Science.gov

Sample records for hydrate gas-solid reaction

  1. Application of the carbon dioxide-barium hydroxide hydrate gas-solid reaction for the treatment of dilute carbon dioxide-bearing gas streams

    SciTech Connect

    Haag, G.L.

    1983-09-01

    The removal of trace components from gas streams via irreversible gas-solid reactions in an area of interest to the chemical engineering profession. This research effort addresses the use of fixed beds of Ba(OH)/sub 2/ hydrate flakes for the removal of an acid gas, CO/sub 2/, from air that contains approx. 330 ppM/sub v/ CO/sub 2/. Areas of investigation encompassed: (1) an extensive literature review of Ba(OH)/sub 2/ hydrate chemistry, (2) microscale studies on 0.150-g samples to develop a better understanding of the reaction, (3) process studies at the macroscale level with 10.2-cm-ID fixed-bed reactors, and (4) the development of a model for predicting fixed-bed performance. Experimental studies indicated fixed beds of commercial Ba(OH)/sub 2/.8H/sub 2/O flakes at ambient temperatures to be capable of high CO/sub 2/-removal efficiencies (effluent concentrations <100 ppB), high reactant utilization (>99%), and an acceptable pressure drop (1.8 kPa/m at a superficial gas velocity of 13 cm/s). Ba(OH)/sub 2/.8H/sub 2/O was determined to be more reactive toward CO/sub 2/ than either Ba(OH)/sub 2/.3H/sub 2/O or Ba(OH)/sub 2/.1H/sub 2/O. A key variable in the development of this fixed-bed process was relative humidity. Operation at conditions with effluent relative humidities >60% resulted in significant recrystallization and restructuring of the flake and subsequent pressure-drop problems.

  2. Process of preparing nitrogen trifluoride by gas-solid reaction

    SciTech Connect

    Aramaki, M.; Kobayashi, Y.; Nakamura, T.; Nakano, H.; Suenaga, T.

    1985-09-24

    NF3 is prepared with good yields by reaction between fluorine gas and an ammonium complex of a metal fluoride, such as (NH4)3AIF6, in solid phase. The metal flouride ammonium complex may be one additionally containing an alkali metal, such as (NH4)2NaAIF6. The gas-solid reaction is carried out preferably at temperatures above 80 C. and at relatively low partial pressures of fluorine in the gas phase of the reaction system, so that the reaction is easy to control.

  3. A Generalized Kinetic Model for Heterogeneous Gas-Solid Reactions

    SciTech Connect

    Xu, Zhijie; Sun, Xin; Khaleel, Mohammad A.

    2012-08-15

    We present a generalized kinetic model for gas-solid heterogeneous reactions taking place at the interface between two phases. The model studies the reaction kinetics by taking into account the reactions at the interface, as well as the transport process within the product layer. The standard unreacted shrinking core model relies on the assumption of quasi-static diffusion that results in a steady-state concentration profile of gas reactant in the product layer. By relaxing this assumption and resolving the entire problem, general solutions can be obtained for reaction kinetics, including the reaction front velocity and the conversion (volume fraction of reacted solid). The unreacted shrinking core model is shown to be accurate and in agreement with the generalized model for slow reaction (or fast diffusion), low concentration of gas reactant, and small solid size. Otherwise, a generalized kinetic model should be used.

  4. Utilization of the Recycle Reactor in Determining Kinetics of Gas-Solid Catalytic Reactions.

    ERIC Educational Resources Information Center

    Paspek, Stephen C.; And Others

    1980-01-01

    Describes a laboratory scale reactor that determines the kinetics of a gas-solid catalytic reaction. The external recycle reactor construction is detailed with accompanying diagrams. Experimental details, application of the reactor to CO oxidation kinetics, interphase gradients, and intraphase gradients are discussed. (CS)

  5. Utilization of the Recycle Reactor in Determining Kinetics of Gas-Solid Catalytic Reactions.

    ERIC Educational Resources Information Center

    Paspek, Stephen C.; And Others

    1980-01-01

    Describes a laboratory scale reactor that determines the kinetics of a gas-solid catalytic reaction. The external recycle reactor construction is detailed with accompanying diagrams. Experimental details, application of the reactor to CO oxidation kinetics, interphase gradients, and intraphase gradients are discussed. (CS)

  6. Moving bed reactor setup to study complex gas-solid reactions.

    PubMed

    Gupta, Puneet; Velazquez-Vargas, Luis G; Valentine, Charles; Fan, Liang-Shih

    2007-08-01

    A moving bed scale reactor setup for studying complex gas-solid reactions has been designed in order to obtain kinetic data for scale-up purpose. In this bench scale reactor setup, gas and solid reactants can be contacted in a cocurrent and countercurrent manner at high temperatures. Gas and solid sampling can be performed through the reactor bed with their composition profiles determined at steady state. The reactor setup can be used to evaluate and corroborate model parameters accounting for intrinsic reaction rates in both simple and complex gas-solid reaction systems. The moving bed design allows experimentation over a variety of gas and solid compositions in a single experiment unlike differential bed reactors where the gas composition is usually fixed. The data obtained from the reactor can also be used for direct scale-up of designs for moving bed reactors.

  7. Venus volcanism: Rate estimates from laboratory studies of sulfur gas-solid reactions

    NASA Technical Reports Server (NTRS)

    Ehlers, K.; Fegley, B., Jr.; Prinn, R. G.

    1989-01-01

    Thermochemical reactions between sulfur-bearing gases in the atmosphere of Venus and calcium-, iron-, magnesium-, and sulfur-bearing minerals on the surface of Venus are an integral part of a hypothesized cycle of thermochemical and photochemical reactions responsible for the maintenance of the global sulfuric acid cloud cover on Venus. SO2 is continually removed from the Venus atmosphere by reaction with calcium bearing minerals on the planet's surface. The rate of volcanism required to balance SO2 depletion by reactions with calcium bearing minerals on the Venus surface can therefore be deduced from a knowledge of the relevant gas-solid reaction rates combined with reasonable assumptions about the sulfur content of the erupted material (gas + magma). A laboratory program was carried out to measure the rates of reaction between SO2 and possible crustal minerals on Venus. The reaction of CaCO3(calcite) + SO2 yields CaSO4 (anhydrite) + CO was studied. Brief results are given.

  8. Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1988-01-01

    The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

  9. Thermostability of Sm2(FeGa)17Cy prepared by gas-solid reaction (GSR)

    NASA Astrophysics Data System (ADS)

    Cao, L.; Handstein, A.; Gebel, B.; Schäfer, R.; Müller, K.-H.

    1997-04-01

    The gas-solid-reaction (GSR) was used to introduce interstitial carbon atoms into Sm2Fe17-xGax compounds with x=0, 0.5, 1, and 2. For this process, powders made from homogenized ingots were annealed at 500 °C under methane for different times. The thermostability increases for small amounts of Ga and the investigation shows that Sm2Fe16.5Ga0.5Cy is stable up to 750 °C. In the case of Sm2Fe15Ga2Cy carburized for 6 h (y=2.0) and 18 h (y=2.2), the x-ray diffraction patterns show the Th2Zn17-type structure only. After annealing at 800 °C for 20 min the 6 h carburized sample shows a small amount of α-Fe and other phases and there is a large Fe content after annealing at 850 °C. For an 18 h carburized sample, less Fe and no other phases have be seen after annealing at 800 °C, i.e., the material is nearly single phase. The result that longer carburization times stabilize the Th2Zn17-type structure could also be manifested by Kerr microscopy. A comparison with mechanically alloyed Sm2Fe15Ga2C2 powders prepared with Sm excess shows that those are very stable up to 900 °C. The density of fine-grained Sm2Fe17-xGaxCy could be increased by hot pressing, but the degree of compaction and the phase purity very sensitively depend on the Ga content.

  10. Opaque Mineral Assemblages at Chondrule Boundaries in the Vigarano CV Chondrite: Evidence for Gas-Solid Reactions Following Chondrule Formation

    NASA Technical Reports Server (NTRS)

    Lauretta, Dante S.

    2004-01-01

    Recent studies of opaque minerals in primitive ordinary chondrites suggest that metal grains exposed at chondrule boundaries were corroded when volatile elements recondensed after the transient heating event responsible for chondrule formation. Metal grains at chondrule boundaries in the Bishunpur (LL3.1) chondrite are rimmed by troilite and fayalite. If these layers formed by gas solid reaction, then the composition of the corrosion products can provide information on the chondrule formation environment. Given the broad similarities among chondrules from different chondrite groups, similar scale layers should occur on chondrules in other primitive meteorite groups. Here I report on metal grains at chondrule boundaries in Vigarano (CV3).

  11. Opaque Mineral Assemblages at Chondrule Boundaries in the Vigarano CV Chondrite: Evidence for Gas-Solid Reactions Following Chondrule Formation

    NASA Technical Reports Server (NTRS)

    Lauretta, Dante S.

    2004-01-01

    Recent studies of opaque minerals in primitive ordinary chondrites suggest that metal grains exposed at chondrule boundaries were corroded when volatile elements recondensed after the transient heating event responsible for chondrule formation. Metal grains at chondrule boundaries in the Bishunpur (LL3.1) chondrite are rimmed by troilite and fayalite. If these layers formed by gas solid reaction, then the composition of the corrosion products can provide information on the chondrule formation environment. Given the broad similarities among chondrules from different chondrite groups, similar scale layers should occur on chondrules in other primitive meteorite groups. Here I report on metal grains at chondrule boundaries in Vigarano (CV3).

  12. Study of gas-solid reactions using coated piezoelectric detectors. Final report, 1 June 1981-1 October 1984

    SciTech Connect

    Guilbault, G.G.

    1985-01-01

    A basic study was conducted to find specific adsorbents for atmospheric pollutants. These pollutants were then placed as coatings on piezoelectric crystals, and these devices were used as detectors for these pollutants. Detectors have been designed for the following compounds at concentrations of ppb-ppm with reproducibilities of better than 3% and detection times of less than 30 sec: (1) organophosphorus compounds (2) mercury (3) carbon monoxide (4) toluene (5) vinyl chloride (6) sulfur dioxide (7) phosgene (8) isocyanates (9) acrylonitrile (10) hydrazine and (11) formaldehyde. Keywords include: Piezoelectric Crystals; Gas solid reactions; Organophosphorus compounds; Mercury; Carbon monoxide; and Phosgene.

  13. Room temperature gas-solid reaction of titanium on glass surfaces forming a very low resistivity layer

    NASA Astrophysics Data System (ADS)

    Solís, Hugo; Clark, Neville; Azofeifa, Daniel; Avendano, E.

    2016-09-01

    Titanium films were deposited on quartz, glass, polyamide and PET substrates in a high vacuum system at room temperature and their electrical resistance monitored in vacuo as a function of thickness. These measurements indicate that a low electrical resistance layer is formed in a gas-solid reaction during the condensation of the initial layers of Ti on glass and quartz substrates. Layers begin to show relative low electrical resistance at around 21 nm for glass and 9nm for quartz. Samples deposited on polyamide and PET do not show this low resistance feature.

  14. A computer controlled system for studying gas-solid state reactions in X-ray diffraction experiments

    NASA Astrophysics Data System (ADS)

    Gaponov, Yu. A.; Yevdokov, O. V.; Sukhorukov, A. V.

    1995-02-01

    An automated system for temperature and pressure control in a reaction chamber for studying gas-solid state reactions in X-ray diffraction experiments with the use of synchrotron radiation (SR) is designed at the Siberian Synchrotron Radiation Center (Budker INP, Novosibirsk). A computer algorithm for controlling the temperature in the reaction chamber was developed. An analysis of the thermal characteristics of the reaction chamber was carried out in the 293-800 K temperature range and in the 0-0.2 MPa range of pressures with an accuracy of 1-3 K and 0.01 MPa respectively. Test experiments on studying the thermal decomposition of some organo-metallic compounds were carried out with the use of the designed system.

  15. Numerical modelling of hydration reactions

    NASA Astrophysics Data System (ADS)

    Vrijmoed, Johannes C.; John, Timm

    2017-04-01

    Mineral reactions are generally accompanied by volume changes. Observations in rocks and thin section indicate that this often occurred by replacement reactions involving a fluid phase. Frequently, the volume of the original rock or mineral seems to be conserved. If the density of the solid reaction products is higher than the reactants, the associated solid volume decrease generates space for a fluid phase. In other words, porosity is created. The opposite is true for an increase in solid volume during reaction, which leads to a porosity reduction. This slows down and may even stop the reaction if it needs fluid as a reactant. Understanding the progress of reactions and their rates is important because reaction generally changes geophysical and rock mechanical properties which will therefore affect geodynamical processes and seismic properties. We studied the case of hydration of eclogite to blueschist in a subduction zone setting. Eclogitized pillow basalt structures from the Tian-Shan orogeny are transformed to blueschist on the rims of the pillow (van der Straaten et al., 2008). Fluid pathways existed between the pillow structures. The preferred hypothesis of blueschist formation is to supply the fluid for hydration from the pillow margins progressing inward. Using numerical modelling we simulate this coupled reaction-diffusion process. Porosity and fluid pressure evolution are coupled to local thermodynamic equilibrium and density changes. The first rim of blueschist that forms around the eclogite pillow increases volume to such a degree that the system is clogged and the reaction stops. Nevertheless, the field evidence suggests the blueschist formation continued. To prevent the system from clogging, a high incoming pore fluid pressure on the pillow boundaries is needed along with removal of mass from the system to accommodate the volume changes. The only other possibility is to form blueschist from any remaining fluid stored in the core of the pillow

  16. Influence of changing particle structure on the rate of gas-solid gasification reactions. Final report, July 1981-March 1984

    SciTech Connect

    Not Available

    1984-04-04

    The objetive of this work is to determine the changes in the particle structure of coal as it undergoes the carbon/carbon dioxide reaction (C + CO/sub 2/ ..-->.. 2CO). Char was produced by heating the coal at a rate of 25/sup 0/C/min to the reaction temperatures of 800/sup 0/C, 900/sup 0/C, 1000/sup 0/C and 1100/sup 0/C. The changes in surface area and effective diffusivity as a result of devolitization were determined. Changes in effective diffusivity and surface area as a function of conversion have been measured for reactions conducted at 800, 900, 1000 and 1100/sup 0/C for Wyodak coal char. The surface areas exhibit a maximum as a function of conversion in all cases. For the reaction at 1000/sup 0/C the maximum in surface area is greater than the maxima determined at all other reaction temperatures. Thermogravimetric rate data were obtained for five coal chars; Wyodak, Wilcox, Cimmeron, Illinois number 6 and Pittsburgh number 6 over the temperature range 800-1100/sup 0/C. All coal chars exhibit a maximum in reaction rate. Five different models for gas-solid reactions were evaluated. The Bhatia/Perlmutter model seems to best represent the data. 129 references, 67 figures, 37 tables.

  17. Molecular engineering of Schiff-base linked covalent polymers with diverse topologies by gas-solid interface reaction.

    PubMed

    Liu, Xuan-He; Guan, Cui-Zhong; Zheng, Qing-Na; Wang, Dong; Wan, Li-Jun

    2015-03-14

    The design and construction of molecular nanostructures with tunable topological structures are great challenges in molecular nanotechnology. Herein, we demonstrate the molecular engineering of Schiff-base bond connected molecular nanostructures. Building module construction has been adopted to modulate the symmetry of resulted one dimensional (1D) and two dimensional (2D) polymers. Specifically, we have designed and constructed 1D linear and zigzag polymers, 2D hexagonal and chessboard molecular nanostructures by varying the number of reactive sites and geometry and symmetry of precursors. It is demonstrated that high-quality conjugated polymers can be fabricated by using gas-solid interface reaction. The on-demanding synthesis of polymeric architectures with diverse topologies paves the way to fabricate molecular miniature devices with various desired functionalities.

  18. Boosting Gas Involved Reactions at Nanochannel Reactor with Joint Gas-Solid-Liquid Interfaces and Controlled Wettability.

    PubMed

    Mi, Li; Yu, Jiachao; He, Fei; Jiang, Ling; Wu, Yafeng; Yang, Lijun; Han, Xiaofeng; Li, Ying; Liu, Anran; Wei, Wei; Zhang, Yuanjian; Tian, Ye; Liu, Songqin; Jiang, Lei

    2017-08-02

    The low solubility of gases in aqueous solution is the major kinetic limitation of reactions that involve gases. To address this challenge, we report a nanochannel reactor with joint gas-solid-liquid interfaces and controlled wettability. As a proof of concept, a porous anodic alumina (PAA) nanochannel membrane with different wettability is used for glucose oxidase (GOx) immobilization, which contacts with glucose aqueous solution on one side, while the other side gets in touch with the gas phase directly. Interestingly, it is observed that the O2 could participate in the enzymatic reaction directly from gas phase through the proposed nanochannels, and a hydrophobic interface is more favorable for the enzymatic reaction due to the rearrangement of GOx structure as well as the high gas adhesion. As a result, the catalytic efficiency of GOx in the proposed interface is increased up to 80-fold compared with that of the free state in traditional aqueous air-saturated electrolyte. This triphase interface with controlled wettability can be generally applied to immobilize enzymes or catalysts with gas substrates for high efficiency.

  19. Gas/solid carbon branching ratios in surface-mediated reactions and the incorporation of carbonaceous material into planetesimals

    NASA Astrophysics Data System (ADS)

    Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia

    2016-07-01

    We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume "filamentous" structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain-grain sticking during low-velocity collisions.

  20. Gas/Solid Carbon Branching Ratios in Surface Mediated Reactions and the Incorporation of Carbonaceous Material into Planetesimals

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia

    2016-01-01

    We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99 for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume filamentous structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain-grain sticking during low-velocity collisions.

  1. A gas-tight Cu K alpha x-ray transparent reaction chamber for high-temperature x-ray diffraction analyses of halide gas/solid reactions.

    PubMed

    Shian, Samuel; Sandhage, Kenneth H

    2009-11-01

    An externally heated, x-ray transparent reaction chamber has been developed to enable the dynamic high temperature x-ray diffraction (HTXRD) analysis of a gas/solid [TiF(4)(g)/SiO(2)(s)] reaction involving a halide gas reactant formed at elevated temperatures (up to 350 degrees C) from a condensed source (TiF(4) powder) sealed within the chamber. The reaction chamber possessed x-ray transparent windows comprised of a thin (13 microm) internal layer of Al foil and a thicker (125 microm) external Kapton film. After sealing the SiO(2) specimens (diatom frustules or Stober spheres) above TiF(4) powder within the reaction chamber, the chamber was heated to a temperature in the range of 160-350 degrees C to allow for internal generation of TiF(4)(g). The TiF(4)(g) underwent a metathetic reaction with the SiO(2) specimen to yield a TiOF(2)(s) product. HTXRD analysis, using Cu K alpha x rays passed through the Kapton/Al windows of the chamber, was used to track the extent of SiO(2) consumption and/or TiOF(2) formation with time. The Al foil inner layer of the windows protected the Kapton film from chemical attack by TiF(4)(g), whereas the thicker, more transparent Kapton film provided the mechanical strength needed to contain this gas. By selecting an appropriate combination of x-ray transparent materials to endow such composite windows with the required thermal, chemical, and mechanical performance, this inexpensive reaction chamber design may be applied to the HTXRD analyses of a variety of gas/solid reactions.

  2. Reaction of disodium cromoglycate with hydrated electrons

    SciTech Connect

    Carmichael, A.J.; Arroyo, C.M.; Cockerham, L.G.

    1988-01-01

    A possible mechanism by which disodium cromoglycate (DSCG) prevents a decrease in regional cerebral blood flow but not hypotension in primates following whole body gamma-irradiation was studied. Several studies have implicated superoxide radicals (O/sub 2//sup -/.) in intestinal and cerebral vascular disorders following ischemia and ionizing radiation, respectively. O/sub 2//sup -/. is formed during radiolysis in the reaction between hydrated electrons (e-aq) and dissolved oxygen. For this reason, the efficiency of DSCG to scavenge e-q and possibly prevent the formation of O/sub 2//sup -/. was studied. Hydrated electrons were produced by photolysis of potassium ferrocyanide solutions. The rate constant, k = 2.92 x 10(10) M-1s-1 for the reaction between e-aq and DSCG was determined in competition experiments using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). This spin trap reacts rapidly with e-aq followed by protonation to yield the ESR observable DMPO-H spin adduct. The results show that DSCG is an efficient e-aq scavenger and may effectively compete with oxygen for e-aq preventing the radiolytic formation of O/sub 2//sup -/..

  3. Application of noncatalytic gas-solid reactions for a single pellet of changing size to the modeling of fluidized-bed combustion of coal char containing sulfur

    SciTech Connect

    Rehmat, A.; Saxena, S.C.; Land, R.H.

    1980-09-01

    A mechanistic model is developed for coal char combustion, with sulfur retention by limestone or dolomite sorbent, in a gas fluidized bed employing noncatalytic single pellet gas-solid reactions. The shrinking core model is employed to describe the kinetics of chemical reactions taking place on a single pellet; changes in pellet size as the reaction proceeds are considered. The solids are assumed to be in back-mix condition whereas the gas flow is regarded to be in plug flow. Most char combustion occurs near the gas distributor plate (at the bottom of the bed), where the bubbles are small and consequently the mass transfer rate is high. For such a case, the analysis is considerably simplified by ignoring the bubble phase since it plays an insignificant role in the overall rate of carbon conversion. Bubble-free operation is also encounterd in the turbulent regime, where the gas flow is quite high and classical bubbles do not exist. Formulation of the model includes setting up heat and mass balance equations pertaining to a single particle (1) exposed to a varying reactant concentration along the height of the bed and (2) whose size changes during reaction. These equations are then solved numerically to account for particles of all sizes in the bed in obtaining the overall carbon conversion efficiency and resultant sulfur retention. In particular, the influence on sorbent requirement of several fluid-bed variables such as oxygen concentration profile, particle size, reaction rate for sulfation reaction, and suflur adsorption efficiency are examined.

  4. Spatially resolved characterization of catalyst-coated membranes by distance-controlled scanning mass spectrometry utilizing catalytic methanol oxidation as gas-solid probe reaction.

    PubMed

    Li, Nan; Assmann, Jens; Schuhmann, Wolfgang; Muhler, Martin

    2007-08-01

    The spatially resolved catalytic activity of a catalyst-coated membrane (CCM), which is the essential part of PEM fuel cells, was visualized rapidly without any damage by a distance-controlled scanning mass spectrometer with an improved resolution of 250 microm. Methanol oxidation was identified as a suitable gas-solid probe reaction for the characterization of local catalytic activity. In addition, defects were manually generated in the CCM to simulate inhomogeneous coating and pinholes. The measurements successfully demonstrated that catalytically active and less active regions can be clearly distinguished. Simultaneously, the local topography was recorded, providing additional information on the location of the scratches and pinholes. The catalytic results were highly reproducible due to the constant-distance feedback loop rendering scanning mass spectrometry a promising tool for the quantitative quality control of CCMs.

  5. Hg reactions in the presence of chlorine species: homogeneous gas phase and heterogeneous gas-solid phase.

    PubMed

    Lee, Tai Gyu; Hedrick, Elizabeth; Biswas, Pratim

    2002-11-01

    The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (alpha), overall rate constant (k'), and activation energy (Ea), were estimated based on the simple overall reaction pathway. The reaction order with respect to C(Hg), k', and Ea were found to be 1.55, 5.07 x 10(-2) exp(-1939.68/T) [(microg/m3)(-055)(s)(-1)]. and 16.13 [kJ/ mol], respectively. The effect of chlorine species (HCl, CH2Cl2) on the in situ Hg capture method previously developed (28) was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.

  6. MERCURY REACTIONS IN THE PRESENCE OF CHLORINE SPECIES: HOMOGENOUS GAS PHASE AND HETEROGENOUS GAS-SOLID PHASE

    EPA Science Inventory

    The kinetics of mercury chlorination (with HC1) were studied using a flow reactor system with an on-line Hg analyzer and spciation sampling using a set of impingers. Kinetic parameters, such as reaction order (a), activation energy (Eu) and the overall rate constant (k') were es...

  7. MERCURY REACTIONS IN THE PRESENCE OF CHLORINE SPECIES: HOMOGENOUS GAS PHASE AND HETEROGENOUS GAS-SOLID PHASE

    EPA Science Inventory

    The kinetics of mercury chlorination (with HC1) were studied using a flow reactor system with an on-line Hg analyzer and spciation sampling using a set of impingers. Kinetic parameters, such as reaction order (a), activation energy (Eu) and the overall rate constant (k') were es...

  8. Design and development of an environmental cell for dynamic in situ observation of gas-solid reactions at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Deshmukh, Pushkarraj Vasant

    In situ monitoring of events in transmission electron microscopy provides information on how materials behave in their true state while varying environmental conditions (i.e. temperature and pressure) and exposure to reactant gas mixtures. In-situ results are usually different from static, post-reaction observations because they provide valuable real time---rather than post mortem---information. To facilitate applications that demand in situ observations, a transmission electron microscope specimen holder assembly has been developed in this dissertation. This assembly incorporates a gas flow and heating mechanism along with a novel window-type environmental cell. A controlled mixture of up to four different gases can be circulated through the cell during an experiment. In addition, the specimen can be heated up to a temperature of 1500°C using a specially designed carbon dioxide laser mechanism. This heating technique provides major advantages over conventional methods in terms of product life, specimen heating time and design size. The cell design incorporates a gas reaction chamber less than 1 mm in height, enclosed between a pair of 20 nm thick silicon nitride windows. The chamber can accommodate a specimen or a grid having a diameter of 3 mm and thicknesses in the range of 50 to 100 microns. The volume for the gas environment within the chamber is approximately 3 mm 3 and the gas path length is less than 1 mm. This holder has been designed by incorporating cutting edge heating and Si3N4 window fabrication technology to achieve excellent resolution along with a low thermal drift. Successful application of the holder has been shown to provide scientists with an economical alternative to dedicated transmission electron microscopes for a vast array of in situ applications. These applications include understanding the basic material properties, catalysis reactions, semiconductor device development, and nano structure fabrication.

  9. Chemical characteristics of mineral trioxide aggregate and its hydration reaction

    PubMed Central

    2012-01-01

    Mineral trioxide aggregate (MTA) was developed in early 1990s and has been successfully used for root perforation repair, root end filling, and one-visit apexification. MTA is composed mainly of tricalcium silicate and dicalcium silicate. When MTA is hydrated, calcium silicate hydrate (CSH) and calcium hydroxide is formed. Formed calcium hydroxide interacts with the phosphate ion in body fluid and form amorphous calcium phosphate (ACP) which finally transforms into calcium deficient hydroxyapatite (CDHA). These mineral precipitate were reported to form the MTA-dentin interfacial layer which enhances the sealing ability of MTA. Clinically, the use of zinc oxide euginol (ZOE) based materials may retard the setting of MTA. Also, the use of acids or contact with excessive blood should be avoided before complete set of MTA, because these conditions could adversely affect the hydration reaction of MTA. Further studies on the chemical nature of MTA hydration reaction are needed. PMID:23429542

  10. Hydration reactions of cement combinations containing vitrified incinerator fly ash

    SciTech Connect

    Dyer, Thomas D.; Dhir, Ravindra K

    2004-05-01

    One treatment option for municipal solid waste incinerator fly ash (IFA) is vitrification. The process yields a material containing reduced levels of trace metals relative to the original ash. The material is glassy and potentially suitable as a cement component in concrete. This paper examines the vitrification of an IFA and studies the hydration reactions of combinations of this vitrified material and Portland cement (PC). Isothermal conduction calorimetry, powder X-ray diffraction (XRD), thermogravimetry (TG) and scanning electron microscopy were employed to study the hydration reactions. As the levels of vitrified ash increase, the quantities of AFt phase produced decrease, whilst quantities of AFm phase increase, due to the reduced levels of sulfate in the vitrified ash. The levels of calcium silicate hydrate (CSH) gel (inferred from estimates of quantities of gel-bound water) remain constant at 28 days regardless of vitrified ash content, indicating that the material is contributing toward the formation of this product.

