Paradigm Shifts

    PubMed Central

    Claro, Francisco; Fuentes, Miguel Angel

    2015-01-01

    We develop here a multi-agent model of the creation of knowledge (scientific progress or technological evolution) within a community of researchers devoted to such endeavors. In the proposed model, agents learn in a physical-technological landscape, and weight is attached to both individual search and social influence. We find that the combination of these two forces together with random experimentation can account for both i) marginal change, that is, periods of normal science or refinements on the performance of a given technology (and in which the community stays in the neighborhood of the current paradigm); and ii) radical change, which takes the form of scientific paradigm shifts (or discontinuities in the structure of performance of a technology) that is observed as a swift migration of the knowledge community towards the new and superior paradigm. The efficiency of the search process is heavily dependent on the weight that agents posit on social influence. The occurrence of a paradigm shift becomes more likely when each member of the community attaches a small but positive weight to the experience of his/her peers. For this parameter region, nevertheless, a conservative force is exerted by the representatives of the current paradigm. However, social influence is not strong enough to seriously hamper individual discovery, and can act so as to empower successful individual pioneers who have conquered the new and superior paradigm. PMID:26418255

  19. Microstrip Antennas with Broadband Integrated Phase Shifting

    NASA Technical Reports Server (NTRS)

    Bernhard, Jennifer T.; Romanofsky, Robert R. (Technical Monitor)

    2001-01-01

    The goal of this research was to investigate the feasibility of using a spiral microstrip antenna that incorporates a thin ferroelectric layer to achieve both radiation and phase shifting. This material is placed between the conductive spiral antenna structure and the grounded substrate. Application of a DC bias between the two arms of the spiral antenna will change the effective permittivity of the radiating structure and the degree of coupling between contiguous spiral arms, therefore changing the phase of the RF signal transmitted or received by the antenna. This could eliminate the need for a separate phase shifter apart from the antenna structure. The potential benefits of such an antenna element compared to traditional phased array elements include: continuous, broadband phase shifting at the antenna, lower overall system losses, lighter, more efficient, and more compact phased arrays, and simpler control algorithms. Professor Jennifer Bernhard, graduate student Gregory Huff, and undergraduate student Brian Huang participated in this effort from March 1, 2000 to February 28, 2001. No inventions resulted from the research undertaken in this cooperative agreement.

  20. Theory of Lamb Shift in Muonic Hydrogen

    NASA Astrophysics Data System (ADS)

    Karshenboim, Savely G.; Korzinin, Evgeny Yu.; Shelyuto, Valery A.; Ivanov, Vladimir G.

    2015-09-01

    There has been for a while a large discrepancy between the values of the proton charge radius measured by the Lamb shift in muonic hydrogen and by other methods. It has already been clear that theory of muonic hydrogen is reliable at the level of this discrepancy and an error there cannot be a reason for the contradiction. Still the status of theory at the level of the uncertainty of the muonic-hydrogen experiment (which is two orders of magnitude below the discrepancy level) requires an additional clarification. Here, we revisit theory of the 2p - 2s Lamb shift in muonic hydrogen. We summarize all the theoretical contributions in order ?5m, including pure quantum electrodynamics (QED) ones as well as those which involve the proton-structure effects. Certain enhanced higher-order effects are also discussed. We basically confirm former QED calculations of other authors, present a review of recent calculations of the proton-structure effects, and treat self-consistently higher-order proton-finite-size corrections. We also overview theory of the 2p states. Eventually, we derive a value of the root-mean-square proton charge radius. It is found to be 0.840 29(55) fm, which is slightly different from that previously published in the literature (0.840 87(39) fm [Antognini et al., Science 339, 417 (2013)]).

  1. Neural signals encoding shifts in beliefs.

    PubMed

    Schwartenbeck, Philipp; FitzGerald, Thomas H B; Dolan, Ray

    2016-01-15

    Dopamine is implicated in a diverse range of cognitive functions including cognitive flexibility, task switching, signalling novel or unexpected stimuli as well as advance information. There is also longstanding line of thought that links dopamine with belief formation and, crucially, aberrant belief formation in psychosis. Integrating these strands of evidence would suggest that dopamine plays a central role in belief updating and more specifically in encoding of meaningful information content in observations. The precise nature of this relationship has remained unclear. To directly address this question we developed a paradigm that allowed us to decompose two distinct types of information content, information-theoretic surprise that reflects the unexpectedness of an observation, and epistemic value that induces shifts in beliefs or, more formally, Bayesian surprise. Using functional magnetic-resonance imaging in humans we show that dopamine-rich midbrain regions encode shifts in beliefs whereas surprise is encoded in prefrontal regions, including the pre-supplementary motor area and dorsal cingulate cortex. By linking putative dopaminergic activity to belief updating these data provide a link to false belief formation that characterises hyperdopaminergic states associated with idiopathic and drug induced psychosis. PMID:26520774

