Sample records for equilibrium oxygen partial

  1. Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

    PubMed

    Guan, Zixuan; Chen, Di; Chueh, William C

    2017-08-30

    The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

  2. A defect model for UO2+x based on electrical conductivity and deviation from stoichiometry measurements

    NASA Astrophysics Data System (ADS)

    Garcia, Philippe; Pizzi, Elisabetta; Dorado, Boris; Andersson, David; Crocombette, Jean-Paul; Martial, Chantal; Baldinozzi, Guido; Siméone, David; Maillard, Serge; Martin, Guillaume

    2017-10-01

    Electrical conductivity of UO2+x shows a strong dependence upon oxygen partial pressure and temperature which may be interpreted in terms of prevailing point defects. A simulation of this property along with deviation from stoichiometry is carried out based on a model that takes into account the presence of impurities, oxygen interstitials, oxygen vacancies, holes, electrons and clusters of oxygen atoms. The equilibrium constants for each defect reaction are determined to reproduce the experimental data. An estimate of defect concentrations and their dependence upon oxygen partial pressure can then be determined. The simulations carried out for 8 different temperatures (973-1673 K) over a wide range of oxygen partial pressures are discussed and resulting defect equilibrium constants are plotted in an Arrhenius diagram. This provides an estimate of defect formation energies which may further be compared to other experimental data or ab-initio and empirical potential calculations.

  3. Solubility of oxygen in a seawater medium in equilibrium with a high-pressure oxy-helium atmosphere.

    PubMed

    Taylor, C D

    1979-06-01

    The molar oxygen concentration in a seawater medium in equilibrium with a high-pressure oxygen-helium atmosphere was measured directly in pressurized subsamples, using a modified version of the Winkler oxygen analysis. At a partial pressure of oxygen of 1 atm or less, its concentration in the aqueous phase was adequately described by Henry's Law at total pressures up to 600 atm. This phenomenon, which permits a straightforward determination of dissolved oxygen within hyperbaric systems, resulted from pressure-induced compensatory alterations in the Henry's Law variables rather than from a true obedience to the Ideal Gas Law. If the partial pressure of a gas contributes significantly to the hydrostatic pressure, Henry's Law is no longer adequate for determining its solubility within the compressed medium.

  4. Oxygen partial pressure sensor

    DOEpatents

    Dees, D.W.

    1994-09-06

    A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

  5. Oxygen partial pressure sensor

    DOEpatents

    Dees, Dennis W.

    1994-01-01

    A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

  6. The structural phase diagram and oxygen equilibrium partial pressure of YBa 2Cu 3O 6+ x studied by neutron powder diffraction and gas volumetry

    NASA Astrophysics Data System (ADS)

    Andersen, N. H.; Lebech, B.; Poulsen, H. F.

    1990-12-01

    An experimental technique based on neutron powder diffraction and gas volumetry is presented and used to study the structural phase diagram of YBa 2Cu 3O 6+ x under equilibrium conditions in an extended part of ( x, T)-phase (0.15< x<0.92 and 25° C< T<725°C). Our experimental observations lend strong support to a recent two-dimensional anisotropic next-nearest-neighbour Ising model calculation (the ASYNNNI model) of the basal plane oxygen ordering based of first principle interaction parameters. Simultaneous measurements of the oxygen equilibrium partial pressure show anomalies, one of which proves the thermodynamic stability of the orthorhombic OII double cell structure. Striking similarity with predictions of recent model calculations support that another anomaly may be interpreted to result from local one-dimensional fluctuations in the distribution of oxygen atoms in the basal plane of tetragonal YBCO. Our pressure data also indicate that x=0.92 is a maximum obtainable oxygen concentration for oxygen pressures below 760 Torr.

  7. Oxygen potentials, oxygen diffusion coefficients and defect equilibria of nonstoichiometric (U,Pu)O2±x

    NASA Astrophysics Data System (ADS)

    Kato, Masato; Watanabe, Masashi; Matsumoto, Taku; Hirooka, Shun; Akashi, Masatoshi

    2017-04-01

    Oxygen potential of (U,Pu)O2±x was evaluated based on defect chemistry using an updated experimental data set. The relationship between oxygen partial pressure and deviation x in (U,Pu)O2±x was analyzed, and equilibrium constants of defect formation were determined as functions of Pu content and temperature. Brouwer's diagrams were constructed using the determined equilibrium constants, and a relational equation to determine O/M ratio was derived as functions of O/M ratio, Pu content and temperature. In addition, relationship between oxygen potential and oxygen diffusion coefficients were described.

  8. The annealing mechanism of the radiation-induced vacancy-oxygen defect in silicon

    NASA Astrophysics Data System (ADS)

    Voronkov, V. V.; Falster, R.; Londos, C. A.

    2012-06-01

    Annealing experiments on the VO defect (the A-centre) produced by radiation in silicon—reported long ago—have been re-examined in order to deduce the two most important properties of VO: its diffusivity and the equilibrium constant for VO dissociation into V + O. The loss rate of VO is accounted for by two major reactions. One is the conventional reaction of the trapping of mobile VO by oxygen, thus producing VO2. The other is an annihilation of vacancies, which coexist in an equilibrium ratio with VO, by radiation-produced interstitial point defects. In some cases, a minor reaction, VO + V, should also be taken into account. The emerging minor defects V2O are also highly mobile. They partially dissociate back and partially get trapped by oxygen producing stable V2O2 defects.

  9. Finite-size versus interface-proximity effects in thin-film epitaxial SrTiO3

    NASA Astrophysics Data System (ADS)

    De Souza, R. A.; Gunkel, F.; Hoffmann-Eifert, S.; Dittmann, R.

    2014-06-01

    The equilibrium electrical conductivity of epitaxial SrTiO3 (STO) thin films was investigated as a function of temperature, 950≤ T/K ≤1100, and oxygen partial pressure, 10-23≤ pO2/bar ≤1. Compared with single-crystal STO, nanoscale thin-film STO exhibited with decreasing film thickness an increasingly enhanced electronic conductivity under highly reducing conditions, with a corresponding decrease in the activation enthalpy of conduction. This implies substantial modification of STO's point-defect thermodynamics for nanoscale film thicknesses. We argue, however, against such a finite-size effect and for an interface-proximity effect. Indeed, assuming trapping of oxygen vacancies at the STO surface and concomitant depletion of oxygen vacancies—and accumulation of electrons—in an equilibrium surface space-charge layer, we are able to predict quantitatively the conductivity as a function of temperature, oxygen partial pressure, and film thickness. Particularly complex behavior is predicted for ultrathin films that are consumed entirely by space charge.

  10. The change of steel surface chemistry regarding oxygen partial pressure and dew point

    NASA Astrophysics Data System (ADS)

    Norden, Martin; Blumenau, Marc; Wuttke, Thiemo; Peters, Klaus-Josef

    2013-04-01

    By investigating the surface state of a Ti-IF, TiNb-IF and a MnCr-DP after several series of intercritical annealing, the impact of the annealing gas composition on the selective oxidation process is discussed. On behalf of the presented results, it can be concluded that not the general oxygen partial pressure in the annealing furnace, which is a result of the equilibrium reaction of water and hydrogen, is the main driving force for the selective oxidation process. It is shown that the amounts of adsorbed gases at the strip surface and the effective oxygen partial pressure resulting from the adsorbed gases, which is mainly dependent on the water content of the annealing furnace, is driving the selective oxidation processes occurring during intercritical annealing. Thus it is concluded, that for industrial applications the dew point must be the key parameter value for process control.

  11. Phase Equilibria of ``Cu2O''-``FeO''-CaO-MgO-Al2O3 Slags at PO2 of 10-8.5 atm in Equilibrium with Metallic Copper for a Copper Slag Cleaning Production

    NASA Astrophysics Data System (ADS)

    Henao, Hector M.; Pizarro, Claudio; Font, Jonkion; Moyano, Alex; Hayes, Peter C.; Jak, Evgueni

    2010-12-01

    Limited data are available on phase equilibria of the multicomponent slag system at the oxygen partial pressures used in the copper smelting, converting, and slag-cleaning processes. Recently, experimental procedures have been developed and have been applied successfully to characterize several complex industrial slags. The experimental procedures involve high-temperature equilibration on a substrate and quenching followed by electron probe X-ray microanalysis. This technique has been used to construct the liquidus for the “Cu2O”-“FeO”-SiO2-based slags with 2 wt pct of CaO, 0.5 wt pct of MgO, and 4.0 wt pct of Al2O3 at controlled oxygen partial pressures in equilibrium with metallic copper. The selected ranges of compositions and temperatures are directly relevant to the copper slag-cleaning processes. The new experimental equilibrium results are presented in the form of ternary sections and as a liquidus temperature vs Fe/SiO2 weight ratio diagram. The experimental results are compared with the FactSage thermodynamic model calculations.

  12. Experimental Investigation of Gas/Slag/Matte/Spinel Equilibria in the Cu-Fe-O-S-Si System at 1473 K (1200 °C) and P(SO2) = 0.25 atm

    NASA Astrophysics Data System (ADS)

    Hidayat, Taufiq; Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

    2018-04-01

    New experimental data were obtained on the gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C) and P(SO2) = 0.25 atm covering Cu concentrations in matte between 42 and 78 wt pct Cu. Accurate measurements were obtained using high-temperature equilibration and the rapid quenching technique, followed by electron-probe X-ray microanalysis of equilibrium phase compositions. The use of spinel substrates made to support the samples ensures equilibrium with this primary phase solid, eliminates crucible contamination, and facilitates direct gas-condensed phase equilibrium and high quenching rates. Particular attention was given to the confirmation of the achievement of equilibrium. The results quantify the relationship between Cu in matte and oxygen partial pressure, sulfur in matte, oxygen in matte, Fe/SiO2 at slag liquidus, sulfur in slag, and dissolved copper in slag.

  13. Interpreting equilibrium-conductivity and conductivity-relaxation measurements to establish thermodynamic and transport properties for multiple charged defect conducting ceramics.

    PubMed

    Zhu, Huayang; Ricote, Sandrine; Coors, W Grover; Kee, Robert J

    2015-01-01

    A model-based interpretation of measured equilibrium conductivity and conductivity relaxation is developed to establish thermodynamic, transport, and kinetics parameters for multiple charged defect conducting (MCDC) ceramic materials. The present study focuses on 10% yttrium-doped barium zirconate (BZY10). In principle, using the Nernst-Einstein relationship, equilibrium conductivity measurements are sufficient to establish thermodynamic and transport properties. However, in practice it is difficult to establish unique sets of properties using equilibrium conductivity alone. Combining equilibrium and conductivity-relaxation measurements serves to significantly improve the quantitative fidelity of the derived material properties. The models are developed using a Nernst-Planck-Poisson (NPP) formulation, which enables the quantitative representation of conductivity relaxations caused by very large changes in oxygen partial pressure.

  14. FirefOx Design Reference fO2 Sensor for Hot, Deep Atmospheres

    NASA Astrophysics Data System (ADS)

    Izenberg, N.; Papadakis, S.; Deglau, D.; Francomacaro, A. S.

    2016-12-01

    Understanding the composition of the lowest portion of Venus' atmosphere is critical to knowing the stable mineralogy of the rocks there. Oxygen gas is a critical trace component, with fugacity, or partial pressure, estimated in the range of 10-19 to 10-22 from early probe measurements down to 22km altitude (Pioneer Venus, Venera), chemical equilibrium measurements, and other modeling. "FirefOx" is a simple oxygen fugacity sensor with the express purpose of determining the partial pressure of oxygen in the lowest scale heights of the Venus atmosphere, and especially the lowest hundreds of meters; the surface atmosphere interface, where the atmosphere and surface move to thermodynamic equilibrium. Knowledge of the fO2 at the surface atmosphere interface is crucial to determining the stable mineralogy of surface materials (e.g. magnetite vs. hematite) and gas chemistry in the near-surface atmosphere FirefOx is a Metal/Metal Oxide oxygen fugacity sensor intended to be mounted on the outside of a Venus descent probe, with electronics housed inside a thermally controlled environment. The sole sensor capability is the precise, accurate detection of the partial pressure of oxygen gas (fO2) in the near-surface environment of Venus, at up to 95-bar pressure (predominantly CO2. Surface temperatures at mean planetary elevation are near 735 K, thus a required operational temperature range of 710-740 K covers a range of near-surface elevations. FirefOx system requirements are low ( 100-200 grams, mass, milliwatt power, several kilobytes total science data). A design reference sensor, composed of custom, Yittria-ZrO ceramic electrolyte, with an encapsulated Pd/PdO standard and patterned Pt electrodes has demonstrated scientifically useful signal-to-noise millivolt level potential at temperatures as low as 620 K, relatable to fO2 by a Nernst equation E = RT/4F ln(PO2/PrefO2) where E = open circuit potential across the sensor electrolyte, R = universal gas constant, T = temperature, F = Faraday constant, PrefO2 = reference oxygen pressure, and PO2 = unknown oxygen pressure of the outside environment. The FirefOx sensor shows promise for direct fO2 measurement on potential upcoming Venus in situ and other deep atmosphere probes.

  15. Thermodynamic evaluation of oxygen behavior in Ti powder deoxidized by Ca reductant

    NASA Astrophysics Data System (ADS)

    Kim, Sun-Joong; Oh, Jung-Min; Lim, Jae-Won

    2016-07-01

    To produce low oxygen Ti powder of less than 1000 mass ppm, commercial Ti powder was deoxidized by two types of Ca reductants: a solid Ca and a Ca vapor. Compared with the iso-oxygen partial pressure in the Ti-O binary phase diagram, the PO2 in the raw Ti powder increased with temperature compared to the reduction reaction of Ca. Therefore, the O2 content in the Ti powder decreased as the deoxidation temperature increased from 873 K, showing a local minima at 1273 K. The oxygen concentration at 1373 K was greater than that at 1273 K because the oxygen solubility of the Ti powder was increased by the equilibrium relation between Ca and CaO. On the basis of the thermodynamic assessment, the deoxidation of Ti powder can be improved by increasing the temperature and lowering the oxygen solubility with the saturation of CaO.

  16. Oxygen self-diffusion mechanisms in monoclinic Zr O2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Yang, Jing; Youssef, Mostafa; Yildiz, Bilge

    2018-01-01

    In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold- and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in Zr O2 -related devices and parametrization for continuum transport modeling.

  17. Instrument for stable high temperature Seebeck coefficient and resistivity measurements under controlled oxygen partial pressure

    DOE PAGES

    Ihlefeld, Jon F.; Brown-Shaklee, Harlan James; Sharma, Peter Anand

    2015-04-28

    The transport properties of ceramic materials strongly depend on oxygen activity, which is tuned by changing the partial oxygen pressure (pO 2) prior to and during measurement. Within, we describe an instrument for highly stable measurements of Seebeck coefficient and electrical resistivity at temperatures up to 1300 K with controlled oxygen partial pressure. An all platinum construction is used to avoid potential materials instabilities that can cause measurement drift. Two independent heaters are employed to establish a small temperature gradient for Seebeck measurements, while keeping the average temperature constant and avoiding errors associated with pO 2-induced drifts in thermocouple readings.more » Oxygen equilibrium is monitored using both an O 2 sensor and the transient behavior of the resistance as a proxy. A pO 2 range of 10 -25–10 0 atm can be established with appropriate gas mixtures. Seebeck measurements were calibrated against a high purity platinum wire, Pt/Pt–Rh thermocouple wire, and a Bi 2Te3 Seebeck coefficient Standard Reference Material. To demonstrate the utility of this instrument for oxide materials we present measurements as a function of pO 2 on a 1 % Nb-doped SrTiO 3 single crystal, and show systematic changes in properties consistent with oxygen vacancy defect chemistry. Thus, an approximately 11% increase in power factor over a pO 2 range of 10 -19–10 -8 atm at 973 K for the donor-doped single crystals is observed.« less

  18. Desulfurization kinetics of molten copper by gas bubbling

    NASA Astrophysics Data System (ADS)

    Fukunaka, Y.; Nishikawa, K.; Sohn, H. S.; Asaki, Z.

    1991-02-01

    Molten copper with 0.74 wt pct sulfur content was desulfurized at 1523 K by bubbling Ar-O2 gas through a submerged nozzle. The reaction rate was significantly influenced not only by the oxygen partial pressure but also by the gas flow rate. Little evolution of SO2 gas was observed in the initial 10 seconds of the oxidation; however, this was followed by a period of high evolution rate of SO2 gas. The partial pressure of SO2 gas decreased with further progress of the desulfurization. The effect of the immersion depth of the submerged nozzle was negligible. The overall reaction is decomposed to two elementary reactions: the desulfurization and the dissolution rate of oxygen. The assumptions were made that these reactions are at equilibrium and that the reaction rates are controlled by mass transfer rates within and around the gas bubble. The time variations of sulfur and oxygen contents in the melt and the SO2 partial pressure in the off-gas under various bubbling conditions were well explained by the mathematical model combined with the reported thermodynamic data of these reactions. Based on the present model, it was anticipated that the oxidation rate around a single gas bubble was mainly determined by the rate of gas-phase mass transfer, but all oxygen gas blown into the melt was virtually consumed to the desulfurization and dissolution reactions before it escaped from the melt surface.

  19. Ab initio investigation of the thermodynamics of cation distribution and of the electronic and magnetic structures in the LiMn2O4 spinel

    NASA Astrophysics Data System (ADS)

    Santos-Carballal, David; Ngoepe, Phuti E.; de Leeuw, Nora H.

    2018-02-01

    The spinel-structured lithium manganese oxide (LiMn2O4 ) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behavior of LiMn2O4 derived from spin-polarized density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn2O4 spinel. This equilibrium degree of inversion is rationalized in terms of the crystal field stabilization effects and the difference between the size of the cations. We compare the atomic charges with the oxidation numbers for each degree of inversion. We found segregation of the Mn charge once these ions occupy the tetrahedral and octahedral sites of the spinel. We have obtained the atomic projections of the electronic band structure and density of states, showing that the normal LiMn2O4 has half-metallic properties, while the fully inverse spinel is an insulator. This material is in the ferrimagnetic state for the inverse and partially inverse cation arrangement. The optimized lattice and oxygen parameters, as well as the equilibrium degree of inversion, are in agreement with the available experimental data. The partial equilibrium degree of inversion is important in the interpretation of the lithium ion migration and surface properties of the LiMn2O4 spinel.

  20. Influence of oxygen partial pressure on surface tension and its temperature coefficient of molten iron

    NASA Astrophysics Data System (ADS)

    Ozawa, S.; Suzuki, S.; Hibiya, T.; Fukuyama, H.

    2011-01-01

    Influences of oxygen partial pressure, PO2, of ambient atmosphere and temperature on surface tension and its temperature coefficient for molten iron were experimentally investigated by an oscillating droplet method using an electromagnetic levitation furnace. We successfully measured the surface tension of molten iron over a very wide temperature range of 780 K including undercooling condition in a well controlled PO2 atmosphere. When PO2 is fixed at 10-2 Pa at the inlet of the chamber, a "boomerang shape" temperature dependence of surface tension was experimentally observed; surface tension increased and then decreased with increasing temperature. The pure surface tension of molten iron was deduced from the negative temperature coefficient in the boomerang shape temperature dependence. When the surface tension was measured under the H2-containing gas atmosphere, surface tension did not show a linear relationship against temperature. The temperature dependence of the surface tension shows anomalous kink at around 1850 K due to competition between the temperature dependence of PO2 and that of the equilibrium constant of oxygen adsorption.

  1. The defect chemistry of UO2 ± x from atomistic simulations

    NASA Astrophysics Data System (ADS)

    Cooper, M. W. D.; Murphy, S. T.; Andersson, D. A.

    2018-06-01

    Control of the defect chemistry in UO2 ± x is important for manipulating nuclear fuel properties and fuel performance. For example, the uranium vacancy concentration is critical for fission gas release and sintering, while all oxygen and uranium defects are known to strongly influence thermal conductivity. Here the point defect concentrations in thermal equilibrium are predicted using defect energies from density functional theory (DFT) and vibrational entropies calculated using empirical potentials. Electrons and holes have been treated in a similar fashion to other charged defects allowing for structural relaxation around the localized electronic defects. Predictions are made for the defect concentrations and non-stoichiometry of UO2 ± x as a function of oxygen partial pressure and temperature. If vibrational entropy is omitted, oxygen interstitials are predicted to be the dominant mechanism of excess oxygen accommodation over only a small temperature range (1265 K-1350 K), in contrast to experimental observation. Conversely, if vibrational entropy is included oxygen interstitials dominate from 1165 K to 1680 K (Busker potential) or from 1275 K to 1630 K (CRG potential). Below these temperature ranges, excess oxygen is predicted to be accommodated by uranium vacancies, while above them the system is hypo-stoichiometric with oxygen deficiency accommodated by oxygen vacancies. Our results are discussed in the context of oxygen clustering, formation of U4O9, and issues for fuel behavior. In particular, the variation of the uranium vacancy concentrations as a function of temperature and oxygen partial pressure will underpin future studies into fission gas diffusivity and broaden the understanding of UO2 ± x sintering.

  2. Thermodynamics Behavior of Germanium During Equilibrium Reactions between FeOx-CaO-SiO2-MgO Slag and Molten Copper

    NASA Astrophysics Data System (ADS)

    Shuva, M. A. H.; Rhamdhani, M. A.; Brooks, G. A.; Masood, S.; Reuter, M. A.

    2016-10-01

    The distribution ratio of germanium (Ge), L_{{Ge}}^{s/m} during equilibrium reactions between magnesia-saturated FeOx-CaO-SiO2 (FCS) slag and molten copper has been measured under oxygen partial pressures from 10-10 to 10-7 atm and at temperatures 1473 to 1623 K (1200 to 1350 °C). It was observed that the Ge distribution ratio increases with increasing oxygen partial pressure, and with decreasing temperature. It was also observed that the distribution ratio is strongly dependent on slag basicity. The distribution ratio was observed to increase with increasing optical basicity. At fixed CaO concentration in the slag, the distribution ratio was found to increase with increasing Fe/SiO2 ratio, tending to a plateau at L_{{Ge}}^{s/m} = 0.8. This behavior is consistent with the assessment of ionic bond fraction carried out in this study, and suggested the acidic nature of germanium oxide (GeO2) in the slag system studied. The characterisation results of the quenched slag suggested that Ge is present in the FeOx-CaO-SiO2-MgO slag predominantly as GeO2. At 1573 K (1300 °C) and p_{{{{O}}2 }} = 10-8 atm, the activity coefficient of GeO2 in the slag was calculated to be in the range of 0.24 to 1.50. The results from the current study suggested that less-basic slag, high operating temperature, and low oxygen partial pressure promote a low Ge distribution ratio. These conditions are desired for maximizing Ge recovery, for example, during pyrometallurgical processing of Ge-containing e-waste through secondary copper smelting. Overall, the thermodynamics data generated from this study can be used for process modeling purposes for improving recovery of Ge in primary and secondary copper smelting processes.

  3. Lunar oxygen production by pyrolysis of regolith

    NASA Technical Reports Server (NTRS)

    Senior, Constance L.

    1991-01-01

    Oxygen represents one of the most desirable products of lunar mining and manufacturing. Among the many processes which have been proposed for oxygen production, pyrolysis stands out as one which is uncomplicated and easy to bootstrap. Pyrolysis or vapor-phase reduction involves heating regolith to temperatures sufficient to allow partial decomposition and vaporization. Some metal oxides give up oxygen upon heating, either in the gas phase to form reduced gaseous species or in the condensed phase to form a metallic phase. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2200 K, giving total gas pressures of 0.001 to 0.1 torr. Bulk regolith can be used as a feedstock without beneficiation with concentrated solar radiation supplying most of energy needed. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts.

  4. Removal of Oxygen from Electronic Materials by Vapor-Phase Processes

    NASA Technical Reports Server (NTRS)

    Palosz, Witold

    1997-01-01

    Thermochemical analyses of equilibrium partial pressures over oxides with and without the presence of the respective element condensed phase, and hydrogen, chalcogens, hydrogen chalcogenides, and graphite are presented. Theoretical calculations are supplemented with experimental results on the rate of decomposition and/or sublimation/vaporization of the oxides under dynamic vacuum, and on the rate of reaction with hydrogen, graphite, and chalcogens. Procedures of removal of a number of oxides under different conditions are discussed.

  5. Reaction rates of oxygen with hemoglobin measured by non-equilibrium facilitated oxygen diffusion through hemoglobin solutions.

    PubMed

    Bouwer, S T; Hoofd, L; Kreuzer, F

    2001-02-16

    The purpose of this study was to verify the concept of non-equilibrium facilitated oxygen diffusion. This work succeeds our previous study, where facilitated oxygen diffusion by hemoglobin was measured at conditions of chemical equilibrium, and which yielded diffusion coefficients of hemoglobin and of oxygen. In the present work chemical non-equilibrium was induced using very thin diffusion layers. As a result, facilitation was decreased as predicted by theory. Thus, this work presents the first experimental demonstration of non-equilibrium facilitated oxygen diffusion. In addition, association and dissociation rate parameters of the reaction between oxygen and bovine and human hemoglobin were calculated and the effect of the homotropic and heterotropic interactions on each rate parameter was demonstrated. The results indicate that the homotropic interaction--which leads to increasing oxygen affinity with increasing oxygenation--is predominantly due to an increase in the association rate. The heterotropic interaction--which leads to decreasing oxygen affinity by anionic ligands--appears to be effected in two ways. Cl- increases the dissociation rate. In contrast, 2,3-diphosphoglycerate decreases the association rate.

  6. [Role of hemoglobin affinity to oxygen in adaptation to hypoxemia].

    PubMed

    Kwasiborski, Przemysław Jerzy; Kowalczyk, Paweł; Zieliński, Jakub; Przybylski, Jacek; Cwetsch, Andrzej

    2010-04-01

    One of the basic mechanisms of adapting to hypoxemia is a decrease in the affinity of hemoglobin for oxygen. This process occurs mainly due to the increased synthesis of 2,3-diphosphoglycerate (2,3-DPG) in the erythrocytes, as well as through the Bohr effect. Hemoglobin with decreased affinity for oxygen increases the oxygenation of tissues, because it gives up oxygen more easily during microcirculation. In foetal circulation, however, at a partial oxygen pressure (pO2) of 25 mmHg in the umbilical vein, the oxygen carrier is type F hemoglobin which has a high oxygen affinity. The commonly accepted role for hemoglobin F is limited to facilitating diffusion through the placenta. Is fetal life the only moment when haemoglobin F is useful? THE AIM OF STUDY was to create a mathematical model, which would answer the question at what conditions an increase, rather than a decrease, in haemoglobin oxygen affinity is of benefit to the body. Using the kinetics of dissociation of oxygen from hemoglobin described by the Hill equation as the basis for further discussion, we created a mathematical model describing the pO2 value in the microcirculatory system and its dependence on arterial blood pO2. The calculations were performed for hemoglobin with low oxygen affinity (adult type) and high-affinity hemoglobin (fetal type). The modelling took into account both physiological and pathological ranges of acid-base equilibrium and tissue oxygen extraction parameters. It was shown that for the physiological range of acid-base equilibrium and the resting level of tissue oxygen extraction parameters, with an arterial blood pO2 of 26.8 mmHg, the higher-affinity hemoglobin becomes the more effective oxygen carrier. It was also demonstrated that the arterial blood pO2, below which the high-affinity hemoglobin becomes the more effective carrier, is dependent on blood pH and the difference between the arterial and venous oxygen saturation levels. Simulations performed for the pathological states showed that acidosis and increased tissue oxygen demand lead to a broadened arterial blood pO2 range, in which the high-affinity hemoglobin is more efficient. Contrary to the widely held view that the only response to hypoxemia is a decrease in haemoglobin oxygen affinity, it was shown that under extreme hypoxemic conditions, an increased haemoglobin oxygen affinity improves the oxygenation of tissues. It was also shown that the dominance of hemoglobin with a high oxygen affinity rapidly exceeds hemoglobin with low oxygen affinity in the case of acidosis with its accompanying high tissue oxygen extraction. In cases of extreme disruptions of the acid-base equilibrium, the dominance of high-oxygen-affinity hemoglobin spans over the entire possible range of pO2 in arterial blood.

  7. Study Program to Develop and Evaluate Die and Container Materials for the Growth of Silicon Ribbons

    NASA Technical Reports Server (NTRS)

    Ounby, P. D.; Yu, B. B.; Barsoum, M. W.

    1979-01-01

    The completion of a major hardware delivery milestone was accomplished with the delivery of three CNTD Si3N4 coated hot pressed Si3N4 crucibles. A limited characterization of the coating was performed at MRL prior to delivery. The coatings were fine grained alpha - Si3N4. It was determined that a two piece die design is required. The importance of the role of oxygen in influencing the attack of the CNTD materials by molten silicon was demonstrated. The stability is greatly enhanced by maintaining the oxygen partial pressure near or below the Si + O2 = SiO2 equilibrium.

  8. Solid state solubility of copper oxides in hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

    2018-06-01

    Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

  9. Oxygen isotopes as a tracer of phosphate sources and cycling in aquatic systems (Invited)

    NASA Astrophysics Data System (ADS)

    Young, M. B.; Kendall, C.; Paytan, A.

    2013-12-01

    The oxygen isotopic composition of phosphate can provide valuable information about sources and processes affecting phosphorus as it moves through hydrologic systems. Applications of this technique in soil and water have become more common in recent years due to improvements in extraction methods and instrument capabilities, and studies in multiple aquatic environments have demonstrated that some phosphorus sources may have distinct isotopic compositions within a given system. Under normal environmental conditions, the oxygen-phosphorus bonds in dissolved inorganic phosphate (DIP) can only be broken by enzymatic activity. Biological cycling of DIP will bring the phosphate oxygen into a temperature-dependent equilibrium with the surrounding water, overprinting any existing isotopic source signals. However, studies conducted in a wide range of estuarine, freshwater, and groundwater systems have found that the phosphate oxygen is often out of biological equilibrium with the water, suggesting that it is common for at least a partial isotopic source signal to be retained in aquatic systems. Oxygen isotope analysis on various potential phosphate sources such as synthetic and organic fertilizers, animal waste, detergents, and septic/wastewater treatment plant effluents show that these sources span a wide range of isotopic compositions, and although there is considerable overlap between the source groups, sources may be isotopically distinct within a given study area. Recent soil studies have shown that isotopic analysis of phosphate oxygen is also useful for understanding microbial cycling across different phosphorus pools, and may provide insights into controls on phosphorus leaching. Combining stable isotope information from soil and water studies will greatly improve our understanding of complex phosphate cycling, and the increasing use of this isotopic technique across different environments will provide new information regarding anthropogenic phosphate inputs and controls on biological cycling within hydrologic systems.

  10. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Merkulov, O.V., E-mail: merkulov@ihim.uran.ru; Samigullin, R.R.; Markov, A.A.

    The electrical conductivity of SrFe{sub 1–x}Sn{sub x}O{sub 3–δ} (x=0.05, 0.10, 017) was measured by a four-probe dc technique in the partial oxygen pressure range of 10{sup –18}–0.5 atm at temperatures between 800 °Ð ÐŽ and 950 °Ð ÐŽ. The oxygen content in these oxides was measured under the same ambient conditions by means of coulometric titration. The thermodynamic analysis of oxygen nonstoichiometry data was carried out to determine the equilibrium constants for defect-formation reactions and to calculate the concentrations of ion and electron charge carriers. The partial contributions of oxygen ions, electrons and holes to charge transport were assessed, and the mobilitymore » of respective carriers was evaluated by an integral examination of the electrical conductivity and oxygen nonstoichiometry data. It has been found that the mobility of holes in SrFe{sub 1−x}Sn{sub x}O{sub 3−δ} varies in the range of ~0.005–0.04 cm{sup 2} V{sup −1} s{sup −1}, linearly increasing with the oxygen content and decreasing with increased tin concentration. The mobility of electron carriers was shown to be independent of the oxygen content. The average migration energy of an electron was estimated to be ~0.45 eV, with that of a hole being ~0.3 eV. - Highlights: • The conductivity and oxygen nonstoichiometry in SrFe{sub 1−x}Sn{sub x}O{sub 3−δ} were measured. • Tin substitution was found to affect insignificantly defect formation reactions. • The hole mobility was found to increase linearly with the oxygen content. • The hole mobility was found to be much higher than the electron mobility.« less

  11. Thermodynamic equilibrium calculations of hydrogen production from the combined processes of dimethyl ether steam reforming and partial oxidation

    NASA Astrophysics Data System (ADS)

    Semelsberger, Troy A.; Borup, Rodney L.

    Thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the combined processes of dimethyl ether (DME) partial oxidation and steam reforming were investigated as a function of oxygen-to-carbon ratio (0.00-2.80), steam-to-carbon ratio (0.00-4.00), temperature (100 °C-600 °C), pressure (1-5 atm) and product species. Thermodynamically, dimethyl ether processed with air and steam generates hydrogen-rich fuel-cell feeds; however, the hydrogen concentration is less than that for pure DME steam reforming. Results of the thermodynamic processing of dimethyl ether indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 °C, oxygen-to-carbon ratios greater than 0.00 and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure has negligible effects on the hydrogen content. Thermodynamically, dimethyl ether can produce concentrations of hydrogen and carbon monoxide of 52% and 2.2%, respectively, at a temperature of 300 °C, and oxygen-to-carbon ratio of 0.40, a pressure of 1 atm and a steam-to-carbon ratio of 1.50. The order of thermodynamically stable products (excluding H 2, CO, CO 2, DME, NH 3 and H 2O) in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol and methyl-ethyl ether; trace amounts of formaldehyde, formic acid and methanol are observed. Ammonia and hydrogen cyanide are also thermodynamically favored products. Ammonia is favored at low temperatures in the range of oxygen-to-carbon ratios of 0.40-2.50 regardless of the steam-to-carbon ratio employed. The maximum ammonia content (i.e., 40%) occurs at an oxygen-to-carbon ratio of 0.40, a steam-to-carbon ratio of 1.00 and a temperature of 100 °C. Hydrogen cyanide is favored at high temperatures and low oxygen-to-carbon ratios with a maximum of 3.18% occurring at an oxygen-to-carbon ratio of 0.40 and a steam-to-carbon ratio of 0.00 in the temperature range of 400 °C-500 °C. Increasing the system pressure shifts the equilibrium toward ammonia and hydrogen cyanide.

  12. New Stagnation Arc Jet Model Design for Testing ADEPT 3-D Carbon Cloth

    NASA Technical Reports Server (NTRS)

    Beck, R.; Chen, Y.-K.; Wercinski, P.; Agrawal, P.; Chavez-Garcia, J.

    2017-01-01

    The ADEPT concept has been considered as an entry, descent and landing system to enable Human Mars class missions. Ground rules for the Mars studies required aerocapture, orbit, and then entry. The design utilizes a 3-D woven carbon cloth fabric as both heatshield and primary structure and design guidelines required 6 layers remaining after all entry events. The peak heating predicted for the ADEPT carbon cloth was 35 Wcm2 and resulting temperatures were predicted to be 1400K. Predictions for carbon mass loss were performed using equilibrium thermochemistry, which is only accurate for T2000K. Carbon oxidation is kinetically controlled at T2000K, and mass loss drops off considerably from equilibrium values. Design of the cloth thickness and mass would be significantly reduced if kinetics were considered. This effort was to design a stagnation test article design that could be used in the AHF with varying levels of oxygen where the results could be used to develop an engineering model to describe the recession rate of the carbon as a function of the partial pressure of monotomic oxygen.

  13. Time required for partial pressure of arterial oxygen equilibration during mechanical ventilation after a step change in fractional inspired oxygen concentration.

    PubMed

    Cakar, N; Tuŏrul, M; Demirarslan, A; Nahum, A; Adams, A; Akýncý, O; Esen, F; Telci, L

    2001-04-01

    To determine the time required for the partial pressure of arterial oxygen (PaO2) to reach equilibrium after a 0.20 increment or decrement in fractional inspired oxygen concentration (FIO2) during mechanical ventilation. A multi-disciplinary ICU in a university hospital. Twenty-five adult, non-COPD patients with stable blood gas values (PaO2/FIO2 > or = 180 on the day of the study) on pressure-controlled ventilation (PCV). Following a baseline PaO2 (PaO2b) measurement at FIO2 = 0.35, the FIO2 was increased to 0.55 for 30 min and then decreased to 0.35 without any other change in ventilatory parameters. Sequential blood gas measurements were performed at 3, 5, 7, 9, 11, 15, 20, 25 and 30 min in both periods. The PaO2 values measured at the 30th min after a step change in FIO2 (FIO2 = 0.55, PaO2[55] and FIO2 = 0.35, PaO2[35]) were accepted as representative of the equilibrium values for PaO2. Each patient's rise and fall in PaO2 over time, PaO2(t), were fitted to the following respective exponential equations: PaO2b + (PaO2[55]-PaO2b)(1-e-kt) and PaO2[55] + (PaO2[35]-PaO2[55])(e-kt) where "t" refers to time, PaO2[55] and PaO2[35] are the final PaO2 values obtained at a new FIO2 of 0.55 and 0.35, after a 0.20 increment and decrement in FIO2, respectively. Time constant "k" was determined by a non-linear fitting curve and 90% oxygenation times were defined as the time required to reach 90% of the final equilibrated PaO2 calculated by using the non-linear fitting curves. Time constant values for the rise and fall periods were 1.01 +/- 0.71 min-1, 0.69 +/- 0.42 min-1, respectively, and 90% oxygenation times for rises and falls in PaO2 periods were 4.2 +/- 4.1 min-1 and 5.5 +/- 4.8 min-1, respectively. There was no significant difference between the rise and fall periods for the two parameters (p > 0.05). We conclude that in stable patients ventilated with PCV, after a step change in FIO2 of 0.20, 5-10 min will be adequate for obtaining a blood gas sample to measure a PaO2 that will be representative of the equilibrium PaO2 value.

  14. Twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+x studied by neutron powder diffraction and gas volumetry

    NASA Astrophysics Data System (ADS)

    Poulsen, H. F.; Andersen, N. H.; Lebech, B.

    1991-02-01

    We report experimental results of twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+ x, which supplement a previous and simultaneous study of the structural phase diagram and oxygen equilibrium partial pressure. Analysis of neutron powder diffraction peak broadening show features which are identified to result from temperature independent twin-domain formation in to different orthorhombic phases with domain sizes and 250 and 350Å, respectively. The oxygen in-diffusion flow shows simple relaxation type behaviour J=J 0 exp( {-t}/{τ}) despite a rather broad particle size distribution. At higher temperatures, τ is activated with activation energies 0.55 and 0.25 eV in the tetragonal and orthorhombic phases, respectively. Comparison between twin-domain sizes and bulk oxygen in-diffusion time constants indicates that the twin-domain boundaries may contribute to the effective bulk oxygen in-diffusion. All our results may be interpreted in terms of the 2D ASYNNNI model description of the oxygen basal plane ordering, and they suggest that recent first principles interaction parameters should be modified.

  15. A determination of the oxygen non-stoichiometry of the oxygen storage material YBaMn{sub 2}O{sub 5+δ}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana

    2015-10-15

    The A-site ordered double-perovskite oxide, YBaMn{sub 2}O{sub 5+δ}, has been of recent interest for possible application as an oxygen storage material. In the present study, the oxygen non-stoichiometry of YBaMn{sub 2}O{sub 5+δ} has been determined as a function of pO{sub 2} at 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that this perovskite oxide has three distinct phases on oxidation/reduction with δ≈0, 0.5 and 1. The stabilities of the YBaMn{sub 2}O{sub 5+δ} phases span a wide range of oxygen partial pressures (∼10{sup −20}≤pO{sub 2}(atm)≤∼1 ) depending on temperature. The phases interconvert at higher pO{submore » 2} values at higher temperatures. The partial molar free energies (Δμ{sub O}) corresponding to the oxidation of YBaMn{sub 2}O{sub 5} to YBaMn{sub 2}O{sub 5.5} and of YBaMn{sub 2}O{sub 5.5} to YBaMn{sub 2}O{sub ∼6} were determined. The value of Δμ{sub O} in both oxidation steps becomes less negative with increasing temperature. At some T and pO{sub 2} conditions, YBaMn{sub 2}O{sub 5+δ} is unstable with respect to decomposition to BaMnO{sub 3−δ} and YMnO{sub 3}. This instability is anticipated from the previous studies of the synthesis of YBaMn{sub 2}O{sub 5+δ} but is more apparent in the present experiments which are necessarily slow in order to achieve equilibrium with respect to the oxygen content. - Highlights: • Determination of the oxygen non-stoichiometry of YBaMn{sub 2}O{sub 5+δ} as a function of pO{sub 2} and T. • Establishments of pO{sub 2} ranges of stability of O{sub 5} and O{sub 5.5} at 650 °C, 700 °C and 750 °C. • Discovery of the kinetic instability of YBaMn{sub 2}O{sub 5+δ} with respect to decomposition to BaMnO{sub 3}−{sub x} and YMnO{sub 3}. • Evaluation of the thermodynamics of the oxidation of YBaMnO{sub 5}.« less

  16. Evolution of Metallicity in Vanadium Dioxide by Creation of Oxygen Vacancies

    NASA Astrophysics Data System (ADS)

    Zhang, Zhen; Zuo, Fan; Wan, Chenghao; Dutta, Aveek; Kim, Jongbum; Rensberg, Jura; Nawrodt, Ronny; Park, Helen Hejin; Larrabee, Thomas J.; Guan, Xiaofei; Zhou, You; Prokes, S. M.; Ronning, Carsten; Shalaev, Vladimir M.; Boltasseva, Alexandra; Kats, Mikhail A.; Ramanathan, Shriram

    2017-03-01

    Tuning of the electronic state of correlated materials is key to their eventual use in advanced electronics and photonics. The prototypical correlated oxide (VO2 ) is insulating at room temperature and transforms to a metallic state when heated to 67 °C (340 K). We report the emergence of a metallic state that is preserved down to 1.8 K by annealing thin films of VO2 at an ultralow oxygen partial pressure (PO2˜10-24 atm ). The films can be reverted back to their original state by annealing in oxygen, and this process can be iterated multiple times. The metallic phase created by oxygen deficiency has a tetragonal rutile structure and contains a large number of oxygen vacancies far beyond the solubility at equilibrium (greater than approximately 50 times). The oxygen starvation reduces the oxidation state of vanadium from V4 + to V3 + and leads to the metallization. The extent of resistance reduction (concurrent with tuning of optical properties) can be controlled by the time-temperature envelope of the annealing conditions since the process is diffusionally driven. This experimental platform, which can extensively tune oxygen vacancies in correlated oxides, provides an approach to study emergent phases and defect-mediated adaptive electronic and structural phase boundary crossovers.

  17. Mechanism of formation and spatial distribution of lead atoms in quartz tube atomizers

    NASA Astrophysics Data System (ADS)

    Johansson, M.; Baxter, D. C.; Ohlsson, K. E. A.; Frech, W.

    1997-05-01

    The cross-sectional and longitudinal spatial distributions of lead atoms in a quartz tube (QT) atomizers coupled to a gas chromatograph have been investigated. A uniform analyte atom distribution over the cross-section was found in a QT having an inner diameter (i.d.) of 7 mm, whereas a 10 mm i.d. QT showed an inhomogeneous distribution. These results accentuate the importance of using QTs with i.d.s below 10 mm to fulfil the prerequirement of the Beer—Lambert law to avoid bent calibration curves. The influence of the make up gas on the formation of lead atoms from alkyllead compounds has been studied, and carbon monoxide was found equally efficient in promoting free atom formation as hydrogen. This suggests that hydrogen radicals are not essential for mediating the atomization of alkyllead in QT atomizers at ˜ 1200 K. Furthermore, thermodynamic equilibrium calculations describing the investigated system were performed supporting the experimental results. Based on the presented data, a mechanism for free lead atom formation in continuously heated QT atomizers is proposed; thermal atomization occurs under thermodynamic equilibrium conditions in a reducing gas. The longitudinal atom distribution has been further investigated applying other make up gases, N 2 and He. These results show the effect of the influx of atmospheric oxygen on the free lead atom formation. Calculations of the partial pressure of oxygen in the atomizer gas phase assuming thermodynamic equilibrium have been undertaken using a convective-diffusional model.

  18. Direct Measurement of Equilibrium Constants for High-Affinity Hemoglobins

    PubMed Central

    Kundu, Suman; Premer, Scott A.; Hoy, Julie A.; Trent, James T.; Hargrove, Mark S.

    2003-01-01

    The biological functions of heme proteins are linked to their rate and affinity constants for ligand binding. Kinetic experiments are commonly used to measure equilibrium constants for traditional hemoglobins comprised of pentacoordinate ligand binding sites and simple bimolecular reaction schemes. However, kinetic methods do not always yield reliable equilibrium constants with more complex hemoglobins for which reaction mechanisms are not clearly understood. Furthermore, even where reaction mechanisms are clearly understood, it is very difficult to directly measure equilibrium constants for oxygen and carbon monoxide binding to high-affinity (KD ≪ 1 μM) hemoglobins. This work presents a method for direct measurement of equilibrium constants for high-affinity hemoglobins that utilizes a competition for ligands between the "target" protein and an array of "scavenger" hemoglobins with known affinities. This method is described for oxygen and carbon monoxide binding to two hexacoordinate hemoglobins: rice nonsymbiotic hemoglobin and Synechocystis hemoglobin. Our results demonstrate that although these proteins have different mechanisms for ligand binding, their affinities for oxygen and carbon monoxide are similar. Their large affinity constants for oxygen, 285 and ∼100 μM−1 respectively, indicate that they are not capable of facilitating oxygen transport. PMID:12770899

  19. Blood oxygen binding in hypoxaemic calves.

    PubMed

    Cambier, Carole; Clerbaux, Thierry; Detry, Bruno; Marville, Vincent; Frans, Albert; Gustin, Pascal

    2002-01-01

    Blood oxygen transport and tissue oxygenation were studied in 28 calves from the Belgian White and Blue breed (20 healthy and 8 hypoxaemic ones). Hypoxaemic calves were selected according to their high respiratory frequency and to their low partial oxygen pressure (PaO2) in the arterial blood. Venous and arterial blood samples were collected, and 2,3-diphosphoglycerate, adenosine triphosphate, chloride, inorganic phosphate and hemoglobin concentrations, and pH, PCO, and PO2 were determined. An oxygen equilibrium curve (OEC) was measured in standard conditions, for each animal. The arterial and venous OEC were calculated, taking body temperature, pH and PCO2 values in arterial and venous blood into account. The oxygen exchange fraction (OEF%), corresponding to the degree of blood desaturation between the arterial and the venous compartments, and the amount of oxygen released at the tissue level by 100 mL of blood (OEF Vol%) were calculated from the arterial and venous OEC combined with the PO2 and hemoglobin concentration. In hypoxaemic calves investigated in this study, the hemoglobin oxygen affinity, measured under standard conditions, was not modified. On the contrary, in vivo acidosis and hypercapnia induced a decrease in the hemoglobin oxygen affinity in arterial blood, which combined to the decrease in PaO2 led to a reduced hemoglobin saturation degree in the arterial compartment. However, this did not impair the oxygen exchange fraction (OEF%), since the hemoglobin saturation degree in venous blood was also diminished.

  20. Constraints on Ureilite Petrogenesis and Carbon-Metal-Silicate Equilibria on the UPB

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Holloway, J. R.

    1992-07-01

    The most important constraints on models of ureilite petrogenesis are 1) Ureilites have lost a basaltic complement (they are ultramafic, extremely depleted in plagiophile elements, enriched in HREE, and have negative Eu anomalies and superchondritic Ca/Al ratios). 2) Ureilites experienced long equilibration times at high T (indicated by coarse grain size, extreme homogeneity of core crystals, correlations between olivine and pyroxene compositions, and metamorphic-like textures), followed by rapid cooling (indicated by structural features of pyroxene and narrow reduction rims on olivine). 3) Ureilites are probably residues (based on mass balance) but partly crystallized from melts. 4) Ureilites are derived from a minimum of six reservoirs that were distinct in oxygen isotopic composition and did not equilibrate with one another (this is consistent with the observation that olivine and pyroxene cores do not show correlations of mg with MnO, Cr2O3, Sm/Eu or Lu/Eu). 5) There is a correlation between oxygen isotopic composition and mg ratio in ureilites. Similar correlations are observed for Allende chondrules and group means of H3-L3-LL3 chondrites (Fig. 1), and are argued to result from nebular processes [1]. 6) If graphite-metal-silicate-CO/CO2 equilibrium was established during melting, then mg ratios of ureilites were determined by depth because CCO redox reactions are strongly pressure-dependent. Cohenite-bearing metallic spherule inclusions in the silicates and euhedral shapes of large graphite crystals in low-shock ureilites have been taken as evidence of equilibrium. Olivine reduction rims, highly variable interstitial metal compositions, and a lack of correlation between mg and metal content argue against equilibrium. 7) Ureilites either lost a low melting-T metal fraction or gained a refractory-rich metal component. (they have high abundances of siderophile elements but show fractionation between [Os, Ir, W, Re] and [Ni, Ga, Ge, Au]). 8) Primordial noble gases were retained in some carbon phases. 9) Ureilites formed at ~4.55 Ga but both Sm-Nd and Rb-Sr isotopic systematics have been subsequently disturbed. Constraints 1-4 are best met if ureilites are partial melt residues produced by ~25% equilibrium partial melting on an oxygen-isotopically heterogeneous parent body in >=6 distinct melting zones. If there was no global magma ocean, km-sized melting zones would not equilibrate oxygen with one another in 10 m.y. Constraints 5 and 6 appear difficult to reconcile. If the UPB inherited a nebular oxygen isotope-mg correlation how could this correlation have survived partial melting? If the melting zones all experienced approximately the same degree of melting (Mn/Mg, Cr/Mg, and HRE provide evidence for this), and silicate equilibria determined mg, then the original correlation may simply have shifted to higher mg, consistent with the position of the ureilite trend relative to the Allende trends (Fig. 1). However, if mg was depth-dependent then it is unlikely that any oxygen isotope-mg correlation would remain. Also, noble gases in carbon would be lost (violating constraint 8) during carbon redox reactions. All constraints would be better met if graphite-metal-silicate-CO/CO2 equilibrium was not established during partial melting. If graphite was primary but a CO/CO2 fluid phase was not present then there would have been no pressure/depth dependence of fO(sub)2. As long as the pressure was sufficiently high (~100-200 bars) to stabilize the most ferroan ureilite (Fo 76) then the more magnesian ureilites would have been stable in the presence of graphite and metal. On the other hand, constraints 7, 8, and 9 could be neatly met if most of the carbon was not primary but a carbon-metal-noble gas assemblage was added as a late component to the ultramafic rocks. The cohenite-bearing metallic spherules are rare and tiny (10-50 micrometers) compared to interstitial metal (mm-sized irregular grains). They appear to have been droplets of immiscible, hypereutectic Fe(Ni)-C liquids that were trapped by crystallizing silicates. In contrast, the interstitial metal and graphite show no evidence of having been a liquid Fe-C alloy and their confinement to grain boundaries and reduction rims is consistent with late addition. Goodrich and Berkley (2) argued that the spherules were carbon-saturated at 1200-1225 degrees C and therefore that the silicate liquid must have contained graphite. However, in the Fe-C system the stable graphite liquidus is much steeper than the metastable cohenite liquidus, and although these alloys were cohenite-saturated, they were not graphite-saturated. Hence, the silicate magma probably did not contain graphite and carbon was not the dominant control on fO(sub)2. Thus, it may be possible to reconcile the main constraints on ureilite petrogenesis without high pressures. [1] R.N. Clayton & T.K. Mayeda (1988] GCA 52, 1313. [2] C.A. Goodrich & J.L. Berkely (1986) GCA 50, 681.

  1. Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

    NASA Astrophysics Data System (ADS)

    Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

    2017-12-01

    The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

  2. Device for measuring the total concentration of oxygen in gases

    DOEpatents

    Isaacs, Hugh S.; Romano, Anthony J.

    1977-01-01

    This invention provides a CO equilibrium in a device for measuring the total concentration of oxygen impurities in a fluid stream. To this end, the CO equilibrium is produced in an electrochemical measuring cell by the interaction of a carbon element in the cell with the chemically combined and uncombined oxygen in the fluid stream at an elevated temperature.

  3. Effect of Humid Aging on the Oxygen Adsorption in SnO₂ Gas Sensors.

    PubMed

    Suematsu, Koichi; Ma, Nan; Watanabe, Ken; Yuasa, Masayoshi; Kida, Tetsuya; Shimanoe, Kengo

    2018-01-16

    To investigate the effect of aging at 580 °C in wet air (humid aging) on the oxygen adsorption on the surface of SnO₂ particles, the electric properties and the sensor response to hydrogen in dry and humid atmospheres for SnO₂ resistive-type gas sensors were evaluated. The electric resistance in dry and wet atmospheres at 350 °C was strongly increased by humid aging. From the results of oxygen partial pressure dependence of the electric resistance, the oxygen adsorption equilibrium constants ( K ₁; for O - adsorption, K ₂; for O 2- adsorption) were estimated on the basis of the theoretical model of oxygen adsorption. The K ₁ and K ₂ in dry and wet atmospheres at 350 °C were increased by humid aging at 580 °C, indicating an increase in the adsorption amount of both O - and O 2- . These results suggest that hydroxyl poisoning on the oxygen adsorption is suppressed by humid aging. The sensor response to hydrogen in dry and wet atmosphere at 350 °C was clearly improved by humid aging. Such an improvement of the sensor response seems to be caused by increasing the oxygen adsorption amount. Thus, the humid aging offers an effective way to improve the sensor response of SnO₂ resistive-type gas sensors in dry and wet atmospheres.

  4. Factors associated with blood oxygen partial pressure and carbon dioxide partial pressure regulation during respiratory extracorporeal membrane oxygenation support: data from a swine model.

    PubMed

    Park, Marcelo; Mendes, Pedro Vitale; Costa, Eduardo Leite Vieira; Barbosa, Edzangela Vasconcelos Santos; Hirota, Adriana Sayuri; Azevedo, Luciano Cesar Pontes

    2016-01-01

    The aim of this study was to explore the factors associated with blood oxygen partial pressure and carbon dioxide partial pressure. The factors associated with oxygen - and carbon dioxide regulation were investigated in an apneic pig model under veno-venous extracorporeal membrane oxygenation support. A predefined sequence of blood and sweep flows was tested. Oxygenation was mainly associated with extracorporeal membrane oxygenation blood flow (beta coefficient = 0.036mmHg/mL/min), cardiac output (beta coefficient = -11.970mmHg/L/min) and pulmonary shunting (beta coefficient = -0.232mmHg/%). Furthermore, the initial oxygen partial pressure and carbon dioxide partial pressure measurements were also associated with oxygenation, with beta coefficients of 0.160 and 0.442mmHg/mmHg, respectively. Carbon dioxide partial pressure was associated with cardiac output (beta coefficient = 3.578mmHg/L/min), sweep gas flow (beta coefficient = -2.635mmHg/L/min), temperature (beta coefficient = 4.514mmHg/ºC), initial pH (beta coefficient = -66.065mmHg/0.01 unit) and hemoglobin (beta coefficient = 6.635mmHg/g/dL). In conclusion, elevations in blood and sweep gas flows in an apneic veno-venous extracorporeal membrane oxygenation model resulted in an increase in oxygen partial pressure and a reduction in carbon dioxide partial pressure 2, respectively. Furthermore, without the possibility of causal inference, oxygen partial pressure was negatively associated with pulmonary shunting and cardiac output, and carbon dioxide partial pressure was positively associated with cardiac output, core temperature and initial hemoglobin.

  5. 21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

  6. 21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

  7. 21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

  8. 21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

  9. 21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

  10. Vanadium oxide thin films produced by magnetron sputtering from a V2O5 target at room temperature

    NASA Astrophysics Data System (ADS)

    de Castro, Marcelo S. B.; Ferreira, Carlos L.; de Avillez, Roberto R.

    2013-09-01

    Vanadium oxide thin films were grown by RF magnetron sputtering from a V2O5 target at room temperature, an alternative route of production of vanadium oxide thin films for infrared detector applications. The films were deposited on glass substrates, in an argon-oxygen atmosphere with an oxygen partial pressure from nominal 0% to 20% of the total pressure. X-ray diffraction (XRD) and X-ray photon spectroscopy (XPS) analyses showed that the films were a mixture of several vanadium oxides (V2O5, VO2, V5O9 and V2O3), which resulted in different colors, from yellow to black, depending on composition. The electrical resistivity varied from 1 mΩ cm to more than 500 Ω cm and the thermal coefficient of resistance (TCR), varied from -0.02 to -2.51% K-1. Computational thermodynamics was used to simulate the phase diagram of the vanadium-oxygen system. Even if plasma processes are far from equilibrium, this diagram provides the range of oxygen pressures that lead to the growth of different vanadium oxide phases. These conditions were used in the present work.

  11. Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

    NASA Technical Reports Server (NTRS)

    Montgomery, Christopher J.; Kosaly, George; Riley, James J.

    1993-01-01

    Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

  12. Factors associated with blood oxygen partial pressure and carbon dioxide partial pressure regulation during respiratory extracorporeal membrane oxygenation support: data from a swine model

    PubMed Central

    Park, Marcelo; Mendes, Pedro Vitale; Costa, Eduardo Leite Vieira; Barbosa, Edzangela Vasconcelos Santos; Hirota, Adriana Sayuri; Azevedo, Luciano Cesar Pontes

    2016-01-01

    Objective The aim of this study was to explore the factors associated with blood oxygen partial pressure and carbon dioxide partial pressure. Methods The factors associated with oxygen - and carbon dioxide regulation were investigated in an apneic pig model under veno-venous extracorporeal membrane oxygenation support. A predefined sequence of blood and sweep flows was tested. Results Oxygenation was mainly associated with extracorporeal membrane oxygenation blood flow (beta coefficient = 0.036mmHg/mL/min), cardiac output (beta coefficient = -11.970mmHg/L/min) and pulmonary shunting (beta coefficient = -0.232mmHg/%). Furthermore, the initial oxygen partial pressure and carbon dioxide partial pressure measurements were also associated with oxygenation, with beta coefficients of 0.160 and 0.442mmHg/mmHg, respectively. Carbon dioxide partial pressure was associated with cardiac output (beta coefficient = 3.578mmHg/L/min), sweep gas flow (beta coefficient = -2.635mmHg/L/min), temperature (beta coefficient = 4.514mmHg/ºC), initial pH (beta coefficient = -66.065mmHg/0.01 unit) and hemoglobin (beta coefficient = 6.635mmHg/g/dL). Conclusion In conclusion, elevations in blood and sweep gas flows in an apneic veno-venous extracorporeal membrane oxygenation model resulted in an increase in oxygen partial pressure and a reduction in carbon dioxide partial pressure 2, respectively. Furthermore, without the possibility of causal inference, oxygen partial pressure was negatively associated with pulmonary shunting and cardiac output, and carbon dioxide partial pressure was positively associated with cardiac output, core temperature and initial hemoglobin. PMID:27096671

  13. S-nitrosylation of GAD65 is implicated in decreased GAD activity and oxygen-induced seizures.

    PubMed

    Gasier, Heath G; Demchenko, Ivan T; Tatro, Lynn G; Piantadosi, Claude A

    2017-07-13

    Breathing oxygen at partial pressures ≥2.5 atmospheres absolute, which can occur in diving and hyperbaric oxygen (HBO 2 ) therapy, can rapidly become toxic to the central nervous system (CNS). This neurotoxicity culminates in generalized EEG epileptiform discharges, tonic-clonic convulsions and ultimately death. Increased production of neuronal nitric oxide (NO) has been implicated in eliciting hyperoxic seizures by altering the equilibrium between glutamatergic and GABAergic synaptic transmission. Inhibition of glutamic acid decarboxylase (GAD) activity in HBO 2 promotes this imbalance; however, the mechanisms by which this occurs is unknown. Therefore, we conducted a series of experiments using mice, a species that is highly susceptible to CNS oxygen toxicity, to explore the possibility that NO modulates GABA metabolism. Mice were exposed to 100% oxygen at 4 ATA for various durations, and brain GAD and GABA transaminase (GABA-T) activity, as well as S-nitrosylation of GAD65 and GAD67 were determined. HBO 2 inhibited GAD activity by 50% and this was negatively correlated with S-nitrosylation of GAD65, whereas GABA-T activity and S-nitrosylation of GAD67 were unaltered. These results suggest a new mechanism by which NO alters GABA metabolism, leading to neuroexcitation and seizures in HBO 2 . Published by Elsevier B.V.

  14. Continuous Structural Transition in Glass-Forming Molten Titanate BaTi 2 O 5

    DOE PAGES

    Alderman, O. L. G.; Benmore, C. J.; Tamalonis, A.; ...

    2016-12-01

    The structure of the model titanate glass former BaTi2O5 has been studied over a wide temperature (T) range in the molten, supercooled, and glassy states under conditions of aerodynamic levitation. Both high-energy X-ray diffraction and Ti K-edge X-ray absorption spectroscopy reveal a continuous structural transition involving reduction of the cation-oxygen (and oxygen-cation) average coordination numbers and bond lengths with increasing T. Ti-0 coordination in the moderately supercooled and equilibrium melt follows a linear trend n(Tio) = 5.4(1)- [3.5(7) x 10(-4)]T [K] (1300 <= T <= 1830 K, T-g = 960 K, T-m = 1660 K). Comparison to the melt-quenched glassmore » implies an increase in partial derivative n(Tio)/partial derivative T at lower T, as T-g is approached from above. Both Ba-0 coordination and bond length also decrease at higher T, and the role of Ba addition is to reduce n(Tio) below its value in pure molten TiO2, which is related to the presence of density maxima in molten BaO-TiO2. Density measurements made by imaging of the levitated melt yielded rho(T) = 4.82(55)- 0.0004(3)T in units of K and g cm(-3). While BaTi2O5 glass likely consists of a fully connected Ti-0 network, free of nonbridging oxygen (NBO) [OTi1 and with at least 13(4)% [OTi3] triclusters, the 1835(40) K equilibrium melt contains at least 10(4)% NBO along with 90(4)% bridging oxygen [OTi2]. The results highlight the fact that glasses can be considered as structural analogues of melts only for those melts deeply supercooled into the glass transition region. The results imply possible fictive T dependence of titanate glass structure, suggesting applications as, e.g., laser written waveguides with large refractive indices and refractive index contrasts. The temperature-dependent structure further implies a super-Arrhenian melt viscosity with consequences for glass manufacture, titanate-rich slags produced in iron smelting, TiO2-bearing magmas, and by analogy silicate melts at high pressures, as found in planetary interiors.« less

  15. Shock-tube measurements of carbon to oxygen atom ratios for incipient soot formation with C2H2, C2H4 and C2H6 fuels

    NASA Technical Reports Server (NTRS)

    Radcliffe, S. W.; Appleton, J. P.

    1971-01-01

    The critical atomic carbon to oxygen ratios, Phi sub C, for incipient soot formation in shock heated acetylene, ethylene, ethane/oxygen/ argon mixtures was measured over the temperature range 2000 K to 2500 K for reactant partial pressures between 0.1 and 0.4 atoms. Absorption of light from a He-Ne laser at 6328A was was used to detect soot. It was observed that the values of Phi sub C for all three fuels increased uniformly with temperature such that at the highest temperatures Phi sub C was considerably greater than unity, i.e. greater than the value of about unity at which solid carbon should have been precipitated on a thermochemical equilibrium basis. Observations were made over periods extending up to about one millisecond, which was well in excess of the time required for the major heat release of the combustion reactions. The relevance of these experimental findings to the problem of soot formation in gas turbine combustion chambers is discussed.

  16. Combustion of hydrogen injected into a supersonic airstream (the SHIP computer program)

    NASA Technical Reports Server (NTRS)

    Markatos, N. C.; Spalding, D. B.; Tatchell, D. G.

    1977-01-01

    The mathematical and physical basis of the SHIP computer program which embodies a finite-difference, implicit numerical procedure for the computation of hydrogen injected into a supersonic airstream at an angle ranging from normal to parallel to the airstream main flow direction is described. The physical hypotheses built into the program include: a two-equation turbulence model, and a chemical equilibrium model for the hydrogen-oxygen reaction. Typical results for equilibrium combustion are presented and exhibit qualitatively plausible behavior. The computer time required for a given case is approximately 1 minute on a CDC 7600 machine. A discussion of the assumption of parabolic flow in the injection region is given which suggests that improvement in calculation in this region could be obtained by use of the partially parabolic procedure of Pratap and Spalding. It is concluded that the technique described herein provides the basis for an efficient and reliable means for predicting the effects of hydrogen injection into supersonic airstreams and of its subsequent combustion.

  17. Vapor pressure and vapor fractionation of silicate melts of tektite composition

    USGS Publications Warehouse

    Walter, Louis S.; Carron, M.K.

    1964-01-01

    The total vapor pressure of Philippine tektite melts of approximately 70 per cent silica has been determined at temperatures ranging from 1500 to 2100??C. This pressure is 190 ?? 40 mm Hg at 1500??C, 450 ?? 50 mm at 1800??C and 850 ?? 70 mm at 2100?? C. Determinations were made by visually observing the temperature at which bubbles began to form at a constant low ambient pressure. By varying the ambient pressure, a boiling point curve was constructed. This curve differs from the equilibrium vapor pressure curve due to surface tension effects. This difference was evaluated by determining the equilibrium bubble size in the melt and calculating the pressure due to surface tension, assuming the latter to be 380 dyn/cm. The relative volatility from tektite melts of the oxides of Na, K, Fe, Al and Si has been determined as a function of temperature, total pressure arid roughly, of oxygen fugacity. The volatility of SiO2 is decreased and that of Na2O and K2O is increased in an oxygen-poor environment. Preliminary results indicate that volatilization at 2100??C under atmospheric pressure caused little or no change in the percentage Na2O and K2O. The ratio Fe3 Fe2 of the tektite is increased in ambient air at a pressure of 9 ?? 10-4 mm Hg (= 106.5 atm O2, partial pressure) at 2000??C. This suggests that tektites were formed either at lower oxygen pressures or that they are a product of incomplete oxidation of parent material with a still lower ferricferrous ratio. ?? 1964.

  18. The Oxygen Equilibrium of Mammalian Hemoglobin

    PubMed Central

    Roughton, F. J. W.

    1965-01-01

    The three chief physicochemical theories of the oxygen-hemoglobin equilibrium in vogue 40 years ago still influence current thought on the problem. Although the Hill theory lost its fundamental basis some 40 years ago, the famous empiric equation to which it gave rise is still much used, as a useful phenomenological expression, only involving two disposable constants. The Haldane theory, of which a difference in aggregation of oxygenated and deoxygenated hemoglobin was a fundamental feature, lay for many years dormant but has recently had an astonishing reawakening through the work on lamprey hemoglobin, which clearly reveals such differences in aggregation. Lamprey hemoglobin might thus be called a "Haldane type" hemoglobin. Adair's four-stage intermediate compound theory still seems applicable in the case of hemoglobins such as those of sheep, whose tetramer molecules do not tend to dissociate into dimers, and which might therefore be called "Adair type" hemoglobins. Horse and human hemoglobins appear to reveal both "Haldane" and "Adair" behaviour. The effects of pH, temperature, and protein concentration on the oxygen-equilibrium of sheep hemoglobin are summarised, and it is shown that, although the equilibrium curves are often isomorphous over their middle range, intensive work at the top and bottom of the curves reveals considerable differences in the relative effects of these factors on the several equilibrium constants of Adair's four intermediate equations. In the last section an account is given of preliminary experimental attempts to interpret the oxygen- and carbon monoxide—equilibrium curves of whole human blood, under physiological conditions in terms of the Adair intermediate compound hypothesis. PMID:5859923

  19. Oxygen Partial Pressure and Oxygen Concentration Flammability: Can They Be Correlated?

    NASA Technical Reports Server (NTRS)

    Harper, Susana A.; Juarez, Alfredo; Perez, Horacio, III; Hirsch, David B.; Beeson, Harold D.

    2016-01-01

    NASA possesses a large quantity of flammability data performed in ISS airlock (30% Oxygen 526mmHg) and ISS cabin (24.1% Oxygen 760 mmHg) conditions. As new programs develop, other oxygen and pressure conditions emerge. In an effort to apply existing data, the question arises: Do equivalent oxygen partial pressures perform similarly with respect to flammability? This paper evaluates how material flammability performance is impacted from both the Maximum Oxygen Concentration (MOC) and Maximum Total Pressures (MTP) perspectives. From these studies, oxygen partial pressures can be compared for both the MOC and MTP methods to determine the role of partial pressure in material flammability. This evaluation also assesses the influence of other variables on flammability performance. The findings presented in this paper suggest flammability is more dependent on oxygen concentration than equivalent partial pressure.