  11. Seismic probing of hydration and dehydration reactions in subduction zones

    NASA Astrophysics Data System (ADS)

    Rondenay, Stéphane; McGary, R. Shane; Halpaap, Felix; Goes, Saskia; Perrin, Alexander; Wang, Hongliang; Huismans, Ritske; Ottemöller, Lars

    2017-04-01

    Over the past decade, high-resolution images based on teleseismic scattered waves have given us new insight into the distribution and movement of water in subduction zones. In particular, these images have shown us where the subducted crust loses the bulk of its water through eclogitization and where the mantle wedge becomes hydrated via serpentinization. The first images provided adequate constraints to infer where these processes occur for uniformly hydrated/dehydrated components of the system. However, we know that this assumption of uniformity does not really apply owing to petrological evidence that prograde and retrograde metamorphic reactions do not proceed uniformly across the subducted crust or mantle wedge. Here, we expand on previous work by (i) comparing high-resolution images from a catalogue that now samples a wide range of subduction zones, and (ii) jointly interpreting these high-resolution images with results from complementary seismic/geodynamic/petrological modelling. Our goal is to generate a set of new models that can help us better constrain the variable levels of hydration within the subducted slab and mantle wedge, and to use these models to better understand how fluid transfer between the various components of the system relates to seismicity. We illustrate these concepts with examples from the Cascadia subduction zone, where we find strong evidence for a layer of metastable gabbro in the lower portion of the subducted crust, and the Western Hellenic subduction zone, where the distribution of intraslab seismicity seems indicative of variable hydration/dehydration regimes along strike.

  12. Reaction coordinate of incipient methane clathrate hydrate nucleation.

    PubMed

    Barnes, Brian C; Knott, Brandon C; Beckham, Gregg T; Wu, David T; Sum, Amadeu K

    2014-11-20

    Nucleation from solution is a ubiquitous phenomenon with relevance to myriad scientific disciplines, including pharmaceuticals, biomineralization, and disease. One prominent example is the nucleation of clathrate hydrates, multicomponent crystalline inclusion compounds relevant to the energy industry where they block pipelines and also constitute a potential vast energy resource. Despite their importance, the molecular mechanism of incipient hydrate formation remains unknown. Herein, we employ advanced molecular simulation tools (pB histogram, equilibrium path sampling) to provide a statistical-mechanical basis for extracting physical insight into the molecular steps by which clathrates form. Through testing the Mutually Coordinated Guest (MCG) order parameter, we demonstrate that both guest (methane) and host (water) structuring are crucial to accurately describe the nucleation of hydrates and determine a critical nucleus size of MCG-1 = 16 at 255 K and 500 bar. Equipped with a validated (and novel) reaction coordinate, subsequent equilibrium path sampling simulations yield the free energy barrier and nucleation rate. The resulting quantitative nucleation process is described by the MCG clustering mechanism. This constitutes a significant advance in the field of hydrates research, as the fitness of a molecular descriptor has never been statistically verified. More broadly, this work has significance to a wide range of multicomponent nucleation contexts wherein the formation mechanism depends on contributions from both solute and solvent.

  13. Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids

    NASA Technical Reports Server (NTRS)

    Zolotov, M. Y.; Mironenko, M. V.; Shock, E. L.

    2005-01-01

    Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid

  14. Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids

    NASA Technical Reports Server (NTRS)

    Zolotov, M. Y.; Mironenko, M. V.; Shock, E. L.

    2005-01-01

    Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid

  15. Pilot scale experiments of magnesia hydration under gas-liquid-solid (three-phase) reaction system

    NASA Astrophysics Data System (ADS)

    Tang, Xiaojia; Lv, Qiwei; Yin, Lin; Nie, Yixing; Jin, Qi; Ji, Yangyuan; Zhu, Yimin

    2017-08-01

    Pilot scale experiments were conducted to prepare magnesium hydroxide by magnesia hydration under gas-liquid-solid (three-phase) reaction system. The effect of reaction pressure, reactivity and particle size of magnesia and the concentration of the pulp on the degree of hydration was investigated. The results indicated that the hydration reaction occurred at the first 30min mainly. During the set reaction condition, degree of hydration of 68% could be obtained at the reaction pressure of 0.2MPa, concentration of pulp of 5%w/w with high reactivity and fine powder. The promotion effect on the degree of hydration caused by the three-phase reaction system was mostly attributed to the exfoliation of steam.

  16. Protein-solvent preferential interactions, protein hydration, and the modulation of biochemical reactions by solvent components

    PubMed Central

    Timasheff, Serge N.

    2002-01-01

    Solvent additives (cosolvents, osmolytes) modulate biochemical reactions if, during the course of the reaction, there is a change in preferential interactions of solvent components with the reacting system. Preferential interactions can be expressed in terms of preferential binding of the cosolvent or its preferential exclusion (preferential hydration). The driving force is the perturbation by the protein of the chemical potential of the cosolvent. It is shown that the measured change of the amount of water in contact with protein during the course of the reaction modulated by an osmolyte is a change in preferential hydration that is strictly a measure of the cosolvent chemical potential perturbation by the protein in the ternary water–protein–cosolvent system. It is not equal to the change in water of hydration, because water of hydration is a reflection strictly of protein–water forces in a binary system. There is no direct relation between water of preferential hydration and water of hydration. PMID:12097640

  17. Solid state tungsten oxide hydrate/tin oxide hydrate electrochromic device prepared by electrochemical reactions

    NASA Astrophysics Data System (ADS)

    Nishiyama, Kentaro; Matsuo, Ryo; Sasano, Junji; Yokoyama, Seiji; Izaki, Masanobu

    2017-03-01

    The solid state electrochromic device composed of tungsten oxide hydrate (WO3(H2O)0.33) and tin oxide hydrate (Sn(O,OH)) has been constructed by anodic deposition of WO3(H2O)0.33 and Sn(O,OH) layers and showed the color change from clear to blue by applying voltage through an Au electrode.

  18. The analysis of magnesium oxide hydration in three-phase reaction system

    SciTech Connect

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  19. In situ measurement of gas-solid interactions in astrophysical dust & planetary analogues

    NASA Astrophysics Data System (ADS)

    Thompson, S. P.; Parker, J. E.; Day, S. J.; Evans, A.; Tang, C. C.

    2012-02-01

    Facilities for studying gas-solid interactions on beamline I11 at the Diamond Light Source are described. Sample evolution in low and high gas pressure capillary cells (1 × 10-7 to 100 bar) with non-contact cooling and heating (80 to 1273 K) can be monitored structurally (X-rays) and spectroscopically (Raman). First results on the dehydration of MgSO4.7H2O, the formation of CO2 clathrate hydrate and the reaction of amorphous CaSiO3 grains with CO2 gas to form CaCO3 are presented to demonstrate the application of these cells to laboratory investigations involving the processing of cosmic dust simulants and planetary materials analogues.

  20. Reactions of laser-ablated U atoms with HF: infrared spectra and quantum chemical calculations of HUF, UH, and UF in noble gas solids.

    PubMed

    Vent-Schmidt, Thomas; Andrews, Lester; Riedel, Sebastian

    2015-03-19

    Reactions of laser-ablated U atoms with HF produce HUF as the major product and UH and UF as minor products, which are identified from their argon and neon matrix infrared spectra. Our assignment of HUF is confirmed by the observation of DUF and close agreement with observed and calculated vibrational frequencies and deuterium shifts in the vibrational frequencies. Our previous observation of the UH diatomic molecule from argon matrix experiments with H2, HD, and D2 as reagents is confirmed through its present observation with HF and DF, and with recent higher level quantum chemical calculations. The HF reaction provides a lower concentration of F in the system and thus simplifies the fluorine chemistry relative to similar U atom reactions with F2, and the new matrix identification of UF here is consistent with recent high level calculations on UF. In addition, we find evidence for the higher oxidation state secondary reaction products UHF2, UHF3, and UH2F2.

  1. Comparison of kinetic and equilibrium reaction models insimulating gas hydrate behavior in porous media

    SciTech Connect

    Kowalsky, Michael B.; Moridis, George J.

    2006-11-29

    In this study we compare the use of kinetic and equilibriumreaction models in the simulation of gas (methane) hydrate behavior inporous media. Our objective is to evaluate through numerical simulationthe importance of employing kinetic versus equilibrium reaction modelsfor predicting the response of hydrate-bearing systems to externalstimuli, such as changes in pressure and temperature. Specifically, we(1) analyze and compare the responses simulated using both reactionmodels for natural gas production from hydrates in various settings andfor the case of depressurization in a hydrate-bearing core duringextraction; and (2) examine the sensitivity to factors such as initialhydrate saturation, hydrate reaction surface area, and numericaldiscretization. We find that for large-scale systems undergoing thermalstimulation and depressurization, the calculated responses for bothreaction models are remarkably similar, though some differences areobserved at early times. However, for modeling short-term processes, suchas the rapid recovery of a hydrate-bearing core, kinetic limitations canbe important, and neglecting them may lead to significantunder-prediction of recoverable hydrate. The use of the equilibriumreaction model often appears to be justified and preferred for simulatingthe behavior of gas hydrates, given that the computational demands forthe kinetic reaction model far exceed those for the equilibrium reactionmodel.

  2. Gas-Solid Displacement Reactions for Converting Silica Diatom Frustules into MgO and TiO2

    SciTech Connect

    Kalem, Tugba

    2004-01-01

    Technology for the microfabrication of freely moving parts began with a Bell Labs microgear spun by an air jet, and electrostatic silicon micro motors in the mid-1980s. It continued with development work on micropositioning of optics, miniature heat exchangers, small fluidic devices, and chemical reaction chambers. Recently, there has been a great deal of interest centered on the design and manufacture of devices of nanometer proportions and this speculation has spawned a new industry named, nanotechnology. Despite the technological and economic promise of this technology, current commercial micro/mesofabrication methods have largely been based upon two-dimensional processing principles which is not well suited to the low-cost mass production of three-dimensional micro devices with complex geometries and meso/nanoscale features. Diatoms are three dimensional (3D) microstructures from nature that provide a practical alternative for nanotechnology and microfabrication. Diatoms (Figure 1) are single-celled micro algae that form rigid cell walls (frustules) composed of amorphous silica. Their dimensions can range from less than 1 micron to several hundreds of microns. They are distributed throughout the world in aquatic, semi-aquatic and moist habitats, and extremely abundant in freshwater and marine ecosystems. Diatoms are thought to be responsible for up to 25% of the world's net primary production of organic carbon (by transforming of carbon dioxide and water into sugars by photosynthesis). Approximately 105 unique diatom frustule shapes have been claimed to exist in nature. The frustules are composed of two valves that fit together like a petri-dish, connected to each other by one or more girdle bands. The frustule wall consists of a nanoporous assembly of silica nanoparticles. They absorb soluble silica from water even at extremely low concentrations and metabolize and deposit it as an external skeleton. Continued reproduction of a single parent diatom

  3. Gas-solid carbonation as a possible source of carbonates in cold planetary environments

    NASA Astrophysics Data System (ADS)

    Garenne, A.; Montes-Hernandez, G.; Beck, P.; Schmitt, B.; Brissaud, O.; Pommerol, A.

    2013-02-01

    Carbonates are abundant sedimentary minerals at the surface and sub-surface of the Earth and they have been proposed as tracers of liquid water in extraterrestrial environments. Their formation mechanism is since generally associated with aqueous alteration processes. Recently, carbonate minerals have been discovered on Mars' surface by different orbitals or rover missions. In particular, the phoenix mission has measured from 1% to 5% of calcium carbonate (calcite type) within the soil (Smith et al., 2009). These occurrences have been reported in area where the relative humidity is significantly high (Boynton et al., 2009). The small concentration of carbonates suggests an alternative process on mineral grain surfaces (as suggested by Shaheen et al., 2010) than carbonation in aqueous conditions. Such an observation could rather point toward a possible formation mechanism by dust-gas reaction under current Martian conditions. To understand the mechanism of carbonate formation under conditions relevant to current Martian atmosphere and surface, we designed an experimental setup consisting of an infrared microscope coupled to a cryogenic reaction cell (IR-CryoCell setup). Three different mineral precursors of carbonates (Ca and Mg hydroxides, and a hydrated Ca silicate formed from Ca2SiO4), low temperature (from -10 to +30 °C), and reduced CO2 pressure (from 100 to 2000 mbar) were utilized to investigate the mechanism of gas-solid carbonation at mineral surfaces. These mineral materials are crucial precursors to form Ca and Mg carbonates in humid environments (0%hydrated Ca silicate. Conversely, only a moderate carbonation is observed for the Mg hydroxide. These results suggest that gas-solid carbonation process or carbonate formation at the dust-water ice-CO2 interfaces could be a currently active Mars' surface

  4. Obsidian hydration profile measurements using a nuclear reaction technique

    USGS Publications Warehouse

    Lee, R.R.; Leich, D.A.; Tombrello, T.A.; Ericson, J.E.; Friedman, I.

    1974-01-01

    AMBIENT water diffuses into the exposed surfaces of obsidian, forming a hydration layer which increases in thickness with time to a maximum depth of 20-40 ??m (ref. 1), this layer being the basic foundation of obsidian dating2,3. ?? 1974 Nature Publishing Group.

  5. Reactions of hydrated electron with various radicals: spin factor in diffusion-controlled reactions.

    PubMed

    Ichino, Takatoshi; Fessenden, Richard W

    2007-04-05

    The reactions of hydrated electron (eaq-) with various radicals have been studied in pulse radiolysis experiments. These radicals are hydroxyl radical (*OH), sulfite radical anion (*SO3-), carbonate radical anion (CO3*-), carbon dioxide radical anion (*CO2-), azidyl radical (*N3), dibromine radical anion (Br2*-), diiodine radical anion (I2*-), 2-hydroxy-2-propyl radical (*C(CH3)2OH), 2-hydroxy-2-methyl-1-propyl radical ((*CH2)(CH3)2COH), hydroxycyclohexadienyl radical (*C6H6OH), phenoxyl radical (C6H5O*), p-methylphenoxyl radical (p-(H3C)C6H4O*), p-benzosemiquinone radical anion (p-OC6H4O*-), and phenylthiyl radical (C6H5S*). The kinetics of eaq- was followed in the presence of the counter radicals in transient optical absorption measurements. The rate constants of the eaq- reactions with radicals have been determined over a temperature range of 5-75 degrees C from the kinetic analysis of systems of multiple second-order reactions. The observed high rate constants for all the eaq- + radical reactions have been analyzed with the Smoluchowski equation. This analysis suggests that many of the eaq- + radical reactions are diffusion-controlled with a spin factor of 1/4, while other reactions with *OH, *N3, Br2*-, I2*-, and C6H5S* have spin factors significantly larger than 1/4. Spin dynamics for the eaq-/radical pairs is discussed to explain the different spin factors. The reactions with *OH, *N3, Br2*-, and I2*- have also been found to have apparent activation energies less than that for diffusion control, and it is suggested that the spin factors for these reactions decrease with increasing temperature. Such a decrease in spin factor may reflect a changing competition between spin relaxation/conversion and diffusive escape from the radical pairs.

  6. Pressure induced reactions amongst calcium aluminate hydrate phases

    SciTech Connect

    Moon, Ju-hyuk; Oh, Jae Eun; Balonis, Magdalena; Glasser, Fredrik P.; Clark, Simon M.; Monteiro, Paulo J.M.

    2011-06-15

    The compressibilities of two AFm phases (straetlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt volume contraction regardless of the molecular size of the pressure-transmitting media. This volume discontinuity could be associated to a structural transition or to the movement of the weakly bound interlayer water molecules in the AFm structure. The experimental results seem to indicate that the pressure-induced dehydration is the dominant mechanism especially with hygroscopic pressure medium. The Birch-Murnaghan equation of state was used to compute the bulk modulus of the minerals. Due to the discontinuity in the pressure-volume diagram, a two stage bulk modulus of each AFm phase was calculated. The abnormal volume compressibility for the AFm phases caused a significant change to their bulk modulus. The reliability of this experiment is verified by comparing the bulk modulus of hydrogarnet with previous studies.

  7. Electron-induced hydration of an alkene: alternative reaction pathways.

    PubMed

    Warneke, Jonas; Wang, Ziyan; Swiderek, Petra; Bredehöft, Jan Hendrik

    2015-03-27

    Electron-induced reactions in condensed mixtures of ethylene and water lead to the synthesis of ethanol, as shown by post-irradiation thermal desorption spectrometry (TDS). Interestingly, this synthesis is not only induced by soft electron impact ionization similar to a previously observed electron-induced hydroamination but also, at low electron energy, by electron attachment to ethylene and a subsequent acid/base reaction with water.

  8. Gas-solid carbonation as a current alternative origin for carbonates in Martian regolith

    NASA Astrophysics Data System (ADS)

    Garenne, A.; Montes-Hernandez, G.; Beck, P.; Schmitt, B.; Brissaud, O.

    2011-12-01

    Carbonates are abundant sedimentary minerals at the surface and sub-surface of Earth and they have been proposed as tracers of liquid water in extraterrestrial environments (e.g. at Mars surface). Its formation mechanism is since generally associated with aqueous alteration processes. Recently, carbonates minerals have been discovered on Mars surface by different orbital or rovers missions. In particular, the phoenix mission has measured from 1 to 5% of calcium carbonate (calcite type). These occurrences have been reported in area were the relative humidity is significantly high (Boynton et al., 2009). The small concentration of carbonates suggests an alternative process than carbonation in aqueous conditions. Such an observation might rather point toward a possible formation mechanism by dust-gas reaction under current Martian conditions. For this reason, in the present study, we designed an experimental setup consisting of an infrared microscope coupled to a cryogenic reaction cell (IR-CryoCell setup) in order to investigate the gas-solid carbonation of three different mineral precursors for carbonates (Ca and Mg hydroxides, and a hydrated Ca silicate formed from Ca2SiO4) at low temperature (from -10 to 25°C) and at reduced CO2 pressure (from 100 to 1000 mbar). These mineral materials are crucial precursors to form respective Ca and Mg carbonates in humid environments (0 < relative humidity < 100%) at dust-CO2 or dust-water ice-CO2 interfaces. The results have revealed a significant and fast carbonation process for Ca hydroxide and hydrated Ca silicate. Conversely, slight carbonation process was observed for Mg hydroxide. These results suggest that gas-solid carbonation process or carbonate formation at the dust-water ice-CO2 interfaces could be a currently active Mars surface process. We note that the carbonation process at low temperature (<0°C) described in the present study could also have important implications on the dust-water ice-CO2 interactions in

  9. Acid-catalyzed reactions of twisted amides in water solution: competition between hydration and hydrolysis.

    PubMed

    Wang, Binju; Cao, Zexing

    2011-10-10

    The acid-catalyzed reactions of twisted amides in water solution were investigated by using cluster-continuum model calculations. In contrast to the previous widely suggested concerted hydration of the C=O group, our calculations show that the reaction proceeds in a practically stepwise manner, and that the hydration and hydrolysis channels of the C-N bond compete. The Eigen ion (H(3)O(+)) is the key species involved in the reaction, and it modulates the hydration and hydrolysis reaction pathways. The phenyl substitution in the twisted amide not only activates the N-CO bond, but also stabilizes the hydrolysis product through n(N)→π(phenyl) delocalization, leading exclusively to the hydrolysis product of the ring-opened carboxylic acid. Generally, the twisted amides are more active than the planar amides, and such a rate acceleration results mainly from the increase in exothermicity in the first N-protonation step; the second step of the nucleophilic attack is less affected by the twisting of the amide bond. The present results show good agreement with the available experimental observations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Pre-donation Hydration and Applied Muscle Tension Combine to Reduce Presyncopal Reactions to Blood Donation

    PubMed Central

    France, Christopher R.; Ditto, Blaine; Wissel, Mary Ellen; France, Janis L.; Dickert, Tara; Rader, Aaron; Sinclair, Kadian; McGlone, Sarah; Trost, Zina; Matson, Erin

    2010-01-01

    BACKGROUND A randomized controlled trial was conducted to test the effects of hydration and applied muscle tensing on presyncopal reactions to blood donation. Both interventions are designed to prevent the decreases in blood pressure that can contribute to such reactions, but due to the distinct physiological mechanisms underlying their pressor responses it was hypothesized that a combined intervention would yield the greatest benefit. STUDY DESIGN AND METHODS Prior to blood donation, first- and second-time blood donors (Mean Age = 20.2 years, SD = 4.9) were randomly assigned to: 1) standard donation, 2) placebo (leg exercise prior to venipuncture), 3) pre-donation water, or 4) pre-donation water and leg exercise during donation. RESULTS Main effects of group were observed for phlebotomist classification of vasovagal reactions, X2 (3) = 8.38, p<0.05, and donor reports of presyncopal reactions, X2 (3) = 13.16, p < 0.01. Follow-up analyses of phlebotomist classifications revealed fewer reactions in the pre-donation water and pre-donation water and leg exercise groups relative to placebo but not standard donation. Follow-up analyses of self-reported reactions revealed that women, but not men, had lower scores in both the pre-donation water and pre-donation water and leg exercise groups relative to both placebo and standard donation. CONCLUSION Pre-donation hydration and a combination of hydration and leg exercise may help attenuate presyncopal reactions in relatively novice donors, although future studies with larger samples are required to confirm this effect. PMID:20113455

  11. Application of hydration reaction on the removal of recalcitrant contaminants in leachate after biological treatment.

    PubMed

    Ziyang, Lou; Yu, Song; Xiaoliang, Chen; Youcai, Zhao; Nanwen, Zhu

    2014-04-01

    Leachate contains amounts of non-biodegradable matters with COD range of 400-1500mg/L after the biological treatment, and should be removed further to attain the Chinese discharge standards. Hydration reaction has the potential to combine and solidify some recalcitrant substances, and thus could be applied as the advanced leachate treatment process. It was found that COD and NH3N decreased from 485 to<250mg/L and 91 to 10mg/L, with the removal rate over 50% and 90% in the first 6d, respectively, and COD and NH3N removal capacity were around 23.7 and 9.2mg/g under the test conditions. The percentage of the substances with low Mn range of<1000 decreased from 32.9% to 3.2% in leachate after hydration reaction. Tricalcium aluminate, tricalcium silicate and dicalcium silicate were the most activity compounds successively for the pollutant removal in leachate, and hydration reaction could be the option for the advanced wastewater treatment process thereafter. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Nucleophilic reactions of bromocyclopentane in the structure-H methane + bromocyclopentane mixed hydrate system at high pressures.

    PubMed

    Matsumoto, Yuuki; Katsuta, Yoshito; Kamo, Fumitaka; Bando, Tatsuya; Makino, Takashi; Sugahara, Takeshi; Ohgaki, Kazunari

    2014-11-26

    Thermodynamic stability boundary in the structure-H methane + bromocyclopentane mixed hydrate system was measured at pressures from 20 to 100 MPa. The thermodynamic stability boundary of the methane + bromocyclopentane mixed hydrate exhibits anomalous behavior under conditions at high pressures and high temperatures. This phenomenon is due to the elimination and substitution reactions of bromocyclopentane to cyclopentene and cyclopentanol, respectively. The nucleophilic reactions of bromocyclopentane are mainly advanced in the liquid bromocyclopentane-rich phases, while it is restrained when bromocyclopentane is enclathrated in hydrate cage.

  13. Stepwise hydration of ionized aromatics. Energies, structures of the hydrated benzene cation, and the mechanism of deprotonation reactions.

    PubMed

    Ibrahim, Yehia M; Meot-Ner Mautner, Michael; Alshraeh, Edreese H; El-Shall, M Samy; Scheiner, Steve

    2005-05-18

    The stepwise binding energies (DeltaHdegree(n-1,n)) of 1-8 water molecules to benzene(.+) [Bz(.+)(H2O)n] were determined by equilibrium measurements using an ion mobility cell. The stepwise hydration energies, DeltaHdegree(n-1,n), are nearly constant at 8.5 +/- 1 kcal mol-1 from n = 1-6. Calculations show that in the n = 1-4 clusters, the benzene(.+) ion retains over 90% of the charge, and it is extremely solvated, that is, hydrogen bonded to an (H2O)n cluster. The binding energies and entropies are larger in the n = 7 and 8 clusters, suggesting cyclic or cage-like water structures. The concentration of the n = 3 cluster is always small, suggesting that deprotonation depletes this ion, consistent with the thermochemistry since associative deprotonation Bz(.+)(H2O)(n-1) + H2O-->C6H5. + (H2O)nH+ is thermoneutral or exothermic for n > or = 4. Associative intracluster proton transfer Bz(.+)(H2O)(n+1) + H2O-->C6H5.(H2O)nH+ would also be exothermic for n > or = 4, but lack of H/D exchange with D2O shows that the proton remains on C6H6(.+) in the observed Bz(.+)(H2O)n clusters. This suggests a barrier to intracluster proton transfer, and as a result, the [Bz(.+)(H2O)n]* activated complexes either undergo dissociative proton transfer, resulting in deprotonation and generation of (H2O)nH+, or become stabilized. The rate constant for the deprotonation reaction shows a uniquely large negative temperature coefficient of K = cT(-67+/-4) (or activation energy of -34+/- 1 kcal mol-1), caused by a multibody mechanism in which five or more components need to be assembled for the reaction.

  14. Solids flow mapping in gas-solid risers

    NASA Astrophysics Data System (ADS)

    Bhusarapu, Satish Babu

    Gas-solid risers are extensively used in many industrial processes for gas-solid reactions (e.g. coal combustion and gasification) and for solid catalyzed gas phase reactions (e.g. fluid catalytic cracking, butane oxidation to maleic anhydride). Ab initio prediction of the complex multiphase fluid dynamics in risers is not yet possible, which makes reactor modeling difficult. In particular, quantification of solids flow and mixing is important. Almost all the experimental techniques used to characterize solids flow lead to appreciable errors in measured variables in large scale, high mass flux systems. In addition, none of the experimental techniques provide all the relevant data required to develop a satisfactory solids flow model. In this study, non-invasive Computer Automated Radioactive Particle Tracking (CARPT) is employed to visualize and quantify the solids dynamics and mixing in the gas-solid riser of a Circulating Fluidized Bed (CFB). A single radioactive tracer particle is monitored during its multiple visits to the riser and with an assumption of ergodicity, the following flow parameters are estimated: (a) Overall solids mass flux in the CFB loop. (b) Solids residence time distribution in the riser and down-comer. (c) Lagrangian and Eulerian solids velocity fields in a fully-developed section of the riser. This includes velocity fluctuations and components of the diffusivity tensor. The existing CARPT technique is extended to large scale systems. A new algorithm, based on a cross-correlation search, is developed for position rendition from CARPT data. Two dimensional solids holdup profiles are estimated using gamma-ray computed tomography. The image quality from the tomography data is improved by implementing an alternating minimization algorithm. This work establishes for the first time a reliable database for local solids dynamic quantities such as time-averaged velocities, Reynolds stresses, eddy diffusivities and turbulent kinetic energy. In addition

  15. Comparison of Kinetic and Equilibrium Reaction Models inSimulating the Behavior of Gas Hydrates in Porous Media

    SciTech Connect

    Kowalsky, Michael B.; Moridis, George J.

    2006-05-12

    In this study we compare the use of kinetic and equilibrium reaction models in the simulation of gas (methane) hydrates in porous media. Our objective is to evaluate through numerical simulation the importance of employing kinetic versus equilibrium reaction models for predicting the response of hydrate-bearing systems to external stimuli, such as changes in pressure and temperature. Specifically, we (1) analyze and compare the responses simulated using both reaction models for production in various geological settings and for the case of depressurization in a core during extraction; and (2) examine the sensitivity to factors such as initial hydrate saturation, hydrate reaction surface area, and numerical discretization. We find that for systems undergoing thermal stimulation and depressurization, the calculated responses for both reaction models are remarkably similar, though some differences are observed at early times. Given these observations, and since the computational demands for the kinetic reaction model far exceed those for the equilibrium reaction model, the use of the equilibrium reaction model often appears to be justified and preferred for simulating the behavior of gas hydrates.

  16. The combined effects of hydration and exercise heat stress on choice reaction time.

    PubMed

    Serwah, N; Marino, F E

    2006-05-01

    The purpose of this investigation was to examine the combined effects of hydration and exercise heat stress on choice reaction time. On three separate occasions eight male subjects performed cycle exercise at approximately 70% of peak power output in warm, humid conditions (31 degrees C, 63% relative humidity) for a maximum of 90 min or until exhaustion. Throughout the trials, subjects ingested either a volume of water equal to fluid loss (100-FR), a volume equivalent to approximately 50% of fluid loss (50-FR), or no fluid (0-FR). A choice reaction time task was undertaken at rest, after 20 min of cycling, 40 min of cycling and at the conclusion of exercise. Mean reaction time for 100-FR was 342.2+/-8.2 ms, 352.4+/-7.5 ms for 50-FR and 345.6+/-8.4 ms for 0-FR and were not significantly different. Choice reaction time was facilitated as the duration of exercise progressed with reaction time at 40 min and conclusion stages of exercise faster than at rest (P<0.005). Choice reaction time and accuracy were affected by the number of choices, with choice reaction time increasing linearly with the number of choices (P<0.005) and rate of incorrect responses increasing in the 4-choice task compared to the 1-choice and 2-choice task (P<0.05). The results indicate that, in up to 90 min of exercise in warm, humid conditions, choice reaction time is not compromised by different levels of hydration.