  2. Charge shift bonding concept in radical ?-dimers.

    PubMed

    Tian, Yong-Hui; Kertesz, Miklos

    2011-12-01

    We show that pancake bonding in radical ?-dimers display features of charge shift (CS) bonding. While the CS bonding concept has been developed to interpret the unusual aspects of ?-bonds around centers with a large number of lone pairs, such as F(2) and HOOH, we find a similar role played by the nonbonding or slightly bonding ?-electron pairs in ?-stacking radical dimers. Arguments and computational evidence indicate that the CS bonding concept developed by Shaik and Hiberty et al. captures essential features of the intermolecular bonding in radical ?-dimers in which the overlap of the two radical centered singly occupied molecular orbitals (SOMOs) play a crucial role. By using the tetracyanoethylene anion dimer, [TCNE](2)(2-), as a model, we show that compared to CAS(2,2) calculations, significant binding contributions are recovered in the calculations simply by including selected intrapair excitations of the SOMO-SOMO bonding orbitals and the nonbonding ?-orbitals. This observation is the basis for the analogy of chemical bonding between pancake bonded radical ?-dimers and other charge shift bonded molecules, such as F(2). By extending the CS bonding concept to a new class of molecules, we find a novel application of the lone pair bond weakening effect (LPBWE) in which the doubly occupied ?-orbitals play the role of lone pairs. PMID:22023671

  3. Automated manual transmission shift sequence controller

    DOEpatents

    Lawrie, Robert E.; Reed, Richard G.; Rausen, David J.

    2000-02-01

    A powertrain system for a hybrid vehicle. The hybrid vehicle includes a heat engine, such as a diesel engine, and an electric machine, which operates as both, an electric motor and an alternator, to power the vehicle. The hybrid vehicle also includes a manual-style transmission configured to operate as an automatic transmission from the perspective of the driver. The engine and the electric machine drive an input shaft which in turn drives an output shaft of the transmission. In addition to driving the transmission, the electric machine regulates the speed of the input shaft in order to synchronize the input shaft during either an upshift or downshift of the transmission by either decreasing or increasing the speed of the input shaft. When decreasing the speed of the input shaft, the electric motor functions as an alternator to produce electrical energy which may be stored by a storage device. Operation of the transmission is controlled by a transmission controller which receives input signals and generates output signals to control shift and clutch motors to effect smooth launch, upshift shifts, and downshifts of the transmission, so that the transmission functions substantially as an automatic transmission from the perspective of the driver, while internally substantially functioning as a manual transmission.

  4. Neural signals encoding shifts in beliefs

    PubMed Central

    Schwartenbeck, Philipp; FitzGerald, Thomas H.B.; Dolan, Ray

    2016-01-01

    Dopamine is implicated in a diverse range of cognitive functions including cognitive flexibility, task switching, signalling novel or unexpected stimuli as well as advance information. There is also longstanding line of thought that links dopamine with belief formation and, crucially, aberrant belief formation in psychosis. Integrating these strands of evidence would suggest that dopamine plays a central role in belief updating and more specifically in encoding of meaningful information content in observations. The precise nature of this relationship has remained unclear. To directly address this question we developed a paradigm that allowed us to decompose two distinct types of information content, information-theoretic surprise that reflects the unexpectedness of an observation, and epistemic value that induces shifts in beliefs or, more formally, Bayesian surprise. Using functional magnetic-resonance imaging in humans we show that dopamine-rich midbrain regions encode shifts in beliefs whereas surprise is encoded in prefrontal regions, including the pre-supplementary motor area and dorsal cingulate cortex. By linking putative dopaminergic activity to belief updating these data provide a link to false belief formation that characterises hyperdopaminergic states associated with idiopathic and drug induced psychosis. PMID:26520774

  5. [Shift- and Nightwork - a scientometric analysis].