  20. A determination of the oxygen non-stoichiometry of the oxygen storage materials LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana

    The A-site ordered double-perovskite oxides, LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr), were synthesized and investigated to understand the effect of A site cation substitution on the oxygen storage properties of these materials. The present results are compared with our previous data for YBaMn{sub 2}O{sub 5+δ}. The results clearly reveal that changing the Ln cation strongly influences the oxidation/reduction behavior of LnBaMn{sub 2}O{sub 5+δ}. Based on thermogravimetric analysis data, oxygen uptake begins at lower temperatures in both air and oxygen in compounds with Ln{sup 3+} ions larger than Y{sup 3+}. These oxides exhibit almost complete and reversible oxygen uptake/release between fully-reduced LnBaMn{submore » 2}O{sub 5} and fully-oxidized LnBaMn{sub 2}O{sub 6} during changes of the oxygen partial pressure between air and 1.99% H{sub 2}/Ar. In addition, the oxygen non-stoichiometries of GdBaMn{sub 2}O{sub 5+δ} and PrBaMn{sub 2}O{sub 5+δ} were determined as a function of pO{sub 2} at 600, 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that these materials have two distinct phases on oxidation/reduction with δ≈0, 0.5 and a third phase with a range of composition with an oxygen content (5+δ) approaching ~6. The stabilities of the LnBaMn{sub 2}O{sub 5+δ} phases extend over a wide range of oxygen partial pressures (∼10{sup −25}≤pO{sub 2} (atm)≤∼1) depending on temperature. Isothermal experiments show that the larger the Ln{sup 3+} cation the lower pO{sub 2} for phase conversion. At some temperatures and pO{sub 2} conditions, the LnBaMn{sub 2}O{sub 5+δ} compounds are unstable with respect to decomposition to BaMnO{sub 3−δ} and LnMnO{sub 3}. This instability is more apparent in Coulometric titration experiments than in thermogravimetric analysis. The Coulometric titration experiments are necessarily slow in order to achieve equilibrium oxygen compositions. - Graphical abstract: Structure of LnBaMn{sub 2}O{sub 5.5} and the variation of stoichiometry of GdBaMn{sub 2}O{sub 5+x} with −log(pO{sub 2}) Display Omitted - Highlights: • Determination of the oxygen non-stoichiometry of GdBaMn{sub 2}O{sub 5+δ} and PrBaMn{sub 2}O{sub 5+δ} as a function of pO{sub 2} and T. • Establishment of pO{sub 2} ranges of stability of O{sub 5} and O{sub 5.5} at 600 °C, 650 °C, 700 °C and 750 °C. • Investigation of the kinetic instability of LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr) with respect to decomposition to BaMnO{sub 3−x} and LnMnO{sub 3} • Comparison of the thermodynamics of the oxidation of LnBaMnO{sub 5} (Ln=Y, Gd, Pr) as a function of the rare earth cation size.« less

  1. Thin film devices used as oxygen partial pressure sensors

    NASA Technical Reports Server (NTRS)

    Canady, K. S.; Wortman, J. J.

    1970-01-01

    Electrical conductivity of zinc oxide films to be used in an oxygen partial pressure sensor is measured as a function of temperature, oxygen partial pressure, and other atmospheric constituents. Time response following partial pressure changes is studied as a function of temperature and environmental changes.

  2. Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

  3. Effects of Oxygen Partial Pressure on the Surface Tension of Liquid Nickel

    NASA Technical Reports Server (NTRS)

    SanSoucie, Michael P.; Rogers, Jan R.; Gowda, Vijaya Kumar Malahalli Shankare; Rodriguez, Justin; Matson, Douglas M.

    2015-01-01

    The NASA Marshall Space Flight Center's electrostatic levitation (ESL) laboratory has been recently upgraded with an oxygen partial pressure controller. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, theoretically in the range from 10-36 to 100 bar. The oxygen control system installed in the ESL laboratory's main chamber consists of an oxygen sensor, oxygen pump, and a control unit. The sensor is a potentiometric device that determines the difference in oxygen activity in two gas compartments (inside the chamber and the air outside of the chamber) separated by an electrolyte, which is yttria-stabilized zirconia. The pump utilizes coulometric titration to either add or remove oxygen. The system is controlled by a desktop control unit, which can also be accessed via a computer. The controller performs temperature control for the sensor and pump, PID-based current loop, and a control algorithm. Oxygen partial pressure has been shown to play a significant role in the surface tension of liquid metals. Oxide films or dissolved oxygen may lead to significant changes in surface tension. The effects of oxygen partial pressure on the surface tension of undercooled liquid nickel will be analyzed, and the results will be presented. The surface tension will be measured at several different oxygen partial pressures while the sample is undercooled. Surface tension will be measured using the oscillating drop method. While undercooled, each sample will be oscillated several times consecutively to investigate how the surface tension behaves with time while at a particular oxygen partial pressure.

  4. Ozone chemical equilibrium in the extended mesopause under the nighttime conditions

    NASA Astrophysics Data System (ADS)

    Belikovich, M. V.; Kulikov, M. Yu.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

    2018-01-01

    For retrieval of atomic oxygen and atomic hydrogen via ozone observations in the extended mesopause region (∼70-100 km) under nighttime conditions, an assumption on photochemical equilibrium of ozone is often used in research. In this work, an assumption on chemical equilibrium of ozone near mesopause region during nighttime is proofed. We examine 3D chemistry-transport model (CTM) annual calculations and determine the ratio between the correct (modeled) distributions of the O3 density and its equilibrium values depending on the altitude, latitude, and season. The results show that the retrieval of atomic oxygen and atomic hydrogen distributions using an assumption on ozone chemical equilibrium may lead to large errors below ∼81-87 km. We give simple and clear semi-empirical criterion for practical utilization of the lower boundary of the area with ozone's chemical equilibrium near mesopause.

  5. Report on ISS Oxygen Production, Resupply, and Partial Pressure Management

    NASA Technical Reports Server (NTRS)

    Schaezler, Ryan; Ghariani, Ahmed; Leonard, Daniel; Lehman, Daniel

    2011-01-01

    The majority of oxygen used on International Space Station (ISS) is for metabolic support and denitrogenation procedures prior to Extra-Vehicular Activities. Oxygen is supplied by various visiting vehicles such as the Progress and Shuttle in addition to oxygen production capability on both the United States On-Orbit Segment (USOS) and Russian Segment (RS). To maintain a habitable atmosphere the oxygen partial pressure is controlled between upper and lower bounds. The full range of the allowable oxygen partial pressure along with the increased ISS cabin volume is utilized as a buffer allowing days to pass between oxygen production or direct addition of oxygen to the atmosphere from reserves. This paper summarizes amount of oxygen supplied and produced from all of the sources and describes past experience of managing oxygen partial pressure along with the range of management options available to the ISS.

  6. Studies on the phase diagram of Pb-Fe-O system and standard molar Gibbs energy of formation of 'PbFe5O8.5' and Pb2Fe2O5

    NASA Astrophysics Data System (ADS)

    Sahu, Sulata Kumari; Ganesan, Rajesh; Gnanasekaran, T.

    2012-07-01

    Partial phase diagram of Pb-Fe-O system has been established by phase equilibration studies over a wide temperature range coupled with high temperature solid electrolyte based emf cells. Ternary oxides are found to coexist with liquid lead only at temperatures above 900 K. At temperatures below 900 K, iron oxides coexist with liquid lead. Standard molar Gibbs energy of formation of ternary oxides 'PbFe5O8.5' and Pb2Fe2O5 were determined by measuring equilibrium oxygen partial pressures over relevant phase fields using emf cells and are given by the following expressions: ΔfGmo 'PbFeO'±1.0(kJ mol)=-2208.1+0.6677(T/K) (917⩽T/K⩽1117) ΔfGmo PbFeO±0.8(kJ mol)=-1178.4+0.3724(T/K) (1050⩽T/K⩽1131) .

  7. Pulsatile Flow and Gas Transport of Blood over an Array of Cylinders

    NASA Astrophysics Data System (ADS)

    Chan, Kit Yan

    2005-11-01

    In the artificial lung, blood passes through an array of micro-fibers and the gas transfer is strongly dependent on the flow field. The blood flow is unsteady and pulsatile. We have numerically simulated pulsatile flow and gas transfer of blood (modeled as a Casson fluid) over arrays of cylindrical micro-fibers. Oxygen and carbon dioxide are assumed to be in local equilibrium with hemoglobin in blood; and the carbon dioxide facilitated oxygen transport is incorporated into the model by allowing the coupling of carbon dioxide partial pressure and oxygen saturation. The pulsatile flow inputs considered are the sinusoidal and the cardiac waveforms. The squared and staggered arrays of arrangement of the cylinders are considered in this study. Gas transport can be enhanced by: increasing the oscillation frequency; increasing the Reynolds number; increasing the oscillation amplitude; decreasing the void fraction; the use of the cardiac pulsatile input. The overall gas transport is greatly enhanced by the presence of hemoglobin in blood even though the non-Newtonian effect of blood tends to decrease the size and strength of vortices. The pressure drop is also presented as it is an important design parameter confronting the heart.

  8. Oxygen and carbon isotope disequilibria in Galapagos corals: isotopic thermometry and calcification physiology

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    McConnaughey, T.A.

    1986-01-01

    Biological carbonate skeletons are built largely from carbon dioxide, which reacts to form carbonate ion within thin extracellular solutions. The light isotopes of carbon and oxygen react faster than the heavy isotopes, depleting the resulting carbonate ions in /sup 13/C and /sup 18/O. Calcium carbonate precipitation occurs sufficiently fast that the skeleton remains out of isotopic equilibrium with surrounding fluids. This explanation for isotopic disequilibrium in biological carbonates was partially simulated in vitro, producing results similar to those seen in non-photosynthetic corals. Photosynthetic corals have higher /sup 13/C//sup 12/C ratios due to the preferential removal of /sup 12/C (as organicmore » carbon) from the reservoir of dissolved inorganic carbon. The oxygen isotopic variations in corals can be used to reconstruct past sea surface temperatures to an accuracy of about 0.5/sup 0/C. The carbon isotopic content of photosynthetic corals provides an indication of cloudiness. Using isotopic data from Galapagos corals, it was possible to construct proxy histories of the El Nino phenomenon. The physiology of skeletogenesis appears to be surprisingly similar in calcium carbonate, calcium phosphate, and silica precipitating systems.« less

  9. Insight of DFT and ab initio atomistic thermodynamics on the surface stability and morphology of In2O3

    NASA Astrophysics Data System (ADS)

    Zhang, Minhua; Wang, Wenyi; Chen, Yifei

    2018-03-01

    In2O3 catalysts show remarkable activity and selectivity in methanol synthesis from CO2 hydrogenation. In order to get insight into the surface stability of this catalyst, density functional theory and ab initio atomistic thermodynamics method were used to investigate the surface free energies of various facets as a function of oxygen chemical potential, as well as the influences of temperature, pressure and gas compositions. The results show that the (111) facet presents lowest surface free energy under oxygen-rich condition, while the indium-terminated (100) facet is the most stable one under oxygen-lean condition. Moreover, we applied Wulff construction to determine the equilibrium shape of In2O3 with different oxygen chemical potentials. The equilibrium shape under oxygen-lean condition is cubic, which only expose (100) facet, while, the equilibrium shape under oxygen-rich condition is octahedron, which only expose (111) facet. Meanwhile, the results agree well with what is observed experimentally. It is further predicted that Wulff shape of In2O3 exists in a truncated octahedron morphology in which the (100) surface becomes predominant plane under CO2 hydrogenation reaction conditions.

  10. [Correlation between the inspired fraction of oxygen, maternal partial oxygen pressure, and fetal partial oxygen pressure during cesarean section of normal pregnancies].

    PubMed

    Castro, Carlos Henrique Viana de; Cruvinel, Marcos Guilherme Cunha; Carneiro, Fabiano Soares; Silva, Yerkes Pereira; Cabral, Antônio Carlos Vieira; Bessa, Roberto Cardoso

    2009-01-01

    Despite changes in pulmonary function, maternal oxygenation is maintained during obstetric regional blocks. But in those situations, the administration of supplementary oxygen to parturients is a common practice. Good fetal oxygenation is the main justification; however, this has not been proven. The objective of this randomized, prospective study was to test the hypothesis of whether maternal hyperoxia is correlated with an increase in fetal gasometric parameters in elective cesarean sections. Arterial blood gases of 20 parturients undergoing spinal block with different inspired fractions of oxygen were evaluated and correlated with fetal arterial blood gases. An increase in maternal inspired fraction of oxygen did not show any correlation with an increase of fetal partial oxygen pressure. Induction of maternal hyperoxia by the administration of supplementary oxygen did not increase fetal partial oxygen pressure. Fetal gasometric parameters did not change even when maternal parameters changed, induced by hyperoxia, during cesarean section under spinal block.

  11. Oxygen supply in aquatic ectotherms: partial pressure and solubility together explain biodiversity and size patterns.

    PubMed

    Verberk, Wilco C E P; Bilton, David T; Calosi, Piero; Spicer, John I

    2011-08-01

    Aquatic ectotherms face the continuous challenge of capturing sufficient oxygen from their environment as the diffusion rate of oxygen in water is 3 x 10(5) times lower than in air. Despite the recognized importance of oxygen in shaping aquatic communities, consensus on what drives environmental oxygen availability is lacking. Physiologists emphasize oxygen partial pressure, while ecologists emphasize oxygen solubility, traditionally expressing oxygen in terms of concentrations. To resolve the question of whether partial pressure or solubility limits oxygen supply in nature, we return to first principles and derive an index of oxygen supply from Fick's classic first law of diffusion. This oxygen supply index (OSI) incorporates both partial pressure and solubility. Our OSI successfully explains published patterns in body size and species across environmental clines linked to differences in oxygen partial pressure (altitude, organic pollution) or oxygen solubility (temperature and salinity). Moreover, the OSI was more accurately and consistently related to these ecological patterns than other measures of oxygen (oxygen saturation, dissolved oxygen concentration, biochemical oxygen demand concentrations) and similarly outperformed temperature and altitude, which covaried with these environmental clines. Intriguingly, by incorporating gas diffusion rates, it becomes clear that actually more oxygen is available to an organism in warmer habitats where lower oxygen concentrations would suggest the reverse. Under our model, the observed reductions in aerobic performance in warmer habitats do not arise from lower oxygen concentrations, but instead through organismal oxygen demand exceeding supply. This reappraisal of how organismal thermal physiology and oxygen demands together shape aerobic performance in aquatic ectotherms and the new insight of how these components change with temperature have broad implications for predicting the responses of aquatic communities to ongoing global climate shifts.

  12. Direct computation of thermodynamic properties of chemically reacting air with consideration to CFD

    NASA Astrophysics Data System (ADS)

    Iannelli, Joe

    2003-10-01

    This paper details a two-equation procedure to calculate exactly mass and mole fractions, pressure, temperature, specific heats, speed of sound and the thermodynamic and jacobian partial derivatives of pressure and temperature for a five-species chemically reacting equilibrium air. The procedure generates these thermodynamic properties using as independent variables either pressure and temperature or density and internal energy, for CFD applications. An original element in this procedure consists in the exact physically meaningful solution of the mass-fraction and mass-action equations. Air-equivalent molecular masses for oxygen and nitrogen are then developed to account, within a mixture of only oxygen and nitrogen, for the presence of carbon dioxide, argon and the other noble gases within atmospheric air. The mathematical formulation also introduces a versatile system non-dimensionalization that makes the procedure uniformly applicable to flows ranging from shock-tube flows with zero initial velocity to aerothermodynamic flows with supersonic/hypersonic free-stream Mach numbers. Over a temperature range of more than 10000 K and pressure and density ranges corresponding to an increase in altitude in standard atmosphere of 30000 m above sea level, the predicted distributions of mole fractions, constant-volume specific heat, and speed of sound for the model five species agree with independently published results, and all the calculated thermodynamic properties, including their partial derivatives, remain continuous, smooth, and physically meaningful.

  13. Selective photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1998-01-01

    A selective photooxidation process for the conversion of hydrocarbon molecules to partially oxygenated derivatives, which comprises the steps of adsorbing a hydrocarbon and oxygen onto a dehydrated zeolite support matrix to form a hydrocarbon-oxygen contact pair, and subsequently exposing the hydrocarbon-oxygen contact pair to visible light, thereby forming a partially oxygenated derivative.

  14. Conversion rate of para-hydrogen to ortho-hydrogen by oxygen: implications for PHIP gas storage and utilization.

    PubMed

    Wagner, Shawn

    2014-06-01

    To determine the storability of para-hydrogen before reestablishment of the room temperature thermal equilibrium mixture. Para-hydrogen was produced at near 100% purity and mixed with different oxygen quantities to determine the rate of conversion to the thermal equilibrium mixture of 75: 25% (ortho: para) by detecting the ortho-hydrogen (1)H nuclear magnetic resonance using a 9.4 T imager. The para-hydrogen to ortho-hydrogen velocity constant, k, near room temperature (292 K) was determined to be 8.27 ± 1.30 L/mol · min(-1). This value was calculated utilizing four different oxygen fractions. Para-hydrogen conversion to ortho-hydrogen by oxygen can be minimized for long term storage with judicious removal of oxygen contamination. Prior calculated velocity rates were confirmed demonstrating a dependence on only the oxygen concentration.

  15. Complications in Determining Oxygen Fugacities From Olivine-Melt Equilibrium Illustrated by the Pu'u'O'o Lavas, Hawaii

    NASA Astrophysics Data System (ADS)

    McCann, V. E.; Barton, M.; Thornber, C. R.

    2005-12-01

    We have shown previously that oxygen fugacities calculated from olivine-melt equilibrium using rim compositions agree well with those calculated from analyzed Fe3+/σFe for MORB and for Icelandic OIB (MORB - average ΔFMQ -0.72 versus -0.70, Iceland average ΔFMQ -0.49 versus -0.58). The agreement between oxygen fugacities calculated from Ol-melt equilibrium and those calculated from analyzed Fe3+/σFe is excellent for individual samples of MORB from the FAMOUS region and Blanco Trough ( difference in calculated ΔFMQ < 0.30). Published analyses of Fe3+/σFe yield oxygen fugacilties of ΔFMQ= -0.72±0.43 for lavas from Kilauea and Mauna Loa, and ΔFMQ=0.91±0.72 for Loihi, very close to those for MORB. Oxygen fugacities determined using carefully selected Ol-melt analyses (ΔFMQ= -0.43±0.32) are in reasonable agreement with those determined from Fe3+/σFe for Kilauea and Mauna Loa, and agreement between fO2 calculated from Ol-melt equilibrium (ΔFMQ= -0.26) and that calculated from Fe3+/σFe (ΔFMQ= -0.64) is excellent for one sample from Kilauea. However, olivine-melt pairs from some samples, including those from the Pu'u'O'o lavas, yield anomalously high or low estimates of fO2 (average ΔFMQ =-0.6907, range -4.07 to +0.34). We suggest that these anomalous values reflect the complex history of olivines in these lavas, in particular the effects of magma mixing. Some olivines in the Pu'u'O'o lavas clearly have rims that are anomalously rich in Fa, whereas others have rims that are anomalously rich in Fo and do not appear to have equilibrium compositions. Given the dependence of olivine composition on melt Fe3+/σFe, there is no simple method to determine the equilibrium composition of olivine for a particular melt. However, detailed zoning profiles and analyses of microphenocrysts allow probable equilibrium compositions to be identified. We suggest that the average fO2 of Hawaiian lavas lies close to (ΔFMQ= -1) based on published results using spinel-melt equilibrium and Fe-Ni exchange between olivine and sulfide liquid. Olivine-glass inclusion data for Koolau samples also suggest (ΔFMQ= ~-1).

  16. Stability and electronic properties of oxygen-doped ZnS polytypes: DFTB study

    NASA Astrophysics Data System (ADS)

    Popov, Ilya S.; Vorokh, Andrey S.; Enyashin, Andrey N.

    2018-06-01

    Synthesis from aqueous solutions is an affordable method for fabrication of II-VI semiconductors. However, application of this method often imposes a disorder of crystal lattice, manifesting as a rich variety of polytypes arising from wurtzite and zinc blende phases. The origin of this disordering still remains debatable. Here, the influence of the most likely impurity at water environment - substitutional oxygen - on the polytypic equilibrium of zinc sulphide is studied by means of density-functional tight-binding method. According to calculations, the inclusion of such oxygen does not affect the polytypic equilibrium. Apart of thermodynamic stability, the electronic and elastic properties of ZnS polytypes are studied as the function of oxygen distribution.

  17. Effects of Environmental Oxygen Content and Dissolved Oxygen on the Surface Tension and Viscosity of Liquid Nickel

    NASA Astrophysics Data System (ADS)

    SanSoucie, M. P.; Rogers, J. R.; Kumar, V.; Rodriguez, J.; Xiao, X.; Matson, D. M.

    2016-07-01

    The NASA Marshall Space Flight Center's electrostatic levitation (ESL) laboratory has recently added an oxygen partial pressure controller. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled in the range from approximately 10^{-28} {to} 10^{-9} bar, while in a vacuum atmosphere. The oxygen control system installed in the ESL laboratory's main chamber consists of an oxygen sensor, oxygen pump, and a control unit. The sensor is a potentiometric device that determines the difference in oxygen activity in two gas compartments (inside the chamber and the air outside of the chamber) separated by an electrolyte. The pump utilizes coulometric titration to either add or remove oxygen. The system is controlled by a desktop control unit, which can also be accessed via a computer. The controller performs temperature control for the sensor and pump, has a PID-based current loop and a control algorithm. Oxygen partial pressure has been shown to play a significant role in the surface tension of liquid metals. Oxide films or dissolved oxygen may lead to significant changes in surface tension. The effects on surface tension and viscosity by oxygen partial pressure in the surrounding environment and the melt dissolved oxygen content will be evaluated, and the results will be presented. The surface tension and viscosity will be measured at several different oxygen partial pressures while the sample is undercooled. Surface tension and viscosity will be measured using the oscillating droplet method.

  18. Fuel cell serves as oxygen level detector

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Monitoring the oxygen level in the air is accomplished by a fuel cell detector whose voltage output is proportional to the partial pressure of oxygen in the sampled gas. The relationship between output voltage and partial pressure of oxygen can be calibrated.

  19. Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

    NASA Astrophysics Data System (ADS)

    Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

    2017-02-01

    Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as "vital effects", could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000 lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

  20. [Effects of gap junction blocking on the oxygen partial pressure in acupoints of the bladder meridian].

    PubMed

    Wang, Qi; Yu, Wei-Chang; Jiang, Hong-Zhi; Chen, Sheng-Li; Zhang, Ming-Min; Kong, E-Sheng; Huang, Guang-Ying

    2010-12-01

    To explore the relation between gap junction and meridian phenomenon. The oxygen partial pressure in acupoints [see text for formula] and in their corresponding non-acupoints of the Bladder Meridian was observed with the needle-type tissue oxygen tension sensor in the gap junction blocking goats by 1-Heptanol injection and the Connexin 43 (Cx43) gene knockout mice. (1) The oxygen partial pressure in acupoints of Bladder Meridian on goats was higher than that in non-acupoints after 1-Heptanol injection with significant differences between them (both P < 0.01). (2) The oxygen partial pressure in acupoints of Bladder Meridian on goats increased significantly after injecting 1-Heptanol as compare with that either injecting normal saline or injecting nothing with significant differences between them (all P < 0.01). (3) The oxygen partial pressure in acupoints of the Bladder Meridian was significantly higher than that in the non-acupoint controls in Cx43 wild type (WT) mice (all P < 0.01). In Cx43 heterozygote (HT) mice, the oxygen partial pressure between acupoints and non-acupoint controls showed no significant differences (all P > 0.05). (4) In acupoints, the oxygen partial pressure in Cx43 WT mice was significantly higher than that in Cx43 HT mice (all P < 0.05), while in the corresponding non-acupoints, this difference had no statistically significant (all P > 0.05). Gap junction maybe the essential factor in signal transduction of acupuncture.

  1. Equivalence of equations describing trace element distribution during equilibrium partial melting

    NASA Technical Reports Server (NTRS)

    Consolmagno, G. J.; Drake, M. J.

    1976-01-01

    It is shown that four equations used for calculating the evolution of trace-element abundances during equilibrium partial melting are mathematically equivalent. The equations include those of Hertogen and Gijbels (1976), Shaw (1970), Schilling (1971), and O'Nions and Clarke (1972). The general form to which all these equations reduce is presented, and an analysis is performed to demonstrate their mathematical equivalence. It is noted that the utility of the general equation flows from the nature of equilibrium (i.e., the final state is independent of the path by which that state is attained).

  2. Pressure Effects on Oxygen Concentration Flammability Thresholds of Materials for Aerospace Applications

    NASA Technical Reports Server (NTRS)

    Hirsch, David; Williams, Jim; Beeson, Harold

    2006-01-01

    Spacecraft materials selection is based on an upward flammability test conducted in a quiescent environment in the highest-expected oxygen-concentration environment. However, NASA s advanced space exploration program is anticipating using various habitable environments. Because limited data is available to support current program requirements, a different test logic is suggested to address these expanded atmospheric environments through the determination of materials self-extinguishment limits. This paper provides additional pressure effects data on oxygen concentration and partial pressure self-extinguishment limits under quiescent conditions. For the range of total pressures tested, the oxygen concentration and oxygen partial pressure flammability thresholds show a near linear function of total pressure. The oxygen concentration/oxygen partial pressure flammability thresholds depend on the total pressure and appear to increase with increasing oxygen concentration (and oxygen partial pressure). For the Constellation Program, the flammability threshold information will allow NASA to identify materials with increased flammability risk because of oxygen concentration and total pressure changes, minimize potential impacts, and allow for development of sound requirements for new spacecraft and extraterrestrial landers and habitats.

  3. Highly Efficient Oxygen-Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion-Based CO2 Capture.

    PubMed

    Imtiaz, Qasim; Kurlov, Alexey; Rupp, Jennifer Lilia Marguerite; Müller, Christoph Rüdiger

    2015-06-22

    Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are emerging thermochemical CO2 capture cycles that allow the capture of CO2 with a small energy penalty. Here, the development of suitable oxygen carrier materials is a key aspect to transfer these promising concepts to practical installations. CuO is an attractive material for CLC and CLOU because of its high oxygen-storage capacity (20 wt %), fast reaction kinetics, and high equilibrium partial pressure of oxygen at typical operating temperatures (850-1000 °C). However, despite its promising characteristics, its low Tammann temperature requires the development of new strategies to phase-stabilize CuO-based oxygen carriers. In this work, we report a strategy based on stabilization by co-precipitated ceria (CeO2-x ), which allowed us to increase the oxygen capacity, coke resistance, and redox stability of CuO-based oxygen carriers substantially. The performance of the new oxygen carriers was evaluated in detail and compared to the current state-of-the-art materials, that is, Al2 O3 -stabilized CuO with similar CuO loadings. We also demonstrate that the higher intrinsic oxygen uptake, release, and mobility in CeO2-x -stabilized CuO leads to a three times higher carbon deposition resistance compared to that of Al2 O3 -stabilized CuO. Moreover, we report a high cyclic stability without phase intermixing for CeO2-x -supported CuO. This was accompanied by a lower reduction temperature compared to state-of-the-art Al2 O3 -supported CuO. As a result of its high resistance towards carbon deposition and fast oxygen uncoupling kinetics, CeO2-x -stabilized CuO is identified as a very promising material for CLC- and CLOU-based CO2 capture architectures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Measurement and Control of Oxygen Partial Pressure in an Electrostatic Levitator

    NASA Technical Reports Server (NTRS)

    SanSoucie, Michael P.; Rogers, Jan R.

    2014-01-01

    Recently the NASA Marshall Space Flight Center electrostatic levitation (ESL) laboratory has been upgraded to include an oxygen control system. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, at elevated temperatures, theoretically in the range from 10(exp -36) to 10(exp 0) bar. The role of active surface agents in liquid metals is fairly well known; however, published surface tension data typically has large scatter, which has been hypothesized to be caused by the presence of oxygen. The surface tension of metals is affected by even a small amount of adsorption of oxygen. It has even been shown that oxygen partial pressures may need to be as low as 10(exp -24) bar to avoid oxidation. While electrostatic levitation is done under high vacuum, oxide films or dissolved oxygen may have significant effects on materials properties, such as surface tension and viscosity. Therefore, the ability to measure and control the oxygen partial pressure within the chamber is highly desirable. The oxygen control system installed at MSFC contains a potentiometric sensor, which measures the oxygen partial pressure, and an oxygen ion pump. In the pump, a pulse-width modulated electric current is applied to yttrium-stabilized zirconia, resulting in oxygen transfer into or out of the system. Also part of the system is a control unit, which consists of temperature controllers for the sensor and pump, PID-based current loop for the ion pump, and a control algorithm. This system can be used to study the effects of oxygen on the thermophysical properties of metals, ceramics, glasses, and alloys. It can also be used to provide more accurate measurements by processing the samples at very low oxygen partial pressures. The oxygen control system will be explained in more detail and an overview of its use and limitations in an electrostatic levitator will be described. Some preliminary measurements have been made, and the results to date will be provided.

  5. A Study of Interactions between Mixing and Chemical Reaction Using the Rate-Controlled Constrained-Equilibrium Method

    NASA Astrophysics Data System (ADS)

    Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, M. Reza H.; Metghalchi, Hameed

    2016-10-01

    The rate-controlled constrained-equilibrium (RCCE) method is employed to study the interactions between mixing and chemical reaction. Considering that mixing can influence the RCCE state, the key objective is to assess the accuracy and numerical performance of the method in simulations involving both reaction and mixing. The RCCE formulation includes rate equations for constraint potentials, density and temperature, which allows taking account of mixing alongside chemical reaction without splitting. The RCCE is a dimension reduction method for chemical kinetics based on thermodynamics laws. It describes the time evolution of reacting systems using a series of constrained-equilibrium states determined by RCCE constraints. The full chemical composition at each state is obtained by maximizing the entropy subject to the instantaneous values of the constraints. The RCCE is applied to a spatially homogeneous constant pressure partially stirred reactor (PaSR) involving methane combustion in oxygen. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The chemical kinetics, comprised of 29 species and 133 reaction steps, is represented by 12 RCCE constraints. The RCCE predictions are compared with those obtained by direct integration of the same kinetics, termed detailed kinetics model (DKM). The RCCE shows accurate prediction of combustion in PaSR with different mixing intensities. The method also demonstrates reduced numerical stiffness and overall computational cost compared to DKM.

  6. Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity of Kilauea basalt

    USGS Publications Warehouse

    Gerlach, T.M.

    1993-01-01

    Volcanic gases collected during episode 1 of the Puu Oo eruption along the east rift zone of Kilauea Volcano, Hawaii, have uniform C-O-H-S-Cl-F compositions that are sharply depleted in CO2. The CO2-poor gases are typical of Type II volcanic gases (gerlach and Graeber, 1985) and were emitted from evolved magma stored for a prolonged period of time in the east rift zone after releasing CO2-rich gases during an earlier period of temporary residence in the summit magma chamber. The samples are remarkably free of contamination by atmospheric gases and meteoric water. Thermodynamic evaluation of the analytical data shows that the episode 1 gases have equilibrium compositions appropriate for temperatures between 935 and 1032??C. Open- and closed-system equilibrium models of species distributions for the episode 1 gases show unequivocally that coexisting lavas buffered the gas oxygen fugacities during cooling. These models indicate that the fO2 buffering process occurs by transfer of oxygen from the major species in the gas phase (H2O, CO2, SO2) to the lava during cooling and that the transfer of oxygen also controls the fugacities of several minor and trace species (H2, CO, H2S, S2, Cl2, F2), in addition to O2 during cooling. Gas/lava exchanges of other components are apparently insignificant and exert little influence, compared to oxygen exchange, during cooling. Oxygen transfer during cooling is variable, presumably reflecting short-term fluctuations in gas flow rates. Higher flow rates restrict the time available for gas/lava oxygen transfer and result in gases with higher equilibrium temperatures. Lower flow rates favor fO2-constrained equilibration by oxygen transfer down to lower temperatures. Thus, the chemical equilibrium preserved in these gases is a heterogeneous equilibrium constrained by oxygen fugacity, and the equilibrium temperatures implied by the compositions of the gases reflect the temperatures at which gas/lava oxygen exchange ceased. This conclusion challenges the common assumption that volcanic gases are released from lava in a state of chemical equilibrium and then continue equilibrating homogeneously with falling temperature until reaction rates are unable to keep pace with cooling. No evidence is found, moreover, that certain gas species are kinetically more responsive and able to equilibrate down to lower temperatures than those of the last gas/lava oxygen exchange. Homogeneous reaction rates in the gas phase are apparently slow compared to the time it took for the gases to move from the last site of gas/lava equilibration to the site of collection. An earlier set of data for higher temperature CO2-rich Type I volcanic gases, which come from sustained summit lava lake eruptions supplied by magma that experienced substantially shorter periods of crustal storage, shows fO2 buffering by oxygen transfer up to 1185??C. Oxygen fugacity measurements in drill holes into ponded lava flows suggest that buffering by oxygen transfer may control the fO2 of residual gases down to several hundred degrees below the solidus in the early stages of cooling. Although the details of the fO2 buffering mechanisms for oxygen transfer are unknown, the fact that fO2 buffering is effective from molten to subsolidus conditions suggests that the reaction mechanisms must change with cooling as the reactants change from predominantly melt, to melt plus crystals, to glass plus crystals. Mass balance calculations suggest that redox reactions between the gas and ferrous/ferric iron in the lava are plausible mechanisms for the oxygen transfer and that the fO2 of the gases is buffered by sliding ferrous/ferric equilibria in the erupting lavas. Contrary to expectations based on models predicting the oxidation of basalt by H2 and CO escape during crustal storage, CO2-rich Type I gases and CO2-poor Type II gases have identical oxygen fugacities despite greatly different crustal storage and degassing histories. Volcanic gas data give a tightly co

  7. Effect of O 2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO 2 thin films

    NASA Astrophysics Data System (ADS)

    Ma, C. Y.; Lapostolle, F.; Briois, P.; Zhang, Q. Y.

    2007-08-01

    Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage ( C- V) measurements to investigate the variation of structure, surface morphology, thickness of SiO 2-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO 2 growth has taken place above approximately 51%. The best C- V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.

  8. Effects of oxygen partial pressure on Li-air battery performance

    NASA Astrophysics Data System (ADS)

    Kwon, Hyuk Jae; Lee, Heung Chan; Ko, Jeongsik; Jung, In Sun; Lee, Hyun Chul; Lee, Hyunpyo; Kim, Mokwon; Lee, Dong Joon; Kim, Hyunjin; Kim, Tae Young; Im, Dongmin

    2017-10-01

    For application in electric vehicles (EVs), the Li-air battery system needs an air intake system to supply dry oxygen at controlled concentration and feeding rate as the cathode active material. To facilitate the design of such air intake systems, we have investigated the effects of oxygen partial pressure (≤1 atm) on the performance of the Li-air cell, which has not been systematically examined. The amounts of consumed O2 and evolved CO2 from the Li-air cell are measured with a custom in situ differential electrochemical gas chromatography-mass spectrometry (DEGC-MS). The amounts of consumed O2 suggest that the oxygen partial pressure does not affect the reaction mechanism during discharge, and the two-electron reaction occurs under all test conditions. On the other hand, the charging behavior varies by the oxygen partial pressure. The highest O2 evolution ratio is attained under 70% O2, along with the lowest CO2 evolution. The cell cycle life also peaks at 70% O2 condition. Overall, an oxygen partial pressure of about 0.5-0.7 atm maximizes the Li-air cell capacity and stability at 1 atm condition. The findings here indicate that the appropriate oxygen partial pressure can be a key factor when developing practical Li-air battery systems.

  9. In situ major and trace element analysis of amphiboles in quartz monzodiorite porphyry from the Tonglvshan Cu-Fe (Au) deposit, Hubei Province, China: insights into magma evolution and related mineralization

    NASA Astrophysics Data System (ADS)

    Duan, Deng-Fei; Jiang, Shao-Yong

    2017-05-01

    The Tonglvshan deposit is the largest Cu-Fe (Au) skarn deposit in the Edong district, which is located in the westernmost part of the Middle and Lower Yangtze River metallogenic belt, China. In this study, we performed a detailed in situ analysis of major and trace elements in amphiboles from the ore-related Tonglvshan quartz monzodiorite porphyry using electron microprobe (EMPA) analysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Two distinct populations of amphiboles, which can be distinguished by their aluminum content, are found in the quartz monzodiorite porphyry. The low-aluminum (Low-Al) amphiboles are subhedral or anhedral and formed at 46.3-73.5 MPa and 713-763 °C. In contrast, the high-aluminum (High-Al) amphiboles are euhedral and formed at 88-165 MPa and 778-854 °C. Some euhedral amphiboles are partially or completely replaced by Low-Al amphibole. The compositions of parental melts in equilibrium with the High-Al amphibole ( Melt 1) and Low-Al amphibole ( Melt 2) were computed by applying solid/liquid partition coefficients. This modeling shows that magma in equilibrium with High-Al amphibole ( Melt 1) underwent 40% fractional crystallization of amphibole, plagioclase and apatite at a depth of 5 km to evolve to magma in equilibrium with Low-Al amphibole ( Melt 2). Copper enrichment occurred in the magma after undergoing fractional crystallization. The magma had a high oxygen fugacity, increasing from NNO + 1 ( Melt 1) through NNO + 2 to HM ( Melt 2), which could have prevented the loss of Cu (and possibly Au) to sulfide minerals during crystallization. Finally, the evolved magma intruded to shallower depths, where it presumably exsolved aqueous ore-forming fluids. Therefore, the large Cu-Fe-Au reserves of the Tonglvshan deposit can likely be attributed to a combination of controlling factors, including high oxygen fugacity, fractional crystallization, fluid exsolution, and a shallow emplacement depth.

  10. Temperature dependence of surface tension of molten iron under reducing gas atmosphere

    NASA Astrophysics Data System (ADS)

    Ozawa, S.; Takahashi, S.; Fukuyama, H.; Watanabe, M.

    2011-12-01

    Surface tension of molten iron was measured under Ar-He-5vol.%H2 gas by oscillating droplet method using electromagnetic levitation furnace in consideration of the temperature dependence of oxygen partial pressure, Po2, of the gas. For comparison, the measurement was carried under Ar-He atmosphere to fix the Po2 of the inlet gas at 10-2Pa. The surface tension was successfully measured over a wide temperature range of about 780K including undercooling condition. When Po2 is fixed at 10-2 Pa, the surface tension increased and then decreased with increasing temperature like a boomerang shape. When the measurement was carried out under the H2-containing gas atmosphere, the temperature dependence of the surface tension shows unique kink at around 1810K instead of liner relationship due to competition between the temperature dependence of the Po2 and that of the equilibrium constant of oxygen adsorption reaction. The relationship between the calculated lnKad with respect to inverse temperature using Szyszkowski model was different between the atmospheric gases.

  11. Using a Microcomputer in the Teaching of Gas-Phase Equilibria: A Numerical Simulation.

    ERIC Educational Resources Information Center

    Hayward, Roger

    1995-01-01

    Describes a computer program that can model the equilibrium processes in the production of ammonia from hydrogen and nitrogen, sulfur trioxide from sulfur dioxide and oxygen, and the nitrogen dioxide-dinitrogen tetroxide equilibrium. Provides information about downloading the program ChemEquilibrium from the World Wide Web. (JRH)

  12. Method and apparatus for monitoring oxygen partial pressure in air masks

    NASA Technical Reports Server (NTRS)

    Kelly, Mark E. (Inventor); Pettit, Donald R. (Inventor)

    2006-01-01

    Method and apparatus are disclosed for monitoring an oxygen partial pressure in an air mask and providing a tactile warning to the user. The oxygen partial pressure in the air mask is detected using an electrochemical sensor, the output signal from which is provided to a comparator. The comparator compares the output signal with a preset reference value or range of values representing acceptable oxygen partial pressures. If the output signal is different than the reference value or outside the range of values, the air mask is vibrated by a vibrating motor to alert the user to a potentially hypoxic condition.

  13. Effect of substrate temperature and oxygen partial pressure on RF sputtered NiO thin films

    NASA Astrophysics Data System (ADS)

    Cheemadan, Saheer; Santhosh Kumar, M. C.

    2018-04-01

    Nickel oxide (NiO) thin films were deposited by RF sputtering process and the physical properties were investigated for varying substrate temperatures and oxygen partial pressure. The variation of the crystallographic orientation and microstructure of the NiO thin films with an increase in substrate temperature were studied. It was observed that NiO thin films deposited at 350 °C shows relatively good crystalline characteristics with a preferential orientation along (111) plane. With the optimum substrate temperature of 350 °C, the NiO thin films were deposited under various oxygen partial pressures at the same experimental conditions. The structural, optical and electrical properties of NiO thin films under varying oxygen partial pressure of 10%–50% were investigated. From XRD it is clear that the films prepared in the pure argon atmosphere were amorphous while the films in oxygen partial pressure exhibited polycrystalline NiO phase. SEM and AFM investigations unveil that the higher substrate temperature improves the microstructure of the thin films. It is revealed that the NiO thin films deposited at oxygen partial pressure of 40% and a substrate temperature of 350 °C, showed higher electrical conductivity with p-type characteristics.

  14. Oxygen partial pressure effects on the RF sputtered p-type NiO hydrogen gas sensors

    NASA Astrophysics Data System (ADS)

    Turgut, Erdal; Çoban, Ömer; Sarıtaş, Sevda; Tüzemen, Sebahattin; Yıldırım, Muhammet; Gür, Emre

    2018-03-01

    NiO thin films were grown by Radio Frequency (RF) Magnetron Sputtering method under different oxygen partial pressures, which are 0.6 mTorr, 1.3 mTorr and 2.0 mTorr. The effects of oxygen partial pressures on the thin films were analyzed through Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Hall measurements. The change in the surface morphology of the thin films has been observed with the SEM and AFM measurements. While nano-pyramids have been obtained on the thin film grown at the lowest oxygen partial pressure, the spherical granules lower than 60 nm in size has been observed for the samples grown at higher oxygen partial pressures. The shift in the dominant XRD peak is realized to the lower two theta angle with increasing the oxygen partial pressures. XPS measurements showed that the Ni2p peak involves satellite peaks and two oxidation states of Ni, Ni2+ and Ni3+, have been existed together with the corresponding splitting in O1s spectrum. P-type conductivity of the grown NiO thin films are confirmed by the Hall measurements with concentrations on the order of 1013 holes/cm-3. Gas sensor measurements revealed minimum of 10% response to the 10 ppm H2 level. Enhanced responsivity of the gas sensor devices of NiO thin films is shown as the oxygen partial pressure increases.

  15. Non-invasive multiwavelength photoplethysmography under low partial pressure of oxygen.

    PubMed

    Fang, Yung Chieh; Tai, Cheng-Chi

    2016-08-01

    A reduction in partial pressure of oxygen in the environment may be caused by a gain in altitude, which reduces the atmospheric pressure; it may also be caused by the carbon dioxide generated from breathing in an enclosed space. Does inhaling oxygen of lower partial pressure affect the oxygen-carrying function of haemoglobin in vivo? This study uses non-invasive multiwavelength photoplethysmography to measure the effects that inhaling this type of oxygen can have on the plethysmography of the appendages of the body (fingertips). The results indicate that under low partial pressure of oxygen, be it the result of a gain in carbon dioxide concentration or altitude, the change in visible light absorption is the biggest for short wavelengths (approximately 620 or 640 nm) near deoxyhaemoglobin, which has higher absorption coefficient. Moreover, increasing carbon dioxide concentration from 5000 to 10,000 ppm doubly reduces the absorption rate of these short wavelengths.

  16. Thin film oxygen partial pressure sensor

    NASA Technical Reports Server (NTRS)

    Wortman, J. J.; Harrison, J. W.; Honbarrier, H. L.; Yen, J.

    1972-01-01

    The development is described of a laboratory model oxygen partial pressure sensor using a sputtered zinc oxide thin film. The film is operated at about 400 C through the use of a miniature silicon bar. Because of the unique resistance versus temperature relation of the silicon bar, control of the operational temperature is achieved by controlling the resistance. A circuit for accomplishing this is described. The response of sputtered zinc oxide films of various thicknesses to oxygen, nitrogen, argon, carbon dioxide, and water vapor caused a change in the film resistance. Over a large range, film conductance varied approximately as the square root of the oxygen partial pressure. The presence of water vapor in the gas stream caused a shift in the film conductance at a given oxygen partial pressure. A theoretical model is presented to explain the characteristic features of the zinc oxide response to oxygen.

  17. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  18. Respiratory gas exchange of high altitude adapted chick embryos

    NASA Technical Reports Server (NTRS)

    Wangensteen, O. D.; Rahn, H.; Burton, R. R.; Smith, A. H.

    1974-01-01

    Study of gas exchange by embryos from chickens acclimatized to an altitude of 3800 m. The oxygen partial pressure and carbon dioxide partial pressure differences across the egg shell were measured and found to be less than the values previously reported for sea-level eggs by about a factor of two. Further measurements of embryonic oxygen consumption and shell conductivity to oxygen indicated that, compared to eggs at sea level, oxygen consumption was reduced by a factor of 0.58 while conductivity to oxygen was increased only by a factor of 1.07 in the high-altitude eggs. These independent measurements predict the change in oxygen partial pressure across the egg shell of the high-altitude eggs to be only 0.54 times that of sea-level eggs; the directly measured factor was 0.53. The authors conclude that at high altitude, a major adaptation of the chick embryo is a reduced metabolism which decreases the change in oxygen partial pressure across the egg shell since its gas conductivity remains essentially unchanged.

  19. Study on the intrinsic defects in ZnO by combing first-principle and thermodynamic calculations

    NASA Astrophysics Data System (ADS)

    Ma, Changmin; Liu, Tingyu; Chang, Qiuxiang

    2015-11-01

    In this paper, the intrinsic point defects in ZnO crystal have been studied by the approach that integrates first-principles, thermodynamic calculations and the contributions of vibrational entropy. With temperature increasing and oxygen partial pressure decreasing, the formation energies of oxygen vacancy (VO), zinc interstitial (Zni) and zinc anti-site (ZnO) are decreasing, while it increases for zinc vacancy (VZn), oxygen interstitial (Oi) and oxygen anti-site (OZn). They are more sensitive to temperature than oxygen partial pressure. There are two interesting phenomena. First, VO or VZn have the lowest formation energies for whole Fermi level at special environment condition (such as at T = 300K, about PO2 = 10-10atm or T = 1500K, about PO2 = 104atm) and intrinsic p-type doping of ZnO is possible by VZn at these special conditions. Second, VO as donors have lowest formation energy for all Fermi level at high temperature and low oxygen partial pressure (T = 1500K, PO2 = 10-10atm). According to our analysis, the VO could produce n-type doping in ZnO at these special conditions and change p-type ZnO to n-type ZnO at condition from low temperature and high oxygen partial pressure to high temperature and low oxygen partial pressure.

  20. Oxygen Partial Pressure Is a Rate-Limiting Parameter for Cell Proliferation in 3D Spheroids Grown in Physioxic Culture Condition.

    PubMed

    Gomes, Aurélie; Guillaume, Ludivine; Grimes, David Robert; Fehrenbach, Jérôme; Lobjois, Valérie; Ducommun, Bernard

    2016-01-01

    The in situ oxygen partial pressure in normal and tumor tissues is in the range of a few percent. Therefore, when studying cell growth in 3D culture systems, it is essential to consider how the physiological oxygen concentration, rather than the one in the ambient air, influences the proliferation parameters. Here, we investigated the effect of reducing oxygen partial pressure from 21% to 5% on cell proliferation rate and regionalization in a 3D tumor spheroid model. We found that 5% oxygen concentration strongly inhibited spheroid growth, changed the proliferation gradient and reduced the 50% In Depth Proliferation index (IDP50), compared with culture at 21% oxygen. We then modeled the oxygen partial pressure profiles using the experimental data generated by culturing spheroids in physioxic and normoxic conditions. Although hypoxia occurred at similar depth in spheroids grown in the two conditions, oxygen partial pressure was a major rate-limiting factor with a critical effect on cell proliferation rate and regionalization only in spheroids grown in physioxic condition and not in spheroids grown at atmospheric normoxia. Our findings strengthen the need to consider conducting experiment in physioxic conditions (i.e., tissue normoxia) for proper understanding of cancer cell biology and the evaluation of anticancer drugs in 3D culture systems.

  1. Classifying Acute Respiratory Distress Syndrome Severity: Correcting the Arterial Oxygen Partial Pressure to Fractional Inspired Oxygen at Altitude.

    PubMed

    Pérez-Padilla, Rogelio; Hernández-Cárdenas, Carmen Margarita; Lugo-Goytia, Gustavo

    2016-01-01

    In the well-known Berlin definition of acute respiratory distress syndrome (ARDS), there is a recommended adjustment for arterial oxygen partial pressure to fractional inspired oxygen (PaO2/FIO2) at altitude, but without a reference as to how it was derived.

  2. Mechanisms controlling the oxygen consumption in experimentally induced hypochloremic alkalosis in calves.

    PubMed

    Cambier, Carole; Clerbaux, Thierry; Amory, Hélène; Detry, Bruno; Florquin, Sandra; Marville, Vincent; Frans, Albert; Gustin, Pascal

    2002-01-01

    The study was carried out on healthy Friesian calves (n = 10) aged between 10 and 30 days. Hypochloremia and alkalosis were induced by intravenous administration of furosemide and isotonic sodium bicarbonate. The venous and arterial blood samples were collected repeatedly. 2,3-diphosphoglycerate (2,3-DPG), hemoglobin and plasmatic chloride concentrations were determined. The red blood cell chloride concentration was also calculated. pH, PCO2 and PO2 were measured in arterial and mixed venous blood. The oxygen equilibrium curve (OEC) was measured in standard conditions. The correspondence of the OEC to the arterial and mixed venous compartments was calculated, taking blood temperature, pH and PCO2 values into account. The oxygen exchange fraction (OEF%), corresponding to the degree of blood desaturation between the arterial and mixed venous compartments and the amount of oxygen released at the tissue level by 100 mL of blood (OEF Vol%) were calculated from the arterial and mixed venous OEC, combined with PO2 and hemoglobin concentration. Oxygen delivery (DO2) was calculated using the arterial oxygen content, the cardiac output measured by thermodilution, and the body weight of the animal. The oxygen consumption (VO2) was derived from the cardiac output, OEF Vol% and body weight values. Despite the plasma hypochloremia, the erythrocyte chloride concentration was not influenced by furosemide and sodium bicarbonate infusion. Due to the alkalosis-induced increase in the 2,3-DPG, the standard OEC was shifted to the right, allowing oxygen to dissociate from hemoglobin more rapidly. These changes opposed the increased affinity of hemoglobin for oxygen induced by alkalosis. Moreover, respiratory acidosis, hemoconcentration, and the slight decrease in the partial oxygen pressure in mixed venous blood (Pvo2) tended to improve the OEF Vol% and maintain the oxygen consumption in a physiological range while the cardiac output, and the oxygen delivery were significantly decreased. It may be concluded that, despite reduced oxygen delivery, oxygen consumption is maintained during experimentally induced hypochloremic alkalosis in healthy 10-30 day old calves.

  3. Analysis on the Oversize Blast Furnace Desulfurization and a Sulfide Capacity Prediction Model Based on Congregated Electron Phase

    NASA Astrophysics Data System (ADS)

    Zhenyang, Wang; Jianliang, Zhang; Gang, An; Zhengjian, Liu; Zhengming, Cheng; Junjie, Huang; Jingwei, Zhang

    2016-02-01

    Through analyzed and regressed the actual productive desulfurization data from the oversize blast furnace (5500 m3) in north China, the relationship between the sulfur distribution parameters and the slag composition in actual production situation was investigated. As the slag and hot metal phases have their own balance sulfur content or sulfur partial pressure in gas phase, respectively, the non-equilibrium of sulfur among gas, slag, and metal phases leads to the transmission and distribution of sulfur. Combined with sulfur transmission reactions between gas, slag and metal phases, C/CO pairs equilibrium, and Wagner model, the measured sulfide capacity can be acquired using sulfur distribution ratio, sulfur activity coefficient, and oxygen activity in hot metal. Based on the theory of congregated electron phase, a new sulfide capacity prediction model (CEPM) has been developed, which has a good liner relationship with the measured sulfide capacity. Thus, using the burden structure for BF, the ironmaking slag composition can be obtained simply and can be used to reliably predict the ironmaking slag desulfurization ability a few hours later after charging under a certain temperature by CEPM.

  4. DEVICE FOR CONTROL OF OXYGEN PARTIAL PRESSURE

    DOEpatents

    Bradner, H.; Gordon, H.S.

    1957-12-24

    A device is described that can sense changes in oxygen partial pressure and cause a corresponding mechanical displacement sufficient to actuate meters, valves and similar devices. A piston and cylinder arrangement contains a charge of crystalline metal chelate pellets which have the peculiar property of responding to variations in the oxygen content of the ambient atmosphere by undergoing a change in dimension. A lever system amplifies the relative displacement of the piston in the cylinder, and actuates the controlled valving device. This partial pressure oxygen sensing device is useful in controlled chemical reactions or in respiratory devices such as the oxygen demand meters for high altitude aircraft.

  5. Influence of oxygen partial pressure on the microstructural and magnetic properties of Er-doped ZnO thin films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Wei-Bin; Li, Fei; Chen, Hong-Ming

    2015-06-15

    Er-doped ZnO thin films have been prepared by using inductively coupled plasma enhanced physical vapor deposition at different O{sub 2}:Ar gas flow ratio (R = 0:30, 1:30, 1:15, 1:10 and 1:6). The influence of oxygen partial pressure on the structural, optical and magnetic properties was studied. It is found that an appropriate oxygen partial pressure (R=1:10) can produce the best crystalline quality with a maximum grain size. The internal strain, estimated by fitting the X-ray diffraction peaks, varied with oxygen partial pressure during growth. PL measurements show that plenty of defects, especially zinc vacancy, exist in Er-doped ZnO films. Allmore » the samples show room-temperature ferromagnetism. Importantly, the saturation magnetization exhibits similar dependency on oxygen partial pressure with the internal strain, which indicates that internal strain has an important effect on the magnetic properties of Er-doped ZnO thin films.« less

  6. Process for conversion of lignin to reformulated, partially oxygenated gasoline

    DOEpatents

    Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

    2001-01-09

    A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

  7. Solubility of carbon dioxide in aqueous mixtures of alkanolamines

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dawodu, O.F.; Meisen, A.

    1994-07-01

    The solubility of CO[sub 2] in water + N-methyldiethanolamine + monoethanolamine (MDEA + MEA) and water + N-methyldiethanolamine + diethanolamine (MDEA + DEA) are reported at two compositions of 3.4 M MDEA + 0.8 M MEA or DEA and 2.1 M MDEA + 2.1 M MEA or DEA at temperatures from 70 to 180 C and CO[sub 2] partial pressures from 100 to 3,850 kPa. The solubility of CO[sub 2] in the blends decreased with an increase in temperature but increased with an increase in CO[sub 2] partial pressure. At low partial pressures of CO[sub 2] and the same totalmore » amine concentration, the equilibrium CO[sub 2] loadings were in the order MDEA + MEA > MDEA + DEA > MDEA. However, at high CO[sub 2] partial pressures, the equilibrium CO[sub 2] loadings in the MDEA solutions were higher than those of the MDEA + MEA and MDEA + DEA blends of equal molar strengths due to the stoichiometric loading limitations of MEA and DEA. The nonadditivity of the equilibrium loadings for single amine systems highlights the need for independent measurements on amine blends.« less

  8. Decline in arterial partial pressure of oxygen after exercise: a surrogate marker of pulmonary vascular obstructive disease in patients with atrial septal defect and severe pulmonary hypertension.

    PubMed

    Laksmivenkateshiah, Srinivas; Singhi, Anil K; Vaidyanathan, Balu; Francis, Edwin; Karimassery, Sundaram R; Kumar, Raman K

    2011-06-01

    To examine the utility of decline in arterial partial pressure of oxygen after exercise as a marker of pulmonary vascular obstructive disease in patients with atrial septal defect and pulmonary hypertension. Treadmill exercise was performed in 18 patients with atrial septal defect and pulmonary hypertension. Arterial blood gas samples were obtained before and after peak exercise. A decline in the arterial pressure of oxygen of more than 10 millimetres of mercury after exercise was considered significant based on preliminary tests conducted on the controls. Cardiac catheterisation was performed in all patients and haemodynamic data sets were obtained on room air, oxygen, and a mixture of oxygen and nitric oxide (30-40 parts per million). There were 10 patients who had more than a 10 millimetres of mercury drop in arterial partial pressure of oxygen after exercise and who had a basal pulmonary vascular resistance index of more than 7 Wood units per square metre. Out of eight patients who had less than a 10 millimetres of mercury drop in arterial partial pressure of oxygen after exercise, seven had a basal pulmonary vascular resistance index of less than 7 Wood units per square metre, p equals 0.0001. A decline in arterial partial pressure of oxygen of more than 10 millimetres of mercury predicted a basal pulmonary vascular resistance index of more than 7 Wood units per square metre with a specificity of 100% and a sensitivity of 90%. A decline in arterial partial pressure of oxygen following exercise appears to predict a high pulmonary vascular resistance index in patients with atrial septal defect and pulmonary hypertension. This test is a useful non-invasive marker of pulmonary vascular obstructive disease in this subset.

  9. DEGRADATION ISSUES IN SOLID OXIDE CELLS DURING HIGH TEMPERATURE ELECTROLYSIS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    M. S. Sohal; J. E. O'Brien; C. M. Stoots

    2012-02-01

    Idaho National Laboratory (INL) is performing high-temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells (SOECs). The project goals are to address the technical and degradation issues associated with the SOECs. This paper provides a summary of various ongoing INL and INL sponsored activities aimed at addressing SOEC degradation. These activities include stack testing, post-test examination, degradation modeling, and a list of issues that need to be addressed in future. Major degradation issues relating to solid oxide fuel cells (SOFC) are relatively better understood than those for SOECs. Some of the degradation mechanisms in SOFCs include contact problemsmore » between adjacent cell components, microstructural deterioration (coarsening) of the porous electrodes, and blocking of the reaction sites within the electrodes. Contact problems include delamination of an electrode from the electrolyte, growth of a poorly (electronically) conducting oxide layer between the metallic interconnect plates and the electrodes, and lack of contact between the interconnect and the electrode. INL's test results on high temperature electrolysis (HTE) using solid oxide cells do not provide a clear evidence whether different events lead to similar or drastically different electrochemical degradation mechanisms. Post-test examination of the solid oxide electrolysis cells showed that the hydrogen electrode and interconnect get partially oxidized and become non-conductive. This is most likely caused by the hydrogen stream composition and flow rate during cool down. The oxygen electrode side of the stacks seemed to be responsible for the observed degradation due to large areas of electrode delamination. Based on the oxygen electrode appearance, the degradation of these stacks was largely controlled by the oxygen electrode delamination rate. University of Utah (Virkar) has developed a SOEC model based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. This model is under continued development. It shows that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, within the electrolyte. The chemical potential within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just under the oxygen electrode (anode)/electrolyte interface, leading to electrode delamination. This theory is being further refined and tested by introducing some electronic conduction in the electrolyte.« less

  10. DEGRADATION ISSUES IN SOLID OXIDE CELLS DURING HIGH TEMPERATURE ELECTROLYSIS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    J. E. O'Brien; C. M. Stoots; V. I. Sharma

    2010-06-01

    Idaho National Laboratory (INL) is performing high-temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells (SOECs). The project goals are to address the technical and degradation issues associated with the SOECs. This paper provides a summary of various ongoing INL and INL sponsored activities aimed at addressing SOEC degradation. These activities include stack testing, post-test examination, degradation modeling, and a list of issues that need to be addressed in future. Major degradation issues relating to solid oxide fuel cells (SOFC) are relatively better understood than those for SOECs. Some of the degradation mechanisms in SOFCs include contact problemsmore » between adjacent cell components, microstructural deterioration (coarsening) of the porous electrodes, and blocking of the reaction sites within the electrodes. Contact problems include delamination of an electrode from the electrolyte, growth of a poorly (electronically) conducting oxide layer between the metallic interconnect plates and the electrodes, and lack of contact between the interconnect and the electrode. INL’s test results on high temperature electrolysis (HTE) using solid oxide cells do not provide a clear evidence whether different events lead to similar or drastically different electrochemical degradation mechanisms. Post-test examination of the solid oxide electrolysis cells showed that the hydrogen electrode and interconnect get partially oxidized and become non-conductive. This is most likely caused by the hydrogen stream composition and flow rate during cool down. The oxygen electrode side of the stacks seemed to be responsible for the observed degradation due to large areas of electrode delamination. Based on the oxygen electrode appearance, the degradation of these stacks was largely controlled by the oxygen electrode delamination rate. University of Utah (Virkar) has developed a SOEC model based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. This model is under continued development. It shows that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, within the electrolyte. The chemical potential within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just under the oxygen electrode (anode)/electrolyte interface, leading to electrode delamination. This theory is being further refined and tested by introducing some electronic conduction in the electrolyte.« less

  11. Electrical conductivity of cobalt doped La 0.8Sr 0.2Ga 0.8Mg 0.2O 3- δ

    NASA Astrophysics Data System (ADS)

    Wang, Shizhong; Wu, Lingli; Liang, Ying

    La 0.8Sr 0.2Ga 0.8Mg 0.2O 3- δ (LSGM8282), La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3- δ (LSGMC5) and La 0.8Sr 0.2Ga 0.8Mg 0.115Co 0.085O 3- δ (LSGMC8.5) were prepared using a conventional solid-state reaction. Electrical conductivities and electronic conductivities of the samples were measured using four-probe impedance spectrometry, four-probe dc polarization and Hebb-Wagner polarization within the temperature range of 973-1173 K. The electrical conductivities in LSGMC5 and LSGMC8.5 increased with decreasing oxygen partial pressures especially in the high (>10 -5 atm) and low oxygen partial pressure regions (<10 -15 atm). However, the electrical conductivity in LSGM8282 had no dependency on the oxygen partial pressure. At temperatures higher than 1073 K, PO2 dependencies of the free electron conductivities in LSGM8282, LSGMC5 and LSGMC8.5 were about -1/4, and PO2 dependencies of the electron hole conductivities were about 0.25, 0.12 and 0.07, respectively. Oxygen ion conductivities in LSGMC5 and LSGMC8.5 increased with decreasing oxygen partial pressures especially in the high and low oxygen partial pressure regions, which was due to the increase in the concentration of oxygen vacancies. The change in the concentration of oxygen vacancies and the valence of cobalt with oxygen partial pressure were determined using a thermo-gravimetric technique. Both the electronic conductivity and oxygen ion conductivity in cobalt doped lanthanum gallate samples increased with increasing concentration of cobalt, suggesting that the concentration of cobalt should be optimized carefully to maintain a high electrical conductivity and close to 1 oxygen ion transference number.

  12. Oxygen Partial Pressure Is a Rate-Limiting Parameter for Cell Proliferation in 3D Spheroids Grown in Physioxic Culture Condition

    PubMed Central

    Gomes, Aurélie; Guillaume, Ludivine; Grimes, David Robert; Fehrenbach, Jérôme; Lobjois, Valérie; Ducommun, Bernard

    2016-01-01

    The in situ oxygen partial pressure in normal and tumor tissues is in the range of a few percent. Therefore, when studying cell growth in 3D culture systems, it is essential to consider how the physiological oxygen concentration, rather than the one in the ambient air, influences the proliferation parameters. Here, we investigated the effect of reducing oxygen partial pressure from 21% to 5% on cell proliferation rate and regionalization in a 3D tumor spheroid model. We found that 5% oxygen concentration strongly inhibited spheroid growth, changed the proliferation gradient and reduced the 50% In Depth Proliferation index (IDP50), compared with culture at 21% oxygen. We then modeled the oxygen partial pressure profiles using the experimental data generated by culturing spheroids in physioxic and normoxic conditions. Although hypoxia occurred at similar depth in spheroids grown in the two conditions, oxygen partial pressure was a major rate-limiting factor with a critical effect on cell proliferation rate and regionalization only in spheroids grown in physioxic condition and not in spheroids grown at atmospheric normoxia. Our findings strengthen the need to consider conducting experiment in physioxic conditions (i.e., tissue normoxia) for proper understanding of cancer cell biology and the evaluation of anticancer drugs in 3D culture systems. PMID:27575790

  13. Influence of oxygen partial pressure on the composition and orientation of strontium-doped lead zirconate titanate thin films.

    PubMed

    Sriram, S; Bhaskaran, M; du Plessis, J; Short, K T; Sivan, V P; Holland, A S

    2009-01-01

    The influence of oxygen partial pressure during the deposition of piezoelectric strontium-doped lead zirconate titanate thin films is reported. The thin films have been deposited by RF magnetron sputtering in an atmosphere of high purity argon and oxygen (in the ratio of 9:1), on platinum-coated silicon substrates (heated to 650 degrees C). The influence of oxygen partial pressure is studied to understand the manner in which the stoichiometry of the thin films is modified, and to understand the influence of stoichiometry on the perovskite orientation. This article reports on the results obtained from films deposited at oxygen partial pressures of 1-5 mTorr. The thin films have been studied using a combination of X-ray photoelectron spectroscopy (XPS), glancing angle X-ray diffraction (GA-XRD), and atomic force microscopy (AFM). XPS analysis highlights the marked influence of variations in oxygen pressure during sputtering, observed by variations in oxygen concentration in the thin films, and in some cases by the undesirable decrease in lead concentration in the thin films. GA-XRD is used to study the relative variations in perovskite peak intensities, and has been used to determine the deposition conditions to attain the optimal combination of stoichiometry and orientation. AFM scans show the marked influence of the oxygen partial pressure on the film morphology.

  14. Measuring Transcutaneous Oxygenation to Validate the Duration Required to Achieve Electrode Equilibration.

    PubMed

    Chiang, Nathaniel; Jain, Jitendra K; Sleigh, Jamie; Vasudevan, Thodur

    2018-06-01

    The transcutaneous oxygenation measurement (TCOM) system is useful in assessing tissue viability. There are no clear recommendations regarding the duration required for the electrode to equilibrate and reliably evaluate tissue oxygenation values. The objective of this study was to validate the duration required to achieve electrode equilibration in a clinical setting. Minute-by-minute recordings using TCOM (TCOM3; Radiometer Medical ApS, Brønshøj, Copenhagen) were obtained for 82 limbs in 50 participants. Twenty-five limbs were in patients with peripheral vascular disease; 30 were in patients with no known peripheral vascular disease; and 27 were in healthy volunteers. Transcutaneous partial pressure of oxygen and carbon dioxide (TcPO2 and TcPCO2) were recorded over a 15-minute period. Participants' TcPO2 decreased and TcPCO2 increased over time. Both changed in a nonlinear fashion, eventually settling at an "equilibrium" where the measurements became stable. The difference in proportional change of TcPO2 between minutes 14 and 15 was 0.8%, and for TcPCO2was 2.9%. Changes in TCOM measurements over time were similar among the 3 groups. This is the first study to target minute-by-minute variation in TcPO2 and TcPCO2 measurements. Recording for a minimum of 15 minutes allows a reliable period for the TCOM electrode to equilibrate to record absolute values and determine wound healing potential.

  15. Solar heating of common lunar minerals for the production of oxygen

    NASA Technical Reports Server (NTRS)

    Senior, C. L.

    1991-01-01

    The purpose of this work was to demonstrate the feasibility of vapor-phase reduction (pyrolysis) of lunar materials to produce oxygen. Solar furnace experiments were conducted on two common lunar minerals, ilmenite and anorthite. Thermodynamic equilibrium calculations predicted that ilmenite should show a larger pressure increase than anorthite under conditions of the experiments and this was confirmed by the experiments. The measured mass loss of the ilmenite sample was consistent with loss of oxygen by reduction of iron in the liquid phase; this result was also predicted from equilibrium calculations. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2500 K, giving total gas pressures of 0.01 to 1 torr. Bulk regolith can be used as a feedstock without extensive beneficiation. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts from the process.

  16. Report on ISS O2 Production, Gas Supply and Partial Pressure Management

    NASA Technical Reports Server (NTRS)

    Schaezler, Ryan N.; Cook, Anthony J.

    2015-01-01

    Oxygen is used on International Space Station (ISS) for metabolic support and denitrogenation procedures prior to Extra-Vehicular Activities. Nitrogen is used to maintain total pressure and account for losses associated with leakage and operational losses. Oxygen and nitrogen have been supplied by various visiting vehicles such as the Progress and Shuttle in addition to the on-orbit oxygen production capability. Starting in 2014, new high pressure oxygen/nitrogen tanks are available to launch on commercial cargo vehicles and will replace the high pressure gas source that Shuttle used to provide. To maintain a habitable atmosphere the oxygen and nitrogen partial pressures are controlled between upper and lower bounds. The full range of the allowable partial pressures along with the increased ISS cabin volume are utilized as a buffer allowing days to pass between oxygen production or direct addition of oxygen and nitrogen to the atmosphere from reserves. This paper summarizes the amount of gas supplied and produced from all of the sources and describes past experience of managing partial pressures along with the range of management options available to the ISS.

  17. Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped Bi-2223 and Ag/Bi-2223 systems

    NASA Astrophysics Data System (ADS)

    Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

    1995-02-01

    Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique that employs an yttria-stabilized zirconia electrolyte. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 750 to 815°C and at oxygen partial pressures ranging from ∼ 0.02 to 0.2 atm should preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of the partial molar quantities ΔS¯( O2) andΔH¯( O2) indicate that the plateau regions in the plot of oxygen partial pressure versus oxygen stoichiometry ( x) can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm.

  18. Enhanced electrodes for solid state gas sensors

    DOEpatents

    Garzon, Fernando H.; Brosha, Eric L.