  17. The reaction of CF2Cl2 with gas-phase hydrated electrons.

    PubMed

    Lengyel, Jozef; van der Linde, Christian; Fárník, Michal; Beyer, Martin K

    2016-09-14

    The reaction of dichlorodifluoromethane (CF2Cl2) with hydrated electrons (H2O)n(-) (n = 30-86) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The hydrated electron reacts with CF2Cl2, forming (H2O)mCl(-) with a rate constant of (8.6 ± 2.2) × 10(-10) cm(3) s(-1), corresponding to an efficiency of 57 ± 15%. The reaction enthalpy was determined using nanocalorimetry, revealing a strongly exothermic reaction with ΔHr(CF2Cl2, 298 K) = -208 ± 41 kJ mol(-1). The combination of the measured reaction enthalpy with thermochemical data from the condensed phase yields a C-Cl bond dissociation enthalpy (BDE) ΔHC-Cl(CF2Cl2, 298 K) = 355 ± 41 kJ mol(-1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs.

  18. First determination of volume changes and enthalpies of the high-pressure decomposition reaction of the structure H methane hydrate to the cubic structure I methane hydrate and fluid methane.

    PubMed

    Ogienko, Andrey G; Tkacz, Marek; Manakov, Andrey Yu; Lipkowski, Janusz

    2007-11-08

    Pressure-temperature (P-T) conditions of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane were studied with a piston-cylinder apparatus at room temperature. For the first time, volume changes accompanying this reaction were determined. With the use of the Clausius-Clapeyron equation the enthalpies of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane have been calculated.

  19. The reaction of ethyl 2-oxo-2H-chromene-3-carboxylate with hydrazine hydrate.

    PubMed

    Abdel-Aziz, Hatem A; Elsaman, Tilal; Attia, Mohamed I; Alanazi, Amer M

    2013-02-06

    Although salicylaldehyde azine (3) was reported in 1985 as the single product of the reaction of ethyl 2-oxo-2H-chromene-3-carboxylate (1) with hydrazine hydrate, we identified another main reaction product, besides 3, which was identified as malono-hydrazide (4). In the last two decades, however, some articles have claimed that this reaction afforded exclusively hydrazide 2 and they have reported the use of this hydrazide 2 as a precursor in the syntheses of several heterocyclic compounds and hydrazones 6. We reported herein a study of the formation of 2 and a facile route for the synthesis of the target compounds N'-arylidene-2-oxo-2H-chromene-3-carbohydrazides 6a-f.

  20. Contrasting reactions of hydrated electron and formate radical with 2-thio analogues of cytosine and uracil.

    PubMed

    Prasanthkumar, Kavanal P; Alvarez-Idaboy, Juan R; Kumar, Pavitra V; Singh, Beena G; Priyadarsini, K Indira

    2016-10-19

    2-Thiocytosine (TC) and 2-thiouracil (TU) were subjected to hydrated electron (eaq(-)), formate radical (CO2˙(-)) and 2-hydroxypropan-2-yl radical ((CH3)2˙COH) reactions in aqueous medium. Transients were characterized by absorption spectroscopy and the experimental findings were rationalized by DFT calculations at LC-ωPBE and M06-2X levels using a 6-311+G(d,p) basis set and SMD solvation. In eaq(-) reactions, a ring N-atom protonated radical of TC and an exocyclic O-atom protonated radical of TU were observed via addition of eaq(-) and subsequent protonation by solvent molecules. However, two competing but simultaneous mechanisms are operative in CO2˙(-) reactions with TC and TU. The first one corresponds to formations of N(O)-atom protonated radicals (similar to eaq(-) reactions); the second mechanism led to 2 center-3 electron, sulfur-sulfur bonded neutral dimer radicals, TCdim˙ and TUdim˙. DFT calculations demonstrated that H-abstraction by CO2˙(-) from TC(TU) results in S-centered radical which upon combination with TC(TU) provide the dimer radical. In some cases, DFT energy profiles were further validated by CBS-QB3//M06-2X calculations. This is the first time report for a contradictory behavior in the mechanisms of eaq(-) and CO2˙(-) reactions with any pyrimidines or their thio analogues.

  1. Thermodynamic forward modeling of retrogressive hydration reactions induced by geofluid infiltration

    NASA Astrophysics Data System (ADS)

    Kuwatani, Tatsu; Toriumi, Mitsuhiro

    2017-01-01

    We have developed a new methodology for forward analysis of retrogressive hydration (rehydration) reactions by an improved thermodynamic forward modeling technique based on a differential thermodynamic approach (Gibbs' method). Based on natural observations and theoretical considerations, the progress of a rehydration reaction is modeled by incorporating a change in the effective bulk composition on account of the breakdown of the non-equilibrated phase and the amount of water infiltration into the system. Forward analyses of rehydration reactions under greenschist-facies conditions show that (1) the reaction progress of rehydration is proportional to the external water supply, and (2) the mineral compositions of equilibrated minerals are mainly controlled by P- T conditions and are similar to those in the global equilibrium model. Calculated results are in accordance with natural observations of rehydration reactions in greenschist-facies rocks, which supports the validity of the proposed model. The proposed model can be used as a basic forward model for various inversion analyses and numerical simulations and thus to understand the distribution and behavior of geofluids.[Figure not available: see fulltext.

  2. A novel system for in-situ observations of early hydration reactions in wet conditions in conventional SEM

    SciTech Connect

    Katz, A.; Bentur, A. . E-mail: bentur@tx.technion.ac.il; Kovler, K.

    2007-01-15

    A novel system enabling wet microscopy in conventional SEM is described and its performance for in-situ study of hydration reactions is demonstrated. The technology is based on a sealed specimen capsule, which is protected from the microscope vacuum by an electron-transparent partition membrane. Thus, the wet sample can be placed and observed in a 'conventional' SEM without the need for drying or employing environmental SEM. Early hydration reactions of gypsum and cement systems were followed during the first 24 h.

  3. Computational studies of the isomerization and hydration reactions of acetaldehyde oxide and methyl vinyl carbonyl oxide.

    PubMed

    Kuwata, Keith T; Hermes, Matthew R; Carlson, Matthew J; Zogg, Cheryl K

    2010-09-02

    Alkene ozonolysis is a major source of hydroxyl radical (*OH), the most important oxidant in the troposphere. Previous experimental and computational work suggests that for many alkenes the measured *OH yields should be attributed to the combined impact of both chemically activated and thermalized syn-alkyl Criegee intermediates (CIs), even though the thermalized CI should be susceptible to trapping by molecules such as water. We have used RRKM/master equation and variational transition state theory calculations to quantify the competition between unimolecular isomerization and bimolecular hydration reactions for the syn and anti acetaldehyde oxide formed in trans-2-butene ozonolysis and for the CIs formed in isoprene ozonolysis possessing syn-methyl groups. Statistical rate theory calculations were based on quantum chemical data provided by the B3LYP, QCISD, and multicoefficient G3 methods, and thermal rate constants were corrected for tunneling effects using the Eckart method. At tropospheric temperatures and pressures, all thermalized CIs with syn-methyl groups are predicted to undergo 1,4-hydrogen shifts from 2 to 8 orders of magnitude faster than they react with water monomer at its saturation number density. For thermalized anti acetaldehyde oxide, the rates of dioxirane formation and hydration should be comparable.

  4. Pulse radiolysis of supercritical water II. Reaction of nitrobenzene with hydrated electrons and hydroxyl radicals.

    SciTech Connect

    Marin, T. W.; Cline, J. A.; Bartels, D. M.; Jonah, C. D.; Takahashi, K.; Chemistry; Hakkaido Univ.

    2003-12-26

    The rate constants for the reactions of nitrobenzene with the hydroxyl radical (OH{sup {sm_bullet}}) and hydrated electron ((e{sup -}){sub aq}) in water have been measured from room temperature to 400 {sup o}C using electron pulse radiolysis and transient absorption spectroscopy. The diffusion-limited reaction of nitrobenzene with (e{sup 0}){sub aq} exhibits temperature-insensitive activation energy up to 300 {sup o}C, indicating that the activation energy for electron diffusion remains high over this range. The (e{sup -}){sub aq} reactivity is explained as a long-range electron transfer, and the results are interpreted in terms of extended Marcus theory and Smoluchowski relationships. At 380 {sup o}C, the rate constant has a density dependence similar to that previously reported for other (e{sup -}){sub aq} scavenging reactions. The reaction rate of nitrobenzene with OH{sup {sm_bullet}} is very insensitive to temperature from room temperature up to 300 {sup o}C, in agreement with previous studies. Above 300 {sup o}C, the rate constant increases as the critical temperature is approached and exceeded. Time-resolved electronic absorption spectra of the nitrobenzene radiolysis transients reveal complex kinetics involving multiple absorbing species.

  5. Calcic micas in the Allende meteorite - Evidence for hydration reactions in the early solar nebula

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; Buseck, Peter R.

    1991-01-01

    Two calcic micas, clintonite and margarite, have been identified in alteration products in a calcium- and aluminum-rich inclusion (CAI) in the Allende meteorite. Clintonite replaces grossular in alteration veins, and margarite occurs as lamellae in anorthite. Their occurrence suggests that, in addition to undergoing high-temperature alteration by a volatile and iron-rich vapor that produced the grossular and anorthite, some CAIs underwent alteration at moderate temperatures (400 K or less). Petrographic evidence suggests that the calcic micas formed before accretion but after the formation of the layered rim sequences that surround the CAI. These calcic micas provide strong evidence that, contrary to theoretical calculations, some hydration reactions occurred in the early solar nebula.

  6. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

    NASA Astrophysics Data System (ADS)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

    2017-09-01

    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  7. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons.

    PubMed

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K

    2017-09-14

    The reaction of HNO3 with hydrated electrons (H2O)n(-) (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH(-)(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3(-)(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol(-1). Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  8. Allene as the parent substrate in zinc-mediated biomimetic hydration reactions of cumulenes.

    PubMed

    Jahn, Burkhard O; Eger, Wilhelm A; Anders, Ernst

    2008-11-07

    The aim of our present investigation is to unravel the general mode of biomimetic activation of a wide variety of cumulenes by carbonic anhydrase (CA) models. Carbonic anhydrases allow the specific recognition, activation and transfer not only of CO2 but also of heteroallenes X=C=Y such as the polar or polarizable examples COS, CS2, H2CCO, and RNCS. Therefore, this enzyme class fulfils the requirements of excellent catalysts with a wide variety of important applications. Can this be extended to the isoelectronic but less reactive allene molecule, H2C=C=CH2 and extremely simplified models as mimetic concept for active center of the carbonic anhydrase? Allene is a waste product in the refinery, i.e. the C3-cut of the naphtha distillation; therefore, any addition product that can be obtained from allene in high yields will be of significant value. We investigated the complete catalytic cycle of a very simple model reaction, the hydration of allene, using density functional theory. Additionally, calculations were performed for the uncatalyzed reaction. There are two possible ways for the nucleophilic attack leading to different products. The zinc hydroxide complex and the water molecule can react at the central or the terminal carbon atoms (positional selectivity), the resulting products are 2-propen-1-ol and propen-2-ol, respectively, acetone. The calculations indicate a significant lower energy barrier for the rate determining step of the formation of propen-2-ol and therefore a well-expressed regioselectivity for the addition of such small molecules. The zinc complex has a pronounced catalytic effect and lowers the activation barrier from 262.5 to 123.9 kJ/mol compared with the uncatalyzed reaction. This work suggests the most probable paths for this reaction and discloses the necessity for the development of novel catalysts.

  9. CO2 sequestration using accelerated gas-solid carbonation of pre-treated EAF steel-making bag house dust.

    PubMed

    El-Naas, Muftah H; El Gamal, Maisa; Hameedi, Suhaib; Mohamed, Abdel-Mohsen O

    2015-06-01

    Mineral CO2 sequestration is a promising process for the reduction of carbon dioxide emissions to the atmosphere. In this paper, alkaline calcium-rich dust particles collected from bag filters of electric arc furnaces (EAF) for steel making were utilized as a viable raw material for mineral CO2 sequestration. The dust particles were pre-treated through hydration, drying and screening. The pre-treated particles were then subjected to direct gas-solid carbonation reaction in a fluidized-bed reactor. The carbonated products were characterized to determine the overall sequestration capacity and the mineralogical structures. Leaching tests were also performed to measure the extracted minerals from the carbonated dust and evaluate the carbonation process on dust stabilization. The experimental results indicated that CO2 could be sequestered using the pre-treated bag house dust. The maximum sequestration of CO2 was 0.657 kg/kg of dust, based on the total calcium content. The highest degree of carbonation achieved was 42.5% and the carbonation efficiency was 69% at room temperature.

  10. Chaos suppression in gas-solid fluidization.

    PubMed

    Pence, Deborah V.; Beasley, Donald E.

    1998-06-01

    Fluidization in granular materials occurs primarily as a result of a dynamic balance between gravitational forces and forces resulting from the flow of a fluid through a bed of discrete particles. For systems where the fluidizing medium and the particles have significantly different densities, density wave instabilities create local pockets of very high void fraction termed bubbles. The fluidization regime is termed the bubbling regime. Such a system is appropriately termed a self-excited nonlinear system. The present study examines chaos suppression resulting from an opposing oscillatory flow in gas-solid fluidization. Time series data representing local, instantaneous pressure were acquired at the surface of a horizontal cylinder submerged in a bubbling fluidized bed. The particles had a weight mean diameter of 345 &mgr;m and a narrow size distribution. The state of fluidization corresponded to the bubbling regime and total air flow rates employed in the present study ranged from 10% to 40% greater than that required for minimum fluidization. The behavior of time-varying local pressure in fluidized beds in the absence of a secondary flow is consistent with deterministic chaos. Kolmogorov entropy estimates from local, instantaneous pressure suggest that the degree of chaotic behavior can be substantially suppressed by the presence of an opposing, oscillatory secondary flow. Pressure signals clearly show a "phase-locking" phenomenon coincident with the imposed frequency. In the present study, the greatest degree of suppression occurred for operating conditions with low primary and secondary flow rates, and a secondary flow oscillation frequency of 15 Hz. (c) 1998 American Institute of Physics.

  11. The coupling of tautomerization to hydration in the transition state on the pyrimidine photohydration reaction path.

    PubMed

    Franzen, S; Skalski, B; Bartolotti, L; Delley, B

    2014-10-07

    The ground state reaction path for formation of the pyrimidine hydrates was calculated using a nudged elastic band (NEB) approach, combined with a calculation of the transition state, and implemented using a numerical basis set in the density functional theory (DFT) code DMol(3). The model systems used for study consist of 1-methyl pyrimidines with a H2O molecule as the reactant, and the corresponding C5-hydro-C6-hydroxypyrimidine as the product. The barrier to addition of water across the C5-C6 π-bond ranges from 43-48 kcal mol(-1) in the 1-methylpyrimidines (1-MP) studied. Similar but slightly smaller barriers of 34-45 kcal mol(-1) were found for the tautomers of the 1-MPs, i.e. the enols of uridine and thymine and imine of cytosine. Comparison of these calculations with previous computational and experimental work suggests that a hot ground state formed by the rapid internal conversion of pyrimidines has sufficient energy to permit crossover from the common form to the tautomeric form of the pyrimidine at the transition state. The hot ground state mechanism can account for the experimentally observed yield and thermal reversion of pyrimidine photohydrates, while simultaneously explaining the effect of photohydrates on the mutation rate.

  12. Radical-based destruction of nitramines in water: kinetics and efficiencies of hydroxyl radical and hydrated electron reactions.

    PubMed

    Mezyk, Stephen P; Razavi, Behnaz; Swancutt, Katy L; Cox, Casandra R; Kiddle, James J

    2012-08-09

    In support of the potential use of advanced oxidation and reduction process technologies for the removal of carcinogenic nitro-containing compounds in water reaction rate constants for the hydroxyl radical and hydrated electron with a series of low molecular weight nitramines (R(1)R(2)-NNO(2)) have been determined using a combination of electron pulse radiolysis and transient absorption spectroscopy. The hydroxyl radical reaction rate constant was fast, ranging from 0.54-4.35 × 10(9) M(-1) s(-1), and seen to increase with increasing complexity of the nitramine alkyl substituents suggesting that oxidation primarily occurs by hydrogen atom abstraction from the alkyl chains. In contrast, the rate constant for hydrated electron reaction was effectively independent of compound structure, (k(av) = (1.87 ± 0.25) × 10(10) M(-1) s(-1)) indicating that the reduction predominately occurred at the common nitramine moiety. Concomitant steady-state irradiation and product measurements under aerated conditions also showed a radical reaction efficiency dependence on compound structure, with the overall radical-based degradation becoming constant for nitramines containing more than four methylene groups. The quantitative evaluation of these efficiency data suggest that some (~40%) hydrated electron reduction also results in quantitative nitramine destruction, in contrast to previously reported electron paramagnetic measurements on these compounds that proposed that this reduction only produced a transient anion adduct that would transfer its excess electron to regenerate the parent molecule.

  13. Catalytic Mechanisms for Cofactor-Free Oxidase-Catalyzed Reactions: Reaction Pathways of Uricase-Catalyzed Oxidation and Hydration of Uric Acid.

    PubMed

    Wei, Donghui; Huang, Xiaoqin; Qiao, Yan; Rao, Jingjing; Wang, Lu; Liao, Fei; Zhan, Chang-Guo

    2017-07-07

    First-principles quantum mechanical/molecular mechanical (QM/MM)-free energy calculations have been performed to uncover how uricase catalyzes metabolic reactions of uric acid (UA), demonstrating that the entire reaction process of UA in uricase consists of two stages-oxidation followed by hydration. The oxidation consists of four steps: (1) chemical transformation from 8-hydroxyxythine to an anionic radical via a proton transfer along with an electron transfer, which is different from the previously proposed electron-transfer mechanism that involves a dianion intermediate (UA(2-)) during the catalytic reaction process; (2) proton transfer to the O2(-) anion (radical); (3) diradical recombination to form a peroxo intermediate; (4) dissociation of H2O2 to generate the dehydrourate. Hydration, for the most favorable pathway, is initiated by the nucleophilic attack of a water molecule on dehydrourate, along with a concerted proton transfer through residue Thr69 in the catalytic site. According to the calculated free energy profile, the hydration is the rate-determining step, and the corresponding free energy barrier of 16.2 kcal/mol is consistent with that derived from experimental kinetic data, suggesting that the computational insights into the catalytic mechanisms are reasonable. The mechanistic insights not only provide a mechanistic base for future rational design of uricase mutants with improved catalytic activity against uric acid as an improved enzyme therapy, but also are valuable for understanding a variety of other cofactor-free oxidase-catalyzed reactions involving an oxygen molecule.

  14. CO2 sequestration using waste concrete and anorthosite tailings by direct mineral carbonation in gas-solid-liquid and gas-solid routes.

    PubMed

    Ben Ghacham, Alia; Cecchi, Emmanuelle; Pasquier, Louis-César; Blais, Jean-François; Mercier, Guy

    2015-11-01

    Mineral carbonation (MC) represents a promising alternative for sequestering CO2. In this work, the CO2 sequestration capacity of the available calcium-bearing materials waste concrete and anorthosite tailings is assessed in gas-solid-liquid and gas-solid routes using 18.2% flue CO2 gas. The objective is to screen for a better potential residue and phase route and as the ultimate purpose to develop a cost-effective process. The results indicate the possibility of removing 66% from inlet CO2 using waste concrete for the aqueous route. However, the results that were obtained with the carbonation of anorthosite were less significant, with 34% as the maximal percentage of CO2 removal. The difference in terms of reactivity could be explained by the accessibility to calcium. In fact, anorthosite presents a framework structure wherein the calcium is trapped, which could slow the calcium dissolution into the aqueous phase compared to the concrete sample, where calcium can more easily leach. In the other part of the study concerning gas-solid carbonation, the results of CO2 removal did not exceed 15%, which is not economically interesting for scaling up the process. The results obtained with waste concrete samples in aqueous phase are interesting. In fact, 34.6% of the introduced CO2 is converted into carbonate after 15 min of contact with the gas without chemical additives and at a relatively low gas pressure. Research on the optimization of the aqueous process using waste concrete should be performed to enhance the reaction rate and to develop a cost-effective process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Early age hydration and pozzolanic reaction in natural zeolite blended cements: Reaction kinetics and products by in situ synchrotron X-ray powder diffraction

    SciTech Connect

    Snellings, R.; Mertens, G.; Cizer, O.; Elsen, J.

    2010-12-15

    The in situ early-age hydration and pozzolanic reaction in cements blended with natural zeolites were investigated by time-resolved synchrotron X-ray powder diffraction with Rietveld quantitative phase analysis. Chabazite and Na-, K-, and Ca-exchanged clinoptilolite materials were mixed with Portland cement in a 3:7 weight ratio and hydrated in situ at 40 {sup o}C. The evolution of phase contents showed that the addition of natural zeolites accelerates the onset of C{sub 3}S hydration and precipitation of CH and AFt. Kinetic analysis of the consumption of C{sub 3}S indicates that the enveloping C-S-H layer is thinner and/or less dense in the presence of alkali-exchanged clinoptilolite pozzolans. The zeolite pozzolanic activity is interpreted to depend on the zeolite exchangeable cation content and on the crystallinity. The addition of natural zeolites alters the structural evolution of the C-S-H product. Longer silicate chains and a lower C/S ratio are deduced from the evolution of the C-S-H b-cell parameter.

  16. Radiosensitization of DNA by Cisplatin Adducts Results from an Increase in the Rate Constant for the Reaction with Hydrated Electrons and Formation of PtI

    PubMed Central

    Behmand, B.; Marignier, J.-L.; Mostafavi, M.; Wagner, J. R.; Hunting, D. J.; Sanche, L.

    2015-01-01

    Pulse radiolysis measurements of the decay of hydrated electrons in solutions containing different concentrations of the oligonucleotide GTG with and without a cisplatin adduct show that the presence of a cisplatin moiety accelerates the reaction between hydrated electrons and the oligonucleotide. The rate constant of the reaction is found to be 2.23 × 1010 mol−1 L s−1, which indicates that it is diffusion controlled. In addition, we show for the first time the formation of a PtI intermediate as a result of the reaction of hydrated electrons with GTG-cisplatin. A putative reaction mechanism is proposed, which may form the basis of the radiosensitization of cancer cells in concomitant chemoradiation therapy with cisplatin. PMID:26098937

  17. Turbulence modeling of gas-solid suspension flows

    NASA Technical Reports Server (NTRS)

    Chen, C. P.

    1988-01-01

    The purpose here is to discuss and review advances in two-phase turbulent modeling techniques and their applications in various gas-solid suspension flow situations. In addition to the turbulence closures, heat transfer effect, particle dispersion and wall effects are partially covered.

  18. Thermochemistry of the Reaction of SF6 with Gas-Phase Hydrated Electrons: A Benchmark for Nanocalorimetry.

    PubMed

    Akhgarnusch, Amou; Höckendorf, Robert F; Beyer, Martin K

    2015-10-01

    The reaction of sulfur hexafluoride with gas-phase hydrated electrons (H2O)n(-), n ≈ 60-130, is investigated at temperatures T = 140-300 K by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. SF6 reacts with a temperature-independent rate of 3.0 ± 1.0 × 10(-10) cm(3) s(-1) via exclusive formation of the hydrated F(-) anion and the SF5(•) radical, which evaporates from the cluster. Nanocalorimetry yields a reaction enthalpy of ΔHR,298K = 234 ± 24 kJ mol(-1). Combined with literature thermochemical data from bulk aqueous solution, these result in an F5S-F bond dissociation enthalpy of ΔH298K = 455 ± 24 kJ mol(-1), in excellent agreement with all high-level quantum chemical calculations in the literature. A combination with gas-phase literature thermochemistry also yields an experimental value for the electron affinity of SF5(•), EA(SF5(•)) = 4.27 ± 0.25 eV.

  19. Estimation of the global amount of submarine gas hydrates formed via microbial methane formation based on numerical reaction-transport modeling and a novel parameterization of Holocene sedimentation

    NASA Astrophysics Data System (ADS)

    Burwicz, E. B.; Rüpke, L. H.; Wallmann, K.

    2011-08-01

    This study provides new estimates for the global offshore methane hydrate inventory formed due to microbial CH production under Quaternary and Holocene boundary conditions. A multi-1D model for particular organic carbon (POC) degradation, gas hydrate formation and dissolution is presented. The novel reaction-transport model contains an open three-phase system of two solid compounds (organic carbon, gas hydrates), three dissolved species (methane, sulfates, inorganic carbon) and one gaseous phase (free methane). The model computes time-resolved concentration profiles for all compounds by accounting for chemical reactions as well as diffusive and advective transport processes. The reaction module builds upon a new kinetic model of POC degradation which considers a down-core decrease in reactivity of organic matter. Various chemical reactions such as organic carbon decay, anaerobic oxidation of methane, methanogenesis, and sulfate reduction are resolved using appropriate kinetic rate laws and constants. Gas hydrates and free gas form if the concentration of dissolved methane exceeds the pressure, temperature, and salinity-dependent solubility limits of hydrates and/or free gas, with a rate given by kinetic parameters. Global input grids have been compiled from a variety of oceanographic, geological and geophysical data sets including a new parameterization of sedimentation rates in terms of water depth. We find prominent gas hydrate provinces offshore Central America where sediments are rich in organic carbon and in the Arctic Ocean where low bottom water temperatures stabilize methane hydrates. The world's total gas hydrate inventory is estimated at 0.82×1013m-2.10×1015mCH (at STP conditions) or, equivalently, 4.18-995 Gt of methane carbon. The first value refers to present day conditions estimated using the relatively low Holocene sedimentation rates; the second value corresponds to a scenario of higher Quaternary sedimentation rates along continental margins. Our

  20. Diffusion and reaction pathways of water near fully hydrated TiO2 surfaces from ab initio molecular dynamics

    NASA Astrophysics Data System (ADS)

    Agosta, Lorenzo; Brandt, Erik G.; Lyubartsev, Alexander P.

    2017-07-01

    Ab initio molecular dynamics simulations are reported for water-embedded TiO2 surfaces to determine the diffusive and reactive behavior at full hydration. A three-domain model is developed for six surfaces [rutile (110), (100), and (001), and anatase (101), (100), and (001)] which describes waters as "hard" (irreversibly bound to the surface), "soft" (with reduced mobility but orientation freedom near the surface), or "bulk." The model explains previous experimental data and provides a detailed picture of water diffusion near TiO2 surfaces. Water reactivity is analyzed with a graph-theoretic approach that reveals a number of reaction pathways on TiO2 which occur at full hydration, in addition to direct water splitting. Hydronium (H3O+) is identified to be a key intermediate state, which facilitates water dissociation by proton hopping between intact and dissociated waters near the surfaces. These discoveries significantly improve the understanding of nanoscale water dynamics and reactivity at TiO2 interfaces under ambient conditions.

  1. Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase.

    PubMed

    Tang, Wai Kit; van der Linde, Christian; Siu, Chi-Kit; Beyer, Martin K

    2017-01-12

    The carbonate radical anion CO3(•-) is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO3(•-) and CO3(•-)(H2O) with HCl under ultrahigh vacuum conditions. Bare CO3(•-) forms OHCl(•-) with a rate constant of 4.2 × 10(-12) cm(3) s(-1), which corresponds to an efficiency of only 0.4%. Hydration accelerates the reaction, and ligand exchange of H2O against HCl proceeds with a rate of 2.7 × 10(-10) cm(3) s(-1). Quantum chemical calculations reveal that OHCl(•-) is best described as an OH(•) hydrogen bonded to Cl(-), while the ligand exchange product is Cl(-)(HCO3(•)). Under tropospheric conditions, where CO3(•-)(H2O) is the dominant species, Cl(-)(HCO3(•)) is efficiently formed. These reactions must be included in models of tropospheric anion chemistry.

  2. Reversal of the relative stability of the isomeric radicals HSO and HOS upon hydration and their reactions with ozone.