    PubMed

    van Mark, Anke; Vitzthum, Karin; Hndorf, Franka; Kloss, Lisa; Quarcoo, David; Groneberg, David A

    2011-04-01

    Economic restructuring processes in Germany require changes within all social and health care systems regarding night shiftwork. The aim of this paper was to analyse research results referring to shift- and nightwork using scientometric methods. A total of 3092 items could be detected. A constant increase in the number of publications per year since 1977, especially since 1990' was obvious. One third of the research results, a total of 884 articles could be assigned to the USA. Great Britain could be identified with 365 articles and France with 244 published articles. Sleep, Ergonomics and Chronobiology International are the most prolific journals. The Swedish scientist Torbjrn Akerstedt is to this date the most acclaimed researcher referring to his issue. He has written 105 articles about shift- and nightwork. He is not only a most efficient author, but also has the highest h-index [30]. Self-citations and multiple co-authorships distort parameters like impact factor and h-index enormously and should be regarded from a critical point of view. PMID:21442214

  6. Shifting seasons, climate change and ecosystem consequences

    NASA Astrophysics Data System (ADS)

    Thackeray, Stephen; Henrys, Peter; Hemming, Deborah; Huntingford, Chris; Bell, James; Leech, David; Wanless, Sarah

    2014-05-01

    In recent decades, the seasonal timing of many biological events (e.g. flowering, breeding, migration) has shifted. These phenological changes are believed to be one of the most conspicuous biological indicators of climate change. Rates and directions of phenological change have differed markedly among species, potentially threatening the seasonal synchrony of key species interactions and ultimately ecosystem functioning. Differences in phenological change among-species at different trophic levels, and with respect to other broad species traits, are likely to be driven by variations in the climatic sensitivity of phenological events. However, as yet, inconsistencies in analytical methods have hampered broad-scale assessments of variation in climate sensitivity among taxonomic and functional groups of organisms. In this presentation, results will be presented from a current collaborative project (http://www.ceh.ac.uk/sci_programmes/shifting-seasons-uk.html) in which many UK long-term data sets are being integrated in order to assess relationships between temperature/precipitation, and the timing of seasonal events for a wide range of plants and animals. Our aim is to assess which organism groups (in which locations/habitats) are most sensitive to climate. Furthermore, the role of anthropogenic climate change as a driver of phenological change is being assessed.

  7. Language lateralization shifts with learning by adults.

    PubMed

    Plante, Elena; Almryde, Kyle; Patterson, Dianne K; Vance, Christopher J; Asbjrnsen, Arve E

    2015-05-01

    For the majority of the population, language is a left-hemisphere lateralized function. During childhood, a pattern of increasing left lateralization for language has been described in brain imaging studies, suggesting that this trait develops. This development could reflect change due to brain maturation or change due to skill acquisition, given that children acquire and refine language skills as they mature. We test the possibility that skill acquisition, independent of age-associated maturation can result in shifts in language lateralization in classic language cortex. We imaged adults exposed to an unfamiliar language during three successive fMRI scans. Participants were then asked to identify specific words embedded in Norwegian sentences. Exposure to these sentences, relative to complex tones, resulted in consistent activation in the left and right superior temporal gyrus. Activation in this region became increasingly left-lateralized with repeated exposure to the unfamiliar language. These results demonstrate that shifts in lateralization can be produced in the short term within a learning context, independent of maturation. PMID:25285756

  8. Isotope shift constant and nuclear charge model

    NASA Astrophysics Data System (ADS)

    Fang, Z.; Redi, O.; Stroke, H. H.

    1992-04-01

    We use the method of Zimmermann [Z. Phys. A 321 (1985) 23-30], which he used to calculate the isotope shift constant for a uniform nuclear charge distribution, to obtain it for a diffuse nuclear charge model. The two models give results that differ slightly on the level of precision of current experiments. The same parameters are used to calculate the model sensitivity of the contributions to the isotope shifts of higher moments of the nuclear charge distribution as formulated by Seltzer [Phys. Rev. 188 (1969) 1916-1919]. These are found to be essentially model independent. Tables are given of the numerical calculations. Nous employons la mthode de Zimmermann [Z. Phys. A 321 (1985) 23-30], qu'il avait utilis dans un calcul de la constante du dplacement isotopique pour une distribution de charge uniforme, pour l'obtenir avec un modle de charge nuclaire avec forme quasi-trapzodale. Les deux modles donnent des rsultats dont la difference excde de peu la prcision des mesures actuelles. Les mmes paramtres sont utiliss pour comparer la dpendance aux deux modles de la contribution au dplacement isotopique des moments plus levs de la distribution de la charge nuclaire dans la formulation de Seltzer [Phys. Rev. 188 (1969) 1916-1919]. On trouve que ces contributions sont essentiellement indpendantes du modle. Des tables de calculs numriques sont prsentes.