    2001-01-01

    A solid state gas sensor generates an electrical potential between an equilibrium electrode and a second electrode indicative of a gas to be sensed. A solid electrolyte substrate has the second electrode mounted on a first portion of the electrolyte substrate and a composite equilibrium electrode including conterminous transition metal oxide and Pt components mounted on a second portion of the electrolyte substrate. The composite equilibrium electrode and the second electrode are electrically connected to generate an electrical potential indicative of the gas that is being sensed. In a particular embodiment of the present invention, the second electrode is a reference electrode that is exposed to a reference oxygen gas mixture so that the electrical potential is indicative of the oxygen in a gas stream.

  19. Sulfur control in ion-conducting membrane systems

    DOEpatents

    Stein, VanEric Edward; Richards, Robin Edward; Brengel, David Douglas; Carolan, Michael Francis

    2003-08-05

    A method for controlling the sulfur dioxide partial pressure in a pressurized, heated, oxygen-containing gas mixture which is contacted with an ion-conducting metallic oxide membrane which permeates oxygen ions. The sulfur dioxide partial pressure in the oxygen-depleted non-permeate gas from the membrane module is maintained below a critical sulfur dioxide partial pressure, p.sub.SO2 *, to protect the membrane material from reacting with sulfur dioxide and reducing the oxygen flux of the membrane. Each ion-conducting metallic oxide material has a characteristic critical sulfur dioxide partial pressure which is useful in determining the required level of sulfur removal from the feed gas and/or from the fuel gas used in a direct-fired feed gas heater.

  20. Real-Time Monitoring of Singlet Oxygen and Oxygen Partial Pressure During the Deep Photodynamic Therapy In Vitro.

    PubMed

    Li, Weitao; Huang, Dong; Zhang, Yan; Liu, Yangyang; Gu, Yueqing; Qian, Zhiyu

    2016-09-01

    Photodynamic therapy (PDT) is an effective noninvasive method for the tumor treatment. The major challenge in current PDT research is how to quantitatively evaluate therapy effects. To our best knowledge, this is the first time to combine multi-parameter detection methods in PDT. More specifically, we have developed a set of system, including the high-sensitivity measurement of singlet oxygen, oxygen partial pressure and fluorescence image. In this paper, the detection ability of the system was validated by the different concentrations of carbon quantum dots. Moreover, the correlation between singlet oxygen and oxygen partial pressure with laser irradiation was observed. Then, the system could detect the signal up to 0.5 cm tissue depth with 660 nm irradiation and 1 cm tissue depth with 980 nm irradiation by using up-conversion nanoparticles during PDT in vitro. Furthermore, we obtained the relationship among concentration of singlet oxygen, oxygen partial pressure and tumor cell viability under certain conditions. The results indicate that the multi-parameter detection system is a promising asset to evaluate the deep tumor therapy during PDT. Moreover, the system might be potentially used for the further study in biology and molecular imaging.

  1. Energetic Metastable Oxygen and Nitrogen Atoms in the Terrestrial Atmosphere

    NASA Technical Reports Server (NTRS)

    Kharchenko, Vasili

    2004-01-01

    We have investigated the impact of hot metastable oxygen atoms on the product yields and rate coefficients of atmospheric reactions involving O( (sup 1)D). The contribution of the metastable oxygen atoms to the thermal balance of the terrestrial atmosphere between 50 and 200 km has been determined. We found that the presence of hot O((sup l)D) atoms in the mesosphere and lower thermosphere significantly increases the production rate of the rotationally-vibrationally excited NO molecules. The computed yield of the NO molecules in N2O+ O((sup 1)D) atmospheric collisions, involving non-Maxwellian distributions of the metastable oxygen atoms, is more than two times larger than the NO-yield at a thermal equilibrium. The calculated non-equilibrium rate and yield functions are important for ozone and nitrous oxide modeling in the stratosphere, mesosphere and lower thermosphere.

  2. [Effect of oxygen tubing connection site on percutaneous oxygen partial pressure and percutaneous carbon dioxide partial pressure in patients with chronic obstructive pulmonary disease during noninvasive positive pressure ventilation].

    PubMed

    Mi, S; Zhang, L M

    2017-04-12

    Objective: We evaluated the effects of administering oxygen through nasal catheters inside the mask or through the mask on percutaneous oxygen partial pressure (PcO(2))and percutaneous carbon dioxide partial pressure (PcCO(2)) during noninvasive positive pressure ventilation (NPPV) to find a better way of administering oxygen, which could increase PcO(2) by increasing the inspired oxygen concentration. Methods: Ten healthy volunteers and 9 patients with chronic obstructive pulmonary disease complicated by type Ⅱ respiratory failure were included in this study. Oxygen was administered through a nasal catheter inside the mask or through the mask (oxygen flow was 3 and 5 L/min) during NPPV. PcO(2) and PcCO(2) were measured to evaluate the effects of administering oxygen through a nasal catheter inside the mask or through the mask, indirectly reflecting the effects of administering oxygen through nasal catheter inside the mask or through the mask on inspired oxygen concentration. Results: Compared to administering oxygen through the mask during NPPV, elevated PcO(2) was measured in administering oxygen through the nasal catheter inside the mask, and the differences were statistically significant ( P <0.05). At the same time, there was no significant change in PcCO(2) ( P >0.05). Conclusion: Administering oxygen through a nasal catheter inside the mask during NPPV increased PcO(2) by increasing the inspired oxygen concentration but did not increase PcCO(2). This method of administering oxygen could conserve oxygen and be suitable for family NPPV. Our results also provided theoretical basis for the development of new masks.

  3. Oxygen-Partial-Pressure Sensor for Aircraft Oxygen Mask

    NASA Technical Reports Server (NTRS)

    Kelly, Mark; Pettit, Donald

    2003-01-01

    A device that generates an alarm when the partial pressure of oxygen decreases to less than a preset level has been developed to help prevent hypoxia in a pilot or other crewmember of a military or other high-performance aircraft. Loss of oxygen partial pressure can be caused by poor fit of the mask or failure of a hose or other component of an oxygen distribution system. The deleterious physical and mental effects of hypoxia cause the loss of a military aircraft and crew every few years. The device is installed in the crewmember s oxygen mask and is powered via communication wiring already present in all such oxygen masks. The device (see figure) includes an electrochemical sensor, the output potential of which is proportional to the partial pressure of oxygen. The output of the sensor is amplified and fed to the input of a comparator circuit. A reference potential that corresponds to the amplified sensor output at the alarm oxygen-partial-pressure level is fed to the second input of the comparator. When the sensed partial pressure of oxygen falls below the minimum acceptable level, the output of the comparator goes from the low state (a few millivolts) to the high state (near the supply potential, which is typically 6.8 V for microphone power). The switching of the comparator output to the high state triggers a tactile alarm in the form of a vibration in the mask, generated by a small 1.3-Vdc pager motor spinning an eccentric mass at a rate between 8,000 and 10,000 rpm. The sensation of the mask vibrating against the crewmember s nose is very effective at alerting the crewmember, who may already be groggy from hypoxia and is immersed in an environment that is saturated with visual cues and sounds. Indeed, the sensation is one of rudeness, but such rudeness could be what is needed to stimulate the crewmember to take corrective action in a life-threatening situation.

  4. The real limits to marine life: a further critique of the Respiration Index

    NASA Astrophysics Data System (ADS)

    Seibel, B. A.; Childress, J. J.

    2012-11-01

    The recently proposed "Respiration Index" (RI = log[PO2]/[PCO2]) suggests that aerobic metabolism is limited by the ratio of reactants (R, oxygen) and products (P, carbon dioxide) according to the thermodynamics of cellular respiration. Here we demonstrate that, because of the large standard free energy change for organic carbon oxidation (ΔG° = -686 kcal mol-1), carbon dioxide can never reach concentrations that would limit the thermodynamics of this reaction. A PCO2 to PO2 ratio of 10503 would be required to reach equilibrium (equilibrium constant, Keq = 10503), where ΔG = 0. Thus a respiration index of -503 would be the real thermodynamic limit to aerobic life. Such a Respiration Index is never reached either in the cell or in the environment. Moreover cellular respiration and oxygen provision are kinetically controlled such that, within limits, environmental oxygen and CO2 concentrations have little to do with intracellular concentrations. The RI is fundamentally different from the aragonite saturation state, a thermodynamic index used to quantify the potential effect of CO2 on calcification rates, because of its failure to incorporate the equilibrium constant of the reaction. Not only is the RI invalid, its use leads to incorrect and dangerous predictions of the threat of changing oxygen and carbon dioxide to marine life. We provide a physiological model that identifies oxygen thresholds, and allows for synergistic effects of ocean acidification and global warming.

  5. The real limits to marine life: a further critique of the Respiration Index

    NASA Astrophysics Data System (ADS)

    Seibel, B. A.; Childress, J. J.

    2013-05-01

    The recently proposed "Respiration Index" (RI = log PO2/PCO2) suggests that aerobic metabolism is limited by the ratio of reactants (oxygen) to products (carbon dioxide) according to the thermodynamics of cellular respiration. Here, we demonstrate further that, because of the large standard free energy change for organic carbon oxidation (ΔG° = -686 kcal mol-1), carbon dioxide can never reach concentrations that would limit the thermodynamics of this reaction. A PCO2 to PO2 ratio of 10503 would be required to reach equilibrium (equilibrium constant, Keq = 10503), where ΔG = 0. Thus, a Respiration Index of -503 would be the real thermodynamic limit to aerobic life. Such a Respiration Index is never reached, either in the cell or in the environment. Moreover, cellular respiration and oxygen provision are kinetically controlled such that, within limits, environmental oxygen and CO2 concentrations have little to do with intracellular concentrations. The RI is fundamentally different from the aragonite saturation state, a thermodynamic index used to quantify the potential effect of CO2 on calcification rates, because of its failure to incorporate the equilibrium constant of the reaction. Not only is the RI invalid, but its use leads to incorrect and misleading predictions of the threat of changing oxygen and carbon dioxide to marine life. We provide a physiological framework that identifies oxygen thresholds and allows for synergistic effects of ocean acidification and global warming.

  6. Spatial Distribution of Oxygen Chemical Potential under Potential Gradients and Theoretical Maximum Power Density with 8YSZ Electrolyte

    NASA Astrophysics Data System (ADS)

    Lim, Dae-Kwang; Im, Ha-Ni; Song, Sun-Ju

    2016-01-01

    The maximum power density of SOFC with 8YSZ electrolyte as the function of thickness was calculated by integrating partial conductivities of charge carriers under various DC bias conditions at a fixed oxygen chemical potential gradient at both sides of the electrolyte. The partial conductivities were successfully taken using the Hebb-Wagner polarization method as a function of temperature and oxygen partial pressure, and the spatial distribution of oxygen partial pressure across the electrolyte was calculated based on Choudhury and Patterson’s model by considering zero electrode polarization. At positive voltage conditions corresponding to SOFC and SOEC, the high conductivity region was expanded, but at negative cell voltage condition, the low conductivity region near n-type to p-type transition was expanded. In addition, the maximum power density calculated from the current-voltage characteristic showed approximately 5.76 W/cm2 at 700 oC with 10 μm thick-8YSZ, while the oxygen partial pressure of the cathode and anode sides maintained ≈0.21 and 10-22 atm.

  7. Oxygen partial pressure influenced structural and optical properties of DC magnetron sputtered ZrO{sub 2} films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kondaiah, P.; Madhavi, V.; Uthanna, S.

    2013-02-05

    Thin films of zirconium oxide (ZrO{sub 2}) were deposited on (100) p-silicon and quartz substrates by sputtering of metallic zirconium target under different oxygen partial pressures in the range 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa. The effect of oxygen partial pressure on the structural and optical properties of the deposited films was systematically investigated. The deposition rate of the films decreased from 3.3 to 1.83 nm/min with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively. The X-ray diffraction profiles revealed that the films exhibit (111) refection of zirconium oxide in monoclinic phase.more » The optical band gap of the films increased from 5.62 to 5.80 eV and refractive index increased from 2.01 to 2.08 with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively.« less

  8. Phase Equilibria in the ZnO-"FeO"-SiO2 System in Reducing Atmosphere and in the ZnO-"FeO"-SiO2-"Cu2O" System in Equilibrium with Liquid Copper Metal at 1250 °C (1523 K)

    NASA Astrophysics Data System (ADS)

    Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

    2018-05-01

    Recent experimental studies in the ZnO-"FeO"-SiO2 system in reducing atmosphere demonstrated significant discrepancies with the current FactSage thermodynamic model developed using previous experimental data in this system in equilibrium with metallic iron and air. The present experimental study on phase equilibria in the ZnO-"FeO"-SiO2-"Cu2O" system in equilibrium with liquid copper at 1250 °C (1523 K) at low copper oxide concentrations in slag was initiated and undertaken to resolve these discrepancies. A high-temperature equilibration-rapid quenching-electron-probe X-ray microanalysis (EPMA) technique using a primary phase substrate support and closed system approach with Cu metal introduced to determine effective equilibrium oxygen partial pressure from the Cumetal/Cu2Oslag equilibria was applied to provide accurate information on the liquidus and corresponding solid compositions in the spinel, willemite, and tridymite primary phase fields. The present results confirmed the accuracy of the FactSage model, resolved discrepancies, and demonstrated significant uncertainties in the recent studies by other authors on the system in the open reducing atmosphere. The present study shows how this closed system approach can be used to obtain key thermodynamic data on phase equilibria in systems containing volatile metal species, overcoming the limitations and uncertainties encountered in conventional open gas/condensed phase equilibration with these systems. The study highlights the importance of the focus on obtaining accurate experimental data and the risks of misleading information from inadequate experimental control and analysis. The study also demonstrates that continuing in-depth critical review and analysis of the elemental reactions taking place in complex systems is an essential step in phase equilibrium research.

  9. Effects of oxygen on responses to heating in two lizard species sampled along an elevational gradient.

    PubMed

    DuBois, P Mason; Shea, Tanner K; Claunch, Natalie M; Taylor, Emily N

    2017-08-01

    Thermal tolerance is an important variable in predictive models about the effects of global climate change on species distributions, yet the physiological mechanisms responsible for reduced performance at high temperatures in air-breathing vertebrates are not clear. We conducted an experiment to examine how oxygen affects three variables exhibited by ectotherms as they heat-gaping threshold, panting threshold, and loss of righting response (the latter indicating the critical thermal maximum)-in two lizard species along an elevational (and therefore environmental oxygen partial pressure) gradient. Oxygen partial pressure did not impact these variables in either species. We also exposed lizards at each elevation to severely hypoxic gas to evaluate their responses to hypoxia. Severely low oxygen partial pressure treatments significantly reduced the gaping threshold, panting threshold, and critical thermal maximum. Further, under these extreme hypoxic conditions, these variables were strongly and positively related to partial pressure of oxygen. In an elevation where both species overlapped, the thermal tolerance of the high elevation species was less affected by hypoxia than that of the low elevation species, suggesting the high elevation species may be adapted to lower oxygen partial pressures. In the high elevation species, female lizards had higher thermal tolerance than males. Our data suggest that oxygen impacts the thermal tolerance of lizards, but only under severely hypoxic conditions, possibly as a result of hypoxia-induced anapyrexia. Copyright © 2017. Published by Elsevier Ltd.

  10. DSMC modeling of flows with recombination reactions

    NASA Astrophysics Data System (ADS)

    Gimelshein, Sergey; Wysong, Ingrid

    2017-06-01

    An empirical microscopic recombination model is developed for the direct simulation Monte Carlo method that complements the extended weak vibrational bias model of dissociation. The model maintains the correct equilibrium reaction constant in a wide range of temperatures by using the collision theory to enforce the number of recombination events. It also strictly follows the detailed balance requirement for equilibrium gas. The model and its implementation are verified with oxygen and nitrogen heat bath relaxation and compared with available experimental data on atomic oxygen recombination in argon and molecular nitrogen.

  11. Partially wrong? Partial equilibrium and the economic analysis of public health emergencies of international concern.

    PubMed

    Beutels, P; Edmunds, W J; Smith, R D

    2008-11-01

    We argue that traditional health economic analysis is ill-equipped to estimate the cost effectiveness and cost benefit of interventions that aim at controlling and/or preventing public health emergencies of international concern (such as pandemic influenza or severe acute respiratory syndrome). The implicit assumption of partial equilibrium within both the health sector itself and--if a wider perspective is adopted--the economy as a whole would be violated by such emergencies. We propose an alternative, with the specific aim of accounting for the behavioural changes and capacity problems that are expected to occur when such an outbreak strikes. Copyright (c) 2008 John Wiley & Sons, Ltd.

  12. Reversible uptake of molecular oxygen by heteroligand Co(II)-L-α-amino acid-imidazole systems: equilibrium models at full mass balance.

    PubMed

    Pająk, Marek; Woźniczka, Magdalena; Vogt, Andrzej; Kufelnicki, Aleksander

    2017-09-19

    The paper examines Co(II)-amino acid-imidazole systems (where amino acid = L-α-amino acid: alanine, asparagine, histidine) which, when in aqueous solutions, activate and reversibly take up dioxygen, while maintaining the structural scheme of the heme group (imidazole as axial ligand and O 2 uptake at the sixth, trans position) thus imitating natural respiratory pigments such as myoglobin and hemoglobin. The oxygenated reaction shows higher reversibility than for Co(II)-amac systems with analogous amino acids without imidazole. Unlike previous investigations of the heteroligand Co(II)-amino acid-imidazole systems, the present study accurately calculates all equilibrium forms present in solution and determines the [Formula: see text]equilibrium constants without using any simplified approximations. The equilibrium concentrations of Co(II), amino acid, imidazole and the formed complex species were calculated using constant data obtained for analogous systems under oxygen-free conditions. Pehametric and volumetric (oxygenation) studies allowed the stoichiometry of O 2 uptake reaction and coordination mode of the central ion in the forming oxygen adduct to be determined. The values of dioxygen uptake equilibrium constants [Formula: see text] were evaluated by applying the full mass balance equations. Investigations of oxygenation of the Co(II)-amino acid-imidazole systems indicated that dioxygen uptake proceeds along with a rise in pH to 9-10. The percentage of reversibility noted after acidification of the solution to the initial pH ranged within ca 30-60% for alanine, 40-70% for asparagine and 50-90% for histidine, with a rising tendency along with the increasing share of amino acid in the Co(II): amino acid: imidazole ratio. Calculations of the share of the free Co(II) ion as well as of the particular complex species existing in solution beside the oxygen adduct (regarding dioxygen bound both reversibly and irreversibly) indicated quite significant values for the systems with alanine and asparagine-in those cases the of oxygenation reaction is right shifted to a relatively lower extent. The experimental results indicate that the "active" complex, able to take up dioxygen, is a heteroligand CoL 2 L'complex, where L = amac (an amino acid with a non-protonated amine group) while L' = Himid, with the N1 nitrogen protonated within the entire pH range under study. Moreover, the corresponding log  [Formula: see text] value at various initial total Co(II), amino acid and imidazole concentrations was found to be constant within the limits of error, which confirms those results. The highest log [Formula: see text] value, 14.9, occurs for the histidine system; in comparison, asparagine is 7.8 and alanine is 9.7. This high value is most likely due to the participation of the additional effective N3 donor of the imidazole side group of histidine. The Co(II)-amac-Himid systems formed by using a [Co(imid) 2 ] n polymer as starting material demonstrate that the reversible uptake of molecular oxygen occurs by forming dimeric μ-peroxy adducts. The essential impact on the electron structure of the dioxygen bridge, and therefore, on the reversibility of O 2 uptake, is due to the imidazole group at axial position (trans towards O 2 ). However, the results of reversibility measurements of O 2 uptake, unequivocally indicate a much higher effectiveness of dioxygenation than in systems in which the oxygen adducts are formed in equilibrium mixtures during titration of solutions containing Co(II) ions, the amino acid and imidazole, separately.

  13. Equivalent air depth: fact or fiction.

    PubMed

    Berghage, T E; McCraken, T M

    1979-12-01

    In mixed-gas diving theory, the equivalent air depth (EAD) concept suggests that oxygen does not contribute to the total tissue gas tension and can therefore be disregarded in calculations of the decompression process. The validity of this assumption has been experimentally tested by exposing 365 rats to various partial pressures of oxygen for various lengths of time. If the EAD assumption is correct, under a constant exposure pressure each incremental change in the oxygen partial pressure would produce a corresponding incremental change in pressure reduction tolerance. Results of this study suggest that the EAD concept does not adequately describe the decompression advantages obtained from breathing elevated oxygen partial pressures. The authors suggest that the effects of breathing oxygen vary in a nonlinear fashion across the range from anoxia to oxygen toxicity, and that a simple inert gas replacement concept is no longer tenable.

  14. Densification and Electrical Properties of Zinc Oxide Varistors Microwave-Sintered Under Different Oxygen Partial Pressures

    NASA Astrophysics Data System (ADS)

    Lin, Cong; Wang, Bo; Xu, Zheng; Peng, Hu

    2012-11-01

    ZnO varistors were prepared by microwave sintering under different oxygen partial pressures. The temperature profile and the densification behavior in different atmospheres were investigated. It was found that the density of ZnO varistors during sintering was the key factor affecting the absorption of microwave energy. The electrical properties, including the nonlinear properties and capacitance-voltage ( C- V) characteristics, were also carefully studied. The results showed that the oxygen partial pressure has significant effects on the electrical properties of ZnO varistors by changing the concentration of defects through a series of reactions involving oxygen during sintering.

  15. Filterability of freshly-collected sickle erythrocytes under venous oxygen pressure without exposure to air.

    PubMed

    Shah, Siddharth; Acholonu, Rhonda Graves; Ohene-Frempong, Kwaku; Asakura, Toshio

    2015-12-01

    We previously found that blood samples collected from steady-state patients with sickle cell disease (SCD) without exposure to air contain a new type of reversibly sickled cells (RSCs) with blunt edges at a level of as high as 78%. Since partial oxygenation of once-deoxygenated sickled cells with pointy edges to near venous oxygen pressure generates similar sickled cells with blunt edges in vitro, we named them as partially oxygenated sickled cells (POSCs). On the other hand, partial deoxygenation of once-oxygenated SS cells to venous oxygen pressure generates partially deoxygenated sickled cells (PDSCs) with pointy edges. In this study, we obtained blood samples from 6 steady-state patients with SCD under venous oxygen pressure without exposure to air, subjected them to various oxygenation/deoxygenation/reoxygenation cycles, and studied their filterability through a membrane filter with pore diameter of 3μm, the theoretical minimum diameter of a capillary. Our results indicated that discocytes, POSCs with blunt edges, and irreversibly sickled cells could deform and pass through the filter, while PDSCs with pointy edges were rigid and could not. The filterability of SS cells seems to be related to the length and amount of deoxy-hemoglobin S fibers in the cells. Copyright © 2015. Published by Elsevier Inc.

  16. Application of a fast Newton-Krylov solver for equilibrium simulations of phosphorus and oxygen

    NASA Astrophysics Data System (ADS)

    Fu, Weiwei; Primeau, François

    2017-11-01

    Model drift due to inadequate spinup is a serious problem that complicates the interpretation of climate change simulations. Even after a 300 year spinup we show that solutions are not only still drifting but often drifting away from their eventual equilibrium over large parts of the ocean. Here we present a Newton-Krylov solver for computing cyclostationary equilibrium solutions of a biogeochemical model for the cycling of phosphorus and oxygen. In addition to using previously developed preconditioning strategies - time-averaging and coarse-graining the Jacobian matrix - we also introduce a new strategy: the adiabatic elimination of a fast variable (particulate organic phosphorus) by slaving it to a slow variable (dissolved inorganic phosphorus). We use transport matrices derived from the Community Earth System Model (CESM) with a nominal horizontal resolution of 1° × 1° and 60 vertical levels to implement and test the solver. We find that the new solver obtains seasonally-varying equilibrium solutions with no visible drift using no more than 80 simulation years.

  17. Hazards of decreasing marine oxygen: the near-term and millennial-scale benefits of meeting the Paris climate targets

    NASA Astrophysics Data System (ADS)

    Battaglia, Gianna; Joos, Fortunat

    2018-06-01

    Ocean deoxygenation is recognized as key ecosystem stressor of the future ocean and associated climate-related ocean risks are relevant for current policy decisions. In particular, benefits of reaching the ambitious 1.5 °C warming target mentioned by the Paris Agreement compared to higher temperature targets are of high interest. Here, we model oceanic oxygen, warming and their compound hazard in terms of metabolic conditions on multi-millennial timescales for a range of equilibrium temperature targets. Scenarios where radiative forcing is stabilized by 2300 are used in ensemble simulations with the Bern3D Earth System Model of Intermediate Complexity. Transiently, the global mean ocean oxygen concentration decreases by a few percent under low forcing and by 40 % under high forcing. Deoxygenation peaks about a thousand years after stabilization of radiative forcing and new steady-state conditions are established after AD 8000 in our model. Hypoxic waters expand over the next millennium and recovery is slow and remains incomplete under high forcing. Largest transient decreases in oxygen are projected for the deep sea. Distinct and near-linear relationships between the equilibrium temperature response and marine O2 loss emerge. These point to the effectiveness of the Paris climate target in reducing marine hazards and risks. Mitigation measures are projected to reduce peak decreases in oceanic oxygen inventory by 4.4 % °C-1 of avoided equilibrium warming. In the upper ocean, the decline of a metabolic index, quantified by the ratio of O2 supply to an organism's O2 demand, is reduced by 6.2 % °C-1 of avoided equilibrium warming. Definitions of peak hypoxia demonstrate strong sensitivity to additional warming. Volumes of water with less than 50 mmol O2 m-3, for instance, increase between 36 % and 76 % °C-1 of equilibrium temperature response. Our results show that millennial-scale responses should be considered in assessments of ocean deoxygenation and associated climate-related ocean risks. Peak hazards occur long after stabilization of radiative forcing and new steady-state conditions establish after AD 8000.

  18. Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea

    NASA Astrophysics Data System (ADS)

    Woo, K. S.; Jo, K.; Edwards, L. R.; Cheng, H.; Wang, Y.; Yoon, H.

    2006-12-01

    Stable isotope data (oxygen and carbon) of carbonate minerals (mostly calcite, but sometimes aragonite) in stalagmites have been the most commonly and widely used proxies for paleoclimatic research. This is based upon the assumption that carbonate minerals precipitated in isotopic equilibrium with dripping waters from stalactites, thus should reflect paleoclimatic variations. The state of equilibrium, so called "Hendy Test", has been commonly used. Hendy (1971) showed that during kinetic fractionation both oxygen and carbon isotopes behaves in a similar way due to faster degassing rate of cabon dioxide, resulting in the enrichment of both isotopes. The stalagmites from three limestone caves (Gwaneum, Eden and Daeya Caves) in Korea were investigated to understand the effects of kinetic fractionation during their growth. The stalagmites are mostly composed of columnar calcites, but contains the layers of cave coral that is composed of fibrous calcite. The cave coral layers should have grown when the supply rate of dripping water decreased significantly. Stable isotope pattern in three stalagmites do not show the same pattern of disequilibrium process. The cave corals in the Eden stalagmite show the enriched carbon and oxygen isotope values (15 and 5 per mil, respectively) that has the same bimodal pattern as suggested by Hendy (1971). However, the cave corals in the Gwaneum stalagmites show the enriched carbon, but depleted oxygen isotope values (3 and 1 per mil, respectively). Also, the calcite layer precipitated in disequilibrium in the Daeya stalagmite show more enriched carbon isotope values by up to 6 per mil, but show more or less the same oxygen isotopic values, compared to the columnar calcite which was precipitated in equilibrium. Therefore, caution should be made to determine the state of equilibrium precipitation of carbonate minerals in stalagmites. The "Hendy Test" may not be the only solution because other types of speleothems can be formed in stalagmites as the supply rate of dripping water changes. Also, different texture in stalagmites can be used as another criteria to determine the degree of equilibrium.

  19. Defects and Transport in Lithium Niobium Trioxide

    NASA Astrophysics Data System (ADS)

    Mehta, Apurva

    1990-01-01

    This dissertation presents work done on characterizing the defects and transport properties of congruent LiNbO _3. The focus of the study is the high temperature (800^circC to 1000^circC) equilibrium defect structure. The majority defects are described in terms of the 'LiNbO_3-ilmenite' defect model previously presented (26). Here the emphasis is placed on quantifying the defect concentrations. Congruent LiNbO_3 is highly nonstoichiometric. The large concentration of ionic defects present are mobile and contribute to electrical conduction. The ionic conduction was separated from the total conduction using defect chemistry and the transference number thus obtained was checked against the transference number obtained in a galvanic cell measurement. LiNbO_3 is an insulator (band gap = 4 eV). Hence one assumes that almost all of the conduction electrons are created by reduction. The degree of oxygen nonstoichiometry, a measure of the extent of chemical reduction, and the electron concentrations, were quantified as a function of oxygen partial pressure and the temperature by coulometric titration. The nonstoichiometry thus obtained was compared with nonstoichiometry obtained by TGA measurements. By fixing the phase composition of the sample in a buffered system, a set of constant composition measurements could be undertaken. These constant composition measurements were used to obtain the enthalpy of formation of conduction electrons, 1.95 eV, and the hopping energy for their motion at elevated temperatures, 0.55 eV, independently. The sum of the two energies was obtained by measuring the temperature dependence of the electronic conduction. The sum of the energies was found to be in excellent agreement with the energy obtained from equilibrium conduction. In conclusion, a quantitative and self-consistent picture of defects and their migration in LiNbO _3 was obtained.

  20. Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

    PubMed

    Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

    2018-05-29

    Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

  1. Thermoelectric power of YBa2Cu3Ox in equilibrium with gas phases

    NASA Astrophysics Data System (ADS)

    Nowotny, J.; Rekas, M.; Weppner, W.

    1988-10-01

    Thermoelectric power (TP) and electrical conductivity (EC) measurements were performed for YEa2Cu3Ox at 1128 K under controlled oxygen partial pressure varying between 50 and 105 Pa. Three regimes are observed for the electrical properties. At lowp_{{text{O}}_{text{2}} } (< 1.6{text{ }} × {text{ 10}}^{text{2}} {text{ }}{text{Pa}}) both TP and EC remain constant withp_{{text{O}}_{text{2}} } . In the medium range(1.6{text{ }} × {text{ 10}}^{text{2}}< p_{{text{O}}_{text{2}} }< 7.6{text{ }} × {text{ 10}}^{text{3}} {text{ Pa)}} sharp changes of both electrical parameters occur; TP changes sign from positive above 4×102 Pa to negative below thisp_{{text{O}}_{text{2}} } value. In the highp_{{text{O}}_{text{2}} } region (>7.6×103 Pa) TP vs logp_{{text{O}}_{text{2}} } exhibits two slopes; 5.1 below 1.5×104 Pa and 8.4 above thisp_{{text{O}}_{text{2}} } value. The slopes can be discussed in terms of the defect structure involving singly and doubly ionized oxygen vacancies below and above 7.6×103 Pa, respectively.

  2. Active nitric oxide produced in the red cell under hypoxic conditions by deoxyhemoglobin-mediated nitrite reduction.

    PubMed

    Nagababu, Enika; Ramasamy, Somasundaram; Abernethy, Darrell R; Rifkind, Joseph M

    2003-11-21

    Recent studies have generated a great deal of interest in a possible role for red blood cells in the transport of nitric oxide (NO) to the microcirculation and the vascular effect of this nitric oxide in facilitating the flow of blood through the microcirculation. Many questions have, however, been raised regarding such a mechanism. We have instead identified a completely new mechanism to explain the role of red cells in the delivery of NO to the microcirculation. This new mechanism results in the production of NO in the microcirculation where it is needed. Nitrite produced when NO reacts with oxygen in arterial blood is reutilized in the arterioles when the partial pressure of oxygen decreases and the deoxygenated hemoglobin formed reduces the nitrite regenerating NO. Nitrite reduction by hemoglobin results in a major fraction of the NO generated retained in the intermediate state where NO is bound to Hb(III) and in equilibrium with the nitrosonium cation bound to Hb(II). This pool of NO, unlike Hb(II)NO, is weakly bound and can be released from the heme. The instability of Hb(III)NO in oxygen and its displacement when flushed with argon requires that reliable determinations of red blood cell NO must be performed on freshly lysed samples without permitting the sample to be oxygenated. In fresh blood samples Hb(III)NO accounts for 75% of the red cell NO with appreciably higher values in venous blood than arterial blood. These findings confirm that nitrite reduction at reduced oxygen pressures is a major source for red cell NO. The formation and potential release from the red cell of this NO could have a major impact in regulating the flow of blood through the microcirculation.

  3. Mathematical Modeling of Ultra-Superheated Steam Gasification

    NASA Astrophysics Data System (ADS)

    Xin, Fen

    Pure steam gasification has been of interest in hydrogen production, but with the challenge of supplying heat for endothermic reactions. Traditional solutions included either combusting feedstocks at the price of decreasing carbon conversion ratio, or using costly heating apparatus. Therefore, a distributed gasifier with an Ultra-Superheated-Steam (USS) generator was invented, satisfying the heat requirement and avoiding carbon combustion in steam gasification. This project developed the first version of the Ultra-Superheated-Steam-Fluidization-Model (USSFM V1.0) for the USS gasifier. A stand-alone equilibrium combustion model was firstly developed to calculate the USS mixture, which was the input to the USSFM V1.0. Model development of the USSFM V1.0 included assumptions, governing equations, boundary conditions, supporting equations and iterative schemes of guessed values. There were three nested loops in the dense bed and one loop in the freeboard. The USSFM V1.0 included one main routine and twenty-four subroutines. The USSFM V1.0 was validated with experimental data from the Enercon USS gasifier. The calculated USS mixture had a trace of oxygen, validating the initial expectation of creating an oxygen-free environment in the gasifier. Simulations showed that the USS mixture could satisfy the gasification heat requirement without partial carbon combustion. The USSFM V1.0 had good predictions on the H2% in all tests, and on other variables at a level of the lower oxygen feed. Provided with higher oxygen feed, the USSFM V1.0 simulated hotter temperatures, higher CO% and lower CO2%. Errors were explained by assumptions of equilibrium combustion, adiabatic reactors, reaction kinetics, etc. By investigating specific modeling data, gas-particle convective heat transfers were found to be critical in energy balance equations of both emulsion gas and particles, while bubble size controlled both the mass and energy balance equations of bubble gas. Parametric study suggested a lower level of oxygen feed for higher content of hydrogen. However, too little oxygen would impede fluidization in the bed. The reasonability of iterative schemes and the stability of USSFM V1.0 were tested by the sensitivity analysis of two guessed values. Analytical Hierarchy Process analysis indicated that large-scale gasification is advantageous for hydrogen production but with impediments of high capital cost and CO2 emissions. This study manifested the USS gasifier offering the possibility of generating H2-rich and CO2-lean syngas in a much cheaper distributed way. Currently, the FORTRAN-based USSFM V1.0 had a good correlation with experimental data with a small oxygen feed. On the demand of wider applications, suggestions were proposed at last for the model improvement in future.

  4. Partial Pressures of Te2 and Thermodynamic Properties of Ga-Te System

    NASA Technical Reports Server (NTRS)

    Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

    2001-01-01

    The partial pressures of Te2 in equilibrium with Ga(1-x)Te(x) samples were measured by optical absorption technique from 450 to 1100 C for compositions, x, between 0.333 and 0.612. To establish the relationship between the partial pressure of Te, and the measured optical absorbance, the calibration runs of a pure Te sample were also conducted to determine the Beer's Law constants. The partial pressures of Te2 in equilibrium with the GaTe(s) and Ga2Te3(s)compounds, or the so-called three-phase curves, were established. These partial pressure data imply the existence of the Ga3Te4(s) compound. From the partial pressures of Te2 over the Ga-Te melts, partial molar enthalpy and entropy of mixing for Te were derived and they agree reasonable well with the published data. The activities of Te in the Ga-Te melts were also derived from the measured partial pressures of Te2. These data agree well with most of the previous results. The possible reason for the high activity of Te measured for x less than 0.60 is discussed.

  5. O 1s core levels in Bi2Sr2CaCu2O8+δ single crystals

    NASA Astrophysics Data System (ADS)

    Parmigiani, F.; Shen, Z. X.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

    1991-02-01

    High-quality Bi2Sr2CaCu2O8+δ superconducting single crystals, annealed at different oxygen partial pressures, have been studied using angular-resolved x-ray photoelectron spectroscopy with a resolution higher than that used in any previous study. Two states of the oxygen, separated by ~=0.7 eV, are unambiguously observed. Examining these components at different angles makes it possible to distinguish bulk from surface components. Using this capability we discover that annealing under lower oxygen partial pressure (1 atm) results in oxygen intercalation beneath the Bi-O surface layer of the crystal, whereas for higher-pressure anneals (12 atm) additional oxygen is found on the Bi-O surfaces. This steplike intercalation mechanism is also confirmed by the changes observed in the Cu and Bi core lines as a function of the annealing oxygen partial pressure.

  6. [Generation of Superoxide Radicals by Complex III in Heart Mitochondria and Antioxidant Effect of Dinitrosyl Iron Complexes at Different Partial Pressure of Oxygen].

    PubMed

    Dudylina, A L; Ivanova, M V; Shumaev, K B; Ruuge, E K

    2016-01-01

    The EPR spin-trapping technique and EPR-oximetry were used to study generation of superoxide radicals in heart mitochondria isolated from Wistar rats under conditions of variable oxygen concentration. Lithium phthalocyanine and TEMPONE-15N-D16 were chosen to determine oxygen content in a gas-permeable capillary tube containing mitochondria. TIRON was used as a spin trap. We investigated the influence of different oxygen concentrations in incubation mixture and demonstrated that heart mitochondria can generate superoxide in complex III at different partial pressure of oxygen as well as under the conditions of deep hypoxia (< 5% O2). Dinitrosyl iron complexes with glutathione (the pharmaceutical drug "Oxacom") exerted an antioxidant effect, regardless of the value of the partial pressure of oxygen, but the magnitude and kinetic characteristics of the effect depended on the concentration of the drug.

  7. Gas Exchange of Algae

    PubMed Central

    Ammann, Elizabeth C. B.; Lynch, Victoria H.

    1966-01-01

    Changes in the oxygen partial pressure of air over the range of 8 to 258 mm of Hg did not adversely affect the photosynthetic capacity of Chlorella pyrenoidosa. Gas exchange and growth measurements remained constant for 3-week periods and were similar to air controls (oxygen pressure of 160 mm of Hg). Oxygen partial pressures of 532 and 745 mm of Hg had an adverse effect on algal metabolism. Carbon dioxide consumption was 24% lower in the gas mixture containing oxygen at a pressure 532 mm of Hg than in the air control, and the growth rate was slightly reduced. Oxygen at a partial pressure of 745 mm of Hg decreased the photosynthetic rate 39% and the growth rate 37% over the corresponding rates in air. The lowered metabolic rates remained constant during 14 days of measurements, and the effect was reversible after this time. Substitution of helium or argon for the nitrogen in air had no effect on oxygen production, carbon dioxide consumption, or growth rate for 3-week periods. All measurements were made at a total pressure of 760 mm of Hg, and all gas mixtures were enriched with 2% carbon dioxide. Thus, the physiological functioning and reliability of a photosynthetic gas exchanger should not be adversely affected by: (i) oxygen partial pressures ranging from 8 to 258 mm of Hg; (ii) the use of pure oxygen at reduced total pressure (155 to 258 mm of Hg) unless pressure per se affects photosynthesis, or (iii) the inclusion of helium or argon in the gas environment (up to a partial pressure of 595 mm of Hg). PMID:5927028

  8. A finite difference scheme for the equilibrium equations of elastic bodies

    NASA Technical Reports Server (NTRS)

    Phillips, T. N.; Rose, M. E.

    1984-01-01

    A compact difference scheme is described for treating the first-order system of partial differential equations which describe the equilibrium equations of an elastic body. An algebraic simplification enables the solution to be obtained by standard direct or iterative techniques.

  9. [Diagnostic importance of the alveolar-arterial oxygen gradient].

    PubMed

    Weinans, Marije A E; Drost-de Klerck, Amanda M; ter Maaten, Jan C

    2012-01-01

    The alveolar-arterial (A-a) oxygen gradient is the difference between the partial pressure of oxygen in the alveoli and the partial pressure of arterial oxygen and can be elevated in the case of pulmonary disease. We describe a 41-year-old patient with pneumonia who presented with abdominal pain, in whom calculation of the A-a gradient could have led to earlier diagnosis. The A-a oxygen gradient is mainly of diagnostic importance and the presented nomogram allows easy and quick interpretation. This might lead to a more frequent use of the A-a oxygen gradient in the future.

  10. Point Defect Structure of Cr203

    DTIC Science & Technology

    1987-10-01

    Calculation of Electron Hole Mobility ........................ 104 6.2.3 Construction of the Defect Concentration vs. Oxygen Pressure Diagram...1000’ to 16000C ............ 123 7.7 Calculated diffusion coefficient vs. oxygen partial pressure diagram for pure Cr203 at 1100 0 C...127 7.10 Calculated parabolic rate constant vs. oxygen partial pressure diagram for pure Cr203 at

  11. 46 CFR 39.40-5 - Operational requirements for vapor balancing-TB/ALL.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... tanks have partial bulkheads, the oxygen content of each area of that tank formed by each partial... vapor collection system must be tested prior to cargo transfer to ensure that the oxygen content in the vapor space does not exceed 8 percent by volume. The oxygen content of each tank must be measured at a...

  12. Oxygen vacancy induced phase formation and room temperature ferromagnetism in undoped and Co-doped TiO2 thin films

    NASA Astrophysics Data System (ADS)

    Mohanty, P.; Mishra, N. C.; Choudhary, R. J.; Banerjee, A.; Shripathi, T.; Lalla, N. P.; Annapoorni, S.; Rath, Chandana

    2012-08-01

    TiO2 and Co-doped TiO2 (CTO) thin films deposited at various oxygen partial pressures by pulsed laser deposition exhibit room temperature ferromagnetism (RTFM) independent of their phase. Films deposited at 0.1 mTorr oxygen partial pressure show a complete rutile phase confirmed from glancing angle x-ray diffraction and Raman spectroscopy. At the highest oxygen partial pressure, i.e. 300 mTorr, although the TiO2 film shows a complete anatase phase, a small peak corresponding to the rutile phase along with the anatase phase is identified in the case of CTO film. An increase in O to Ti/(Ti+Co) ratio with increase in oxygen partial pressure is observed from Rutherford backscattering spectroscopy. It is revealed from x-ray photoelectron spectroscopy (XPS) that oxygen vacancies are found to be higher in the CTO film than TiO2, while the valency of cobalt remains in the +2 state. Therefore, the CTO film deposited at 300 mTorr does not show a complete anatase phase unlike the TiO2 film deposited at the same partial pressure. We conclude that RTFM in both films is not due to impurities/contaminants, as confirmed from XPS depth profiling and cross-sectional transmission electron microscopy (TEM), but due to oxygen vacancies. The magnitude of moment, however, depends not only on the phase of TiO2 but also on the crystallinity of the films.

  13. Reversible effects of oxygen partial pressure on genes associated with placental angiogenesis and differentiation in primary-term cytotrophoblast cell culture.

    PubMed

    Debiève, F; Depoix, C; Gruson, D; Hubinont, C

    2013-09-01

    Timely regulated changes in oxygen partial pressure are important for placental formation. Disturbances could be responsible for pregnancy-related diseases like preeclampsia and intrauterine growth restriction. We aimed to (i) determine the effect of oxygen partial pressure on cytotrophoblast differentiation; (ii) measure mRNA expression and protein secretion from genes associated with placental angiogenesis; and (iii) determine the reversibility of these effects at different oxygen partial pressures. Term cytotrophoblasts were incubated at 21% and 2.5% O2 for 96 hr, or were switched between the two oxygen concentrations after 48 hr. Real-time PCR and enzyme-linked immunosorbent assays (ELISAs) were used to evaluate cell fusion and differentiation, measuring transcript levels for those genes involved in cell fusion and placental angiogenesis, including VEGF, PlGF, VEGFR1, sVEGFR1, sENG, INHA, and GCM1. Cytotrophoblasts underwent fusion and differentiation in 2.5% O2 . PlGF expression was inhibited while sVEGFR1 expression increased. VEGF and sENG mRNA expressions increased in 2.5% compared to 21% O2 , but no protein was detected in the cell supernatants. Finally, GCM1 mRNA expression increased during trophoblast differentiation at 21% O2 , but was inhibited at 2.5% O2 . These mRNA expression effects were reversed by returning the cells to 21% O2 . Thus, low-oxygen partial pressure does not inhibit term-cytotrophoblast cell fusion and differentiation in vitro. Lowering the oxygen partial pressure from 21% to 2.5% caused normal-term trophoblasts to reversibly modify their expression of genes associated with placental angiogenesis. This suggests that modifications observed in pregnancy diseases such as preeclampsia or growth retardation are probably due to an extrinsic effect on trophoblasts. Copyright © 2013 Wiley Periodicals, Inc.

  14. Method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

    DOEpatents

    Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

    2000-01-01

    A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbon monoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

  15. Imaging the equilibrium state and magnetization dynamics of partially built hard disk write heads

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Valkass, R. A. J., E-mail: rajv202@ex.ac.uk; Yu, W.; Shelford, L. R.

    Four different designs of partially built hard disk write heads with a yoke comprising four repeats of NiFe (1 nm)/CoFe (50 nm) were studied by both x-ray photoemission electron microscopy (XPEEM) and time-resolved scanning Kerr microscopy (TRSKM). These techniques were used to investigate the static equilibrium domain configuration and the magnetodynamic response across the entire structure, respectively. Simulations and previous TRSKM studies have made proposals for the equilibrium domain configuration of similar structures, but no direct observation of the equilibrium state of the writers has yet been made. In this study, static XPEEM images of the equilibrium state of writer structures weremore » acquired using x-ray magnetic circular dichroism as the contrast mechanism. These images suggest that the crystalline anisotropy dominates the equilibrium state domain configuration, but competition with shape anisotropy ultimately determines the stability of the equilibrium state. Dynamic TRSKM images were acquired from nominally identical devices. These images suggest that a longer confluence region may hinder flux conduction from the yoke into the pole tip: the shorter confluence region exhibits clear flux beaming along the symmetry axis, whereas the longer confluence region causes flux to conduct along one edge of the writer. The observed variations in dynamic response agree well with the differences in the equilibrium magnetization configuration visible in the XPEEM images, confirming that minor variations in the geometric design of the writer structure can have significant effects on the process of flux beaming.« less

  16. Decomposition of poly(amide-imide) film enameled on solid copper wire using atmospheric pressure non-equilibrium plasma.

    PubMed

    Sugiyama, Kazuo; Suzuki, Katsunori; Kuwasima, Shusuke; Aoki, Yosuke; Yajima, Tatsuhiko

    2009-01-01

    The decomposition of a poly(amide-imide) thin film coated on a solid copper wire was attempted using atmospheric pressure non-equilibrium plasma. The plasma was produced by applying microwave power to an electrically conductive material in a gas mixture of argon, oxygen, and hydrogen. The poly(amide-imide) thin film was easily decomposed by argon-oxygen mixed gas plasma and an oxidized copper surface was obtained. The reduction of the oxidized surface with argon-hydrogen mixed gas plasma rapidly yielded a metallic copper surface. A continuous plasma heat-treatment process using a combination of both the argon-oxygen plasma and argon-hydrogen plasma was found to be suitable for the decomposition of the poly(amide-imide) thin film coated on the solid copper wire.

  17. A comparison of Redlich-Kister polynomial and cubic spline representations of the chemical potential in phase field computations

    DOE PAGES

    Teichert, Gregory H.; Gunda, N. S. Harsha; Rudraraju, Shiva; ...

    2016-12-18

    Free energies play a central role in many descriptions of equilibrium and non-equilibrium properties of solids. Continuum partial differential equations (PDEs) of atomic transport, phase transformations and mechanics often rely on first and second derivatives of a free energy function. The stability, accuracy and robustness of numerical methods to solve these PDEs are sensitive to the particular functional representations of the free energy. In this communication we investigate the influence of different representations of thermodynamic data on phase field computations of diffusion and two-phase reactions in the solid state. First-principles statistical mechanics methods were used to generate realistic free energymore » data for HCP titanium with interstitially dissolved oxygen. While Redlich-Kister polynomials have formed the mainstay of thermodynamic descriptions of multi-component solids, they require high order terms to fit oscillations in chemical potentials around phase transitions. Here, we demonstrate that high fidelity fits to rapidly fluctuating free energy functions are obtained with spline functions. As a result, spline functions that are many degrees lower than Redlich-Kister polynomials provide equal or superior fits to chemical potential data and, when used in phase field computations, result in solution times approaching an order of magnitude speed up relative to the use of Redlich-Kister polynomials.« less

  18. Investigation of La xSr 1-xCo yM 1-yO 3-δ (M = Mn Fe) perovskite materials as thermochemical energy storage media

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Babiniec, Sean Michael; Coker, Eric Nicholas; Miller, James E.

    2015-06-23

    Materials in the La xSr 1–xCo yMn 1–yO 3–δ (LSCM) and La xSr 1–xCo yFe 1–yO 3–δ (LSCF) families are candidates for high-temperature thermochemical energy storage due to their facility for cyclic endothermic reduction and exothermic oxidation. A set of 16 LSCM and 21 LSCF compositions were synthesized by a modified Pechini method and characterized by powder X-ray diffraction and thermogravimetric analysis. All materials were found to be various symmetries of the perovskite phase. LSCM was indexed as tetragonal, cubic, rhombohedral, or orthorhombic as a function of increased lanthanum content. For LSCF, compositions containing low lanthanum content were indexed asmore » cubic while materials with high lanthanum content were indexed as rhombohedral. An initial screening of redox activity was completed by thermogravimetric analysis for each composition. The top three compositions with the greatest recoverable redox capacity for each family were further characterized in equilibrium thermogravimetric experiments over a range of temperatures and oxygen partial pressures. As a result, these equilibrium experiments allowed the extraction of thermodynamic parameters for LSCM and LSCF compositions operated in thermochemical energy storage conditions.« less

  19. Evaluation of Nd:YAG laser on partial oxygen saturation of pulpal blood in anterior hypersensitive teeth.

    PubMed

    Birang, Reza; Kaviani, Naser; Mohammadpour, Mehdi; Abed, Ahmad Moghareh; Gutknecht, Norbert; Mir, Maziar

    2008-07-01

    Dentine hypersensitivity has of long been known to be a common clinical problem in dental practices. Lasers have recently come to play a prominent role in the treatment of this disorder. They might, however, cause dental pulp damage. This study was conducted to evaluate the effect of Nd:yttrium-aluminum-garnet (YAG) laser on partial oxygen saturation of pulpal blood in sensitive anterior teeth. In this clinical trial, 65 hypersensitive teeth were selected and randomly allocated to two groups. The study group involved Nd:YAG laser treatment, while no treatment was employed for the control group. Using a pulse oximetry system, evaluations were preformed of the partial oxygen saturation in the pulpal blood before, immediately after, 1 week after, and 1 month after the treatment. The results were analyzed using the SPSS software and repeated-measures analysis of variance and paired-samples t tests. The mean partial oxygen saturation of the blood was found to be 85.4% in the study group, which was not significantly different from that of the control group. No significant differences were observed in the control group between the means obtained from pretreatment and post-treatment intervals (P > 0.05). The Post-treatment partial oxygen saturation mean rose to 89.3% (P = 0.001) and remained constant throughout the following week after it. However, no significant differences were found between the pretreatment partial oxygen saturation mean and the same measurement 1 month after treatment (P = 0.702). Nd:YAG laser therapy for dentine desensitization of anterior teeth caused no persistent changes in the partial oxygen saturation of pulpal blood. It may, therefore, be concluded that the diffusion of heat induced by the Nd:YAG laser into the pulp within the limit of the desensitization parameters cause no irreversible damages in the dental pulp.

  20. A combined experimental and computational thermodynamic investigation of the U-Th-O system

    DOE PAGES

    McMurray, Jake Wesley; Voit, Stewart L.; Besmann, Theodore M.

    2016-03-21

    Here, the thermodynamics of the U–Th–O system have been assessed using the Calphad method. The compound energy formalism (CEF) and a partially ionic two-sublattice liquid model (TSLM) were used for the fluorite U 1–yTh yO 2±x, γ-(U,Th) 4O 9, and the U–Th–O melt. The O 2 activity of fluorite U 1–yTh yO 2±x with temperature and composition was determined by thermogravimetric analysis. Thermodynamic studies for the Th–O binary and U–Th–O ternary available in the open literature were critically reviewed. A self-consistent data set was selected and compiled with the equilibrium oxygen pressures determined by thermogravimetry in order to optimize themore » adjustable parameters of models selected to represent the phases in the Th–O and U–Th–O systems.« less

  1. Processes for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil, and apparatuses for treating biomass-derived pyrolysis oil

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Baird, Lance Awender; Brandvold, Timothy A.

    Processes and apparatuses for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil are provided herein. An exemplary process for washing a spent ion exchange bed employed in purification of biomass-derived pyrolysis oil includes the step of providing a ion-depleted pyrolysis oil stream having an original oxygen content. The ion-depleted pyrolysis oil stream is partially hydrotreated to reduce the oxygen content thereof, thereby producing a partially hydrotreated pyrolysis oil stream having a residual oxygen content that is less than the original oxygen content. At least a portion of the partially hydrotreated pyrolysis oil stream is passed throughmore » the spent ion exchange bed. Water is passed through the spent ion exchange bed after passing at least the portion of the partially hydrotreated pyrolysis oil stream therethrough.« less

  2. Noninvasive oxygen partial pressure measurement of human body fluids in vivo using magnetic resonance imaging.

    PubMed

    Zaharchuk, Greg; Busse, Reed F; Rosenthal, Guy; Manley, Geoffery T; Glenn, Orit A; Dillon, William P

    2006-08-01

    The oxygen partial pressure (pO2) of human body fluids reflects the oxygenation status of surrounding tissues. All existing fluid pO2 measurements are invasive, requiring either microelectrode/optode placement or fluid removal. The purpose of this study is to develop a noninvasive magnetic resonance imaging method to measure the pO2 of human body fluids. We developed an imaging paradigm that exploits the paramagnetism of molecular oxygen to create quantitative images of fluid oxygenation. A single-shot fast spin echo pulse sequence was modified to minimize artifacts from motion, fluid flow, and partial volume. Longitudinal relaxation rate (R1 = 1/T1) was measured with a time-efficient nonequilibrium saturation recovery method and correlated with pO2 measured in phantoms. pO2 images of human and fetal cerebrospinal fluid, bladder urine, and vitreous humor are presented and quantitative oxygenation levels are compared with prior literature estimates, where available. Significant pO2 increases are shown in cerebrospinal fluid and vitreous following 100% oxygen inhalation. Potential errors due to temperature, fluid flow, and partial volume are discussed. Noninvasive measurements of human body fluid pO2 in vivo are presented, which yield reasonable values based on prior literature estimates. This rapid imaging-based measurement of fluid oxygenation may provide insight into normal physiology as well as changes due to disease or during treatment.

  3. Oxygen desaturations triggered by partial seizures: implications for cardiopulmonary instability in epilepsy

    NASA Technical Reports Server (NTRS)

    Blum, A. S.; Ives, J. R.; Goldberger, A. L.; Al-Aweel, I. C.; Krishnamurthy, K. B.; Drislane, F. W.; Schomer, D. L.

    2000-01-01

    PURPOSE: The occurrence of hypoxemia in adults with partial seizures has not been systematically explored. Our aim was to study in detail the temporal dynamics of this specific type of ictal-associated hypoxemia. METHODS: During long-term video/EEG monitoring (LTM), patients underwent monitoring of oxygen saturation using a digital Spo2 (pulse oximeter) transducer. Six patients (nine seizures) were identified with oxygen desaturations after the onset of partial seizure activity. RESULTS: Complex partial seizures originated from both left and right temporal lobes. Mean seizure duration (+/-SD) was 73 +/- 18 s. Mean Spo2 desaturation duration was 76 +/- 19 s. The onset of oxygen desaturation followed seizure onset with a mean delay of 43 +/- 16 s. Mean (+/-SD) Spo2 nadir was 83 +/- 5% (range, 77-91%), occurring an average of 35 +/- 12 s after the onset of the desaturation. One seizure was associated with prolonged and recurrent Spo2 desaturations. CONCLUSIONS: Partial seizures may be associated with prominent oxygen desaturations. The comparable duration of each seizure and its subsequent desaturation suggests a close mechanistic (possibly causal) relation. Spo2 monitoring provides an added means for seizure detection that may increase LTM yield. These observations also raise the possibility that ictal ventilatory dysfunction could play a role in certain cases of sudden unexpected death in epilepsy in adults with partial seizures.

  4. A Tightly Coupled Non-Equilibrium Magneto-Hydrodynamic Model for Inductively Coupled RF Plasmas

    DTIC Science & Technology

    2016-02-29

    development a tightly coupled magneto-hydrodynamic model for Inductively Coupled Radio- Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE...for Inductively Coupled Radio-Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State... thermodynamic variable. This choice allows one to hide the non-linearity of the gas (total) thermal conductivity κ and can partially alle- 2 viate numerical

  5. Plasma Jet Interactions with Liquids in Partial Fulfillment of an NRL Karles Fellowship

    DTIC Science & Technology

    2015-11-30

    deposition), modify (e.g., chemical functionalization), and etch (in Si technology) materials. In low- pressure non- equilibrium discharge plasmas... equilibrium discharge plasmas, associated with the above processes, the electron population is much more energetic than both the ions and neutral gas...to be crucial to the advancements of these fields1, 2. Background: Atmospheric-pressure, non- equilibrium (APNE) plasmas, like low-pressure plasmas

  6. ATMOSPHERIC CHEMISTRY FOR ASTROPHYSICISTS: A SELF-CONSISTENT FORMALISM AND ANALYTICAL SOLUTIONS FOR ARBITRARY C/O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Heng, Kevin; Tsai, Shang-Min; Lyons, James R., E-mail: kevin.heng@csh.unibe.ch

    2016-01-10

    We present a self-consistent formalism for computing and understanding the atmospheric chemistry of exoplanets from the viewpoint of an astrophysicist. Starting from the first law of thermodynamics, we demonstrate that the van’t Hoff equation (which describes the equilibrium constant), Arrhenius equation (which describes the rate coefficients), and procedures associated with the Gibbs free energy (minimization, rescaling) have a common physical and mathematical origin. We address an ambiguity associated with the equilibrium constant, which is used to relate the forward and reverse rate coefficients, and restate its two definitions. By necessity, one of the equilibrium constants must be dimensionless and equatemore » to an exponential function involving the Gibbs free energy, while the other is a ratio of rate coefficients and must therefore possess physical units. We demonstrate that the Arrhenius equation takes on a functional form that is more general than previously stated without recourse to tagging on ad hoc functional forms. Finally, we derive analytical models of chemical systems, in equilibrium, with carbon, hydrogen, and oxygen. We include acetylene and are able to reproduce several key trends, versus temperature and carbon-to-oxygen ratio, published in the literature. The rich variety of behavior that mixing ratios exhibit as a function of the carbon-to-oxygen ratio is merely the outcome of stoichiometric book-keeping and not the direct consequence of temperature or pressure variations.« less

  7. Atmospheric Chemistry for Astrophysicists: A Self-consistent Formalism and Analytical Solutions for Arbitrary C/O

    NASA Astrophysics Data System (ADS)

    Heng, Kevin; Lyons, James R.; Tsai, Shang-Min

    2016-01-01

    We present a self-consistent formalism for computing and understanding the atmospheric chemistry of exoplanets from the viewpoint of an astrophysicist. Starting from the first law of thermodynamics, we demonstrate that the van’t Hoff equation (which describes the equilibrium constant), Arrhenius equation (which describes the rate coefficients), and procedures associated with the Gibbs free energy (minimization, rescaling) have a common physical and mathematical origin. We address an ambiguity associated with the equilibrium constant, which is used to relate the forward and reverse rate coefficients, and restate its two definitions. By necessity, one of the equilibrium constants must be dimensionless and equate to an exponential function involving the Gibbs free energy, while the other is a ratio of rate coefficients and must therefore possess physical units. We demonstrate that the Arrhenius equation takes on a functional form that is more general than previously stated without recourse to tagging on ad hoc functional forms. Finally, we derive analytical models of chemical systems, in equilibrium, with carbon, hydrogen, and oxygen. We include acetylene and are able to reproduce several key trends, versus temperature and carbon-to-oxygen ratio, published in the literature. The rich variety of behavior that mixing ratios exhibit as a function of the carbon-to-oxygen ratio is merely the outcome of stoichiometric book-keeping and not the direct consequence of temperature or pressure variations.

  8. Positron beam study of indium tin oxide films on GaN

    NASA Astrophysics Data System (ADS)

    Cheung, C. K.; Wang, R. X.; Beling, C. D.; Djurisic, A. B.; Fung, S.

    2007-02-01

    Variable energy Doppler broadening spectroscopy has been used to study open-volume defects formed during the fabrication of indium tin oxide (ITO) thin films grown by electron-beam evaporation on n-GaN. The films were prepared at room temperature, 200 and 300 °C without oxygen and at 200 °C under different oxygen partial pressures. The results show that at elevated growth temperatures the ITO has fewer open volume sites and grows with a more crystalline structure. High temperature growth, however, is not sufficient in itself to remove open volume defects at the ITO/GaN interface. Growth under elevated temperature and under partial pressure of oxygen is found to further reduce the vacancy type defects associated with the ITO film, thus improving the quality of the film. Oxygen partial pressures of 6 × 10-3 mbar and above are found to remove open volume defects associated with the ITO/GaN interface. The study suggests that, irrespective of growth temperature and oxygen partial pressure, there is only one type of defect in the ITO responsible for trapping positrons, which we tentatively attribute to the oxygen vacancy.

  9. Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped and lead-free Bi-2212 systems

    NASA Astrophysics Data System (ADS)

    Tetenbaum, M.; Hash, M.; Tani, B. S.; Maroni, V. A.

    1996-02-01

    Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi 2- zPb zSr 2Ca 1Cu 2O x superconducting ceramics in the temperature range ≈ 700-815°C by means of an oxygen-titration techique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities Δ overlineH(O 2) and Δ overlineS(O 2) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressure can be represented by the diphasic CuOCu 2O system.

  10. In vivo integrated photoacoustic and confocal microscopy of hemoglobin oxygen saturation and oxygen partial pressure.

    PubMed

    Wang, Yu; Hu, Song; Maslov, Konstantin; Zhang, Yu; Xia, Younan; Wang, Lihong V

    2011-04-01

    We developed dual-modality microscope integrating photoacoustic microscopy (PAM) and fluorescence confocal microscopy (FCM) to noninvasively image hemoglobin oxygen saturation (sO₂) and oxygen partial pressure (pO₂) in vivo in single blood vessels with high spatial resolution. While PAM measures sO₂ by imaging hemoglobin optical absorption at two wavelengths, FCM quantifies pO₂ using phosphorescence quenching. The variations of sO₂ and pO₂ values in multiple orders of vessel branches under hyperoxic (100% oxygen) and normoxic (21% oxygen) conditions correlate well with the oxygen-hemoglobin dissociation curve. In addition, the total concentration of hemoglobin is imaged by PAM at an isosbestic wavelength.

  11. Non-equilibrium thermodynamics, maximum entropy production and Earth-system evolution.

    PubMed

    Kleidon, Axel

    2010-01-13

    The present-day atmosphere is in a unique state far from thermodynamic equilibrium. This uniqueness is for instance reflected in the high concentration of molecular oxygen and the low relative humidity in the atmosphere. Given that the concentration of atmospheric oxygen has likely increased throughout Earth-system history, we can ask whether this trend can be generalized to a trend of Earth-system evolution that is directed away from thermodynamic equilibrium, why we would expect such a trend to take place and what it would imply for Earth-system evolution as a whole. The justification for such a trend could be found in the proposed general principle of maximum entropy production (MEP), which states that non-equilibrium thermodynamic systems maintain steady states at which entropy production is maximized. Here, I justify and demonstrate this application of MEP to the Earth at the planetary scale. I first describe the non-equilibrium thermodynamic nature of Earth-system processes and distinguish processes that drive the system's state away from equilibrium from those that are directed towards equilibrium. I formulate the interactions among these processes from a thermodynamic perspective and then connect them to a holistic view of the planetary thermodynamic state of the Earth system. In conclusion, non-equilibrium thermodynamics and MEP have the potential to provide a simple and holistic theory of Earth-system functioning. This theory can be used to derive overall evolutionary trends of the Earth's past, identify the role that life plays in driving thermodynamic states far from equilibrium, identify habitability in other planetary environments and evaluate human impacts on Earth-system functioning. This journal is © 2010 The Royal Society

  12. Oxygen-depleted zones inside reproductive structures of Brassicaceae: implications for oxygen control of seed development

    NASA Technical Reports Server (NTRS)

    Porterfield, D. M.; Kuang, A.; Smith, P. J.; Crispi, M. L.; Musgrave, M. E.

    1999-01-01

    Growth of Arabidopsis thaliana (L.) Heynh. in decreasing oxygen partial pressures revealed a linear decrease in seed production below 15 kPa, with a complete absence of seed production at 2.5 kPa oxygen. This control of plant reproduction by oxygen had previously been attributed to an oxygen effect on the partitioning between vegetative and reproductive growth. However, plants grown in a series of decreasing oxygen concentrations produced progressively smaller embryos that had stopped developing at progressively younger stages, suggesting instead that their growth is limited by oxygen. Internal oxygen concentrations of buds, pistils, and developing siliques of Brassica rapa L. and siliques of Arabidopsis were measured using a small-diameter glass electrode that was moved into the structures using a micromanipulator. Oxygen partial pressures were found to be lowest in the developing perianth (11.1 kPa) and pistils (15.2 kPa) of the unopened buds. Pollination reduced oxygen concentration inside the pistils by 3 kPa after just 24 h. Inside Brassica silique locules, partial pressures of oxygen averaged 12.2 kPa in darkness, and increased linearly with increasing light levels to 16.2 kPa. Measurements inside Arabidopsis siliques averaged 6.1 kPa in the dark and rose to 12.2 kPa with light. Hypoxia in these microenvironments is postulated to be the point of control of plant reproduction by oxygen.

  13. Hemoglobin in Frankia, a Nitrogen-Fixing Actinomycete†

    PubMed Central

    Tjepkema, John D.; Cashon, Robert E.; Beckwith, Jason; Schwintzer, Christa R.

    2002-01-01

    Frankia strain CcI3 grown in culture produced a hemoglobin which had optical absorption bands typical of a hemoglobin and a molecular mass of 14.1 kDa. Its equilibrium oxygen binding constant was 274 nM, the oxygen dissociation rate constant was 56 s−1, and the oxygen association rate constant was 206 μM−1 s−1. PMID:11976149

  14. Cerebral hemodynamics at altitude: effects of hyperventilation and acclimatization on cerebral blood flow and oxygenation.

    PubMed

    Sanborn, Matthew R; Edsell, Mark E; Kim, Meeri N; Mesquita, Rickson; Putt, Mary E; Imray, Chris; Yow, Heng; Wilson, Mark H; Yodh, Arjun G; Grocott, Mike; Martin, Daniel S

    2015-06-01

    Alterations in cerebral blood flow (CBF) and cerebral oxygenation are implicated in altitude-associated diseases. We assessed the dynamic changes in CBF and peripheral and cerebral oxygenation engendered by ascent to altitude with partial acclimatization and hyperventilation using a combination of near-infrared spectroscopy, transcranial Doppler ultrasound, and diffuse correlation spectroscopy. Peripheral (Spo2) and cerebral (Scto2) oxygenation, end-tidal carbon dioxide (ETCO2), and cerebral hemodynamics were studied in 12 subjects using transcranial Doppler and diffuse correlation spectroscopy (DCS) at 75 m and then 2 days and 7 days after ascending to 4559 m above sea level. After obtaining baseline measurements, subjects hyperventilated to reduce baseline ETCO2 by 50%, and a further set of measurements were obtained. Cerebral oxygenation and peripheral oxygenation showed a divergent response, with cerebral oxygenation decreasing at day 2 and decreasing further at day 7 at altitude, whereas peripheral oxygenation decreased on day 2 before partially rebounding on day 7. Cerebral oxygenation decreased after hyperventilation at sea level (Scto2 from 68.8% to 63.5%; P<.001), increased after hyperventilation after 2 days at altitude (Scto2 from 65.6% to 69.9%; P=.001), and did not change after hyperventilation after 7 days at altitude (Scto2 from 62.2% to 63.3%; P=.35). An intensification of the normal cerebral hypocapnic vasoconstrictive response occurred after partial acclimatization in the setting of divergent peripheral and cerebral oxygenation. This may help explain why hyperventilation fails to improve cerebral oxygenation after partial acclimatization as it does after initial ascent. The use of DCS is feasible at altitude and provides a direct measure of CBF indices with high temporal resolution. Copyright © 2015 Wilderness Medical Society. Published by Elsevier Inc. All rights reserved.

  15. Thermodynamic and nonstoichiometric behavior of the lead-doped Bi-2223 system

    NASA Astrophysics Data System (ADS)

    Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

    1994-12-01

    Electromotive force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 700 to 815°C and at oxygen partial pressures ranging from ∼0.02 to 0.2 atm should tend to preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of partial molar quantities indicate that the plateau regions can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm. Long-duration post anneals of silver-clad Bi-2223 filaments at 825°C and an oxygen partial pressure of 0.075 atm eliminated Bi-2212 intergrowths with a concomitant increase in the superconducting transition sharpness.