    PubMed

    Steudel, Ralf; Steudel, Yana

    2010-04-01

    The radical HSO is an oxidation product of pollutants such as H(2)S and CH(3)SH in Earth's atmosphere. For the first time, the interaction of HSO and its tautomer HOS with single water molecules to yield the hydrates HSO.nH(2)O and HOS.nH(2)O was studied for n = 1-3, applying the high-level G3X(MP2) theory. A large number of structures corresponding to local minima on the potential energy surfaces has been identified. While gaseous HSO is more stable than HOS, the enthalpy diffference between HSO.nH(2)O and HOS.nH(2)O decreases with increasing degree of hydration and becomes practically zero for n = 3. Thus, in aqueous solution as well as in fog and rain droplets, HOS is expected to compete with HSO. The barrier for the tautomerization of HSO to HOS is dramatically lowered by the presence of water molecules since a cyclic transition state allows a concerted proton shift within the system of neighboring hydrogen bonds. The corresponding activation enthalpy of only 73.5 kJ mol(-1) predicted for the transformation of HSO.2H(2)O into HOS.2H(2)O may be compared to the 202 kJ mol(-1) reported for the tautomerization of the unhydrated gaseous HSO/HOS molecules. The impact of water of hydration on the fundamental vibrational modes of HSO and HOS has also been studied. Furthermore, HOS is predicted to dimerize at low temperatures to give two van der Waals molecules with singlet (symmetry C(2)) or triplet configuration (symmetry C(2h)), the latter being more stable than the singlet isomer. The disproportionation of 2HSO to H(2)S and SO(2) is predicted to be exothermic by -263.5 kJ mol(-1). The reaction of HSO with ozone to HSO(2) and O(2) is also strongly exothermic by -274.0 kJ mol(-1) and seems to proceed without any barrier. HOS forms a 1:1 van der Waals complex with O(3); the redox reaction of its two components is calculated as exothermic by -410.9 kJ mol(-1) and results in a rather stable adduct between HOSO and O(2) with the structure of a peroxo isomer of HOSO(3

  3. Feasibility of gas/solid carboligation: conversion of benzaldehyde to benzoin using thiamine diphosphate-dependent enzymes.

    PubMed

    Mikolajek, R; Spiess, A C; Büchs, J

    2007-05-10

    A carboligation was investigated for the first time as an enzymatic gas phase reaction, where benzaldehyde was converted to benzoin using thiamine diphosphate (ThDP)-dependent enzymes, namely benzaldehyde lyase (BAL) and benzoylformate decarboxylase (BFD). The biocatalyst was immobilized per deposition on non-porous support. Some limitations of the gas/solid biocatalysis are discussed based on this carboligation and it is also demonstrated that the solid/gas system is an interesting tool for more volatile products.

  4. Exit channel dynamics in a micro-hydrated SN2 reaction of the hydroxyl anion.

    PubMed

    Otto, R; Brox, J; Trippel, S; Stei, M; Best, T; Wester, R

    2013-08-29

    We report on the reaction dynamics of the monosolvated SN2 reaction of cold OH(-)(H2O) with CH3I that have been studied using crossed beam ion imaging. Two SN2 reaction channels are possible for this reaction: Formation of unsolvated I(-) and of solvated I(-)(H2O) products. We find a strong preference for the formation of unsolvated I(-) reaction products with respect to the energetically favored reaction toward solvated I(-)(H2O). Angle differential cross section measurements reveal similar velocity and angular distributions for all solvated and parts of the unsolvated reaction products. We furthermore find that the contribution of these two products to the total product flux can be described by the same collision energy dependence. We interpret our findings in terms of a joint reaction mechanism in which a CH3OH(H2O)···I(-) complex is formed that decays into either solvated or unsolvated products. Quantum chemical calculation are used to support this assumption.

  5. Tuning the composition of guest molecules in clathrate hydrates: NMR identification and its significance to gas storage.

    PubMed

    Seo, Yutaek; Lee, Jong-Won; Kumar, Rajnish; Moudrakovski, Igor L; Lee, Huen; Ripmeester, John A

    2009-08-03

    Gas hydrates represent an attractive way of storing large quantities of gas such as methane and carbon dioxide, although to date there has been little effort to optimize the storage capacity and to understand the trade-offs between storage conditions and storage capacity. In this work, we present estimates for gas storage based on the ideal structures, and show how these must be modified given the little data available on hydrate composition. We then examine the hypothesis based on solid-solution theory for clathrate hydrates as to how storage capacity may be improved for structure II hydrates, and test the hypothesis for a structure II hydrate of THF and methane, paying special attention to the synthetic approach used. Phase equilibrium data are used to map the region of stability of the double hydrate in P-T space as a function of the concentration of THF. In situ high-pressure NMR experiments were used to measure the kinetics of reaction between frozen THF solutions and methane gas, and (13)C MAS NMR experiments were used to measure the distribution of the guests over the cage sites. As known from previous work, at high concentrations of THF, methane only occupies the small cages in structure II hydrate, and in accordance with the hypothesis posed, we confirm that methane can be introduced into the large cage of structure II hydrate by lowering the concentration of THF to below 1.0 mol %. We note that in some preparations the cage occupancies appear to fluctuate with time and are not necessarily homogeneous over the sample. Although the tuning mechanism is generally valid, the composition and homogeneity of the product vary with the details of the synthetic procedure. The best results, those obtained from the gas-liquid reaction, are in good agreement with thermodynamic predictions; those obtained for the gas-solid reaction do not agree nearly as well.

  6. Bis(allyl)-ruthenium(iv) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions.

    PubMed

    Tomás-Mendivil, Eder; Francos, Javier; González-Fernández, Rebeca; González-Liste, Pedro J; Borge, Javier; Cadierno, Victorio

    2016-09-14

    Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η(3):η(3)-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η(3):η(3)-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P([double bond, length as m-dash]O)H. The compounds [RuCl2(η(3):η(3)-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η(3):η(3)-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η(3):η(3)-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η(3):η(3)-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.

  7. Fluidization onset and expansion of gas-solid fluidized beds

    SciTech Connect

    Jones, O.C.; Shin, T.S.

    1984-08-01

    A simple, mass conservation-based, kinematic model is presented for accurately predicting both the onset of fluidization and the degree of (limit of) bed expansion in bubbling gas-solid fluidized beds. The model is consistant with inception correlations exisiting in the literature. Since the method has a sound physical basis, it might be expected to provide scaling between laboratory-scale fluidized beds and large-scale systems. This scaling ability, however, remains to be demonstrated as does the application to pressurized systems and where the terminal Reynolds numbers exceed 1000, (Archimedes numbers over about 3.2 x 10/sup 5/).

  8. Rate constants measured for hydrated electron reactions with peptides and proteins

    NASA Technical Reports Server (NTRS)

    Braams, R.

    1968-01-01

    Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

  9. A new approach in quantitative in-situ XRD of cement pastes: Correlation of heat flow curves with early hydration reactions

    SciTech Connect

    Hesse, Christoph; Goetz-Neunhoeffer, Friedlinde; Neubauer, Juergen

    2011-01-15

    XRD measurements of the hydration of synthetical cement (SyCem) were used to calculate the resulting heat flow from changes in the phase content. Calculations were performed by application of thermodynamic data. The comparison with data recorded from heat flow calorimetry was in good agreement with the calculated heat flow. The initial maximum of heat flow mainly is caused by the aluminate reaction. During the entire main period the silicate reaction dominates hydration with a high and long first maximum of heat flow. The second but less intense heat flow maximum - only visible as a shoulder in most of the technical cements - can be attributed to an acceleration of the aluminate reaction with the enhanced dissolution of C{sub 3}A and the final formation of ettringite. Moreover, the investigation showed that the dissolution process of C{sub 3}A is directly controlled by the availability of the calcium sulfate phases.

  10. Mechanism of maltal hydration catalyzed by. beta. -amylase: Role of protein structure in controlling the steric outcome of reactions catalyzed by a glycosylase

    SciTech Connect

    Kitahata, Sumio ); Chiba, S. ); Brewer, C.F.; Hehre, E.J. )

    1991-07-09

    Crystalline (monomeric) soybean and (tetrameric) sweet potato {beta}-amylase were shown to catalyze the cis hydration of maltal ({alpha}-D-glucopyranosyl-2-deoxy-D-arabino-hex-1-enitol) to form {beta}-2-deoxymaltose. As reported earlier with the sweet potato enzyme, maltal hydration in D{sub 2}O by soybean {beta}-amylase was found to exhibit an unusually large solvent deuterium kinetic isotope effect (V{sub H}/V{sub D}=6.5), a reaction rate linearly dependent on the mole fraction of deuterium, and 2-deoxy-(2(a)-{sup 2}H)maltose as product. These results indicate (for each {beta}-amylase) that protonation is the rate-limiting step in a reaction involving a nearly symmetric one-proton transition state and that maltal is specifically protonated from above the double bond. That maltal undergoes cis hydration provides evidence in support of a general-acid-catalyzed, carbonium ion mediated reaction. Of fundamental significance is that {beta}-amylase protonates maltal from a direction opposite that assumed for protonating strach, yet creates products of the same anomeric configuration from both. Such stereochemical dichotomy argues for the overriding role of protein structures is dictating the steric outcome of reactions catalyzed by a glycosylase, by limiting the approach and orientation of water or other acceptors to the reaction center.

  11. Nanoplate-like tungsten trioxide (hydrate) films prepared by crystal-seed-assisted hydrothermal reaction

    NASA Astrophysics Data System (ADS)

    Wang, P.; Yang, L.; Dai, B.; Yang, Z.; Guo, S.; Zhu, J.

    2017-07-01

    Vertically-aligned WO3 nanoplates on transparent conducting fluorine-doped tin oxide (FTO) glass were prepared by a facile template-free crystal-seed-assisted hydrothermal method. The effects of the hydrothermal temperature and reaction time on the crystal structure and morphology of the products were investigated by XRD and SEM. The XRD results showed that the as-prepared thin films obtained below 150∘C comprised orthorhombic WO3 ṡ H2O and completely converted to monoclinic WO3 at 180∘C. It was also noted that there was a phase transformation from orthorhombic to monoclinic by increasing the reaction time from 1 to 12 h. SEM analysis revealed that WO3 thin films are composed of plate-like nanostructures.

  12. Muonium reactions with chloroacetic acid in water: Contrasts with H atoms and hydrated electrons

    NASA Astrophysics Data System (ADS)

    Stadlbauer, John M.; Venkateswaran, Krishnan; Walker, David C.

    1997-09-01

    Muonium atoms react with chloroacetic acid and chloroacetate ions in dilute aqueous solution with rate constants of 2.3 × 10 6 and 9.1 × 10 5 dm 3 mol -1 s -1 respectively. These are compared with the reactions of 1H atoms (and e aq-) and discussed in terms of a pair of competing kinetic isotope effects. Muonium reacts at least eight times faster than H overall, and probably 28 times faster in forming Cl -. It behaves as a nucleophile, thus resembling e aq- more than H, in reacting faster with the acid than the anion. Muonium's reactions must be governed to a considerable extent by quantum-mechanical effects arising from its very small mass.

  13. Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy

    PubMed Central

    2009-01-01

    Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (± 0.1) × 10-5 s-1 for a solution:solid of 10:1 and 1.6 (± 0.8) × 10-4 s-1 for a solution:solid of 5:1 (batch mode; T = 150°C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at δiso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (± 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR. PMID:19144195

  14. Theory for Indirect Conduction in Dense, Gas-Solid Systems

    NASA Astrophysics Data System (ADS)

    Lattanzi, Aaron; Hrenya, Christine

    2016-11-01

    Heat transfer in dense gas-solid systems is dominated by conduction, and critical to the operation of rotary-kilns, catalytic cracking, and heat exchangers with solid particles as the heat transfer fluid. In particular, the indirect conduction occurring between two bodies separated by a thin layer of fluid can significantly impact the heat transfer within gas-solid systems. Current state-of-the-art models for indirect conduction assume that particles are surrounded by a static "fluid lens" and that one-dimensional conduction occurs through the fluid lens when the lens overlaps another body. However, attempts to evaluate the effect of surface roughness and fluid lens thickness (theoretical inputs) on indirect conduction have been restricted to static, single-particle cases. By contrast, here we quantify these effects for dynamic, multi-particle systems. This analysis is compared to outputs from computational fluid dynamics and discrete element method (CFD-DEM) simulations of heat transfer in a packed bed and flow down a heated ramp. Analytical predictions for model sensitivity are found to be in agreement with simulation results and differ greatly from the static, single-particle analysis. Namely, indirect conduction in static systems is found to be most sensitive to surface roughness, while dynamic systems are sensitive to the fluid lens thickness.

  15. Reaction-driven cracking during hydration and carbonation of olivine: Implications for in situ CO2 capture and storage

    NASA Astrophysics Data System (ADS)

    Kelemen, P. B.; Hirth, G.

    2011-12-01

    Reactions forming serpentine and/or Mg-carbonates via reaction of fluid with olivine may increase the solid volume, due to increasing solid mass and decreasing solid density, provided that fluid is supplied in an open system, and that dissolution does not remove significant solid mass. Increasing solid volume can create deviatoric stress within a rock, potentially causing fracture. In turn, this can provide a positive feedback to the alteration process, maintaining or increasing permeability and reactive surface area. This could be important - or even essential - for proposed in situ mineral carbonation for CO2 storage, and potentially for geological CO2 capture from surface waters. We use several methods to estimate the 'force of crystallization' during hydration and carbonation of olivine. The free energy changes driving these processes can potentially generate overpressures of 100's to 1000's of MPa. These potential stresses are larger for a given temperature for carbonation compared to serpentinization. Thermodynamic upper bounds can be compared to estimates based on microstructure in natural samples. Evans (Int Geol Rev 2004) and Jamtveit et al. (EPSL 2008) provide microphotographs of igneous troctolites, with interstitial plagioclase surrounding rounded olivine grains. The olivine grains are partially serpentinized, and the plagioclase has closely spaced fractures interpreted as a result of expansion during serpentinization. Strain energy due to expansion should be greater than surface energy on new fractures. Spacing and length of fractures in plagioclase yields a minimum of about 260 MPa for the differential stress. Alternatively, if fractures did not form, elastic stress in the plagioclase resulting from expansion during serpentinization should be proportional to the strain. Because some strain could be accommodated by irreversible mechanisms, such as friction and dilation on cracks and/or viscous flow, this yields a maximum stress of 270 MPa. The close

  16. Reaction of cis-3-chloroacrylic acid dehalogenase with an allene substrate, 2,3-butadienoate: hydration via an enamine.

    PubMed

    Schroeder, Gottfried K; Johnson, William H; Huddleston, Jamison P; Serrano, Hector; Johnson, Kenneth A; Whitman, Christian P

    2012-01-11

    cis-3-Chloroacrylic acid dehalogenase (cis-CaaD) catalyzes the hydrolytic dehalogenation of cis-3-haloacrylates to yield malonate semialdehyde. The enzyme processes other substrates including an allene (2,3-butadienoate) to produce acetoacetate. In the course of a stereochemical analysis of the cis-CaaD-catalyzed reaction using this allene, the enzyme was unexpectedly inactivated in the presence of NaBH(4) by the reduction of a covalent enzyme-substrate bond. Covalent modification was surprising because the accumulated evidence for cis-CaaD dehalogenation favored a mechanism involving direct substrate hydration mediated by Pro-1. However, the results of subsequent mechanistic, pre-steady state and full progress kinetic experiments are consistent with a mechanism in which an enamine forms between Pro-1 and the allene. Hydrolysis of the enamine or an imine tautomer produces acetoacetate. Reduction of the imine species is likely responsible for the observed enzyme inactivation. This is the first reported observation of a tautomerase superfamily member functioning by covalent catalysis. The results may suggest that some fraction of the cis-CaaD-catalyzed dehalogenation of cis-3-haloacrylates also proceeds by covalent catalysis.

  17. Fast in situ x-ray-diffraction studies of chemical reactions: A synchrotron view of the hydration of tricalcium aluminate

    NASA Astrophysics Data System (ADS)

    Jupe, A. C.; Turrillas, X.; Barnes, P.; Colston, S. L.; Hall, C.; Häusermann, D.; Hanfland, M.

    1996-06-01

    We report observations on the early hydration of tricalcium aluminate, the most reactive component of Portland cement, using rapid-energy dispersive diffraction on a high brilliance synchrotron source. In situ observations of the hydration process over short time scales, and through bulk samples, reveal an intermediate calcium aluminate hydrate appearing just prior to the formation of the final stable hydrate, demonstrating the nucleating role of this intermediate. The superior quality of the data is sufficient to yield concentration versus time plots for each phase over the whole hydration sequence. This improvement derives from being able to use smaller diffracting volumes and consequent removal of time smearing due to inhomogenetics, and thus now offers the possibility of extending the technique in terms of time resolution and diversity of system.

  18. Free Radical Chemistry of Disinfection Byproducts 1: Kinetics of Hydrated Electron and Hydroxyl Radical Reactions with Halonitromethanes in Water

    SciTech Connect

    B. J. Mincher; R. V. Fox; S. P. Mezyk; T. Helgeson; S. K. Cole; W. J. Cooper; P. R. Gardinali

    2006-01-01

    Halonitromethanes are disinfection-byproducts formed during ozonation and chlorine/chloramine treatment of waters that contain bromide ion and natural organic matter. In this study, the chemical kinetics of the free-radical-induced degradations of a series of halonitromethanes were determined. Absolute rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reaction with both chlorinated and brominated halonitromethanes were measured using the techniques of electron pulse radiolysis and transient absorption spectroscopy. The bimolecular rate constants obtained, k (M-1 s-1), for eaq-/OH, respectively, were the following: chloronitromethane (3.01 ± 0.40) × 1010/(1.94 ± 0.32) × 108; dichloronitromethane (3.21 ± 0.17) × 1010/(5.12 ± 0.77) × 108; bromonitromethane (3.13 ± 0.06) × 1010/(8.36 ± 0.57) × 107; dibromonitromethane (3.07 ± 0.40) × 1010/(4.75 ± 0.98) × 108; tribromonitromethane (2.29 ± 0.39) × 1010/(3.25 ± 0.67) × 108; bromochloronitromethane (2.93 ± 0.47) × 1010/(4.2 ± 1.1) × 108; bromodichloronitromethane (2.68 ± 0.13) × 1010/(1.02 ± 0.15) × 108; and dibromochloronitromethane (2.95 ± 0.43) × 1010 / (1.80 ± 0.31) × 108 at room temperature and pH ~7. Comparison data were also obtained for hydroxyl radical reaction with bromoform (1.50 ± 0.05) × 108, bromodichloromethane (7.11 ± 0.26) × 107, and chlorodibromomethane (8.31 ± 0.25) × 107 M-1 s-1, respectively. These rate constants are compared to recently obtained data for trichloronitromethane and bromonitromethane, as well as to other established literature data for analogous compounds.

  19. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-06-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  20. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-01-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  1. Normal stress differences in a sheared gas-solid suspension

    NASA Astrophysics Data System (ADS)

    Saha, Saikat; Alam, Meheboob

    2016-11-01

    The stress tensor and normal stress differences are analyzed for a homogeneously sheared gas-solid suspension using Enskog-Boltzmann equation. Inelastic particles are suspended in a viscous fluid of viscosity μf and experience a Stokes drag force. Viscous heating due to shear is compensated by (i) the inelastic collisions between particles and (ii) the drag force experienced by the particles due to the interstitial fluid. Rheology of the particle phase is analyzed with anisotropic-Gaussian as the single particle distribution function. The first (N1) and second (N2) normal stress differences are computed as functions of the density (ν), Stokes number (St) and restitution coefficient (e). A comparison with the existing simulation data shows an excellent agreement for both N1 and N2 over the predictions from other Grad-level theories. Finally, in the limit of St -> ∞ (μf -> 0), the related results from the conventional theory of dry granular flows are recovered.

  2. Hydrated magnesium cations Mg+(H2O)n, n ≈ 20-60, exhibit chemistry of the hydrated electron in reactions with O2 and CO2.

    PubMed

    van der Linde, Christian; Akhgarnusch, Amou; Siu, Chi-Kit; Beyer, Martin K

    2011-09-15

    Ion-molecule reactions of Mg(+)(H(2)O)(n), n ≈ 20-60, with O(2) and CO(2) are studied by Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry. O(2) and CO(2) are taken up by the clusters. Both reactions correspond to the chemistry of hydrated electrons (H(2)O)(n)(-). Density functional theory calculations predicted that the solvation structures of Mg(+)(H(2)O)(16) contain a hydrated electron that is solvated remotely from a hexa-coordinated Mg(2+). Ion-molecule reactions between Mg(+)(H(2)O)(16) and O(2) or CO(2) are calculated to be highly exothermic. Initially, a solvent-separated ion pair is formed, with the hexa-coordinated Mg(2+) ionic core being well separated from the O(2)(•-) or CO(2)(•-). Rearrangements of the solvation structure are possible and produce a contact-ion pair in which one water molecule in the first solvation shell of Mg(2+) is replaced by O(2)(•-) or CO(2)(•-). © 2011 American Chemical Society

  3. Compact apparatus for photogeneration of hydrated electrons

    NASA Technical Reports Server (NTRS)

    Hart, E.; Schmidt, K.

    1970-01-01

    Flash-photolysis instrument generates hydrated electrons and studies their reactions. It has a three-dimensional, multiple-reaction cell and the capacity to produce up to .1 micromole hydrated electron in a single 40 microsec light pulse.

  4. Sequestration of flue gas CO₂ by direct gas-solid carbonation of air pollution control system residues.

    PubMed

    Tian, Sicong; Jiang, Jianguo

    2012-12-18

    Direct gas-solid carbonation reactions of residues from an air pollution control system (APCr) were conducted using different combinations of simulated flue gas to study the impact on CO₂ sequestration. X-ray diffraction analysis of APCr determined the existence of CaClOH, whose maximum theoretical CO₂ sequestration potential of 58.13 g CO₂/kg APCr was calculated by the reference intensity ratio method. The reaction mechanism obeyed a model of a fast kinetics-controlled process followed by a slow product layer diffusion-controlled process. Temperature is the key factor in direct gas-solid carbonation and had a notable influence on both the carbonation conversion and the CO₂ sequestration rate. The optimal CO₂ sequestrating temperature of 395 °C was easily obtained for APCr using a continuous heating experiment. CO₂ content in the flue gas had a definite influence on the CO₂ sequestration rate of the kinetics-controlled process, but almost no influence on the final carbonation conversion. Typical concentrations of SO₂ in the flue gas could not only accelerate the carbonation reaction rate of the product layer diffusion-controlled process, but also could improve the final carbonation conversion. Maximum carbonation conversions of between 68.6% and 77.1% were achieved in a typical flue gas. Features of rapid CO₂ sequestration rate, strong impurities resistance, and high capture conversion for direct gas-solid carbonation were proved in this study, which presents a theoretical foundation for the applied use of this encouraging technology on carbon capture and storage.

  5. Generalized gas-solid adsorption modeling: Single-component equilibria

    SciTech Connect

    Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas; DePaoli, David W.

    2015-01-07

    Over the last several decades, modeling of gas–solid adsorption at equilibrium has generally been accomplished through the use of isotherms such as the Freundlich, Langmuir, Tóth, and other similar models. While these models are relatively easy to adapt for describing experimental data, their simplicity limits their generality to be used with many different sets of data. This limitation forces engineers and scientists to test each different model in order to evaluate which one can best describe their data. Additionally, the parameters of these models all have a different physical interpretation, which may have an effect on how they can be further extended into kinetic, thermodynamic, and/or mass transfer models for engineering applications. Therefore, it is paramount to adopt not only a more general isotherm model, but also a concise methodology to reliably optimize for and obtain the parameters of that model. A model of particular interest is the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm. The GSTA isotherm has enormous flexibility, which could potentially be used to describe a variety of different adsorption systems, but utilizing this model can be fairly difficult due to that flexibility. To circumvent this complication, a comprehensive methodology and computer code has been developed that can perform a full equilibrium analysis of adsorption data for any gas-solid system using the GSTA model. The code has been developed in C/C++ and utilizes a Levenberg–Marquardt’s algorithm to handle the non-linear optimization of the model parameters. Since the GSTA model has an adjustable number of parameters, the code iteratively goes through all number of plausible parameters for each data set and then returns the best solution based on a set of scrutiny criteria. Data sets at different temperatures are analyzed serially and then linear correlations with temperature are made for the parameters of the model. The end result is a full set of

  6. Generalized gas-solid adsorption modeling: Single-component equilibria

    DOE PAGES

    Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas; ...

    2015-01-07

    Over the last several decades, modeling of gas–solid adsorption at equilibrium has generally been accomplished through the use of isotherms such as the Freundlich, Langmuir, Tóth, and other similar models. While these models are relatively easy to adapt for describing experimental data, their simplicity limits their generality to be used with many different sets of data. This limitation forces engineers and scientists to test each different model in order to evaluate which one can best describe their data. Additionally, the parameters of these models all have a different physical interpretation, which may have an effect on how they can bemore » further extended into kinetic, thermodynamic, and/or mass transfer models for engineering applications. Therefore, it is paramount to adopt not only a more general isotherm model, but also a concise methodology to reliably optimize for and obtain the parameters of that model. A model of particular interest is the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm. The GSTA isotherm has enormous flexibility, which could potentially be used to describe a variety of different adsorption systems, but utilizing this model can be fairly difficult due to that flexibility. To circumvent this complication, a comprehensive methodology and computer code has been developed that can perform a full equilibrium analysis of adsorption data for any gas-solid system using the GSTA model. The code has been developed in C/C++ and utilizes a Levenberg–Marquardt’s algorithm to handle the non-linear optimization of the model parameters. Since the GSTA model has an adjustable number of parameters, the code iteratively goes through all number of plausible parameters for each data set and then returns the best solution based on a set of scrutiny criteria. Data sets at different temperatures are analyzed serially and then linear correlations with temperature are made for the parameters of the model. The end result is a full set

  7. Comparison of hydration reactions for "piano-stool" RAPTA-B and [Ru(η6- arene)(en)Cl]+ complexes: Density functional theory computational study

    NASA Astrophysics Data System (ADS)

    Chval, Zdeněk; Futera, Zdeněk; Burda, Jaroslav V.

    2011-01-01

    The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl2 (from the RAPTA family) and [Ru(arene)(en)Cl]+ (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP/6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt/Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal/mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

  8. Comparison of hydration reactions for "piano-stool" RAPTA-B and [Ru(η6-arene)(en)Cl]+ complexes: density functional theory computational study.

    PubMed

    Chval, Zdeněk; Futera, Zdeněk; Burda, Jaroslav V

    2011-01-14

    The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl(2) (from the RAPTA family) and [Ru(arene)(en)Cl](+) (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP∕6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt∕Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal∕mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

  9. Optical instrumentation and study of gas-solid suspension flows

    SciTech Connect

    Ling, S.C.; Pao, H.P.

    1990-09-01

    A new technique and particle detecting system for the quantification of local fluid flow velocities, particle concentrations and size distributions in gas-solid suspension flows has been successfully developed and constructed. A new 2-inch diameter pneumatic-pipe test-loop facility for study of solids transport flows has been built and in operation. In order to check scaling law developed from the experimental results in the 2-inch pipe, a 4-inch pipe test-loop facility was also designed and constructed. In the past, the mechanics of suspended-solid flow have not been solved in a closed form due to the lack of a model for the turbulent field to pick up solid particles from the flow boundary. In this research project, we have identified the existence of micro-hairpin vortices as a major mechanism for the lifting of solid particles from the flow boundary. This permits one to formulate a realistic model. That is, the introduction of a particle source term in the governing transport equation for the suspended particles. The resultant solution predicts the correct critical flow conditions for the initial pickup of different sizes of solid particles and their subsequent concentrations in the flow field. 21 figs.

  10. Unmasking the Action of Phosphinous Acid Ligands in Nitrile Hydration Reactions Catalyzed by Arene-Ruthenium(II) Complexes.

    PubMed

    Tomás-Mendivil, Eder; Cadierno, Victorio; Menéndez, María I; López, Ramón

    2015-11-16

    The catalytic hydration of benzonitrile and acetonitrile has been studied by employing different arene-ruthenium(II) complexes with phosphinous (PR2OH) and phosphorous acid (P(OR)2OH) ligands as catalysts. Marked differences in activity were found, depending on the nature of both the P-donor and η(6)-coordinated arene ligand. Faster transformations were always observed with the phosphinous acids. DFT computations unveiled the intriguing mechanism of acetonitrile hydration catalyzed by these arene-ruthenium(II) complexes. The process starts with attack on the nitrile carbon atom of the hydroxyl group of the P-donor ligand instead of on a solvent water molecule, as previously suggested. The experimental results presented herein for acetonitrile and benzonitrile hydration catalyzed by different arene-ruthenium(II) complexes could be rationalized in terms of such a mechanism.

  11. Statistical thermodynamics of aerosols and the gas-solid Joule-Thomson effect

    NASA Astrophysics Data System (ADS)

    Pierotti, Robert A.; Rybolt, Thomas R.