  9. Edge technique for measurement of laser frequency shifts including the Doppler shift

    NASA Technical Reports Server (NTRS)

    Korb, Larry (inventor)

    1991-01-01

    A method is disclosed for determining the frequency shift in a laser system by transmitting an outgoing laser beam. An incoming laser beam having a frequency shift is received. A first signal is acquired by transmitting a portion of the incoming laser beam to an energy monitor detector. A second signal is acquired by transmitting a portion of the incoming laser beam through an edge filter to an edge detector, which derives a first normalized signal which is proportional to the transmission of the edge filter at the frequency of the incoming laser beam. A second normalized signal is acquired which is proportional to the transmission of the edge filter at the frequency of the outgoing laser beam. The frequency shift is determined by processing the first and second normalized signals.

  10. Advantages of shift changeovers with meetings: ergonomic analysis of shift supervisors' activity in aircraft building.

    PubMed

    Le Bris, Valérie; Barthe, Béatrice; Marquié, Jean-Claude; Kerguelen, Alain; Aubert, Sophie; Bernadou, Bernadette

    2012-03-01

    Good shift changeovers contribute to ensuring continuity and reliability in shift work. In situations where production is not maintained 24 h a day, changeovers with meetings (SCM) between the two work teams (written plus oral face-to-face handovers) alternate with changeovers without meetings (SCnM; written handovers only). An ergonomic work analysis on an aircraft assembly line showed that (1) incoming and outgoing operators met during the overlap time allotted by the company, and (2) the content of the exchanges was richer for SCMs than for SCnMs. SCMs enabled the operators to pass on and process more aspects of their work than SCnMs did. SCMs also allowed incoming operators to validate their predictions, and enabled both outgoing and incoming operators to update their mental models and work together on peripheral aspects of the technical process over a greater time span. The findings highlight the importance of allowing overlap time in shift work. PMID:21843879

  11. The effect of zopiclone 7.5 mg on the sleep, mood and performance of shift workers.

    PubMed

    Moon, C A; Hindmarch, I; Holland, R L

    1990-04-01

    Shift workers often complain of an inability to sleep well between successive periods of work. The purpose of the study was to assess the influence of zopiclone, hypnotic with minimal residual effects, on work-time performance and mood. In this double-blind, cross-over study, 12 healthy male volunteers, aged between 18 and 35 years, from the Royal Air Force, working 12 h shifts in radar installations, were given zopiclone 7.5 mg at bed time or placebo for 2 shift cycles in a randomized order. Zopiclone significantly improved night time sleep, with a trend towards improvement of day-time sleep. There was no effect on psychomotor performance (assessed by critical flicker fusion threshold, choice reaction time and digit symbol substitution test) nor on mood (assessed by visual analogue scales). It can be concluded that zopiclone is a safe hypnotic which can be used by shift workers without impairing work time performance. PMID:2201732

  12. Quantitative Measurement of the Doppler Shift at an Ultrasonic Frequency

    ERIC Educational Resources Information Center

    Nerbun, R. C.; Leskovec, R. A.

    1976-01-01

    Discussed is a Doppler shift laboratory experiment for an introductory college physics course. Ultrasonic transducers and a digital phase detector circuit "black box" are used to overcome room noise and "standing waves" and to produce an observable frequency shift. (SL)

  13. Using rigorous selection criteria to investigate marine range shifts

    NASA Astrophysics Data System (ADS)

    Przeslawski, Rachel; Falkner, Inke; Ashcroft, Michael B.; Hutchings, Pat

    2012-11-01

    We reassess whether range shifts in marine organisms are occurring in a direction predicted by causation due to climate using two different methods: a global meta-analysis and a regional analysis of museum records focussing on marine molluscs. Globally we used rigorous selection criteria to investigate studies describing range shifts in marine organisms, including exclusion of single-species studies and those that inferred range shifts through shifting abundance. For each species meeting these criteria (311 species from 13 studies), the distance in kilometres moved per year was calculated, and life history characteristics such as mobility, habitat, dispersal potential and trophic level were recorded to assess if these were linked to the shifts. We also examined the potential correlation between changing sea surface temperatures and range shifts. Regionally we analysed the intertidal mollusc collection of the Australian Museum and Museum of Victoria and consulted with mollusc experts to determine if museum records could be used to detect range shifts in marine invertebrates. The global meta-analysis showed that individual species shifted on average 8.9 km polewards per year. Range shifts were not significantly related to temperature change or life history characteristics with the exception of intertidal and nearshore subtidal fauna showing poleward shifts (6.8 and 14.3 km per decade, respectively) and shelf fauna showing a slight equatorial shift (2.7 km per decade). Our regional analysis showed that 54 of the 634 mollusc species examined shifted their range into or out of the well-surveyed Sydney region. However, closer examination by mollusc experts revealed that the evidence for these shifts was unreliable, and we conclude that caution is required when using museum records in range shift studies. Overall, our study supports previous research showing a poleward shift in response to climate change, although this is an order of magnitude less than values reported in the only other meta-analysis on marine range shifts, possibly owing to the strict selection criteria applied here.