  16. Effect of oxygen atoms dissociated by non-equilibrium plasma on flame of methane oxygen and argon pre-mixture gas

    NASA Astrophysics Data System (ADS)

    Akashi, Haruaki; Yoshinaga, Tomokazu; Sasaki, Koichi

    2014-10-01

    For more efficient way of combustion, plasma-assisted combustion has been investigated by many researchers. But it is very difficult to clarify the effect of plasma even on the flame of methane. Because there are many complex chemical reactions in combustion system. Sasaki et al. has reported that the flame length of methane and air premixed burner shortened by irradiating microwave power. They also measured emission from Second Positive Band System of nitrogen during the irradiation. The emission indicates existence of high energy electrons which are accelerated by the microwave. The high energy electrons also dissociate oxygen molecules easily and oxygen atom would have some effects on the flame. But the dissociation ratio of oxygen molecules by the non-equilibrium plasma is significantly low, compared to that in the combustion reaction. To clarify the effect of dissociated oxygen atoms on the flame, dependence of dissociation ratio of oxygen on the flame has been examined using CHEMKIN. It is found that in the case of low dissociation ratio of 10-6, the ignition of the flame becomes slightly earlier. It is also found that in the case of high dissociation ratio of 10-3, the ignition time becomes significantly earlier by almost half. This work was supported by KAKENHI (22340170).

  17. CHROMOSPHERIC MODELS AND THE OXYGEN ABUNDANCE IN GIANT STARS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dupree, A. K.; Avrett, E. H.; Kurucz, R. L., E-mail: dupree@cfa.harvard.edu

    Realistic stellar atmospheric models of two typical metal-poor giant stars in Omega Centauri, which include a chromosphere (CHR), influence the formation of optical lines of O i: the forbidden lines (λ6300, λ6363) and the infrared triplet (λλ7771−7775). One-dimensional semi-empirical non-local thermodynamic equilibrium (LTE) models are constructed based on observed Balmer lines. A full non-LTE formulation is applied for evaluating the line strengths of O i, including photoionization by the Lyman continuum and photoexcitation by Lyα and Lyβ. Chromospheric models (CHR) yield forbidden oxygen transitions that are stronger than those in radiative/convective equilibrium (RCE) models. The triplet oxygen lines from highmore » levels also appear stronger than those produced in an RCE model. The inferred oxygen abundance from realistic CHR models for these two stars is decreased by factors of ∼3 as compared to values derived from RCE models. A lower oxygen abundance suggests that intermediate-mass AGB stars contribute to the observed abundance pattern in globular clusters. A change in the oxygen abundance of metal-poor field giants could affect models of deep mixing episodes on the red giant branch. Changes in the oxygen abundance can impact other abundance determinations that are critical to astrophysics, including chemical tagging techniques and galactic chemical evolution.« less

  18. Energy expenditure in space flight (doubly labelled water method) (8-IML-1)

    NASA Technical Reports Server (NTRS)

    Parsons, Howard G.

    1992-01-01

    The objective of the Energy Expenditure in Space Flight (ESS) experiment is to demonstrate and evaluate the doubly labeled water method of measuring the energy expended by crew members during approximately 7 days in microgravity. The doubly labeled water technique determines carbon dioxide production which is then used to calculate energy expenditure. The method relies on the equilibrium between oxygen in respiratory carbon dioxide and oxygen in body water. Because of this equilibrium, the kinetic of water turnover and respiration are interdependent. Under normal conditions, man contains small but significant amounts of deuterium and oxygen 18. Deuterium is eliminated from the body as water while oxygen 18 is eliminated as water and carbon dioxide. The difference in the turnover rates in the two isotopes is proportional to the carbon dioxide production. Deliberately enriching the total body water with both of these isotopes allows the isotope turnovers to be accurately measured in urine, plasma, or saliva samples. The samples are taken to the laboratory for analysis using an ion-ratio spectrometer.

  19. Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Shock, Everetr L.; Koretsky, Carla M.

    1995-04-01

    Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

  20. A flowing liquid test system for assessing the linearity and time-response of rapid fibre optic oxygen partial pressure sensors.

    PubMed

    Chen, R; Hahn, C E W; Farmery, A D

    2012-08-15

    The development of a methodology for testing the time response, linearity and performance characteristics of ultra fast fibre optic oxygen sensors in the liquid phase is presented. Two standard medical paediatric oxygenators are arranged to provide two independent extracorporeal circuits. Flow from either circuit can be diverted over the sensor under test by means of a system of rapid cross-over solenoid valves exposing the sensor to an abrupt change in oxygen partial pressure, P O2. The system is also capable of testing the oxygen sensor responses to changes in temperature, carbon dioxide partial pressure P CO2 and pH in situ. Results are presented for a miniature fibre optic oxygen sensor constructed in-house with a response time ≈ 50 ms and a commercial fibre optic sensor (Ocean Optics Foxy), when tested in flowing saline and stored blood. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Modeling of the oxygen reduction reaction for dense LSM thin films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, Tao; Liu, Jian; Yu, Yang

    In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

  2. Modeling of the oxygen reduction reaction for dense LSM thin films

    DOE PAGES

    Yang, Tao; Liu, Jian; Yu, Yang; ...

    2017-10-17

    In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

  3. Education Policy and Intergenerational Transfers in Equilibrium. NBER Working Paper No. 18782

    ERIC Educational Resources Information Center

    Abbott, Brant; Gallipoli, Giovanni; Meghir, Costas; Violante, Giovanni L.

    2013-01-01

    This paper compares partial and general equilibrium effects of alternative financial aid policies intended to promote college participation. We build an overlapping generations life-cycle, heterogeneous-agent, incomplete-markets model with education, labor supply, and consumption/saving decisions. Altruistic parents make inter vivos transfers to…

  4. Solid-phase microextraction method for the determination of hexanal in hazelnuts as an indicator of the interaction of active packaging materials with food aroma compounds.

    PubMed

    Pastorelli, S; Valzacchi, S; Rodriguez, A; Simoneau, C

    2006-11-01

    Fatty foods are susceptible to lipid oxidation resulting in deterioration of product quality due to the generation of off-flavours. Hexanal is a good indicator of rancidity. Therefore, a method based on solid-phase microextraction (SPME) coupled to gas chromatograph with flame ionization detection was developed to determine hexanal formation in hazelnuts during storage. Optimum conditions were as follows: carboxen-polydimethylsiloxane 75 microm fibre, extraction time 10 min, equilibrium time 10 min and equilibrium temperature 60 degrees C. The effect of oxygen scavengers on the oxidation process was also evaluated by measuring hexanal formation in hazelnuts stored with/without oxygen absorber sachets. Oxygen scavengers were shown to reduce oxidation; however, analysis of the sachet revealed that other volatile compounds from the headspace were also absorbed.

  5. High enthalpy arc-heated plasma flow diagnostics by tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lin, Xin; Chen, Lianzhong; Zeng, Hui; Ou, Dongbin; Dong, Yonghui

    2017-05-01

    This paper reports the laser absorption measurements of atomic oxygen in the FD04 arc-heater at China Academy of Aerospace Aerodynamics (CAAA). An atomic oxygen absorption line at 777.19 nm is utilizied for detecting the population of electronically excited oxygen atom in an air plasma flow. A scanned-wavelength direct absorption mode is used in this study. The laser is scanned in wavelength across the absorption feature at a rate of 200 Hz. Under the assumption of thermal equilibrium, time-resolved temperature measurements are obtained on one line-of-sight in the arc-heater. The good agreement of the temperature inferred from the sonic throat method suggests the equilibrium assumption is valid. These results illustrate the feasibility of the diode laser sensors for flow parameters in high enthalpy arc-heated facilities.

  6. Thermochemical analyses of the oxidative vaporization of metals and oxides by oxygen molecules and atoms

    NASA Technical Reports Server (NTRS)

    Kohl, F. J.; Leisz, D. M.; Fryburg, G. C.; Stearns, C. A.

    1977-01-01

    Equilibrium thermochemical analyses are employed to describe the vaporization processes of metals and metal oxides upon exposure to molecular and atomic oxygen. Specific analytic results for the chromium-, platinum-, aluminum-, and silicon-oxygen systems are presented. Maximum rates of oxidative vaporization predicted from the thermochemical considerations are compared with experimental results for chromium and platinum. The oxidative vaporization rates of chromium and platinum are considerably enhanced by oxygen atoms.

  7. Non-Equilibrium Chemistry of O-Rich AGB Stars as Revealed by ALMA

    NASA Astrophysics Data System (ADS)

    Wong, Ka Tat

    2018-04-01

    Chemical models suggest that pulsation driven shocks propagating from the stellar surfaces of oxygen-rich evolved stars to the dust formation zone trigger non-equilibrium chemistry in the shocked gas near the star, including the formation of carbon-bearing molecules in the stellar winds dominated by oxygen-rich chemistry. Recent long-baseline ALMA observations are able to give us a detailed view of the molecular line emission and absorption at an angular resolution of a few stellar radii. I am going to present the latest results from the ALMA observations of IK Tau and o Cet in late 2017, with a particular focus on HCN.

  8. A hybrid QM/MM simulation study of intramolecular proton transfer in the pyridoxal 5'-phosphate in the active site of transaminase: influence of active site interaction on proton transfer.

    PubMed

    Dutta Banik, Sindrila; Chandra, Amalendu

    2014-09-25

    Pyridoxal 5'-phosphate (PLP) Schiff base, a versatile cofactor, exhibits a tautomeric equilibrium that involves an intramolecular proton transfer between the N-protonated zwitterionic ketoenamine tautomer and the O-protonated covalent enolimine tautomer. It has been postulated that for the catalytic activity, the PLP has to be in the zwitterionic ketoenamine tautomeric form. However, the exact position of the tautomeric equilibrium of Schiff base in the active site of PLP-dependent enzyme is not known yet. In the present work, we investigated the tautomeric equilibrium for the external aldimine state of PLP aspartate (PLP-Asp) Schiff base in the active site of aspartate aminotransferase (AspAT) using combined quantum mechanical and molecular mechanical simulations. The main focus of the present study is to analyze the factors that control the tautomeric equilibrium in the active sites of various PLP-dependent enzymes. The results show that the ketoenamine tautomer is more preferred than the enolimine tautomer both in the gas and aqueous phases as well as in the active site of AspAT. Current simulations show that the active site of AspAT is more suitable for the ketoenamine tautomer compared to the enolimine tautomer. Interestingly, the Tyr225 acts as a proton donor to the phenolic oxygen in the ketoenamine tautomer, while in the covalent enolimine tautomer, it acts as a proton acceptor to the phenolic oxygen. Finally, the metadynamics study confirms this result. The calculated free energy barrier is about 7.5 kcal/mol. A comparative analysis of the microenvironment created by the active site residues of three different PLP-dependent enzymes (aspartate aminotransferase, Dopa decarboxylase, and Ala-racemase) has been carried out to understand the controlling factor(s) of the tautomeric equilibrium. The analysis shows that the intermolecular hydrogen bonding between active site residues and the phenolic oxygen of PLP shifts the tautomeric equilibrium toward the N-protonated ketoenamine tautomeric form.

  9. Measurement of alveolar oxygen partial pressure in the rat lung using Carr-Purcell-Meiboom-Gill spin-spin relaxation times of hyperpolarized 3He and 129Xe at 74 mT.

    PubMed

    Kraayvanger, Ryan J; Bidinosti, Christopher P; Dominguez-Viqueira, William; Parra-Robles, Juan; Fox, Matthew; Lam, Wilfred W; Santyr, Giles E

    2010-11-01

    Regional measurement of alveolar oxygen partial pressure can be obtained from the relaxation rates of hyperpolarized noble gases, (3) He and (129) Xe, in the lungs. Recently, it has been demonstrated that measurements of alveolar oxygen partial pressure can be obtained using the spin-spin relaxation rate (R(2) ) of (3) He at low magnetic field strengths (<0.1 T) in vivo. R(2) measurements can be achieved efficiently using the Carr-Purcell-Meiboom-Gill pulse sequence. In this work, alveolar oxygen partial pressure measurements based on Carr-Purcell-Meiboom-Gill R(2) values of hyperpolarized (3) He and (129) Xe in vitro and in vivo in the rat lung at low magnetic field strength (74 mT) are presented. In vitro spin-spin relaxivity constants for (3) He and (129) Xe were determined to be (5.2 ± 0.6) × 10(-6) Pa(-1) sec(-1) and (7.3 ± 0.4) × 10(-6) Pa(-1) s(-1) compared with spin-lattice relaxivity constants of (4.0 ± 0.4) × 10(-6) Pa(-1) s(-1) and (4.3 ± 1.3) × 10(-6) Pa(-1) s(-1), respectively. In vivo experimental measurements of alveolar oxygen partial pressure using (3) He in whole rat lung show good agreement (r(2) = 0.973) with predictions based on lung volumes and ventilation parameters. For (129) Xe, multicomponent relaxation was observed with one component exhibiting an increase in R(2) with decreasing alveolar oxygen partial pressure. Copyright © 2010 Wiley-Liss, Inc.

  10. Oxygen Saturation Surrounding Deep Water Formation Events in the Labrador Sea From Argo-O2 Data

    NASA Astrophysics Data System (ADS)

    Wolf, Mitchell K.; Hamme, Roberta C.; Gilbert, Denis; Yashayaev, Igor; Thierry, Virginie

    2018-04-01

    Deep water formation supplies oxygen-rich water to the deep sea, spreading throughout the ocean by means of the global thermohaline circulation. Models suggest that dissolved gases in newly formed deep water do not come to equilibrium with the atmosphere. However, direct measurements during wintertime convection are scarce, and the controls over the extent of these disequilibria are poorly quantified. Here we show that, when convection reached deeper than 800 m, oxygen in the Labrador Sea was consistently undersaturated at -6.1% to -7.6% at the end of convection. Deeper convection resulted in greater undersaturation, while convection ending later in the year resulted in values closer to equilibrium, from which we produce a predictive relationship. We use dissolved oxygen data from six profiling Argo floats in the Labrador Sea between 2003 and 2016, allowing direct observations of wintertime convection. Three of the six optode oxygen sensors displayed substantial average in situ drift of -3.03 μmol O2 kg-1 yr-1 (-0.94% O2 yr-1), which we corrected to stable deepwater oxygen values from repeat ship surveys. Observations of low oxygen intrusions during restratification and a simple mixing calculation demonstrate that lateral processes act to lower the oxygen inventory of the central Labrador Sea. This suggests that the Labrador Sea is a net sink for atmospheric oxygen, but uncertainties in parameterizing gas exchange limit our ability to quantify the net uptake. Our results constrain the oxygen concentration of newly formed Labrador Sea Water and allow more precise estimates of oxygen utilization and nutrient regeneration in this water mass.

  11. Non-equilibrium kinetics of plasma-assisted combustion: the role of electronically excited atoms and molecules

    NASA Astrophysics Data System (ADS)

    Popov, Nikolay

    2016-09-01

    A review of experimental and theoretical investigations of the effect of electronically excited atoms and molecules on the induction delay time and on the shift of the ignition temperature threshold of combustible mixtures is presented. At relatively low initial gas temperature, the effect of excited O(1D) atoms on the oxidation and reforming of combustible mixtures is quite significant due to the high rates of reactions of O(1D) atoms with hydrogen and hydrocarbon molecules. The singlet oxygen molecules, O2(a1Δg) , participate both in chain initiation and chain branching reactions, but the effect of O2(a1Δg) in the ignition processes is generally less important compared to the oxygen atoms. To reduce the ignition delay time and decrease the temperature threshold of fuel-air mixtures, the use of gas discharges with relatively high E/N values is recommended. In this case the reactions of electronically excited N2(A3Σu+ , B3πg , C3πu , a'1Σu-) molecules, and atomic particles in ground and electronically excited states are extremely important. The energy stored in electronic excitation of atoms and molecules is spent on the additional dissociation of oxygen and fuel molecules, on the fast gas heating, and finally to the triggering of chain branching reactions. This work was partially supported by AOARD AFOSR, FA2386-13-1-4064 grant and Linked International Laboratory LIA KaPPA (France-Russia).

  12. Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.; Serra, Jessica

    2009-01-01

    Carbon-fiber reinforced SiC (C/SiC) composites are proposed for leading edge applications of hypersonic vehicles due to the superior strength of carbon fibers at high temperatures (greater than 1500 C). However, the vulnerability of the carbon fibers in C/SiC to oxidation over a wide range of temperatures remains a problem. Previous oxidation studies of C/SiC have mainly been conducted in air or oxygen, so that the oxidation behavior of C/SiC at reduced oxygen partial pressures of the hypersonic flight regime are less well understood. In this study, both carbon fibers and C/SiC composites were oxidized over a wide range of temperatures and oxygen partial pressures to facilitate the understanding and modeling of C/SiC oxidation kinetics for hypersonic flight conditions.

  13. Effects of various oxygen partial pressures on Ti-doped ZnO thin film transistors fabricated on flexible plastic substrate

    NASA Astrophysics Data System (ADS)

    Cui, Guodong; Han, Dedong; Yu, Wen; Shi, Pan; Zhang, Yi; Huang, Lingling; Cong, Yingying; Zhou, Xiaoliang; Zhang, Xiaomi; Zhang, Shengdong; Zhang, Xing; Wang, Yi

    2016-04-01

    By applying a novel active layer of titanium zinc oxide (TiZO), we have successfully fabricated fully transparent thin-film transistors (TFTs) with a bottom gate structure fabricated on a flexible plastic substrate at low temperatures. The effects of various oxygen partial pressures during channel deposition were studied to improve the device performance. We found that the oxygen partial pressure during channel deposition has a significant impact on the performance of TiZO TFTs, and that the TFT developed under 10% oxygen partial pressure exhibits superior performance with a low threshold voltage (V th) of 2.37 V, a high saturation mobility (μsat) of 125.4 cm2 V-1 s-1, a steep subthreshold swing (SS) of 195 mV/decade and a high I on/I off ratio of 3.05 × 108. These results suggest that TiZO thin films are promising for high-performance fully transparent flexible TFTs and displays.

  14. The Effect of Oxygen Partial Pressure on Microstructure and Properties of Fe40Al Alloy Sintered under Vacuum

    PubMed Central

    Siemiaszko, Dariusz; Kowalska, Beata; Jóźwik, Paweł; Kwiatkowska, Monika

    2015-01-01

    This paper presents the results of studies on the influence of oxygen partial pressure (vacuum level in the chamber) on the properties of FeAl intermetallics. One of the problems in the application of classical methods of prepared Fe-Al intermetallic is the occurrence of oxides. Applying a vacuum during sintering should reduce this effect. In order to analyze the effect of oxygen partial pressure on sample properties, five samples were processed (by a pressure-assisted induction sintering—PAIS method) under the following pressures: 3, 8, 30, 80, and 300 mbar (corresponding to oxygen partial pressures of 0.63, 1.68, 6.3, 16.8, and 63 mbar, respectively). The chemical and phase composition, hardness, density, and microstructure observations indicate that applying a vacuum significantly impacts intermetallic samples. The compact sintered at pressure 3 mbar is characterized by the most homogeneous microstructure, the highest density, high hardness, and nearly homogeneous chemical composition. PMID:28788015

  15. Corneal Equilibrium Flux as a Function of Corneal Surface Oxygen Tension.

    PubMed

    Compañ, Vicente; Aguilella-Arzo, Marcel; Weissman, Barry A

    2017-06-01

    Oxygen is essential for aerobic mammalian cell physiology. Oxygen tension (PO2) should reach a minimum at some position within the corneal stroma, and oxygen flux should be zero, by definition, at this point as well. We found the locations and magnitudes of this "corneal equilibrium flux" (xmin) and explored its physiological implications. We used an application of the Monod kinetic model to calculate xmin for normal human cornea as anterior surface PO2 changes from 155 to 20 mmHg. We find that xmin deepens, broadens, and advances from 1.25 μm above the endothelial-aqueous humor surface toward the epithelium (reaching a position 320 μm above the endothelial-aqueous humor surface) as anterior corneal surface PO2 decreases from 155 to 20 mmHg. Our model supports an anterior corneal oxygen flux of 9 μL O2 · cm · h and an epithelial oxygen consumption of approximately 4 μL O2 · cm · h. Only at the highest anterior corneal PO2 does our model predict that oxygen diffuses all the way through the cornea to perhaps reach the anterior chamber. Of most interest, corneal oxygen consumption should be supported down to a corneal surface PO2 of 60 to 80 mmHg but declines below this range. We conclude that the critical oxygen tension for hypoxia induced corneal swelling is more likely this range rather than a fixed value.

  16. Phase development in the Bi 2Sr 2CaCu 2O y system . Effects of oxygen pressure

    NASA Astrophysics Data System (ADS)

    List, F. A.; Hsu, H.; Cavin, O. B.; Porter, W. D.; Hubbard, C. R.; Kroeger, D. M.

    1992-11-01

    Studies have been undertaken using thermal analysis, in conjunction with high-temperature and room temperature X-ray diffraction, fraction, to elucidate phase relationships during thermal processing of thick films of initially phase pure Bi 2Sr 2CaCu 2O y (2212) on silver substrates in various oxygen-containing atmospheres (0.001 to 100% O 2). Exothermic events on cooling at 10°C/min from a partially liquid state vary with oxygen partial pressure and can be grouped into three sets (I-III). Set I is prominent for 0.001% and 0.1% O 2 in the range of 740-775°C and is believed to be associated with the crystallization of a Cu-free ∼ Bi 5Sr 3Ca 1 oxide phase. Set II results from the crystallization of 2212; it is observed for p(O 2)≥1.0% in the temperature range 800-870°C. Set III appears for 21% and 100% O 2 in the temperature range 880-910°C, and its origin is not clear from the results of this study. Subsequent room temperature X-ray diffraction from these samples suggests that in general high oxygen partial pressures (100% O 2) tend to favor the formation of Bi 2Sr 2CuO 6 (2201), whereas low oxygen partial pressures (0.001-0.1% O 2) lead to the formation of a Cu-free, Bi-Sr-Ca oxide phase. The 2212 phase forms at this cooling rate predominantly for intermediate oxygen partial pressures (7.6-21% O 2). High-temperature X-ray diffraction during cooling (2°C/h) from the partially liquid state shows a pronounced dependence of the order of evolution of crystalline 2212 and 2201 phases on p(O 2). For an oxygen partial pressure of 1.0% the formation of 2212 precedes that of 2201, whereas for 0.01% O 2 2201 crystallizes at a higher temperature than 2212. The implications of these results pertaining to thermal processing of thick 2212 films are discussed.

  17. Effects of sample size, number of markers, and allelic richness on the detection of spatial genetic pattern

    USGS Publications Warehouse

    Landguth, Erin L.; Gedy, Bradley C.; Oyler-McCance, Sara J.; Garey, Andrew L.; Emel, Sarah L.; Mumma, Matthew; Wagner, Helene H.; Fortin, Marie-Josée; Cushman, Samuel A.

    2012-01-01

    The influence of study design on the ability to detect the effects of landscape pattern on gene flow is one of the most pressing methodological gaps in landscape genetic research. To investigate the effect of study design on landscape genetics inference, we used a spatially-explicit, individual-based program to simulate gene flow in a spatially continuous population inhabiting a landscape with gradual spatial changes in resistance to movement. We simulated a wide range of combinations of number of loci, number of alleles per locus and number of individuals sampled from the population. We assessed how these three aspects of study design influenced the statistical power to successfully identify the generating process among competing hypotheses of isolation-by-distance, isolation-by-barrier, and isolation-by-landscape resistance using a causal modelling approach with partial Mantel tests. We modelled the statistical power to identify the generating process as a response surface for equilibrium and non-equilibrium conditions after introduction of isolation-by-landscape resistance. All three variables (loci, alleles and sampled individuals) affect the power of causal modelling, but to different degrees. Stronger partial Mantel r correlations between landscape distances and genetic distances were found when more loci were used and when loci were more variable, which makes comparisons of effect size between studies difficult. Number of individuals did not affect the accuracy through mean equilibrium partial Mantel r, but larger samples decreased the uncertainty (increasing the precision) of equilibrium partial Mantel r estimates. We conclude that amplifying more (and more variable) loci is likely to increase the power of landscape genetic inferences more than increasing number of individuals.

  18. Effects of sample size, number of markers, and allelic richness on the detection of spatial genetic pattern

    USGS Publications Warehouse

    Landguth, E.L.; Fedy, B.C.; Oyler-McCance, S.J.; Garey, A.L.; Emel, S.L.; Mumma, M.; Wagner, H.H.; Fortin, M.-J.; Cushman, S.A.

    2012-01-01

    The influence of study design on the ability to detect the effects of landscape pattern on gene flow is one of the most pressing methodological gaps in landscape genetic research. To investigate the effect of study design on landscape genetics inference, we used a spatially-explicit, individual-based program to simulate gene flow in a spatially continuous population inhabiting a landscape with gradual spatial changes in resistance to movement. We simulated a wide range of combinations of number of loci, number of alleles per locus and number of individuals sampled from the population. We assessed how these three aspects of study design influenced the statistical power to successfully identify the generating process among competing hypotheses of isolation-by-distance, isolation-by-barrier, and isolation-by-landscape resistance using a causal modelling approach with partial Mantel tests. We modelled the statistical power to identify the generating process as a response surface for equilibrium and non-equilibrium conditions after introduction of isolation-by-landscape resistance. All three variables (loci, alleles and sampled individuals) affect the power of causal modelling, but to different degrees. Stronger partial Mantel r correlations between landscape distances and genetic distances were found when more loci were used and when loci were more variable, which makes comparisons of effect size between studies difficult. Number of individuals did not affect the accuracy through mean equilibrium partial Mantel r, but larger samples decreased the uncertainty (increasing the precision) of equilibrium partial Mantel r estimates. We conclude that amplifying more (and more variable) loci is likely to increase the power of landscape genetic inferences more than increasing number of individuals. ?? 2011 Blackwell Publishing Ltd.

  19. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    NASA Astrophysics Data System (ADS)

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

    2017-10-01

    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading to a relatively constant foraminifer calcite δ18O-temperature relationship (-0.21 ± 0.01‰/°C). The lower average coral δ18O data relative to foraminifers and other calcifiers is best explained by the precipitation of internal DIC derived from hydrated CO2 in a high-pH calcifying fluid and minimal subsequent DIC-H2O isotopic equilibration. This leads to a reduced and variable coral aragonite δ18O-temperature relationship (-0.11 to -0.22‰/°C). Together, the model presented here reconciles observations of oxygen isotope fractionation over a range of CaCO3-DIC-H2O systems.

  20. Control of magnetization reversal in oriented strontium ferrite thin films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Roy, Debangsu, E-mail: debangsu@physics.iisc.ernet.in; Anil Kumar, P. S.

    2014-02-21

    Oriented Strontium Ferrite films with the c axis orientation were deposited with varying oxygen partial pressure on Al{sub 2}O{sub 3}(0001) substrate using Pulsed Laser Deposition technique. The angle dependent magnetic hysteresis, remanent coercivity, and temperature dependent coercivity had been employed to understand the magnetization reversal of these films. It was found that the Strontium Ferrite thin film grown at lower (higher) oxygen partial pressure shows Stoner-Wohlfarth type (Kondorsky like) reversal. The relative importance of pinning and nucleation processes during magnetization reversal is used to explain the type of the magnetization reversal with different oxygen partial pressure during growth.

  1. Analytic Approximation of Carbon Condensation Issues in Type ii Supernovae

    NASA Astrophysics Data System (ADS)

    Clayton, Donald D.

    2013-01-01

    I present analytic approximations for some issues related to condensation of graphite, TiC, and silicon carbide in oxygen-rich cores of supernovae of Type II. Increased understanding, which mathematical analysis can support, renders researchers more receptive to condensation in O-rich supernova gases. Taking SN 1987A as typical, my first analysis shows why the abundance of CO molecules reaches an early maximum in which free carbon remains more abundant than CO. This analysis clarifies why O-rich gas cannot oxidize C if 56Co radioactivity is as strong as in SN 1987A. My next analysis shows that the CO abundance could be regarded as being in chemical equilibrium if the CO molecule is given an effective binding energy rather than its laboratory dissociation energy. The effective binding energy makes the thermal dissociation rate of CO equal to its radioactive dissociation rate. This preserves possible relevance for the concept of chemical equilibrium. My next analysis shows that the observed abundances of CO and SiO molecules in SN 1987A rule out frequent suggestions that equilibrium condensation of SUNOCONs has occurred following atomic mixing of the He-burning shell with more central zones in such a way as to reproduce roughly the observed spectrum of isotopes in SUNOCONs while preserving C/O > 1. He atoms admixed along with the excess carbon would destroy CO and SiO molecules, leaving their observed abundances unexplained. The final analysis argues that a chemical quasiequilibrium among grains (but not gas) may exist approximately during condensation, so that its computational use is partially justified as a guide to which mineral phases would be stable against reactions with gas. I illustrate this point with quasiequilibrium calculations by Ebel & Grossman that have shown that graphite is stable even when O/C >1 if prominent molecules are justifiably excluded from the calculation of chemical equilibrium.

  2. SYNTHESIS OF PARTIAL-OXYGENATED HYDROCARBONS USING PHOTOCATALYSIS IN A LAMINAR FALLING FILM SLURRY REACTOR

    EPA Science Inventory

    The search for "Green" alternative processes for the oxidation of hydrocarbons selectively to partial oxygenates has been the subject of intense chemical research for many years. The USEPA is currently investigating an alternative synthesis pathway for the production of alcoho...

  3. SYNTHESIS OF PARTIALLY-OXYGENATED HYDROCARBONS USING PHOTOCATALYSIS IN A LAMINAR FALLING FILM SLURRY REACTOR

    EPA Science Inventory

    The search for "Green" alternative processes for the oxidation of hydrocarbons selectively to partial oxygenates has been the subject of intense chemical research for many years. The USEPA is currently investigating an alternative synthesis pathway for the production of alcoho...

  4. Growth of the microalgae Neochloris oleoabundans at high partial oxygen pressures and sub-saturating light intensity.

    PubMed

    Sousa, Cláudia; de Winter, Lenneke; Janssen, Marcel; Vermuë, Marian H; Wijffels, René H

    2012-01-01

    The effect of partial oxygen pressure on growth of Neochloris oleoabundans was studied at sub-saturating light intensity in a fully-controlled stirred tank photobioreactor. At the three partial oxygen pressures tested (P(O)₂= 0.24; 0.63; 0.84 bar), the specific growth rate was 1.38; 1.36 and 1.06 day(-1), respectively. An increase of the P(CO)₂from 0.007 to 0.02 bar at P(O₂) of 0.84 bar resulted in an increase in the growth rate from 1.06 to 1.36 day(-1). These results confirm that the reduction of algal growth at high oxygen concentrations at sub-saturating light conditions is mainly caused by competitive inhibition of Rubisco. This negative effect on growth can be overcome by restoring the O(2)/CO(2) ratio by an increase in the partial carbon dioxide pressure. In comparison to general practice (P(O(2)) = 0.42 bar), working at partial O(2) pressure of 0.84 bar could reduce the energy requirement for degassing by a factor of 3-4. Copyright © 2011 Elsevier Ltd. All rights reserved.

  5. A Model for Siderophile Element Distribution in Planetary Differentiation

    NASA Technical Reports Server (NTRS)

    Humayun, M.; Rushmer, T.; Rankenburg, K.; Brandon, A. D.

    2005-01-01

    Planetary differentiation begins with partial melting of small planetesimals. At low degrees of partial melting, a sulfur-rich liquid segregates by physical mechanisms including deformation-assisted porous flow. Experimental studies of the physical mechanisms by which Fe-S melts segregate from the silicate matrix of a molten H chondrite are part of a companion paper. Geochemical studies of these experimental products revealed that metallic liquids were in equilibrium with residual metal in the H chondrite matrix. This contribution explores the geochemical signatures produced by early stages of core formation. Particularly, low-degree partial melt segregation of Fe-S liquids leaves residual metal in the silicate matrix. Some achondrites appear to be residues of partial melting, e.g., ureilites, which are known to contain metal. The metal in these achondrites may show a distinct elemental signature. To quantify the effect of sulfur on siderophile element contents of residual metal we have developed a model based on recent parametrizations of equilibrium solid metal-liquid metal partitioning experiments.

  6. The impact of dissolved oxygen on sulfate radical-induced oxidation of organic micro-pollutants: A theoretical study.

    PubMed

    Zhang, Rui; Wang, Xiaoxiang; Zhou, Lei; Liu, Zhu; Crump, Doug

    2018-05-15

    Sulfate radical (SO 4 .- )-induced oxidation is an important technology in advanced oxidation processes (AOPs) for the removal of pollutants. To date, few studies have assessed the effects of dissolved oxygen (DO) on the SO 4 .- -induced oxidation of organic micro-pollutants. In the present work, a quantum chemical calculation was used to investigate the influence of the external oxygen molecule on the Gibbs free energy (G pollutant ) and HOMO-LUMO gap (ΔE) of 15 organic micro-pollutants representing four chemical categories. Several thermodynamic and statistical models were combined with the data from the quantum chemical calculation to illustrate the impact of DO on the oxidation of organic micro-pollutants by SO 4 .- . Results indicated that the external oxygen molecule increased G pollutant of all studied chemicals, which implies DO has the potential to decrease the energy barrier of the SO 4 .- -induced oxidation and shift the chemical equilibrium of the reaction towards the side of products. From the perspective of kinetics, DO can accelerate the oxidation by decreasing ΔE of organic micro-pollutants. In addition, changes of G pollutant and ΔE of the SO 4 .- -induced oxidation were both significantly different between open-chain and aromatic chemicals, and these differences were partially attributed to the difference of polarizability of these two types of chemicals. Furthermore, we revealed that all changes of G pollutant and ΔE induced by DO were dependent on the DO content. Our study emphasizes the significance of DO on the oxidation of organic micro-pollutants by SO 4 .- , and also provides a theoretical method to study the effect of components in wastewater on removal of organic pollutants in AOPs. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Phase relations in the system Cu-Gd-O and Gibbs energy of formation of CuGd[sub 2]O[sub 4

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jacob, K.T.; Mathews, T.; Hajra, J.P.

    1993-07-01

    The phase relations in the system Cu-Gd-O have been determined at 1,273 K by X-ray diffraction, optical microscopy, and electron microprobe analysis of samples equilibrated in quartz ampules and in pure oxygen. Only one ternary compound, CuGd[sub 2]O[sub 4], was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt, Cu[sub 2]O + CuGd[sub 2]O[sub 4] + Gd[sub 2]O[sub 3]//(Y[sub 2]O[sub 3])ZrO[sub 2]//CuO + Cu[sub 2]O, Pt in the temperature range of 900 to 1,350 K. For the formation of CuGd[sub 2]O[sub 4] from its binary component oxides, CuOmore » (s) + Gd[sub 2]O[sub 3] (s) [r arrow] CuGd[sub 2]O[sub 4] (s) [Delta]G[degree] = 8230 - 11.2T([plus minus]50)J/mol. Since the formation is endothermic, CuGd[sub 2]O[sub 4] becomes thermodynamically unstable with respect to CuO and Gd[sub 2]O[sub 3] below 735 K. When the oxygen partial pressure over CuGd[sub 2]O[sub 4] is lowered, it decomposes according to the reaction 4CuGd[sub 2]O[sub 4] (s) [r arrow] 4Gd[sub 2]O[sub 3] (s) + 2Cu[sub 2]O (s) + O[sub 2] (g) for which the equilibrium oxygen potential is given by [Delta][mu][sub o][sub 2] = [minus]227,970 + 143.2T([plus minus]500)J/mol. An oxygen potential diagram for the system Cu-Gd-O at 1,273 is presented.« less

  8. Oxygen isotope fractionation in the siderite-water system between 8.5 and 62 °C

    NASA Astrophysics Data System (ADS)

    van Dijk, Joep; Fernandez, Alvaro; Müller, Inigo A.; Lever, Mark; Bernasconi, Stefano M.

    2018-01-01

    The oxygen isotope composition of siderites can be used to deduce the temperature and/or oxygen isotope composition of the fluids from which they precipitated. Previous siderite-water oxygen isotope fractionation calibrations are not well constrained at temperatures below 33 °C where most of the siderite forms at the Earth's surface. Moreover, the few experimental low temperature calibration points available are possibly inaccurate as the corresponding siderites may not have formed in equilibrium with the solution. In this study, we synthesized siderite in the laboratory from 8.5 to 62 °C, using both active-degassing experiments and microbial cultures. We used the enzyme carbonic anhydrase, which significantly reduces the equilibration time of oxygen isotopes among all dissolved inorganic carbon (DIC) species and water to minimize siderite formation out of equilibrium. Our calibration is based on many more data points than previous calibrations and significantly reduces the uncertainty in siderite-water oxygen isotope fractionation in natural siderites formed at low temperatures. The best fit equation is 1000 * ln α = 19.67 ± 0.42(103/T) -36.27 ± 1.34 where α (1000+δ18Osiderite/1000+δ18Owater) is the fractionation factor and T is the temperature in Kelvin.

  9. Linkage Disequilibrium in a Finite Population That Is Partially Selfing

    PubMed Central

    Golding, G. B.; Strobeck, C.

    1980-01-01

    The linkage disequilibrium expected in a finite, partially selfing population is analyzed, assuming the infinite allele model. Formulas for the expected sum of squares of the linkage disequilibria and the squared standard linkage disequilibrium are derived from the equilibrium values of sixteen inbreeding coefficients required to describe the behavior of the system. These formulas are identical to those obtained with random mating if the effective population size Ne = (1-½S)N and the effective recombination value re = (1-S)r/(1-½S), where S is the proportion of selfing, are substituted for the population size and the recombination value. Therefore, the effect of partial selfing at equilibrium is to reduce the population size by a factor 1-½S and the recombination value by a factor (1-S)/(1-½S). PMID:17249017

  10. Earth's Core-Mantle equilibrium and a heat sink at the Core Mantle Boundary

    NASA Astrophysics Data System (ADS)

    Alfe, D.; Pozzo, M.; Davies, C. J.; Gubbins, D.

    2016-12-01

    Chemical equilibrium between the two sides of the core mantle boundary (CMB) has longbeen debated. If the core is well mixed and in equilibrium with the inner coredisequilibrium at the CMB seems inevitable. Indeed, a number of experiments pointto a possible non-equilibrium configuration in which the core liquid iron mixture wouldbe undersaturated in oxygen. As discussed by several authors, this chemical imbalancecould result in the formation of an oxygen rich layer at the top of the core, and astratification, which could explain a seismic anomaly claimed by some authors.Here we have revisited the core-mantle equilibrium by calculating the chemical potentialof FeO in both liquid iron mixtures and solid Periclase at CMB conditions, usingfirst principles methods based on quantum mechanics and standard statistical mechanics.We find that FeO is favoured in the liquid mixture, with an equilibrium O concentrationthat is much larger than that of the bulk core. In addition, we find that the heat ofreaction of the FeO dissolution form the mantle to the core is positive, making thereaction endothermic, and therefore providing a heat sink at the top of the core.The power lost in the heat sink depends on the rate of FeO dissolution, and we discussa scenario which could result in a heat sink of several TW. This sink would absorbsome of the heat conducted along the core adiabat and reduce the CMB heat flux.

  11. Sickling of red blood cells through rapid oxygen exchange in microfluidic drops.

    PubMed

    Abbyad, Paul; Tharaux, Pierre-Louis; Martin, Jean-Louis; Baroud, Charles N; Alexandrou, Antigoni

    2010-10-07

    We have developed a microfluidic approach to study the sickling of red blood cells associated with sickle cell anemia by rapidly varying the oxygen partial pressure within flowing microdroplets. By using the perfluorinated carrier oil as a sink or source of oxygen, the oxygen level within the water droplets quickly equilibrates through exchange with the surrounding oil. This provides control over the oxygen partial pressure within an aqueous drop ranging from 1 kPa to ambient partial pressure, i.e. 21 kPa. The dynamics of the oxygen exchange is characterized through fluorescence lifetime measurements of a ruthenium compound dissolved in the aqueous phase. The gas exchange is shown to occur primarily during and directly after droplet formation, in 0.1 to 0.5 s depending on the droplet diameter and speed. The controlled deoxygenation is used to trigger the polymerization of hemoglobin within sickle red blood cells, encapsulated in drops. This process is observed using polarization microscopy, which yields a robust criterion to detect polymerization based on transmitted light intensity through crossed polarizers.

  12. Simple method to enhance positive bias stress stability of In-Ga-Zn-O thin-film transistors using a vertically graded oxygen-vacancy active layer.

    PubMed

    Park, Ji Hoon; Kim, Yeong-Gyu; Yoon, Seokhyun; Hong, Seonghwan; Kim, Hyun Jae

    2014-12-10

    We proposed a simple method to deposit a vertically graded oxygen-vacancy active layer (VGA) to enhance the positive bias stress (PBS) stability of amorphous indium gallium zinc oxide (a-IGZO) thin-film transistors (TFTs). We deposited a-IGZO films by sputtering (target composition; In2O3:Ga2O3:ZnO = 1:1:1 mol %), and the oxygen partial pressure was varied during deposition so that the front channel of the TFTs was fabricated with low oxygen partial pressure and the back channel with high oxygen partial pressure. Using this method, we were able to control the oxygen vacancy concentration of the active layer so that it varied with depth. As a result, the turn-on voltage shift following a 10 000 s PBS of optimized VGA TFT was drastically improved from 12.0 to 5.6 V compared with a conventional a-IGZO TFT, without a significant decrease in the field effect mobility. These results came from the self-passivation effect and decrease in oxygen-vacancy-related trap sites of the VGA TFTs.

  13. Some aspects of the thermodynamic behaviour of the lead-doped Bi-2223 system

    NASA Astrophysics Data System (ADS)

    Tetenbaum, M.; Maroni, V. A.

    1996-02-01

    A thermodynamic assessment of lead-doped Bi-2223 with emphasis on compositions and oxygen partial pressures within the homogeneity region prior to solid-state decomposition is presented. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Long-term metastability was indicated during cycling over a temperature range of ∼ 700-815°C of a lead-doped Bi-2223 sample having an oxygen-deficient stoichiometry of 9.64 prior to solid-state decomposition corresponding to the diphasic CuOCu 2O system. A trend of increasing negative values of the partial molar enthalpy Δ overlineH( O 2) and entropy Δ overlineS( O2 with increasing oxygen deficiency of the condensed phase indicated an increase in ordering of the cuprate structure prior to solid-state decomposition.

  14. Oxygen Exposure Resulting in Arterial Oxygen Tensions Above the Protocol Goal Was Associated With Worse Clinical Outcomes in Acute Respiratory Distress Syndrome.

    PubMed

    Aggarwal, Neil R; Brower, Roy G; Hager, David N; Thompson, B Taylor; Netzer, Giora; Shanholtz, Carl; Lagakos, Adrian; Checkley, William

    2018-04-01

    High fractions of inspired oxygen may augment lung damage to exacerbate lung injury in patients with acute respiratory distress syndrome. Participants enrolled in Acute Respiratory Distress Syndrome Network trials had a goal partial pressure of oxygen in arterial blood range of 55-80 mm Hg, yet the effect of oxygen exposure above this arterial oxygen tension range on clinical outcomes is unknown. We sought to determine if oxygen exposure that resulted in a partial pressure of oxygen in arterial blood above goal (> 80 mm Hg) was associated with worse outcomes in patients with acute respiratory distress syndrome. Longitudinal analysis of data collected in these trials. Ten clinical trials conducted at Acute Respiratory Distress Syndrome Network hospitals between 1996 and 2013. Critically ill patients with acute respiratory distress syndrome. None. We defined above goal oxygen exposure as the difference between the fraction of inspired oxygen and 0.5 whenever the fraction of inspired oxygen was above 0.5 and when the partial pressure of oxygen in arterial blood was above 80 mm Hg. We then summed above goal oxygen exposures in the first five days to calculate a cumulative above goal oxygen exposure. We determined the effect of a cumulative 5-day above goal oxygen exposure on mortality prior to discharge home at 90 days. Among 2,994 participants (mean age, 51.3 yr; 54% male) with a study-entry partial pressure of oxygen in arterial blood/fraction of inspired oxygen that met acute respiratory distress syndrome criteria, average cumulative above goal oxygen exposure was 0.24 fraction of inspired oxygen-days (interquartile range, 0-0.38). Participants with above goal oxygen exposure were more likely to die (adjusted interquartile range odds ratio, 1.20; 95% CI, 1.11-1.31) and have lower ventilator-free days (adjusted interquartile range mean difference of -0.83; 95% CI, -1.18 to -0.48) and lower hospital-free days (adjusted interquartile range mean difference of -1.38; 95% CI, -2.09 to -0.68). We observed a dose-response relationship between the cumulative above goal oxygen exposure and worsened clinical outcomes for participants with mild, moderate, or severe acute respiratory distress syndrome, suggesting that the observed relationship is not primarily influenced by severity of illness. Oxygen exposure resulting in arterial oxygen tensions above the protocol goal occurred frequently and was associated with worse clinical outcomes at all levels of acute respiratory distress syndrome severity.

  15. Improved resolution of single channel dwell times reveals mechanisms of binding, priming, and gating in muscle AChR

    PubMed Central

    Mukhtasimova, Nuriya; daCosta, Corrie J.B.

    2016-01-01

    The acetylcholine receptor (AChR) from vertebrate skeletal muscle initiates voluntary movement, and its kinetics of activation are crucial for maintaining the safety margin for neuromuscular transmission. Furthermore, the kinetic mechanism of the muscle AChR serves as an archetype for understanding activation mechanisms of related receptors from the Cys-loop superfamily. Here we record currents through single muscle AChR channels with improved temporal resolution approaching half an order of magnitude over our previous best. A range of concentrations of full and partial agonists are used to elicit currents from human wild-type and gain-of-function mutant AChRs. For each agonist–receptor combination, rate constants are estimated from maximum likelihood analysis using a kinetic scheme comprised of agonist binding, priming, and channel gating steps. The kinetic scheme and rate constants are tested by stochastic simulation, followed by incorporation of the experimental step response, sampling rate, background noise, and filter bandwidth. Analyses of the simulated data confirm all rate constants except those for channel gating, which are overestimated because of the established effect of noise on the briefest dwell times. Estimates of the gating rate constants were obtained through iterative simulation followed by kinetic fitting. The results reveal that the agonist association rate constants are independent of agonist occupancy but depend on receptor state, whereas those for agonist dissociation depend on occupancy but not on state. The priming rate and equilibrium constants increase with successive agonist occupancy, and for a full agonist, the forward rate constant increases more than the equilibrium constant; for a partial agonist, the forward rate and equilibrium constants increase equally. The gating rate and equilibrium constants also increase with successive agonist occupancy, but unlike priming, the equilibrium constants increase more than the forward rate constants. As observed for a full and a partial agonist, the gain-of-function mutation affects the relationship between rate and equilibrium constants for priming but not for channel gating. Thus, resolving brief single channel currents distinguishes priming from gating steps and reveals how the corresponding rate and equilibrium constants depend on agonist occupancy. PMID:27353445

  16. Operation and testing of Mark 10 Mod 3 underwater breathing apparatus

    NASA Technical Reports Server (NTRS)

    Milwee, W. I., Jr.

    1972-01-01

    Performance tests on a closed circuit, mixed gas underwater breathing apparatus are reported. The equipment is designed to provide a minimum diving duration of four hours at 1500 ft below sea surface; it senses oxygen partial pressure in the breathing gas mix and controls oxygen content of the breathing gas within narrow limits about a preset value. The breathing circuit subsystem provides respirable gas to the diver and removes carbon dioxide and moisture from the expired gas. Test results indicate undesirable variations in oxygen partial pressure with oxygen addition and insufficient carbon dioxide absorption.

  17. Partial melting of the Allende (CV3) meteorite - Implications for origins of basaltic meteorites

    NASA Technical Reports Server (NTRS)

    Jurewicz, A. J. G.; Mittlefehldt, D. W.; Jones, J. H.

    1991-01-01

    Eucrites and angrites are distinct types of basaltic meteorites whose origins are poorly known. Experiments in which samples of the Allende (CV3) carbonaceous chondrite were partially melted indicate that partial melts can resemble either eucrites or angrites, depending only on the oxygen fugacity. Melts are eucritic if this variable is below that of the iron-wuestite buffer or angritic if above it. With changing pressure, the graphite-oxygen redox reaction can produce oxygen fugacities that are above or below those of the iron-wuestite buffer. Therefore, a single, homogeneous, carbonaceous planetoid greater than 110 kilometers in radius could produce melts of drastically different composition, depending on the depth of melting.

  18. IRREVERSIBLE PROCESSES IN A PLASMA

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Balescu, R.

    1959-04-01

    ABS>The characteristic divergences caused by long-range phenomena in gases can be eliminated in equilibrium situations by partial summations of terms individually divergent but whose sum converges. It is shown how the recently developed diagram technique enables treatment of non-equilibrium cases by a rigorous asymptotic method. The general ideas underlying the approach are briefly indicated. (T.R. H.)

  19. Equilibrium oxygen storage capacity of ultrathin CeO 2-δ depends non-monotonically on large biaxial strain

    DOE PAGES

    Gopal, Chirranjeevi Balaji; Garcia-Melchor, Max; Lee, Sang Chul; ...

    2017-05-18

    Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion–electron conducting oxides. However, its effect on oxygen storage capacity is not well established. Here, we fabricate ultrathin, coherently strained films of CeO 2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up to a fourfold enhancement in equilibrium oxygen storage capacity under both compression and tension. This non-monotonic variation with strain departs from the conventional wisdom based on a chemical expansion dominated behaviour. Through depth profiling, film thickness variations and a coupled photoemission–thermodynamic analysis of space-charge effects, we showmore » that the enhanced reducibility is not dominated by interfacial effects. On the basis of ab initio calculations of oxygen vacancy formation incorporating defect interactions and vibrational contributions, we suggest that the non-monotonicity arises from the tetragonal distortion under large biaxial strain. Finally, these results may guide the rational engineering of multilayer and core–shell oxide nanomaterials.« less

  20. Surface properties of thermionic electrodes

    NASA Technical Reports Server (NTRS)

    Stickney, R. E.

    1972-01-01

    A quasi-equilibrium model which provides semiquantitative predictions of the oxygen reaction with refractory metals was developed at high temperature and low pressure. Extensive experimental data was obtained on adsorption and work function properties for a wide variety of adsorbates (Cs, K, Na, I, Br, Cl, and O) on several refractory metals (W, Ta, Mo, and Re). Conclusions and recommendations for research on alkali metal adsorption, oxygen adsorption, and adsorption of cesium - oxygen mixtures are included.

  1. Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils.

    PubMed

    Tian, Liyan; Guo, Qingjun; Zhu, Yongguan; He, Huijun; Lang, Yunchao; Hu, Jian; Zhang, Han; Wei, Rongfei; Han, Xiaokun; Peters, Marc; Yang, Junxing

    2016-12-01

    Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ 18 O P ) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L -1 NaHCO 3 (pH = 8.5), 0.1 mol L -1 NaOH and 1 mol L -1 HCl) of agricultural soils from the Beijing area. The δ 18 O P results of the water extracts and NaHCO 3 extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ 18 O P value of the water extracts and NaHCO 3 extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ 18 O P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ 18 O P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ 18 O p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.

  2. Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ni Mingjiang, E-mail: xiaohanxi_2@163.com; Xiao Hanxi; Chemistry and Chemical Engineering School, Hunan University of Science and Technology, Xiangtan

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer The combustion efficiency of waste printed circuit boards (PCBs) depends on temperature, excess air factor, and high temperature zone residence time. Temperature has the most significant impact. Under the proposed condition, combustion of waste PCBs alone is quite complete within the furnace. Black-Right-Pointing-Pointer High temperature prompts a more complete bromine release and conversion. When temperature is high enough, 99.9% organobrominated compounds, the potential precursors for brominated dixoins formation, are destroyed efficiently and convert to inorganic bromine in flue gas, as HBr and Br{sub 2}. Black-Right-Pointing-Pointer Temperature has crucial influence over the inhibition of HBr conversion to Br{sub 2},more » while the oxygen partial pressure plays a reverse role in the conversion to a very small extent. Increasing temperature will decrease the volume percentage ratio of Br{sub 2}/HBr in flue gas greatly. Black-Right-Pointing-Pointer The thermodynamic equilibrium approach of bromine conversion was investigated. The two forms of inorganic bromine in flue gas substantially reach thermodynamic equilibrium within 0.25 s. Under the proposed operating condition, the reaction of Br transfer and conversion finish. - Abstract: High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br{sub 2}) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400 Degree-Sign C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT{sub HT}) was set at 0.25, 0.5, or 0.75 s. Combustion efficiency depends on temperature, EAF and RT{sub HT}; temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br{sub 2} depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br{sub 2}, whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25 s. High temperature is required to improve the combustion performance: at 1200 Degree-Sign C or higher, an EAF of 1.3 or more, and a RT{sub HT} exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%). According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br{sub 2}/HBr in flue gas greatly.« less

  3. Phase diagram of the Pr-Mn-O system in composition-temperature-oxygen pressure coordinates

    NASA Astrophysics Data System (ADS)

    Vedmid', L. B.; Yankin, A. M.; Fedorova, O. M.; Kozin, V. M.

    2016-05-01

    The phase relations in the Pr-Mn-O system were studied by the static method at lowered oxygen pressure in combination with thermal analysis and high-temperature X-ray diffraction. The equilibrium oxygen pressure in dissociation of PrMn2O5 and PrMnO3 was measured, and the thermodynamic characteristics of formation of these compounds from elements were calculated. The P- T- x phase diagram of the Pr-Mn-O system was constructed in the "composition-oxygen pressure-temperature" coordinates.

  4. Alteration of striatal dopamine levels under various partial pressure of oxygen in pre-convulsive and convulsive phases in freely-moving rats.

    PubMed

    Lavoute, Cécile; Weiss, Michel; Risso, Jean-Jacques; Rostain, Jean-Claude

    2014-02-01

    The purpose of this study was to investigate the change in the striatal dopamine (DA) level in freely-moving rat exposed to different partial pressure of oxygen (from 1 to 5 ATA). Some works have suggested that DA release by the substantia nigra pars compacta (SNc) neurons in the striatum could be disturbed by hyperbaric oxygen (HBO) exposure, altering therefore the basal ganglia activity. Such changes could result in a change in glutamatergic and GABAergic control of the dopaminergic neurons into the SNc. Such alterations could provide more information about the oxygen-induced seizures observed at 5 ATA in rat. DA-sensitive electrodes were implanted into the striatum under general anesthesia. After 1 week rest, awaked rats were exposed to oxygen-nitrogen mixture at a partial pressure of oxygen of 1, 2, 3, 4 and 5 ATA. DA level was monitored continuously (every 3 min) by in vivo voltammetry before and during HBO exposure. HBO induced a decrease in DA level in relationship to the increase in partial pressure of oxygen from 1 ATA to 4 ATA (-15 % at 1 ATA, -30 % at 2 ATA, -40 % at 3 ATA, -45 % at 4 ATA), without signs of oxygen toxicity. At 5 ATA, DA level strongly decreases (-75 %) before seizure which occurred after 27 min ± 7 HBO exposure. After the epileptic seizure the decrease in DA level disappeared. These changes and the biphasic effect of HBO were discussed in function of HBO action on neurochemical regulations of the nigro striatal pathway.

  5. Experimental testing of olivine-melt equilibrium models at high temperatures

    NASA Astrophysics Data System (ADS)

    Krasheninnikov, S. P.; Sobolev, A. V.; Batanova, V. G.; Kargaltsev, A. A.; Borisov, A. A.

    2017-08-01

    Data are presented on the equilibrium compositions of olivine and melts in the products of 101 experiments performed at 1300-1600°C, atmospheric pressure, and controlled oxygen fugacity by means of new equipment at the Vernadsky Institute. It was shown that the available models of the olivine-melt equilibrium describe with insufficient adequacy the natural systems at temperatures over 1400°C. The most adequate is the model by Ford et al. (1983). However, this model overestimates systematically the equilibrium temperature with underestimating by 20-40°C at 1450-1600°C. These data point to the need for developing a new, improved quantitative model of the olivine-melt equilibrium for high-temperature magnesian melts, as well as to the possibility of these studies on the basis of the equipment presented.

  6. Partial pressures of oxygen, phosphorus and fluorine in some lunar lavas

    NASA Technical Reports Server (NTRS)

    Nash, W. P.; Hausel, W. D.

    1973-01-01

    Lunar sample 14310 is a feldspar-rich basalt which shows no evidence of shock deformation or recrystallization. Pyroxenes include Mg-rich orthopyroxene, pigeonite and augite; pyroxferroite occurs in the interstitial residuum. Plagioclase feldspars are zoned from An(96) to An(67), and variations in feldspar compositions do not necessarily indicate loss of Na during eruption of the lava. Opaque phases include ilmenite, ulvospinel, metallic iron, troilite, and schreibersite. Both whitlockite and apatite are present, and the interstitial residua contain baddeleyite, tranquillityite and barium-rich sanidine. Theoretical calculations provide estimates of partial pressures of oxygen, phosphorus, and fluorine in lunar magmas. In general, partial pressures of oxygen are restricted by the limiting assemblages of iron-wuestite and ilmenite-iron-rutile; phosphorus partial pressures are higher in lunar magmas than in terrestrial lavas. The occurrence of whitlockite indicates significantly lower fugacities of fluorine in lunar magmas than in terrestrial magmas.

  7. Prolonged partial cardiopulmonary bypass in rats.

    PubMed

    Alexander, B; Al Ani, H R

    1983-07-01

    Membrane oxygenators have been shown to be atraumatic during cardiopulmonary bypass. A novel design for a membrane tubing oxygenator originated in this laboratory was used for prolonged partial supportive cardiopulmonary bypass in lambs and displayed excellent biocompatability characteristics. This was miniaturized, to result in a prime volume of 12 ml, in order to investigate the feasibility of prolonged partial supportive cardiopulmonary bypass in rats. The performance of this miniaturized circuit over perfusion periods up to 6 hr is described, with particular reference to hematological changes.

  8. Surface acoustic wave oxygen sensor

    NASA Technical Reports Server (NTRS)

    Collman, James P.; Oglesby, Donald M.; Upchurch, Billy T.; Leighty, Bradley D.; Zhang, Xumu; Herrmann, Paul C.

    1994-01-01

    A surface acoustic wave (SAW) device that responds to oxygen pressure was developed by coating a 158 MHz quartz surface acoustic wave (SAW) device with an oxygen binding agent. Two types of coatings were used. One type was prepared by dissolving an oxygen binding agent in a toluene solution of a copolymer containing the axial ligand. A second type was prepared with an oxygen binding porphyrin solution containing excess axial ligand without a polymer matrix. In the polymer based coatings, the copolymer served to provide the axial ligand to the oxygen binding agent and as a coating matrix on the surface of the SAW device. The oxygen sensing SAW device has been shown to bind oxygen following a Langmuir isotherm and may be used to measure the equilibrium constant of the oxygen binding compound in the coating matrix.

  9. The Lack of Chemical Equilibrium does not Preclude the Use of the Classical Nucleation Theory in Circumstellar Outflows

    NASA Technical Reports Server (NTRS)

    Paquette, John A.; Nuth, Joseph A., III

    2011-01-01

    Classical nucleation theory has been used in models of dust nucleation in circumstellar outflows around oxygen-rich asymptotic giant branch stars. One objection to the application of classical nucleation theory (CNT) to astrophysical systems of this sort is that an equilibrium distribution of clusters (assumed by CNT) is unlikely to exist in such conditions due to a low collision rate of condensable species. A model of silicate grain nucleation and growth was modified to evaluate the effect of a nucleation flux orders of magnitUde below the equilibrium value. The results show that a lack of chemical equilibrium has only a small effect on the ultimate grain distribution.

  10. Diffusion and Monod kinetics model to determine in vivo human corneal oxygen-consumption rate during soft contact lens wear

    PubMed Central

    Del Castillo, Luis F.; da Silva, Ana R. Ferreira; Hernández, Saul I.; Aguilella, M.; Andrio, Andreu; Mollá, Sergio; Compañ, Vicente

    2014-01-01

    Purpose We present an analysis of the corneal oxygen consumption Qc from non-linear models, using data of oxygen partial pressure or tension (pO2) obtained from in vivo estimation previously reported by other authors.1 Methods Assuming that the cornea is a single homogeneous layer, the oxygen permeability through the cornea will be the same regardless of the type of lens that is available on it. The obtention of the real value of the maximum oxygen consumption rate Qc,max is very important because this parameter is directly related with the gradient pressure profile into the cornea and moreover, the real corneal oxygen consumption is influenced by both anterior and posterior oxygen fluxes. Results Our calculations give different values for the maximum oxygen consumption rate Qc,max, when different oxygen pressure values (high and low pO2) are considered at the interface cornea-tears film. Conclusion Present results are relevant for the calculation on the partial pressure of oxygen, available at different depths into the corneal tissue behind contact lenses of different oxygen transmissibility. PMID:25649636

  11. Novel materials for electrochemical power sources—introduction of PUREBLACK ® Carbons

    NASA Astrophysics Data System (ADS)

    Barsukov, Igor V.; Gallego, Maritza A.; Doninger, Joseph E.

    Graphitization heat treatment of a precursor carbon black was seen to effectively produce a wide variety of forms of partially graphitized nano-sized carbonaceous materials with a set of unique properties, some of which are reported in this paper in comparison with those properties of the precursor carbon material. These novel materials were given the name of PUREBLACK ® Carbons. Among some of the unique properties are: higher conductivity than that of acetylene type carbon blacks due to PUREBLACK ® Carbon's particles having more graphitic structure; very low to zero volatile content (external oxygen, sulfur, etc., groups, which are often believed to be the cause of initiation of self-discharge reactions in batteries); very low equilibrium moisture pickup (20 ppm level), which makes it particularly attractive in lithium metal or lithium-ion based electrochemical systems; high purity. Electrochemical testing of the newly proposed PUREBLACK ® Carbons in several battery systems offers significant promise that it presents a viable solution to the needs of industry.

  12. Integrated Experimental and Modelling Research for Non-Ferrous Smelting and Recycling Systems

    NASA Astrophysics Data System (ADS)

    Jak, Evgueni; Hidayat, Taufiq; Shishin, Denis; Mehrjardi, Ata Fallah; Chen, Jiang; Decterov, Sergei; Hayes, Peter

    The chemistries of industrial pyrometallurgical non-ferrous smelting and recycling processes are becoming increasingly complex. Optimisation of process conditions, charge composition, temperature, oxygen partial pressure, and partitioning of minor elements between phases and different process streams require accurate description of phase equilibria and thermodynamics which are the focus of the present research. The experiments involve high temperature equilibration in controlled gas atmospheres, rapid quenching and direct measurement of equilibrium phase compositions with quantitative microanalytical techniques including electron probe X-ray microanalysis and Laser Ablation ICP-MS. The thermodynamic modelling is undertaken using computer package FactSage with the quasi-chemical model for the liquid slag phase and other advanced models. Experimental and modelling studies are combined into an integrated research program focused on the major elements Cu-Pb-Fe-O-Si-S system, slagging Al, Ca, Mg and other minor elements. The ongoing development of the research methodologies has resulted in significant advances in research capabilities. Examples of applications are given.

  13. Vibrational non-equilibrium in the hydrogen-oxygen reaction. Comparison with experiment

    NASA Astrophysics Data System (ADS)

    Skrebkov, Oleg V.

    2015-03-01

    A theoretical model is proposed for the chemical and vibrational kinetics of hydrogen oxidation based on consistent accounting of the vibrational non-equilibrium of the HO2 radical that forms as a result of the bimolecular recombination H+O2 → HO2. In the proposed model, the chain branching H+O2 = O+OH and inhibiting H+O2+M = HO2+M formal reactions are treated (in the terms of elementary processes) as a single multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and unimolecular decay of the comparatively long-lived vibrationally excited HO2 radical, which is able to react and exchange energy with the other components of the mixture. The model takes into account the vibrational non-equilibrium of the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1Δ), and the main reaction product H2O. It is shown that the hydrogen-oxygen reaction proceeds in the absence of vibrational equilibrium, and the vibrationally excited HO2(v) radical acts as a key intermediate in a fundamentally important chain branching process and in the generation of electronically excited species O2(1Δ), O(1D), and OH(2Σ+). The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 < T < 2500 K, 0.5 < p < 4 atm. It is demonstrated that this approach is promising from the standpoint of reconciling the predictions of the theoretical model with experimental data obtained by different authors for various compositions and conditions using different methods. For T < 1500 K, the nature of the hydrogen-oxygen reaction is especially non-equilibrium, and the vibrational non-equilibrium of the HO2 radical is the essence of this process. The quantitative estimation of the vibrational relaxation characteristic time of the HO2 radical in its collisions with H2 molecules has been obtained as a result of the comparison of different experimental data on induction time measurements with the relevant calculations.

  14. Oxygen exchange at gas/oxide interfaces: how the apparent activation energy of the surface exchange coefficient depends on the kinetic regime.

    PubMed

    Fielitz, Peter; Borchardt, Günter

    2016-08-10

    In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R] are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk ("on top" of the correlation between KO and [Fraktur R] for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO(1/2) observed for a large number of oxides in the mixed or diffusion controlled regime, respectively.

  15. Variable range hopping in ZnO films

    NASA Astrophysics Data System (ADS)

    Ali, Nasir; Ghosh, Subhasis

    2018-04-01

    We report the variable range hopping in ZnO films grown by RF magnetron sputtering in different argon and oxygen partial pressure. It has been found that Mott variable range hopping dominant over Efros variable range hopping in all ZnO films. It also has been found that hopping distance and energy increases with increasing oxygen partial pressure.

  16. Structural and electrical properties of sputter deposited ZnO thin films

    NASA Astrophysics Data System (ADS)

    Muhammed Shameem P., V.; Mekala, Laxman; Kumar, M. Senthil

    2018-05-01

    The growth of zinc oxide thin films having different oxygen content was achieved at ambient temperature by reactive dc magnetron sputtering technique and their structural and electrical properties are studied. The structural studies show that the films are polycrystalline with a preferential orientation of the grains along the c-axis [002], which increases with increase in oxygen partial pressure. The grain size and the surface roughness of the zinc oxide films are found to decrease with increasing oxygen partial pressure. It is observed that the resistivity of the zinc oxide films can be tuned from semiconducting to insulating regime by varying the oxygen content.

  17. OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Byrn, Marianne; Calvin, Melvin

    1965-12-01

    Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

  18. Putting A Human Face on Equilibrium

    NASA Astrophysics Data System (ADS)

    Glickstein, Neil

    2005-03-01

    A short biography of chemist Fritz Haber is used to personalize the abstract concepts of equilibrium chemistry for high school students in an introductory course. In addition to giving the Haber Bosch process an historic, an economic, and a scientific background the reading and subsequent discussion allows students for whom the human perspective is of paramount importance a chance to investigate the irony of balance or equilibrium in Haber's life story. Since the inclusion of the Haber biography, performance in the laboratory and on examinations for those students who are usually only partially engaged has dramatically improved.

  19. Thermodynamics of Titanium-Aluminum-Oxygen Alloys Studied

    NASA Technical Reports Server (NTRS)

    Copland, Evan H.; Jacobson, Nathan S.

    2001-01-01

    Titanium-aluminum alloys are promising intermediate-temperature alloys for possible compressor applications in gas-turbine engines. These materials are based on the a2-Ti3Al + g-TiAl phases. The major issue with these materials is high oxygen solubility in a2-Ti3Al, and oxidation of unsaturated alloys generally leads to mixed non-protective TiO2+Al2O3 scales. From phase diagram studies, oxygen saturated a2-Ti3Al(O) is in equilibrium with Al2O3; however, oxygen dissolution has a detrimental effect on mechanical properties and cannot be accepted. To better understand the effect of oxygen dissolution, we examined the thermodynamics of titanium-aluminum-oxygen alloys.

  20. Effects of decreasing activated carbon particle diameter from 30 μm to 140 nm on equilibrium adsorption capacity.

    PubMed

    Pan, Long; Nishimura, Yuki; Takaesu, Hideki; Matsui, Yoshihiko; Matsushita, Taku; Shirasaki, Nobutaka

    2017-11-01

    The capacity of activated carbon particles with median diameters (D50s) of >∼1 μm for adsorption of hydrophobic micropollutants such as 2-methylisolborneol (MIB) increases with decreasing particle size because the pollutants are adsorbed mostly on the exterior (shell) of the particles owing to the limited diffusion penetration depth. However, particles with D50s of <1 μm have not been thoroughly investigated. Here, we prepared particles with D50s of ∼30 μm-∼140 nm and evaluated their adsorption capacities for MIB and several other environmentally relevant adsorbates. The adsorption capacities for low-molecular-weight adsorbates, including MIB, deceased with decreasing particle size for D50s of less than a few micrometers, whereas adsorption capacities increased with decreasing particle size for larger particles. The oxygen content of the particles increased substantially with decreasing particle size for D50s of less than a few micrometers, and oxygen content was negatively correlated with adsorption capacity. The decrease in adsorption capacity with decreasing particle size for the smaller particles was due to particle oxidation during the micromilling procedure used to decrease D50 to ∼140 nm. When oxidation was partially inhibited, the MIB adsorption capacity decrease was attenuated. For high-molecular-weight adsorbates, adsorption capacity increased with decreasing particle size over the entire range of tested particle sizes, even though particle oxygen content increased with decreasing particle size. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Solubility and diffusion of oxygen in phospholipid membranes.