    1984-04-01

    Due to the adsorption of a gas by a solid, it is expected that an aerosol created by dispersing a fine powder in a gas would have unique thermodynamic properties not found in pure or mixed gases. The virial equation of state associated with an aerosol dusty gas is obtained from statistical thermodynamic considerations. In the theoretical model presented here, the aerosol is considered to be a two component fluid made up of solid particles and gas molecules. The aerosol virial equation of state is used to derive an expression for the Joule-Thomson effect associated with a gas-solid dispersion. The magnitude of the gas-solid Joule-Thomson effect is expressed in terms of gas and gas-solid virial coefficients. Previous adsorption data for an argon-porous carbon system is used to obtain gas-solid virial coefficients and to predict the magnitude of the gas-solid Joule-Thomson effect. A significant enhancement of the Joule-Thomson effect is predicted for gas-solid systems which display a strong interaction. For example, at a temperature of 300 K an argon-Saran 746 porous carbon aerosol system at a concentration of (0.4 g of powder/l of gas) is predicted to have a gas-solid Joule-Thomson coefficient of 3.6 K/atm which is ten times greater than the effect for pure argon.

  12. Rapid gas hydrate formation process

    DOEpatents

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  13. Unraveling the reaction mechanism on nitrile hydration catalyzed by [Pd(OH2)4]2+: insights from theory.

    PubMed

    Tílvez, Elkin; Menéndez, María I; López, Ramón

    2013-07-01

    Density functional theory methodologies combined with continuum and discrete-continuum descriptions of solvent effects were used to investigate the [Pd(OH2)4](2+)-catalyzed acrylonitrile hydration to yield acrylamide. According to our results, the intramolecular hydroxide attack mechanism and the external addition mechanism of a water molecule with rate-determining Gibbs energy barriers in water solution of 27.6 and 28.3 kcal/mol, respectively, are the most favored. The experimental kinetic constants of the hydration started by hydroxide, k(OH), and water, k(H2O), attacks for the cis-[Pd(en)(OH2)2](2+)-catalyzed dichloroacetonitrile hydration rendered Gibbs energy barriers whose energy difference, 0.7 kcal/mol, is the same as that obtained in the present study. Our investigation reveals the nonexistence of the internal attack of a water ligand for Pd-catalyzed nitrile hydration. At the low pHs used experimentally, the equilibrium between [Pd(OH2)3(nitrile)](2+) and [Pd(OH2)2(OH)(nitrile)](+) is completely displaced to [Pd(OH2)3(nitrile)](2+). Experimental studies in these conditions stated that water acts as a nucleophile, but they could not distinguish whether it was a water ligand, an external water molecule, or a combination of both possibilities. Our theoretical explorations clearly indicate that the external water mechanism becomes the only operative one at low pHs. On the basis of this mechanistic proposal it is also possible to ascribe an (1)H NMR signal experimentally detected to the presence of a unidentate iminol intermediate and to explain the influence of nitrile concentration reported experimentally for nitriles other than acrylonitrile in the presence of aqua-Pd(II) complexes. Therefore, our theoretical point of view on the mechanism of nitrile hydration catalyzed by aqua-Pd(II) complexes can shed light on these relevant processes at a molecular level as well as afford valuable information that can help in designing new catalysts in milder and more

  14. Investigation of Gas Solid Fluidized Bed Dynamics with Non-Spherical Particles

    SciTech Connect

    Choudhuri, Ahsan

    2013-06-30

    One of the largest challenges for 21st century is to fulfill global energy demand while also reducing detrimental impacts of energy generation and use on the environment. Gasification is a promising technology to meet the requirement of reduced emissions without compromising performance. Coal gasification is not an incinerating process; rather than burning coal completely a partial combustion takes place in the presence of steam and limited amounts of oxygen. In this controlled environment, a chemical reaction takes place to produce a mixture of clean synthetic gas. Gas-solid fluidized bed is one such type of gasification technology. During gasification, the mixing behavior of solid (coal) and gas and their flow patterns can be very complicated to understand. Many attempts have taken place in laboratory scale to understand bed hydrodynamics with spherical particles though in actual applications with coal, the particles are non-spherical. This issue drove the documented attempt presented here to investigate fluidized bed behavior using different ranges of non-spherical particles, as well as spherical. For this investigation, various parameters are controlled that included particle size, bed height, bed diameter and particle shape. Particles ranged from 355 µm to 1180 µm, bed diameter varied from 2 cm to 7 cm, two fluidized beds with diameters of 3.4 cm and 12.4 cm, for the spherical and non-spherical shaped particles that were taken into consideration. Pressure drop was measured with increasing superficial gas velocity. The velocity required in order to start to fluidize the particle is called the minimum fluidization velocity, which is one of the most important parameters to design and optimize within a gas-solid fluidized bed. This minimum fluidization velocity was monitored during investigation while observing variables factors and their effect on this velocity. From our investigation, it has been found that minimum fluidization velocity is independent of bed

  15. Lattice Boltzmann simulation of gas-solid adsorption processes at pore scale level

    NASA Astrophysics Data System (ADS)

    Zhou, L.; Qu, Z. G.; Chen, L.; Tao, W. Q.

    2015-11-01

    A two-dimensional lattice Boltzmann (LB) approach was established to implement kinetic concentration boundary conditions in interfacial mass-transfer processes and to simulate the adsorption process in porous media at pore scale and mesoscopic levels. A general treatment was applied to conduct three types of concentration boundary conditions effectively and accurately. Applicability for adsorption was verified by two benchmark examples, which were representative of the interparticle mass transport and intraparticle mass transport in the adsorption system, respectively. The gas-solid adsorption process in reconstructed porous media at the pore scale level was numerically investigated. Mass-transfer processes of the adsorption reaction were simulated by executing Langmuir adsorption kinetics on surfaces of adsorbent particles. Meanwhile, the homogeneous solid diffusion model (HSDM) was used for mass transport in interior particles. The transient adsorbed amount was obtained in detail, and the impact of flow condition, porosity, and adsorbent particle size on the entire dynamic adsorption performance was investigated. The time needed to approach steady state decreased with increased fluid velocity. Transient adsorption capability and time consumption to equilibrium were nearly independent of porosity, whereas increasing pore size led to a moderating adsorption rate and more time was consumed to approach the saturation adsorption. Benefiting from the advantages of the LB method, both bulk and intraparticle mass transfer performances during adsorption can be obtained using the present pore scale approach. Thus, interparticle mass transfer and intraparticle mass transfer are the two primary segments, and intraparticle diffusion has the dominant role.

  16. Direct gas-solid carbonation kinetics of steel slag and the contribution to in situ sequestration of flue gas CO(2) in steel-making plants.

    PubMed

    Tian, Sicong; Jiang, Jianguo; Chen, Xuejing; Yan, Feng; Li, Kaimin

    2013-12-01

    Direct gas-solid carbonation of steel slag under various operational conditions was investigated to determine the sequestration of the flue gas CO2 . X-ray diffraction analysis of steel slag revealed the existence of portlandite, which provided a maximum theoretical CO2 sequestration potential of 159.4 kg CO 2 tslag (-1) as calculated by the reference intensity ratio method. The carbonation reaction occurred through a fast kinetically controlled stage with an activation energy of 21.29 kJ mol(-1) , followed by 10(3) orders of magnitude slower diffusion-controlled stage with an activation energy of 49.54 kJ mol(-1) , which could be represented by a first-order reaction kinetic equation and the Ginstling equation, respectively. Temperature, CO2 concentration, and the presence of SO2 impacted on the carbonation conversion of steel slag through their direct and definite influence on the rate constants. Temperature was the most important factor influencing the direct gas-solid carbonation of steel slag in terms of both the carbonation conversion and reaction rate. CO2 concentration had a definite influence on the carbonation rate during the kinetically controlled stage, and the presence of SO2 at typical flue gas concentrations enhanced the direct gas-solid carbonation of steel slag. Carbonation conversions between 49.5 % and 55.5 % were achieved in a typical flue gas at 600 °C, with the maximum CO2 sequestration amount generating 88.5 kg CO 2 tslag (-1) . Direct gas-solid carbonation of steel slag showed a rapid CO2 sequestration rate, high CO2 sequestration amounts, low raw-material costs, and a large potential for waste heat utilization, which is promising for in situ carbon capture and sequestration in the steel industry.

  17. Multifunctional Co0.85Se/graphene hybrid nanosheets: controlled synthesis and enhanced performances for the oxygen reduction reaction and decomposition of hydrazine hydrate

    NASA Astrophysics Data System (ADS)

    Zhang, Lin-Fei; Zhang, Chun-Yang

    2014-01-01

    Ultrathin nanosheets possess novel electronic structures and physical properties as compared with their corresponding bulk samples. However, the controlled synthesis of ultrathin monolayer nanosheets still remains a great challenge due to the lack of an intrinsic driving force for anisotropic growth of two-dimensional (2D) structures. Here we demonstrate, for the first time to our knowledge, the in situ synthesis of large-scale ultrathin single-crystalline Co0.85Se nanosheets on graphene oxide (GO) sheets, with a thickness of 3 nm. Owing to the synergetic chemical coupling effects between GO and Co0.85Se, the Co0.85Se/graphene hybrid nanosheets exhibit the highest catalytic performance among the available cobalt chalcogenide-based catalysts for the oxygen reduction reaction (ORR). Moreover, Co0.85Se/graphene hybrid nanosheets can catalyze the decomposition of hydrazine hydrate rapidly, with 97% of hydrazine hydrate being degraded in 12 min and the degradation rate remaining constant over 10 consecutive cycles, thus having great potential as long-term catalysts in wastewater treatment.Ultrathin nanosheets possess novel electronic structures and physical properties as compared with their corresponding bulk samples. However, the controlled synthesis of ultrathin monolayer nanosheets still remains a great challenge due to the lack of an intrinsic driving force for anisotropic growth of two-dimensional (2D) structures. Here we demonstrate, for the first time to our knowledge, the in situ synthesis of large-scale ultrathin single-crystalline Co0.85Se nanosheets on graphene oxide (GO) sheets, with a thickness of 3 nm. Owing to the synergetic chemical coupling effects between GO and Co0.85Se, the Co0.85Se/graphene hybrid nanosheets exhibit the highest catalytic performance among the available cobalt chalcogenide-based catalysts for the oxygen reduction reaction (ORR). Moreover, Co0.85Se/graphene hybrid nanosheets can catalyze the decomposition of hydrazine hydrate rapidly

  18. Anode materials for sour natural gas solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Danilovic, Nemanja

    Novel anode catalysts have been developed for sour natural gas solid oxide fuel cell (SOFC) applications. Sour natural gas comprises light hydrocarbons, and typically also contains H2S. An alternative fuel SOFC that operates directly on sour natural gas would reduce the overall cost of plant construction and operation for fuel cell power generation. The anode for such a fuel cell must have good catalytic and electrocatalytic activity for hydrocarbon conversion, sulfur-tolerance, resistance to coking, and good electronic and ionic conductivity. The catalytic activity and stability of ABO3 (A= La, Ce and/or Sr, B=Cr and one or more of Ti, V, Cr, Fe, Mn, or Co) perovskites as SOFC anode materials depends on both A and B, and are modified by substituents. The materials have been prepared by both solid state and wet-chemical methods. The physical and chemical characteristics of the materials have been fully characterized using electron microscopy, XRD, calorimetry, dilatometry, particle size and area, using XPS and TGA-DSC-MS. Electrochemical performance was determined using potentiodynamic and potentiostatic cell testing, electrochemical impedance analysis, and conductivity measurements. Neither Ce0.9Sr0.1VO3 nor Ce0.9 Sr0.1Cr0.5V0.5O3 was an active anode for oxidation of H2 and CH4 fuels. However, active catalysts comprising Ce0:9Sr0:1V(O,S)3 and Ce0.9Sr 0.1Cr0.5V0.5(O,S)3 were formed when small concentrations of H2S were present in the fuels. The oxysulfides formed in-situ were very active for conversion of H2S. The maximum performance improved from 50 mW cm-2 to 85 mW cm -2 in 0.5% H2S/CH4 at 850°C with partial substitution of V by Cr in Ce0.9Sr0.1V(O,S)3. Selective conversion of H2S offers potential for sweetening of sour gas without affecting the hydrocarbons. Perovskites La0.75Sr0.25Cr0.5X 0.5O3--delta, (henceforth referred to as LSCX, X=Ti, Mn, Fe, Co) are active for conversion of H2, CH4 and 0.5% H2S/CH4. The order of activity in the different fuels depends on

  19. Setup for in situ investigation of gases and gas/solid interfaces by soft x-ray emission and absorption spectroscopy

    SciTech Connect

    Benkert, A. E-mail: l.weinhardt@kit.edu; Blum, M.; Meyer, F.; Wilks, R. G.; Yang, W.; Bär, M.; and others

    2014-01-15

    We present a novel gas cell designed to study the electronic structure of gases and gas/solid interfaces using soft x-ray emission and absorption spectroscopies. In this cell, the sample gas is separated from the vacuum of the analysis chamber by a thin window membrane, allowing in situ measurements under atmospheric pressure. The temperature of the gas can be regulated from room temperature up to approximately 600 °C. To avoid beam damage, a constant mass flow can be maintained to continuously refresh the gaseous sample. Furthermore, the gas cell provides space for solid-state samples, allowing to study the gas/solid interface for surface catalytic reactions at elevated temperatures. To demonstrate the capabilities of the cell, we have investigated a TiO{sub 2} sample behind a mixture of N{sub 2} and He gas at atmospheric pressure.

  20. Open-source MFIX-DEM software for gas-solids flows: Part I verification studies

    SciTech Connect

    Garg, Rahul; Galvin, Janine; Li, Tingwen; Pannala, Sreekanth

    2012-01-01

    With rapid advancements in computer hardware, it is now possible to perform large simulations of granular flows using the Discrete Element Method (DEM). As a result, solids are increasingly treated in a discrete Lagrangian fashion in the gas solids flow community. In this paper, the open-source MFIX-DEM software is described that can be used for simulating the gas solids flow using an Eulerian reference frame for the continuum fluid and a Lagrangian discrete framework (Discrete Element Method) for the particles. This method is referred to as the continuum discrete method (CDM) to clearly make a distinction between the ambiguity of using a Lagrangian or Eulerian reference for either continuum or discrete formulations. This freely available CDM code for gas solids flows can accelerate the research in computational gas solids flows and establish a baseline that can lead to better closures for the continuum modeling (or traditionally referred to as two fluid model) of gas solids flows. In this paper, a series of verification cases is employed which tests the different aspects of the code in a systematic fashion by exploring specific physics in gas solids flows before exercising the fully coupled solution on simple canonical problems. It is critical to have an extensively verified code as the physics is complex with highly-nonlinear coupling, and it is difficult to ascertain the accuracy of the results without rigorous verification. These series of verification tests set the stage not only for rigorous validation studies (performed in part II of this paper) but also serve as a procedure for testing any new developments that couple continuum and discrete formulations for gas solids flows.

  1. Direct gas-solid carbonation of serpentinite residues in the absence and presence of water vapor: a feasibility study for carbon dioxide sequestration.

    PubMed

    Veetil, Sanoopkumar Puthiya; Pasquier, Louis-César; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra; Mercier, Guy

    2015-09-01

    Mineral carbonation of serpentinite mining residue offers an environmentally secure and permanent storage of carbon dioxide. The strategy of using readily available mining residue for the direct treatment of flue gas could improve the energy demand and economics of CO2 sequestration by avoiding the mineral extraction and separate CO2 capture steps. The present is a laboratory scale study to assess the possibility of CO2 fixation in serpentinite mining residues via direct gas-solid reaction. The degree of carbonation is measured both in the absence and presence of water vapor in a batch reactor. The gas used is a simulated gas mixture reproducing an average cement flue gas CO2 composition of 18 vol.% CO2. The reaction parameters considered are temperature, total gas pressure, time, and concentration of water vapor. In the absence of water vapor, the gas-solid carbonation of serpentinite mining residues is negligible, but the residues removed CO2 from the feed gas possibly due to reversible adsorption. The presence of small amount of water vapor enhances the gas-solid carbonation, but the measured rates are too low for practical application. The maximum CO2 fixation obtained is 0.07 g CO2 when reacting 1 g of residue at 200 °C and 25 barg (pCO2 ≈ 4.7) in a gas mixture containing 18 vol.% CO2 and 10 vol.% water vapor in 1 h. The fixation is likely surface limited and restricted due to poor gas-solid interaction. It was identified that both the relative humidity and carbon dioxide-water vapor ratio have a role in CO2 fixation regardless of the percentage of water vapor.

  2. Predicting second gas-solid virial coefficients using calculated molecular properties on various carbon surfaces.

    PubMed

    Rybolt, Thomas R; Janeksela, Vanessa E; Hooper, Dana N; Thomas, Howard E; Carrington, Nathan A; Williamson, Eric J

    2004-04-01

    Gas-solid chromatography was used to obtain values of the second gas-solid virial coefficient, B2s, in the temperature range from 343 to 493 K for seven adsorbate gases: methane, ethane, propane, chloromethane, chlorodifluoromethane, dimethyl ether, and sulfur hexafluoride. Carboxen-1000, a 1200 m2/g carbon molecular sieve (Supelco Inc.), was used as the adsorbent. These data were combined with earlier work to make a combined data set of 36 different adsorbate gases variously interacting with from one to four different carbon surfaces. All B2s values were extrapolated to 403 K to create a set of 65 different gas-solid B2s values at a fixed temperature. The B2s value for a given gas-solid system can be converted to a chromatographic retention time at any desired flow rate and can be converted to the amount of gas adsorbed at any pressure in the low-coverage, Henry's law region. Beginning with a theoretical equation for the second gas-solid virial coefficient, various quantitative structure retention relations (QSRR) were developed and used to correlate the B2s values for different gas adsorbates with different carbon surfaces. Two calculated adsorbate molecular parameters (molar refractivity and connectivity index), when combined with two adsorbent parameters (surface area and a surface energy contribution to the gas-solid interaction), provided an effective correlation (r2 = 0.952) of the 65 different B2s values. The two surface parameters provided a simple yet useful representation of the structure and energy of the carbon surfaces and thus our correlations considered variation in both the adsorbate gas and the adsorbent solid.

  3. Method and apparatus for the separation of a gas-solids mixture in a circulating fluidized bed reactor

    SciTech Connect

    Vimalchand, Pannalal; Liu, Guohai; Peng, WanWang

    2010-08-10

    The system of the present invention includes a centripetal cyclone for separating particulate material from a particulate laden gas solids stream. The cyclone includes a housing defining a conduit extending between an upstream inlet and a downstream outlet. In operation, when a particulate laden gas-solids stream passes through the upstream housing inlet, the particulate laden gas-solids stream is directed through the conduit and at least a portion of the solids in the particulate laden gas-solids stream are subjected to a centripetal force within the conduit.

  4. Strategy for understanding gas-solid riser hydrodynamics and other LANL status items

    SciTech Connect

    Kashiwa, B. A.

    2002-01-01

    The talk presents the status of work in progress in the area of momentum transport theory in turbulent gas-solid multiphase flow. Previous installments have reported details of the theory, and validation results. This talk provides a grand overview of how the details of dynamic simulations in 3D, 2D, 1D and 0D, all fit together to form a consistent strategy for understanding gas-solid riser hydrodynamics. The circulating fluidized bed is the canonical example for showing how the strategy works. Performance of the procedure is shown by comparison to data recently obtained by Sandia National Laboratory. Status of other LANL efforts is also mentioned.

  5. Low-frequency sound transmission through a gas-solid interface.

    PubMed

    Godin, Oleg A

    2011-02-01

    Sound transmission through gas-solid interfaces is usually very weak because of the large contrast in wave impedances at the interface. Here, it is shown that diffraction effects can lead to a dramatic increase in the transparency of gas-solid interfaces at low frequencies, resulting in the bulk of energy emitted by compact sources within a solid being radiated into a gas. The anomalous transparency is made possible by power fluxes in evanescent body waves and by excitation of interface waves. Sound transmission into gas is found to be highly sensitive to absorption of elastic waves within a solid.

  6. Venturi design for metering solids flow in gas-solids suspentions

    SciTech Connect

    Crowe, C T

    1981-01-01

    Objective is to study the use of the venturi to meter gas-solids at larger particle size the modifying the inlet geometry and using a laser-light attenuation system at the venturi throat. Three tasks are reported: (1) study of influence of venturi approach angle on meter sensitivity to solids loading; (2) use of a quasi one-dimensional numerical model to optimize the inlet geometry for limestone transport to a fluidized bed; and (3) study adequacy of annular venturi and a gas-solids flowmeter. (DLC)

  7. Chemistry of large hydrated anion clusters X sup minus (H sub 2 O) sub n , n = 0 minus 59 and X = OH, O, O sub 2 , and O sub 3. 3. Reaction of SO sub 2

    SciTech Connect

    Yang, X.; Castleman, A.W. Jr. )

    1991-08-08

    Sulfur dioxide is a very important species in the atmosphere, and it is also well established that it is one of the key trace neutral reactants involved in the negative ion chemistry of the stratosphere. The kinetics and mechanisms of reactions of large hydrated anion clusters X{sup {minus}}(H{sub 2}O){sub n=0{minus}59}, X = O, OH, O{sub 2}, and O{sub 3}, with SO{sub 2} are studied in a fast flow reactor under well-defined temperatures and pressures. All the clusters, except OH{sup {minus}}, react with SO{sub 2} at near the collision limit; the reactions of the hydrated anions are found to proceed mainly via a ligand switching mechanism where a few water ligands are replaced by one SO{sub 2} molecule which leads to the formation of stable reaction products. At low temperatures and large cluster sizes, association eventually dominates the reaction mechanism. Interestingly, slow rate constants (k < 10{sup {minus}13} cm{sup 3}/s) are found for the reactions between protonated water clusters, H{sup +}(H{sub 2}O){sub n = 1{minus}60} and SO{sub 2}, which show that different signs of charge on the hydrated clusters lead to different reaction mechanisms, and hence alter the reaction kinetics. The possible application of the present results to atmospheric ion chemistry and aqueous solution chemistry are also briefly discussed.

  8. Prevention of syncopal-type reactions after whole blood donation: a cluster-randomized trial assessing hydration and muscle tension exercise.

    PubMed

    Morand, Chrystelle; Coudurier, Nicole; Rolland, Carole; Thoret, Sophie; Legrand, Dominique; Tiberghien, Pierre; Bosson, Jean-Luc

    2016-10-01

    The prevention of presyncopal and syncopal reactions to whole blood donation is important for both the donor's safety and their retention as blood donors. The best strategy to achieve this remains debated. A prospective cluster-randomized trial comparing three hydration modes (500 mL of an isotonic drink, 500 mL of water, just before phlebotomy, or advice to drink [control arm]) coupled or not with light muscle tensing exercises, was carried out in mobile and fixed units of two regional blood centers in southeast France between January and July 2014. The main outcome was the cumulative incidence of presyncope (feeling faint) and syncope (fainting) at the donation site or in the 48 hours after leaving the site. Secondary outcomes were the cumulative incidence of these adverse events during donation, immediately after blood donation, or within 48 hours. Overall, presyncope or syncope occurred in 5.5% of the 4576 donors. Compared to controls, drinking 500 mL (isotonic solution or water) significantly reduced the rate of events (odds ratio [OR], 0.74; 95% confidence interval [CI], 0.55-0.99; p = 0.041) independently of muscle tensing exercise. Muscle tensing exercises significantly reduced syncopal-type reactions during the donation (OR, 0.64; 95% CI, 0.42-0.98; p = 0.041), and an isotonic drink significantly reduced delayed off-site syncopal-type reactions (OR, 0.62; 95% CI, 0.40-0.98; p = 0.040) and tiredness after donation (OR, 0.75; 95% CI, 0.59-0.94; p = 0.014). Drinking 500mL of water or isotonic drink close to phlebotomy is useful in preventing presyncopal or syncopal reactions in blood donors. Isotonic drinks have the advantage of preventing delayed reactions and tiredness after whole blood donation. © 2016 AABB.

  9. Gas-Solid Dynamics at Disordered and Adsorbate Covered Surfaces

    DTIC Science & Technology

    1992-09-02

    interesting physical problems in which non-linear reactions occur at localized defects. The Lotka - Volterra system is considered, in which the source, sink...Dynamics. A. Optimal Control of Molecular Motion 1. Optimal Control of Quantum-Mechanical Systems : Existence, Numerical Approximations, and...Applicationsl The optimal control of the path to a specified final state of a quantum-mechanical system is investigated. The problem is formulated as a

  10. Gas hydrates

    SciTech Connect

    Berecz, E.; Balla-Achs, M.

    1983-01-01

    In the presence of water, particularly at low temperatures, many industrial gas systems under pressure tend to form solid crystalline compounds. These compounds are referred to as gas hydrates, and result from the association of the gas molecules with water. This book draws attention to the theoretical, practical and technological aspects of this interesting and important class of compounds. The topics covered include the structures, properties and thermodynamic characteristics of the gas hydrates, the changes induced in the equilibrium conditions by additives, and the methods and studies relating to the prevention and elimination of hydrate plugs in technological operations with industrial gases. In the discussion of the technological aspects, special emphasis is given to the production and transportation of natural gas and to the application of freon coolants. Such questions as the possibility of the desalination of seawater and the formation of gas hydrates in interplanetary space are also dealt with.

  11. A new quantification method based on SEM-EDS to assess fly ash composition and study the reaction of its individual components in hydrating cement paste

    SciTech Connect

    Durdziński, Paweł T.; Dunant, Cyrille F.; Haha, Mohsen Ben; Scrivener, Karen L.

    2015-07-15

    Calcareous fly ashes are high-potential reactive residues for blended cements, but their qualification and use in concrete are hindered by heterogeneity and variability. Current characterization often fails to identify the dominant, most reactive, amorphous fraction of the ashes. We developed an approach to characterize ashes using electron microscopy. EDS element composition of millions of points is plotted in a ternary frequency plot. A visual analysis reveals number and ranges of chemical composition of populations: silicate, calcium-silicate, aluminosilicate, and calcium-rich aluminosilicate. We quantified these populations in four ashes and followed their hydration in two Portland-ash systems. One ash reacted at a moderate rate: it was composed of 70 vol.% of aluminosilicates and calcium-silicates and reached 60% reaction at 90 days. The other reacted faster, reaching 60% at 28 days due to 55 vol.% of calcium-rich aluminosilicates, but further reaction was slower and 15 vol.% of phases, the silica-rich ones, did not react.

  12. DEVELOPMENT OF LOW-DIFFUSION FLUX-SPLITTING METHODS FOR DENSE GAS-SOLID FLOWS

    EPA Science Inventory

    The development of a class of low-diffusion upwinding methods for computing dense gas-solid flows is presented in this work. An artificial compressibility/low-Mach preconditioning strategy is developed for a hyperbolic two-phase flow equation system consisting of separate solids ...

  13. DEVELOPMENT OF LOW-DIFFUSION FLUX-SPLITTING METHODS FOR DENSE GAS-SOLID FLOWS

    EPA Science Inventory

    The development of a class of low-diffusion upwinding methods for computing dense gas-solid flows is presented in this work. An artificial compressibility/low-Mach preconditioning strategy is developed for a hyperbolic two-phase flow equation system consisting of separate solids ...

  14. Effects of olivine fabric, melt-rock reaction, and hydration on the seismic properties of peridotites: Insight from the Luobusha ophiolite in the Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Sun, Shengsi; Ji, Shaocheng; Michibayashi, Katsuyoshi; Salisbury, Matthew

    2016-05-01

    In order to constrain the effects of olivine fabric, melt-rock reaction, and hydration on the seismic properties and anisotropy of mantle rocks, we investigated serpentinized peridotites from the Luobusha ophiolite in the Indus-Tsangpo suture of the Tibetan Plateau. A-type and almost random olivine crystal-preferred orientations (CPO) occur in harzburgite and dunite samples, respectively. The dunite resulted from interactions of harzburgite with boninitic melt at ~800-970°C, yielding pyroxene dissolution and olivine precipitation. The olivine neoblasts formed from the melt-rock reaction show no evidence of dislocation creep and developed almost random CPO. Hence, the melt-rock reaction reduced seismic anisotropy. Our results together with those from the literature indicate that A-, B-, C-, D-, and E-type CPOs of olivine generally induce Vp anisotropy patterns with Vp(X) > Vp(Y) > Vp(Z), Vp(Y) > Vp(X) > Vp(Z), Vp(Z) > Vp(X) > Vp(Y), Vp(X) > Vp(Y) ≈ Vp(Z), and Vp(X) > Vp(Z) > Vp(Y), respectively. The effect of serpentinization was calibrated by the comparison of seismic velocities and anisotropy measured up to 600 MPa with the values calculated from the CPO data. Although the low-temperature (LT, <300°C) serpentinization (lizardite and chrysotile) decreases Vp by ~6-10% and Vs by ~12%, it does not change the anisotropy pattern because the mesh-texture characterized by serpentine veins perpendicular to the principal structural directions (X, Y, and Z) reduces the velocities in these orthogonal directions to almost equal extent. Thus, the magnitude of seismic anisotropy alone cannot be used as an indicator of the degree of LT serpentinization in the mantle rocks. Furthermore, Birch's law is found to hold when peridotites undergo serpentinization.