  14. Hydrogen evolution reaction catalyst

    DOEpatents

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  15. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it…

  16. Chemical Reaction Problem Solving.

    ERIC Educational Resources Information Center

    Veal, William

    1999-01-01

    Discusses the role of chemical-equation problem solving in helping students predict reaction products. Methods for helping students learn this process must be taught to students and future teachers by using pedagogical skills within the content of chemistry. Emphasizes that solving chemical reactions should involve creative cognition where…

  17. Degradations and Rearrangement Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Jianbo

    This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

  18. THE CUTANEOUS TRICHOPHYTIN REACTION

    PubMed Central

    Amberg, Samuel

    1910-01-01

    There exists a far-reaching analogy between the cutaneous trichophytin reaction and the cutaneous tuberculin reaction. Both indicate that the organism is the seat of a definite infection or that it has passed through such an infection. Both may persist for a long time after the active disease has come to rest, indicating that the infection has left the organism in a state of altered reactivityallergy. Under certain conditions both may be of diagnostic value, but since the reaction persists for a long time after the infection has passed, the negative reaction may be of greater value, excluding the existence of a specific infection. The analogy of the trichophytin reaction with the tuberculin reaction is not only limited to the obvious clinical manifestations, but, as in the tuberculin reaction, it can be shown that with uniform concentration of antibody, the intensity of the reaction is dependent on the concentration of the trichophytin. A tentative explanation of the halo formation is offered, based on a rapidly renewed formation of antibody stimulated probably by the entrance of a small amount of allergen into the general circulation. PMID:19867336

  19. Oscillating Reactions: Two Analogies

    ERIC Educational Resources Information Center

    Petruševski, Vladimir M.; Stojanovska, Marina I.; Šoptrajanov, Bojan T.

    2007-01-01

    Oscillating chemical reactions are truly spectacular phenomena, and demonstrations are always appreciated by the class. However, explaining such reactions to high school or first-year university students is problematic, because it may seem that no acceptable explanation is possible unless the students have profound knowledge of both physical…

  20. Clock Reaction: Outreach Attraction

    ERIC Educational Resources Information Center

    Carpenter, Yuen-ying; Phillips, Heather A.; Jakubinek, Michael B.

    2010-01-01

    Chemistry students are often introduced to the concept of reaction rates through demonstrations or laboratory activities involving the well-known iodine clock reaction. For example, a laboratory experiment involving thiosulfate as an iodine scavenger is part of the first-year general chemistry laboratory curriculum at Dalhousie University. With

  1. Clock Reaction: Outreach Attraction

    ERIC Educational Resources Information Center

    Carpenter, Yuen-ying; Phillips, Heather A.; Jakubinek, Michael B.

    2010-01-01

    Chemistry students are often introduced to the concept of reaction rates through demonstrations or laboratory activities involving the well-known iodine clock reaction. For example, a laboratory experiment involving thiosulfate as an iodine scavenger is part of the first-year general chemistry laboratory curriculum at Dalhousie University. With…

  2. Precompound Reactions: Basic Concepts

    SciTech Connect

    Weidenmueller, H. A.

    2008-04-17

    Because of the non-zero nuclear equilibration time, the compound-nucleus scattering model fails when the incident energy exceeds 10 or 20 MeV, and precompound reactions become important. Basic ideas used in the quantum-statistical approaches to these reactions are described.

  3. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it

  4. Chemical Reaction Problem Solving.

    ERIC Educational Resources Information Center

    Veal, William

    1999-01-01

    Discusses the role of chemical-equation problem solving in helping students predict reaction products. Methods for helping students learn this process must be taught to students and future teachers by using pedagogical skills within the content of chemistry. Emphasizes that solving chemical reactions should involve creative cognition where

  5. Nuclear Reaction Data Centers

    SciTech Connect

    McLane, V.; Nordborg, C.; Lemmel, H.D.; Manokhin, V.N.

    1988-01-01

    The cooperating Nuclear Reaction Data Centers are involved in the compilation and exchange of nuclear reaction data for incident neutrons, charged particles and photons. Individual centers may also have services in other areas, e.g., evaluated data, nuclear structure and decay data, reactor physics, nuclear safety; some of this information may also be exchanged between interested centers. 20 refs., 1 tab.

  6. Frequency shifting with a solid-state switching capacitor

    NASA Technical Reports Server (NTRS)

    Mattauch, R. J.; Viola, T. J., Jr.