    PubMed

    Möller, Matías N; Li, Qian; Chinnaraj, Mathivanan; Cheung, Herbert C; Lancaster, Jack R; Denicola, Ana

    2016-11-01

    The transport of oxygen and other nonelectrolytes across lipid membranes is known to depend on both diffusion and solubility in the bilayer, and to be affected by changes in the physical state and by the lipid composition, especially the content of cholesterol and unsaturated fatty acids. However, it is not known how these factors affect diffusion and solubility separately. Herein we measured the partition coefficient of oxygen in liposome membranes of dilauroyl-, dimiristoyl- and dipalmitoylphosphatidylcholine in buffer at different temperatures using the equilibrium-shift method with electrochemical detection. The apparent diffusion coefficient was measured following the fluorescence quenching of 1-pyrenedodecanoate inserted in the liposome bilayers under the same conditions. The partition coefficient varied with the temperature and the physical state of the membrane, from below 1 in the gel state to above 2.8 in the liquid-crystalline state in DMPC and DPPC membranes. The partition coefficient was directly proportional to the partial molar volume and was then associated to the increase in free-volume in the membrane as a function of temperature. The apparent diffusion coefficients were corrected by the partition coefficients and found to be nearly the same, with a null dependence on viscosity and physical state of the membrane, probably because the pyrene is disturbing the surrounding lipids and thus becoming insensitive to changes in membrane viscosity. Combining our results with those of others, it is apparent that both solubility and diffusion increase when increasing the temperature or when comparing a membrane in the gel to one in the fluid state. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. [How did the earth's oxygen atmosphere originate?].

    PubMed

    Schäfer, G

    2004-09-01

    The planet earth did not carry an oxygen atmosphere from the beginning. Though oxygen could arise from radiation mediated water splitting, these processes were not efficient enough to create a global gas atmosphere. Oxygen in the latter is a product of the photosynthetic activity of early green organisms. Only after biological mass-formation of oxygen the UV-protective ozone layer could develop, then enabeling life to move from water onto land. This took billions of years. The basics of the processes of biological oxygen liberation and utilization are described in the following as well as the importance of their steady state equilibrium. Also a hint is given to oxygen as a toxic compound though being a chemical prerequisite for aerobic life on earth.

  3. Theoretical Performance of Liquid Hydrogen with Liquid Oxygen as a Rocket Propellant

    NASA Technical Reports Server (NTRS)

    Gordon, Sanford; McBride, Bonnie J.

    1959-01-01

    Theoretical rocket performance for both equilibrium and frozen composition during expansion was calculated for the propellant combination liquid hydrogen and liquid oxygen at four chamber pressures (60, 150, 300, and 600 lb/sq in. abs) and a wide range of pressure ratios (1 to 4000) and oxidant-fuel ratios (1.190 to 39.683). Data are given to estimate performance parameters at chamber pressures other than those for which data are tabulated. The parameters included are specific impulse, specific impulse in vacuum, combustion-chamber temperature, nozzle-exit temperature, molecular weight, molecular-weight derivatives, characteristic velocity, coefficient of thrust, ratio of nozzle-exit area to throat area, specific heat at constant pressure, isentropic exponent, viscosity, thermal conductivity, Mach number, and equilibrium gas compositions.

  4. Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

    NASA Astrophysics Data System (ADS)

    Hayles, J.; Shen, B.; Homann, M.; Yeung, L.

    2017-12-01

    One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

  5. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

    2015-07-01

    The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸O Gth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II) aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.« less

  6. Oxygen partial pressure dependence of thermoelectric power factor in polycrystalline n-type SrTiO3: Consequences for long term stability in thermoelectric oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Peter A.; Brown-Shaklee, Harlan J.; Ihlefeld, Jon F.

    2017-04-01

    The Seebeck coefficient and electrical conductivity have been measured as functions of oxygen partial pressure over the range of 10-22 to 10-1 atm at 1173 K for a 10% niobium-doped SrTiO3 ceramic with a grain size comparable to the oxygen diffusion length. Temperature-dependent measurements performed from 320 to 1275 K for as-prepared samples reveal metallic-like conduction and good thermoelectric properties. However, upon exposure to progressively increasing oxygen partial pressure, the thermoelectric power factor decreased over time scales of 24 h, culminating in a three order of magnitude reduction over the entire operating range. Identical measurements on single crystal samples show negligible changes in the power factor so that the instability of ceramic samples is primarily tied to the kinetics of grain boundary diffusion. This work provides a framework for understanding the stability of thermoelectric properties in oxides under different atmospheric conditions. The control of the oxygen atmosphere remains a significant challenge in oxide thermoelectrics.

  7. Method to Estimate the Dissolved Air Content in Hydraulic Fluid

    NASA Technical Reports Server (NTRS)

    Hauser, Daniel M.

    2011-01-01

    In order to verify the air content in hydraulic fluid, an instrument was needed to measure the dissolved air content before the fluid was loaded into the system. The instrument also needed to measure the dissolved air content in situ and in real time during the de-aeration process. The current methods used to measure the dissolved air content require the fluid to be drawn from the hydraulic system, and additional offline laboratory processing time is involved. During laboratory processing, there is a potential for contamination to occur, especially when subsaturated fluid is to be analyzed. A new method measures the amount of dissolved air in hydraulic fluid through the use of a dissolved oxygen meter. The device measures the dissolved air content through an in situ, real-time process that requires no additional offline laboratory processing time. The method utilizes an instrument that measures the partial pressure of oxygen in the hydraulic fluid. By using a standardized calculation procedure that relates the oxygen partial pressure to the volume of dissolved air in solution, the dissolved air content is estimated. The technique employs luminescent quenching technology to determine the partial pressure of oxygen in the hydraulic fluid. An estimated Henry s law coefficient for oxygen and nitrogen in hydraulic fluid is calculated using a standard method to estimate the solubility of gases in lubricants. The amount of dissolved oxygen in the hydraulic fluid is estimated using the Henry s solubility coefficient and the measured partial pressure of oxygen in solution. The amount of dissolved nitrogen that is in solution is estimated by assuming that the ratio of dissolved nitrogen to dissolved oxygen is equal to the ratio of the gas solubility of nitrogen to oxygen at atmospheric pressure and temperature. The technique was performed at atmospheric pressure and room temperature. The technique could be theoretically carried out at higher pressures and elevated temperatures.

  8. Thermal non-equilibrium in porous medium adjacent to vertical plate: ANN approach

    NASA Astrophysics Data System (ADS)

    Ahmed, N. J. Salman; Ahamed, K. S. Nazim; Al-Rashed, Abdullah A. A. A.; Kamangar, Sarfaraz; Athani, Abdulgaphur

    2018-05-01

    Thermal non-equilibrium in porous medium is a condition that refers to temperature discrepancy in solid matrix and fluid of porous medium. This type of flow is complex flow requiring complex set of partial differential equations that govern the flow behavior. The current work is undertaken to predict the thermal non-equilibrium behavior of porous medium adjacent to vertical plate using artificial neural network. A set of neurons in 3 layers are trained to predict the heat transfer characteristics. It is found that the thermal non-equilibrium heat transfer behavior in terms of Nusselt number of fluid as well as solid phase can be predicted accurately by using well-trained neural network.

  9. Non-equilibrium Properties of a Pumped-Decaying Bose-Condensed Electron–Hole Gas in the BCS–BEC Crossover Region

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hanai, R.; Littlewood, P. B.; Ohashi, Y.

    2016-03-01

    We theoretically investigate a Bose-condensed exciton gas out of equilibrium. Within the framework of the combined BCS-Leggett strong-coupling theory with the non-equilibrium Keldysh formalism, we show how the Bose-Einstein condensation (BEC) of excitons is suppressed to eventually disappear, when the system is in the non-equilibrium steady state. The supply of electrons and holes from the bath is shown to induce quasi-particle excitations, leading to the partial occupation of the upper branch of Bogoliubov single-particle excitation spectrum. We also discuss how this quasi-particle induction is related to the suppression of exciton BEC, as well as the stability of the steady state.

  10. Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity of Kilauea basalt

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gerlach, T.M.

    1993-02-01

    Volcanic gases collected during episode 1 of the Puu Oo eruption along the east rift zone of Kilauea Volcano, Hawaii, have uniform C-O-H-S-Cl-F compositions that are sharply depleted in CO[sub 2]. The CO[sub 2]-poor gases are typical of Type II volcanic gases (GERLACH and GRAEBER, 1985) and were emitted from evolved magma stored for a prolonged period of time in the east rift zone after releasing CO[sub 2]-rich gases during an earlier period of temporary residence in the summit magma chamber. The samples are remarkably free of contamination by atmospheric gases and meteoric water. Thermodynamic evaluation of the analytical datamore » shows that the episode 1 gases have equilibrium compositions appropriate for temperatures between 935 and 1032[degrees]C. Open- and closed-system equilibrium models of species distributions for the episode 1 gases show unequivocally that coexisting lavas buffered the gas oxygen fugacities during cooling. These models indicate that the F[sub o[sub 2

  11. Olivine-Orthopyroxene Equilibrium in Metal-rich Systems: Applications to Achondrites and Equilibrated Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Benedix, G. K.; McCoy, T. J.

    2003-01-01

    Olivine and orthopyroxene are major minerals in every type of stony meteorite. The majority of achondritic meteorites and silicate-bearing iron meteorites have experienced high temperatures. If these temperatures persisted for an extended period of time then the iron contents of olivine and orthopyroxene should be in equilibrium. In their study of ungrouped clasts and chondritic meteorites, suggested that the equilibrium compositions of olivine and orthopyroxene should fall on a mixing line between LL chondrites and aubrites. Here we show that this is not necessarily the case and that a range of FeO contents in olivine and orthopyroxene can be in equilibrium with each other. The key parameters that determine the equilibrium Fe content in these minerals are temperature, oxygen fugacity (fO2), and silica activity (aSiO2).

  12. New electrolyte may increase life of polarographic oxygen sensors

    NASA Technical Reports Server (NTRS)

    Albright, C. F.

    1967-01-01

    Electrolyte increases life on oxygen sensors in a polarograph used for measuring the partial pressure of oxygen in a gas mixture. It consists of a solution of lithium chloride, dimethyl acetamide and water.

  13. Oxygen isotope geospeedometry by SIMS

    NASA Astrophysics Data System (ADS)

    Bonamici, C. E.; Valley, J. W.

    2013-12-01

    Geospeedometry, a discipline closely related and complimentary to thermochronology, exploits the phenomenon of diffusion in order to extract rate and duration information for segments of a rock's thermal history. Geospeedometry data, when anchored in absolute time by geochronologic data, allow for the construction of detailed temperature-time paths for specific terranes and geologic processes. We highlight the developing field of SIMS-based oxygen isotope geospeedometry with an application from granulites of the Adirondack Mountains (New York) and discuss potential future applications based on a recently updated and expanded modeling tool, the Fast Grain Boundary diffusion program (FGB; Eiler et al. 1994). Equilibrium oxygen isotope ratios in minerals are a function of temperature and bulk rock composition. In dynamic systems, intragrain oxygen isotope zoning can develop in response to geologic events that affect the thermal state of a rock and/or induce recrystallization, especially tectonic deformation and fluid infiltration. As an example, titanite grains from late-Grenville shear zones in the northwestern Adirondack Mountains exhibit a range of δ18O zoning patterns that record post-peak metamorphic cooling, episodic fluid infiltration, and deformation-facilitated recrystallization. Many titanite grains preserve smooth, core-to-rim decreasing, diffusional δ18O profiles, which are amenable to diffusion modeling. FGB models that best fit the measured δ18O profiles indicate cooling from ~700-500°C in just 2-5 m.y., a rapid thermal change signaling the final gravitational collapse of the late-Grenville orogen. Titanite can also be utilized as a U-Pb chronometer, and comparison of δ18O and U-Pb age zoning patterns within the Adirondack titanites pins the episode of rapid cooling inferred from the δ18O record to some time between 1054 and 1047 Ma. The expanded capabilities of FGB also allow for evaluation of a range of heating-cooling histories for the Adirondack granulites. Diffusional δ18O zoning profiles in titanite are best fit by complete re-equilibration at temperatures above 675 °C followed by rapid, monotonic cooling; FGB models that include only partial re-equilibration and/or episodes of reheating along the retrograde path do not fit the observed δ18O profiles. Beyond the Adirondack titanite example, FGB can be used as a predictive tool to target either specific minerals within a rock or specific rock types within a terrane for oxygen isotope geospeedometry and zoning studies. FGB generates predictions of δ18O zoning for all minerals in a rock of a given mineralogy and heating-cooling history. Different minerals within the same rock will record different segments of the thermal and fluid history based on their individual diffusivities, phase stabilities, and propensities for deformation-induced/facilitated recrystallization. It should therefore be possible to extract long thermal histories from a single sample by measuring oxygen isotope zoning profiles across several minerals with different partial retention zones for oxygen.

  14. Calibration Of Partial-Pressure-Of-Oxygen Sensors

    NASA Technical Reports Server (NTRS)

    Yount, David W.; Heronimus, Kevin

    1995-01-01

    Report and analysis of, and discussion of improvements in, procedure for calibrating partial-pressure-of-oxygen sensors to satisfy Spacelab calibration requirements released. Sensors exhibit fast drift, which results in short calibration period not suitable for Spacelab. By assessing complete process of determining total drift range available, calibration procedure modified to eliminate errors and still satisfy requirements without compromising integrity of system.

  15. Computation of the unsteady facilitated transport of oxygen in hemoglobin

    NASA Technical Reports Server (NTRS)

    Davis, Sanford

    1990-01-01

    The transport of a reacting permeant diffusing through a thin membrane is extended to more realistic dissociation models. A new nonlinear analysis of the reaction-diffusion equations, using implicit finite-difference methods and direct block solvers, is used to study the limits of linearized and equilibrium theories. Computed curves of molecular oxygen permeating through hemoglobin solution are used to illustrate higher-order reaction models, the effect of concentration boundary layers at the membrane interfaces, and the transient buildup of oxygen flux.

  16. Methods and apparatus for reducing corrosion in refractory linings

    DOEpatents

    Poeppel, Roger B.; Greenberg, Sherman; Diercks, Dwight R.

    1987-01-01

    Methods and apparatus are provided for reducing corrosion in a refractory lining of a liquid-containing vessel used in direct steelmaking processes. The vessel operates at between about 1600.degree. C. and about 1800.degree. C. and an oxygen partial pressure of about 10.sup.-12 atmospheres, creating slag which is rich in FeO. The refractory lining includes a significant level of chromium oxide (Cr.sub.2 O.sub.3), and has small interconnected pores which may be filled with a gas mixture having a higher total pressure and oxygen partial pressure than the total pressure and oxygen partial pressure associted with the liquid against the lining of the vessel. The gas mixture is forced through the pores of the lining so that the pores are continuously filled with the mixture. In this manner, the gas mixture creates a blanket which increases the oxygen partial pressure at the lining enough to maintain the chromium in the lining in a selected valence state in which the chromium has decreased solubility in the FeO slag, thereby reducing corrosion by the FeO and increasing the useful life of the refractory lining.

  17. Observations of Circumstellar Thermochemical Equilibrium: The Case of Phosphorus

    NASA Technical Reports Server (NTRS)

    Milam, Stefanie N.; Charnley, Steven B.

    2011-01-01

    We will present observations of phosphorus-bearing species in circumstellar envelopes, including carbon- and oxygen-rich shells 1. New models of thermochemical equilibrium chemistry have been developed to interpret, and constrained by these data. These calculations will also be presented and compared to the numerous P-bearing species already observed in evolved stars. Predictions for other viable species will be made for observations with Herschel and ALMA.

  18. Cation disorder and gas phase equilibrium in an YBa 2Cu 3O 7- x superconducting thin film

    NASA Astrophysics Data System (ADS)

    Shin, Dong Chan; Ki Park, Yong; Park, Jong-Chul; Kang, Suk-Joong L.; Yong Yoon, Duk

    1997-02-01

    YBa 2Cu 3O 7- x superconducting thin films have been grown by in situ off-axis rf sputtering with varying oxygen pressure, Ba/Y ratio in a target, and deposition temperature. With decreasing oxygen pressure, increasing Ba/Y ratio, increasing deposition temperature, the critical temperature of the thin films decreased and the c-axis length increased. The property change of films with the variation of deposition variables has been explained by a gas phase equilibrium of the oxidation reaction of Ba and Y. Applying Le Chatelier's principle to the oxidation reaction, we were able to predict the relation of deposition variables and the resultant properties of thin films; the prediction was in good agreement with the experimental results. From the relation between the three deposition variables and gas phase equilibrium, a 3-dimensional processing diagram was introduced. This diagram has shown that the optimum deposition condition of YBa 2Cu 3O 7- x thin films is not a fixed point but can be varied. The gas phase equilibrium can also be applied to the explanation of previous results that good quality films were obtained at low deposition temperature using active species, such as O, O 3, and O 2+.

  19. Carbon and oxygen isotope fractionation in non-marine ostracods: results from a 'natural culture' environment

    NASA Astrophysics Data System (ADS)

    Keatings, K. W.; Heaton, T. H. E.; Holmes, J. A.

    2002-05-01

    Carbon and oxygen isotope analysis of ostracods living in the near-constant conditions of spring-fed ponds in southern England allowed accurate determination of the ostracod's calcite-water 13C/12C and 18O/16O fractionations. The 13C/12C fractionations of two species, Candona candida and Pseudocandona rostrata, correspond to values expected for isotopic equilibrium with the pond's dissolved inorganic carbon at the measured temperature (11°C) and pH (6.9), whilst those of a third species, Herpetocypris reptans, would represent equilibrium at a slightly higher pH (7.1). The 18O/16O fractionations confirm two previous studies in being larger, by up to 3‰, than those 'traditionally' regarded as representing equilibrium. When the measured fractionations are considered in the context of more recent work, however, they can be explained in terms of equilibrium if the process of calcite formation at the ostracod lamella occurs at a relatively low pH (≤7) irrespective of the pH of the surrounding water. The pH of calcite formation, and therefore the calcite-water 18O/16O fractionation, may be species and stage (adult versus juvenile) specific, and related to the rate of calcification.

  20. Oxygen availability and spreading depolarizations provide complementary prognostic information in neuromonitoring of aneurysmal subarachnoid hemorrhage patients.

    PubMed

    Winkler, Maren Kl; Dengler, Nora; Hecht, Nils; Hartings, Jed A; Kang, Eun J; Major, Sebastian; Martus, Peter; Vajkoczy, Peter; Woitzik, Johannes; Dreier, Jens P

    2017-05-01

    Multimodal neuromonitoring in neurocritical care increasingly includes electrocorticography to measure epileptic events and spreading depolarizations. Spreading depolarization causes spreading depression of activity (=isoelectricity) in electrically active tissue. If the depression is long-lasting, further spreading depolarizations occur in still isoelectric tissue where no activity can be suppressed. Such spreading depolarizations are termed isoelectric and are assumed to indicate energy compromise. However, experimental and clinical recordings suggest that long-lasting spreading depolarization-induced depression and isoelectric spreading depolarizations are often recorded outside of the actual ischemic zones, allowing the remote diagnosis of delayed cerebral ischemia after aneurysmal subarachnoid hemorrhage. Here, we analyzed simultaneous electrocorticography and tissue partial pressure of oxygen recording in 33 aneurysmal subarachnoid hemorrhage patients. Multiple regression showed that both peak total depression duration per recording day and mean baseline tissue partial pressure of oxygen were independent predictors of outcome. Moreover, tissue partial pressure of oxygen preceding spreading depolarization was similar and differences in tissue partial pressure of oxygen responses to spreading depolarization were only subtle between isoelectric spreading depolarizations and spreading depressions. This further supports that, similar to clustering of spreading depolarizations, long spreading depolarization-induced periods of isoelectricity are useful to detect energy compromise remotely, which is valuable because the exact location of future developing pathology is unknown at the time when the neurosurgeon implants recording devices.

  1. Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

    NASA Technical Reports Server (NTRS)

    Opila, E. J.; Serra, J. L.

    2007-01-01

    T-300 carbon fibers and T-300 carbon fiber reinforced silicon carbide composites (C/SiC) were oxidized in flowing reduced oxygen partial pressure environments at a total pressure of one atmosphere (0.5 atm O2, 0.05 atm O2 and 0.005 atm O2, balance argon). Experiments were conducted at four temperatures (816deg, 1149deg, 1343deg, and 1538 C). The oxidation kinetics were monitored using thermogravimetric analysis. T-300 fibers were oxidized to completion for times between 0.6 and 90 h. Results indicated that fiber oxidation kinetics were gas phase diffusion controlled. Oxidation rates had an oxygen partial pressure dependence with a power law exponent close to one. In addition, oxidation rates were only weakly dependent on temperature. The C/SiC coupon oxidation kinetics showed some variability, attributed to differences in the number and width of cracks in the SiC seal coat. In general, weight losses were observed indicating oxidation of the carbon fibers dominated the oxidation behavior. Low temperatures and high oxygen pressures resulted in the most rapid consumption of the carbon fibers. At higher temperatures, the lower oxidation rates were primarily attributed to crack closure due to SiC thermal expansion, rather than oxidation of SiC since these reduced rates were observed even at the lowest oxygen partial pressures where SiC oxidation is minimal.

  2. Relating oxygen partial pressure, saturation and content: the haemoglobin-oxygen dissociation curve.

    PubMed

    Collins, Julie-Ann; Rudenski, Aram; Gibson, John; Howard, Luke; O'Driscoll, Ronan

    2015-09-01

    The delivery of oxygen by arterial blood to the tissues of the body has a number of critical determinants including blood oxygen concentration (content), saturation (S O2 ) and partial pressure, haemoglobin concentration and cardiac output, including its distribution. The haemoglobin-oxygen dissociation curve, a graphical representation of the relationship between oxygen satur-ation and oxygen partial pressure helps us to understand some of the principles underpinning this process. Historically this curve was derived from very limited data based on blood samples from small numbers of healthy subjects which were manipulated in vitro and ultimately determined by equations such as those described by Severinghaus in 1979. In a study of 3524 clinical specimens, we found that this equation estimated the S O2 in blood from patients with normal pH and S O2 >70% with remarkable accuracy and, to our knowledge, this is the first large-scale validation of this equation using clinical samples. Oxygen saturation by pulse oximetry (S pO2 ) is nowadays the standard clinical method for assessing arterial oxygen saturation, providing a convenient, pain-free means of continuously assessing oxygenation, provided the interpreting clinician is aware of important limitations. The use of pulse oximetry reduces the need for arterial blood gas analysis (S aO2 ) as many patients who are not at risk of hypercapnic respiratory failure or metabolic acidosis and have acceptable S pO2 do not necessarily require blood gas analysis. While arterial sampling remains the gold-standard method of assessing ventilation and oxygenation, in those patients in whom blood gas analysis is indicated, arterialised capillary samples also have a valuable role in patient care. The clinical role of venous blood gases however remains less well defined.

  3. Ionization and excitation in cool giant stars. I - Hydrogen and helium

    NASA Technical Reports Server (NTRS)

    Luttermoser, Donald G.; Johnson, Hollis R.

    1992-01-01

    The influence that non-LTE radiative transfer has on the electron density, ionization equilibrium, and excitation equilibrium in model atmospheres representative of both oxygen-rich and carbon-rich red giant stars is demonstrated. The radiative transfer and statistical equilibrium equations are solved self-consistently for H, H(-), H2, He I, C I, C II, Na I, Mg I, Mg II, Ca I, and Ca II in a plane-parallel static medium. Calculations are made for both radiative-equilibrium model photospheres alone and model photospheres with attached chromospheric models as determined semiempirically with IUE spectra of g Her (M6 III) and TX Psc (C6, 2). The excitation and ionization results for hydrogen and helium are reported.

  4. Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream

    DOEpatents

    Kromer, Brian R.; Litwin, Michael M.; Kelly, Sean M.

    2016-09-27

    A method and system for generating electrical power in which a high pressure synthesis gas stream generated in a gasifier is partially oxidized in an oxygen transport membrane based reactor, expanded and thereafter, is combusted in an oxygen transport membrane based boiler. A low pressure synthesis gas slip stream is split off downstream of the expanders and used as the source of fuel in the oxygen transport membrane based partial oxidation reactors to allow the oxygen transport membrane to operate at low fuel pressures with high fuel utilization. The combustion within the boiler generates heat to raise steam to in turn generate electricity by a generator coupled to a steam turbine. The resultant flue gas can be purified to produce a carbon dioxide product.

  5. [Peroxynitrite effect on the haemoglobin oxygen affinity in vitro in presence of different partial pressure of carbon dioxide].

    PubMed

    Stepuro, T L; Zinchuk, V V

    2011-08-01

    Peroxynitrite (ONOO-) besides its toxic possesses regulatory action that includes the modulation of oxygen binding properties of blood. The aim of this work was to estimate ONOO- effect on the haemoglobin oxygen affinity (HOA) in vitro in presence of different partial pressure of carbon dioxide (CO2). The ONOO- presence in venous blood in conditions of hypercapnia induced oxyhaemoglobin dissociation curve shift leftward while in hypocapnic conditions the result of a different character was obtained. The revealed effect of ONOO- is realized, possibly, through various modifications ofhaemoglobin whose formation is dependent on the CO2 pressure. The ONOO- influences the HOA in different manner that can be important in regulation of blood oxygenation in lungs and maintenance of oxygen consumption in tissues.

  6. Measurement of Local Partial Pressure of Oxygen in the Brain Tissue under Normoxia and Epilepsy with Phosphorescence Lifetime Microscopy.

    PubMed

    Zhang, Cong; Bélanger, Samuel; Pouliot, Philippe; Lesage, Frédéric

    2015-01-01

    In this work a method for measuring brain oxygen partial pressure with confocal phosphorescence lifetime microscopy system is reported. When used in conjunction with a dendritic phosphorescent probe, Oxyphor G4, this system enabled minimally invasive measurements of oxygen partial pressure (pO2) in cerebral tissue with high spatial and temporal resolution during 4-AP induced epileptic seizures. Investigating epileptic events, we characterized the spatio-temporal distribution of the "initial dip" in pO2 near the probe injection site and along nearby arterioles. Our results reveal a correlation between the percent change in the pO2 signal during the "initial dip" and the duration of seizure-like activity, which can help localize the epileptic focus and predict the length of seizure.

  7. Determination of flash point in air and pure oxygen using an equilibrium closed bomb apparatus.

    PubMed

    Kong, Dehong; am Ende, David J; Brenek, Steven J; Weston, Neil P

    2003-08-29

    The standard closed testers for flash point measurements may not be feasible for measuring flash point in special atmospheres like oxygen because the test atmosphere cannot be maintained due to leakage and the laboratory safety can be compromised. To address these limitations we developed a new "equilibrium closed bomb" (ECB). The ECB generally gives lower flash point values than standard closed cup testers as shown by the results of six flammable liquids. The present results are generally in good agreement with the values calculated from the reported lower flammability limits and the vapor pressures. Our measurements show that increased oxygen concentration had little effect on the flash points of the tested flammable liquids. While generally regarded as non-flammable because of the lack of observed flash point in standard closed cup flash point testers, dichloromethane is known to form flammable mixtures. The flash point of dichloromethane in oxygen measured in the ECB is -7.1 degrees C. The flash point of dichloromethane in air is dependent on the type and energy of the ignition source. Further research is being carried out to establish the relationship between the flash point of dichloromethane and the energy of the ignition source.

  8. Optical conductivity of partially oxidized graphene from first principles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nasehnia, F., E-mail: f.nasehnia@gmail.com; Seifi, M., E-mail: Seifi@guilan.ac.ir

    2015-07-07

    We investigate the geometry, electronic structure, and optical properties of partially oxidized graphene using density functional theory. Our calculations show that oxygen atoms are chemisorbed on graphene plane and distort carbon atoms vertically, with almost no change in the in-plane structure. The ground state configurations for different oxygen coverages ranging from 2% to 50% (O/C ratio) are calculated and show the strong tendency of oxygen adatoms to aggregate and form discrete islands on graphene plane. It is found that the opened band gap due to oxygen functionalization depends on the oxygen density and the adsorption configuration. The gap is notmore » significant for oxygen densities lower than 8%. The optical conductivities are calculated in the infrared, visible, and ultraviolet regions and show different characteristic features depending on the degree of oxidation. These results imply that optical measurement techniques can be employed to monitor oxidation (or reduction) process as contact-free methods.« less

  9. Observation of decreasing resistivity of amorphous indium gallium zinc oxide thin films with an increasing oxygen partial pressure

    NASA Astrophysics Data System (ADS)

    Singh, Anup K.; Adhikari, Sonachand; Gupta, Rajeev; Deepak

    2017-01-01

    We have investigated the electrical resistivity behavior in amorphous indium gallium zinc oxide (a-IGZO) thin films. It is well known that resistivity increases as the film is deposited at a higher and higher oxygen partial pressure; we also record the same. However, in process we have discovered a remarkable region, in the oxygen deficient condition, that the resistivity shows an inverse behavior. This leads to the possibility that resistive films, suitable for thin film transistors, can also be obtained in oxygen deficient deposition conditions. Optical spectroscopic investigation could discern between a-IGZO films grown in oxygen deficient and oxygen rich conditions. The related resistivity behavior could be correlated to the presence of sub-bandgap states in films deposited in oxygen deficiency. These subgap states appear to be due to defects arising from local variations around the cations or oxygen atoms. The likely cause is an increase in Ga relative to In around O atom and the nature of cation-cation interaction when an oxygen atom is missing.

  10. Preflight studies on tolerance of pocket mice to oxygen and heat. IV - Observations on the brain

    NASA Technical Reports Server (NTRS)

    Bailey, O. T.; Ordy, J. M.; Haymaker, W.

    1975-01-01

    Experiments designed to ascertain the effects of oxygen at 8, 10, and 12 psi partial pressure on the brains of pocket mice (Perognathus longimembris) were carried out at room temperature (24 C, 75 F) and at 32 C (90 F). The animals exposed to 8-12 psi at 32 C had been in earlier KO2 oxygen tests. Five animals exposed either to 10 or 12 psi (517 mm or 620 mm Hg) O2 partial pressure at 32 C died during the course of the tests, possibly as a consequence of injury sustained by the earlier O2 partial pressure testing. Autopsy was not carried out. In the other 36 exposed animals, no pathological changes were observed in the brain. It is thus highly probable that oxygen pressures at the hyperbaric levels to which the pocket mice would be exposed during the Apollo XVII mission would not result in any lesions in the brain.

  11. Triple oxygen isotopes and clumped isotopes in modern vertebrate and dinosaur biominerals: Records of paleoecology, paleoaridity, and paleo-carbon-cycling

    NASA Astrophysics Data System (ADS)

    Hu, H.; Passey, B. H.; Lehmann, S. B.; Levin, N. E.; Montanari, S.; Chin, K.; Johnson, B. J.

    2015-12-01

    The parameter Δ17O describes the departure of δ17O from an expected equilibrium relationship with δ18O, which can be caused by factors such as evaporation of parent waters, and photochemical reactions among oxygen-bearing gases in stratosphere. Hence, the Δ17O of water records information about environmental aridity, and the Δ17O of atmospheric O2 is related to atmospheric concentrations of CO2 and O2, and gross primary productivity (GPP). Vertebrates incorporate Δ17O signals of input water (e.g. drinking water and free food water) and atmospheric O2 into body water through respiration, and biominerals forming in equilibrium with body water can preserve this signal over geological timescales. The preservation of fossil biominerals can be evaluated by clumped isotopes as they record the temperature of mineralization, be it primary mineralization in the living animal (at body temperature), or secondary mineralization during diagenesis. We can distinguish the alteration of samples from the deviation between observed clumped isotope temperatures and plausible body temperatures. Meanwhile, diagenesis tends to moderate Δ17O of biominerals towards Δ17O of meteoric waters, such that measured Δ17O values reflect the minimum anomaly in fossil samples. Thus, preservation of anomalous Δ17O indicates at least partial preservation of the original signal. We present Δ17O data from both modern vertebrate and fossil dinosaur biominerals. We use a 17O-enabled body water model to explore the influence of aridity and dietary ecology on animal Δ17O, and to predict the degree of dilution of the atmospheric O2 Δ17O signal by other sources of oxygen to the animal. We observe: 1) animals consuming more leaf water than drinking water are "evaporation sensitive" (ES) animals, and have lower Δ17O relative to "evaporation insensitive" animals in the same climates; 2) ES animals from arid climates have lower Δ17O values compared to ES animals from humid climates, which forms the basis of a paleoaridity proxy; and 3) anomalously low body water Δ17O values are observed for some of the dinosaur samples, indicating a significantly different carbon cycle during that time, with pCO2 up to 3250±1250 ppm during late Jurassic assuming present day GPP and pO2.

  12. Simultaneous measurement of brain tissue oxygen partial pressure, temperature, and global oxygen consumption during hibernation, arousal, and euthermy in non-sedated and non-anesthetized Arctic ground squirrels.

    PubMed

    Ma, Yilong; Wu, Shufen

    2008-09-30

    This study reports an online temperature correction method for determining tissue oxygen partial pressure P(tO2) in the striatum and a novel simultaneous measurement of brain P(tO2) and temperature (T(brain)) in conjunction with global oxygen consumption V(O2) in non-sedated and non-anesthetized freely moving Arctic ground squirrels (AGS, Spermophilus parryii). This method fills an important research gap-the lack of a suitable method for physiologic studies of tissue P(O2) in hibernating or other cool-blooded species. P(tO2) in AGS brain during euthermy (21.22+/-2.06 mmHg) is significantly higher (P=0.016) than during hibernation (13.21+/-0.46 mmHg) suggests brain oxygenation in the striatum is normoxic during euthermy and hypoxic during hibernation. These results in P(tO2) are different from blood oxygen partial pressure P(aO2) in AGS, which are significantly lower during euthermy than during hibernation and are actually hypoxic during euthermy and normoxic during hibernation in our previous study. This intriguing difference between the P(O2) of brain tissue and blood during these two physiological states suggests that regional mechanisms in the brain play a role in maintaining tissue oxygenation and protect against hypoxia during hibernation.

  13. Diffusion and Monod kinetics model to determine in vivo human corneal oxygen-consumption rate during soft contact lens wear.

    PubMed

    Del Castillo, Luis F; da Silva, Ana R Ferreira; Hernández, Saul I; Aguilella, M; Andrio, Andreu; Mollá, Sergio; Compañ, Vicente

    2015-01-01

    We present an analysis of the corneal oxygen consumption Qc from non-linear models, using data of oxygen partial pressure or tension (P(O2) ) obtained from in vivo estimation previously reported by other authors. (1) METHODS: Assuming that the cornea is a single homogeneous layer, the oxygen permeability through the cornea will be the same regardless of the type of lens that is available on it. The obtention of the real value of the maximum oxygen consumption rate Qc,max is very important because this parameter is directly related with the gradient pressure profile into the cornea and moreover, the real corneal oxygen consumption is influenced by both anterior and posterior oxygen fluxes. Our calculations give different values for the maximum oxygen consumption rate Qc,max, when different oxygen pressure values (high and low P(O2)) are considered at the interface cornea-tears film. Present results are relevant for the calculation on the partial pressure of oxygen, available at different depths into the corneal tissue behind contact lenses of different oxygen transmissibility. Copyright © 2014. Published by Elsevier Espana.

  14. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  15. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-17

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  16. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-24

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  17. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    2001-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  18. Oxygen sensor for monitoring gas mixtures containing hydrocarbons

    DOEpatents

    Ruka, Roswell J.; Basel, Richard A.

    1996-01-01

    A gas sensor measures O.sub.2 content of a reformable monitored gas containing hydrocarbons H.sub.2 O and/or CO.sub.2, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system.

  19. Oxygen sensor for monitoring gas mixtures containing hydrocarbons

    DOEpatents

    Ruka, R.J.; Basel, R.A.

    1996-03-12

    A gas sensor measures O{sub 2} content of a reformable monitored gas containing hydrocarbons, H{sub 2}O and/or CO{sub 2}, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system. 4 figs.

  20. Combined Hyperbaric Oxygen Partial Pressure at 1.4 Bar with Infrared Radiation: A Useful Tool To Improve Tissue Hypoxemia?

    PubMed

    Dünnwald, Tobias; Held, Julia; Balan, Petru; Pecher, Otto; Zeiger, Thomas; Hartig, Frank; Mur, Erich; Weiss, Günter; Schobersberger, Wolfgang

    2018-06-13

    Tissue hypoxia contributes to the pathogenesis of several acute and chronic diseases. Hyperbaric oxygen therapy (HBO) and whole-body warming using low-temperature infrared technology (LIT) are techniques that might improve hypoxemia. Combining HBO and LIT as hyperbaric oxygen therapy combined with low-temperature infrared radiation (HBOIR) might be an approach that results in positive synergistic effects on oxygenation. LIT increases blood flow and could reduce HBO-induced vasoconstriction, and hyperoxia could compensate for the increased metabolic oxygen requirements mediated by LIT. Both LIT and HBO increase the oxygen diffusion distance in the tissues. HBOIR at 0.5 bar has been shown to be safe and feasible. However, physiological responses and the safety of HBOIR at an increased oxygen (O2) partial pressure of 1.4 bar or 2.4 atmospheres absolute (ATA) still need to be determined. The hope is that should HBOIR at an increased oxygen partial pressure of 1.4 bar be safe, future studies to examine its efficacy in patients with clinical conditions, which include peripheral arterial disease (PAD) or wound healing disorders, will follow. The results of pilot studies have shown that HBOIR at an overload pressure is safe and well tolerated in healthy participants but can generate moderate cardiovascular changes and an increase in body temperature. From the findings of this pilot study, due to its potential synergistic effects, HBOIR could be a promising tool for the treatment of human diseases associated with hypoxemia.

  1. Carbon and oxygen isotopic disequilibrium during calcification of Globigerina bulloides in the Southern ocean

    NASA Astrophysics Data System (ADS)

    K, P.; Ghosh, P.; N, A.

    2015-12-01

    Oxygen and carbon isotopes in planktonic foraminifera Globigerina bulloides recovered from the water column of 0-1000 m depth across the meridional transect i.e. 10°N to 53°S of Indian ocean were compared with the available data from the core-top samples across the same transect. We also recorded in situ temperatures of the water column based on probe (CTD) profiles. The δ18O and δ13C values measured in the core top samples matches with the tow results. The equilibrium δ18O of calcite calculated from known temperature and δ18O of water column allowed us to compare the observed δ18O of formaminieral shell with the expected equilibrium values. Our comparison of carbonate composition in the samples between 10°N till 40°S showed excellent match with the expected equilibrium δ18O values established from the water collected at depth range of ~75-200m, however beyond 40°S the disequilibrium was pronounced with heavier δ18O (enriched by ~1.5‰) recorded in the carbonate as compared with the expected equilibrium δ18O values established from water. This observation was further verified with δ13C measurement of shell carbonates comparing with the equilibrium δ13C of calcite calculated with known temperature and δ13C of dissolved inorganic carbon in the water column. The δ13C of the shell carbonate was found heavier as compared to the expected equilibrium δ13C. Both δ18O and δ13C showed simultaneous enrichment signature in the region beyond 40°S suggesting role of processes such as leaching along with dissolution of shell carbonate in a relatively acidic condition.

  2. Partially autoionizing states of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Petrosky, V. E.

    1974-01-01

    Certain Rydberg states and an intershell transition of atomic oxygen were shown to partially autoionize, and to produce emission spectra competitive with autoionization. These states are forbidden to autoionize on the basis of LS coupling; but they were observed both in emission spectroscopy and in photoelectron spectroscopy. The results explain an unidentified structure in the 584 Angstrom He I atomic O spectrum observed by previous investigators.

  3. Singlet Delta oxygen generation for chemical oxygen-iodine lasers

    NASA Astrophysics Data System (ADS)

    Georges, E.; Mouthon, A.; Barraud, R.

    To improve the overall efficiency of chemical oxygen-iodine lasers, it is necessary to increase the generator production and yield of singlet delta oxygen at low and high pressure, respectively, for subsonic and supersonic lasers. The water vapor content must also be as low as possible. A generator model based on gas-liquid reaction and liquid-vapor equilibrium theories is presented. From model predictions, operating conditions have been drawn to attain the following experimental results in a bubble-column: by increasing the superficial gas velocity, the production of singlet delta oxygen is largely improved at low pressure; by mixing chlorine with an inert gas before injection in the reactor, this yield is maintained constant up to higher pressure.

  4. Effect of Electroacupuncture on Transcutaneous Oxygen Partial Pressure During Hyperbaric Oxygen Therapy in Healthy Individuals.

    PubMed

    Qu, Lan; Ye, Yong; Li, Chunfeng; Gao, Guangkai

    2015-01-01

    The goal of hyperbaric oxygen therapy (HBOT) is to increase the oxygen (O₂) supply to the body significantly. Because of the toxic side effects and complications of hyperbaric oxygen (HBO₂), the environmental pressure and treatment time must be restricted. The research team hypothesized that other therapies administered during HBOT could safely improve the value of the arterial oxygen partial pressure (PaO₂) during HBOT and improve its therapeutic effect. The study intended to investigate whether electroacupuncture (EA) while receiving HBOT had a greater effect for healthy individuals than HBOT or EA alone or EA combined with normobaric pure oxygen (pure O₂). The research team designed a randomized, controlled trial. The study was performed in the Department of Hyperbaric Medicine at the No. 401 Hospital of the People's Liberation Army in Qingdao, China. A total of 81 volunteers were recruited. After thorough physical examination and laboratory testing, 21 volunteers were excluded from the study. Participants included 60 healthy volunteers. Participants were randomly assigned to 1 of 4 groups of 15 participants each: (1) an HBOT group, (2) an EA group, (3) an EA During HBOT group, and (4) an EA Combined With Pure O₂group. Because at the current technology level a blood gas analyzer cannot test PaO₂during HBOT, transcutaneous oxygen partial pressure (PtcO₂) of the participants was tested instead. Before, during, and after EA, variations in PtcO₂were monitored in each group. For the EA During HBOT group, (1) the increase in PtcO₂during EA was significantly greater than that observed for the other 3 groups (P > .05). The EA During HBOT method provided improvements in the efficacy, safety, and tolerability of HBOT, and the study's results partially demonstrated the accuracy of the research team's hypothesis that EA therapy applied during HBOT could safely improve the value of PtcO₂(PaO₂) during HBOT and produce a greater therapeutic effect.

  5. Electrons, life and the evolution of Earth's oxygen cycle.

    PubMed

    Falkowski, Paul G; Godfrey, Linda V

    2008-08-27

    The biogeochemical cycles of H, C, N, O and S are coupled via biologically catalysed electron transfer (redox) reactions. The metabolic processes responsible for maintaining these cycles evolved over the first ca 2.3 Ga of Earth's history in prokaryotes and, through a sequence of events, led to the production of oxygen via the photobiologically catalysed oxidation of water. However, geochemical evidence suggests that there was a delay of several hundred million years before oxygen accumulated in Earth's atmosphere related to changes in the burial efficiency of organic matter and fundamental alterations in the nitrogen cycle. In the latter case, the presence of free molecular oxygen allowed ammonium to be oxidized to nitrate and subsequently denitrified. The interaction between the oxygen and nitrogen cycles in particular led to a negative feedback, in which increased production of oxygen led to decreased fixed inorganic nitrogen in the oceans. This feedback, which is supported by isotopic analyses of fixed nitrogen in sedimentary rocks from the Late Archaean, continues to the present. However, once sufficient oxygen accumulated in Earth's atmosphere to allow nitrification to out-compete denitrification, a new stable electron 'market' emerged in which oxygenic photosynthesis and aerobic respiration ultimately spread via endosymbiotic events and massive lateral gene transfer to eukaryotic host cells, allowing the evolution of complex (i.e. animal) life forms. The resulting network of electron transfers led a gas composition of Earth's atmosphere that is far from thermodynamic equilibrium (i.e. it is an emergent property), yet is relatively stable on geological time scales. The early coevolution of the C, N and O cycles, and the resulting non-equilibrium gaseous by-products can be used as a guide to search for the presence of life on terrestrial planets outside of our Solar System.

  6. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kuhn, M., E-mail: kuhnm@mit.edu; Hashimoto, S.; Sato, K.

    The oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} has been the topic of various reports in the literature, but has been exclusively measured at high oxygen partial pressures, pO{sub 2}, and/or elevated temperatures. For applications of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}}, such as solid oxide fuel cell cathodes or oxygen permeation membranes, knowledge of the oxygen nonstoichiometry and thermo-chemical stability over a wide range of pO{sub 2} is crucial, as localized low pO{sub 2} could trigger failure of the material and device. By employing coulometric titration combined with thermogravimetry, the oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} was measured at highmore » and intermediate pO{sub 2} until the material decomposed (at log(pO{sub 2}/bar) Almost-Equal-To -4.5 at 1073 K). For a gradually reduced sample, an offset in oxygen content suggests that La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} forms a 'super-reduced' solid solution before decomposing. When the sample underwent alternate reduction-oxidation, a hysteresis-like pO{sub 2} dependence of the oxygen content in the decomposition pO{sub 2} range was attributed to the reversible formation of ABO{sub 3} and A{sub 2}BO{sub 4} phases. Reduction enthalpy and entropy were determined for the single-phase region and confirmed interpolated values from the literature. - Graphical abstract: Oxygen nonstoichiometry (shown as 3-{delta}) of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} as a function of pO{sub 2} at 773-1173 K. The experimental data were obtained by thermogravimetric analysis (TG) and coulometric titration (measured either by a simple reduction (CT1) or a 'two-step-forward one-step-back' reduction-oxidation (CT2) procedure). D1 and D2 denote the decomposition pO{sub 2}. The solid lines are the fit to the thermogravimetry and CT1 data. The dashed lines represent the non-equilibrium region where the sample shows a super-reduced state. Highlights: Black-Right-Pointing-Pointer Oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} at intermediate temperatures and p(O2). Black-Right-Pointing-Pointer Experimental confirmation of previously interpolated reduction enthalpy. Black-Right-Pointing-Pointer Decomposition p(O2) assessed by coulometric titration. Black-Right-Pointing-Pointer Hysteresis-like p(O2) dependence of oxygen content at decomposition p(O2).« less

  7. Work function and surface stability of tungsten-based thermionic electron emission cathodes

    NASA Astrophysics Data System (ADS)

    Jacobs, Ryan; Morgan, Dane; Booske, John

    2017-11-01

    Materials that exhibit a low work function and therefore easily emit electrons into vacuum form the basis of electronic devices used in applications ranging from satellite communications to thermionic energy conversion. W-Ba-O is the canonical materials system that functions as the thermionic electron emitter commercially used in a range of high-power electron devices. However, the work functions, surface stability, and kinetic characteristics of a polycrystalline W emitter surface are still not well understood or characterized. In this study, we examined the work function and surface stability of the eight lowest index surfaces of the W-Ba-O system using density functional theory methods. We found that under the typical thermionic cathode operating conditions of high temperature and low oxygen partial pressure, the most stable surface adsorbates are Ba-O species with compositions in the range of Ba0.125O-Ba0.25O per surface W atom, with O passivating all dangling W bonds and Ba creating work function-lowering surface dipoles. Wulff construction analysis reveals that the presence of O and Ba significantly alters the surface energetics and changes the proportions of surface facets present under equilibrium conditions. Analysis of previously published data on W sintering kinetics suggests that fine W particles in the size range of 100-500 nm may be at or near equilibrium during cathode synthesis and thus may exhibit surface orientation fractions well described by the calculated Wulff construction.

  8. Copper isotope signatures in modern marine sediments

    NASA Astrophysics Data System (ADS)

    Little, Susan H.; Vance, Derek; McManus, James; Severmann, Silke; Lyons, Timothy W.

    2017-09-01

    The development of metal stable isotopes as tools in paleoceanography requires a thorough understanding of their modern marine cycling. To date, no Cu isotope data has been published for modern sediments deposited under low oxygen conditions. We present data encompassing a broad spectrum of hydrographic and redox regimes, including continental margin and euxinic (sulphide-containing) settings. Taken together with previously published data from oxic settings, these data indicate that the modern oceanic sink for Cu has a surprisingly homogeneous isotopic composition of about +0.3‰ (δ65Cu, relative to NIST SRM976). We suggest that this signature reflects one of two specific water-column processes: (1) an equilibrium isotope fractionation between soluble, isotopically heavy, Cu complexed to strong organic ligands and an isotopically light pool sorbed to particles that deliver Cu to the sediment, or (2) an equilibrium isotope fractionation between the same isotopically heavy ligand-bound pool and the particle reactive free Cu2+ species, with the latter being scavenged by particulates and thereby delivered to the sediment. An output flux of about +0.3‰ into sediments is isotopically light relative to the known inputs to the ocean (at around +0.6‰) and the seawater value of +0.6 to +0.9‰, suggesting the presence of an as yet unidentified isotopically light source of Cu to the oceans. We hypothesize that this source may be hydrothermal, or may result from the partial dissolution of continentally derived particles.

  9. Determination of Oxygen Fugacity using Olivine-Melt Equilibrium: Implications for the Redox States of Mid-Ocean Ridge Basalt, Ocean Island Basalt, and Island Arc Basalt Mantle Source Regions

    NASA Astrophysics Data System (ADS)

    Peterman, K. J.; Bryson, S.; Rilling-Hall, S.; Barton, M.

    2017-12-01

    In order to connect volcanic rocks to their mantle sources, it is essential to consider redox equilibria and their dependence on temperature, pressure, chemical composition, and oxygen fugacity. Oxygen fugacity (fO2) is an intensive variable that strongly affects the behavior of those elements in magmas that are sensitive to changes in redox state, such as Fe, and therefore Mg-Fe silicates, such as olivine. Since fO2 plays an important role in fractional crystallization, in principle it is possible to estimate fO2 from analyses of olivine in equilibrium with the melt. This research describes a new method based on this principle called the Olivine-Melt Equilibrium Method. The Fe3+ and Fe2+ contents of melt in equilibrium with olivine are calculated from the relationship of Gee and Sack (1988) that describes the partitioning of Mg and Fe2+ between olivine and melt. The Fe3+ and Fe2+ contents of the melt are then used to calculate the fO2 at which olivine and melt are in equilibrium using the model of Kress and Carmichael (1991) for the relationship between Fe3+/Fe2+ , fO2, T, P, and melt composition. We have calculated oxygen fugacities from published analyses of coexisting glass and olivine pairs in 1020 samples from three different tectonic settings. The results (expressed as ΔFMQ) for Mid-Ocean Ridge Basalts from the Mid-Atlantic Ridge (-1.55 ± 0.75), the East Pacific Rise (-0.65 ± 0.51), the Juan de Fuca Ridge (-0.77 ± 0.42), and the Galápagos Spreading Center (+0.08 ± 0.48) agree with results obtained using other methods and average -1.09 ± 0.89. Ocean Island Basalts from Iceland and the Galápagos Islands (ΔFMQ = -0.43 ± 0.71 and -0.33 ± 0.35 respectively) also yield values consistent with those obtained by other methods and fall in the same range as MORB. However, lavas from the Canary Islands are more oxidized than typical MORB and OIB, with values (average = +0.68 ± 0.52) approaching those for island arc magmas. We obtain ΔFMQ = +1.03 ± 0.52 for olivine-melt pairs from Sunda arc basalts. The results for MORB and OIB potentially provide evidence for redox heterogeneity in the mantle, possibly as the result of crustal recycling. However it is necessary to evaluate the possibility that fO2 changes during magma ascent before concluding that the oxygen fugacities of erupted magmas directly reflect those of the mantle source regions.

  10. Study of Chromium Oxide Activities in EAF Slags

    NASA Astrophysics Data System (ADS)

    Yan, Baijun; Li, Fan; Wang, Hui; Sichen, Du

    2016-02-01

    The activity coefficients of chromium in Cu-Cr melts were determined by equilibrating liquid copper with solid Cr2O3 in CO-CO2 atmosphere. The temperature dependence of the activity coefficients of chromium in Cu-Cr melts could be expressed as lg γ_{Cr}(s)^{0} = { 3 2 5 9( ± 1 8 6} )/T - 0. 5 9( { ± 0. 1} ). Based on the above results, the activities of bivalent and trivalent chromium oxide in some slags at 1873 K (1600 °C) were measured. The slags were equilibrated with Cu-Cr melts under two oxygen partial pressures ( {p_{O}_{ 2} }} } = 6.9 × 10-4 and 1.8 × 10-6 Pa, respectively). The morphology of the quenched slags and the solubility of chromium oxide in the melts were investigated by EPMA, SEM, and XRD. Under both oxygen partial pressures, the slags were saturated by the solid solution MgAl2- x Cr x O4- δ . At the low oxygen partial pressure (1.8 × 10-6 Pa), the content of Cr in the liquid phase varied from 0.4 to 1.6 mass pct with the total Cr content in the slags increasing from 1.3 to 10.8 mass pct. At the high oxygen partial pressure (6.9 × 10-4 Pa), the content of Cr in the liquid phase decreased to the level of 0.2 to 0.6 mass pct. Both the activities of CrO and Cr2O3 in slag were found to increase approximately linearly with the increase of the total Cr content in slag. While the oxygen partial pressure had minor effect on the activity of Cr2O3 in the slag, it had significant effect on the activity of CrO.

  11. Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

    PubMed

    Keedakkadan, Habeeb Rahman; Abe, Osamu

    2015-04-30

    The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic and molecular fractionations, and this fractionation by molecular sieves can be corrected by the amount of molecular sieve used in the experiment. The reproducibility of the method was tested by the measurement of the oxygen isotope ratios of dissolved oxygen at equilibrium with atmospheric air. We confirmed that the choice of methods for making air-equilibrated water was not related to the magnitude of isotope fractionation, whereas there was a difference between seawater and deionized water. Copyright © 2015 John Wiley & Sons, Ltd.

  12. Neuroprotection of hyperbaric oxygen therapy in sub-acute traumatic brain injury: not by immediately improving cerebral oxygen saturation and oxygen partial pressure.

    PubMed

    Zhou, Bao-Chun; Liu, Li-Jun; Liu, Bing

    2016-09-01

    Although hyperbaric oxygen (HBO) therapy can promote the recovery of neural function in patients who have suffered traumatic brain injury (TBI), the underlying mechanism is unclear. We hypothesized that hyperbaric oxygen treatment plays a neuroprotective role in TBI by increasing regional transcranial oxygen saturation (rSO 2 ) and oxygen partial pressure (PaO 2 ). To test this idea, we compared two groups: a control group with 20 healthy people and a treatment group with 40 TBI patients. The 40 patients were given 100% oxygen of HBO for 90 minutes. Changes in rSO 2 were measured. The controls were also examined for rSO 2 and PaO 2 , but received no treatment. rSO 2 levels in the patients did not differ significantly after treatment, but levels before and after treatment were significantly lower than those in the control group. PaO 2 levels were significantly decreased after the 30-minute HBO treatment. Our findings suggest that there is a disorder of oxygen metabolism in patients with sub-acute TBI. HBO does not immediately affect cerebral oxygen metabolism, and the underlying mechanism still needs to be studied in depth.

  13. Operational considerations in monitoring oxygen levels at the National Transonic Facility

    NASA Technical Reports Server (NTRS)

    Zalenski, M. A.; Rowe, E. L.; Mcphee, J. R.

    1985-01-01

    Laboratory monitoring of the level of oxygen in sample gas mixtures is a process which can be performed with accurate and repeatable results. Operations at the National Transonic Facility require the storage and pumping of large volumes of liquid nitrogen. To protect against the possibility of a fault resulting in a localized oxygen deficient atmosphere, the facility is equipped with a monitoring system with an array of sensors. During the early operational stages, the system produced recurrent alarms, none of which could be traced to a true oxygen deficiency. A thorough analysis of the system was undertaken with primary emphasis placed on the sensor units. These units sense the partial pressure of oxygen which, after signal conditioning, is presented as a % by volume indication at the system output. It was determined that many of the problems experienced were due to a lack of proper accounting for the partial pressure/% by volume relationship, with a secondary cause being premature sensor failure. Procedures were established to consider atmospherically induced partial pressure variations. Sensor rebuilding techniques were examined, and those elements contributing to premature sensor failure were identified. The system now operates with a high degree of confidence and reliability.

  14. Oxidation of SiC Fiber-Reinforced SiC Matrix Composites with a BN Interphase

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth; Boyd, Meredith K.

    2010-01-01

    SiC-fiber reinforced SiC matrix composites with a BN interphase were oxidized in reduced oxygen partial pressures of oxygen to simulate the environment for hypersonic vehicle leading edge applications. The constituent fibers as well as composite coupons were oxidized in oxygen partial pressures ranging from 1000 ppm O2 to 5% O2 balance argon. Exposure temperatures ranged from 816 C to 1353 C (1500 F to 2450 F). The oxidation kinetics of the coated fibers were monitored by thermogravimetric analysis (TGA). An initial rapid transient weight gain was observed followed by parabolic kinetics. Possible mechanisms for the transient oxidation are discussed. One edge of the composite coupon seal coat was ground off to simulate damage to the composite which allowed oxygen ingress to the interior of the composite. Oxidation kinetics of the coupons were characterized by scanning electron microscopy since the weight changes were minimal. It was found that sealing of the coupon edge by silica formation occurred. Differences in the amount and morphology of the sealing silica as a function of time, temperature and oxygen partial pressure are discussed. Implications for use of these materials for hypersonic vehicle leading edge materials are summarized.

  15. The thermodynamic properties of oxygen and nitrogen

    NASA Technical Reports Server (NTRS)

    Stewart, R. B.; Jacobsen, R. T.; Myers, A. F.

    1972-01-01

    The development of a single equation of state for oxygen and nitrogen based on the thermodynamic properties of the gases is described. The coefficients of the equation of state were determined by simultaneous least squares fits to values of isochoric heat capacity and saturation density values used to define the criteria for phase equilibrium. Tables of data for the conditions of both gases are included.

  16. The major volume /density/ of solid oxygen in equilibrium with vapor

    NASA Technical Reports Server (NTRS)

    Roder, H. M.

    1979-01-01

    Data from the literature on the molar volume of solid oxygen have been compiled and critically analyzed. A correlated and thermodynamically consistent set of molar volumes, including the volume changes at the various solid phase transitions, is presented. Evidence for the existence of a delta-solid phase is reviewed. Uncertainties in the data and in the recommended set of values are discussed.

  17. Quadriceps oxygenation during isometric exercise in sailing.

    PubMed

    Vogiatzis, I; Tzineris, D; Athanasopoulos, D; Georgiadou, O; Geladas, N

    2008-01-01

    The aim of the present study was to investigate why blood lactate after prolonged quadriceps contraction during hiking is only marginally increased. Eight sailors performed five 3-min hiking bouts interspersed with 5-s recovery periods. Whole body oxygen uptake, heart rate and lactate were recorded, along with continuous-wave near-infrared spectroscopy measures of quadriceps oxygenation. The time for 50% re-oxygenation was also assessed as an indication of the degree of localized oxygen delivery stress. Hiking elicited a significant (p = 0.001) increase in mean (+/- SD) heart rate (124 +/- 10 beats . min (-1)) which was accompanied by a disproportionately low oxygen uptake (12 +/- 2 ml.kg(-1).min(-1)). Lactate was significantly (p = 0.001) increased throughout hiking manoeuvres, though post-exercise it remained low (3.2 +/- 0.9 mmol.l(-1)). During the hiking bouts mean quadriceps oxygenation was significantly (p = 0.001) reduced compared to baseline (by 33 +/- 5%), indicating an imbalance between muscle oxygen accessibility and oxygen demand. During rest intervals quadriceps oxygenation was partially restored. After the end of the final bout the time for 50 % re-oxygenation was only 8 +/- 2 s, whereas recovery of quadriceps oxygenation and oxygen uptake was completed within 3 min. We conclude that the observed low lactate could be attributed to the small oxygen and energy deficits during hiking as the muscles' oxygen accessibility is presumably partially restored during the brief rest intervals.

  18. Measurement of Local Partial Pressure of Oxygen in the Brain Tissue under Normoxia and Epilepsy with Phosphorescence Lifetime Microscopy

    PubMed Central

    Zhang, Cong; Bélanger, Samuel; Pouliot, Philippe; Lesage, Frédéric

    2015-01-01

    In this work a method for measuring brain oxygen partial pressure with confocal phosphorescence lifetime microscopy system is reported. When used in conjunction with a dendritic phosphorescent probe, Oxyphor G4, this system enabled minimally invasive measurements of oxygen partial pressure (pO2) in cerebral tissue with high spatial and temporal resolution during 4-AP induced epileptic seizures. Investigating epileptic events, we characterized the spatio-temporal distribution of the "initial dip" in pO2 near the probe injection site and along nearby arterioles. Our results reveal a correlation between the percent change in the pO2 signal during the "initial dip" and the duration of seizure-like activity, which can help localize the epileptic focus and predict the length of seizure. PMID:26305777

  19. The determination of density and molecular weight distributions of lipoproteins by sedimentation equilibrium.

    PubMed

    Jeffrey, P D; Nichol, L W; Smith, G D

    1975-01-25

    A method is presented by which an experimental record of total concentration as a function of radial distance, obtained in a sedimentation equilibrium experiment conducted with a noninteracting mixture in the absence of a density gradient, may be analyzed to obtain the unimodal distributions of molecular weight and of partial molar volume when these vary concomitantly and continuously. Particular attention is given to the caracterization of classes of lipoproteins exhibiting Gaussian distributions of these quantities, although the analysis is applicable to other types of unimodal distribution. Equations are also formulated permitting the definition of the corresponding distributions of partial specific volume and of density. The analysis procedure is based on a method (employing Laplace transforms) developed previously, but differs from it in that it avoids the necessity of differentiating experimental results, which introduces error. The method offers certain advantages over other procedures used to characterize and compare lipoprotein samples (exhibiting unimodal distributions) with regard to the duration of the experiment, economy of the sample, and, particularly, the ability to define in principle all of the relevant distributions from one sedimentation equilibrium experiment and an external measurement of the weight average partial specific volume. These points and the steps in the analysis procedure are illustrated with experimental results obtained in the sedimentation equilibrium of a sample of human serum low density lipoprotein. The experimental parameters (such as solution density, column height, and angular velocity) used in the conduction of these experiments were selected on the basis of computer-simulated examples, which are also presented. These provide a guide for other workers interested in characterizing lipoproteins of this class.

  20. A Computational Method for Determining the Equilibrium Composition and Product Temperature in a LH2/LOX Combustor

    NASA Technical Reports Server (NTRS)

    Sozen, Mehmet

    2003-01-01

    In what follows, the model used for combustion of liquid hydrogen (LH2) with liquid oxygen (LOX) using chemical equilibrium assumption, and the novel computational method developed for determining the equilibrium composition and temperature of the combustion products by application of the first and second laws of thermodynamics will be described. The modular FORTRAN code developed as a subroutine that can be incorporated into any flow network code with little effort has been successfully implemented in GFSSP as the preliminary runs indicate. The code provides capability of modeling the heat transfer rate to the coolants for parametric analysis in system design.

  1. Against the grain: The physical properties of anisotropic partially molten rocks

    NASA Astrophysics Data System (ADS)

    Ghanbarzadeh, S.; Hesse, M. A.; Prodanovic, M.

    2014-12-01

    Partially molten rocks commonly develop textures that appear close to textural equilibrium, where the melt network evolves to minimize the energy of the melt-solid interfaces, while maintaining the dihedral angle θ at solid-solid-melt contact lines. Textural equilibrium provides a powerful model for the melt distribution that controls the petro-physical properties of partially molten rocks, e.g., permeability, elastic moduli, and electrical resistivity. We present the first level-set computations of three-dimensional texturally equilibrated melt networks in rocks with an anisotropic fabric. Our results show that anisotropy induces wetting of smaller grain boundary faces for θ > 0 at realistic porosities ϕ < 3%. This was previously not thought to be possible at textural equilibrium and reconciles the theory with experimental observations. Wetting of the grain boundary faces leads to a dramatic redistribution of the melt from the edges to the faces that introduces strong anisotropy in the petro-physical properties such as permeability, effective electrical conductivity and mechanical properties. Figure, on left, shows that smaller grain boundaries become wetted at relatively low melt fractions of 3% in stretched polyhedral grains with elongation factor 1.5. Right plot represents the ratio of melt electrical conductivity to effective conductivity of medium (known as formation factor) as an example of anisotropy in physical properties. The plot shows that even slight anisotropy in grains induces considerable anisotropy in electrical properties.

  2. Effect of stirring on the safety of flammable liquid mixtures.

    PubMed

    Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

    2010-05-15

    Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  3. Oxygen fugacity of gases and rocks from Momotombo Volcano, Nicaragua: Application to volcanological monitoring

    NASA Astrophysics Data System (ADS)

    Benhamou, G.; Allard, P.; Sabroux, J. C.; Vitter, G.; Dajlevic, D.; Creusot, A.

    1988-12-01

    The oxygen fugacity (fO2) and the fO2 versus T°C relationship of high-temperature (600°-860°C) gas emissions from Momotombo volcano, Nicaragua, was determined from both field electrochemical measurements (electrolytic cell assembly) and thermodynamic computations on gas samples collected between 1978 and 1985. It was then compared with the intrinsic fO2 of fresh and altered lavas from the last eruption (1905), as measured between 500° and 1100°C in laboratory. The electrochemical results show that the oxygen fugacity of Momotombo fumaroles, at equivalent temperature, is much higher than that of the fresh 1905 lava (˜FMQ buffer) and closer to that of their altered wall rocks (˜FMQ buffer). The equilibrium O2 fugacities calculated from the chemistry of gas samples confirm this pattern. However, they suggest that the gas mixtures preserve the (variable) memory of a higher thermal equilibrium achieved at depth, under temperature and fO2 conditions of up to 1050°C and 10-9.0 atm, respectively, which correspond to the cross over between the fO2-T gas and lava trends. These data thus support the idea that Momotombo volcanic gases, released in a period of increasing activity, escape from a shallow magma body before suffering a variable oxidation during their ascent through both unbuffered cooling and reactions with environmental fluids and rocks. This late oxidation is weaker at central fumaroles than at peripherical ones. While between 1978 and 1985 the temperature of the hottest fumarole increased from 750° to 865°-900°C, the equilibrium fO2 of the gas decreased by nearly one order of magnitude (at comparable equilibrium temperature). Such an evolution presumably reflects an increasing connection between the surface exhalations and the magma degassing at depth along with time. This work underlines the possibility of monitoring the processes of magma ascent and gas-magma separation within a volcano before an eruption by continuously recording the changes of both oxygen fugacity and temperature in hot fumaroles.

  4. Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO₂.

    PubMed

    Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

    2016-03-24

    In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO₂ powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO₂ films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO₂ up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO₂. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model.

  5. Oxygen partial pressure influence on the character of InGaZnO thin films grown by PLD

    NASA Astrophysics Data System (ADS)

    Lu, Yi; Wang, Li

    2012-11-01

    The amorphous oxide semiconductors (AOSs) are promising for emerging large-area optoelectronic applications because of capability of large-area, uniform deposition at low temperatures such as room temperature (RT). Indium-gallium-zinc oxide (InGaZnO) thin film is a promising amorphous semiconductors material in thin film transistors (TFT) for its excellent electrical properties. In our work, the InGaZnO thin films are fabricated on the SiO2 glass using pulsed laser deposition (PLD) in the oxygen partial pressure altered from 1 to 10 Pa at RT. The targets were prepared by mixing Ga2O3, In2O3, and ZnO powder at a mol ratio of 1: 7: 2 before the solid-state reactions in a tube furnace at the atmospheric pressure. The targets were irradiated by an Nd:YAG laser(355nm). Finally, we have three films of 270nm, 230nm, 190nm thick for 1Pa, 5Pa, 10Pa oxygen partial pressure. The product thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), Hall-effect investigation. The comparative study demonstrated the character changes of the structure and electronic transport properties, which is probably occurred as a fact of the different oxygen partial pressure used in the PLD.

  6. Gel Filtration Of Dilute Human Embryonic Hemoglobins Reveals Basis For Their Increased Oxygen Binding

    PubMed Central

    Manning, Lois R.; Popowicz, Anthony M.; Padovan, Julio C.; Chait, Brian T.; Manning, James M.

    2016-01-01

    This report establishes a correlation between two known properties of the human embryonic hemoglobins-- their weak subunit assemblies as demonstrated here by gel filtration at very dilute protein concentrations and their high oxygen affinities and reduced cooperativities reported previously by others but without a mechanistic basis. We demonstrate here that their high oxygen affinities are a consequence of their weak assemblies. Weak vs strong hemoglobin tetramers represent a regulatory mechanism to modulate oxygen binding capacity by altering the equilibrium between the various steps in the assembly process that can be described as an inverse allosteric effect. PMID:27965062

  7. Gel filtration of dilute human embryonic hemoglobins reveals basis for their increased oxygen binding.

    PubMed

    Manning, Lois R; Popowicz, Anthony M; Padovan, Julio C; Chait, Brian T; Manning, James M

    2017-02-15

    This report establishes a correlation between two known properties of the human embryonic hemoglobins-- their weak subunit assemblies as demonstrated here by gel filtration at very dilute protein concentrations and their high oxygen affinities and reduced cooperativities reported previously by others but without a mechanistic basis. We demonstrate here that their high oxygen affinities are a consequence of their weak assemblies. Weak vs strong hemoglobin tetramers represent a regulatory mechanism to modulate oxygen binding capacity by altering the equilibrium between the various steps in the assembly process that can be described as an inverse allosteric effect. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Carbon Dioxide Fluctuations Are Associated with Changes in Cerebral Oxygenation and Electrical Activity in Infants Born Preterm.