  15. Using a novel technique to shape a refractory castable by Cold Isostatic Pressing and a study of the effect of pressure on the hydration reaction of high-alumina cement

    NASA Astrophysics Data System (ADS)

    Emadi, Rahmatollah; Monshi, Ahmad; Shafyei, Ali

    2007-02-01

    Calcium aluminate cements are the most hydraulically setting cements used for refractory castables. The anhydrous phases of this type of cements incorporate CA, CA2 and traces of C12A7 and alpha-alumina where C and A stand for CaO and Al2O3, respectively. Hydration starts to form the hexagonal crystals of CAH10 (H denoting H2O) and C2AH8, which convert to the cubic crystals of C3AH6 and AH3 by the passage of hydration time. In this work, Al2O3-C (alumina-graphite) castables were shaped by cold isostatic pressing at 100 to 400 bars (≈100 to 400 Kg/cm2). Hydration and conversion reactions were studied using the Ratio of Slopes Method for quantitative XRD studies after 3 and 28 days. The results showed that by increasing the pressure, the kinetics of the hydration reaction will increase and higher strengths can be obtained, which supports the idea of forming this graphite containing castable by Cold Isostatic Pressing (CIP) in industrial applications for special refractories.

  16. Apparent stoichiometry of water in proton hydration and proton dehydration reactions in CH3CN/H2O solutions.

    PubMed

    Kalish, Noa Ben-Menachem; Shandalov, Elisabetha; Kharlanov, Vladimir; Pines, Dina; Pines, Ehud

    2011-04-28

    Gradual solvation of protons by water is observed in liquids by mixing strong mineral acids with various amounts of water in acetonitrile solutions, a process which promotes rapid dissociation of the acids in these solutions. The stoichiometry of the reaction XH(+) + n(H(2)O) = X + (H(2)O)(n)H(+) was studied for strong mineral acids (negatively charged X, X = ClO(4)¯, Cl¯, Br¯, I¯, CF(3)SO(3)¯) and for strong cationic acids (uncharged X, X = R*NH(2), H(2)O). We have found by direct quantitative analysis preference of n = 2 over n = 1 for both groups of proton transfer reactions at relatively low water concentrations in acetonitrile. At high water concentrations, we have found that larger water solvates must also be involved in the solvation of the proton while the spectral features already observed for n = 2, H(+)(H(2)O)(2), remain almost unchanged at large n values up to at least 10 M of water.

  17. Chloral hydrate

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 00 / 006 TOXICOLOGICAL REVIEW OF CHLORAL HYDRATE ( CAS No . 302 - 17 - 0 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) August 2000 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been reviewed in accordance w

  18. Computational Study of Chemical Reaction Dynamics at the Gas-Solid Interface.

    DTIC Science & Technology

    1978-11-20

    list of conditions has been produced detailing the conditions under which useful vibrational population inversions may be expected in the molecules produced from such heterogeneous catalysis . (Author)

  19. An improved external recycle reactor for determining gas-solid reaction kinetics

    NASA Technical Reports Server (NTRS)

    Miller, Irvin M.; Hoyt, Ronald F.

    1987-01-01

    These improvements in the recycle system effectively eliminate initial concentration variation by two modifications: (1) a vacuum line connection to the recycle loop which permits this loop to be evacuated and then filled with the test gas mixture to slightly above atmospheric pressure; and (2) a bypass line across the reactor which permits the reactor to be held under vacuum while the rest of the recycle loop is filled with test gas. A three-step procedure for bringing the feed gas mixture into contact with the catalyst at time zero is described.

  20. CO{sub 2} reaction with hydrated class H well cement under geologic sequestration conditions: effects of flyash admixtures

    SciTech Connect

    Barbara G. Kutchko; Brian R. Strazisar; Nicolas Huerta; Gregory V. Lowry; David A. Dzombak; Niels Thaulow

    2009-05-15

    The rate and mechanism of reaction of pozzolan-amended Class H cement exposed to both supercritical CO{sub 2} and CO{sub 2}-saturated brine were determined under geologic sequestration conditions to assess the potential impact of cement degradation in existing wells on CO{sub 2} storage integrity. The pozzolan additive chosen, Type F flyash, a by-product of coal combustion, is the most common additive used in cements for well sealing in oil-gas field operations. The 35:65 and 65:35 (v/v) pozzolan-cement blends were exposed to supercritical CO{sub 2} and CO{sub 2}-saturated brine and underwent cement carbonation. Extrapolation of the carbonation rate for the 35:65 case suggests a penetration depth of 170-180 mm for both the CO{sub 2}-saturated brine and supercritical CO{sub 2} after 30 years. Despite alteration in both pozzolan systems, the reacted cement remained relatively impermeable to fluid flow after exposure to brine solution saturated with CO{sub 2}, with values well below the American Petroleum Institute recommended maximum well cement permeability of 200 {mu}D. Analyses of 50:50 pozzolan-cement cores from a production well in a sandstone reservoir exhibited carbonation and low permeability to brine solution saturated with CO{sub 2}, which are consistent with our laboratory findings. 16 refs., 4 figs., 1 tab.

  1. CO2 reaction with hydrated class H well cement under geologic sequestration conditions: effects of flyash admixtures.

    PubMed

    Kutchko, Barbara G; Strazisar, Brian R; Huerta, Nicolas; Lowry, Gregory V; Dzombak, David A; Thaulow, Niels

    2009-05-15

    The rate and mechanism of reaction of pozzolan-amended Class H cement exposed to both supercritical CO2 and CO2-saturated brine were determined under geologic sequestration conditions to assess the potential impact of cement degradation in existing, wells on CO2 storage integrity. The pozzolan additive chosen, Type F flyash, is the most common additive used in cements for well sealing in oil-gas field operations. The 35:65 and 65:35 (v/v) pozzolan-cement blends were exposed to supercritical CO2 and CO2-saturated brine and underwent cement carbonation. Extrapolation of the carbonation rate for the 35:65 case suggests a penetration depth of 170-180 mm for both the CO2-saturated brine and supercritical CO2 after 30 years. Despite alteration in both pozzolan systems, the reacted cement remained relatively impermeable to fluid flow after exposure to brine solution saturated with CO2, with values well below the American Petroleum Institute recommended maximum well cement permeability of 200 microD. Analyses of 50: 50 pozzolan-cement cores from a production well in a sandstone reservoir exhibited carbonation and low permeability to brine solution saturated with CO2, which are consistent with our laboratory findings.

  2. Evaluation of wall boundary condition parameters for gas-solids fluidized bed simulations

    SciTech Connect

    Li, Tingwen; Benyahia, Sofiane

    2013-10-01

    Wall boundary conditions for the solids phase have significant effects on numerical predictions of various gas-solids fluidized beds. Several models for the granular flow wall boundary condition are available in the open literature for numerical modeling of gas-solids flow. In this study, a model for specularity coefficient used in Johnson and Jackson boundary conditions by Li and Benyahia (AIChE Journal, 2012, 58, 2058-2068) is implemented in the open-source CFD code-MFIX. The variable specularity coefficient model provides a physical way to calculate the specularity coefficient needed by the partial-slip boundary conditions for the solids phase. Through a series of 2-D numerical simulations of bubbling fluidized bed and circulating fluidized bed riser, the model predicts qualitatively consistent trends to the previous studies. Furthermore, a quantitative comparison is conducted between numerical results of variable and constant specularity coefficients to investigate the effect of spatial and temporal variations in specularity coefficient.

  3. Hyperfine dipole-dipole broadening of selective reflection spectroscopy at the gas-solid interface

    NASA Astrophysics Data System (ADS)

    Meng, Tengfei; Ji, Zhonghua; Zhao, Yanting; Xiao, Liantuan; Jia, Suotang

    2016-09-01

    We theoretically and experimentally investigate hyperfine dipole-dipole broadening in the selective reflection (SR) spectroscopy at the gas-solid interface with the atomic density of 1014-1015 cm-3. The two-level SR theory considering pump beam and dipole-dipole interaction between excited-state atom and ground-state atom is presented. The numerical simulation of the SR spectrum is in agreement with experimental results. The reduction of spectral width is observed by introducing a pump beam which is an effective technique to improve the resolution of spectroscopy. We analyze the dependence of dipole-dipole broadening on atomic density and pump beam power. This study is helpful for the description of the SR spectroscopy at the gas-solid interface where the Doppler broadening is comparable with dipole-dipole broadening.

  4. [Hydration in clinical practice].

    PubMed

    Maristany, Cleofé Pérez-Portabella; Segurola Gurruchaga, Hegoi

    2011-01-01

    Water is an essential foundation for life, having both a regulatory and structural function. The former results from active and passive participation in all metabolic reactions, and its role in conserving and maintaining body temperature. Structurally speaking it is the major contributer to tissue mass, accounting for 60% of the basis of blood plasma, intracellular and intersticial fluid. Water is also part of the primary structures of life such as genetic material or proteins. Therefore, it is necessary that the nurse makes an early assessment of patients water needs to detect if there are signs of electrolyte imbalance. Dehydration can be a very serious problem, especially in children and the elderly. Dehydrations treatment with oral rehydration solution decreases the risk of developing hydration disorders, but even so, it is recommended to follow preventive measures to reduce the incidence and severity of dehydration. The key to having a proper hydration is prevention. Artificial nutrition encompasses the need for precise calculation of water needs in enteral nutrition as parenteral, so the nurse should be part of this process and use the tools for calculating the patient's requirements. All this helps to ensure an optimal nutritional status in patients at risk. Ethical dilemmas are becoming increasingly common in clinical practice. On the subject of artificial nutrition and hydration, there isn't yet any unanimous agreement regarding hydration as a basic care. It is necessary to take decisions in consensus with the health team, always thinking of the best interests of the patient.

  5. An innovative gas-solid torbed reactor for the recycling industries

    NASA Astrophysics Data System (ADS)

    Dodson, C. E.; Lakshmanan, V. I.

    1998-07-01

    Gas-solid Torbed reactors have been developed for processing a wide range of materials. The reactors have facilitated several novel recycling projects in countries where they are used. One of the major advantages of these reactors when applied to the recycling industries is the compactness of the plant and its inherent ability to be scaled down and fully automated to better match the volume requirements of this sector.

  6. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    NASA Astrophysics Data System (ADS)

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; D'Espinose de Lacaillerie, Jean-Baptiste

    2016-03-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

  7. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    PubMed Central

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  8. Non-intrusive measurement and hydrodynamics characterization of gas-solid fluidized beds: a review

    NASA Astrophysics Data System (ADS)

    Sun, Jingyuan; Yan, Yong

    2016-11-01

    Gas-solid fluidization is a well-established technique to suspend or transport particles and has been applied in a variety of industrial processes. Nevertheless, our knowledge of fluidization hydrodynamics is still limited for the design, scale-up and operation optimization of fluidized bed reactors. It is, therefore, essential to characterize the two-phase flow behaviours in gas-solid fluidized beds and monitor the fluidization processes for control and optimization. A range of non-intrusive techniques have been developed or proposed for measuring the fluidization dynamic parameters and monitoring the flow status without disturbing or distorting the flow fields. This paper presents a comprehensive review of the non-intrusive measurement techniques and the current state of knowledge and experience in the characterization and monitoring of gas-solid fluidized beds. These techniques are classified into six main categories as per sensing principles, electrostatic, acoustic emission and vibration, visualization, particle tracking, laser Doppler anemometry and phase Doppler anemometry as well as pressure-fluctuation methods. Trends and future developments in this field are also discussed.

  9. A study of pneumatic conveying of gas-solid flow for industrial application

    NASA Astrophysics Data System (ADS)

    Al-Khateeb, Khalid A. S.; Tasnim, Rumana; Khan, Sheroz; Mohammod, Musse; Arshad, Atika; Shobaki, Mohammed M.; Haider, Samnan; Saquib, Nazmus; Rahman, Tawfilur

    2013-12-01

    The complicated nature of gas-solids' physical properties have challenged the researchers over past decades who have led their efforts in developing its' flow sensing and measurement methods. The term 'gas-solid flow' signifies dilute- or dense-phase flow with a very little concentration of solids. For conducting such flow measurement, generally velocity profile and volumetric concentration of the flow particles being conveyed are needed to be measured. An important application of gas-solid flow has taken root in the form of biomass flow in pneumatic conveying systems, and its' online measurement has proven to be an exigent research pursuit. Additionally the other applications have been explored in power plants, food, chemical and automobiles industries as well. This paper aims at exploring the evolution of flow measurement methods along with a brief explanation on existing fundamental sensing techniques. Furthermore, the most recent patents developed for such measurements in pneumatic conveying pipelines are scrutinized along with their concomitant pros and cons.

  10. Magnesium hydroxide extracted from a magnesium-rich mineral for CO{sub 2} sequestration in a gas-solid system

    SciTech Connect

    Pao-Chung Lin; Cheng-Wei Huang; Ching-Ta Hsiao; Hsisheng Teng

    2008-04-15

    Magnesium hydroxide extracted from magnesium-bearing minerals is considered a promising agent for binding CO{sub 2} as a carbonate mineral in a gas-solid reaction. An efficient extraction route consisting of hydrothermal treatment on serpentine in HCl followed by NaOH titration for Mg(OH){sub 2} precipitation was demonstrated. The extracted Mg(OH){sub 2} powder had a mean crystal domain size as small as 12 nm and an apparent surface area of 54 m{sup 2}/g. Under one atmosphere of 10 vol% CO{sub 2}/N{sub 2}, carbonation of the serpentine-derived Mg(OH){sub 2} to 26% of the stoichiometric limit was achieved at 325{sup o}C in 2 h; while carbonation of a commercially available Mg(OH){sub 2}, with a mean crystal domain size of 33 nm and an apparent surface area of 3.5 m{sup 2}/g, reached only 9% of the stoichiometric limit. The amount of CO{sub 2} fixation was found to be inversely proportional to the crystal domain size of the Mg(OH){sub 2} specimens. The experimental data strongly suggested that only a monolayer of carbonates was formed on the crystal domain boundary in the gas-solid reaction, with little penetration of the carbonates into the crystal domain. 24 refs., 6 figs., 2 tabs.

  11. Olefin hydration

    SciTech Connect

    Butt, M.H.D.; Waller, F.J.

    1993-08-03

    An improved process for the hydration of olefins to alcohols is described wherein the improvement comprises contacting said olefins with the catalytic composition comprising a perfluorinated ion-exchange polymer containing sulfonic acid groups supported on an inert carrier wherein said carrier comprises calcined shot coke with a mean pore diameter of about 1,000 Angstroms in the presence of water at a temperature of from about 180 C to about 250 C.

  12. Rate constant and arrhenius parameter determination for the reaction of the hydrated electron with iodomethane, iodoethane, 1-iodopropane and 2-iodopropane in aqueous solution

    NASA Astrophysics Data System (ADS)

    Mezyk, Stephen P.

    1997-04-01

    The techniques of electron pulse radiolysis and absorption spectroscopy have been used to directly measure rate constants for the hydrated electron reaction with CH 3I, C 2H 5I, 1-C 3H 7I and 2-C 3H 7I. At 25°C, specific values of (1.78 ± 0.05) ×x 10 10, (1.57 ± 0.07) × 10 10, (1.05 ± 0.06) × 10 10 and (1.05 ± 0.03) × 10 10 dm 3 mol -1 s -1 were determined for these compounds respectively, with corresponding overall activation energiesof 16.9 ± 1.3 (3.2-35.5°C), 19.5 ± 1.1 (3.3-51.6°C), 16.60 ± 0.65 (2.5-85.1°C) and 12.94 ± 0.44 (2.5-84.5°C) kJ mol -1. The slight curvature observed in the Arrhenius plots for the three larger iodoalkanes suggests that these rate constants are influenced by both diffusion and chemical processes. By fitting the measured temperature-dependent rate constants to the general equation 1/ kobs = 1 / kdiff + 1/ kreact, where kobs, is the measured rate constant, kdiff is the encounter rate constant of the two reacting species and kreact is the rate constant that would be measured if diffusion of the species was not rate influencing, specific Arrhenius parameters for only the chemical component have also been determined.

  13. Hydrate habitat

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    Whoever said there is nothing new under the sun did not delve deeply enough to the bottom of the ocean. There in the Gulf of Mexico, about 150 miles south of New Orleans, scientists have just discovered what could be a new species of centipede—like worms living on or within gas hydrates— mounds of methane ice— rising from the ocean floor.Scientists have previously recognized an association between some bacteria and these hydrates. However, this is the first discovery of a higher life form there.

  14. Fundamentals of multiphase, gas-solid and gas-liquid flows in porous media

    NASA Astrophysics Data System (ADS)

    Mazaheri, Ali Reza

    This thesis is concerned with fundamentals and applications of multiphase and particulate flows. The study contains three parts covering gas-liquid flows through porous media, gas-solid flows and Chemical-Mechanical Polishing (CMP). A continuum model for multiphase fluid flows through poro-elastic media is developed. It is shown that the present theory leads to the extended Darcy's law and contains, as its special case, Biot's theory of saturated poro-elastic media. The capillary pressure formulation derived from the new model is used and the equation governing the evolution of the saturation and its temporal variation in porous media is derived. The resulting nonlinear diffusion equation is then solved numerically. The results show that the capillary hysteresis occurs when the temporal variation of saturation is included. Application of the developed model to CO2 sequestration is discussed. Computer simulations of dilute Gas-Solid flows in complex geometry regions are studied. A procedure for handling particle trajectory analysis in unstructured grid is developed. Examples of particle transport and removal in human lung and hot-gas cleaning systems are presented. The simulation results for the human lung show that the capture efficiency is affected by the turbulence in the upper three bifurcation airways. Computer simulations of gas-solid flows in hot-gas cleaning for a demonstration scale filtration system is studied in details. Alternative designs of the filter vessel are proposed. The corresponding vessel performance are numerically simulated. Chemical mechanical polishing (CMP) has become critical to the fabrication of advanced multilevel integrated circuit in microelectronic industry. The effect of course surface roughness of abrasive particles on the polishing rate in CMP is studied. The effects of slurry pH and double layer attraction and repulsion on chemical-mechanical polishing are also studied. It is shown that the slurry pH and colloidal forces

  15. Chemistry of large hydrated anion clusters X sup minus (H sub 2 O) sub n , n = 0-59 and X = OH, O, O sub 2 , and O sub 3. 2. Reaction of CH sub 3 CN

    SciTech Connect

    Yang, X.; Zhang, X.; Castleman, A.W. Jr. )

    1991-10-31

    The kinetics and mechanisms of the gas-phase reactions of acetonitrile with large hydrated anion clusters X{sup {minus}}(H{sub 2}O){sub n = 0-59}, X = OH, O, O{sub 2}, and O{sub 3}, were studied in a fast flow reactor under thermal conditions. OH{sup {minus}}(H{sub 2}O){sub n = 0-1} react with CH{sub 3}CN at near collision rate via proton-transfer and ligand-switching mechanisms; further hydration greatly reduces the reactivity of OH{sup {minus}}(H{sub 2}O){sub n>1} due to the thermodynamic instability of the products compared to the reactants. On the contrary, for all cluster sizes studied, O{sup {minus}}(H{sub 2}O){sub n} reacts with CH{sub 3}CN at near the collision rate via a hydrogen transfer from acetonitrile to the anion clusters. A new reaction channel was found for the reaction of O{sup {minus}} with CH{sub 3}CN to form CHCN{sup {minus}}, which can react further with CH{sub 3}CN to form CH{sub 2}CN and CH{sub 2}CN{sup {minus}}. Only very slow associations were observed for the reactions of O{sub 2}{sup {minus}} and O{sub 3}{sup {minus}} and their hydrates. The possible application of the present experimental results to an understanding of the hydrolysis mechanism of C H{sub 3}CN in aqueous solution in the presence of OH{sup {minus}} and protons as a catalyst is also discussed.

  16. Microscopic Processes at the Gas-Solid Interface of Compound Semiconductors.

    DTIC Science & Technology

    1981-03-01

    AGO35 PI ETN MV NJD TOFEETIA ENIERN AD-T FG20 2 MICROSCOPIC PROCESSES AT THE GAS-SOLID INTERFACE OF COMPOUND SE-ETC(U) UUCMAR 81 P MARK . A KAHN...1. A. Kahn, G. Cisneros, M. Bonn and P. Mark , Surf. Sct., 71 (1978) 387. 2. A. Kahn, E. So and P. Mark , J. Vac. Sci. Technol., 15, No. 2, (1978) 580...4 3. A. Kahn, E. So and P. Mark , J. Vac. Sc. Technol., 15, (1978) 1223. 4. R.J. Meyer, C.B. Duke, A. Paton, J.L. Yeh, J.C. Tsang, A. Kahn and P. Mark

  17. Secondary ions from condensed gas solids by singly and multiply charged ion impacts

    NASA Astrophysics Data System (ADS)

    Tachibana, T.; Fukai, K.; Naemura, I.; Koizumi, T.; Hirayama, T.

    2009-11-01

    Ion desorption from a condensed gas solid Ne impacted by singly- and multiply-charged Arq+ ions (q = 1-7) has been investigated. Various secondary ions such as cluster ions, Ne+n (n = 2-20) as well as atomic ions are observed. Mass spectral patterns, thickness dependence of the yields, and kinetic energy distributions of the desorbed Ne+n (n = 1,2) depend strongly on the projectile charge state. These results indicate that the dissipation of the projectile potential energy on the surface leads to the desorption of the monomer and small cluster ions by a Coulomb repulsion between adjacent target ions.

  18. Sequential hydration energies of the sulfate ion, from determinations of the equilibrium constants for the gas-phase reactions: SO4(H2O)(n)2- = SO4(H2O)(n-1)2- + H2O.

    PubMed

    Blades, Arthur T; Kebarle, Paul

    2005-09-22

    Sequential hydration energies of SO4(H2O)(n)2- were obtained from determinations of the equilibrium constants of the following reactions: SO4(H2O)(n)2- = SO4(H2O)(n-1)2- + H2O. The SO4(2-) ions were produced by electrospray and the equilibrium constants Kn,n-1 were determined with a reaction chamber attached to a mass spectrometer. Determinations of Kn,n-1 at different temperatures were used to obtain DeltaG0n,n-1, DeltaH0 n,n-1, and DeltaS0n,n-1 for n = 7 to 19. Interference of the charge separation reaction SO4(H2O)(n)2- = HSO4(H2O)(n-k)- + OH(H2O)(k-1)- at higher temperatures prevented determinations for n < 7. The DeltaS0n,n-1 values obtained are unusually low and this indicates very loose, disordered structures for the n > or = 7 hydrates. The DeltaH0n,n-1 values are compared with theoretical values DeltaEn,n-1, obtained by Wang, Nicholas, and Wang. Rate constant determinations of the dissociation reactions n,n - 1, obtained with the BIRD method by Wong and Williams, showed relatively lower rates for n = 6 and 12, which indicate that these hydrates are more stable. No discontinuities of the DeltaG0n,n-1 values indicating an unusually stable n = 12 hydrate were observed in the present work. Rate constants evaluated from the DeltaG0n,n-1 results also fail to indicate a lower rate for n = 12. An analysis of the conditions used in the two types of experiments indicates that the different results reflect the different energy distributions expected at the dissociation threshold. Higher internal energies prevail in the equilibrium measurements and allow the participation of more disordered transition states in the reaction.

  19. The effect of restricted hydration on the rate of reaction of glucose 6-phosphate dehydrogenase, phosphoglucose isomerase, hexokinase and fumarase. Relevance for metabolism in xeric (near-dry) conditions

    PubMed Central

    Stevens, Evelyn; Stevens, Lewis

    1979-01-01

    A method is described for the measurement of enzyme activity under xeric conditions. The reaction mixtures had water contents ranging between 0.1 and 0.6g/g of reaction mixture. For glucose 6-phosphate dehydrogenase, hexokinase and fumarase, enzyme activity became detectable (about 0.05% of the fully hydrated rate) when the water content was about 0.2g/g of reaction mixture, and for phosphoglucose isomerase, around 0.15g/g of reaction mixture. With the water content raised to 0.3g/g of reaction mixture the reaction rates were only increased to 0.1–3% of the fully hydrated rate. When the combined rates for phosphoglucose isomerase and glucose 6-phosphate dehydrogenase were measured, reasonable agreement was found between the experimental data and those calculated from the individual experimentally determined rates on the assumption that diffusion was not further limiting. A method was devised for measuring the diffusion coefficients of low-molecular-weight substances in solutions having low water contents. The diffusion coefficients of riboflavin in sorbitol solution decreased by about 100-fold when the water content of the latter was reduced from 3 to 0.25g/g of sorbitol. It is concluded that to detect enzyme activity a certain minimal amount of water is required and that above this minimum the rate is still restricted by diffusion limitation. The relevance of the results to the physical state of water in reaction mixtures and to metabolism in seeds and spores in xeric conditions is discussed. PMID:475753

  20. Organocatalytic Enantioselective Synthesis of α-Hydroxyketones through a Friedel-Crafts Reaction of Naphthols and Activated Phenols with Aryl- and Alkylglyoxal Hydrates.

    PubMed

    Vila, Carlos; Quintero, Lucia; Blay, Gonzalo; Muñoz, M Carmen; Pedro, José R

    2016-11-04

    An efficient organocatalytic asymmetric synthesis of α-hydroxyketones has been developed. Quinine-derived thiourea catalyzed the enantioselective Friedel-Crafts alkylation of naphthols and activated phenols with aryl- and alkylglyoxal hydrates, providing the corresponding chiral α-hydroxyketones with high yields (up to 97%) and excellent enantioselectivities (up to 99% ee).

  1. Open-source MFIX-DEM software for gas-solids flows: Part II Validation studies

    SciTech Connect

    Li, Tingwen; Garg, Rahul; Galvin, Janine; Pannala, Sreekanth

    2012-01-01

    With rapid advancements in computer hardware and numerical algorithms, computational fluid dynamics (CFD) has been increasingly employed as a useful tool for investigating the complex hydrodynamics inherent in multiphase flows. An important step during the development of a CFD model and prior to its application is conducting careful and comprehensive verification and validation studies. Accordingly, efforts to verify and validate the open-source MFIX-DEM software, which can be used for simulating the gas solids flow using an Eulerian reference frame for the continuum fluid and a Lagrangian discrete framework (Discrete Element Method) for the particles, have been made at the National Energy Technology Laboratory (NETL). In part I of this paper, extensive verification studies were presented and in this part, detailed validation studies of MFIX-DEM are presented. A series of test cases covering a range of gas solids flow applications were conducted. In particular the numerical results for the random packing of a binary particle mixture, the repose angle of a sandpile formed during a side charge process, velocity, granular temperature, and voidage profiles from a bounded granular shear flow, lateral voidage and velocity profiles from a monodisperse bubbling fluidized bed, lateral velocity profiles from a spouted bed, and the dynamics of segregation of a binary mixture in a bubbling bed were compared with available experimental data, and in some instances with empirical correlations. In addition, sensitivity studies were conducted for various parameters to quantify the error in the numerical simulation.

  2. Numerical Simulation of Dense Gas-Solid Fluidized Beds: A Multiscale Modeling Strategy

    NASA Astrophysics Data System (ADS)

    van der Hoef, M. A.; van Sint Annaland, M.; Deen, N. G.; Kuipers, J. A. M.

    2008-01-01

    Gas-solid fluidized beds are widely applied in many chemical processes involving physical and/or chemical transformations, and for this reason they are the subject of intense research in chemical engineering science. Over the years, researchers have developed a large number of numerical models of gas-fluidized beds that describe gas-solid flow at different levels of detail. In this review, we discriminate these models on the basis of whether a Lagrangian or a Eulerian approach is used for the gas and/or particulate flow and subsequently classify them into five main categories, three of which we discuss in more detail. Specifically, these are resolved discrete particle models (also called direct numerical simulations), unresolved discrete particle models (also called discrete element models), and two-fluid models. For each of the levels of description, we give the general equations of motion and indicate how they can be solved numerically by finite-difference techniques, followed by some illustrative examples of a fluidized bed simulation. Finally, we address some of the challenges ahead in the multiscale modeling of gas-fluidized beds.