    1973-01-01

    Frequency shifting, commonly used in electronic signal processing, is applied in tuning, automatic frequency control, antenna element switching, phase shifting, etc. Frequency shifting can be accomplished economically and reliably with simple circuit comprising conventional resistor and solid-state switching device which can be equivalent to two capacitors, depending on switching state.

  7. Method for measuring Doppler shifts in arc-heated flows.

    PubMed

    Aeschliman, D P; Hill, R A

    1972-01-01

    A novel method of determining both the Doppler and Stark shifts in a single measurement of spectral lines emitted by the arc-heated flow from a plasma jet has been successfully demonstrated. The method uses a spherical mirror arranged with its optical axis coincident with the optical axis of a Fabry-Perot interferometer and with its center of curvature at the center line of the flow. The common optical axis lies at an angle to the flow. With this system, both red-and blue-shifted line profiles are recorded in the same spectral scan. If conditions are such that the red-and blue-shifted profiles are not resolvable, the blue-shifted component is chopped so that the recorded signal consists of the envelopes of both the red-shifted profile and the superimposed red-and blue-shifted profiles. The wavelength difference between the blue-and red-shifted line profiles is exactly twice the Doppler shift integrated along a line of sight through the flow and is independent of a Stark shift. The Stark shift is given by the wavelength difference between the absolute line center and the midpoint of the red-and blue-shifted lines. Abel inversion of integrated line shift data has yielded radial velocity profiles to an accuracy of +/-3% in a supersonic, arc-heated argon flow. PMID:20111470

  8. Statistical properties of phase-shift algorithms

    NASA Astrophysics Data System (ADS)

    Rathjen, C.

    1995-09-01

    Statistical properties of phase-shift algorithms are investigated for the case of additive Gaussian intensity noise. Based on a bivariate normal distribution, a generally valid probability-density function for the random phase error is derived. This new description of the random phase error shows properties that cannot be obtained through Gaussian error propagation. The assumption of a normally distributed phase error is compared with the derived probability-density function. For small signal-to-noise ratios the assumption of a normally distributed phase error is not valid. Additionally, it is shown that some advanced systematic-error-compensating algorithms have a disadvantageous effect on the random phase error. error, systematic error, additive Gaussian noise, phase-measuring interferometry.

  9. Phase-shifting point diffraction interferometer

    DOEpatents

    Medecki, Hector

    1998-01-01

    Disclosed is a point diffraction interferometer for evaluating the quality of a test optic. In operation, the point diffraction interferometer includes a source of radiation, the test optic, a beam divider, a reference wave pinhole located at an image plane downstream from the test optic, and a detector for detecting an interference pattern produced between a reference wave emitted by the pinhole and a test wave emitted from the test optic. The beam divider produces separate reference and test beams which focus at different laterally separated positions on the image plane. The reference wave pinhole is placed at a region of high intensity (e.g., the focal point) for the reference beam. This allows reference wave to be produced at a relatively high intensity. Also, the beam divider may include elements for phase shifting one or both of the reference and test beams.

  10. Phase-shifting point diffraction interferometer

    DOEpatents

    Medecki, H.

    1998-11-10

    Disclosed is a point diffraction interferometer for evaluating the quality of a test optic. In operation, the point diffraction interferometer includes a source of radiation, the test optic, a beam divider, a reference wave pinhole located at an image plane downstream from the test optic, and a detector for detecting an interference pattern produced between a reference wave emitted by the pinhole and a test wave emitted from the test optic. The beam divider produces separate reference and test beams which focus at different laterally separated positions on the image plane. The reference wave pinhole is placed at a region of high intensity (e.g., the focal point) for the reference beam. This allows reference wave to be produced at a relatively high intensity. Also, the beam divider may include elements for phase shifting one or both of the reference and test beams. 8 figs.

  11. Quantum walks with random phase shifts

    SciTech Connect

    Kosik, Jozef; Buzek, Vladimir; Hillery, Mark

    2006-08-15

    We investigate quantum walks in multiple dimensions with different quantum coins. We augment the model by assuming that at each step the amplitudes of the coin state are multiplied by random phases. This model enables us to study in detail the role of decoherence in quantum walks and to investigate the quantum-to-classical transition. We also provide classical analog of the quantum random walks studied. Interestingly enough, it turns out that the classical counterparts of some quantum random walks are classical random walks with a memory and biased coin. In addition random phase shifts 'simplify' the dynamics (the cross-interference terms of different paths vanish on average) and enable us to give a compact formula for the dispersion of such walks.

  12. Cooperative Lamb shift in an ellipsoid

    SciTech Connect

    Friedberg, Richard; Manassah, Jamal T.