    PubMed

    Dix, Laura Marie Louise; Weeke, Lauren Carleen; de Vries, Linda Simone; Groenendaal, Floris; Baerts, Willem; van Bel, Frank; Lemmers, Petra Maria Anna

    2017-08-01

    To evaluate the effects of acute arterial carbon dioxide partial pressure changes on cerebral oxygenation and electrical activity in infants born preterm. This retrospective observational study included ventilated infants born preterm with acute fluctuations of continuous end-tidal CO 2 (etCO 2 ) as a surrogate marker for arterial carbon dioxide partial pressure, during the first 72 hours of life. Regional cerebral oxygen saturation and fractional tissue oxygen extraction were monitored with near-infrared spectroscopy. Brain activity was monitored with 2-channel electroencephalography. Spontaneous activity transients (SATs) rate (SATs/minute) and interval between SATs (in seconds) were calculated. Ten-minute periods were selected for analysis: before, during, and after etCO 2 fluctuations of ≥5  mm Hg. Thirty-eight patients (mean ± SD gestational age of 29 ± 1.8 weeks) were included, with 60 episodes of etCO 2 increase and 70 episodes of etCO 2 decrease. During etCO 2 increases, brain oxygenation increased (regional cerebral oxygen saturation increased, fractional tissue oxygen extraction decreased; P < .01) and electrical activity decreased (SATs/minute decreased, interval between SATs increased; P < .01). All measures recovered when etCO 2 returned to baseline. During etCO 2 decreases, brain oxygenation decreased (regional cerebral oxygen saturation decreased, fractional tissue oxygen extraction decreased; P < .01) and brain activity increased (SATs/minute increased, P < .05), also with recovery after return of etCO 2 to baseline. An acute increase in etCO 2 is associated with increased cerebral oxygenation and decreased brain activity, whereas an acute decrease is associated with decreased cerebral oxygenation and slightly increased brain activity. Combining continuous CO 2 monitoring with near-infrared spectroscopy may enable the detection of otherwise undetected fluctuations in arterial carbon dioxide partial pressure that may be harmful to the neonatal brain. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Ameliorating effects of fluorocarbon emulsion on sickle red blood cell-induced obstruction in an ex vivo vasculature.

    PubMed

    Kaul, D K; Liu, X; Nagel, R L

    2001-11-15

    In sickle cell (SS) vaso-occlusion, the culminating event is blockage of blood vessels by sickled red blood cells (SS RBCs). As shown in animal models, SS RBC-induced vaso-occlusion is often partial, allowing for a residual flow, hence oxygen delivery to partially occluded vessels could reduce vaso-occlusion. The efficacy of an oxygenated perflubron-based fluorocarbon emulsion (PFE) was tested for its anti-vaso-occlusive effects in the ex vivo mesocecum vasculature of the rat. Microvascular obstruction was induced by the infusion of deoxygenated SS RBCs into ex vivo preparations with or without pretreatment with platelet-activating factor (PAF). PAF induced enhanced SS RBC-endothelium interactions, leading to greater vaso-occlusion. Microvascular blockage resulted in increased peripheral resistance units (PRU). Deoxygenated SS RBCs caused a persistent 1.5-fold PRU increase in untreated preparations and approximately a 2-fold PRU increase in PAF-treated preparations. The greater PRU in PAF-treated preparations was caused by widespread adhesion and postcapillary blockage. Oxygenated PFE, but not deoxygenated PFE, resulted in PRU decreases to baseline values in both groups of experiments (with or without PAF). The PRU decrease caused by oxygenated PFE infusion was caused by unsickling of SS RBCs in partially occluded vessels, with no antiadhesive effect on already adherent SS RBCs as assessed by intravital microscopy. PFE had no effect on vascular tone. The efficacy of PFE appears to result from its greater capacity to dissolve oxygen (10-fold higher than plasma). The dislodgement of trapped SS RBCs and an increase in wall shear rates will help reverse the partial obstruction. Thus, oxygenated PFE is capable of reducing SS RBC-induced vaso-occlusion, and further development of this approach is advisable.

  10. Kinetic hindrance of Fe(II) oxidation at alkaline pH and in the presence of nitrate and oxygen in a facultative wastewater stabilization pond.

    PubMed

    Rockne, Karl J

    2007-02-15

    To better understand the dynamics of Fe2 + oxidation in facultative wastewater stabilization ponds, water samples from a three-pond system were taken throughout the period of transition from anoxic conditions with high aqueous Fe2 + levels in the early spring to fully aerobic conditions in late spring. Fe2 + levels showed a highly significant correlation with pH but were not correlated with dissolved oxygen (DO). Water column Fe2 + levels were modeled using the kinetic rate law for Fe2 + oxidation of Sung and Morgan.[5] The fitted kinetic coefficients were 5 +/- 3 x 10(6) M(- 2) atm(-1) min(-1); more than six orders of magnitude lower than typically reported. Comparison of four potential Fe redox couples demonstrated that the rhoepsilon was at least 3-4 orders of magnitude higher than would be expected based on internal equilibrium. Surprisingly, measured nitrate and DO (when present) were typically consistent with both nitrate (from denitrification) and DO levels (from aerobic respiration) predicted from equilibrium. Although the hydrous Fe oxide/FeCO3 couple was closest to equilibrium and most consistent with the observed pH dependence (in contrast to predicted lepidocrocite), Fe2 + oxidation is kinetically hindered, resulting in up to 10(7)-fold higher levels than expected based on both kinetic and equilibrium analyses.

  11. Unitarity limits on the mass and radius of dark matter particles

    NASA Technical Reports Server (NTRS)

    Griest, Kim; Kamionkowski, Marc

    1989-01-01

    Using partial wave unitarity and the observed density of the Universe, it is show that a stable elementary particle which was once in thermal equilibrium cannot have a mass greater than 340 TeV. An extended object which was once in thermal equilibrium cannot have a radius less than 7.5 x 10(exp -7) fm. A lower limit to the relic abundance of such particles is also found.

  12. Phase Equilibrium of TiO2 Nanocrystals in Flame-Assisted Chemical Vapor Deposition.

    PubMed

    Liu, Changran; Camacho, Joaquin; Wang, Hai

    2018-01-19

    Nano-scale titanium oxide (TiO 2 ) is a material useful for a wide range of applications. In a previous study, we showed that TiO 2 nanoparticles of both rutile and anatase crystal phases could be synthesized over the size range of 5 to 20 nm in flame-assisted chemical vapor deposition. Rutile was unexpectedly dominant in oxygen-lean synthesis conditions, whereas anatase is the preferred phase in oxygen-rich gases. The observation is in contrast to the 14 nm rutile-anatase crossover size derived from the existing crystal-phase equilibrium model. In the present work, we made additional measurements over a wider range of synthesis conditions; the results confirm the earlier observations. We propose an improved model for the surface energy that considers the role of oxygen desorption at high temperatures. The model successfully explains the observations made in the current and previous work. The current results provide a useful path to designing flame-assisted chemical vapor deposition of TiO 2 nanocrystals with controllable crystal phases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Interaction between phases in the liquid–gas system

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Berry, R. S., E-mail: bmsmirnov@gmail.com; Smirnov, B. M.

    This work analyzes the equilibrium between a liquid and a gas over this liquid separated by an interface. Various gas forms exist inside the liquid: dissolved gas molecules attached to solvent molecules, free gas molecules, and gaseous bubbles. Thermodynamic equilibrium is maintained between two phases; the first phase is the liquid containing dissolved and free molecules, and the second phase is the gas over the liquid and bubbles inside it. Kinetics of gas transition between the internal and external gas proceeds through bubbles and includes the processes of bubbles floating up and bubble growth as a result of association duemore » to the Smoluchowski mechanism. Evolution of a gas in the liquid is considered using the example of oxygen in water, and numerical parameters of this system are given. In the regime under consideration for an oxygen–water system, transport of oxygen into the surrounding air proceeds through micron-size bubbles with lifetimes of hours. This regime is realized if the total number of oxygen molecules in water is small compared with the numbers of solvated and free molecules in the liquid.« less

  14. Oxygen interaction with hexagonal OsB 2 at high temperature

    DOE PAGES

    Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina; ...

    2016-08-10

    The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure,more » sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.« less

  15. Oxygen interaction with hexagonal OsB 2 at high temperature

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina

    The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure,more » sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.« less

  16. Topical oxygen emulsion: a novel wound therapy.

    PubMed

    Davis, Stephen C; Cazzaniga, Alejandro L; Ricotti, Carlos; Zalesky, Paul; Hsu, Li-Chien; Creech, Jeffrey; Eaglstein, William H; Mertz, Patricia M

    2007-10-01

    To investigate the use of a topical oxygen emulsion (TOE), consisting of a supersaturated oxygen suspension using perfluorocarbon components, on second-degree burns and partial-thickness wounds. Oxygen is a required substance for various aspects of wound repair, and increased oxygen tension in a wound has been shown to stimulate phagocytosis and to reduce the incidence of wound infection. Second-degree burns and partial-thickness wounds were created on the backs of specific pathogen-free pigs. Wounds were then randomly assigned to 1 of the following treatment groups: TOE, TOE vehicle, or air-exposed control. Wounds were assessed for complete epithelialization using a salt-split technique. The TOE was able to significantly (P = .001) enhance the rate of epithelialization compared with both vehicle and untreated control. These data suggest that topical oxygen may be beneficial for acute and burn wounds. The results obtained from this double-blind, control, in vivo study demonstrate that TOE can significantly enhance the rate of epithelialization of partial-thickness excisional wounds and second-degree burns. These findings could have considerable clinical implications for patients with surgical and burn wounds by providing functional skin at an earlier date to act as a barrier against environmental factors, such as bacteria invasion. Other types of wounds may also benefit from this therapy (eg, chronic wounds and surgical incisions). Additional studies, including clinical studies, are warranted.

  17. TIME DEPENDENT NONEQUILIBRIUM IONIZATION OF TRANSITION REGION LINES OBSERVED WITH IRIS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Martínez-Sykora, Juan; Pontieu, Bart De; Hansteen, Viggo H.

    The properties of nonstatistical equilibrium ionization of silicon and oxygen ions are analyzed in this work. We focus on five solar targets (quiet Sun; coronal hole; plage; quiescent active region, AR; and flaring AR) as observed with the Interface Region Imaging Spectrograph (IRIS). IRIS is best suited for this work owing to the high cadence (up to 0.5 s), high spatial resolution (up to 0.″32), and high signal-to-noise ratios for O iv λ1401 and Si iv λ1402. We find that the observed intensity ratio between lines of three times ionized silicon and oxygen ions depends on their total intensity and that this correlationmore » varies depending on the region observed (quiet Sun, coronal holes, plage, or active regions) and on the specific observational objects present (spicules, dynamic loops, jets, microflares, or umbra). In order to interpret the observations, we compare them with synthetic profiles taken from 2D self-consistent radiative MHD simulations of the solar atmosphere, where the statistical equilibrium or nonequilibrium treatment of silicon and oxygen is applied. These synthetic observations show vaguely similar correlations to those in the observations, i.e., between the intensity ratios and their intensities, but only in the nonequilibrium case do we find that (some of) the observations can be reproduced. We conclude that these lines are formed out of statistical equilibrium. We use our time-dependent nonequilibrium ionization simulations to describe the physical mechanisms behind these observed properties.« less

  18. Oxygen transport properties estimation by DSMC-CT simulations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bruno, Domenico; Frezzotti, Aldo; Ghiroldi, Gian Pietro

    Coupling DSMC simulations with classical trajectories calculations is emerging as a powerful tool to improve predictive capabilities of computational rarefied gas dynamics. The considerable increase of computational effort outlined in the early application of the method (Koura,1997) can be compensated by running simulations on massively parallel computers. In particular, GPU acceleration has been found quite effective in reducing computing time (Ferrigni,2012; Norman et al.,2013) of DSMC-CT simulations. The aim of the present work is to study rarefied Oxygen flows by modeling binary collisions through an accurate potential energy surface, obtained by molecular beams scattering (Aquilanti, et al.,1999). The accuracy ofmore » the method is assessed by calculating molecular Oxygen shear viscosity and heat conductivity following three different DSMC-CT simulation methods. In the first one, transport properties are obtained from DSMC-CT simulations of spontaneous fluctuation of an equilibrium state (Bruno et al, Phys. Fluids, 23, 093104, 2011). In the second method, the collision trajectory calculation is incorporated in a Monte Carlo integration procedure to evaluate the Taxman’s expressions for the transport properties of polyatomic gases (Taxman,1959). In the third, non-equilibrium zero and one-dimensional rarefied gas dynamic simulations are adopted and the transport properties are computed from the non-equilibrium fluxes of momentum and energy. The three methods provide close values of the transport properties, their estimated statistical error not exceeding 3%. The experimental values are slightly underestimated, the percentage deviation being, again, few percent.« less

  19. Effect of Six Days of Staging on Physiologic Adjustments and Acute Mountain Sickness During Ascent to 4300 Meters

    DTIC Science & Technology

    2009-01-01

    respiratory alkalosis due to hyperventilation that was partially compensated for by increased excretion of HCO3 to maintain a normal pH following...carbon dioxide; RER, respiratory exchange quotient; Sao2, arterial oxygen saturation; Paco2, partial pressure of capillary-arterialized carbon dioxide...dioxide production; E=O2, ventilatory equivalent for oxygen; E=CO2, ventilatory equivalent for carbon dioxide; RER, respiratory exchange quotient

  20. Methanol partial oxidation on Ag(111) from first principles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.

    In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

  1. Methanol partial oxidation on Ag(111) from first principles

    DOE PAGES

    Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.; ...

    2016-10-26

    In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

  2. Method for forming bismuth-based superconducting ceramics

    DOEpatents

    Maroni, Victor A.; Merchant, Nazarali N.; Parrella, Ronald D.

    2005-05-17

    A method for reducing the concentration of non-superconducting phases during the heat treatment of Pb doped Ag/Bi-2223 composites having Bi-2223 and Bi-2212 superconducting phases is disclosed. A Pb doped Ag/Bi-2223 composite having Bi-2223 and Bi-2212 superconducting phases is heated in an atmosphere having an oxygen partial pressure not less than about 0.04 atmospheres and the temperature is maintained at the lower of a non-superconducting phase take-off temperature and the Bi-2223 superconducting phase grain growth take-off temperature. The oxygen partial pressure is varied and the temperature is varied between about 815.degree. C. and about 835.degree. C. to produce not less than 80 percent conversion to Pb doped Bi-2223 superconducting phase and not greater than about 20 volume percent non-superconducting phases. The oxygen partial pressure is preferably varied between about 0.04 and about 0.21 atmospheres. A product by the method is disclosed.

  3. An Evolutionary Comparison of the Handicap Principle and Hybrid Equilibrium Theories of Signaling.

    PubMed

    Kane, Patrick; Zollman, Kevin J S

    2015-01-01

    The handicap principle has come under significant challenge both from empirical studies and from theoretical work. As a result, a number of alternative explanations for honest signaling have been proposed. This paper compares the evolutionary plausibility of one such alternative, the "hybrid equilibrium," to the handicap principle. We utilize computer simulations to compare these two theories as they are instantiated in Maynard Smith's Sir Philip Sidney game. We conclude that, when both types of communication are possible, evolution is unlikely to lead to handicap signaling and is far more likely to result in the partially honest signaling predicted by hybrid equilibrium theory.

  4. Linear and nonlinear stability criteria for compressible MHD flows in a gravitational field

    NASA Astrophysics Data System (ADS)

    Moawad, S. M.; Moawad

    2013-10-01

    The equilibrium and stability properties of ideal magnetohydrodynamics (MHD) of compressible flow in a gravitational field with a translational symmetry are investigated. Variational principles for the steady-state equations are formulated. The MHD equilibrium equations are obtained as critical points of a conserved Lyapunov functional. This functional consists of the sum of the total energy, the mass, the circulation along field lines (cross helicity), the momentum, and the magnetic helicity. In the unperturbed case, the equilibrium states satisfy a nonlinear second-order partial differential equation (PDE) associated with hydrodynamic Bernoulli law. The PDE can be an elliptic or a parabolic equation depending on increasing the poloidal flow speed. Linear and nonlinear Lyapunov stability conditions under translational symmetric perturbations are established for the equilibrium states.

  5. Partial Reform Equilibrium in Russia: A Case Study of the Political Interests of and in the Russian Gas and Oil Industry

    NASA Astrophysics Data System (ADS)

    Everett, Rabekah

    While several theories abound that attempt to explain the obstacles to democracy in Russia, Joel Hellman's partial reform equilibrium model is an institutional theory that illustrates how weak institutions, combined with an instrumentalist cultural approach to the law and authoritarian-minded leadership, allowed the struggle over interests to craft and determine the nature of Russia's political structure. This thesis builds on the work of Hellman by using the partial reform theory to understand the evolution of interest infiltration and their impact on the formation of policies and institutions in favour of the elites or winners from 2004 to the present time period that allow them to wield law as a political weapon. The hypothesis posits that through their vested interests in state politics, the political and economic elites of the oil and gas industry have successfully stalled reform in Russia resulting in partial reform equilibrium. This is illustrated in a case study that was designed to collect the names, backgrounds, and social networks of gas and oil executives in order to determine how many of them have a history of, or are currently working as, ministers in the government or representatives in the Federation Council. The objective being to measure the degree to which gas and oil interests are present in government decision-making and conversely, the degree to which the government is present in the gas and oil industry. The thesis stresses the importance of institutional structure in determining Russia's political evolution, and uses vested interests as a primary source of structural institutional change, while also stressing on the social and international implications of this evolution.

  6. Magnetar giant flares in multipolar magnetic fields. I. Fully and partially open eruptions of flux ropes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Huang, Lei; Yu, Cong, E-mail: muduri@shao.ac.cn, E-mail: cyu@ynao.ac.cn

    2014-04-01

    We propose a catastrophic eruption model for the enormous energy release of magnetars during giant flares, in which a toroidal and helically twisted flux rope is embedded within a force-free magnetosphere. The flux rope stays in stable equilibrium states initially and evolves quasi-statically. Upon the loss of equilibrium, the flux rope cannot sustain the stable equilibrium states and erupts catastrophically. During the process, the magnetic energy stored in the magnetosphere is rapidly released as the result of destabilization of global magnetic topology. The magnetospheric energy that could be accumulated is of vital importance for the outbursts of magnetars. We carefullymore » establish the fully open fields and partially open fields for various boundary conditions at the magnetar surface and study the relevant energy thresholds. By investigating the magnetic energy accumulated at the critical catastrophic point, we find that it is possible to drive fully open eruptions for dipole-dominated background fields. Nevertheless, it is hard to generate fully open magnetic eruptions for multipolar background fields. Given the observational importance of the multipolar magnetic fields in the vicinity of the magnetar surface, it would be worthwhile to explore the possibility of the alternative eruption approach in multipolar background fields. Fortunately, we find that flux ropes may give rise to partially open eruptions in the multipolar fields, which involve only partial opening of background fields. The energy release fractions are greater for cases with central-arcaded multipoles than those with central-caved multipoles that emerged in background fields. Eruptions would fail only when the centrally caved multipoles become extremely strong.« less

  7. Method and apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

    DOEpatents

    Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H.J.

    2000-01-01

    An apparatus and a method are disclosed for converting hydrocarbon fuel or an alcohol into hydrogen gas and carbon dioxide. The apparatus includes a first vessel having a partial oxidation reaction zone and a separate steam reforming reaction zone that is distinct from the partial oxidation reaction zone. The first vessel has a first vessel inlet at the partial oxidation reaction zone and a first vessel outlet at the steam reforming zone. The reformer also includes a helical tube extending about the first vessel. The helical tube has a first end connected to an oxygen-containing source and a second end connected to the first vessel at the partial oxidation reaction zone. Oxygen gas from an oxygen-containing source can be directed through the helical tube to the first vessel. A second vessel having a second vessel inlet and second vessel outlet is annularly disposed about the first vessel. The helical tube is disposed between the first vessel and the second vessel and gases from the first vessel can be directed through second vessel.

  8. CO2 content of andesitic melts at graphite-saturated upper mantle conditions with implications for redox state of oceanic basalt source regions and remobilization of reduced carbon from subducted eclogite

    NASA Astrophysics Data System (ADS)

    Eguchi, James; Dasgupta, Rajdeep

    2017-03-01

    We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO2 contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1-3 GPa, 1375-1550 °C, and fO2 of FMQ -3.2 to FMQ -2.3 and the resulting experimental glasses were analyzed for CO2 and H2O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO2 content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO2 as molecular CO2: ln( K 0) = -21.79 ± 0.04, Δ V 0 = 32.91 ± 0.65 cm3mol-1, Δ H 0 = 107 ± 21 kJ mol-1, and dissolution of CO2 as CO3 2-: ln (K 0 ) = -21.38 ± 0.08, Δ V 0 = 30.66 ± 1.33 cm3 mol-1, Δ H 0 = 42 ± 37 kJ mol-1, where K 0 is the equilibrium constant at some reference pressure and temperature, Δ V 0 is the volume change of reaction, and Δ H 0 is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO2 contents and CO2/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO2 contents and CO2/Nb ratios of CO2-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO2-enriched basalts, and suggests that fO2 measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO2-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.

  9. [The effects of oxygen partial pressure changes on the osteometric markers of the bone tissue in rats].

    PubMed

    Berezovs'kyĭ, V Ia; Zamors'ka, T M; Ianko, R V

    2013-01-01

    Our purpose was to investigate the oxygen partial pressure changes on the osteometric and biochemical markers of bone tissue in rats. It was shown that breathing of altered gas mixture did not change the mass, general length, sagittal diameter and density thigh-bones in 12-month Wistar male-rats. The dosed normobaric hypoxia increased the activity of alkaline phosphatase and decreased the activity of tartrate-resistant acid phosphatase. At the same time normobaric hyperoxia with 40 and 90% oxygen conversely decreased the activity of alkaline phosphatase and increased the activity of tartrate-resistant acid phosphatase.

  10. Simultaneous imaging of cerebral partial pressure of oxygen and blood flow during functional activation and cortical spreading depression

    PubMed Central

    Sakadžić, Sava; Yuan, Shuai; Dilekoz, Ergin; Ruvinskaya, Svetlana; Vinogradov, Sergei A.; Ayata, Cenk; Boas, David A.

    2009-01-01

    We developed a novel imaging technique that provides real-time two-dimensional maps of the absolute partial pressure of oxygen and relative cerebral blood flow in rats by combining phosphorescence lifetime imaging with laser speckle contrast imaging. Direct measurement of blood oxygenation based on phosphorescence lifetime is not significantly affected by changes in the optical parameters of the tissue during the experiment. The potential of the system as a novel tool for quantitative analysis of the dynamic delivery of oxygen to support brain metabolism was demonstrated in rats by imaging cortical responses to forepaw stimulation and the propagation of cortical spreading depression waves. This new instrument will enable further study of neurovascular coupling in normal and diseased brain. PMID:19340106

  11. Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate

    NASA Astrophysics Data System (ADS)

    Colman, A. S.

    2016-02-01

    Phosphohydrolytic enzymes play an important role in phosphorus remineralization. As they release phosphate (Pi) from various organophosphorus compounds, these enzymes facilitate the transfer of oxygen atoms from water to the phosphoryl moieties. Most such enzymatic reactions impart a significant isotopic fractionation to the oxygen transferred. If this reaction occurs within a cell, then the resultant oxygen isotope signal is overprinted by continued recycling of the Pi. However, if this reaction occurs extracellularly, then the isotopic signal will be preserved until the Pi is transported back into a cell. Thus, the oxygen isotope composition of Pi (δ18Op) in an aquatic ecosystem can serve as a useful indicator of the mechanisms by which P is remineralized. We develop a time-dependent model illustrating the sensitivity of the δ18O of dissolved phosphate to various modes of P remineralization. The model is informed by cell lysis experiments that reveal the relative proportions of P­i that are directly liberated from cytosol vs. regenerated from co-liberated dissolved organic phosphorus compounds via extracellular hydrolysis. By incorporating both cellular uptake and release fluxes of P, we show that the degree of isotopic disequilibrium in an aquatic ecosystem can be a strong indicator of P remineralization mode. Apparent oxygen isotope equilibrium between Pi and water arises in this model as a steady-state scenario in which fractionation upon cellular uptake of Pi counterbalances the hydrolytic source flux of disequilibrated Pi. Low and high rates of extracellular phosphohydrolase activity are shown to produce steady-state δ18Op values that are respectively above or below thermodynamic equilibrium compositions.

  12. Effects of inoculum type and bulk dissolved oxygen concentration on achieving partial nitrification by entrapped-cell-based reactors.

    PubMed

    Rongsayamanont, Chaiwat; Limpiyakorn, Tawan; Khan, Eakalak

    2014-07-01

    An entrapment of nitrifiers into gel matrix is employed as a tool to fulfill partial nitrification under non-limiting dissolved oxygen (DO) concentrations in bulk solutions. This study aims to clarify which of these two attributes, inoculum type and DO concentration in bulk solutions, is the decisive factor for partial nitrification in an entrapped-cell based system. Four polyvinyl alcohol entrapped inocula were prepared to have different proportions of nitrite-oxidizing bacteria (NOB) and nitrite-oxidizing activity. At a DO concentration of 3 mg l(-1), the number of active NOB cells in an inoculum was the decisive factor for partial nitrification enhancement. However, when the DO concentration was reduced to 2 mg l(-1), all entrapped cell inocula showed similar degrees of partial nitrification. The results suggested that with the lower bulk DO concentration, the preparation of entrapped cell inocula is not useful as the DO level becomes the decisive factor for achieving partial nitrification. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. The Bohr Effect Is Not a Likely Promoter of Renal Preglomerular Oxygen Shunting

    PubMed Central

    Olgac, Ufuk; Kurtcuoglu, Vartan

    2016-01-01

    The aim of this study was to evaluate whether possible preglomerular arterial-to-venous oxygen shunting is affected by the interaction between renal preglomerular carbon dioxide and oxygen transport. We hypothesized that a reverse (venous-to-arterial) shunting of carbon dioxide will increase partial pressure of carbon dioxide and decrease pH in the arteries and thereby lead to increased oxygen offloading and consequent oxygen shunting. To test this hypothesis, we employed a segment-wise three-dimensional computational model of coupled renal oxygen and carbon dioxide transport, wherein coupling is achieved by shifting the oxygen-hemoglobin dissociation curve in dependence of local changes in partial pressure of carbon dioxide and pH. The model suggests that primarily due to the high buffering capacity of blood, there is only marginally increased acidity in the preglomerular vasculature compared to systemic arterial blood caused by carbon dioxide shunting. Furthermore, effects of carbon dioxide transport do not promote but rather impair preglomerular oxygen shunting, as the increase in acidity is higher in the veins compared to that in the arteries. We conclude that while substantial arterial-to-venous oxygen shunting might take place in the postglomerular vasculature, the net amount of oxygen shunted at the preglomerular vasculature appears to be marginal. PMID:27833564

  14. Toxicology

    NASA Technical Reports Server (NTRS)

    Macewen, J. W.

    1973-01-01

    Oxygen toxicity is examined, including the effects of oxygen partial pressure variations on toxicity and oxygen effects on ozone and nitrogen dioxide toxicity. Toxicity of fuels and oxidizers, such as hydrazines, are reported. Carbon monoxide, spacecraft threshold limit values, emergency exposure limits, spacecraft contaminants, and water quality standards for space missions are briefly summarized.

  15. Zero added oxygen for high quality sputtered ITO. A data science investigation of reduced Sn-content and added Zr

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peshek, Timothy J.; Burst, James M.; Coutts, Timothy J.

    Here, we demonstrate mobilities of >45 cm 2/V s for sputtered tin-doped indium oxide (ITO) films at zero added oxygen. All films were deposited with 5 wt. % SnO 2, instead of the more conventional 8–10 wt. %, and had varying ZrO 2 content from 0 to 3 wt. %, with a subsequent reduction in In 2O 3 content. Moreover, these films were deposited by radio-frequency magnetron sputtering from nominally stoichiometric targets with varying oxygen partial pressure in the sputter ambient. Anomalous behavior was discovered for films with no Zr-added, where a bimodality of high and low mobilities was discoveredmore » for nominally similar growth conditions. However, all films showed the lowest resistivity and highest mobilities when the oxygen partial pressure in the sputter ambient was zero. This result is contrasted with several other reports of ITO transport performance having a maximum for small but nonzero oxygen partial pressure. Our result is attributed to the reduced concentration of SnO 2. The addition of ZrO 2 yielded the highest mobilities at >55 cm 2/V s and the films showed a modest increase in optical transmission with increasing Zr-content.« less

  16. Effect of oxygen partial pressure on oxidation of Mo-metal

    NASA Astrophysics Data System (ADS)

    Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

    2018-05-01

    This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

  17. Endothelial microvesicles in hypoxic hypoxia diseases.

    PubMed

    Deng, Fan; Wang, Shuang; Xu, Riping; Yu, Wenqian; Wang, Xianyu; Zhang, Liangqing

    2018-05-29

    Hypoxic hypoxia, including abnormally low partial pressure of inhaled oxygen, external respiratory dysfunction-induced respiratory hypoxia and venous blood flow into the arterial blood, is characterized by decreased arterial oxygen partial pressure, resulting in tissue oxygen deficiency. The specific characteristics include reduced arterial oxygen partial pressure and oxygen content. Hypoxic hypoxia diseases (HHDs) have attracted increased attention due to their high morbidity and mortality and mounting evidence showing that hypoxia-induced oxidative stress, coagulation, inflammation and angiogenesis play extremely important roles in the physiological and pathological processes of HHDs-related vascular endothelial injury. Interestingly, endothelial microvesicles (EMVs), which can be induced by hypoxia, hypoxia-induced oxidative stress, coagulation and inflammation in HHDs, have emerged as key mediators of intercellular communication and cellular functions. EMVs shed from activated or apoptotic endothelial cells (ECs) reflect the degree of ECs damage, and elevated EMVs levels are present in several HHDs, including obstructive sleep apnoea syndrome and chronic obstructive pulmonary disease. Furthermore, EMVs have procoagulant, proinflammatory and angiogenic functions that affect the pathological processes of HHDs. This review summarizes the emerging roles of EMVs in the diagnosis, staging, treatment and clinical prognosis of HHDs. © 2018 The Authors. Journal of Cellular and Molecular Medicine published by John Wiley & Sons Ltd and Foundation for Cellular and Molecular Medicine.

  18. Zero added oxygen for high quality sputtered ITO. A data science investigation of reduced Sn-content and added Zr

    DOE PAGES

    Peshek, Timothy J.; Burst, James M.; Coutts, Timothy J.; ...

    2016-01-19

    Here, we demonstrate mobilities of >45 cm 2/V s for sputtered tin-doped indium oxide (ITO) films at zero added oxygen. All films were deposited with 5 wt. % SnO 2, instead of the more conventional 8–10 wt. %, and had varying ZrO 2 content from 0 to 3 wt. %, with a subsequent reduction in In 2O 3 content. Moreover, these films were deposited by radio-frequency magnetron sputtering from nominally stoichiometric targets with varying oxygen partial pressure in the sputter ambient. Anomalous behavior was discovered for films with no Zr-added, where a bimodality of high and low mobilities was discoveredmore » for nominally similar growth conditions. However, all films showed the lowest resistivity and highest mobilities when the oxygen partial pressure in the sputter ambient was zero. This result is contrasted with several other reports of ITO transport performance having a maximum for small but nonzero oxygen partial pressure. Our result is attributed to the reduced concentration of SnO 2. The addition of ZrO 2 yielded the highest mobilities at >55 cm 2/V s and the films showed a modest increase in optical transmission with increasing Zr-content.« less

  19. Moderate hyperventilation during intravenous anesthesia increases net cerebral lactate efflux.

    PubMed

    Grüne, Frank; Kazmaier, Stephan; Sonntag, Hans; Stolker, Robert Jan; Weyland, Andreas

    2014-02-01

    Hyperventilation is known to decrease cerebral blood flow (CBF) and to impair cerebral metabolism, but the threshold in patients undergoing intravenous anesthesia is unknown. The authors hypothesized that reduced CBF associated with moderate hyperventilation might impair cerebral aerobic metabolism in patients undergoing intravenous anesthesia. Thirty male patients scheduled for coronary surgery were included in a prospective, controlled crossover trial. Measurements were performed under fentanyl-midazolam anesthesia in a randomized sequence aiming at partial pressures of carbon dioxide of 30 and 50 mmHg. Endpoints were CBF, blood flow velocity in the middle cerebral artery, and cerebral metabolic rates for oxygen, glucose, and lactate. Global CBF was measured using a modified Kety-Schmidt technique with argon as inert gas tracer. CBF velocity of the middle cerebral artery was recorded by transcranial Doppler sonography. Data were presented as mean (SD). Two-sided paired t tests and one-way ANOVA for repeated measures were used for statistical analysis. Moderate hyperventilation significantly decreased CBF by 60%, blood flow velocity by 41%, cerebral oxygen delivery by 58%, and partial pressure of oxygen of the jugular venous bulb by 45%. Cerebral metabolic rates for oxygen and glucose remained unchanged; however, net cerebral lactate efflux significantly increased from -0.38 (2.18) to -2.41(2.43) µmol min 100 g. Moderate hyperventilation, when compared with moderate hypoventilation, in patients with cardiovascular disease undergoing intravenous anesthesia increased net cerebral lactate efflux and markedly reduced CBF and partial pressure of oxygen of the jugular venous bulb, suggesting partial impairment of cerebral aerobic metabolism at clinically relevant levels of hypocapnia.

  20. Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO2

    PubMed Central

    Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

    2016-01-01

    In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO2 powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO2 films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO2 up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO2. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model. PMID:28773351

  1. Atomic oxygen protective coating with resistance to undercutting at defect sites

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

    1994-01-01

    Structures composed at least partially of an organic substrate may be protected from oxidation by applying a catalyst onto said substrate for promoting the combination of atomic oxygen to molecular oxygen. The structure may also be protected by applying both a catalyst and an atomic oxygen shielding layer onto the substrate. The structures to be protected include spacecraft surfaces.

  2. Changes of oxygen content in facial skin before and after cigarette smoking.

    PubMed

    Fan, Guo-Biao; Wu, Pei-Lan; Wang, Xue-Min

    2012-11-01

    Cigarette smoking not only causes systemic health problems, but may also be an underlying cause of premature skin aging. Cigarette smokers frequently have morphological changes in facial skin that may be attributed to reduced oxygen in this region. The purpose of this study was to measure the oxygen content in facial skin before and after smoking. Twenty-five volunteers participated in this study. Changes in oxygen content of the facial skin were measured before and after 30 min of cigarette smoking. Skin temperature and oxygen content were evaluated in the periorbital and periolar regions. There was a significant increase in temperature after smoking. The oxy hemoglobin and partial pressure of oxygen decreased in both the periocular and perioral areas after smoking. There were no changes in deoxy hemoglobin and partial pressure of carbon dioxide at these areas. Significant changes were seen in temperature and oxygen content after only 30 min of smoking. The results from this study suggest that alterations in the skin temperature and oxygen content in facial skin after smoking may be an underlying cause of premature skin aging. © 2011 John Wiley & Sons A/S.

  3. Origin and history of chondrite regolith, fragmental and impact-melt breccias from Spain

    NASA Technical Reports Server (NTRS)

    Casanova, I.; Keil, K.; Wieler, R.; San Miguel, A.; King, E. A.

    1990-01-01

    Six ordinary chondrite breccias from the Museo Nacional de Ciencias Naturales, Madrid (Spain), are described and classified as follows: the solar gas-rich regolith breccia Oviedo (H5); the premetamorphic fragmental breccias Cabezo de Mayo (type 6, L-LL), and Sevilla (LL4); the fragmental breccias Canellas (H4) and Gerona (H5); and the impact melt breccia, Madrid (L6). It is confirmed that chondrites with typical light-dark structures and petrographic properties typical of regolith breccias may (Oviedo) or may not (Canellas) be solar gas-rich. Cabezo de Mayo and Sevilla show convincing evidence that they were assembled prior to peak metamorphism and were equilibrated during subsequent reheating. Compositions of olivine and low-Ca pyroxene in host chondrite and breccia clasts in Cabezo de Mayo are transitional between groups L and LL. It is suggested, based on mineralogic and oxygen isotopic compositions of host and clasts, that the rock formed on the L parent body by mixing, prior to peak metamorphism. This was followed by partial equilibrium of two different materials: the indigenous L chondrite host and exotic LL melt rock clasts.

  4. Origin and history of chondrite regolith, fragmental and impact-melt breccias from Spain

    NASA Astrophysics Data System (ADS)

    Casanova, I.; Keil, K.; Wieler, R.; San Miguel, A.; King, E. A.

    1990-06-01

    Six ordinary chondrite breccias from the Museo Nacional de Ciencias Naturales, Madrid (Spain), are described and classified as follows: the solar gas-rich regolith breccia Oviedo (H5); the premetamorphic fragmental breccias Cabezo de Mayo (type 6, L-LL), and Sevilla (LL4); the fragmental breccias Canellas (H4) and Gerona (H5); and the impact melt breccia, Madrid (L6). It is confirmed that chondrites with typical light-dark structures and petrographic properties typical of regolith breccias may (Oviedo) or may not (Canellas) be solar gas-rich. Cabezo de Mayo and Sevilla show convincing evidence that they were assembled prior to peak metamorphism and were equilibrated during subsequent reheating. Compositions of olivine and low-Ca pyroxene in host chondrite and breccia clasts in Cabezo de Mayo are transitional between groups L and LL. It is suggested, based on mineralogic and oxygen isotopic compositions of host and clasts, that the rock formed on the L parent body by mixing, prior to peak metamorphism. This was followed by partial equilibrium of two different materials: the indigenous L chondrite host and exotic LL melt rock clasts.

  5. The primary solar-type atmosphere surrounding the accreting Earth: H2O-induced high surface temperature.

    NASA Astrophysics Data System (ADS)

    Sasaki, S.

    In the solar nebula, a growing planet attracts ambient gas to form a solar-type atmosphere. The structure of this H2-He atmosphere is calculated assuming the Earth was formed in the nebula. The blanketing effect of the atmosphere renders the planetary surface molten when the planetary mass exceeds 0.2 ME (ME being the present Earth's mass). Reduction of the surface melt by atmospheric H2 should add a large amount of H2O to the atmosphere: under the quartz-iron-fayalite oxygen buffer, partial pressure ratio P(H2O)/P(H2) becomes higher than 0.1. Enhancing opacity and gas mean molecular weight, the excess H2O raises the temperature and renders the atmosphere in convective equilibrium, while the dissociation of H2 suppresses the adiabatic temperature gradient. The surface temperature of the proto-Earth can be as high as 4700K when its mass is 1 ME. Such a high temperature may accelerate the evaporation of surface materials. A deep totally-molten magma ocean should exist in the accretion Earth.

  6. Nonflat equilibrium liquid shapes on flat surfaces.

    PubMed

    Starov, Victor M

    2004-01-15

    The hydrostatic pressure in thin liquid layers differs from the pressure in the ambient air. This difference is caused by the actions of surface forces and capillary pressure. The manifestation of the surface force action is the disjoining pressure, which has a very special S-shaped form in the case of partial wetting (aqueous thin films and thin films of aqueous electrolyte and surfactant solutions, both free films and films on solid substrates). In thin flat liquid films the disjoining pressure acts alone and determines their thickness. However, if the film surface is curved then both the disjoining and the capillary pressures act simultaneously. In the case of partial wetting their simultaneous action results in the existence of nonflat equilibrium liquid shapes. It is shown that in the case of S-shaped disjoining pressure isotherm microdrops, microdepressions, and equilibrium periodic films exist on flat solid substrates. Criteria are found for both the existence and the stability of these nonflat equilibrium liquid shapes. It is shown that a transition from thick films to thinner films can go via intermediate nonflat states, microdepressions and periodic films, which both can be more stable than flat films within some range of hydrostatic pressure. Experimental investigations of shapes of the predicted nonflat layers can open new possibilities of determination of disjoining pressure in the range of thickness in which flat films are unstable.

  7. Stability of high-speed boundary layers in oxygen including chemical non-equilibrium effects

    NASA Astrophysics Data System (ADS)

    Klentzman, Jill; Tumin, Anatoli

    2013-11-01

    The stability of high-speed boundary layers in chemical non-equilibrium is examined. A parametric study varying the edge temperature and the wall conditions is conducted for boundary layers in oxygen. The edge Mach number and enthalpy ranges considered are relevant to the flight conditions of reusable hypersonic cruise vehicles. Both viscous and inviscid stability formulations are used and the results compared to gain insight into the effects of viscosity and thermal conductivity on the stability. It is found that viscous effects have a strong impact on the temperature and mass fraction perturbations in the critical layer and in the viscous sublayer near the wall. Outside of these areas, the perturbations closely match in the viscous and inviscid models. The impact of chemical non-equilibrium on the stability is investigated by analyzing the effects of the chemical source term in the stability equations. The chemical source term is found to influence the growth rate of the second Mack mode instability but not have much of an effect on the mass fraction eigenfunction for the flow parameters considered. This work was supported by the AFOSR/NASA/National Center for Hypersonic Laminar-Turbulent Transition Research.

  8. Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

    USGS Publications Warehouse

    Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

    1978-01-01

    Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

  9. The distribution of chromium among orthopyroxene, spinel and silicate liquid at atmospheric pressure

    NASA Technical Reports Server (NTRS)

    Barnes, S. J.

    1986-01-01

    The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.

  10. Mechanical Integrity of Flexible In-Zn-Sn-O Film for Flexible Transparent Electrode

    NASA Astrophysics Data System (ADS)

    Kim, Young Sung; Oh, Se-In; Choa, Sung-Hoon

    2013-05-01

    The mechanical integrity of transparent In-Zn-Sn-O (IZTO) films is investigated using outer/inner bending, stretching, and twisting tests. Amorphous IZTO films are grown using a pulsed DC magnetron sputtering system with an IZTO target on a polyimide substrate at room temperature. Changes in the optical and electrical properties of IZTO films depend on the oxygen partial pressure applied during the film deposition process. In the case of 3% oxygen partial pressure, the IZTO films exhibit s resistivity of 8.3×10-4 Ω cm and an optical transmittance of 86%. The outer bending test shows that the critical bending radius decreases from 10 to 7.5 mm when the oxygen partial pressure is increased from 1 to 3%. The inner bending test reveals that the critical bending radius of all IZTO films is 3.5 mm regardless of oxygen partial pressure. The IZTO films also show excellent mechanical reliability in the bending fatigue tests of more than 10,000 cycles. In the uniaxial stretching tests, the electrical resistance of the IZTO film does not change until a strain of 2.4% is reached. The twisting tests demonstrate that the electrical resistance of IZTO films remains unchanged up to 25°. These results suggest that IZTO films have excellent mechanical durability and flexibility in comparison with already reported crystallized indium tin oxide (ITO) films.

  11. Nonflammable organic-base paint for oxygen-rich atmospheres

    NASA Technical Reports Server (NTRS)

    Harwell, R. J.; Key, C. F.; Krupnick, A. C.

    1971-01-01

    New paint formulations, which combine aqueous latex paints with inorganic pigments and additives, produce coatings that are self-extinguishing in pure oxygen at pressures up to twice the partial pressure of atmospheric oxygen. A paint formulation in percent by weight is given and the properties of resultant coatings are discussed.

  12. Turbulent piloted partially-premixed flames with varying levels of O2/N2: stability limits and PDF calculations

    NASA Astrophysics Data System (ADS)

    Juddoo, Mrinal; Masri, Assaad R.; Pope, Stephen B.

    2011-12-01

    This paper reports measured stability limits and PDF calculations of piloted, turbulent flames of compressed natural gas (CNG) partially-premixed with either pure oxygen, or with varying levels of O2/N2. Stability limits are presented for flames of CNG fuel premixed with up to 20% oxygen as well as CNG-O2-N2 fuel where the O2 content is varied from 8 to 22% by volume. Calculations are presented for (i) Sydney flame B [Masri et al. 1988] which uses pure CNG as well as flames B15 to B25 where the CNG is partially-premixed with 15-25% oxygen by volume, respectively and (ii) Sandia methane-air (1:3 by volume) flame E [Barlow et al. 2005] as well as new flames E15 and E25 that are partially-premixed with 'reconstituted air' where the O2 content in nitrogen is 15 and 25% by volume, respectively. The calculations solve a transported PDF of composition using a particle-based Monte Carlo method and employ the EMST mixing model as well as detailed chemical kinetics. The addition of oxygen to the fuel increases stability, shortens the flames, broadens the reaction zone, and shifts the stoichiometric mixture fraction towards the inner side of the jet. It is found that for pure CNG flames where the reaction zone is narrow (∼0.1 in mixture fraction space), the PDF calculations fail to reproduce the correct level of local extinction on approach to blow-off. A broadening in the reaction zone up to about 0.25 in mixture fraction space is needed for the PDF/EMST approach to be able to capture these finite-rate chemistry effects. It is also found that for the same level of partial premixing, increasing the O2/N2 ratio increases the maximum levels of CO and NO but shifts the peak to richer mixture fractions. Over the range of oxygenation investigated here, stability limits have shown to improve almost linearly with increasing oxygen levels in the fuel and with increasing the contribution of release rate from the pilot.

  13. Crystal-liquid-vapor equilibrium experiments at high temperature (less than or equal to 1800 C) and low, controlled oxygen and hydrogen pressure (10(-1) to 10(-9) PA)

    NASA Technical Reports Server (NTRS)

    Mysen, B. O.

    1987-01-01

    Evidence from carbonaceous chrondrites points to refractory oxides in the system CaO-MgO-Al2O3-TiO2-SiO2-Fe-O as being among the earliest phases to condense from the solar nebula. It is necessary to establish the equilibrium relationships between the relevant crystalline and amorphous phases before the chemical constraints can be meaningfully applied to models of solar system history. Preliminary experiments on earth show that such experiments are feasible. Earth-based experiments suffer from several unavoidable problems. These problems can be overcome by experimentation in the Space Station where the experiments can be conducted under near static pressure conditions and where total pressure equals the sum of controlled hydrogen and oxygen pressures and can be controlled for periods exceeding several hours.

  14. 57Fe Mössbauer spectroscopy of mineral assemblages in mantle spinel lherzolites from Cenozoic alkali basalt, eastern China: Petrological applications

    NASA Astrophysics Data System (ADS)

    Hao, Xi-Luo; Li, Yi-Liang

    2013-01-01

    Mineral assemblages in spinel lherzolite xenoliths from the Cenozoic alkali basalt of eastern China were analyzed by 57Fe Mössbauer spectroscopy for Fe3+/ΣFe and distribution of Fe2+/Fe3+ in non-equivalent crystal cites. Orthopyroxene, clinopyroxene and spinel have 0.08-0.13, 0.19-0.31 and 0.13-0.23 Fe3+/ΣFe, respectively. The cation-exchange equilibrium temperatures, Fe3+ partition coefficient and oxygen fugacity of the upper mantle peridotites were calculated. The equilibrium temperatures are between 1103 K and 1405 K consistent with those reported elsewhere. The oxygen fugacities of spinel lherzolites calculated with olivine-orthopyroxene-spinel (ΔlogƒO2 from - 1.1 to 0) and clinopyroxene-olivine-orthopyroxene oxybarometers (ΔlogƒO2 from - 2.0 to 0.7) are consistent with previously reported upper mantle values.

  15. Implementation of Radiation, Ablation, and Free Energy Minimization Modules for Coupled Simulations of Hypersonic Flow

    NASA Technical Reports Server (NTRS)

    Gnoffo, Peter A.; Johnston, Christopher O.; Thompson, Richard A.

    2009-01-01

    A description of models and boundary conditions required for coupling radiation and ablation physics to a hypersonic flow simulation is provided. Chemical equilibrium routines for varying elemental mass fraction are required in the flow solver to integrate with the equilibrium chemistry assumption employed in the ablation models. The capability also enables an equilibrium catalytic wall boundary condition in the non-ablating case. The paper focuses on numerical implementation issues using FIRE II, Mars return, and Apollo 4 applications to provide context for discussion. Variable relaxation factors applied to the Jacobian elements of partial equilibrium relations required for convergence are defined. Challenges of strong radiation coupling in a shock capturing algorithm are addressed. Results are presented to show how the current suite of models responds to a wide variety of conditions involving coupled radiation and ablation.

  16. Thin-film nano-thermogravimetry applied to praseodymium-cerium oxide films at high temperatures

    NASA Astrophysics Data System (ADS)

    Schröder, Sebastian; Fritze, Holger; Bishop, Sean; Chen, Di; Tuller, Harry L.

    2018-05-01

    High precision measurements of oxygen nonstoichiometry δ in thin film metal oxides MaOb±δ at elevated temperatures and controlled oxygen partial pressures pO2 are reported with the aid of resonant microbalances. The resonant microbalances applied here consisted of y-cut langasite (La3Ga5SiO14) and CTGS (Ca3TaGa3Si2O14) piezoelectric resonators, operated in the thickness shear mode at ˜5 MHz. Measurements of variations in δ of Pr0.1Ce0.9O2-δ (PCO) films are reported for the oxygen partial pressure range from 10-8 bar to 0.2 bar at 700 °C, and these results were found to be in good agreement with previously reported oxygen nonstoichiometry δ data derived from chemical capacitance studies. The PCO thin-films were deposited via pulsed laser deposition on both sides of the resonators, whose series resonance frequency was tracked, converted into mass changes and, finally, into nonstoichiometry. The nonstoichiometry was observed to reach a plateau as the oxygen partial pressure dropped below about 10-5 bar, the behavior being attributed to the full reduction of Pr to the trivalent state. These resonators enable stable operation up to temperatures above 1000 °C, thereby maintaining high mass resolution suitable for determining oxygen nonstoichiometry variations in thin films deposited on such resonators. For the given experimental conditions, a mass resolution of ˜50 ng was achieved at 700 °C with the CTGS resonator.

  17. Coexpression of Human α- and Circularly Permuted β-Globins Yields a Hemoglobin with Normal R State but Modified T State Properties†

    PubMed Central

    Asmundson, Anna L.; Taber, Alexandria M.; van der Walde, Adella; Lin, Danielle H.; Olson, John S.; Anthony-Cahill, Spencer J.

    2009-01-01

    For the first time, a circularly permuted human β-globin (cpβ) has been coexpressed with human α-globin in bacterial cells and shown to associate to form α-cpβ hemoglobin in solution. Flash photolysis studies of α-cpβ show markedly biphasic CO and O2 kinetics with the amplitudes for the fast association phases being dominant due the presence of large amounts of high-affinity liganded hemoglobin dimers. Extensive dimerization of liganded but not deoxygenated α-cpβ was observed by gel chromatography. The rate constants for O2 and CO binding to the R state forms of α-cpβ are almost identical to those of native HbA (k′R(CO) ≈ 5.0 μM−1 s−1; k′R(O2) ≈ 50 μM−1 s−1), and the rate of O2 dissociation from fully oxygenated α-cpβ is also very similar to that observed for HbA (kR(O2) ≈ 21–28 s−1). When the equilibrium deoxyHb form of α-cpβ is reacted with CO in rapid mixing experiments, the observed time courses are monophasic and the observed bimolecular association rate constant is ∼1.0 μM−1 s−1, which is intermediate between the R state rate measured in partial photolysis experiments (∼5 μM−1 s−1) and that observed for T state deoxyHbA (k′T(CO) ≈ 0.1 to 0.2 μM−1 s−1). Thus the deoxygenated permutated β subunits generate an intermediate, higher affinity, deoxyHb quaternary state. This conclusion is supported by equilibrium oxygen binding measurements in which α-cpβ exhibits a P50 of ∼1.5 mmHg and a low n-value (∼1.3) at pH 7, 20 °C, compared to 8.5 mmHg and n ≈ 2.8 for native HbA under identical, dilute conditions. PMID:19397368

  18. Effect of reducing inspired oxygen concentration on oxygenation parameters during general anaesthesia in horses in lateral or dorsal recumbency.

    PubMed

    Uquillas, E; Dart, C M; Perkins, N R; Dart, A J

    2018-01-01

    To compare the effects of two concentrations of oxygen delivered to the anaesthetic breathing circuit on oxygenation in mechanically ventilated horses anaesthetised with isoflurane and positioned in dorsal or lateral recumbency. Selected respiratory parameters and blood lactate were measured and oxygenation indices calculated, before and during general anaesthesia, in 24 laterally or dorsally recumbent horses. Horses were randomly assigned to receive 100% or 60% oxygen during anaesthesia. All horses were anaesthetised using the same protocol and intermittent positive pressure ventilation (IPPV) was commenced immediately following anaesthetic induction and endotracheal intubation. Arterial blood gas analysis was performed and oxygenation indices calculated before premedication, immediately after induction, at 10 and 45 min after the commencement of mechanical ventilation, and in recovery. During anaesthesia, the arterial partial pressure of oxygen was adequate in all horses, regardless of position of recumbency or the concentration of oxygen provided. At 10 and 45 min after commencing IPPV, the arterial partial pressure of oxygen was lower in horses in dorsal recumbency compared with those in lateral recumbency, irrespective of the concentration of oxygen supplied. Based on oxygenation indices, pulmonary function during general anaesthesia in horses placed in dorsal recumbency was more compromised than in horses in lateral recumbency, irrespective of the concentration of oxygen provided. During general anaesthesia, using oxygen at a concentration of 60% instead of 100% maintains adequate arterial oxygenation in horses in dorsal or lateral recumbency. However, it will not reduce pulmonary function abnormalities induced by anaesthesia and recumbency. © 2017 Australian Veterinary Association.

  19. First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

    NASA Astrophysics Data System (ADS)

    Qi, Y.; Liu, X.; Kang, J.; He, L.

    2017-12-01

    Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

  20. Hemoglobin Hiroshima (β143 histidine → aspartic acid): a newly identified fast moving beta chain variant associated with increased oxygen affinity and compensatory erythremia

    PubMed Central

    Hamilton, Howard B.; Iuchi, Iwao; Miyaji, Takaoki; Shibata, Susumu

    1969-01-01

    During a survey for hemoglobinopathies in over 9000 residents of Hiroshima Prefecture, Japan, a fast moving hemoglobin was identified in eight members of three generations in a Japanese family. The abnormal hemoglobin, named Hb Hiroshima, constitutes about 50% of the total hemoglobin in hemolysates from the carriers who have a mild erythremia but are otherwise apparently clinically unaffected. All preparations of Hb Hiroshima have increased affinity for oxygen, by either tonometric or oxygen electrode determinations. At pH 7.0, the oxygen pressure, P50 required to half saturate an unfractionated hemolysate from a carrier was one-half that of Hb A, and the P50 of a purified sample containing no Hb A was one-fourth that of Hb A. The pH dependence of the oxygen equilibrium (Bohr effect) is below normal, as shown by the absolute value of the Bohr effect factor which is about half that of Hb A, in the pH range between 7.0 and 7.4. The Hill constant, n, for Hb Hiroshima between pH 7.0 and 7.4 is 2-2.4, compared to 2.8-3 for Hb A under the same conditions, indicating reduction of, but not complete abolition of heme-heme interaction. Urea dissociation and canine hybridization tests located the biochemical lesion in the beta chain. Fingerprints (Ingram), carboxypeptidase digestion, and amino acid analysis demonstrated that the substitution was at residue 143 in the beta chain, where histidine was replaced by aspartic acid. In contrast to other recently described high oxygen affinity mutants that show intact Bohr effects, all three of the major characteristics of the reversible combination of hemoglobin with oxygen (oxygen equilibrium, heme-heme interaction, and pH dependence) are affected in Hb Hiroshima. A tentative interpretation of these effects, relating structure to function, is offered in terms of recently developed models of normal hemoglobin. Images PMID:5773089

  1. An Evolutionary Comparison of the Handicap Principle and Hybrid Equilibrium Theories of Signaling

    PubMed Central

    Kane, Patrick; Zollman, Kevin J. S.

    2015-01-01

    The handicap principle has come under significant challenge both from empirical studies and from theoretical work. As a result, a number of alternative explanations for honest signaling have been proposed. This paper compares the evolutionary plausibility of one such alternative, the “hybrid equilibrium,” to the handicap principle. We utilize computer simulations to compare these two theories as they are instantiated in Maynard Smith’s Sir Philip Sidney game. We conclude that, when both types of communication are possible, evolution is unlikely to lead to handicap signaling and is far more likely to result in the partially honest signaling predicted by hybrid equilibrium theory. PMID:26348617

  2. Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

    2016-02-01

    We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

  3. STRUCTURE AND PHYSICAL PROPERTIES OF SOLID AND LIQUID VANADIUM PENTOXIDE.

    DTIC Science & Technology

    The electrical resistivity of near-stoichiometric crystalline V2O5 was measured as a function of crystal orientation and oxygen partial pressure from...25C to 300C. Conductivity is insensitive to ambient atmosphere. The activation energy for conduction is 0.20 ev. Molten V2O5 , however, is...sensitive to oxygen partial pressure. Its conductivity is proportional to P-O2 to the -1/6th power. Anomalously high electrical resistivity was observed for glassy V2O5 films. (Author)

  4. 40 CFR 61.341 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... to industrial organic chemicals, organic pesticide products, pharmaceutical preparations, paint and allied products, fertilizers, and agricultural chemicals. Examples of chemical manufacturing plants...). Maximum organic vapor pressure means the equilibrium partial pressure exerted by the waste at the...

  5. Advances in Probes and Methods for Clinical EPR Oximetry

    PubMed Central

    Hou, Huagang; Khan, Nadeem; Jarvis, Lesley A.; Chen, Eunice Y.; Williams, Benjamin B.; Kuppusamy, Periannan

    2015-01-01

    EPR oximetry, which enables reliable, accurate, and repeated measurements of the partial pressure of oxygen in tissues, provides a unique opportunity to investigate the role of oxygen in the pathogenesis and treatment of several diseases including cancer, stroke, and heart failure. Building on significant advances in the in vivo application of EPR oximetry for small animal models of disease, we are developing suitable probes and instrumentation required for use in human subjects. Our laboratory has established the feasibility of clinical EPR oximetry in cancer patients using India ink, the only material presently approved for clinical use. We now are developing the next generation of probes, which are both superior in terms of oxygen sensitivity and biocompatibility including an excellent safety profile for use in humans. Further advances include the development of implantable oxygen sensors linked to an external coupling loop for measurements of deep-tissue oxygenations at any depth, overcoming the current limitation of 10 mm. This paper presents an overview of recent developments in our ability to make meaningful measurements of oxygen partial pressures in human subjects under clinical settings. PMID:24729217

  6. Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

    NASA Technical Reports Server (NTRS)

    Heinemann, K.; Rao, D. B.; Douglass, D. L.

    1975-01-01

    Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

  7. Plateau Waves of Intracranial Pressure and Partial Pressure of Cerebral Oxygen.

    PubMed

    Lang, Erhard W; Kasprowicz, Magdalena; Smielewski, Peter; Pickard, John; Czosnyka, Marek

    2016-01-01

    This study investigates 55 intracranial pressure (ICP) plateau waves recorded in 20 patients after severe traumatic brain injury (TBI) with a focus on a moving correlation coefficient between mean arterial pressure (ABP) and ICP, called PRx, which serves as a marker of cerebrovascular reactivity, and a moving correlation coefficient between ABP and cerebral partial pressure of oxygen (pbtO2), called ORx, which serves as a marker for cerebral oxygen reactivity. ICP and ICPamplitude increased significantly during the plateau waves, whereas CPP and pbtO2 decreased significantly. ABP, ABP amplitude, and heart rate remained unchanged. In 73 % of plateau waves PRx increased during the wave. ORx showed an increase during and a decrease after the plateau waves, which was not statistically significant. Our data show profound cerebral vasoparalysis on top of the wave and, to a lesser extent, impairment of cerebral oxygen reactivity. The different behavior of the indices may be due to the different latencies of the cerebral blood flow and oxygen level control mechanisms. While cerebrovascular reactivity is a rapidly reacting mechanism, cerebral oxygen reactivity is slower.

  8. New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

    NASA Astrophysics Data System (ADS)

    Sade, Ziv; Halevy, Itay

    2017-10-01

    CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

  9. Effect of oxygen partial pressure and VO2 content on hexagonal WO3 thin films synthesized by pulsed laser deposition technique

    NASA Astrophysics Data System (ADS)

    Kaushal, Ajay; Kaur, Davinder

    2011-06-01

    We report on the effect of oxygen partial pressure and vacuum annealing on structural and optical properties of pulsed laser-deposited nanocrystalline WO3 thin films. XRD results show the hexagonal phase of deposited WO3 thin films. The crystallite size was observed to increase with increase in oxygen partial pressure. Vacuum annealing changed the transparent as-deposited WO3 thin film to deep shade of blue color which increases the optical absorption of the film. The origin of this blue color could be due to the presence of oxygen vacancies associated with tungsten ions in lower oxidation states. In addition, the effects of VO2 content on structural, electrochemical, and optical properties of (WO3)1- x (VO2) x nanocomposite thin films have also been systematically investigated. Cyclic voltammogram exhibits a modification with the appearance of an extra cathodic peak for VO2-WO3 thin film electrode with higher VO2 content ( x ≥ 0.2). Increase of VO2 content in (WO3)1- x (VO2) x films leads to red shift in optical band gap.

  10. Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

    2017-02-01

    A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

  11. The oxidation state of the mantle and the extraction of carbon from Earth's interior.

    PubMed

    Stagno, Vincenzo; Ojwang, Dickson O; McCammon, Catherine A; Frost, Daniel J

    2013-01-03

    Determining the oxygen fugacity of Earth's silicate mantle is of prime importance because it affects the speciation and mobility of volatile elements in the interior and has controlled the character of degassing species from the Earth since the planet's formation. Oxygen fugacities recorded by garnet-bearing peridotite xenoliths from Archaean lithosphere are of particular interest, because they provide constraints on the nature of volatile-bearing metasomatic fluids and melts active in the oldest mantle samples, including those in which diamonds are found. Here we report the results of experiments to test garnet oxythermobarometry equilibria under high-pressure conditions relevant to the deepest mantle xenoliths. We present a formulation for the most successful equilibrium and use it to determine an accurate picture of the oxygen fugacity through cratonic lithosphere. The oxygen fugacity of the deepest rocks is found to be at least one order of magnitude more oxidized than previously estimated. At depths where diamonds can form, the oxygen fugacity is not compatible with the stability of either carbonate- or methane-rich liquid but is instead compatible with a metasomatic liquid poor in carbonate and dominated by either water or silicate melt. The equilibrium also indicates that the relative oxygen fugacity of garnet-bearing rocks will increase with decreasing depth during adiabatic decompression. This implies that carbon in the asthenospheric mantle will be hosted as graphite or diamond but will be oxidized to produce carbonate melt through the reduction of Fe(3+) in silicate minerals during upwelling. The depth of carbonate melt formation will depend on the ratio of Fe(3+) to total iron in the bulk rock. This 'redox melting' relationship has important implications for the onset of geophysically detectable incipient melting and for the extraction of carbon dioxide from the mantle through decompressive melting.

  12. Using permeable membranes to produce hydrogen and oxygen from water

    NASA Technical Reports Server (NTRS)

    Sanders, A. P.; Williams, R. J.; Downs, W. R.; Mcbryar, H.

    1975-01-01

    Concept may make it profitable to obtain hydrogen fuel from water. Laboratory tests have demonstrated that method enables decomposition of water several orders of magnitude beyond equilibrium state where only small amounts of free hydrogen are present.

  13. Singlet delta oxygen generation for Chemical Oxygen-Iodine Lasers

    NASA Astrophysics Data System (ADS)

    Georges, E.; Mouthon, A.; Barraud, R.

    1991-10-01

    The development of Chemical Oxygen-Iodine Lasers is based on the generation of singlet delta oxygen. To improve the overall efficiency of these lasers, it is necessary to increase the generator production and yield of singlet delta oxygen at low and high pressure, respectively, for subsonic and supersonic lasers. Furthermore, the water vapor content must be as low as possible. A generator model, based on gas-liquid reaction and liquid-vapor equilibrium theories associated with thermophysical evaluations is presented. From model predictions, operating conditions have been drawn to attain the following experimental results in a bubble-column: by increasing the superficial gas velocity, the production of singlet delta oxygen is largely improved at low pressure; by mixing chlorine with an inert gas before injection in the reactor, this yield is maintained constant up to higher pressure. A theoretical analysis of these experimental results and their consequences for both subsonic and supersonic lasers are presented.

  14. Predicting Intracranial Pressure and Brain Tissue Oxygen Crises in Patients With Severe Traumatic Brain Injury.

    PubMed

    Myers, Risa B; Lazaridis, Christos; Jermaine, Christopher M; Robertson, Claudia S; Rusin, Craig G

    2016-09-01

    To develop computer algorithms that can recognize physiologic patterns in traumatic brain injury patients that occur in advance of intracranial pressure and partial brain tissue oxygenation crises. The automated early detection of crisis precursors can provide clinicians with time to intervene in order to prevent or mitigate secondary brain injury. A retrospective study was conducted from prospectively collected physiologic data. intracranial pressure, and partial brain tissue oxygenation crisis events were defined as intracranial pressure of greater than or equal to 20 mm Hg lasting at least 15 minutes and partial brain tissue oxygenation value of less than 10 mm Hg for at least 10 minutes, respectively. The physiologic data preceding each crisis event were used to identify precursors associated with crisis onset. Multivariate classification models were applied to recorded data in 30-minute epochs of time to predict crises between 15 and 360 minutes in the future. The neurosurgical unit of Ben Taub Hospital (Houston, TX). Our cohort consisted of 817 subjects with severe traumatic brain injury. Our algorithm can predict the onset of intracranial pressure crises with 30-minute advance warning with an area under the receiver operating characteristic curve of 0.86 using only intracranial pressure measurements and time since last crisis. An analogous algorithm can predict the start of partial brain tissue oxygenation crises with 30-minute advanced warning with an area under the receiver operating characteristic curve of 0.91. Our algorithms provide accurate and timely predictions of intracranial hypertension and tissue hypoxia crises in patients with severe traumatic brain injury. Almost all of the information needed to predict the onset of these events is contained within the signal of interest and the time since last crisis.

  15. Process for generation of hydrogen gas from various feedstocks using thermophilic bacteria

    DOEpatents

    Ooteghem, Suellen Van

    2005-09-13

    A method for producing hydrogen gas is provided comprising selecting a bacteria from the Order Thermotogales, subjecting the bacteria to a feedstock and to a suitable growth environment having an oxygen concentration below the oxygen concentration of water in equilibrium with air; and maintaining the environment at a predetermined pH and at a temperature of at least approximately 45.degree. C. for a time sufficient to allow the bacteria to metabolize the feedstock.

  16. Structure of 1:1 complex of 1-naphthylmethyl ester of monensin A with sodium perchlorate studied by X-ray, FT-IR and ab initio methods

    NASA Astrophysics Data System (ADS)

    Huczyński, Adam; Janczak, Jan; Brzezinski, Bogumil

    2012-12-01

    A new crystalline complex formed between 1-naphthylmethyl ester of the naturally occurring antibiotic - monensin A (MON8) with sodium perchlorate has been obtained and studied using X-ray crystallography and FT-IR spectroscopy. The X-ray data of the complex show that MON8 forms a pseudo-cyclic structure stabilised by one weak intramolecular hydrogen bond and the sodium cation co-ordinated by two oxygen atoms of hydroxyl groups and four etheric oxygen atoms in the hydrophilic sphere. Within this structure the oxygen atoms of the ester groups are not involved in the coordination of sodium cation. In contrast to the solid state structure of the complex, in acetonitrile solution an equilibrium between two structures, in which the oxygen atom of the carbonyl ester group is either involved or not involved in the complexation of the sodium cation, is found. In acetonitrile this equilibrium is shifted towards the latter structure i.e. the structure existing in the solid state. The gas-phase structure of [MON8sbnd Na]+ cation as shown the ab initio MO calculations is comparable with the crystal one. Three-dimensional molecular electrostatic potential calculated for the neutral MON8 and [MON8sbnd Na]+ molecules is helpful for understanding the structural aspects of the sodium complex formation.

  17. Gd Ba Cu O bulk superconductors fabricated by a seeded infiltration growth technique under reduced oxygen partial pressure

    NASA Astrophysics Data System (ADS)

    Iida, K.; Babu, N. H.; Shi, Y. H.; Cardwell, D. A.; Murakami, M.