  3. Digital image processing based mass flow rate measurement of gas/solid two-phase flow

    NASA Astrophysics Data System (ADS)

    Song, Ding; Peng, Lihui; Lu, Geng; Yang, Shiyuan; Yan, Yong

    2009-02-01

    With the rapid growth of the process industry, pneumatic conveying as a tool for the transportation of a wide variety of pulverized and granular materials has become widespread. In order to improve plant control and operational efficiency, it is essential to know the parameters of the particle flow. This paper presents a digital imaging based method which is capable of measuring multiple flow parameters, including volumetric concentration, velocity and mass flow rate of particles in the gas/solid two phase flow. The measurement system consists of a solid state laser for illumination, a low-cost CCD camera for particle image acquisition and a microcomputer with bespoke software for particle image processing. The measurements of particle velocity and volumetric concentration share the same sensing hardware but use different exposure time and different image processing methods. By controlling the exposure time of the camera a clear image and a motion blurred image are obtained respectively. The clear image is thresholded by OTSU method to identify the particles from the dark background so that the volumetric concentration is determined by calculating the ratio between the particle area and the total area. Particle velocity is derived from the motion blur length, which is estimated from the motion blurred images by using the travelling wave equation method. The mass flow rate of particles is calculated by combining the particle velocity and volumetric concentration. Simulation and experiment results indicate that the proposed method is promising for the measurement of multiple parameters of gas/solid two-phase flow.

  4. FORCE2: A multidimensional flow program for gas solids flow theory guide

    SciTech Connect

    Burge, S.W.

    1991-05-01

    This report describes the theory and structure of the FORCE2 flow program. The manual describes the governing model equations, solution procedure and their implementation in the computer program. FORCE2 is an extension of an existing B&V multidimensional, two-phase flow program. FORCE2 was developed for application to fluid beds by flow implementing a gas-solids modeling technology derived, in part, during a joint government -- industry research program, ``Erosion of FBC Heat Transfer Tubes,`` coordinated by Argonne National Laboratory. The development of FORCE2 was sponsored by ASEA-Babcock, an industry participant in this program. This manual is the principal documentation for the program theory and organization. Program usage and post-processing of code predictions with the FORCE2 post-processor are described in a companion report, FORCE2 -- A Multidimensional Flow Program for Fluid Beds, User`s Guide. This manual is segmented into sections to facilitate its usage. In section 2.0, the mass and momentum conservation principles, the basis for the code, are presented. In section 3.0, the constitutive relations used in modeling gas-solids hydrodynamics are given. The finite-difference model equations are derived in section 4.0 and the solution procedures described in sections 5.0 and 6.0. Finally, the implementation of the model equations and solution procedure in FORCE2 is described in section 7.0.

  5. Clathrate hydrates in nature.

    PubMed

    Hester, Keith C; Brewer, Peter G

    2009-01-01

    Scientific knowledge of natural clathrate hydrates has grown enormously over the past decade, with spectacular new findings of large exposures of complex hydrates on the sea floor, the development of new tools for examining the solid phase in situ, significant progress in modeling natural hydrate systems, and the discovery of exotic hydrates associated with sea floor venting of liquid CO2. Major unresolved questions remain about the role of hydrates in response to climate change today, and correlations between the hydrate reservoir of Earth and the stable isotopic evidence of massive hydrate dissociation in the geologic past. The examination of hydrates as a possible energy resource is proceeding apace for the subpermafrost accumulations in the Arctic, but serious questions remain about the viability of marine hydrates as an economic resource. New and energetic explorations by nations such as India and China are quickly uncovering large hydrate findings on their continental shelves.

  6. Study of Formation Mechanisms of Gas Hydrate

    NASA Astrophysics Data System (ADS)

    Yang, Jia-Sheng; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2015-04-01

    Gas hydrates, which had been found in subsurface geological environments of deep-sea sediments and permafrost regions, are solid crystalline compounds of gas molecules and water. The estimated energy resources of hydrates are at least twice of that of the conventional fossil fuel in the world. Gas hydrates have a great opportunity to become a dominating future energy. In the past years, many laboratory experiments had been conducted to study chemical and thermodynamic characteristics of gas hydrates in order to investigate the formation and dissociation mechanisms of hydrates. However, it is difficult to observe the formation and dissociation of hydrates in a porous media from a physical experiment directly. The purpose of this study was to model the dynamic formation mechanisms of gas hydrate in porous media by reservoir simulation. Two models were designed for this study: 1) a closed-system static model with separated gas and water zones; this model was a hydrate equilibrium model to investigate the behavior of the formation of hydrates near the initial gas-water contact; and 2) an open-system dynamic model with a continuous bottom-up gas flow; this model simulated the behavior of gas migration and studied the formation of hydrates from flowed gas and static formation water in porous media. A phase behavior module was developed in this study for reservoir simulator to model the pressure-volume-temperature (PVT) behavior of hydrates. The thermodynamic equilibriums and chemical reactions were coupled with the phase behavior module to have functions modelling the formation and dissociation of hydrates from/to water and gas. The simulation models used in this study were validated from the code-comparison project proposed by the NETL. According to the modelling results of the closed-system static model, we found that predominated location for the formation of hydrates was below the gas-water contact (or at the top of water zone). The maximum hydrate saturation

  7. Quantum State-Resolved Reactive and Inelastic Scattering at Gas-Liquid and Gas-Solid Interfaces

    NASA Astrophysics Data System (ADS)

    Grütter, Monika; Nelson, Daniel J.; Nesbitt, David J.

    2012-06-01

    Quantum state-resolved reactive and inelastic scattering at gas-liquid and gas-solid interfaces has become a research field of considerable interest in recent years. The collision and reaction dynamics of internally cold gas beams from liquid or solid surfaces is governed by two main processes, impulsive scattering (IS), where the incident particles scatter in a few-collisions environment from the surface, and trapping-desorption (TD), where full equilibration to the surface temperature (T{TD}≈ T{s}) occurs prior to the particles' return to the gas phase. Impulsive scattering events, on the other hand, result in significant rotational, and to a lesser extent vibrational, excitation of the scattered molecules, which can be well-described by a Boltzmann-distribution at a temperature (T{IS}>>T{s}). The quantum-state resolved detection used here allows the disentanglement of the rotational, vibrational, and translational degrees of freedom of the scattered molecules. The two examples discussed are (i) reactive scattering of monoatomic fluorine from room-temperature ionic liquids (RTILs) and (ii) inelastic scattering of benzene from a heated (˜500 K) gold surface. In the former experiment, rovibrational states of the nascent HF beam are detected using direct infrared absorption spectroscopy, and in the latter, a resonace-enhanced multi-photon-ionization (REMPI) scheme is employed in combination with a velocity-map imaging (VMI) device, which allows the detection of different vibrational states of benzene excited during the scattering process. M. E. Saecker, S. T. Govoni, D. V. Kowalski, M. E. King and G. M. Nathanson Science 252, 1421, 1991. A. M. Zolot, W. W. Harper, B. G. Perkins, P. J. Dagdigian and D. J. Nesbitt J. Chem. Phys 125, 021101, 2006. J. R. Roscioli and D. J. Nesbitt Faraday Disc. 150, 471, 2011.

  8. Particle acceleration model for gas--solid suspensions at moderate Reynolds numbers

    NASA Astrophysics Data System (ADS)

    Tenneti, Sudheer; Garg, Rahul; Hrenya, Christine; Fox, Rodney; Subramaniam, Shankar

    2009-11-01

    Particle granular temperature plays an important role in the prediction of core annular structure in riser flows. The covariance of fluctuating particle acceleration and fluctuating particle velocity governs the evolution of the granular temperature in homogeneous suspensions undergoing elastic collisions. Koch and co--workers (Phys. Fluid. 1990, JFM 1999) showed that the granular temperature has a source term due to hydrodynamic interactions in gas--solid suspensions in the Stokes flow regime. We performed direct numerical simulations (DNS) of freely evolving suspensions at moderate Reynolds numbers using the immersed boundary method (IBM). We found that simple extension of a class of mean particle acceleration models to their instantaneous counterparts does not predict the correct fluctuating particle acceleration--fluctuating velocity covariance that is obtained from DNS. The fluctuating particle velocity autocorrelation function decay and the Lagrangian structure function obtained from DNS motivate the use of a Langevin model for the instantaneous particle acceleration.

  9. Toluene vapor capture by activated carbon particles in a dual gas-solid cyclone system.

    PubMed

    Lim, Yun Hui; Ngo, Khanh Quoc; Park, Young Koo; Jo, Young Min

    2012-08-01

    Capturing of odorous compounds such as toluene vapor by a particulate-activated carbon adsorbent was investigated in a gas-solid cyclone, which is one type of mobile beds. The test cyclone was early modified with the post cyclone (PoC) and a spiral flow guide to the vortex finder. The proposed process may contribute to the reduction of gases and dust from industrial exhausts, especially when dealing with a low concentration of odorous elements and a large volume ofdust flow. In this device, the toluene capturing efficiency at a 400 ppm concentration rose up to 77.4% when using activated carbon (AC) particles with a median size of 27.03 microm. A maximum 96% of AC particles could be collected for reuse depending on the size and flow rate. The AC regenerated via thermal treatment showed an adsorption potential up to 66.7% throughout repeated tests.

  10. Study of Gas Solid Flow Characteristics in Cyclone Inlet Ducts of A300Mwe CFB Boiler

    NASA Astrophysics Data System (ADS)

    Tang, J. Y.; Lu, X. F.; Lai, J.; Liu, H. Z.

    Gas solid flow characteristics in cyclone's inlet duct of a 300MW CFB boiler were studied in a cold circulating fluidized bed (CFB) experimental setup according to a 410t/h CFB boiler with a scale of 10∶1. Tracer particles were adopted in the experiment and their motion trajectories in the two kinds of cyclone's inlet ducts were photographed by a high-speed camera. By analyzing the motion trajectories of tracer particles, acceleration performance of particle phases in the two inlet ducts was obtained. Results indicate that the acceleration performance of particles in the long inlet duct is better than that in the short inlet duct, but the pressure drop of the long inlet duct is higher. Meanwhile, under the same operating conditions, both the separation efficiency and the pressure drop of the cyclone are higher when the cyclone is connected with the long inlet duct. Figs 11, Tabs 4 and refs 10.

  11. Characteristics of dilute gas-solids suspensions in drag reducing flow

    NASA Technical Reports Server (NTRS)

    Kane, R. S.; Pfeffer, R.

    1973-01-01

    Measurements were performed on dilute flowing gas-solids suspensions and included data, with particles present, on gas friction factors, velocity profiles, turbulence intensity profiles, turbulent spectra, and particle velocity profiles. Glass beads of 10 to 60 micron diameter were suspended in air at Reynolds numbers of 10,000 to 25,000 and solids loading ratios from 0 to 4. Drag reduction was achieved for all particle sizes in vertical flow and for the smaller particle sizes in horizontal flow. The profile measurements in the vertical tube indicated that the presence of particles thickened the viscous sublayer. A quantitative theory based on particle-eddy interaction and viscous sublayer thickening has been proposed.

  12. An approach for drag correction based on the local heterogeneity for gas-solid flows

    SciTech Connect

    Li, Tingwen; Wang, Limin; Rogers, William; Zhou, Guofeng; Ge, Wei

    2016-09-22

    The drag models typically used for gas-solids interaction are mainly developed based on homogeneous systems of flow passing fixed particle assembly. It has been shown that the heterogeneous structures, i.e., clusters and bubbles in fluidized beds, need to be resolved to account for their effect in the numerical simulations. Since the heterogeneity is essentially captured through the local concentration gradient in the computational cells, this study proposes a simple approach to account for the non-uniformity of solids spatial distribution inside a computational cell and its effect on the interaction between gas and solid phases. Finally, to validate this approach, the predicted drag coefficient has been compared to the results from direct numerical simulations. In addition, the need to account for this type of heterogeneity is discussed for a periodic riser flow simulation with highly resolved numerical grids and the impact of the proposed correction for drag is demonstrated.

  13. An approach for drag correction based on the local heterogeneity for gas-solid flows

    DOE PAGES

    Li, Tingwen; Wang, Limin; Rogers, William; ...

    2016-09-22

    The drag models typically used for gas-solids interaction are mainly developed based on homogeneous systems of flow passing fixed particle assembly. It has been shown that the heterogeneous structures, i.e., clusters and bubbles in fluidized beds, need to be resolved to account for their effect in the numerical simulations. Since the heterogeneity is essentially captured through the local concentration gradient in the computational cells, this study proposes a simple approach to account for the non-uniformity of solids spatial distribution inside a computational cell and its effect on the interaction between gas and solid phases. Finally, to validate this approach, themore » predicted drag coefficient has been compared to the results from direct numerical simulations. In addition, the need to account for this type of heterogeneity is discussed for a periodic riser flow simulation with highly resolved numerical grids and the impact of the proposed correction for drag is demonstrated.« less

  14. Electrostatic sensors applied to the measurement of electric charge transfer in gas solids pipelines

    NASA Astrophysics Data System (ADS)

    Woodhead, S. R.; Denham, J. C.; Armour-Chelu, D. I.

    2005-01-01

    This paper describes the development of a number of electric charge sensors. The sensors have been developed specifically to investigate triboelectric charge transfer which takes place between particles and the pipeline wall, when powdered materials are conveyed through a pipeline using air. A number of industrial applications exist for such gas solids pipelines, including pneumatic conveyors, vacuum cleaners and dust extraction systems. The build-up of electric charge on pipelines and powdered materials can lead to electrostatic discharge and so is of interest from a safety viewpoint. The charging of powders can also adversely affect their mechanical handling characteristics and so is of interest to handling equipment engineers. The paper presents the design of the sensors, the design of the electric charge test rig and electric charge measurement test results.

  15. Revisiting low-fidelity two-fluid models for gas-solids transport

    NASA Astrophysics Data System (ADS)

    Adeleke, Najeem; Adewumi, Michael; Ityokumbul, Thaddeus

    2016-08-01

    Two-phase gas-solids transport models are widely utilized for process design and automation in a broad range of industrial applications. Some of these applications include proppant transport in gaseous fracking fluids, air/gas drilling hydraulics, coal-gasification reactors and food processing units. Systems automation and real time process optimization stand to benefit a great deal from availability of efficient and accurate theoretical models for operations data processing. However, modeling two-phase pneumatic transport systems accurately requires a comprehensive understanding of gas-solids flow behavior. In this study we discuss the prevailing flow conditions and present a low-fidelity two-fluid model equation for particulate transport. The model equations are formulated in a manner that ensures the physical flux term remains conservative despite the inclusion of solids normal stress through the empirical formula for modulus of elasticity. A new set of Roe-Pike averages are presented for the resulting strictly hyperbolic flux term in the system of equations, which was used to develop a Roe-type approximate Riemann solver. The resulting scheme is stable regardless of the choice of flux-limiter. The model is evaluated by the prediction of experimental results from both pneumatic riser and air-drilling hydraulics systems. We demonstrate the effect and impact of numerical formulation and choice of numerical scheme on model predictions. We illustrate the capability of a low-fidelity one-dimensional two-fluid model in predicting relevant flow parameters in two-phase particulate systems accurately even under flow regimes involving counter-current flow.

  16. Increasing Gas Hydrate Formation Temperature for Desalination of High Salinity Produced Water with Secondary Guests

    SciTech Connect

    Cha, Jong-Ho; Seol, Yongkoo

    2013-10-07

    We suggest a new gas hydrate-based desalination process using water-immiscible hydrate formers; cyclopentane (CP) and cyclohexane (CH) as secondary hydrate guests to alleviate temperature requirements for hydrate formation. The hydrate formation reactions were carried out in an isobaric condition of 3.1 MPa to find the upper temperature limit of CO2 hydrate formation. Simulated produced water (8.95 wt % salinity) mixed with the hydrate formers shows an increased upper temperature limit from -2 °C for simple CO2 hydrate to 16 and 7 °C for double (CO2 + CP) and (CO2 + CH) hydrates, respectively. The resulting conversion rate to double hydrate turned out to be similar to that with simple CO2 hydrate at the upper temperature limit. Hydrate formation rates (Rf) for the double hydrates with CP and CH are shown to be 22 and 16 times higher, respectively, than that of the simple CO2 hydrate at the upper temperature limit. Such mild hydrate formation temperature and fast formation kinetics indicate increased energy efficiency of the double hydrate system for the desalination process. Dissociated water from the hydrates shows greater than 90% salt removal efficiency for the hydrates with the secondary guests, which is also improved from about 70% salt removal efficiency for the simple hydrates.

  17. Carbon dioxid sequestration in natural gas hydrates: Thermodynamic considerations

    NASA Astrophysics Data System (ADS)

    Schicks, J. M.; Beeskow-Strauch, B.; Luzi, M.; Girod, M.; Erzinger, J.

    2009-12-01

    Due to the increasing energy demands natural gas hydrates become more and more of interest. The huge amount of hydrocarbons - mainly CH4 - stored in natural hydrate reservoirs suggest the use of natural gas hydrates as an energy resource. However, the combustion of this fossil fuel results in an undesired increase of CO2 in the atmosphere. Therefore, a combination of CH4 production on the one hand and the CO2 sequestration on the other hand seems to be ideal. Several investigations regarding the exchange reaction of CH4 with CO2 using pure methane hydrates and pure CO2 or CO2-N2-mixtures have been performed as laboratory studies in the past. Some showed exchange rates up to 85% and concluded that the driving force of this exchange reaction is the higher stability of CO2 hydrates compared to methane hydrates (e.g. Park et al. 2006). However, natural conditions may differ: natural gas hydrates may contain higher hydrocarbons or H2S, which have significant impact in terms of a higher stability of the mixed hydrate phase compared to pure CH4- and CO2-hydrates. Primary results of our investigations on the exchange reaction of a mixed CH4-C3H8-hydrate with CO2 indicates that although the stability of mixed CH4-C3H8-hydrate is significantly shifted to higher temperatures and lower pressures compared to pure CH4-, mixed CH4-CO2- and pure CO2-hydrates, it changes in the presence of CO2 from a structure II hydrate phase to form a structure I CH4-CO2-hydrate which subsequently transforms to CO2-hydrate. This process starts at the interface between gas and hydrate and continues slowly into the bulk phase. These observation lead to the following conclusions: - The driving force of the exchange reaction is less the stability with respect to temperature and pressure conditions of the hydrate phase but rather the chemical equilibrium state in terms of concentration gradients between hydrate and surrounding gas phase - After the initial formation of a CO2-CH4- or CO2 hydrate layer

  18. Multiphasic finite element modeling of concrete hydration

    SciTech Connect

    Buffo-Lacarriere, L.; Sellier, A. . E-mail: alain.sellier@insa-toulouse.fr; Escadeillas, G.; Turatsinze, A.

    2007-02-15

    This paper presents a model predicting the development of hydration and its consequences on temperature and water content. As it considers the effects of climatic conditions, the proposed model is a promising tool to evaluate the temperature, hydric and hydration fields of structures in situ. The hydration model predicts the hydration evolution of several main species (not only clinker but also mineral additions like fly ash or silica fume for instance). For each component, the modeling considers hydration development and chemical interaction between reactions. It also takes into account temperature and water content effects on reaction kinetics through thermal and hydric activation. Hydration development in turn modifies the thermal and hydric states of material. The result is a numerical model coupling hydration, and the thermal and hydric states of cement-based material. The model was tested on a 27 m{sup 3} concrete block in situ equipped with temperature sensors situated in the core and close to the face exposed to solar radiation.

  19. Keggin heteropolyacid H3PW12O40 supported on different oxides for catalytic and catalytic photo-assisted propene hydration.

    PubMed

    Marcì, G; García-López, E; Bellardita, M; Parisi, F; Colbeau-Justin, C; Sorgues, S; Liotta, L F; Palmisano, L

    2013-08-28

    Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas-solid regime at atmospheric pressure and 85 °C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active both for catalytic and catalytic photo-assisted reactions. The Keggin type POM was completely and partially degraded, when supported on ZnO and Al2O3, respectively, and these binary solids always resulted as inactive for both catalytic and catalytic photo-assisted reactions. The supported Keggin POM species played a key role both for the catalytic and the photo-assisted catalytic reactions, due to their strong acidity and ability to form strong oxidant species under UV irradiation, respectively. The contemporary presence of heat and UV light improved the activity of almost all POM supported materials. All materials were characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM), diffuse reflectance spectroscopy (DRS), determination of the conduction and valence band energy by photovoltage measurements, Fourier transform infrared spectroscopy (FTIR), NH3-TPD experiments and time resolved microwave conductivity (TRMC).

  20. Clathrate hydrates in cometary nuclei and porosity

    NASA Technical Reports Server (NTRS)

    Smoluchowski, R.

    1988-01-01

    Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

  1. Henry`s law gas-solid chromatography and correlations of virial coefficients for hydrocarbons, chlorofluorocarbons, ethers, and sulfur hexafluoride adsorbed onto carbon

    SciTech Connect

    Rybolt, T.R.; Epperson, M.T.; Weaver, H.W.; Thomas, H.E.; Clare, S.E.; Manning, B.M.; McClung, J.T.

    1995-07-01

    Gas-solid chromatography was used to determine the Henry`s law second gas-solid virial coefficients within the temperature range of 314--615 K for ethane, propane, butane, isobutane, pentane, hexane, heptane, chloromethane, dichloromethane, trichloromethane, tetrachloromethane, trichlorofluoromethane (Freon 11), chlorodifluoromethane (Freon 22), dichlorodifluoromethane (Freon 12), methyl ether, ethyl ether, and sulfur hexafluoride with Carbopack B, a microporous carbon adsorbent. The temperature dependence of the second gas-solid virial coefficients of these adsorbates was used in conjunction with analyses based on a graphical method, a single-surface numeric integration method, a single-surface analytic expression method, and a two-surface analytic expression method to determine the gas-solid interaction energies and other parameters. The interaction energies were correlated with a ratio of the critical temperature divided by the square root of the critical pressure. The four methods were compared in their abilities to successfully calculate second gas-solid virial coefficient values.

  2. Reactions of Cg10062, a cis-3-Chloroacrylic Acid Dehalogenase Homologue, with Acetylene and Allene Substrates: Evidence for a Hydration-Dependent Decarboxylation.

    PubMed

    Huddleston, Jamison P; Johnson, William H; Schroeder, Gottfried K; Whitman, Christian P

    2015-05-19

    Cg10062 is a cis-3-chloroacrylic acid dehalogenase (cis-CaaD) homologue from Corynebacterium glutamicum with an unknown function and an uninformative genomic context. It shares 53% pairwise sequence similarity with cis-CaaD including the six active site amino acids (Pro-1, His-28, Arg-70, Arg-73, Tyr-103, and Glu-114) that are critical for cis-CaaD activity. However, Cg10062 is a poor cis-CaaD: it lacks catalytic efficiency and isomer specificity. Two acetylene compounds (propiolate and 2-butynoate) and an allene compound, 2,3-butadienoate, were investigated as potential substrates. Cg10062 functions as a hydratase/decarboxylase using propiolate as well as the cis-3-chloro- and 3-bromoacrylates, generating mixtures of malonate semialdehyde and acetaldehyde. The two activities occur sequentially at the active site using the initial substrate. With 2,3-butadienoate and 2-butynoate, Cg10062 functions as a hydratase and converts both to acetoacetate. Mutations of the proposed water-activating residues (E114Q, E114D, and Y103F) have a range of consequences from a reduction in wild type activity to a switch of activities (i.e., hydratase into a hydratase/decarboxylase or vice versa). The intermediates for the hydration and decarboxylation products can be trapped as covalent adducts to Pro-1 when NaCNBH3 is incubated with the E114D mutant and 2,3-butadienoate or 2-butynoate, and the Y103F mutant and 2-butynoate. Three mechanisms are presented to explain these findings. One mechanism involves the direct attack of water on the substrate, whereas the other two mechanisms use covalent catalysis in which a covalent bond forms between Pro-1 and the hydration product or the substrate. The strengths and weaknesses of the mechanisms and the implications for Cg10062 function are discussed.

  3. Application of a gas-solid fluidized bed separator for shredded municipal bulky solid waste separation.

    PubMed

    Sekito, T; Matsuto, T; Tanaka, N

    2006-01-01

    A laboratory-scale gas-solid fluidized bed separator able to separate fractions of 5.6-50mm was used for separation of shredded municipal bulky waste (SBW) into combustibles and incombustibles. In batch-scale tests, it was found that accumulation of SBW in the bottom of the bed significantly reduced the separation efficiency. In this study, stirring was shown to be effective in preventing this accumulation. Flexible sheet materials such as paper and film plastics also significantly decreased the separation efficiency. In batch-scale tests, an overall efficiency of 90% was obtained when flexible materials such as film plastics and paper were excluded from the feed SBW. In continuous feeding tests, purities of the float and sink fractions attained 95% and 86% efficiencies, respectively, with an overall efficiency of 79%. The effect of feedstock shape on separation efficiency was also investigated. This study revealed that large particles can be properly separated on the basis of density, while the shape of the material significantly influenced behavior in the fluidizing bed.

  4. Real time mass flux measurements of gas-solid suspensions at low velocities

    SciTech Connect

    Saunders, J H; Chao, B T; Soo, S L

    1981-01-01

    In previous work, measurement of the particulate mass flux was made based upon a novel electrostatic technique. A small conducting wire sensor was inserted in the flow and as each particle hit the sensor an individual pulse of current was identified. Through suitable electronic circuitry, the number of pulses in a given time were counted. This was a direct measure of the number of particle-probe collisions which was related to local particle mass flow. The technique is currently limited to monodisperse suspensions. A primary advantage of the impact counter system is that the output does not depend upon the magnitude of the actual charge transfer. As long as the pulses are sufficiently above the noise level, variations in charge transfer will not affect the measurement. For the current work, the technique was applied to vertical gas-solid flow where the fluid velocity was slightly above the particle terminal velocity. Under these conditions a sufficient signal to noise ratio was not found. The Cheng-Soo charge transfer theory indicated that the low particle-sensor impact velocity was responsible. The probe system was then modified by extracting a particulate sample isokinetically and accelerating the particles to a sufficient velocity by an area reduction in the sampling tube. With this technique the signal to noise ratio was about 12 to 1. Mass flux results are shown to compare favorably with filter collection and weighing.

  5. Research of the gas-solid flow character based on the DEM method

    NASA Astrophysics Data System (ADS)

    Wang, Xueyao; Xiao, Yunhan

    2011-12-01

    Numerical simulation of gas-solid flow behaviors in a rectangular fluidized bed is carried out three dimensionally by the discrete element method (DEM). Euler method and Lagrange method are employed to deal with the gas phase and solid phase respectively. The collided force among particles, striking force between particle and wall, drag force, gravity, Magnus lift force and Saffman lift force are considered when establishing the mathematic models. Soft-sphere model is used to describe the collision of particles. In addition, the Euler method is also used for modeling the solid phase to compare with the results of DEM. The flow patterns, particle mean velocities, particles' diffusion and pressure drop of the bed under typical operating conditions are obtained. The results show that the DEM method can describe the detailed information among particles, while the Euler-Euler method cannot capture the micro-scale character. No matter which method is used, the diffusion of particles increases with the increase of gas velocity. But the gathering and crushing of particles cannot be simulated, so the energy loss of particles' collision cannot be calculated and the diffusion by using the Euler-Euler method is larger. In addition, it is shown by DEM method, with strengthening of the carrying capacity, more and more particles can be schlepped upward and the dense suspension upflow pattern can be formed. However, the results given by the Euler-Euler method are not consistent with the real situation.

  6. Origin of melting point depression for rare gas solids confined in carbon pores

    NASA Astrophysics Data System (ADS)

    Morishige, Kunimitsu; Kataoka, Takaaki

    2015-07-01

    To obtain insights into the mechanism of the melting-point depression of rare gas solids confined in crystalline carbon pores, we examined the freezing and melting behavior of Xe and Ar confined to the crystalline pores of ordered mesoporous carbons as well as compressed exfoliated graphite compared to the amorphous pores of ordered mesoporous silicas, by means of X-ray diffraction. For the Xe and Ar confined to the crystalline carbon pores, there was no appreciable thermal hysteresis between freezing and melting. Furthermore, the position of the main diffraction peak did not change appreciably on freezing and melting. This strongly suggests that the liquids confined in the carbon pores form a multilayered structure parallel to the smooth walls. For the Xe and Ar confined to the amorphous silica pores, on the other hand, the position of the main diffraction peak shifted into higher scattering angle on freezing suggested that the density of the confined solid is distinctly larger than for the confined liquid. Using compressed exfoliated graphite with carbon walls of higher crystallinity, we observed that three-dimensional (3D) microcrystals of Xe confined in the slit-shaped pores melted to leave the unmelted bilayers on the pore walls below the bulk triple point. The lattice spacing of the 3D microcrystals confined is larger by ˜0.7% than that of the bilayer next to the pore walls in the vicinity of the melting point.