    2010-06-15

    It has been long known that the global cooperative Lamb shift (CLS) in a large superradiantly emitting sphere has equal magnitude but opposite sign to that of a slab. This result was obtained from QED in 1973 for samples of uniform density. This change of sign holds as well for a Gaussian density distribution. The same result is also obtained for either density in the scalar simplification of QED now in frequent use. Since the CLS must be a continuous function of shape, and the slab resembles a limiting case of oblate ellipsoid, there must be some shape of ellipsoid for which the CLS is zero. We report a calculation of CLS for a Gaussian distribution of general azimuthally symmetric ellipsoidal shape. The CLS is found to vanish when the mean square radius is twice as great transversely as longitudinally.

  13. Shifted power method for computing tensor eigenvalues.

    SciTech Connect

    Mayo, Jackson R.; Kolda, Tamara Gibson

    2010-07-01

    Recent work on eigenvalues and eigenvectors for tensors of order m >= 3 has been motivated by applications in blind source separation, magnetic resonance imaging, molecular conformation, and more. In this paper, we consider methods for computing real symmetric-tensor eigenpairs of the form Ax{sup m-1} = lambda x subject to ||x||=1, which is closely related to optimal rank-1 approximation of a symmetric tensor. Our contribution is a shifted symmetric higher-order power method (SS-HOPM), which we show is guaranteed to converge to a tensor eigenpair. SS-HOPM can be viewed as a generalization of the power iteration method for matrices or of the symmetric higher-order power method. Additionally, using fixed point analysis, we can characterize exactly which eigenpairs can and cannot be found by the method. Numerical examples are presented, including examples from an extension of the method to finding complex eigenpairs.

  14. Shifted power method for computing tensor eigenpairs.

    SciTech Connect

    Mayo, Jackson R.; Kolda, Tamara Gibson

    2010-10-01

    Recent work on eigenvalues and eigenvectors for tensors of order m {>=} 3 has been motivated by applications in blind source separation, magnetic resonance imaging, molecular conformation, and more. In this paper, we consider methods for computing real symmetric-tensor eigenpairs of the form Ax{sup m-1} = {lambda}x subject to {parallel}x{parallel} = 1, which is closely related to optimal rank-1 approximation of a symmetric tensor. Our contribution is a novel shifted symmetric higher-order power method (SS-HOPM), which we showis guaranteed to converge to a tensor eigenpair. SS-HOPM can be viewed as a generalization of the power iteration method for matrices or of the symmetric higher-order power method. Additionally, using fixed point analysis, we can characterize exactly which eigenpairs can and cannot be found by the method. Numerical examples are presented, including examples from an extension of the method to fnding complex eigenpairs.

  15. Dynamic point shifting in null screen videokeratometry

    NASA Astrophysics Data System (ADS)

    Rodrguez-Rodrguez, M. I.; Jaramillo Nez, A.; Daz Uribe, R.

    2011-08-01

    For obtaining the shape of the corneal surface through the Null Screen method, a numeric integration procedure must be carried out; perhaps, the simplest integration method is the trapezoid rule. This method, however, is limited by the truncation error. It has been shown previously [1-6] that the point shifting method allows the reduction of this error by adding many more evaluation points so reducing the average spacing between evaluation points. To do so, an array of LCD's must be used to display the moving Null Screen. In this paper we propose to use three LCD forming a triangular prism, instead of a cylindrical Null Screen [3] for measuring the shape of the human corneas. The null screen design will be described and some experimental results obtained with calibration spheres used to simulate the corneal surface will be presented.

  16. Magnetoplasmonic isolators utilizing the nonreciprocal phase shift.

    PubMed

    Firby, C J; Elezzabi, A Y

    2016-02-01

    We propose a long-range magnetoplasmonic waveguide structure, based on cerium-substituted yttrium iron garnets, that is capable of achieving a useful ?/2 nonreciprocal phase shift within one propagation length. Incorporating this plasmonic geometry into a Mach-Zehnder interferometer allows for the implementation of an efficient, integrable isolator scheme with an insertion loss of 2.51 dB and an extinction ratio of 22.82 dB. With a small footprint of 6.410-3??mm2 and nanoscale waveguide dimensions, we envision this device to be a key building block in the development of nanoplasmonic integrated circuitry. PMID:26907424

  17. Shifting environmental baselines in the Red Sea.

    PubMed

    Price, A R G; Ghazi, S J; Tkaczynski, P J; Venkatachalam, A J; Santillan, A; Pancho, T; Metcalfe, R; Saunders, J