    2006-06-01

    Single-grain Gd-Ba-Cu-O (GdBCO) bulk superconductors have been grown by a seeded infiltration and growth (SIG) technique under a 1% O2+N2 atmosphere using a generic MgO-doped Nd-Ba-Cu-O (MgO-NdBCO) seed placed on the sample surface at room temperature (the so-called the cold-seeding method). Partial melting of the MgO-NdBCO seeds fabricated in air under notionally identical thermal processing conditions, however, limited the reliability of this bulk GdBCO single-grain process. The observed seed decomposition is attributed to the dependence of the peritectic temperature Tp of MgO-doped Nd1+xBa2-xCu3Oy solid solution (MgO-doped Nd-123ss, where ss indicates solid solution) compounds on both oxygen partial pressure during the melt process and the level of solid solution (x). The peritectic decomposition temperature of MgO-doped Nd-123ss, with x ranging from 0 to 0.5 under p(O2) = 1.00 atm, was observed to remain constant at 1120 °C. Tp was observed to decrease linearly as a function of solid solution level, on the other hand, under oxygen partial pressures of both p(O2) = 0.21 and 0.01 atm. Based on these results, MgO-doped NdBCO seed crystals should be grown under reduced oxygen partial pressure in order to obtain a stable MgO-doped NdBCO seed crystal suitable for cold-seeding processes of large-grain (RE)BCO bulk superconductors (where RE is a rare earth element).

  18. Nanocrystalline films for gas-reactive applications

    DOEpatents

    Eastman, Jeffrey A.; Thompson, Loren J.

    2004-02-17

    A gas sensor for detection of oxidizing and reducing gases, including O.sub.2, CO.sub.2, CO, and H.sub.2, monitors the partial pressure of a gas to be detected by measuring the temperature rise of an oxide-thin-film-coated metallic line in response to an applied electrical current. For a fixed input power, the temperature rise of the metallic line is inversely proportional to the thermal conductivity of the oxide coating. The oxide coating contains multi-valent cation species that change their valence, and hence the oxygen stoichiometry of the coating, in response to changes in the partial pressure of the detected gas. Since the thermal conductivity of the coating is dependent on its oxygen stoichiometry, the temperature rise of the metallic line depends on the partial pressure of the detected gas. Nanocrystalline (<100 nm grain size) oxide coatings yield faster sensor response times than conventional larger-grained coatings due to faster oxygen diffusion along grain boundaries rather than through grain interiors.

  19. A comparative study on NbOx films reactively sputtered from sintered and cold gas sprayed targets

    NASA Astrophysics Data System (ADS)

    Lorenz, Roland; O'Sullivan, Michael; Fian, Alexander; Sprenger, Dietmar; Lang, Bernhard; Mitterer, Christian

    2018-04-01

    The aim of this work is to evaluate novel cold gas sprayed Nb targets in a reactive sputter deposition process of thin films with respect to the widely used sintered Nb targets. With the exception of a higher target discharge voltage of ∼100 V for the cold gas sprayed targets and the thus higher film growth rate compared to sintered targets, NbOx films with comparable microstructure and properties were obtained for both target variants. The amorphous films with thicknesses between 2.9 and 4.9 μm present an optical shift from dark and non-transparent towards transparent properties, as the oxygen partial pressure increases. X-ray photoelectron spectroscopy confirms the occurrence of the Nb5+ oxidation state for the highest oxygen partial pressure, while Nb4+ is additionally present at lower oxygen partial pressure settings. With a maximal transparency of ∼80% and a refractive index of ∼2.5, the transparent films show characteristics similar to Nb2O5.

  20. Chemical reactions and morphological stability at the Cu/Al2O3 interface.

    PubMed

    Scheu, C; Klein, S; Tomsia, A P; Rühle, M

    2002-10-01

    The microstructures of diffusion-bonded Cu/(0001)Al2O3 bicrystals annealed at 1000 degrees C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high-resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20-35 nm thick interfacial CuAlO2 layer formed, which crystallises in the rhombohedral structure. However, the CuAlO2 layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle-like structure was observed. The needles are several millimetres long, approximately 10 microm wide and approximately 1 microm thick. They consist of CuAlO2 with alternating rhombohedral and hexagonal structures. Solid-state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as-bonded sample.

  1. Zero added oxygen for high quality sputtered ITO: A data science investigation of reduced Sn-content and added Zr

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peshek, Timothy J.; Burst, James M.; Coutts, Timothy J.

    The authors demonstrate mobilities of >45 cm{sup 2}/V s for sputtered tin-doped indium oxide (ITO) films at zero added oxygen. All films were deposited with 5 wt. % SnO{sub 2}, instead of the more conventional 8–10 wt. %, and had varying ZrO{sub 2} content from 0 to 3 wt. %, with a subsequent reduction in In{sub 2}O{sub 3} content. These films were deposited by radio-frequency magnetron sputtering from nominally stoichiometric targets with varying oxygen partial pressure in the sputter ambient. Anomalous behavior was discovered for films with no Zr-added, where a bimodality of high and low mobilities was discovered for nominally similar growth conditions.more » However, all films showed the lowest resistivity and highest mobilities when the oxygen partial pressure in the sputter ambient was zero. This result is contrasted with several other reports of ITO transport performance having a maximum for small but nonzero oxygen partial pressure. This result is attributed to the reduced concentration of SnO{sub 2}. The addition of ZrO{sub 2} yielded the highest mobilities at >55 cm{sup 2}/V s and the films showed a modest increase in optical transmission with increasing Zr-content.« less

  2. Effect of antioxidant oxidation potential in the oxygen radical absorption capacity (ORAC) assay.

    PubMed

    Bisby, Roger H; Brooke, Rachel; Navaratnam, Suppiah

    2008-06-01

    The "oxygen radical absorption capacity" (ORAC) assay (Ou, B., Hampsch-Woodill, M., Prior, R.L. (2001). Development and validation of an improved oxygen radical absorbance capacity assay using fluorescein as the fluorescent probe. Journal of Agricultural and Food Chemistry 49, 4619-4626) is widely employed to determine antioxidant content of foods and uses fluorescein as a probe for oxidation by peroxyl radicals. Kinetic modeling of the ORAC assay suggests that the lag phase for loss of fluorescence results from equilibrium between antioxidant and fluorescein radicals and the value of the equilibrium constant determines the shape of the lag phase. For an efficient antioxidant this constitutes a "repair" reaction for fluoresceinyl radicals and produces a well defined lag phase. The lag phase becomes less marked with increasing oxidation potential of the antioxidant. Pulse radiolysis confirms that fluoresceinyl radicals are rapidly (k∼10(9)dm(3)mol(-1)s(-1)) reduced by Trolox C, a water soluble vitamin E analogue. ORAC assays of phenols with varying oxidation potentials suggest that it might be employed to obtain an estimate of the redox potential of antioxidants within food materials. Copyright © 2007 Elsevier Ltd. All rights reserved.

  3. Optical measurements of atomic oxygen concentration, temperature and nitric oxide production rate in flames

    NASA Astrophysics Data System (ADS)

    Myhr, Franklin Henry

    An optical method for measuring nitric oxide (NO) production rates in flames was developed and characterized in a series of steady, one-dimensional, atmospheric-pressure laminar flames of 0.700 Hsb2/0.199 Nsb2/0.101 COsb2 or 0.700 CHsb4/0.300 Nsb2 (by moles) with dry air, with equivalence ratios from 0.79 to 1.27. Oxygen atom concentration, (O), was measured by two-photon laser-induced fluorescence (LIF), temperature was measured by ultraviolet Rayleigh scattering, and nitrogen concentration was calculated from supplied reactant flows; together this information was used to calculate the NO production rate through the thermal (Zel'dovich) mechanism. Measurements by two other techniques were compared with results from the above method. In the first comparison, gas sampling was used to measure axial NO concentration profiles, the slopes of which were multiplied by velocity to obtain total NO production rates. In the second comparison, LIF measurements of hydroxyl radical (OH) were used with equilibrium water concentrations and a partial equilibrium assumption to find (O). Nitric oxide production rates from all three methods agreed reasonably well. Photolytic interference was observed during (O) LIF measurements in all of the flames; this is the major difficulty in applying the optical technique. Photolysis of molecular oxygen in lean flames has been well documented before, but the degree of interference observed in the rich flames suggests that some other molecule is also dissociating; the candidates are OH, CO, COsb2 and Hsb2O. An extrapolative technique for removing the effects of photolysis from (O) LIF measurements worked well in all flames where NO production was significant. Using the optical method to measure NO production rates in turbulent flames will involve a tradeoff among spatial resolution, systematic photolysis error, and random shot noise. With the conventional laser system used in this work, a single pulse with a resolution of 700 mum measured NO production rates as low as 2×10sp{-3}\\ gmol/msp3-s with photolysis error less than a factor of two and random shot noise of 35%. By using a double-pulse technique and relaxing the spatial resolution to 2 mm, production rates down to 2×10sp{-5}\\ gmol/msp3-s can be measured with shot noise of 22%. Extension to two-dimensional imaging will require a multipass cell or very large pulse energy (˜200 mJ at 226 nm).

  4. Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

    NASA Astrophysics Data System (ADS)

    Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

    2018-03-01

    Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd < Ag < Cu series, the increasing chemical activity of metal nanoparticles raises the degree of oxygen sorption due to its chemisorption and subsequent reduction, while the role of the molecular chemisorption stage increases in the Cu < Ag < Pd series. Metal particles or their oxides are shown to act as adsorption sites on the surface and in the pores of the ion-exchanger matrix; the equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

  5. Oxygen Effect on the Properties of Epitaxial (110) La0.7Sr0.3MnO3 by Defect Engineering.

    PubMed

    Rasic, Daniel; Sachan, Ritesh; Temizer, Namik K; Prater, John; Narayan, Jagdish

    2018-06-20

    The multiferroic properties of mixed valence perovskites such as lanthanum strontium manganese oxide (La 0.7 Sr 0.3 MnO 3 ) (LSMO) demonstrate a unique dependence on oxygen concentration, thickness, strain, and orientation. To better understand the role of each variable, a systematic study has been performed. In this study, epitaxial growth of LSMO (110) thin films with thicknesses ∼15 nm are reported on epitaxial magnesium oxide (111) buffered Al 2 O 3 (0001) substrates. Four LSMO films with changing oxygen concentration have been investigated. The oxygen content in the films was controlled by varying the oxygen partial pressure from 1 × 10 -4 to 1 × 10 -1 Torr during deposition and subsequent cooldown. X-ray diffraction established the out-of-plane and in-plane plane matching to be (111) MgO ∥ (0001) Al 2 O 3 and ⟨11̅0⟩ MgO ∥ ⟨101̅0⟩ Al 2 O 3 for the buffer layer with the substrate, and an out-of-plane lattice matching of (110) LSMO ∥ (111) MgO for the LSMO layer. For the case of the LSMO growth on MgO, a novel growth mode has been demonstrated, showing that three in-plane matching variants are present: (i) ⟨11̅0⟩ LSMO ∥ ⟨11̅0⟩ MgO , (ii) ⟨11̅0⟩ LSMO ∥ ⟨101̅⟩ MgO , and (iii) ⟨11̅0⟩ LSMO ∥ ⟨01̅1⟩ MgO . The atomic resolution scanning transmission electron microscopy (STEM) images were taken of the interfaces that showed a thin, ∼2 monolayer intermixed phase while high-angle annular dark field (HAADF) cross-section images revealed 4/5 plane matching between the film and the buffer and similar domain sizes between different samples. Magnetic properties were measured for all films and the gradual decrease in saturation magnetization is reported with decreasing oxygen partial pressure during growth. A systematic increase in the interplanar spacing was observed by X-ray diffraction of the films with lower oxygen concentration, indicating the decrease in the lattice constant in the plane due to the point defects. Samples demonstrated an insulating behavior for samples grown under low oxygen partial pressure and semiconducting behavior for the highest oxygen partial pressures. Magnetotransport measurements showed ∼36.2% decrease in electrical resistivity with an applied magnetic field of 10 T at 50 K and ∼1.3% at room temperature for the highly oxygenated sample.

  6. Hyperoxia is Associated with Increased Mortality in Patients Treated with Mild Therapeutic Hypothermia after Sudden Cardiac Arrest

    PubMed Central

    Janz, David R.; Hollenbeck, Ryan D.; Pollock, Jeremy S.; McPherson, John A.; Rice, Todd W.

    2012-01-01

    Objective To determine if higher levels of partial pressure of arterial oxygen are associated with in-hospital mortality and poor neurologic status at hospital discharge in patients treated with mild therapeutic hypothermia after sudden cardiac arrest. Design Retrospective analysis of a prospective cohort study Patients A total of 170 consecutive patients treated with therapeutic hypothermia in the cardiovascular care unit of an academic tertiary care hospital. Interventions None. Measurements and Main Results Of 170 patients, 77 (45.2%) survived to hospital discharge. Survivors had a significantly lower maximum partial pressure of arterial oxygen(198 mmHg, IQR 152.5–282) measured in the first 24 hours following cardiac arrest compared to nonsurvivors (254 mmHg, IQR 172–363, p = .022). A multivariable analysis including age, time to return of spontaneous circulation, the presence of shock, bystander CPR, and initial rhythm revealed that higher levels of the partial pressure of arterial oxygen were significantly associated with increased in-hospital mortality (odds ratio 1.439, 95% confidence interval 1.028–2.015, p = 0.034) and poor neurologic status at hospital discharge (odds ratio 1.485, 95% confidence interval 1.032–2.136, p = 0.033). Conclusions Higher levels of the maximum measured partial pressure of arterial oxygen are associated with increased in-hospital mortality and poor neurologic status on hospital discharge in patients treated with mild therapeutic hypothermia after sudden cardiac arrest. PMID:22971589

  7. Oxygen diffusion in nanocrystalline yttria-stabilized zirconia: the effect of grain boundaries.

    PubMed

    De Souza, Roger A; Pietrowski, Martha J; Anselmi-Tamburini, Umberto; Kim, Sangtae; Munir, Zuhair A; Martin, Manfred

    2008-04-21

    The transport of oxygen in dense samples of yttria-stabilized zirconia (YSZ), of average grain size d approximately 50 nm, has been studied by means of 18O/16O exchange annealing and secondary ion mass spectrometry (SIMS). Oxygen diffusion coefficients (D*) and oxygen surface exchange coefficients (k*) were measured for temperatures 673

  8. Equilibrium Partitioning Sediment Guidelines (ESGs) for the ...

    EPA Pesticide Factsheets

    ... PLC = partial life-cycle ... 5 ii mini iiiiiiiii iiiiiii mi 1 1 iii mini ii i B : - Benthic vs WQC i— w ~_ ~ _ o° _ -0 ° - - - ii mini iiiiiiiii iiiiiii iiiiiiiii mini ii 0.1 ... PhD thesis. ...

  9. Study program to develop and evaluate die and container materials for the growth of silicon ribbons. [for development of low cost solar cells

    NASA Technical Reports Server (NTRS)

    Addington, L. A.; Ownby, P. D.; Yu, B. B.; Barsoum, M. W.; Romero, H. V.; Zealer, B. G.

    1979-01-01

    The development and evaluation of proprietary coatings of pure silicon carbide, silicon nitride, and aluminum nitride on less pure hot pressed substrates of the respective ceramic materials, is described. Silicon sessile drop experiments were performed on coated test specimens under controlled oxygen partial pressure. Prior to testing, X-ray diffraction and SEM characterization was performed. The reaction interfaces were characterized after testing with optical and scanning electron microscopy and Auger electron spectroscopy. Increasing the oxygen partial pressure was found to increase the molten silicon contact angle, apparently because adsorbed oxygen lowers the solid-vapor interfacial free energy. It was also found that adsorbed oxygen increased the degree of attack of molten silicon upon the chemical vapor deposited coatings. Cost projections show that reasonably priced, coated, molten silicon resistant refractory material shapes are obtainable.

  10. Oxygen monitor for semi-closed rebreathers: design and use for estimating metabolic oxygen consumption

    NASA Astrophysics Data System (ADS)

    Clarke, John R.; Southerland, David

    1999-07-01

    Semi-closed circuit underwater breathing apparatus (UBA) provide a constant flow of mixed gas containing oxygen and nitrogen or helium to a diver. However, as a diver's work rate and metabolic oxygen consumption varies, the oxygen percentages within the UBA can change dramatically. Hence, even a resting diver can become hypoxic and become at risk for oxygen induced seizures. Conversely, a hard working diver can become hypoxic and lose consciousness. Unfortunately, current semi-closed UBA do not contain oxygen monitors. We describe a simple oxygen monitoring system designed and prototyped at the Navy Experimental Diving Unit. The main monitor components include a PIC microcontroller, analog-to-digital converter, bicolor LED, and oxygen sensor. The LED, affixed to the diver's mask is steady green if the oxygen partial pressure is within pre- defined acceptable limits. A more advanced monitor with a depth senor and additional computational circuitry could be used to estimate metabolic oxygen consumption. The computational algorithm uses the oxygen partial pressure and the diver's depth to compute O2 using the steady state solution of the differential equation describing oxygen concentrations within the UBA. Consequently, dive transients induce errors in the O2 estimation. To evalute these errors, we used a computer simulation of semi-closed circuit UBA dives to generate transient rich data as input to the estimation algorithm. A step change in simulated O2 elicits a monoexponential change in the estimated O2 with a time constant of 5 to 10 minutes. Methods for predicting error and providing a probable error indication to the diver are presented.

  11. A Low-Oxygenated Subpopulation of Pancreatic Islets Constitutes a Functional Reserve of Endocrine Cells

    PubMed Central

    Olsson, Richard; Carlsson, Per-Ola

    2011-01-01

    OBJECTIVE The blood perfusion of pancreatic islets is highly variable and tightly regulated by the blood glucose concentration. Thus, oxygen levels are considered crucial for islet metabolism and function. Although islet oxygenation has been extensively studied in vitro, little is known about it in vivo. The current study aimed to investigate the oxygenation of the endocrine pancreas in vivo. RESEARCH DESIGN AND METHODS The reductive metabolism of 2-nitroimidazoles, such as pimonidazole, has previously been extensively used in studies of oxygen metabolism both in vitro and in vivo. At tissue oxygen levels <10 mmHg, pimonidazole accumulates intracellularly and may thereafter be detected by means of immunohistochemistry. Islet oxygenation was investigated in normal, 60% partially pancreatectomized, as well as whole-pancreas–transplanted rats. Moreover, leucine-dependent protein biosynthesis was performed using autoradiography to correlate islet oxygenation with metabolic activity. RESULTS In vivo, 20–25% of all islets in normal rats showed low oxygenation (pO2 <10 mmHg). Changes in the islet mass, by means of whole-pancreas transplantation, doubled the fraction of low-oxygenated islets in the endogenous pancreas of transplanted animals, whereas this fraction almost completely disappeared after a 60% partial pancreatectomy. Moreover, oxygenation was related to metabolism, since well-oxygenated islets in vivo had 50% higher leucine-dependent protein biosynthesis, which includes (pro)insulin biosynthesis. CONCLUSIONS The current study suggests a novel subpopulation of dormant low-oxygenated islets, which seems to constitute a functional reserve of endocrine cells. This study establishes a novel perspective on the use of the endocrine pancreas in glucose homeostasis. PMID:21788581

  12. Bulk viscosity of the Lennard-Jones fluid for a wide range of states computed by equilibrium molecular dynamics

    NASA Astrophysics Data System (ADS)

    Hoheisel, C.; Vogelsang, R.; Schoen, M.

    1987-12-01

    Accurate data for the bulk viscosity ηv have been obtained by molecular dynamics calculations. Many thermodynamic states of the Lennard-Jones fluid were considered. The Green-Kubo integrand of ηv is analyzed in terms of partial correlation functions constituting the total one. These partial functions behave rather differently from those found for the shear viscosity or the thermal conductivity. Generally the total autocorrelation function of ηv shows a steeper initial decay and a more pronounced long time form than those of the shear viscosity or the thermal conductivity. For states near transition to solid phases, like the pseudotriple point of argon, the Green-Kubo integrand of ηv has a significantly longer ranged time behavior than that of the shear viscosity. Hence, for the latter states, a systematic error is expected for ηv using equilibrium molecular dynamics for its computation.

  13. Local equilibrium of mafic enclaves and granitoids of the Turtle pluton, southeast California: Mineral, chemical, and isotopic evidence

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Allen, C.M.

    Major element and trace element compositions of whole rocks, mineral compositions, and Rb-Sr isotopic compositions of enclave and host granitoid pairs from the Early Cretaceous, calc-alkaline Turtle pluton of southeastern California suggest that the local environmental profoundly affects some enclave types. In the Turtle pluton, where the source of fine-grained, mafic enclaves can be deduced to be magmatic by the presence of partially disaggregated basaltic dikes, mineral chemistry suggests partial or complete local equilibrium among mineral species in the enclave and its host granitoid. Because of local Rb-Sr isotopic equilibration between fine-grained enclaves and host granitoid, one cannot use Srmore » isotopes to distinguish an enclave source independent of its host rocks from an enclave source related to the enclosing pluton. However, preliminary Nd isotopic data suggest an independent, mantle source for enclaves.« less

  14. Effects of changing body position on oxygenation and arterial blood pressures in foals anesthetized with guaifenesin, ketamine, and xylazine.

    PubMed

    Braun, Christina; Trim, Cynthia M; Eggleston, Randy B

    2009-01-01

    To investigate the impact of a change in body position on blood gases and arterial blood pressures in foals anesthetized with guaifenesin, ketamine, and xylazine. Prospective, randomized experimental study. Twelve Quarter Horse foals, age of 5.4 +/-0.9 months and weighing 222 +/- 48 kg. Foals were anesthetized with guaifenesin, ketamine, and xylazine for 40 minutes in lateral recumbency and then assigned to a change in lateral recumbency after hoisting (Group 1, n = 6), or no change (Group 2, n = 6). Oxygen 15 L minute(-1) was insufflated into the endotracheal tube throughout anesthesia. Arterial blood pressure, heart rate, respiratory rate (f(R)), inspired fraction of oxygen (FIO(2)), and end-tidal carbon dioxide (PE'CO(2)) were measured every 5 minutes. Arterial pH and blood gases [arterial partial pressure of oxygen (PaO(2)), arterial partial pressure of carbon dioxide (PaCO(2))] were measured at 10, 30, and 40 minutes after induction, and 5 minutes after hoisting. Alveolar dead space ventilation and PaO(2)/FIO(2) were calculated. Two repeated measures models were used. All hypothesis tests were two-sided and significance level was alpha = 0.05. All values are presented as least square means +/- SE. Values at time-matched points from the two groups were not significantly different so they were combined. Arterial partial pressure of oxygen decreased significantly from 149 +/- 14.4 mmHg before hoisting to 92 +/- 11.6 mmHg after hoisting (p = 0.0013). The PaO(2)/FIO(2) ratio decreased from 275 +/- 30 to 175 +/- 24 (p = 0.0055). End-tidal carbon dioxide decreased significantly from 48.7 +/- 1.6 to 44.5 +/- 1.2 mmHg (p = 0.021). Arterial partial pressure of carbon dioxide, blood pressures and heart rates measured 5 minutes after hoisting were not different from measurements obtained before hoisting. Hoisting decreased PaO(2) in anesthetized healthy foals. Administration of supplemental oxygen is recommended to counter the decrease in oxygenation and PaO(2) measurement is necessary to detect early changes.

  15. Oxygen isotope heterogeneity and disequilibria of olivine crystals in large volume Holocene basalts from Iceland: Evidence for magmatic digestion and erosion of Pleistocene hyaloclastites

    NASA Astrophysics Data System (ADS)

    Bindeman, Ilya; Gurenko, Andrey; Sigmarsson, Olgeir; Chaussidon, Marc

    2008-09-01

    This work considers petrogenesis of the largest Holocene basaltic fissure eruptions of Iceland, which are also the largest in the world: Laki (1783-84 AD, 15 km 3), Eldgjá (934 AD, 18 km 3), Veidivötn (900, 1480 AD, multiple eruptions, >2 km 3), Núpahraun (ca. 4000 BP, >1 km 3) and Thjórsárhraun (ca 8000 BP, >20 km 3). We present oxygen isotope laser fluorination analyses of 55 individual and bulk olivine crystals, coexisting individual and bulk plagioclase phenocrysts, and their host basaltic glasses with average precision of better than 0.1‰ (1SD). We also report O isotope analyses of cores and rims of 61 olivine crystals by SIMS with average precision on single spots of 0.24‰ (1SD) in 13 samples coupled with electron microprobe data for major and trace elements in these olivines. Within each individual sample, we have found that basaltic glass is relatively homogeneous with respect to oxygen isotopes, plagioclase phenocrysts exhibit crystal to crystal variability, while individual olivines span from the values in equilibrium with the low-δ 18O matrix glass to those being three permil higher in δ 18O than the equilibrium. Olivine cores with maximum value of 5.2‰ are found in many of these basalts and suggest that the initial magma was equilibrated with normal-δ 18O mantle. No olivines or their intracrystalline domains are found with bulk or spot value higher than those found in MORB olivines. The δ 18O variability of 0.3-3‰ exists for olivine grains from different lavas, and variable core-to-rim oxygen isotopic zoning is present in selected olivine grains. Many olivines in the same sample are not zoned, while a few grains are zoned with respect to oxygen isotopes and exhibit small core-to-core variations in Fe-Mg, Ni, Mn, Ca. Grains that are zoned in both Mg# and δ 18O exhibit positive correlation of these two parameters. Electron microprobe analysis shows that most olivines equilibrated with the transporting melt, and thin Fe-richer rim is present around many grains, regardless of the degree of olivine-melt oxygen isotope disequilibrium. The preservation of isotopic and compositional zoning in selected grains, and subtle to severe Δ 18O (melt-olivine) and Δ 18O (plagioclase-olivine) disequilibria suggests rather short crystal residence times of years to centuries. Synglacially-altered upper crustal, tufaceous hyaloclastites of Pleistocene age serve as a viable source for low-δ 18O values in Holocene basalts through assimilation, mechanical and thermal erosion, and devolatilization of stoped blocks. Cumulates formed in response to cooling during assimilation, and xenocrysts derived from hyaloclastites, contribute to the diverse δ 18O crystalline cargo. The magma plumbing systems under each fissure are likely to include a network of interconnected dikes and sills with high magma flow rates that contribute to the efficacy of magmatic erosion of large quantities (10-60% mass) of hyaloclastites required by isotopic mass balance. Olivine diversity and the pervasive lack of phenocryst-melt oxygen isotopic equilibrium suggest that a common approach of analyzing bulk olivine for oxygen isotopes, as a proxy for the basaltic melt or to infer mantle δ 18O value, needs to proceed with caution. The best approach is to analyze olivine crystals individually and demonstrate their equilibrium with matrix.

  16. Plasma Equilibrium in a Magnetic Field with Stochastic Field-Line Trajectories

    NASA Astrophysics Data System (ADS)

    Krommes, J. A.; Reiman, A. H.

    2008-11-01

    The nature of plasma equilibrium in a magnetic field with stochastic field lines is examined, expanding upon the ideas first described by Reiman et al. The magnetic partial differential equation (PDE) that determines the equilibrium Pfirsch-Schlüter currents is treated as a passive stochastic PDE for μj/B. Renormalization leads to a stochastic Langevin equation for μ in which the resonances at the rational surfaces are broadened by the stochastic diffusion of the field lines; even weak radial diffusion can significantly affect the equilibrium, which need not be flattened in the stochastic region. Particular attention is paid to satisfying the periodicity constraints in toroidal configurations with sheared magnetic fields. A numerical scheme that couples the renormalized Langevin equation to Ampere's law is described. A. Reiman et al, Nucl. Fusion 47, 572--8 (2007). J. A. Krommes, Phys. Reports 360, 1--351.

  17. Spreading of a pendant liquid drop underneath a textured substrate

    NASA Astrophysics Data System (ADS)

    Mistry, Aashutosh; Muralidhar, K.

    2018-04-01

    A pendant drop spreading underneath a partially wetting surface from an initial shape to its final equilibrium configuration and contact angle is studied. A mathematical formulation that quantifies spreading behavior of liquid drops over textured surfaces is discussed. The drop volume and the equilibrium contact angle are treated as parameters in the study. The unbalanced force at the three-phase contact line is modeled as being proportional to the degree of departure from the equilibrium state. Model predictions are verified against the available experimental data in the literature. Results show that the flow dynamics is strongly influenced by the fluid properties, drop volume, and contact angle of the liquid with the partially wetting surface. The drop exhibits rich dynamical behavior including inertial oscillations and gravitational instability, given that gravity tries to detach the drop against wetting contributions. Flow characteristics of drop motion, namely, the radius of the footprint, slip length, and dynamic contact angle in the pendant configuration are presented. Given the interplay among the competing time-dependent forces, a spreading drop can momentarily be destabilized and not achieve a stable equilibrium shape. Instability is then controlled by the initial drop shape as well. The spreading model is used to delineate stable and unstable regimes in the parameter space. Predictions of the drop volume based on the Young-Laplace equation are seen to be conservative relative to the estimates of the dynamical model discussed in the present study.

  18. Gettering capsule for removing oxygen from liquid lithium systems

    NASA Technical Reports Server (NTRS)

    Tower, L. K.; Breitwieser, R.

    1973-01-01

    Capsule consisting of tantalum shell lined with tantalum screen and partially filled with lithium and pieces of yttrium is immersed in hot lithium stream. Oxygen is removed from stream by being absorbed by gettering capsule. Oxygen passes through capsule wall and into lithium inside capsule where it reacts with yttrium to form Y2O3.

  19. Degradation and recovery of iron doped barium titanate single crystals via modulus spectroscopy and thermally stimulated depolarization current

    NASA Astrophysics Data System (ADS)

    Carter, J. J.; Bayer, T. J. M.; Randall, C. A.

    2017-04-01

    Understanding resistance degradation during the application of DC bias and recovery after removing the DC bias provides insight into failure mechanisms and defects in dielectric materials. In this experiment, modulus spectroscopy and thermally stimulated depolarization current (TSDC) techniques were used to characterize the degradation and recovery of iron-doped barium titanate single crystals. Modulus spectroscopy is a very powerful analytical tool applied during degradation and recovery to observe changes in the local conductivity distribution. During degradation, oxygen vacancies migrate to the cathode region, and a counter flow of oxygen anions migrates towards the anode. With increasing time during degradation, the distribution of conductivity broadens only slightly exhibiting crucial differences to iron doped strontium titanate. After removing the DC bias, the recovery shows that a second previously unobserved and distinct conductivity maximum arises in the modulus data. This characteristic with two maxima related to different conductivities in the anode and cathode region is what can be expected from the published defect chemistry. It will be concluded that only the absence of an external electric field during recovery measurements permits the observation of local conductivity measurements without the presence of non-equilibrium conditions such as charge injection. Equilibrium conductivity as a function of oxygen vacancy concentration is described schematically. Oxygen vacancy migration during degradation and recovery is verified by TSDC analysis. We establish a self-consistent rationale of the transient changes in the modulus and TSDC for the iron doped barium titanate single crystal system including electron, hole and oxygen vacancy conductivity. During degradation, the sample fractured.

  20. A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts.

    PubMed

    Stolper, Daniel A; Keller, C Brenhin

    2018-01-18

    The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O 2 ) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe 3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

  1. A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts

    NASA Astrophysics Data System (ADS)

    Stolper, Daniel A.; Keller, C. Brenhin

    2018-01-01

    The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O2) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

  2. Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sridharan, Niyanth; Isheim, D.; Seidman, David N.

    Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

  3. Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

    DOE PAGES

    Sridharan, Niyanth; Isheim, D.; Seidman, David N.; ...

    2016-12-14

    Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

  4. The effects of nickel and sulphur on the core-mantle partitioning of oxygen in Earth and Mars

    NASA Astrophysics Data System (ADS)

    Tsuno, Kyusei; Frost, Daniel J.; Rubie, David C.

    2011-03-01

    Constraints on the partitioning of oxygen between silicates, oxides, and metallic liquids are important for determining the amount of oxygen that may have entered the cores of terrestrial planets and to identify likely reactions at the core-mantle boundary. Several previous studies have examined oxygen partitioning between liquid Fe metal and ferropericlase, however, the cores of terrestrial planets also contain nickel and most likely sulphur. We have performed experiments to examine the effects of both nickel and sulphur on the partitioning of oxygen between ferropericlase and liquid Fe alloy up to pressures of 24.5 GPa in the temperature range 2430-2750 K using a multianvil press. The results show that at a fixed oxygen fugacity the proportion of oxygen that partitions into liquid metal will decrease by approximately 1-2 mol% on the addition of 10-20 mol% nickel to the liquid. The addition of around 30 mol% sulphur will, on the other hand, increase the metal oxygen content by approximately 10 mol%. Experiments to examine the combined effects of both nickel and sulphur, show a decrease in the effect of nickel on oxygen partitioning as the sulphur content of the metal increases. We expand an existing thermodynamic model for the partitioning of oxygen at high pressures and temperatures to include the effects of nickel and sulphur by fitting these experimental data, with further constraints provided by existing phase equilibria studies at similar conditions in the Fe-S and Fe-O-S systems. Plausible terrestrial core sulphur contents have little effect on oxygen partitioning. When our model is extrapolated to conditions of the present day terrestrial core-mantle boundary, the presence of nickel is found to lower the oxygen content of the outer core that is in equilibrium with the expected mantle ferropericlase FeO content, by approximately 1 weight %, in comparison to nickel free calculations. In agreement with nickel-free experiments, this implies that the Earth's outer core is undersaturated in oxygen with respect to plausible mantle FeO contents, which will result in either the depletion of FeO from the base of the mantle or cause the development of an outer core layer that is enriched in oxygen. The oxygen content of the more sulphur-rich Martian core would be in the range 2-4 wt.% if it is in equilibrium with the FeO-rich Martian mantle.

  5. Molecular-level Analysis of Shock-wave Physics and Derivation of the Hugoniot Relations for Soda-lime Glass

    DTIC Science & Technology

    2011-06-17

    based glasses like fused silica and soda - lime glass , the polyhedral central cation is silicon. In this case, each silicon is surrounded by four oxygen...to two network forming cations) oxygen atoms per network polyhedron. The equilibrium values for this parameter in fused silica and soda - lime glass ...Molecular-level analysis of shock-wave physics and derivation of the Hugoniot relations for soda - lime glass M. Grujicic • B. Pandurangan • W. C. Bell

  6. Computational Model for Oxygen Transport and Consumption in Human Vitreous

    PubMed Central

    Filas, Benjamen A.; Shui, Ying-Bo; Beebe, David C.

    2013-01-01

    Purpose. Previous studies that measured liquefaction and oxygen content in human vitreous suggested that exposure of the lens to excess oxygen causes nuclear cataracts. Here, we developed a computational model that reproduced available experimental oxygen distributions for intact and degraded human vitreous in physiologic and environmentally perturbed conditions. After validation, the model was used to estimate how age-related changes in vitreous physiology and structure alter oxygen levels at the lens. Methods. A finite-element model for oxygen transport and consumption in the human vitreous was created. Major inputs included ascorbate-mediated oxygen consumption in the vitreous, consumption at the posterior lens surface, and inflow from the retinal vasculature. Concentration-dependent relations were determined from experimental human data or estimated from animal studies, with the impact of all assumptions explored via parameter studies. Results. The model reproduced experimental data in humans, including oxygen partial pressure (Po2) gradients (≈15 mm Hg) across the anterior-posterior extent of the vitreous body, higher oxygen levels at the pars plana relative to the vitreous core, increases in Po2 near the lens after cataract surgery, and equilibration in the vitreous chamber following vitrectomy. Loss of the antioxidative capacity of ascorbate increases oxygen levels 3-fold at the lens surface. Homogeneous vitreous degeneration (liquefaction), but not partial posterior vitreous detachment, greatly increases oxygen exposure to the lens. Conclusions. Ascorbate content and the structure of the vitreous gel are critical determinants of lens oxygen exposure. Minimally invasive surgery and restoration of vitreous structure warrant further attention as strategies for preventing nuclear cataracts. PMID:24008409

  7. Computational model for oxygen transport and consumption in human vitreous.

    PubMed

    Filas, Benjamen A; Shui, Ying-Bo; Beebe, David C

    2013-10-15

    Previous studies that measured liquefaction and oxygen content in human vitreous suggested that exposure of the lens to excess oxygen causes nuclear cataracts. Here, we developed a computational model that reproduced available experimental oxygen distributions for intact and degraded human vitreous in physiologic and environmentally perturbed conditions. After validation, the model was used to estimate how age-related changes in vitreous physiology and structure alter oxygen levels at the lens. A finite-element model for oxygen transport and consumption in the human vitreous was created. Major inputs included ascorbate-mediated oxygen consumption in the vitreous, consumption at the posterior lens surface, and inflow from the retinal vasculature. Concentration-dependent relations were determined from experimental human data or estimated from animal studies, with the impact of all assumptions explored via parameter studies. The model reproduced experimental data in humans, including oxygen partial pressure (Po2) gradients (≈15 mm Hg) across the anterior-posterior extent of the vitreous body, higher oxygen levels at the pars plana relative to the vitreous core, increases in Po2 near the lens after cataract surgery, and equilibration in the vitreous chamber following vitrectomy. Loss of the antioxidative capacity of ascorbate increases oxygen levels 3-fold at the lens surface. Homogeneous vitreous degeneration (liquefaction), but not partial posterior vitreous detachment, greatly increases oxygen exposure to the lens. Ascorbate content and the structure of the vitreous gel are critical determinants of lens oxygen exposure. Minimally invasive surgery and restoration of vitreous structure warrant further attention as strategies for preventing nuclear cataracts.

  8. Gyrokinetic Magnetohydrodynamics and the Associated Equilibrium

    NASA Astrophysics Data System (ADS)

    Lee, W. W.; Hudson, S. R.; Ma, C. H.

    2017-10-01

    A proposed scheme for the calculations of gyrokinetic MHD and its associated equilibrium is discussed related a recent paper on the subject. The scheme is based on the time-dependent gyrokinetic vorticity equation and parallel Ohm's law, as well as the associated gyrokinetic Ampere's law. This set of equations, in terms of the electrostatic potential, ϕ, and the vector potential, ϕ , supports both spatially varying perpendicular and parallel pressure gradients and their associated currents. The MHD equilibrium can be reached when ϕ -> 0 and A becomes constant in time, which, in turn, gives ∇ . (J|| +J⊥) = 0 and the associated magnetic islands. Examples in simple cylindrical geometry will be given. The present work is partially supported by US DoE Grant DE-AC02-09CH11466.

  9. Computing diffusivities from particle models out of equilibrium

    NASA Astrophysics Data System (ADS)

    Embacher, Peter; Dirr, Nicolas; Zimmer, Johannes; Reina, Celia

    2018-04-01

    A new method is proposed to numerically extract the diffusivity of a (typically nonlinear) diffusion equation from underlying stochastic particle systems. The proposed strategy requires the system to be in local equilibrium and have Gaussian fluctuations but it is otherwise allowed to undergo arbitrary out-of-equilibrium evolutions. This could be potentially relevant for particle data obtained from experimental applications. The key idea underlying the method is that finite, yet large, particle systems formally obey stochastic partial differential equations of gradient flow type satisfying a fluctuation-dissipation relation. The strategy is here applied to three classic particle models, namely independent random walkers, a zero-range process and a symmetric simple exclusion process in one space dimension, to allow the comparison with analytic solutions.

  10. Clinical recommendations for high altitude exposure of individuals with pre-existing cardiovascular conditions

    PubMed Central

    Parati, Gianfranco; Agostoni, Piergiuseppe; Basnyat, Buddha; Bilo, Grzegorz; Brugger, Hermann; Coca, Antonio; Festi, Luigi; Giardini, Guido; Lironcurti, Alessandra; Luks, Andrew M; Maggiorini, Marco; Modesti, Pietro A; Swenson, Erik R; Williams, Bryan; Bärtsch, Peter; Torlasco, Camilla

    2018-01-01

    Abstract Take home figureAdapted from Bärtsch and Gibbs2 Physiological response to hypoxia. Life-sustaining oxygen delivery, in spite of a reduction in the partial pressure of inhaled oxygen between 25% and 60% (respectively at 2500 m and 8000 m), is ensured by an increase in pulmonary ventilation, an increase in cardiac output by increasing heart rate, changes in vascular tone, as well as an increase in haemoglobin concentration. BP, blood pressure; HR, heart rate; PaCO2, partial pressure of arterial carbon dioxide. PMID:29340578

  11. Pathophysiological effect of fat embolism in a canine model of pulmonary contusion.

    PubMed

    Elmaraghy, A W; Aksenov, S; Byrick, R J; Richards, R R; Schemitsch, E H

    1999-08-01

    The objective of this study was to determine the individual and combined effects of pulmonary contusion and fat embolism on the hemodynamics and pulmonary pathophysiology in a canine model of acute traumatic pulmonary injury. After a thoracotomy, twenty-one skeletally mature dogs were randomly assigned to one of three groups. Unilateral pulmonary contusion alone was produced in Group 1 (seven dogs); pulmonary contusion and fat embolism, in Group 2 (seven dogs); and fat embolism alone, in Group 3 (seven dogs). Pulmonary contusion was produced by standardized compression of the left lung with a piezoelectric force transducer. Fat embolism was produced by femoral and tibial reaming followed by pressurization of the intramedullary canals. Cardiac output, systolic blood pressure, peak airway pressure, pulmonary arterial pressure, pulmonary capillary wedge pressure, partial pressure of arterial oxygen, and partial pressure of carbon dioxide were monitored for all groups. From these data, several outcome parameters were calculated: total thoracic compliance, alveolar-arterial oxygen gradient, and ratio of partial pressure of arterial oxygen to fractional inspired oxygen concentration. All of the dogs were killed after eight hours, and tissue samples were obtained from the brain, kidneys, and lungs for histological analysis. Lung samples were assigned scores for pulmonary edema (the presence of fluid in the alveoli) and inflammation (the presence of neutrophils or hyaline membranes, or both). The percentage of the total area occupied by fat was determined. Pulmonary contusion alone caused a significant increase in the alveolar-arterial oxygen gradient but only after seven hours (p = 0.034). Fat embolism alone caused a significant transient decrease in systolic blood pressure (p = 0.001) and a significant transient increase in pulmonary arterial pressure (p = 0.01) and pulmonary capillary wedge pressure (p = 0.015). Fat embolism alone also caused a significant sustained decrease in the ratio of partial pressure of arterial oxygen to fractional inspired oxygen concentration (p = 0.0001) and a significant increase in the alveolar-arterial oxygen gradient (p = 0.0001). The combination of pulmonary contusion and fat embolism caused a significant transient increase in pulmonary capillary wedge pressure (p = 0.0013) as well as a significant sustained decrease in partial pressure of arterial oxygen (p = 0.0001) and a significant decrease in systolic blood pressure (p = 0.001) that lasted for an hour. Pulmonary contusion followed by fat embolism caused a significant increase in peak airway pressure (p = 0.015), alveolar-arterial oxygen gradient (p = 0.0001), and pulmonary arterial pressure (p = 0.01), and these effects persisted for five hours. Total thoracic compliance was decreased 6.4 percent by pulmonary contusion alone, 4.6 percent by fat embolism alone, and 23.5 percent by pulmonary contusion followed by fat embolism. The ratio of partial pressure of arterial oxygen to fractional inspired oxygen concentration was decreased 23.7 percent by pulmonary contusion alone, 52.3 percent by fat embolism alone, and 65.8 percent by pulmonary contusion followed by fat embolism. The mean pulmonary edema score was significantly higher with the combined injury than with either injury alone (p = 0.0001). None of the samples from the lungs demonstrated inflammation. Fat embolism combined with pulmonary contusion resulted in a significantly greater mean percentage of the area occupied by fat in the noncontused right lung than in the contused left lung (p = 0.001); however, no significant difference between the right and left lungs could be detected with fat embolism alone. The mean percentage of the glomerular and cerebral areas occupied by fat was greater with fat embolism combined with pulmonary contusion than with fat embolism alone (p = 0.0001 and p = 0.01, respectively). (ABSTRACT TRUNCATED)

  12. Biodegradation of chlorobenzene under hypoxic and mixed hypoxic-denitrifying conditions.

    PubMed

    Nestler, Holger; Kiesel, Bärbel; Kaschabek, Stefan R; Mau, Margit; Schlömann, Michael; Balcke, Gerd Ulrich

    2007-12-01

    Pseudomonas veronii strain UFZ B549, Acidovorax facilis strain UFZ B530, and a community of indigenous groundwater bacteria, adapted to oxygen limitation, were cultivated on chlorobenzene and its metabolites 2-chloro-cis,cis-muconate and acetate/succinate under hypoxic and denitrifying conditions. Highly sensitive approaches were used to maintain defined low oxygen partial pressures in an oxygen-re-supplying headspace. With low amounts of oxygen available all cultures converted chlorobenzene, though the pure strains accumulated 3-chlorocatechol and 2-chloro-cis,cis-muconate as intermediates. Under strictly anoxic conditions no chlorobenzene transformation was observed, while 2-chloro-cis,cis-muconate, the fission product of oxidative ring cleavage, was readily degraded by the investigated chlorobenzene-degrading cultures at the expense of nitrate as terminal electron acceptor. Hence, we conclude that oxygen is an obligatory reactant for initial activation of chlorobenzene and fission of the aromatic ring, but it can be partially replaced by nitrate in respiration. The tendency to denitrify in the presence of oxygen during growth on chlorobenzene appeared to depend on the oxygen availability and the efficiency to metabolize chlorobenzene under oxygen limitation, which is largely regulated by the activity of the intradiol ring fission dioxygenase. Permanent cultivation of a groundwater consortium under reduced oxygen levels resulted in enrichment of a community almost exclusively composed of members of the beta-Proteobacteria and Bacteroidetes. Thus, it is deduced that these strains can still maintain high activities of oxygen-requiring enzymes that allow for efficient CB transformation under hypoxic conditions.

  13. High Oxygen Partial Pressure Decreases Anemia-Induced Heart Rate Increase Equivalent to Transfusion

    PubMed Central

    Feiner, John R.; Finlay-Morreale, Heather E.; Toy, Pearl; Lieberman, Jeremy A.; Viele, Maurene K.; Hopf, Harriet W.; Weiskopf, Richard B.

    2011-01-01

    Background Anemia is associated with morbidity and mortality and frequently leads to transfusion of erythrocytes. We sought to compare directly the effect of high inspired oxygen fraction vs. transfusion of erythrocytes on the anemia-induced increased heart rate (HR) in humans undergoing experimental acute isovolemic anemia. Methods We combined HR data from healthy subjects undergoing experimental isovolemic anemia in seven studies performed by our group. We examined HR changes associated with breathing 100% oxygen by non-rebreathing face mask vs. transfusion of erythrocytes at their nadir hemoglobin (Hb) concentration of 5 g/dL. Data were analyzed using a mixed-effects model. Results HR had an inverse linear relationship to hemoglobin concentration with a mean increase of 3.9 beats per minute per gram of Hb (beats/min/g Hb) decrease (95% confidence interval [CI], 3.7 – 4.1 beats/min/g Hb), P < 0.0001. Return of autologous erythrocytes significantly decreased HR by 5.3 beats/min/g Hb (95% CI, 3.8 – 6.8 beats/min/g Hb) increase, P < 0.0001. HR at nadir Hb of 5.6 g/dL (95% CI, 5.5 – 5.7 g/dL) when breathing air (91.4 beats/min; 95% CI, 87.6 – 95.2 beats/min) was reduced by breathing 100% oxygen (83.0 beats/min; 95% CI, 79.0 -87.0 beats/min), P < 0.0001. The HR at hemoglobin 5.6 g/dL when breathing oxygen was equivalent to the HR at Hb 8.9 g/dL when breathing air. Conclusions High arterial oxygen partial pressure reverses the heart rate response to anemia, probably owing to its usability, rather than its effect on total oxygen content. The benefit of high arterial oxygen partial pressure has significant potential clinical implications for the acute treatment of anemia and results of transfusion trials. PMID:21768873

  14. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  15. Agent-Centric Approach for Cybersecurity Decision-Support with Partial Observability

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tipireddy, Ramakrishna; Chatterjee, Samrat; Paulson, Patrick R.

    Generating automated cyber resilience policies for real-world settings is a challenging research problem that must account for uncertainties in system state over time and dynamics between attackers and defenders. In addition to understanding attacker and defender motives and tools, and identifying “relevant” system and attack data, it is also critical to develop rigorous mathematical formulations representing the defender’s decision-support problem under uncertainty. Game-theoretic approaches involving cyber resource allocation optimization with Markov decision processes (MDP) have been previously proposed in the literature. Moreover, advancements in reinforcement learning approaches have motivated the development of partially observable stochastic games (POSGs) in various multi-agentmore » problem domains with partial information. Recent advances in cyber-system state space modeling have also generated interest in potential applicability of POSGs for cybersecurity. However, as is the case in strategic card games such as poker, research challenges using game-theoretic approaches for practical cyber defense applications include: 1) solving for equilibrium and designing efficient algorithms for large-scale, general problems; 2) establishing mathematical guarantees that equilibrium exists; 3) handling possible existence of multiple equilibria; and 4) exploitation of opponent weaknesses. Inspired by advances in solving strategic card games while acknowledging practical challenges associated with the use of game-theoretic approaches in cyber settings, this paper proposes an agent-centric approach for cybersecurity decision-support with partial system state observability.« less

  16. Chemical Looping Combustion Reactions and Systems

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sarofim, Adel; Lighty, JoAnn; Smith, Philip

    2014-03-01

    Chemical Looping Combustion (CLC) is one promising fuel-combustion technology, which can facilitate economic CO{sub 2} capture in coal-fired power plants. It employs the oxidation/reduction characteristics of a metal, or oxygen carrier, and its oxide, the oxidizing gas (typically air) and the fuel source may be kept separate. This topical report discusses the results of four complementary efforts: (5.1) the development of process and economic models to optimize important design considerations, such as oxygen carrier circulation rate, temperature, residence time; (5.2) the development of high-performance simulation capabilities for fluidized beds and the collection, parameter identification, and preliminary verification/uncertainty quantification; (5.3) themore » exploration of operating characteristics in the laboratoryscale bubbling bed reactor, with a focus on the oxygen carrier performance, including reactivity, oxygen carrying capacity, attrition resistance, resistance to deactivation, cost and availability; and (5.4) the identification of kinetic data for copper-based oxygen carriers as well as the development and analysis of supported copper oxygen carrier material. Subtask 5.1 focused on the development of kinetic expressions for the Chemical Looping with Oxygen Uncoupling (CLOU) process and validating them with reported literature data. The kinetic expressions were incorporated into a process model for determination of reactor size and oxygen carrier circulation for the CLOU process using ASPEN PLUS. An ASPEN PLUS process model was also developed using literature data for the CLC process employing an iron-based oxygen carrier, and the results of the process model have been utilized to perform a relative economic comparison. In Subtask 5.2, the investigators studied the trade-off between modeling approaches and available simulations tools. They quantified uncertainty in the high-performance computing (HPC) simulation tools for CLC bed applications. Furthermore, they performed a sensitivity analysis for velocity, height and polydispersity and compared results against literature data for experimental studies of CLC beds with no reaction. Finally, they present an optimization space using simple non-reactive configurations. In Subtask 5.3, through a series of experimental studies, behavior of a variety of oxygen carriers with different loadings and manufacturing techniques was evaluated under both oxidizing and reducing conditions. The influences of temperature, degree of carrier conversion and thermodynamic driving force resulting from the difference between equilibrium and system O{sub 2} partial pressures were evaluated through several experimental campaigns, and generalized models accounting for these influences were developed to describe oxidation and oxygen release. Conversion of three solid fuels with widely ranging reactivities was studied in a small fluidized bed system, and all but the least reactive fuel (petcoke) were rapidly converted by oxygen liberated from the CLOU carrier. Attrition propensity of a variety of carriers was also studied, and the carriers produced by freeze granulation or impregnation of preformed substrates displayed the lowest rates of attrition. Subtask 5.4 focused on gathering kinetic data for a copper-based oxygen carrier to assist with modeling of a functioning chemical looping reactor. The kinetics team was also responsible for the development and analysis of supported copper oxygen carrier material.« less

  17. The study of excited oxygen molecule gas species production and quenching on thermal protection system materials

    NASA Technical Reports Server (NTRS)

    Nordine, Paul C.; Fujimoto, Gordon T.; Greene, Frank T.

    1987-01-01

    The detection of excited oxygen and ozone molecules formed by surface catalyzed oxygen atom recombination and reaction was investigated by laser induced fluorescence (LIF), molecular beam mass spectrometric (MBMS), and field ionization (FI) techniques. The experiment used partially dissociated oxygen flows from a microwave discharge at pressures in the range from 60 to 400 Pa or from an inductively coupled RF discharge at atmospheric pressure. The catalyst materials investigated were nickel and the reaction cured glass coating used for Space Shuttle reusable surface insulation tiles. Nonradiative loss processes for the laser excited states makes LIF detection of O2 difficult such that formation of excited oxygen molecules could not be detected in the flow from the microwave discharge or in the gaseous products of atom loss on nickel. MBMS experiments showed that ozone was a product of heterogeneous O atom loss on nickel and tile surfaces at low temperatures and that ozone is lost on these materials at elevated temperatures. FI was separately investigated as a method by which excited oxygen molecules may be conveniently detected. Partial O2 dissociation decreases the current produced by FI of the gas.

  18. Characterization of an activity from the strict anaerobe Roseburia cecicola that degrades DNA when exposed to air.

    PubMed Central

    O'Connor, L T; Savage, D C

    1993-01-01

    Roseburia cecicola is an obligately anaerobic bacterium that is extremely sensitive to oxygen. Genomic DNA isolated from cells exposed to air for even a brief period (< 5 min) is partially degraded, while DNA extracted from cells maintained in an anaerobic environment remains intact. Cells exposed to air for longer and longer periods yield DNA which is progressively degraded into fragments with decreasing sizes. Oxygen toxicity for this anaerobe appears to result, at least in part, from degradation of its genomic DNA. Cell lysates of the organism exhibited a similar ability to degrade exogenous sources of DNA when assayed in vitro under aerobic conditions. A substance that degrades both DNA and RNA when incubated aerobically was partially purified from such lysates. It has an approximate molecular weight of 2,800 and is unlikely to be a protein. It requires a reducing agent for activity and can be inhibited by catalase and peroxidase but not superoxide dismutase. The rate at which it degrades DNA in vitro can be enhanced by temperatures above 37 degrees C or by oxygen at partial pressures above atmospheric pressure. These results suggest that this substance degrades nucleic acids by a mechanism involving oxygen radicals. Images PMID:8335626

  19. Investigation of CNTD Mechanism and its Effect on Microstructural Properties.

    DTIC Science & Technology

    1980-10-01

    Equilibrium Degree of Completion of SiCl4 Reduction 31 as a Function of Temperature, Pressure and Degree ofDilution. 9. Equilibrium Degree of Completion...Disproportionation Study with SiCl4 . A) 500/2500X B) 600/3000X 11. Morphology of Deposit Made in the Silicon Halide 39 Disproportionation Study with SiHCl 3. A...at a constant ratio of SiCl4 to NH 3 of 0.2 (except run #29, see Table A-1 Appendix I). The active gas partial pressure was calculated according to the

  20. The jumbo squid, Dosidicus gigas (Ommastrephidae), living in oxygen minimum zones I: Oxygen consumption rates and critical oxygen partial pressures

    NASA Astrophysics Data System (ADS)

    Trueblood, Lloyd A.; Seibel, Brad A.

    2013-10-01

    Dosidicus gigas is a large, metabolically active, epipelagic squid known to undertake diel vertical migrations across a large temperature and oxygen gradient in the Eastern Pacific. Hypoxia is known to cause metabolic suppression in D. gigas. However, the precise oxygen level at which metabolic suppression sets in is unknown. Here we describe a novel ship-board swim tunnel respirometer that was used to measure metabolic rates and critical oxygen partial pressures (Pcrit) for adult squids (2-7kg). Metabolic rate measurements were validated by comparison to the activity of the Krebs cycle enzyme, citrate synthase, in mantle muscle tissue (2-17kg). We recorded a mean routine metabolic rate of 5.91μmolg-1h-1 at 10°C and 12.62μmolg-1h-1 at 20°C. A temperature coefficient, Q10, of 2.1 was calculated. D. gigas had Pcrits of 1.6 and 3.8kPa at 10 and 20°C, respectively. Oxygen consumption rate (MO2) varied with body mass (M) according to MO2=11.57M-0.12±0.03 at 10°C. Citrate synthase activity varied with body mass according to Y=9.32M-0.19±0.02.

  1. The effect of bladder outlet obstruction on tissue oxygen tension and blood flow in the pig bladder.

    PubMed

    Greenland, J E; Hvistendahl, J J; Andersen, H; Jörgensen, T M; McMurray, G; Cortina-Borja, M; Brading, A F; Frøkiaer, J

    2000-06-01

    To investigate the effect of partial bladder outlet obstruction on detrusor blood flow and oxygen tension (PdetO2) in female pigs. Detrusor-layer oxygen tension and blood flow were measured using oxygen-sensitive electrode and radiolabelled microsphere techniques in five female Large White pigs with a partial urethral obstruction and in five sham-operated controls. The effects of chronic outlet obstruction on bladder weight, and cholinergic nerve density and distribution, are also described. In the obstructed bladders, blood flow and oxygen tension were, respectively, 54.9% and 74.3% of control values at low bladder volume, and 47.5% and 42.5% at cystometric capacity. Detrusor blood flow declined by 27.8% and 37.5% in the control and obstructed bladders, respectively, as a result of bladder filling, whilst PdetO2 did not decrease in the controls, but fell by 42.7% in the obstructed bladders. Bladder weight increased whilst cholinergic nerve density decreased in the obstructed animals. In pigs with chronic bladder outlet obstruction, blood flow and oxygen tension in the detrusor layer were lower than in control animals. In addition, increasing detrusor pressure during filling caused significantly greater decreases in blood flow and oxygen tension in the obstructed than in the control bladders.

  2. Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations

    DOE PAGES

    Ji, Ho-Il; Davenport, Timothy C.; Gopal, Chirranjeevi Balaji; ...

    2016-07-18

    The redox kinetics of undoped ceria (CeO 2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO 2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant k chem is found to obey the correlation log(k chem/cm s -1) = (0.84 ± 0.02) × log(pO 2/atm) - (0.99 ± 0.05) and increases withmore » oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.« less

  3. Comparing CT perfusion with oxygen partial pressure in a rabbit VX2 soft-tissue tumor model.

    PubMed

    Sun, Chang-Jin; Li, Chao; Lv, Hai-Bo; Zhao, Cong; Yu, Jin-Ming; Wang, Guang-Hui; Luo, Yun-Xiu; Li, Yan; Xiao, Mingyong; Yin, Jun; Lang, Jin-Yi

    2014-01-01

    The aim of this study was to evaluate the oxygen partial pressure of the rabbit model of the VX2 tumor using a 64-slice perfusion CT and to compare the results with that obtained using the oxygen microelectrode method. Perfusion CT was performed for 45 successfully constructed rabbit models of a VX2 brain tumor. The perfusion values of the brain tumor region of interest, the blood volume (BV), the time to peak (TTP) and the peak enhancement intensity (PEI) were measured. The results were compared with the partial pressure of oxygen (PO2) of that region of interest obtained using the oxygen microelectrode method. The perfusion values of the brain tumor region of interest in 45 successfully constructed rabbit models of a VX2 brain tumor ranged from 1.3-127.0 (average, 21.1 ± 26.7 ml/min/ml); BV ranged from 1.2-53.5 ml/100g (average, 22.2 ± 13.7 ml/100g); PEI ranged from 8.7-124.6 HU (average, 43.5 ± 28.7 HU); and TTP ranged from 8.2-62.3 s (average, 38.8 ± 14.8 s). The PO2 in the corresponding region ranged from 0.14-47 mmHg (average, 16 ± 14.8 mmHg). The perfusion CT positively correlated with the tumor PO2, which can be used for evaluating the tumor hypoxia in clinical practice.

  4. Hypothesis: the regulation of the partial pressure of oxygen by the serotonergic nervous system in hypoxia.

    PubMed

    Devereux, Diana; Ikomi-Kumm, Julie

    2013-03-01

    The regulation of the partial pressure of oxygen by the serotonergic nervous system in hypoxia is a hypothesis, which proposes an inherent operative system in homo sapiens that allows central nervous system and endocrine-mediated vascular system adaption to variables in partial pressure of oxygen, pH and body composition, while maintaining sufficient oxygen saturation for the immune system and ensuring protection of major organs in hypoxic and suboptimal conditions. While acknowledging the importance of the Henderson-Hasselbalch equation in the regulation of acid base balance, the hypothesis seeks to define the specific neuroendocrine/vascular mechanisms at work in regulating acid base balance in hypoxia and infection. The SIA (serotonin-immune-adrenergic) system is proposed as a working model, which allows central nervous system and endocrine-mediated macro- and micro vascular 'fine tuning'. The neurotransmitter serotonin serves as a 'hypoxic sensor' in concert with other operators to orchestrate homeostatic balance in normal and pathological states. The SIA system finely regulates oxygen, fuel and metabolic buffering systems at local sites to ensure optimum conditions for the immune response. The SIA system is fragile and its operation may be affected by infection, stress, diet, environmental toxins and lack of exercise. The hypothesis provides new insight in the area of neuro-gastroenterology, and emphasizes the importance of diet and nutrition as a complement in the treatment of infection, as well as the normalization of intestinal flora following antibiotic therapy. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations.

    PubMed

    Ji, Ho-Il; Davenport, Timothy C; Gopal, Chirranjeevi Balaji; Haile, Sossina M

    2016-08-03

    The redox kinetics of undoped ceria (CeO2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant kchem is found to obey the correlation log(kchem/cm s(-1)) = (0.84 ± 0.02) × log(pO2/atm) - (0.99 ± 0.05) and increases with oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.

  6. Changes in Oxygen Partial Pressure in the Vitreous Body and Arterial Blood of Rabbits Depending on Oxygen Concentration in Inspired Mixture.

    PubMed

    Amkhanitskaya, L I; Nikolaeva, G V; Sokolova, N A

    2015-07-01

    We demonstrated that the vitreous body of one-month-old rabbits becomes a "reservoir" for storage and accumulation of oxygen after exposure to additional oxygenation of the organism (O2 concentrations in inspired gas mixture were 40, 60, 85, and 99%). The higher was O2 concentration in inspired mixture, the higher was oxygen saturation of the blood and vitreous body. O2 concentration of 40% was relatively safe for eye tissues. O2 concentration >60% induced oxygen accumulation in the vitreous body, which can be a provoking factor for the development of oxygen-induced pathologies.

  7. Oxidation kinetics of molten copper sulfide

    NASA Astrophysics Data System (ADS)

    Alyaser, A. H.; Brimacombe, J. K.

    1995-02-01

    The oxidation kinetics of molten Cu2S baths, during top lancing with oxygen/nitrogen (argon) mixtures, have been investigated as a function of oxygen partial pressure (0.2 to 0.78), bath temperature (1200 °C to 1300 °C), gas flow rate (1 to 4 L/min), and bath mixing. Surface-tension-driven flows (the Marangoni effect) were observed both visually and photographically. Thus, the oxidation of molten Cu2S was found to progress in two distinct stages, the kinetics of which are limited by the mass transfer of oxygen in the gas phase to the melt surface. During the primary stage, the melt is partially desulfurized while oxygen dissolves in the liquid sulfide. Upon saturation of the melt with oxygen, the secondary stage commences in which surface and bath reactions proceed to generate copper and SO2 electrochemically. A mathematical model of the reaction kinetics has been formulated and tested against the measurements. The results of this study shed light on the process kinetics of the copper blow in a Peirce-Smith converter or Mitsubishi reactor.

  8. Phase equilibrium constraints on the origin of basalts, picrites, and komatiites

    NASA Astrophysics Data System (ADS)

    Herzberg, C.; O'Hara, M. J.

    1998-07-01

    Experimental phase equilibrium studies at pressures ranging from 1 atm to 10 GPa are sufficient to constrain the origin of igneous rocks formed along oceanic ridges and in hotspots. The major element geochemistry of MORB is dominated by partial crystallization at low pressures in the oceanic crust and uppermost mantle, forcing compliance with liquid compositions in low-pressure cotectic equilibrium with olivine, plagioclase and often augite too; parental magmas to MORB formed by partial melting, mixing, and pooling have not survived these effects. Similarly, picrites and komatiites can transform to basalts by partial crystallization in the crust and lithosphere. However, parental picrites and komatiites that were successful in erupting to the surface typically have compositions that can be matched to experimentally-observed anhydrous primary magmas in equilibrium with harzburgite [L+Ol+Opx] at 3.0 to 4.5 GPa. This pressure is likely to represent an average for pooled magmas that collected at the top of a plume head as it flattened below the lithosphere. There is substantial uniformity in the normative olivine content of primary magmas at all depths in a plume melt column, and this results in pooled komatiitic magmas that are equally uniform in normative olivine. However, the imposition of pressure above 3 GPa produces picrites and komatiites with variations in normative enstatite and Al 2O 3 that reveal plume potential temperature and depths of initial melting. Hotter plumes begin to melt deeper than cooler plumes, yielding picrites and komatiites that are enriched in normative enstatite and depleted in Al 2O 3 because of a deeper column within which orthopyroxene can dissolve during decompression. Pressures of initial melting span the 4 to 10 GPa range, increasing in the following order: Iceland, Hawaii, Gorgona, Belingwe, Barberton. Parental komatiites and picrites from a single plume also exhibit internal variability in normative enstatite and Al 2O 3, indicating either a poorly mixed partial melt aggregation process in the plume or the imposition of partial crystallization of olivine-orthopyroxenite on a well-mixed parental magma. Plume shape and thermal structure can also influence the petrology and geochemistry of picrites and komatiites. Liquids extracted from harzburgite residues [L+Ol+Opx] will dominate magmatism in a plume head, and can erupt to form komatiites in oceanic plateaus. Liquids extracted from garnet peridotite residues in a plume axis will gain in importance when the plume head partially solidifies and is removed from the hotspot by a moving lithosphere, as is the case for Hawaii. The paradoxical involvement of garnet indicated by the heavy rare earth elements in picrites that otherwise have a harzburgite signature in Hawaii can be explained by the mixing and collection of magmas from the plume axis. Volcanic rocks from Hawaii and Gorgona and xenoliths from cratonic mantle provide evidence for the importance of partial crystallization of plume magmas when they encounter a cold lithosphere. Harzburgite residua and olivine-orthopyroxene cumulates formed in plumes can yield compositionally distinct lithospheric mantle which is buoyant, and this could have provided an important foundation for the stabilization of the first continents.

  9. Influence of preadsorbed oxygen on the sign and magnitude of the chemisorption-induced resistance change for H2 adsorption onto Fe films

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1986-01-01

    Measurements have been made of the chemisorption-induced resistance change for H2 adsorbed onto Fe film substrates predosed with fixed coverages of chemisorbed oxygen. The measurements were made at temperatures from 295 to 340 K and for estimated oxygen coverages of less than 0.1 monolayers. Two distinct resistance change components were observed in both the adsorption kinetics and the equilibrium isotherms: a positive component which is associated with the adsorption of H2 onto a clean Fe surface, and a negative component which was correlated with the presence of the chemisorbed oxygen. The resistance change isotherms can be fit with a model which assumes that each of the resistance change components result from dissociative chemisorbed hydrogen. Possible mechanisms for the chemisorbed-oxygen-induced negative resistance change are discussed.

  10. Electrical and optical properties of nitrogen doped SnO{sub 2} thin films deposited on flexible substrates by magnetron sputtering

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Fang, Feng, E-mail: fangfeng@seu.edu.cn; Zhang, Yeyu; Wu, Xiaoqin

    2015-08-15

    Graphical abstract: The best SnO{sub 2}:N TCO film: about 80% transmittance and 9.1 × 10{sup −4} Ω cm. - Highlights: • Nitrogen-doped tin oxide film was deposited on PET by RF-magnetron sputtering. • Effects of oxygen partial pressure on the properties of thin films were investigated. • For SnO{sub 2}:N film, visible light transmittance was 80% and electrical resistivity was 9.1 × 10{sup −4} Ω cm. - Abstract: Nitrogen-doped tin oxide (SnO{sub 2}:N) thin films were deposited on flexible polyethylene terephthalate (PET) substrates at room temperature by RF-magnetron sputtering. Effects of oxygen partial pressure (0–4%) on electrical and optical propertiesmore » of thin films were investigated. Experimental results showed that SnO{sub 2}:N films were amorphous state, and O/Sn ratios of SnO{sub 2}:N films were deviated from the standard stoichiometry 2:1. Optical band gap of SnO{sub 2}:N films increased from approximately 3.10 eV to 3.42 eV as oxygen partial pressure increased from 0% to 4%. For SnO{sub 2}:N thin films deposited on PET, transmittance was about 80% in the visible light region. The best transparent conductive oxide (TCO) deposited on flexible PET substrates was SnO{sub 2}:N thin films preparing at 2% oxygen partial pressure, the transmittance was about 80% and electrical conductivity was about 9.1 × 10{sup −4} Ω cm.« less

  11. Ozone formation behind pulsed-laser-generated blast waves in oxygen

    NASA Astrophysics Data System (ADS)

    Stricker, J.; Parker, J. G.

    1984-12-01

    The formation of ozone behind blast waves in oxygen generated by a pulsed laser has been investigated both experimentally and theoretically, over cell pressure range of 0.68-27 atm. Ozone buildup formed by successive pulses was monitored by recording UV absorption at 2540 Å. It was found that, as the number of pulses increase, the rate of ozone formation decreased until finally an equilibrium concentration was reached. This equilibrium magnitude was determined by the condition that the number of ozone molecules produced by the wave equals the number decomposed by the same wave. The decomposition and formation of O3 during a single pulse were monitored by time-resolved UV absorption measurements. In order to provide a fundamental basis for interpretation of the mechanism of ozone formation, a mathematical model was developed. Although qualitatively measurements and theory agree, the data, mainly on the number of O3 molecules produced per pulse, is in significant disagreement. Several possible explanations of this discrepancy are given.

  12. OXYGENATION OF HYDROCARBONS USING NANOSTRUCTURED TIO2 AS A PHOTOCATALYST: A GREEN ALTERNATIVE

    EPA Science Inventory

    High-value organic compounds have been synthesized successfully from linear and cyclic saturated hydrocarbons by a photocatalytic oxidation process using a semiconductor material, titanium dioxide (TiO2). Various hydrocarbons were partially oxygenated in both aqueous and gaseous...

  13. Electron transfer between cytochrome. alpha. and copper A in cytochrome c oxidase: A perturbed equilibrium study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Morgan, J.E.; Li, P.M.; Jang, D.J.

    1989-08-22

    Intramolecular electron transfer in partially reduced cytochrome c oxidase has been studied by the perturbed equilibrium method. The authors have prepared a three-electron-reduced, CO-inhibited form of the enzyme in which cytochrome a and copper A are partially reduced and in an intramolecular redox equilibrium. When these samples were irradiated with a nitrogen laser to photodissociate the bound CO, changes in absorbance at 598 and 830 nm were observed which were consistent with a fast electron transfer from cytochrome a to copper A. The absorbance changes at 598 nm gave an apparent rate of 17,000 {plus minus} 2,000 s{sup {minus}1} (1more » {sigma}), at pH 7.0 and 25.5{degree}C. These changes were not observed in either the CO mixed-valence or the CO-inhibited fully reduced forms of the enzyme. The rate was fastest at about pH 8.0, falling off toward both lower and higher pHs. There was a small but clear temperature dependence. The process was also observed in the cytochrome c-cytochrome c oxidase high-affinity complex. The electron equilibration measured between cytochrome {alpha} and copper A is far faster than any rate measured or inferred previously for this process.« less

  14. PH2O and simulated hypobaric hypoxia.

    PubMed

    Conkin, Johnny

    2011-12-01

    Some manufacturers of reduced oxygen (O2) breathing devices claim a comparable hypobaric hypoxia (HH) training experience by providing F1O2 < 0.209 at or near sea level pressure to match the ambient oxygen partial pressure (iso-PO2) of the target altitude. I conclude after a review of literature from investigators and manufacturers that these devices may not properly account for the 47 mmHg of water vapor partial pressure that reduces the inspired partial pressure of oxygen (P1O2), which is substantial at higher altitude relative to sea level. Consequently, some devices claiming an equivalent HH experience under normobaric conditions would significantly overestimate the HH condition, especially when simulating altitudes above 10,000 ft (3048 m). At best, the claim should be that the devices provide an approximate HH experience since they only duplicate the ambient PO2 at sea level as at altitude. An approach to reduce the overestimation and standardize the operation is to at least provide machines that create the same P1O2 conditions at sea level as at the target altitude, a simple software upgrade.

  15. Vacancies and holes in bulk and at 180° domain walls in lead titanate

    NASA Astrophysics Data System (ADS)

    Paillard, Charles; Geneste, Grégory; Bellaiche, Laurent; Dkhil, Brahim

    2017-12-01

    Domain walls (DWs) in ferroic materials exhibit a plethora of unexpected properties that are different from the adjacent ferroic domains. Still, the intrinsic/extrinsic origin of these properties remains an open question. Here, density functional theory calculations are used to investigate the interaction between vacancies and 180° DWs in the prototypical ferroelectric PbTiO3, with a special emphasis on cationic vacancies and released holes. All vacancies are more easily formed within the DW than in the domains. This is interpreted, using a phenomenological model, as the partial compensation of an extra-tensile stress when the defect is created inside the DW. Oxygen vacancies are found to be always fully ionized, independently of the thermodynamic conditions, while cationic vacancies can be either neutral or partially ionized (oxygen-rich conditions), or fully ionized (oxygen-poor conditions). Therefore, in oxidizing conditions, holes are induced by neutral and partially ionized Pb vacancies. In the bulk PbTiO3, these holes are more stable as delocalized rather than small polarons, but at DWs, the two forms are found to be possible.

  16. Effect of oxygen partial pressure on the density of antiphase boundaries in Fe3O4 thin films on Si(100)

    NASA Astrophysics Data System (ADS)

    Singh, Suraj Kumar; Husain, Sajid; Kumar, Ankit; Chaudhary, Sujeet

    2018-02-01

    Polycrystalline Fe3O4 thin films were grown on Si(100) substrate by reactive DC sputtering at different oxygen partial pressures PO2 for controlling the growth associated density of antiphase boundaries (APBs). The micro-Raman analyses were performed to study the structural and electronic properties in these films. The growth linked changes in the APBs density are probed by electron-phonon coupling strength (λ) and isothermal magnetization measurements. The estimated values of λ are found to vary from 0.39 to 0.56 with the increase in PO2 from 2.2 × 10-5 to 3.0 × 10-5 Torr, respectively. The saturation magnetization (saturation field) values are found to increase (decrease) from 394 (5.9) to 439 (3.0) emu/cm3 (kOe) with the increase in PO2 . The sharp Verwey transition (∼120 K), low saturation field, high saturation magnetization and low value of λ (comparable to the bulk value ∼0.51) clearly affirm the negligible amount of APBs in the high oxygen partial pressure deposited thin films.

  17. Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ryerson, F J

    The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such dissolution cannot be resolved in SEM images. The sluggish nature of diffusion in zircon may require that fractionation factors be determined by direct hydrothermal synthesis of zircon rather than by mineral-fluid exchange.« less

  18. Supplemental oxygen effect on hypoxemia at moderate altitude in patients with COPD.

    PubMed

    Kelly, Paul T; Swanney, Maureen P; Stanton, Josh D; Frampton, Chris; Peters, Matthew J; Beckert, Lutz E

    2009-09-01

    Altitude exposure will cause moderate to severe hypoxemia in patients with chronic obstructive pulmonary disease (COPD). Supplemental oxygen can be used to attenuate this hypoxemia; however, individual response is variable and difficult to predict. The aim of this study was to assess the efficacy of oxygen supplementation in patients with COPD at a barometric pressure similar to that of a commercial aircraft cabin. Following sea-level (40 m) arterial blood gases measurements, 18 patients with COPD were driven to altitude (2086 m), where blood gases were repeated at rest and while on 2 L x min(-1) of supplementary oxygen (altitude O2). Ascent from sea level to altitude caused significant hypoxemia (75 +/- 9 vs. 51 +/- 6 mmHg), which was partially reversed by supplemental oxygen (64 +/- 9 mmHg). Oxygen supplementation did not significantly alter PaCO2 levels (vs. altitude PaCO2). There was a significant relationship between the sea-level CaO2 versus the altitude O2 CaO2 (r = 0.89, P < 0.001). There was a significant relationship (r = 0.81, P < 0.001) between altitude-induced desaturation and resaturation with the administration of oxygen. There was a significant negative correlation (r = -0.74, P < 0.001) between baseline K(CO) and the improvement in CaO2 with the administration of oxygen. Low-flow supplemental oxygen during acute altitude exposure will partially reverse altitude-induced hypoxemia in patients with COPD. Patients with diffusion impairments are likely to experience the greatest altitude desaturation, but will gain the most benefit from supplemental oxygen. Supplemental oxygen, delivered at 2 L x min(-1), should maintain clinically acceptable oxygenation during commercial air travel in patients with COPD.

  19. Equilibrium chemistry down to 100 K. Impact of silicates and phyllosilicates on the carbon to oxygen ratio

    NASA Astrophysics Data System (ADS)

    Woitke, P.; Helling, Ch.; Hunter, G. H.; Millard, J. D.; Turner, G. E.; Worters, M.; Blecic, J.; Stock, J. W.

    2018-06-01

    We have introduced a fast and versatile computer code, GGCHEM, to determine the chemical composition of gases in thermo-chemical equilibrium down to 100 K, with or without equilibrium condensation. We have reviewed the data for molecular equilibrium constants, kp(T), from several sources and discussed which functional fits are most suitable for low temperatures. We benchmarked our results against another chemical equilibrium code. We collected Gibbs free energies, ΔGf⊖, for about 200 solid and liquid species from the NIST-JANAF database and the geophysical database SUPCRTBL. We discussed the condensation sequence of the elements with solar abundances in phase equilibrium down to 100 K. Once the major magnesium silicates Mg2SiO4[s] and MgSiO3[s] have formed, the dust to gas mass ratio jumps to a value of about 0.0045 which is significantly lower than the often assumed value of 0.01. Silicate condensation is found to increase the carbon to oxygen ratio (C/O) in the gas from its solar value of 0.55 up to 0.71, and, by the additional intake of water and hydroxyl into the solid matrix, the formation of phyllosilicates at temperatures below 400 K increases the gaseous C/O further to about 0.83. Metallic tungsten (W) is the first condensate found to become thermodynamically stable around 1600-2200 K (depending on pressure), several hundreds of Kelvin before subsequent materials such as zirconium dioxide (ZrO2) or corundum (Al2O3) can condense. We briefly discuss whether tungsten, despite its low abundance of 2 × 10-7 times the silicon abundance, could provide the first seed particles for astrophysical dust formation. GGCHEM code is publicly available at http://https://github.com/pw31/GGchemTable D.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A1

  20. Equilibrium structure of δ-Bi(2)O(3) from first principles.

    PubMed

    Music, Denis; Konstantinidis, Stephanos; Schneider, Jochen M

    2009-04-29

    Using ab initio calculations, we have systematically studied the structure of δ-Bi(2)O(3) (fluorite prototype, 25% oxygen vacancies) probing [Formula: see text] and combined [Formula: see text] and [Formula: see text] oxygen vacancy ordering, random distribution of oxygen vacancies with two different statistical descriptions as well as local relaxations. We observe that the combined [Formula: see text] and [Formula: see text] oxygen vacancy ordering is the most stable configuration. Radial distribution functions for these configurations can be classified as discrete (ordered configurations) and continuous (random configurations). This classification can be understood on the basis of local structural relaxations. Up to 28.6% local relaxation of the oxygen sublattice is present in the random configurations, giving rise to continuous distribution functions. The phase stability obtained may be explained with the bonding analysis. Electron lone-pair charges in the predominantly ionic Bi-O matrix may stabilize the combined [Formula: see text] and [Formula: see text] oxygen vacancy ordering.

  1. Isolated oxygen defects in 3C- and 4H-SiC: A theoretical study

    NASA Astrophysics Data System (ADS)

    Gali, A.; Heringer, D.; Deák, P.; Hajnal, Z.; Frauenheim, Th.; Devaty, R. P.; Choyke, W. J.

    2002-09-01

    Ab initio calculations in the local-density approximation have been carried out in SiC to determine the possible configurations of the isolated oxygen impurity. Equilibrium geometry and occupation levels were calculated. Substitutional oxygen in 3C-SiC is a relatively shallow effective mass like double donor on the carbon site (OC) and a hyperdeep double donor on the Si site (OSi). In 4H-SiC OC is still a double donor but with a more localized electron state. In 3C-SiC OC is substantially more stable under any condition than OSi or interstitial oxygen (Oi). In 4H-SiC OC is also the most stable one except for heavy n-type doping. We propose that OC is at the core of the electrically active oxygen-related defect family found by deep level transient spectroscopy in 4H-SiC. The consequences of the site preference of oxygen on the SiC/SiO2 interface are discussed.

  2. Oxygen potential of (U 0.88Pu 0.12)O 2±x and (U 0.7Pu 0.3)O 2±x at high temperatures of 1673-1873 K

    NASA Astrophysics Data System (ADS)

    Kato, M.; Takeuchi, K.; Uchida, T.; Sunaoshi, T.; Konashi, K.

    2011-07-01

    The oxygen potential of (U 0.88Pu 0.12)O 2±x (-0.0119 < x < 0.0408) and (U 0.7Pu 0.3)O 2±x (-0.0363 < x < 0.0288) was measured at high temperatures of 1673-1873 K using gas equilibrium method with thermo gravimeter. The measured data were analyzed by a defect chemistry model. Expressions were derived to represent the oxygen potential based on defect chemistry as functions of temperature and oxygen-to-metal ratio. The thermodynamic data, ΔG, ΔH and ΔS, at stoichiometric composition were obtained. The expressions can be used for in situ determination of the oxygen-to-metal ratio by the gas-equilibration method. The calculation results were consistent with measured data. It was estimated that addition of 1 wt.% Pu content increased oxygen potential of uranium and plutonium mixed oxide by 2-5 kJ/mol.

  3. The free energies of partially open coronal magnetic fields

    NASA Technical Reports Server (NTRS)

    Low, B. C.; Smith, D. F.

    1993-01-01

    A simple model of the low corona is examined in terms of a static polytropic atmosphere in equilibrium with a global magnetic field. The question posed is whether magnetostatic states with partially open magnetic fields may contain magnetic energies in excess of those in fully open magnetic fields. Based on the analysis presented here, it is concluded that the cross-field electric currents in the pre-eruption corona are a viable source of the bulk of the energies in a mass ejection and its associated flare.

  4. Phase compatibilities of YBa2Cu3O(9-delta) type structure in quintenary systems Y-Ba-Cu-O-X (impurity)

    NASA Technical Reports Server (NTRS)

    Karen, P.; Fjellvag, H.; Kjekshus, A.

    1990-01-01

    Electrical transport properties of the oxidic high T(sub c) superconductors are significantly affected by the presence of minor amounts of various elements adventing as impurities, e.g., from the chemical environment during manufacturing. YBa2Cu3O(9-delta) is prone to an extinction of the superconductivity on (partial) substitution of all four elemental components. E.g., Pr (for Y), La (for Ba), Zn (for Cu) or peroxygroup (for O) substituents will alter some of the superconductivity preconditions, like mixed valence state in Cu3O7/O(9-delta) network or structural distortion of the network. Although various pseudoternary chemical equilibrium phase diagrams of the Y(O)-Ba(O)-Cu(O) system now are available, no consensus is generally shown, however, this is partly due to lack of compatible definitions of the equilibrium conditions. Less information is available about the phase compatibilities in the appropriate quaternary phase diagram (including oxygen) and virtually no information exists about any pentenary phase diagrams (including one impurity). Unfortunately, complexity of such systems, stemming both from number of quaternary or pentenary compounds and from visualizing the five-component phase system, limits this presentation to more or less close surroundings of the YBa2Cu3O(9-delta) type phase in appropriate pseudoquaternary or pseudopseudoternary diagrams, involving Y-Ba-Cu and O, O-CO2, alkaline metals, Mg and alkaline earths, and Sc and most of the 3-d and 4-f elements. The systems were investigated by means of x ray diffraction, neutron diffraction and chemical analytical methods on samples prepared by sol-gel technique from citrates. The superconductivity was characterized by measuring the diamagnetic susceptibility by SQUID.

  5. Early Petrologic Processes on the Ureilite Parent Body

    NASA Technical Reports Server (NTRS)

    Singletary, S. J.; Grove, T. L.

    2003-01-01

    We present a petrographic and petrologic analysis of 21 olivine-pigeonite ureilites, along with new experimental results on melt compositions predicted to be in equilibrium with ureilite compositions. We conclude that these ureilites are the residues of a partial melting/smelting event. Textural evidence preserved in olivine and pigeonite record the extent of primary smelting. In pigeonite cores, we observe fine trains of iron metal inclusions that formed by the reduction of olivine to pigeonite and metal during primary smelting. Olivine cores lack metal inclusions but the outer grain boundaries are variably reduced by a late-stage reduction event. The modal proportion of pigeonite and percentage of olivine affected by late stage reduction are inversely related and provide an estimation of the degree of primary smelting during ureilite petrogenesis. In our sample suite, this correlation holds for 16 of the 21 samples examined. Olivine-pigeonite-liquid phase equilibrium constraints are used to obtain temperature estimates for the ureilite samples examined. Inferred smelting temperatures range from approximately 1150 C to just over 1300 C and span the range of estimates published for ureilites containing two or more pyroxenes. Temperature is also positively correlated with modal percent pigeonite. Smelting temperature is inversely correlated with smelting depth--the hottest olivine-pigeonite ureilites coming from the shallowest depth in the ureilite parent body. The highest temperature samples also have oxygen isotopic signatures that fall toward the refractory inclusion-rich end of the carbonaceous chondrite-anhydrous mineral (CCAM) slope 1 mixing line. These temperature-depth variations in the ureilite parent body could have been created by a heterogeneous distribution of heat producing elements, which would indicate that isotopic heterogeneities existed in the material from which the ureilite parent body was assembled.

  6. Positive selection in octopus haemocyanin indicates functional links to temperature adaptation.

    PubMed

    Oellermann, Michael; Strugnell, Jan M; Lieb, Bernhard; Mark, Felix C

    2015-07-05

    Octopods have successfully colonised the world's oceans from the tropics to the poles. Yet, successful persistence in these habitats has required adaptations of their advanced physiological apparatus to compensate impaired oxygen supply. Their oxygen transporter haemocyanin plays a major role in cold tolerance and accordingly has undergone functional modifications to sustain oxygen release at sub-zero temperatures. However, it remains unknown how molecular properties evolved to explain the observed functional adaptations. We thus aimed to assess whether natural selection affected molecular and structural properties of haemocyanin that explains temperature adaptation in octopods. Analysis of 239 partial sequences of the haemocyanin functional units (FU) f and g of 28 octopod species of polar, temperate, subtropical and tropical origin revealed natural selection was acting primarily on charge properties of surface residues. Polar octopods contained haemocyanins with higher net surface charge due to decreased glutamic acid content and higher numbers of basic amino acids. Within the analysed partial sequences, positive selection was present at site 2545, positioned between the active copper binding centre and the FU g surface. At this site, methionine was the dominant amino acid in polar octopods and leucine was dominant in tropical octopods. Sites directly involved in oxygen binding or quaternary interactions were highly conserved within the analysed sequence. This study has provided the first insight into molecular and structural mechanisms that have enabled octopods to sustain oxygen supply from polar to tropical conditions. Our findings imply modulation of oxygen binding via charge-charge interaction at the protein surface, which stabilize quaternary interactions among functional units to reduce detrimental effects of high pH on venous oxygen release. Of the observed partial haemocyanin sequence, residue 2545 formed a close link between the FU g surface and the active centre, suggesting a role as allosteric binding site. The prevalence of methionine at this site in polar octopods, implies regulation of oxygen affinity via increased sensitivity to allosteric metal binding. High sequence conservation of sites directly involved in oxygen binding indicates that functional modifications of octopod haemocyanin rather occur via more subtle mechanisms, as observed in this study.

  7. OXYGEN ABUNDANCES IN CEPHEIDS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Luck, R. E.; Andrievsky, S. M.; Korotin, S. N.

    2013-07-01

    Oxygen abundances in later-type stars, and intermediate-mass stars in particular, are usually determined from the [O I] line at 630.0 nm, and to a lesser extent, from the O I triplet at 615.7 nm. The near-IR triplets at 777.4 nm and 844.6 nm are strong in these stars and generally do not suffer from severe blending with other species. However, these latter two triplets suffer from strong non-local thermodynamic equilibrium (NLTE) effects and thus see limited use in abundance analyses. In this paper, we derive oxygen abundances in a large sample of Cepheids using the near-IR triplets from an NLTEmore » analysis, and compare those abundances to values derived from a local thermodynamic equilibrium (LTE) analysis of the [O I] 630.0 nm line and the O I 615.7 nm triplet as well as LTE abundances for the 777.4 nm triplet. All of these lines suffer from line strength problems making them sensitive to either measurement complications (weak lines) or to line saturation difficulties (strong lines). Upon this realization, the LTE results for the [O I] lines and the O I 615.7 nm triplet are in adequate agreement with the abundance from the NLTE analysis of the near-IR triplets.« less

  8. Templated synthesis of copper(II) azacyclam complexes using urea as a locking fragment and their metal-enhanced binding tendencies towards anions.

    PubMed

    Boiocchi, Massimo; Fabbrizzi, Luigi; Garolfi, Mauro; Licchelli, Maurizio; Mosca, Lorenzo; Zanini, Cristina

    2009-10-26

    Copper(II) azacyclam complexes 3(2+) and 4(2+) were obtained through a metal-templated procedure involving the pertinent open-chain tetramine, formaldehyde and a phenylurea derivative as a locking fragment. Both metal complexes can establish interactions with anions through the metal centre and the amide NH group. Equilibrium studies in DMSO by a spectrophotometric titration technique were carried out to assess the affinity of 3(2+) and 4(2+) towards anions. While the NH group of an amide model compound and the metal centre of the plain Cu(II)(azacyclam)(2+) complex do not interact at all with anions, 3(2+) and 4(2+) establish strong interactions with oxo anions, profiting from a pronounced cooperative effect. In particular, 1) they form stable 1:1 and 1:2 complexes with H(2)PO(4) (-) ions in a stepwise mode with both hydrogen-bonding and metal-ligand interactions, and 2) in the presence of CH(3)COO(-), they undergo deprotonation of the amido NH group and thus profit from axial coordination of the partially negatively charged carbonyl oxygen atom in a scorpionate binding mode.

  9. Diffusion of cations in chromia layers grown on iron-base alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lobnig, R.E.; Hennesen, K.; Grabke, H.J.

    Diffusion of the cations Cr, Fe, Mn, and Ni in Cr{sub 2}O{sub 3} has been investigated at 1,173 K. The diffusion measurements were performed on chromia layers grown on the model alloys Fe-20Cr and Fe-20Cr-12Ni in order to consider effects of small amounts of dissolved alien cations in Cr{sub 2}O{sub 3}. The samples were diffusion annealed in H{sub 2}-H{sub 2}O at an oxygen partial pressure close to the Cr{sub 2}O{sub 3}/Cr equilibrium. For all tracers the lattice-diffusion coefficients are 3-5 orders of magnitude smaller than the grain-boundary diffusion coefficients. The lattice diffusivity of Mn is about two orders of magnitudemore » greater than the other lattice-diffusion coefficients, especially in Cr{sub 2}O{sub 3} grown on Fe-20Cr-12Ni. The values of the diffusion coefficients for Cr, Fe, and Ni are in the same range. Diffusion of the tracers in Cr{sub 2}O{sub 3} grown on different alloys did not show significant differences with the exception of Mn.« less

  10. Calculating surface ocean pCO2 from biogeochemical Argo floats equipped with pH: An uncertainty analysis

    NASA Astrophysics Data System (ADS)

    Williams, N. L.; Juranek, L. W.; Feely, R. A.; Johnson, K. S.; Sarmiento, J. L.; Talley, L. D.; Dickson, A. G.; Gray, A. R.; Wanninkhof, R.; Russell, J. L.; Riser, S. C.; Takeshita, Y.

    2017-03-01

    More than 74 biogeochemical profiling floats that measure water column pH, oxygen, nitrate, fluorescence, and backscattering at 10 day intervals have been deployed throughout the Southern Ocean. Calculating the surface ocean partial pressure of carbon dioxide (pCO2sw) from float pH has uncertainty contributions from the pH sensor, the alkalinity estimate, and carbonate system equilibrium constants, resulting in a relative standard uncertainty in pCO2sw of 2.7% (or 11 µatm at pCO2sw of 400 µatm). The calculated pCO2sw from several floats spanning a range of oceanographic regimes are compared to existing climatologies. In some locations, such as the subantarctic zone, the float data closely match the climatologies, but in the polar Antarctic zone significantly higher pCO2sw are calculated in the wintertime implying a greater air-sea CO2 efflux estimate. Our results based on four representative floats suggest that despite their uncertainty relative to direct measurements, the float data can be used to improve estimates for air-sea carbon flux, as well as to increase knowledge of spatial, seasonal, and interannual variability in this flux.

  11. Simulation of water vapor condensation on LOX droplet surface using liquid nitrogen

    NASA Technical Reports Server (NTRS)

    Powell, Eugene A.

    1988-01-01

    The formation of ice or water layers on liquid oxygen (LOX) droplets in the Space Shuttle Main Engine (SSME) environment was investigated. Formulation of such ice/water layers is indicated by phase-equilibrium considerations under conditions of high partial pressure of water vapor (steam) and low LOX droplet temperature prevailing in the SSME preburner or main chamber. An experimental investigation was begun using liquid nitrogen as a LOX simulant. A monodisperse liquid nitrogen droplet generator was developed which uses an acoustic driver to force the stream of liquid emerging from a capillary tube to break up into a stream of regularly space uniformly sized spherical droplets. The atmospheric pressure liquid nitrogen in the droplet generator reservoir was cooled below its boiling point to prevent two phase flow from occurring in the capillary tube. An existing steam chamber was modified for injection of liquid nitrogen droplets into atmospheric pressure superheated steam. The droplets were imaged using a stroboscopic video system and a laser shadowgraphy system. Several tests were conducted in which liquid nitrogen droplets were injected into the steam chamber. Under conditions of periodic droplet formation, images of 600 micron diameter liquid nitrogen droplets were obtained with the stroboscopic video systems.

  12. Temperature effect on behaviour, oxygen consumption, ammonia excretion and tolerance limit of the post larvae of shrimp Penaeus indicus.

    PubMed

    Krishnamoorthy, R; Mohamed, E H Syed; Rao, T Subba; Venugopalanj, V P; Hameed, P Shahul

    2008-01-01

    The present study has been carried out to know the effect of temperature on behaviour, equilibrium loss and tolerance limit of the post larvae of shrimp Penaeus indicus. The experimental temperatures were selected based on the thermal tolerance limit. The experiments were conducted at a specific temperature for duration of 48 hr. The thermal tolerance experiments were conducted in two ways: in direct exposure and in gradually increasing temperature. The upper and lower lethal temperatures for the post larvae of shrimp P. indicus were 43.5 degrees C and 8 degrees C respectively. During tolerance experiment, no mortality was observed at 33 degrees C and 35 degrees C. But at 38 degrees C with gradual increase in temperature, 30% loss of equilibrium and mortality were recorded in 24.31 hrs and 25.07 hrs, and the remaining 70% were alive. On the contrary, when the post larvae of shrimps were directly exposed to 38 degrees C, almost 80% loss of equilibrium and mortality were recorded in 30.22 hrs and 30.40 hrs, remaining 20% were alive. At 40 degrees C with gradual increase in temperature, 100% loss of equilibrium and mortality were recorded in 25.32 hrs and 25.56 hrs. On the other hand, when the post larvae of shrimps were directly exposed to 40 degrees C, 100% loss of equilibrium was observed in 0.37 hrs and mortality in 1.40 hrs. These behavioral responses include an elevated temperature of 12 degrees C, surfacing, dashing against glass wall, jumping out of the water, etc. In general, the rate of oxygen consumption and ammonia excretion was found to enhance with increasing temperature. In the present study, it was found that gradual increase in temperature favours the shellfish population to escape from the thermal exposure as compared to direct exposure.

  13. Multiple stable isotope fronts during non-isothermal fluid flow

    NASA Astrophysics Data System (ADS)

    Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

    2018-02-01

    Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

  14. Micro system comprising 96 micro valves on a titer plate

    NASA Astrophysics Data System (ADS)

    Krabbe, S.; Flitsch, D.; Büchs, J.; Schomburg, W. K.

    2016-10-01

    A system of 96 micro valves has been developed and mounted on top of a 48-well micro titer plate providing two valves for each well controlling its air inlet and outlet. Testing of the valve system showed that all valves are working and are opened and closed reliably. A pneumatic system is switching inlet and outlet valves independently of each other. The geometry of the feed channels ensures an equal air flow through all wells, when the valves are open. Between the micro valves, one optical fibre was inserted through the lid of each well allowing measuring the oxygen partial pressure in the enclosed air volume by fluorescence sensor spots. Escherichia coli bacteria were grown inside the wells and their metabolism was observed by the oxygen partial pressure change due to respiration. In all 48 wells, the same oxygen transfer rate was observed within an averaged standard deviation of 1 mmol/L/h. The oxygen transfer rate differences compared to a macroscopic standard shake flask system were overall compatible within their uncertainties.

  15. A Burke-Schumann analysis of diffusion-flame structures supported by a burning droplet

    NASA Astrophysics Data System (ADS)

    Nayagam, Vedha; Dietrich, Daniel L.; Williams, Forman A.

    2017-07-01

    A Burke-Schumann description of three different regimes of combustion of a fuel droplet in an oxidising atmosphere, namely the premixed-flame regime, the partial-burning regime and the diffusion-flame regime, is presented by treating the fuel and oxygen leakage fractions through the flame as known parameters. The analysis shows that the burning-rate constant, the flame-standoff ratio, and the flame temperature in these regimes can be obtained from the classical droplet-burning results by suitable definitions of an effective ambient oxygen mass fraction and an effective fuel concentration in the droplet interior. The results show that increasing oxygen leakage alone through the flame lowers both the droplet burning rate and the flame temperature, whereas leakage of fuel alone leaves the burning rate unaffected while reducing the flame temperature and moving the flame closer to the droplet surface. Solutions for the partial-burning regime are shown to exist only for a limited range of fuel and oxygen leakage fractions.

  16. Oxygen nonstoichiometry and thermodynamic quantities in solid solution SrFe1-xSnxO3-δ

    NASA Astrophysics Data System (ADS)

    Merkulov, O. V.; Markov, A. A.; Leonidov, I. A.; Patrakeev, M. V.; Kozhevnikov, V. L.

    2018-06-01

    The oxygen content (3-δ) variations in tin substituted derivatives SrFe1-xSnxO3-δ, where x = 0.05, 0.1, 0.17 and 0.25, of perovskite-like strontium ferrite, have been studied by coulometric titration measurements within oxygen partial pressure (pO2) range 10-19-10-2 atm at 800-950 °С. The obtained dependencies of (3-δ) from pO2 and temperature are used for calculations of partial molar thermodynamic functions of oxygen in the oxide structure. It is found that a satisfactory explanation of the experimental results can be attained within frameworks of the ideal solution model with ion and electron defects appearing in the result of oxidation and disproportionation of iron cations. The increase of the oxidation reaction enthalpy with tin content is consistent with the increase of the unit cell parameter, i.e., the stretch and relaxation of Fe-O chemical bonds.

  17. Low-Tidal-Volume Ventilation in the Acute Respiratory Distress Syndrome

    PubMed Central

    Malhotra, Atul

    2008-01-01

    A 55-year-old man who is 178 cm tall and weighs 95 kg is hospitalized with community-acquired pneumonia and progressively severe dyspnea. His arterial oxygen saturation while breathing 100% oxygen through a face mask is 76%; a chest radiograph shows diffuse alveolar infiltrates with air bronchograms. He is intubated and receives mechanical ventilation; ventilator settings include a tidal volume of 1000 ml, a positive end-expiratory pressure (PEEP) of 5 cm of water, and a fraction of inspired oxygen (FiO2) of 0.8. With these settings, peak airway pressure is 50 to 60 cm of water, plateau airway pressure is 38 cm of water, partial pressure of arterial oxygen is 120 mm Hg, partial pressure of carbon dioxide is 37 mm Hg, and arterial blood pH is 7.47. The diagnosis of the acute respiratory distress syndrome (ARDS) is made. An intensive care specialist evaluates the patient and recommends changing the current ventilator settings and implementing a low-tidal-volume ventilation strategy. PMID:17855672

  18. Predicting the effects of coastal hypoxia on vital rates of the planktonic copepod Acartia tonsa Dana.

    PubMed

    Elliott, David T; Pierson, James J; Roman, Michael R

    2013-01-01

    We describe a model predicting the effects of low environmental oxygen on vital rates (egg production, somatic growth, and mortality) of the coastal planktonic copepod Acartia tonsa. Hypoxic conditions can result in respiration rate being directly limited by oxygen availability. We hypothesized that A. tonsa egg production, somatic growth, and ingestion rates would all respond in a similar manner to low oxygen conditions, as a result of oxygen dependent changes in respiration rate. Rate data for A. tonsa egg production, somatic growth, and ingestion under low environmental oxygen were compiled from the literature and from supplementary experiments. The response of these rates to oxygen was compared by converting all to the analogous units in terms of oxygen utilization, which we termed analogous respiration rate. These analogous respiration rates, along with published measurements of respiration rates, were used to parameterize and evaluate the relationship between A. tonsa respiration rate and environmental oxygen. At 18 °C, our results suggest that A. tonsa experiences sub-lethal effects of hypoxia below an oxygen partial pressure of 8.1 kPa (~3.1 mg L(-1) = 2.3 mL L(-1)). The results of this study can be used to predict the effects of hypoxia on A. tonsa growth and mortality as related to environmental temperature and oxygen partial pressure. Such predictions will be useful as a way to incorporate the effects of coastal hypoxia into population, community, or ecosystem level models that include A. tonsa. This approach can also be used to characterize the effects of hypoxia on other aquatic organisms.

  19. Fiber-Optic Based Compact Gas Leak Detection System

    NASA Technical Reports Server (NTRS)

    deGroot, Wim A.

    1995-01-01

    A propellant leak detection system based on Raman scattering principles is introduced. The proposed system is flexible and versatile as the result of the use of optical fibers. It is shown that multiple species can be monitored simultaneously. In this paper oxygen, nitrogen, carbon monoxide, and hydrogen are detected and monitored. The current detection sensitivity for both hydrogen and carbon monoxide is 1% partial pressure at ambient conditions. The sensitivity for oxygen and nitrogen is 0.5% partial pressure. The response time to changes in species concentration is three minutes. This system can be used to monitor multiple species at several locations.

  20. 30 CFR 36.43 - Determination of exhaust-gas composition.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... of fuel consumption, pressures, temperatures, and other data significant in the safe operation of diesel equipment. (b) Exhaust-gas samples shall be analyzed for carbon dioxide, oxygen, carbon monoxide....45). The engine shall be at temperature equilibrium before exhaust-gas samples are collected or other...

  1. 30 CFR 36.43 - Determination of exhaust-gas composition.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... of fuel consumption, pressures, temperatures, and other data significant in the safe operation of diesel equipment. (b) Exhaust-gas samples shall be analyzed for carbon dioxide, oxygen, carbon monoxide....45). The engine shall be at temperature equilibrium before exhaust-gas samples are collected or other...

  2. 30 CFR 36.43 - Determination of exhaust-gas composition.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... of fuel consumption, pressures, temperatures, and other data significant in the safe operation of diesel equipment. (b) Exhaust-gas samples shall be analyzed for carbon dioxide, oxygen, carbon monoxide....45). The engine shall be at temperature equilibrium before exhaust-gas samples are collected or other...

  3. 30 CFR 36.43 - Determination of exhaust-gas composition.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... of fuel consumption, pressures, temperatures, and other data significant in the safe operation of diesel equipment. (b) Exhaust-gas samples shall be analyzed for carbon dioxide, oxygen, carbon monoxide....45). The engine shall be at temperature equilibrium before exhaust-gas samples are collected or other...

  4. 30 CFR 36.43 - Determination of exhaust-gas composition.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... of fuel consumption, pressures, temperatures, and other data significant in the safe operation of diesel equipment. (b) Exhaust-gas samples shall be analyzed for carbon dioxide, oxygen, carbon monoxide....45). The engine shall be at temperature equilibrium before exhaust-gas samples are collected or other...

  5. A Double-Blinded, Randomized Comparison of Medetomidine-Tiletamine-Zolazepam and Dexmedetomidine-Tiletamine-Zolazepam Anesthesia in Free-Ranging Brown Bears (Ursus Arctos)

    PubMed Central

    Cattet, Marc; Zedrosser, Andreas; Stenhouse, Gordon B.; Küker, Susanne; Evans, Alina L.; Arnemo, Jon M.

    2017-01-01

    We compared anesthetic features, blood parameters, and physiological responses to either medetomidine-tiletamine-zolazepam or dexmedetomidine-tiletamine-zolazepam using a double-blinded, randomized experimental design during 40 anesthetic events of free-ranging brown bears (Ursus arctos) either captured by helicopter in Sweden or by culvert trap in Canada. Induction was smooth and predictable with both anesthetic protocols. Induction time, the need for supplemental drugs to sustain anesthesia, and capture-related stress were analyzed using generalized linear models, but anesthetic protocol did not differentially affect these variables. Arterial blood gases and acid-base status, and physiological responses were examined using linear mixed models. We documented acidemia (pH of arterial blood < 7.35), hypoxemia (partial pressure of arterial oxygen < 80 mmHg), and hypercapnia (partial pressure of arterial carbon dioxide ≥ 45 mmHg) with both protocols. Arterial pH and oxygen partial pressure were similar between groups with the latter improving markedly after oxygen supplementation (p < 0.001). We documented dose-dependent effects of both anesthetic protocols on induction time and arterial oxygen partial pressure. The partial pressure of arterial carbon dioxide increased as respiratory rate increased with medetomidine-tiletamine-zolazepam, but not with dexmedetomidine-tiletamine-zolazepam, demonstrating a differential drug effect. Differences in heart rate, respiratory rate, and rectal temperature among bears could not be attributed to the anesthetic protocol. Heart rate increased with increasing rectal temperature (p < 0.001) and ordinal day of capture (p = 0.002). Respiratory rate was significantly higher in bears captured by helicopter in Sweden than in bears captured by culvert trap in Canada (p < 0.001). Rectal temperature significantly decreased over time (p ≤ 0.05). Overall, we did not find any benefit of using dexmedetomidine-tiletamine-zolazepam instead of medetomidine-tiletamine-zolazepam in the anesthesia of brown bears. Both drug combinations appeared to be safe and reliable for the anesthesia of free-ranging brown bears captured by helicopter or by culvert trap. PMID:28118413

  6. The importance of dissolved free oxygen during formation of sandstone-type uranium deposits

    USGS Publications Warehouse

    Granger, Harry Clifford; Warren, C.G.

    1979-01-01

    One factor which distinguishes t, he genesis of roll-type uranium deposits from the Uravan Mineral Belt and other sandstone-type uranium deposits may be the presence and concentration of dissolved free oxygen in the ore-forming. solutions. Although dissolved oxygen is a necessary prerequisite for the formation of roll-type deposits, it is proposed that a lack of dissolved oxygen is a prerequisite for the Uravan deposits. Solutions that formed both types of deposits probably had a supergene origin and originated as meteoric water in approximate equilibrium with atmospheric oxygen. Roll-type deposits were formed where the Eh dropped abruptly following consumption of the oxygen by iron sulfide minerals and creation of kinetically active sulfur species that could reduce uranium. The solutions that formed the Uravan deposits, on the other hand, probably first equilibrated with sulfide-free ferrous-ferric detrital minerals and fossil organic matter in the host rock. That is, the uraniferous solutions lost their oxygen without lowering their Eh enough to precipitate uranium. Without oxygen, they then. became incapable of oxidizing iron sulfide minerals. Subsequent localization and formation of ore bodies from these oxygen-depleted solutions, therefore, was not necessarily dependent on large reducing capacities.

  7. Partial nitrification using aerobic granules in continuous-flow reactor: rapid startup.

    PubMed

    Wan, Chunli; Sun, Supu; Lee, Duu-Jong; Liu, Xiang; Wang, Li; Yang, Xue; Pan, Xiangliang

    2013-08-01

    This study applied a novel strategy to rapid startup of partial nitrification in continuous-flow reactor using aerobic granules. Mature aerobic granules were first cultivated in a sequencing batch reactor at high chemical oxygen demand in 16 days. The strains including the Pseudoxanthomonas mexicana strain were enriched in cultivated granules to enhance their structural stability. Then the cultivated granules were incubated in a continuous-flow reactor with influent chemical oxygen deamnad being stepped decreased from 1,500 ± 100 (0-19 days) to 750 ± 50 (20-30 days), and then to 350 ± 50 mg l(-1) (31-50 days); while in the final stage 350 mg l(-1) bicarbonate was also supplied. Using this strategy the ammonia-oxidizing bacterium, Nitrosomonas europaea, was enriched in the incubated granules to achieve partial nitrification efficiency of 85-90% since 36 days and onwards. The partial nitrification granules were successfully harvested after 52 days, a period much shorter than those reported in literature. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Atomic Resonance Radiation Energetics Investigation as a Diagnostic Method for Non-Equilibrium Hypervelocity Flows

    NASA Technical Reports Server (NTRS)

    Meyer, Scott A.; Bershader, Daniel; Sharma, Surendra P.; Deiwert, George S.

    1996-01-01

    Absorption measurements with a tunable vacuum ultraviolet light source have been proposed as a concentration diagnostic for atomic oxygen, and the viability of this technique is assessed in light of recent measurements. The instrumentation, as well as initial calibration measurements, have been reported previously. We report here additional calibration measurements performed to study the resonance broadening line shape for atomic oxygen. The application of this diagnostic is evaluated by considering the range of suitable test conditions and requirements, and by identifying issues that remain to be addressed.

  9. Co-processing CH4 and oxygenates on Mo/H-ZSM-5: 2. CH4-CO2 and CH4-HCOOH mixtures.

    PubMed

    Bedard, Jeremy; Hong, Do-Young; Bhan, Aditya

    2013-08-07

    Co-processing of formic acid or carbon dioxide with CH4 (FA/CH4 = 0.01-0.03 and CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 catalysts at 950 K with the prospect of kinetically coupling dehydrogenation and deoxygenation cycles results instead in a two-zone, staged bed reactor configuration consisting of upstream oxygenate/CH4 reforming and downstream CH4 dehydroaromatization. The addition of an oxygenate co-feed (oxygenate/CH4 = 0.01-0.03) causes oxidation of the active molybdenum carbide catalyst while producing CO and H2 until completely converted. Forward rates of C6H6 synthesis are unaffected by the introduction of an oxygenate co-feed after rigorously accounting for the thermodynamic reversibility caused by the H2 produced in oxygenate reforming reactions and the fraction of the active catalyst deemed unavailable for CH4 DHA. All effects of co-processing oxygenates with CH4 can be construed in terms of an approach to equilibrium.

  10. Cobalt porphyrin-mediated oxygen transport in a polymer membrane. Effect of the cobalt porphyrin structure on the oxygen-binding reaction, oxygen-diffusion constants, and oxygen-transport efficiency

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nishide, Hiroyuki; Suzuki, Takayuki; Kawakami, Hiroyoshi

    1994-05-12

    New derivatives of (meso-[alpha],[alpha],[alpha],[alpha]-tetrakis(o-pivalamidophenyl)porphinato)cobalt (CoPs) were characterized by oxygen-binding equilibrium and rate constants of the cobalt centered in the porphyrins. They depended on the structure of the porphyrin; for example, the rate constants of oxygen binding and dissociation (k[sub on] and k[sub off]) for [alpha][sup 3][beta]-CoP[sub 4]P were 3 and 20 times as large as those for [alpha][sup 4]-CoB[sub 4]P, respectively. Oxygen transport through the polymer membranes containing CoPs as the fixed oxygen carriers was facilitated and was affected by the oxygen-binding character or the structure of CoPs. The logarithmically linear correlation of the oxygen-dissociation rate constant of CoPs (k[submore » off] = (3-66) x 10[sup 3] S[sup [minus]1]) with the diffusion constant of oxygen via CoPs fixed in the membranes (D[sub cc] = (3-140) x 10[sup [minus]9] cm[sup 2] s[sup [minus]1]) was given for those six CoP derivatives. 26 refs., 5 figs., 2 tabs.« less

  11. Why is the partial oxygen pressure of human tissues a crucial parameter? Small molecules and hypoxia

    PubMed Central

    Carreau, Aude; Hafny-Rahbi, Bouchra El; Matejuk, Agata; Grillon, Catherine; Kieda, Claudine

    2011-01-01

    Abstract Oxygen supply and diffusion into tissues are necessary for survival. The oxygen partial pressure (pO2), which is a key component of the physiological state of an organ, results from the balance between oxygen delivery and its consumption. In mammals, oxygen is transported by red blood cells circulating in a well-organized vasculature. Oxygen delivery is dependent on the metabolic requirements and functional status of each organ. Consequently, in a physiological condition, organ and tissue are characterized by their own unique ‘tissue normoxia’ or ‘physioxia’ status. Tissue oxygenation is severely disturbed during pathological conditions such as cancer, diabetes, coronary heart disease, stroke, etc., which are associated with decrease in pO2, i.e. ‘hypoxia’. In this review, we present an array of methods currently used for assessing tissue oxygenation. We show that hypoxia is marked during tumour development and has strong consequences for oxygenation and its influence upon chemotherapy efficiency. Then we compare this to physiological pO2 values of human organs. Finally we evaluate consequences of physioxia on cell activity and its molecular modulations. More importantly we emphasize the discrepancy between in vivo and in vitro tissue and cells oxygen status which can have detrimental effects on experimental outcome. It appears that the values corresponding to the physioxia are ranging between 11% and 1% O2 whereas current in vitro experimentations are usually performed in 19.95% O2, an artificial context as far as oxygen balance is concerned. It is important to realize that most of the experiments performed in so-called normoxia might be dangerously misleading. PMID:21251211

  12. Why is the partial oxygen pressure of human tissues a crucial parameter? Small molecules and hypoxia.

    PubMed

    Carreau, Aude; El Hafny-Rahbi, Bouchra; Matejuk, Agata; Grillon, Catherine; Kieda, Claudine

    2011-06-01

    Oxygen supply and diffusion into tissues are necessary for survival. The oxygen partial pressure (pO(2)), which is a key component of the physiological state of an organ, results from the balance between oxygen delivery and its consumption. In mammals, oxygen is transported by red blood cells circulating in a well-organized vasculature. Oxygen delivery is dependent on the metabolic requirements and functional status of each organ. Consequently, in a physiological condition, organ and tissue are characterized by their own unique 'tissue normoxia' or 'physioxia' status. Tissue oxygenation is severely disturbed during pathological conditions such as cancer, diabetes, coronary heart disease, stroke, etc., which are associated with decrease in pO(2), i.e. 'hypoxia'. In this review, we present an array of methods currently used for assessing tissue oxygenation. We show that hypoxia is marked during tumour development and has strong consequences for oxygenation and its influence upon chemotherapy efficiency. Then we compare this to physiological pO(2) values of human organs. Finally we evaluate consequences of physioxia on cell activity and its molecular modulations. More importantly we emphasize the discrepancy between in vivo and in vitro tissue and cells oxygen status which can have detrimental effects on experimental outcome. It appears that the values corresponding to the physioxia are ranging between 11% and 1% O(2) whereas current in vitro experimentations are usually performed in 19.95% O(2), an artificial context as far as oxygen balance is concerned. It is important to realize that most of the experiments performed in so-called normoxia might be dangerously misleading. © 2011 The Authors Journal of Cellular and Molecular Medicine © 2011 Foundation for Cellular and Molecular Medicine/Blackwell Publishing Ltd.

  13. Optimal control of a coupled partial and ordinary differential equations system for the assimilation of polarimetry Stokes vector measurements in tokamak free-boundary equilibrium reconstruction with application to ITER

    NASA Astrophysics Data System (ADS)

    Faugeras, Blaise; Blum, Jacques; Heumann, Holger; Boulbe, Cédric

    2017-08-01

    The modelization of polarimetry Faraday rotation measurements commonly used in tokamak plasma equilibrium reconstruction codes is an approximation to the Stokes model. This approximation is not valid for the foreseen ITER scenarios where high current and electron density plasma regimes are expected. In this work a method enabling the consistent resolution of the inverse equilibrium reconstruction problem in the framework of non-linear free-boundary equilibrium coupled to the Stokes model equation for polarimetry is provided. Using optimal control theory we derive the optimality system for this inverse problem. A sequential quadratic programming (SQP) method is proposed for its numerical resolution. Numerical experiments with noisy synthetic measurements in the ITER tokamak configuration for two test cases, the second of which is an H-mode plasma, show that the method is efficient and that the accuracy of the identification of the unknown profile functions is improved compared to the use of classical Faraday measurements.

  14. Does shaking increase the pressure inside a bottle of champagne?

    PubMed

    Vreme, A; Pouligny, B; Nadal, F; Liger-Belair, G

    2015-02-01

    Colas, beers and sparkling wines are all concentrated solutions of carbon dioxide in aqueous solvents. Any such carbonated liquid is ordinarily conditioned inside a closed bottle or a metal can as a liquid-gas 2-phase system. At thermodynamic equilibrium, the partial pressure of carbon-dioxide in the gas phase and its concentration in the liquid are proportional (Henry's law). In practical conditions and use (transport, opening of the container, exterior temperature change, etc.), Henry's equilibrium can be perturbed. The goal of this paper is to describe and understand how the system responds to such perturbations and evolves towards a new equilibrium state. Formally, we investigate the dynamics around Henry's equilibrium of a closed system, through dedicated experiments and modeling. We focus on the response to a sudden pressure change and to mechanical shaking (the latter point inspired the article's title). Observations are rationalized through basic considerations including molecular diffusion, bubble dynamics (based on Epstein-Plesset theory) and chemi-convective hydrodynamic instabilities. Copyright © 2014 Elsevier Inc. All rights reserved.

  15. Statistical approach to partial equilibrium analysis

    NASA Astrophysics Data System (ADS)

    Wang, Yougui; Stanley, H. E.

    2009-04-01

    A statistical approach to market equilibrium and efficiency analysis is proposed in this paper. One factor that governs the exchange decisions of traders in a market, named willingness price, is highlighted and constitutes the whole theory. The supply and demand functions are formulated as the distributions of corresponding willing exchange over the willingness price. The laws of supply and demand can be derived directly from these distributions. The characteristics of excess demand function are analyzed and the necessary conditions for the existence and uniqueness of equilibrium point of the market are specified. The rationing rates of buyers and sellers are introduced to describe the ratio of realized exchange to willing exchange, and their dependence on the market price is studied in the cases of shortage and surplus. The realized market surplus, which is the criterion of market efficiency, can be written as a function of the distributions of willing exchange and the rationing rates. With this approach we can strictly prove that a market is efficient in the state of equilibrium.

  16. Reactive solute transport in streams: 1. Development of an equilibrium- based model

    USGS Publications Warehouse

    Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

    1996-01-01

    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  17. USE OF SEDIMENT PROFILE IMAGERY TO ESTIMATE NEAR-BOTTOM DISSOLVED OXYGEN REGIMES

    EPA Science Inventory

    The U.S. EPA, Atlantic Ecology Division is developing empirical stressor-response models for nitrogen pollution in partially enclosed coastal systems using dissolved oxygen (DO) as one of the system responses. We are testing a sediment profile image camera as a surrogate indicat...

  18. IMPROVING PHOTOCATALYTIC PROPERTIES OF TIO2 THROUGH THIN FILM COATING AND METAL DOPING VIA FLAME AEROSOL COATING METHOD

    EPA Science Inventory

    There has been an increasing demand for efficient, economical and environmentally friendly methods for partial oxidation of hydrocarbons by molecular oxygen, to desirable industrial feedstock oxygenates. Current processes are energy intensive, have low conversion efficiencies and...

  19. The Persistence of the Candle-and-Cylinder Misconception.

    ERIC Educational Resources Information Center

    Birk, James P.; Lawson, Anton E.

    1999-01-01

    Argues that the candle-and-cylinder demonstration does not show that air is composed of 21% oxygen. Finds that the heating of air results in a partial expulsion of air, and that the flame is extinguished by a local, rather than a complete, consumption of oxygen. (WRM)

  20. Study of Cleanliness of High Nitrogen Steel in ESR

    NASA Astrophysics Data System (ADS)

    Xuwei, Tang; Rong, Zhu

    This paper compares inclusions in high nitrogen steel before and after ESR process, analyzes the influence of slag systems and total oxygen content in consumable ingots. The total oxygen content is reduced apparently during ESR process, which indicates good effects on removal of inclusions. In the experiment, it shows that different slag systems will affect the result of inclusions removal significantly; proper w(CaO/Al2O3) will reduce the level of inclusions and total oxygen content in ESR ingots. In ESR process, the type and chemical composition of inclusions have no difference when oxygen content in consumable ingots is different, which means O content in consumable ingots have no direct relationship with cleanliness of ESR ingots. In typical inclusions, w(MnO)/w(MnO+Al2O3)≈0.23 0.32. The total oxygen content of ESR ingots keeps between 20 30ppm when the oxygen contents in consumable ingots are diverse from 40 to 100ppm. Meanwhile, this paper studies desulfurization process of high nitrogen steel in ESR, analyzes the influence of slag systems a nd remelting rates on desulfurization efficiency. The results indicate that the average size and quant ity of sulfide inclusion decrease after ESR process. The typical inclusion after ESR process is MnS+Al2O3. Slag system with proper CaO content has higher sulfur partition ratio, which leads to better desulfurization effect. The desulfurization rate changes greatly with different remelting rates, which indicates the kinetic parameter has more influence in desulfurization. The reason of this phenomenon is that the process of desulfurization can be considered as a non-equilibrium reaction, which differs with thermodynamic equilibrium. In kinetic study, it is founded that the desulfurization efficiency increases with higher remelting area, sulfur partition and lower remelting rate, which is different from experiment. The desulfurization efficiency decreases firstly and then recovers when remelting rate drops. The enrichment of sulfide in slag results in resulfurization in steel, which leads to lower desulfurization efficiency.

  1. Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

    NASA Astrophysics Data System (ADS)

    Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

    2017-12-01

    The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical results, measurements of site-specific isotopic fractionation properties could improve our understanding and the interpretation of isotopic records in apatites.

  2. Preflight studies on tolerance of pocket mice to oxygen and heat. III - Effects on eyes

    NASA Technical Reports Server (NTRS)

    Philpott, D. E.; Corbett, R. L.; Black, S.; Takahashi, A.; Leaffer, D.

    1975-01-01

    A study was made of the eyes of eight pocket mice exposed to oxygen at partial pressures of 8, 10, or 12 psi over a period of 7 d. At the termination of the exposure, the animals were decompressed to sea-level O2, either immediately or over a period of 30, 60, or 90 min. No pathological changes were found in any of the eyes, except in the retina of one of the animals exposed to 12 psi O2. Here, only a single rod photoreceptor was found damaged, an observation not regarded as significant. Hence, an oxygen partial pressure as high as 12 psi in the canister in which pocket mice were expected to fly on Apollo XVII would probably have no deleterious effect on the eyes of the animals.

  3. Partial oxidation of methane by pulsed corona discharges

    NASA Astrophysics Data System (ADS)

    Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

    2014-09-01

    Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

  4. [Observation on changes of oxygen partial pressure in the deep tissues along the large intestine meridian during acupuncture in healthy subjects].

    PubMed

    Chen, Ming; Hu, Xiang-long; Wu, Zu-xing

    2010-06-01

    To observe changes of the partial oxygen pressure in the deep tissues along the Large Intestine Meridian (LIM) during acupuncture stimulation, so as to reveal the characteristics of energy metabolism in the tissues along the LIM. Thirty-one healthy volunteer subjects were enlisted in the present study. Partial oxygen pressure (POP) in the tissues (at a depth of about 1.5 cm) of acupoints Binao (LI 14), Shouwuli (LI 13), Shousanli (LI 10), 2 non-acupoints [the midpoints between Quchi (LI 11) and LI 14, and between Yangxi (LI 5) and LI 11) of the LIM, and 10 non-meridian points, 1.5-2.0 cm lateral and medial to each of the tested points of the LIM was detected before, during and after electroacupuncture (EA) stimulation of Hegu (LI 4) by using a tissue oxygen tension needle-like sensor. In normal condition, the POP values in the deep tissues along the LIM were significantly higher than those of the non-meridian control points on its bilateral sides. During and after EA of Hegu (LI 4), the POP levels decreased significantly in the deep tissues along the LIM in comparison with pre-EA (P < 0.01), and had no apparent changes in the non-meridian control points (P > 0.05). POP is significantly higher in the deep tissues along the LIM of healthy subjects under normal conditions, which can be downregulated by EA of Hegu (LI 4), suggesting an increase of both the utilization rate of oxygen and energy metabolism after EA.

  5. Physiology of Oxygen Breathing in Pilots: A Brief Review

    DTIC Science & Technology

    2018-03-23

    brief review Abstract This non-exhaustive survey presents literature describing some effects of breathing oxygen partial pressures between...CG, J Butler, AB DuBois (1959). Some effects of restriction of chest cage expansion on pulmonary function in man: an experimental study. J Clin...Effects of Submerged Breathing of Air or Oxygen. Navy Experimental Diving Unit TR 02-14, Panama City, FL. http://archive.rubicon- foundation.org/3483

  6. Catalytic reforming of methane to syngas in an oxygen-permeative membrane reactor

    NASA Astrophysics Data System (ADS)

    Urano, Takeshi; Kubo, Keiko; Saito, Tomoyuki; Hitomi, Atsushi

    2011-05-01

    For fuel cell applications, partial oxidative reforming of methane to syngas, hydrogen and carbon monoxide, was performed via a dense oxygen-permeative ceramic membrane composed by both ionic and electronic conductive materials. The modification of Ni-based catalyst by noble metals was investigated to increase oxygen permeation flux and decrease carbon deposition during reforming reaction. The role of each component in catalyst was also discussed.

  7. Effects of hypobaria and hypoxia on seed germination of six plant species

    NASA Astrophysics Data System (ADS)

    Tang, Yongkang; Gao, Feng; Guo, Shuangsheng; Li, Fang

    2014-10-01

    Hypobaria (low pressure) is typically associated with hypoxia (low oxygen partial pressure). There are several advantages of growing higher plants under hypobaria in the moon or mars habitat. The objectives of this research were to investigate the seed germination of six plant species under hypobaric and ambient total pressure conditions. Seeds were sown and germinated under three levels of total atmospheric pressure (101, 30 and 10 kPa) and three levels of oxygen partial pressures (21, 6 and 2 kPa) in an 8-day study. Hypoxia (6 or 2 kPa) significantly inhibited all seed germination under three levels of total atmospheric pressure by increasing the electrical conductivity and the optical density, decreasing the seed germination percentage and seed dehydrogenase activity and inhibiting the growth of the shoots and roots. Hypobaria (30 or 10 kPa) markedly improved seed germination and root growth by enhancing the oxygen diffusion rate under hypoxic conditions (6 or 2 kPa). The seeds of three dicot plants (lettuce, Chinese cabbage and cucumber) were more sensitive to hypoxia caused by hypobaria than were those of three monocot plants (maize, wheat and rice); lettuce and cucumber seeds had the highest sensitivity, whereas rice seeds had the lowest sensitivity. This research demonstrates that six experimental seeds can germinate normally under hypobaria (30 kPa), but the oxygen partial pressure should not be less than 6 kPa.

  8. The Effects of Bougie Diameters on Tissue Oxygen Levels After Sleeve Gastrectomy: A Randomized Experimental Trial

    PubMed

    Konca, Can; Yılmaz, Ali Abbas; Çelik, Süleyman Utku; Kayılıoğlu, Selami Ilgaz; Paşaoğlu, Özge Tuğçe; Ceylan, Halil Arda; Genç, Volkan

    2018-05-29

    Staple-line leak is the most frightening complication of laparoscopic sleeve gastrectomy and several predisposing factors such as using improper staple sizes regardless of gastric wall thickness, narrower bougie diameter and ischemia of the staple line are asserted. To evaluate the effects of different bougie diameters on tissue oxygen partial pressure at the esophagogastric junction after sleeve gastrectomy. A randomized and controlled animal experiment with 1:1:1:1 allocation ratio. Thirty-two male Wistar Albino rats were randomly divided into 4 groups of 8 each. While 12-Fr bougies were used in groups 1 and 3, 8-Fr bougies were used in groups 2 and 4. Fibrin sealant application was also carried out around the gastrectomy line after sleeve gastrectomy in groups 3 and 4. Burst pressure of gastrectomy line, tissue oxygen partial pressure and hydroxyproline levels at the esophagogastric junction were measured and compared among groups. Mortality was detected in 2 out of 32 rats (6.25%) and one of them was in group 2 and the cause of this mortality was gastric leak. Gastric leak was detected in 2 out of 32 rats (6.25%). There was no significant difference in terms of burst pressures, tissue oxygen partial pressure and tissue hydroxyproline levels among the 4 groups. The use of narrower bougie along with fibrin sealant has not had a negative effect on tissue perfusion and wound healing.

  9. Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.; Boyd, Meredith

    2010-01-01

    SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

  10. Defect formation in LaGa(Mg,Ni)O3-δ : A statistical thermodynamic analysis validated by mixed conductivity and magnetic susceptibility measurements

    NASA Astrophysics Data System (ADS)

    Naumovich, E. N.; Kharton, V. V.; Yaremchenko, A. A.; Patrakeev, M. V.; Kellerman, D. G.; Logvinovich, D. I.; Kozhevnikov, V. L.

    2006-08-01

    A statistical thermodynamic approach to analyze defect thermodynamics in strongly nonideal solid solutions was proposed and validated by a case study focused on the oxygen intercalation processes in mixed-conducting LaGa0.65Mg0.15Ni0.20O3-δ perovskite. The oxygen nonstoichiometry of Ni-doped lanthanum gallate, measured by coulometric titration and thermogravimetric analysis at 923-1223K in the oxygen partial pressure range 5×10-5to0.9atm , indicates the coexistence of Ni2+ , Ni3+ , and Ni4+ oxidation states. The formation of tetravalent nickel was also confirmed by the magnetic susceptibility data at 77-600K , and by the analysis of p -type electronic conductivity and Seebeck coefficient as function of the oxygen pressure at 1023-1223K . The oxygen thermodynamics and the partial ionic and hole conductivities are strongly affected by the point-defect interactions, primarily the Coulombic repulsion between oxygen vacancies and/or electron holes and the vacancy association with Mg2+ cations. These factors can be analyzed by introducing the defect interaction energy in the concentration-dependent part of defect chemical potentials expressed by the discrete Fermi-Dirac distribution, and taking into account the probabilities of local configurations calculated via binomial distributions.

  11. SPECIES - EVALUATING THERMODYNAMIC PROPERTIES, TRANSPORT PROPERTIES & EQUILIBRIUM CONSTANTS OF AN 11-SPECIES AIR MODEL

    NASA Technical Reports Server (NTRS)

    Thompson, R. A.

    1994-01-01

    Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the diskettes are compressed using the PKWARE archiving tools. The utility to unarchive the files, PKUNZIP.EXE, is included. This program was last updated in 1991. SUN and SunOS are registered trademarks of Sun Microsystems, Inc.

  12. Behavior and impact of sulfur incorporation in Zinc Oxysulfide alloy grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Ma, Jingrui; Tang, Kun; Mao, Haoyuan; Ye, Jiandong; Zhu, Shunming; Xu, Zhonghua; Yao, Zhengrong; Gu, Shulin; Zheng, Youdou

    2018-03-01

    Highly mismatched ZnO1-xSx:N alloy films with various x were deposited on c-plane sapphire substrates by a near-equilibrium method, metal-organic chemical vapor deposition. The sulfur concentration in the films could be tuned by changing the flow rate of H2S during the growth process. The films that could maintain single phase have an upper limit for x ∼ 0.15, which is smaller than the x values obtained from other non-equilibrium-grown samples (x ∼ 0.23). When x > 0.15, phases other than the wurtzite ZnO (W-ZnO) one appeared. Those phases were ascribed to the sulfur-diluted W-ZnO like phase, low x W-ZnO like phase, and high x W-ZnS like phase. The S contents in different phase has been determined by using Vegard's law and the X-ray photoelectron spectroscopy. Meanwhile, the compositional dependence of the bandgap energy in the ZnO1-xSx alloyed material has been investigated and studied comparing with other reported results. The dispersed bowing parameter b and the mechanism of the phase separation in samples grown by both the near-equilibrium method and the non-equilibrium one have also been discussed based on the difference of the atomic radius and electronegativity of the oxygen and sulfur atoms. Furthermore, the Raman and photoluminescence spectra have shown that the sulfur incorporation may suppress zinc interstitials related defects, while the oxygen vacancies related defects may be easily formed at the same time. These results indicate that ZnO1-xSx films could be beneficial to the realization of p-type doping in ZnO, although no obvious p-type characteristic has been attained in the work yet.

  13. Linear air-fuel sensor development

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Garzon, F.; Miller, C.

    1996-12-14

    The electrochemical zirconia solid electrolyte oxygen sensor, is extensively used for monitoring oxygen concentrations in various fields. They are currently utilized in automobiles to monitor the exhaust gas composition and control the air-to-fuel ratio, thus reducing harmful emission components and improving fuel economy. Zirconia oxygen sensors, are divided into two classes of devices: (1) potentiometric or logarithmic air/fuel sensors; and (2) amperometric or linear air/fuel sensors. The potentiometric sensors are ideally suited to monitor the air-to-fuel ratio close to the complete combustion stoichiometry; a value of about 14.8 to 1 parts by volume. This occurs because the oxygen concentration changesmore » by many orders of magnitude as the air/fuel ratio is varied through the stoichiometric value. However, the potentiometric sensor is not very sensitive to changes in oxygen partial pressure away from the stoichiometric point due to the logarithmic dependence of the output voltage signal on the oxygen partial pressure. It is often advantageous to operate gasoline power piston engines with excess combustion air; this improves fuel economy and reduces hydrocarbon emissions. To maintain stable combustion away from stoichiometry, and enable engines to operate in the excess oxygen (lean burn) region several limiting-current amperometric sensors have been reported. These sensors are based on the electrochemical oxygen ion pumping of a zirconia electrolyte. They typically show reproducible limiting current plateaus with an applied voltage caused by the gas diffusion overpotential at the cathode.« less

  14. Index of stations: surface-water data-collection network of Texas, September 1998

    USGS Publications Warehouse

    Gandara, Susan C.; Barbie, Dana L.

    1999-01-01

    As of September 30, 1998, the surface-water data-collection network of Texas (table 1) included 313 continuous-recording streamflow stations (D), 22 gage-height record only stations (G), 23 crest-stage partial-record stations (C), 39 flood-hydrograph partial-record stations (H), 25 low-flow partial-record stations (L), 1 continuous-recording temperature station (M1), 25 continuous-recording temperature and conductivity stations (M2), 3 continuous-recording temperature, conductivity, and dissolved oxygen stations (M3), 13 continuous-recording temperature, conductivity, dissolved oxygen, and pH stations (M4), 5 daily chemical-quality stations (Qd), 133 periodic chemical-quality stations (Qp), 16 reservoir/lake surveys for water quality (Qs), and 70 continuous or daily reservoir-content stations (R). Plate 1 identifies the major river basins in Texas and shows the location of the stations listed in table 1.

  15. Stable, Ultra-Low Residence Time Partial Oxidation

    DOEpatents

    Schmidt, Lanny D.; Hickman, Daniel A.

    1997-07-15

    A process for the catalytic partial oxidation of methane in gas phase at very short residence time (800,000 to 12,000,000 hr.sup.-1) by contacting a gas stream containing methane and oxygen with a metal supported catalyst, such as platinum deposited on a ceramic monolith.

  16. Serum metabolites from walnut-fed aged rats attenuate stress-induced neurotoxicity in brain cells in vitro

    USDA-ARS?s Scientific Manuscript database

    The shift in equilibrium towards excess reactive oxygen or nitrogen species production from innate antioxidant defense in brain is a critical factor in the declining neural functions and cognitive deficits accompanying age. In aging, there are noticeable alterations in the membrane microenvironment,...

  17. Thermodynamics of cell adhesion. II. Freely mobile repellers.

    PubMed Central

    Torney, D C; Dembo, M; Bell, G I

    1986-01-01

    The equilibrium adhesion of a cell or vesicle to a substrate is analyzed in a theoretical model in which two types of mobile molecules in the cell membrane are of interest: receptors that can form bonds with fixed ligands in the substrate and repellers that repel the substrate. If the repulsion between the repeller molecule and substrate is greater than kT, there is substantial redistribution of the repellers from the contact area. Coexisting equilibrium states are observed having comparable free energies (a) with unstretched bonds and repeller redistribution and (b) with stretched bonds and partial redistribution. PMID:3955182

  18. Heat transfer in porous medium embedded with vertical plate: Non-equilibrium approach - Part A

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Badruddin, Irfan Anjum; Quadir, G. A.

    2016-06-08

    Heat transfer in a porous medium embedded with vertical flat plate is investigated by using thermal non-equilibrium model. Darcy model is employed to simulate the flow inside porous medium. It is assumed that the heat transfer takes place by natural convection and radiation. The vertical plate is maintained at isothermal temperature. The governing partial differential equations are converted into non-dimensional form and solved numerically using finite element method. Results are presented in terms of isotherms and streamlines for various parameters such as heat transfer coefficient parameter, thermal conductivity ratio, and radiation parameter.

  19. Quantum statistical mechanics of dense partially ionized hydrogen

    NASA Technical Reports Server (NTRS)

    Dewitt, H. E.; Rogers, F. J.

    1972-01-01

    The theory of dense hydrogen plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. The statistical mechanical calculation of the plasma equation of state is intended for stellar interiors. The general approach is extended to the calculation of the equation of state of the outer layers of large planets.

  20. Electron-Impact Excitation Cross Sections for Modeling Non-Equilibrium Gas

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Liu, Yen; Panesi, Marco; Munafo, Alessandro; Wray, Alan; Carbon, Duane F.

    2015-01-01

    In order to provide a database for modeling hypersonic entry in a partially ionized gas under non-equilibrium, the electron-impact excitation cross sections of atoms have been calculated using perturbation theory. The energy levels covered in the calculation are retrieved from the level list in the HyperRad code. The downstream flow-field is determined by solving a set of continuity equations for each component. The individual structure of each energy level is included. These equations are then complemented by the Euler system of equations. Finally, the radiation field is modeled by solving the radiative transfer equation.

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