    2014-01-15

    The Red Sea is among the world's top marine biodiversity hotspots. We re-examined coastal ecosystems at sites surveyed during the 1980s using the same methodology. Coral cover increased significantly towards the north, mirroring the reverse pattern for mangroves and other sedimentary ecosystems. Latitudinal patterns are broadly consistent across both surveys and with results from independent studies. Coral cover showed greatest change, declining significantly from a median score of 4 (1000-9999 m(2)) to 2 (10-99m(2)) per quadrat in 2010/11. This may partly reflect impact from coastal construction, which was evident at 40% of sites and has significantly increased in magnitude over 30 years. Beach oil has significantly declined, but shore debris has increased significantly. Although substantial, levels are lower than at some remote ocean atolls. While earlier reports have suggested that the Red Sea is generally healthy, shifting environmental baselines are evident from the current study. PMID:24246651

  18. Shift work, jet lag, and female reproduction.

    PubMed

    Mahoney, Megan M

    2010-01-01

    Circadian rhythms and "clock gene" expression are involved in successful reproductive cycles, mating, and pregnancy. Alterations or disruptions of biological rhythms, as commonly occurs in shift work, jet lag, sleep deprivation, or clock gene knock out models, are linked to significant disruptions in reproductive function. These impairments include altered hormonal secretion patterns, reduced conception rates, increased miscarriage rates and an increased risk of breast cancer. Female health may be particularly susceptible to the impact of desynchronizing work schedules as perturbed hormonal rhythms can further influence the expression patterns of clock genes. Estrogen modifies clock gene expression in the uterus, ovaries, and suprachiasmatic nucleus, the site of the primary circadian clock mechanism. Further work investigating clock genes, light exposure, ovarian hormones, and reproductive function will be critical for indentifying how these factors interact to impact health and susceptibility to disease. PMID:20224815

  19. Using tensor light shifts to measure and cancel a cell's quadrupolar frequency shift

    NASA Astrophysics Data System (ADS)

    Peck, S. K.; Lane, N.; Ang, D. G.; Hunter, L. R.

    2016-02-01

    We have developed a technique that uses the tensor light shift to measure and cancel the frequency shift produced by the quadrupolar anisotropy of a vapor cell. We demonstrate the technique on the 6 S1 /2 ,F =4 level of Cs using the D1 transition. The method extends our ability to study quadrupolar wall interactions beyond diamagnetic atoms. We have deduced the twist angle per wall adhesion for cesium on an alkene coating to be θCs -alkene=1.4 mrad . This value is about 37 times larger than the twist angle observed in 131Xe, suggesting that it is not produced by the interaction of the nuclear quadrupole moment with a collisional electric-field gradient. Alternative mechanisms that may be responsible for the observed quadrupolar frequency shifts are discussed. By canceling the cell-induced quadrupole shift we have extended our cells' effective spin-relaxation times by as much as a factor of 2. This cancellation improves magnetometer sensitivity in highly anisotropic cells and could reduce systematic uncertainties in some precision measurements.

  20. Inflammatory reaction - communication of cells.

    PubMed

    Terheyden, Hendrik; Stadlinger, Bernd; Sanz, Mariano; Garbe, Annette I; Meyle, Jörg

    2014-04-01

    This article presents scientific background information on the animated 3D film "Inflammatory Reactions - Communication of Cells" (Quintessence Publications, ISBN 978-1-85097-231-0). Gingivitis and periodontitis are understood as the result of a coordinated action of a few clearly identified cellular players who communicate with each other via cytokines. For didactic reasons, the course of a periodontal infection is described here in four phases: (1) bacterial biofilm formation and development of a host response in the marginal periodontium, (2) innate immune response leading to gingivitis, (3) role of the adaptive immune system in attachment loss and pocket formation, and (4) down-regulation of inflammation and periodontal regeneration and repair following biofilm removal. The control of the cells is discussed as a cytokine network, which can be modulated in pro- or anti-inflammatory direction depending on the control of the bacterial infection. Degradation of soft tissue structural proteins like collagen and proteoglycans by matrix metalloproteinases and degradation of hard tissue matrix by osteoclasts are explained as an interference of the immune system with the natural equilibrium of tissue remodeling. Five mechanisms of promotion of bone loss through the influence of the immune system are described. One example is bone resorption as a consequence of the shift of the RANKL/osteoprotegerin balance by soluble RANKL synthesized by CD4(+) Th 1 cells as well as the interference with the coupling of osteoclasts and osteoblasts through dedifferentiation of osteoblasts by TNFα. Finally, the signaling required for down-regulation of inflammatory reactions and the reasons for the incomplete regeneration after periodontal bone loss are discussed. PMID:23600659