  7. Origin of melting point depression for rare gas solids confined in carbon pores

    SciTech Connect

    Morishige, Kunimitsu Kataoka, Takaaki

    2015-07-21

    To obtain insights into the mechanism of the melting-point depression of rare gas solids confined in crystalline carbon pores, we examined the freezing and melting behavior of Xe and Ar confined to the crystalline pores of ordered mesoporous carbons as well as compressed exfoliated graphite compared to the amorphous pores of ordered mesoporous silicas, by means of X-ray diffraction. For the Xe and Ar confined to the crystalline carbon pores, there was no appreciable thermal hysteresis between freezing and melting. Furthermore, the position of the main diffraction peak did not change appreciably on freezing and melting. This strongly suggests that the liquids confined in the carbon pores form a multilayered structure parallel to the smooth walls. For the Xe and Ar confined to the amorphous silica pores, on the other hand, the position of the main diffraction peak shifted into higher scattering angle on freezing suggested that the density of the confined solid is distinctly larger than for the confined liquid. Using compressed exfoliated graphite with carbon walls of higher crystallinity, we observed that three-dimensional (3D) microcrystals of Xe confined in the slit-shaped pores melted to leave the unmelted bilayers on the pore walls below the bulk triple point. The lattice spacing of the 3D microcrystals confined is larger by ∼0.7% than that of the bilayer next to the pore walls in the vicinity of the melting point.

  8. Fine-Grid Eulerian Simulation of Sedimenting Particles: Liquid-Solid and Gas-Solid Systems

    NASA Astrophysics Data System (ADS)

    Zaheer, Muhammad; Hamid, Adnan; Ullah, Atta

    2017-06-01

    A computational study of mono-dispersed spherical sedimenting particles was performed with Eulerian two-fluid model (TFM). The aim was to investigate the applicability and accuracy of TFM with proper closure laws from kinetic theory of granular flow (KTGF) for sedimentation studies. A three-dimensional cubical box with full periodic boundaries was employed. The volume fraction of particles (ϕs) was varied from very low (ϕs = 0.01) to dense regimes (ϕs = 0.4), for two different types of fluids, i.e., gas and liquid. It is observed that the results for liquid-solid sedimentation are in good agreement with simulation studies and experimental correlation of Richardson and Zaki. However, for gas-solid system, results show different behavior at low volume fractions, which is more pronounced with increasing Stokes number. This can be attributed to inhomogeneous distribution of solid particles in gas phase at dilute concentrations, which causes meso-scale clusters and streamers formation. It is concluded that the ratio of density of particles to density of fluid which appears in Stokes number plays critical role in settling behavior of particles.

  9. Lattice Boltzmann simulation of the gas-solid adsorption process in reconstructed random porous media.

    PubMed

    Zhou, L; Qu, Z G; Ding, T; Miao, J Y

    2016-04-01

    The gas-solid adsorption process in reconstructed random porous media is numerically studied with the lattice Boltzmann (LB) method at the pore scale with consideration of interparticle, interfacial, and intraparticle mass transfer performances. Adsorbent structures are reconstructed in two dimensions by employing the quartet structure generation set approach. To implement boundary conditions accurately, all the porous interfacial nodes are recognized and classified into 14 types using a proposed universal program called the boundary recognition and classification program. The multiple-relaxation-time LB model and single-relaxation-time LB model are adopted to simulate flow and mass transport, respectively. The interparticle, interfacial, and intraparticle mass transfer capacities are evaluated with the permeability factor and interparticle transfer coefficient, Langmuir adsorption kinetics, and the solid diffusion model, respectively. Adsorption processes are performed in two groups of adsorbent media with different porosities and particle sizes. External and internal mass transfer resistances govern the adsorption system. A large porosity leads to an early time for adsorption equilibrium because of the controlling factor of external resistance. External and internal resistances are dominant at small and large particle sizes, respectively. Particle size, under which the total resistance is minimum, ranges from 3 to 7 μm with the preset parameters. Pore-scale simulation clearly explains the effect of both external and internal mass transfer resistances. The present paper provides both theoretical and practical guidance for the design and optimization of adsorption systems.

  10. Pneumatic nebulization gas-solid extraction of triazine herbicides in vegetable.

    PubMed

    Li, Na; Jin, Haiyan; Nian, Li; Wang, Yeqiang; Lei, Lei; Zhang, Rui; Zhang, Hanqi; Yu, Yong

    2013-08-23

    The pneumatic nebulization gas-solid extraction (PN-GSE) high-performance liquid chromatography (HPLC) was developed and applied to the extraction, separation and determination of triazine herbicides in vegetables. The herbicides were ultrasonically extracted from vegetables with 70% methanol in water. Then the extract was introduced to PN-GSE system to further clean-up. The experimental parameters, including type and concentration of extraction solvent, ratio of solvent to sample, pH value of sample solution and PN-GSE solution, extraction time, temperature, type of sorbent, flow rate of carrier gas, pumping rate of gas, and kind and volume of elution solvent, were investigated and optimized. The limits of detection for seven herbicides range from 0.59 to 1.05μg/kg. The recoveries of the herbicides are in the range of 86.2-110.6% and relative standard deviations are equal or less than 7.51%, when the present method was applied to the analysis of spiked samples. The present method was applied to the analysis of real samples and the results were satisfactory.

  11. Origin of melting point depression for rare gas solids confined in carbon pores.

    PubMed

    Morishige, Kunimitsu; Kataoka, Takaaki

    2015-07-21

    To obtain insights into the mechanism of the melting-point depression of rare gas solids confined in crystalline carbon pores, we examined the freezing and melting behavior of Xe and Ar confined to the crystalline pores of ordered mesoporous carbons as well as compressed exfoliated graphite compared to the amorphous pores of ordered mesoporous silicas, by means of X-ray diffraction. For the Xe and Ar confined to the crystalline carbon pores, there was no appreciable thermal hysteresis between freezing and melting. Furthermore, the position of the main diffraction peak did not change appreciably on freezing and melting. This strongly suggests that the liquids confined in the carbon pores form a multilayered structure parallel to the smooth walls. For the Xe and Ar confined to the amorphous silica pores, on the other hand, the position of the main diffraction peak shifted into higher scattering angle on freezing suggested that the density of the confined solid is distinctly larger than for the confined liquid. Using compressed exfoliated graphite with carbon walls of higher crystallinity, we observed that three-dimensional (3D) microcrystals of Xe confined in the slit-shaped pores melted to leave the unmelted bilayers on the pore walls below the bulk triple point. The lattice spacing of the 3D microcrystals confined is larger by ∼0.7% than that of the bilayer next to the pore walls in the vicinity of the melting point.

  12. Effect of particle inertia on fluid turbulence in gas-solid disperse flow

    NASA Astrophysics Data System (ADS)

    Mito, Yoichi

    2016-11-01

    The effect of particle inertia on the fluid turbulence in gas-solid disperse flow through a vertical channel has been examined by using a direct numerical simulation, to calculate the gas velocities seen by the particles, and a simplified non-stationary flow model, in which a uniform distribution of solid spheres of density ratio of 1000 are added into the fully-developed turbulent gas flow in an infinitely wide channel. The gas flow is driven downward with a constant pressure gradient. The frictional Reynolds number defined with the frictional velocity before the addition of particles, v0*, is 150. The feedback forces are calculated using a point force method. Particle diameters of 0.95, 1.3 and 1.9, which are made dimensionless with v0* and the kinematic viscosity, and volume fractions, ranging from 1 ×10-4 to 2 ×10-3 , in addition to the one-way coupling cases, are considered. Gravitational effect is not clearly seen where the fluid turbulence is damped by feedback effect. Gas flow rate increases with the decrease in particle inertia, that causes the increase in feedback force. Fluid turbulence decreases with the increase in particle inertia, that causes the increase in diffusivity of feedback force and of fluid turbulence. This work was supported by JSPS KAKENHI Grant Number 26420097.

  13. Advanced instrumentation for local measurement of gas-solid suspension flows

    NASA Astrophysics Data System (ADS)

    Ling, S. C.; Pao, H. P.

    The study of gas-solid suspension flow is being conducted in two parts: the lifting of heavy particles from the flow boundary by micro-hairpin vortices and the design of an optical instrument to investigate the characteristics of turbulent flows has particle-size concentrations. The study of micro-hairpin vortices is based on the observation of these vortices in a cavitation water-tunnel. The micro-vortices exist within the laminar and intermediate sublayer of the turbulent flow field where the velocity gradient is most intense. These vortices are believed to be the major production source of turbulence which are also responsible for the picking up of heavy solid particles from the flow boundary at the bottom of the pipe. However, this important transport mechanism near the bottom boundary was not taken into account in all previous theories of solid transport. It is hoped that this work will provide a more basic understanding on the mechanics of solid transport. Our major research effort in this quarter has been concentrated on the construction of the experimental test-setup and the development of an optical particle-size and concentration detector. The optical detector also provides the information on flow characteristics.

  14. Experimental Research on Gas-Solid Flow in a Square Cyclone Separator with Double Inlets

    NASA Astrophysics Data System (ADS)

    Xiong, B.; Lu, X. F.; Amano, R. S.; Shu, C.

    A square cyclone separator with double inlets was developed for a new type Circulating Fluidized Bed (CFB) boiler arrangement scheme including two furnaces. Experiments on the performance and gas-solid flow recorded by a high-speed photography have been conducted in a cold test rig with a separator cross section 400mm×400mm. Experimental results indicated that with the inlet velocity of 22.4m/s and the inlet solids concentration of 4.9g/m3, the cut size is 15 μm, the critical size is 75μm, and the pressure drop coefficient is 1.7. The performance is also affected by the inlet velocity and solids concentration. The trajectory of particles shows that the particles swirl in the region near the wall and are easily separated. Especially, the instantaneous separation occurred at the corner is very significant for the improvement of the collection efficiency with the high inlet solids concentration for CFB boiler.

  15. Lattice Boltzmann simulation of the gas-solid adsorption process in reconstructed random porous media

    NASA Astrophysics Data System (ADS)

    Zhou, L.; Qu, Z. G.; Ding, T.; Miao, J. Y.

    2016-04-01

    The gas-solid adsorption process in reconstructed random porous media is numerically studied with the lattice Boltzmann (LB) method at the pore scale with consideration of interparticle, interfacial, and intraparticle mass transfer performances. Adsorbent structures are reconstructed in two dimensions by employing the quartet structure generation set approach. To implement boundary conditions accurately, all the porous interfacial nodes are recognized and classified into 14 types using a proposed universal program called the boundary recognition and classification program. The multiple-relaxation-time LB model and single-relaxation-time LB model are adopted to simulate flow and mass transport, respectively. The interparticle, interfacial, and intraparticle mass transfer capacities are evaluated with the permeability factor and interparticle transfer coefficient, Langmuir adsorption kinetics, and the solid diffusion model, respectively. Adsorption processes are performed in two groups of adsorbent media with different porosities and particle sizes. External and internal mass transfer resistances govern the adsorption system. A large porosity leads to an early time for adsorption equilibrium because of the controlling factor of external resistance. External and internal resistances are dominant at small and large particle sizes, respectively. Particle size, under which the total resistance is minimum, ranges from 3 to 7 μm with the preset parameters. Pore-scale simulation clearly explains the effect of both external and internal mass transfer resistances. The present paper provides both theoretical and practical guidance for the design and optimization of adsorption systems.

  16. Particle size measurement in gas-solid two-phase flow using acoustic sensors

    NASA Astrophysics Data System (ADS)

    Guo, Miao; Yan, Yong; Hu, Yonghui; Sun, Duo; Qian, Xiangcheng; Han, Xiaojuan

    2014-04-01

    Acoustic Emission (AE) technology is a promising way to non-intrusively measure the size of particles in pneumatic conveying pipelines. In AE-based particle sizing, extracting representative features from an AE signal and establishing the relationship between the features and particle size are essential. In this paper, AE signals from particles of different sizes are collected from a gas-solid flow test rig. Wavelet analysis is used to denoise the signals. The denoising performance of different wavelet parameters (wavelet function, decomposition level and thresholding) is compared based on signal-to-noise ratio and signal smoothness. The particle size is predicted through a neural network with energy fraction features extracted through wavelet analysis as the network inputs. Experimental results demonstrate that the relative error of the particle sizing system is no greater than 23%. An updated version of this article was published on 31 October 2014. The Corrigendum attached to the corrected article PDF file explains the changes made to the original paper.

  17. Saturation region of helium ionization detector for gas-solid and gas-liquid chromatography

    SciTech Connect

    Andrawes, F.F.; Brazell, R.S.; Gibson, E.K.

    1980-05-01

    In the saturation region of the helium detector field intensity, the detector response is independent of the electrical field. In this region (at applied potential between 200 to 2000 volts per centimeter of electrode surface) the detector is operated at a low background current, and a low noise level, but it still exhibits a stable and sensitive response. The detector in this region can be operated with high purity grade helium without any further elaborate purification processes to yield a positive response to all compounds and gases tested. The operation of the detector in this mode has been adapted to both gas-solid and gas-liquid chromatography, with temperature programming. A sample can be introduced to the column via a gas sampling injection valve or via a syringe by direct injection into a modified injection port. The detector response is linear over a range of 10/sup 6/ units with a detection limit in the picogram range for organic compounds. 11 figures.

  18. Gas hydrate and humans

    USGS Publications Warehouse

    Kvenvolden, K.A.

    2000-01-01

    The potential effects of naturally occurring gas hydrate on humans are not understood with certainty, but enough information has been acquired over the past 30 years to make preliminary assessments possible. Three major issues are gas hydrate as (1) a potential energy resource, (2) a factor in global climate change, and (3) a submarine geohazard. The methane content is estimated to be between 1015 to 1017 m3 at STP and the worldwide distribution in outer continental margins of oceans and in polar regions are significant features of gas hydrate. However, its immediate development as an energy resource is not likely because there are various geological constraints and difficult technological problems that must be solved before economic recovery of methane from hydrate can be achieved. The role of gas hydrate in global climate change is uncertain. For hydrate methane to be an effective greenhouse gas, it must reach the atmosphere. Yet there are many obstacles to the transfer of methane from hydrate to the atmosphere. Rates of gas hydrate dissociation and the integrated rates of release and destruction of the methane in the geo/hydro/atmosphere are not adequately understood. Gas hydrate as a submarine geohazard, however, is of immediate and increasing importance to humans as our industrial society moves to exploit seabed resources at ever-greater depths in the waters of our coastal oceans. Human activities and installations in regions of gas-hydrate occurrence must take into account the presence of gas hydrate and deal with the consequences of its presence.

  19. Glass powder blended cement hydration modelling

    NASA Astrophysics Data System (ADS)

    Saeed, Huda

    The use of waste materials in construction is among the most attractive options to consume these materials without affecting the environment. Glass is among these types of potential waste materials. In this research, waste glass in powder form, i.e. glass powder (GP) is examined for potential use in enhancing the characteristics of concrete on the basis that it is a pozzolanic material. The experimental and the theoretical components of the work are carried out primarily to prove that glass powder belongs to the "family" of the pozzolanic materials. The chemical and physical properties of the hydrated activated glass powder and the hydrated glass powder cement on the microstructure level have been studied experimentally and theoretically. The work presented in this thesis consists of two main phases. The first phase contains experimental investigations of the reaction of glass powder with calcium hydroxide (CH) and water. In addition, it includes experiments that are aimed at determining the consumption of water and CH with time. The reactivity, degree of hydration, and nature of the pore solution of the glass powder-blended cement pastes and the effect of adding different ratios of glass powder on cement hydration is also investigated. The experiments proved that glass powder has a pozzolanic effect on cement hydration; hence it enhances the chemical and physical properties of cement paste. Based on the experimental test results, it is recommended to use a glass powder-to-cement ratio (GP/C) of 10% as an optimum ratio to achieve the best hydration and best properties of the paste. Two different chemical formulas for the produced GP C-S-H gel due to the pure GP and GP-CH pozzolanic reaction hydration are proposed. For the pure GP hydration, the produced GP C-S-H gel has a calcium-to-silica ratio (C/S) of 0.164, water-to-silica ratio (H/S) of 1.3 and sodium/silica ratio (N/S) of 0.18. However, for the GP-CH hydration, the produced GP C-S-H gel has a C/S ratio of 1

  20. [Raman spectroscopic investigation of hydrogen storage in nitrogen gas hydrates].

    PubMed

    Meng, Qing-guo; Liu, Chang-ling; Ye, Yu-guang; Li, Cheng-feng

    2012-08-01

    Recently, hydrogen storage using clathrate hydrate as a medium has become a hotspot of hydrogen storage research In the present paper, the laser Raman spectroscopy was used to study the hydrogen storage in nitrogen hydrate. The synthetic nitrogen hydrate was reacted with hydrogen gas under relatively mild conditions (e.g., 15 MPa, -18 degrees C). The Raman spectra of the reaction products show that the hydrogen molecules have enclathrated the cavities of the nitrogen hydrate, with multiple hydrogen cage occupancies in the clathrate cavities. The reaction time is an important factor affecting the hydrogen storage in nitrogen hydrate. The experimental results suggest that nitrogen hydrates are expected to be an effective media for hydrogen storage.

  1. Properties and hydration products of lightweight and expansive cements. Part II: Hydration products

    SciTech Connect

    Lilkov, V.; Djabarov, N.; Bechev, G.; Petrov, O.

    1999-10-01

    The type and quantity of hydration products in cement stone (plain cement, lightweight cement with cenospheres, and cement mixed with expansive additive) hydrated at 20 and 75 C were studied. The changes in the cement stone structure under the influence of lightweight and expansive additives and raised hardening temperature were studied with complex thermal analysis, infrared spectroscopy, powder X-ray diffraction analysis, and scanning electron microscopy. In the case of raised hardening temperature, the cenospheres and the expansive additive improve the crystallization of hydration products. A chemical reaction between the cenospheres and portlandite formed from the cement hydration was observed, accompanied by a decrease of the portlandite quantity. The expansive additive stimulates the formation of hydration products, which were thermally stable and decompose at temperatures above 600 C.

  2. A marine electromagnetic survey to detect gas hydrate at Hydrate Ridge, Oregon

    NASA Astrophysics Data System (ADS)

    Weitemeyer, K. A.; Constable, S.; Tréhu, A. M.

    2011-10-01

    Gas hydrates are a potential energy resource and hazard for drilling and infrastructure, yet estimates of global volume vary by over three orders of magnitude. Hydrates are electrically resistive compared to water saturated sediment and so electromagnetic methods provide an additional tool to seismic surveys and drilling for determining hydrate saturations. A marine electromagnetic survey was carried out at Hydrate Ridge, Oregon, USA, with the aim of testing the use of controlled source electromagnetic (CSEM) and magnetotelluric (MT) methods to map gas hydrate and free gas below the gas hydrate stability zone. A 2-D CSEM inversion supports the scenario deduced from previous seismic and drilling results, which indicate two mechanisms of hydrate emplacement: a transport-dominated and reaction-dominated regime. A prominent resistive region of 2.5-4 Ωm at a depth of about 130 mbsf, near the seismic bottom simulating reflector (BSR), suggests that 27 to 46 per cent of the bulk volume is filled with hydrate, depending on whether Archie's Law or the Hashin-Strikman bounds are used. This is representative of a reaction-dominated regime for hydrate emplacement, and where a significant low velocity zone exists based on a seismic tomography inversion, suggests large quantities of free gas below the BSR. Electrical resistivity logging while drilling (LWD) data show general agreement with the CSEM inversion model except for a CSEM-derived resistive region at seismic horizon A, known to transport free gas into the gas hydrate stability zone. Inversion of MT data collected simultaneously during the CSEM survey provides a complimentary low-resolution image of the shallow sediments and shows folding in the accretionary complex sediments similar to that imaged by a tomographic seismic velocity model.

  3. Gas Hydrate Nucleation Processes

    NASA Astrophysics Data System (ADS)

    David, R. E.; Zatsepina, O.; Phelps, T. J.

    2003-12-01

    The onset of gas hydrate nucleation is greatly affected by the thermal history of the water that forms its lattice structure. Hydrate formation experiments were performed in a 72 liter pressure vessel by bubbling carbon dioxide through a 1 liter column at hydrate formation pressures (1.4 to 3.7 MPa) and temperatures (275.0 to 278.0 K) to quantify this effect. They show that when even a fraction ( e. g. 20 %) of the water in which hydrate has formed was recently frozen and thawed, the overpressurization for nucleation was reduced by an average of 50 % versus experiments performed in distilled water. In those experiments where a lower overpressure is present when hydrate nucleated, they tended to form on the surface of bubbles, whereas when a higher amount of overpressure was necessary for hydrate to nucleate, they appeared to form abruptly on bubble surfaces as well as from the bulk liquid phase. In approximation of classical nucleation, hydrate formation could be described as occurring by the spontaneous joining together of arising components of the hydrate lattice. In water that was frozen, and kept at a low temperature (< 275 K), molecular simulation models predict the predominance of water molecules organized as penatmeters, a possible subunit of the hydrate lattice. Our results suggest that in nature, initiation of hydrate formation may be strongly influenced by temperature dependant pre-structuring of water molecules prior to their contact with gas.

  4. Hydrocarbon selectivity model for gas-solid Fischer-Tropsch synthesis on precipitated iron catalysts

    SciTech Connect

    Laan, G.P. van der; Beenackers, A.A.C.M.

    1999-04-01

    The kinetics of the gas-solid Fischer-Tropsch (FT) synthesis over a commercial Fe-Cu-K-SiO{sub 2} catalyst was studied in a continuous spinning basket reactor. Experimental conditions were varied as follows: reactor pressure of 0.8--3.2 MPa, H{sub 2}/CO feed ratio = 0.5--2.0, and a space velocity of 0.5--2.0 {times} 10{sup {minus}3} Nm{sup 3}/kg{sub cat} s at a constant temperature of 523 K. A new product distribution model for linear hydrocarbons is proposed. Deviations from conventional Anderson-Schulz-Flory distribution can be quantitatively described with an {alpha}-olefin readsorption product distribution model. The experimentally observed relatively high yield of methane, relatively low yield of ethene, and both the exponential decrease of the olefin-to-paraffin ratio and the change of the chain growth parameter with chain length can all be predicted from this new model. It combines a mechanistic model of olefin readsorption with kinetics of chain growth and termination on the same catalytic sites. The hydrocarbon formation is based on the surface carbide mechanism by CH{sub 2} insertion. The olefin readsorption rate depends on the chain length because of increasing physisorption strength on the catalyst surface and increasing solubility in FT wax with increasing chain length. Interfacial concentrations of reactive olefins near the gas-wax and wax-catalyst surface are used in the kinetic model. With optimization of three parameters per experimental product distribution, the olefin readsorption product distribution model proved to predict product selectivities accurately over the entire range of experimental conditions. The relative deviations are 10.1% and 9.1% for the selectivity to paraffins and olefins with n < 11, respectively.

  5. Dynamics of kinetic energy transfer in homogeneous bidisperse gas-solid flow using particle-resolved direct numerical simulation

    NASA Astrophysics Data System (ADS)

    Mehrabadi, Mohammad; Subramaniam, Shankar

    2015-11-01

    While considerable insight has been gained into the dynamics of energy transfer in monodisperse gas-solid flows, much less is known about polydisperse systems where particles have a size distribution. For instance, the conservation of interphase turbulent kinetic energy transfer (ITKET) principle for monodisperse gas-solid flow (Xu and Subramaniam, Phys. Fluids, 2007) states that the power provided by the mean pressure gradient to sustain a mean slip velocity between the fluid phase and solid phase is equal to the mixture ITKET of the suspension, which is then partitioned into sources of velocity fluctuations in the gas and solid phases. As a first step towards understanding the dynamics of energy transfer in polydisperse suspensions, we analyze the extension of this conservation principle to a bidisperse suspension. Here the mixture ITKET is partitioned into sources of velocity fluctuations of the fluid phase as well as the large and small particle size classes. PR-DNS results of homogeneous bidisperse gas-solid flow are then used to verify this extended conservation principle. With these insights we can begin to answer interesting questions such as the role of energy transfer in promoting segregation or mixing of particle sizes.

  6. A new model for two-dimensional numerical simulation of pseudo-2D gas-solids fluidized beds

    SciTech Connect

    Li, Tingwen; Zhang, Yongmin

    2013-10-11

    Pseudo-two dimensional (pseudo-2D) fluidized beds, for which the thickness of the system is much smaller than the other two dimensions, is widely used to perform fundamental studies on bubble behavior, solids mixing, or clustering phenomenon in different gas-solids fluidization systems. The abundant data from such experimental systems are very useful for numerical model development and validation. However, it has been reported that two-dimensional (2D) computational fluid dynamic (CFD) simulations of pseudo-2D gas-solids fluidized beds usually predict poor quantitative agreement with the experimental data, especially for the solids velocity field. In this paper, a new model is proposed to improve the 2D numerical simulations of pseudo-2D gas-solids fluidized beds by properly accounting for the frictional effect of the front and back walls. Two previously reported pseudo-2D experimental systems were simulated with this model. Compared to the traditional 2D simulations, significant improvements in the numerical predictions have been observed and the predicted results are in better agreement with the available experimental data.

  7. Origins of hydration lubrication.

    PubMed

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-14

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication.

  8. Flow Mapping in a Gas-Solid Riser via Computer Automated Radioactive Particle Tracking (CARPT)

    SciTech Connect

    Muthanna Al-Dahhan; Milorad P. Dudukovic; Satish Bhusarapu; Timothy J. O'hern; Steven Trujillo; Michael R. Prairie

    2005-06-04

    Statement of the Problem: Developing and disseminating a general and experimentally validated model for turbulent multiphase fluid dynamics suitable for engineering design purposes in industrial scale applications of riser reactors and pneumatic conveying, require collecting reliable data on solids trajectories, velocities ? averaged and instantaneous, solids holdup distribution and solids fluxes in the riser as a function of operating conditions. Such data are currently not available on the same system. Multiphase Fluid Dynamics Research Consortium (MFDRC) was established to address these issues on a chosen example of circulating fluidized bed (CFB) reactor, which is widely used in petroleum and chemical industry including coal combustion. This project addresses the problem of lacking reliable data to advance CFB technology. Project Objectives: The objective of this project is to advance the understanding of the solids flow pattern and mixing in a well-developed flow region of a gas-solid riser, operated at different gas flow rates and solids loading using the state-of-the-art non-intrusive measurements. This work creates an insight and reliable database for local solids fluid-dynamic quantities in a pilot-plant scale CFB, which can then be used to validate/develop phenomenological models for the riser. This study also attempts to provide benchmark data for validation of Computational Fluid Dynamic (CFD) codes and their current closures. Technical Approach: Non-Invasive Computer Automated Radioactive Particle Tracking (CARPT) technique provides complete Eulerian solids flow field (time average velocity map and various turbulence parameters such as the Reynolds stresses, turbulent kinetic energy, and eddy diffusivities). It also gives directly the Lagrangian information of solids flow and yields the true solids residence time distribution (RTD). Another radiation based technique, Computed Tomography (CT) yields detailed time averaged local holdup profiles at

  9. Kinetics of the reaction of iron blast furnace slag/hydrated lime sorbents with SO{sub 2} at low temperatures: effects of the presence of CO{sub 2}, O{sub 2}, and NOx

    SciTech Connect

    Liu, C.F.; Shih, S.M.

    2009-09-15

    The effects of the presence of CO{sub 2}, O{sub 2}, and NOx in the flue gas on the kinetics of the sulfation of blast furnace slag/hydrated lime sorbents at low temperatures were studied using a differential fixed-bed reactor. When O{sub 2} and NOx were not present simultaneously, the reaction kinetics was about the same as that under the gas mixtures containing SO{sub 2}, H{sub 2}O, and N{sub 2} only, being affected mainly by the relative humidity. The sulfation of sorbents can be described by the surface coverage model and the model equations derived for the latter case. When both O{sub 2} and NOx, were present, the sulfation of sorbents was greatly enhanced, forming a great amount of sulfate in addition to sulfite. The surface coverage model is still valid in this case, but the model equations obtained show a more marked effect of relative humidity and negligible effects of SO{sub 2} concentration and temperature on the reaction. The effect of sorbent composition on the reaction kinetics was entirely represented by the effects of the initial specific surface area (S{sub g0}) and the Ca molar content (M{sup -1}) of sorbent. The initial conversion rate of sorbent increased linearly with increasing S{sub g0}, and the ultimate conversion increased linearly with increasing S{sub g0}M{sup -1}. The model equations obtained in this work are applicable to describe the kinetics of the sulfation of the sorbents in the low-temperature dry and semidry fine gas desulfurization processes either with an upstream NOx, removal unit or without.111

  10. Mechanism of kinetic energy transfer in homogeneous bidisperse gas-solid flow and its implications for segregation

    NASA Astrophysics Data System (ADS)

    Mehrabadi, Mohammad; Subramaniam, Shankar

    2017-02-01

    Most gas-solid flows encountered in nature and industrial applications are polydisperse, and the segregation or mixing of particle classes in polydisperse gas-solid flows is a phenomenon of great practical importance. A statistically homogeneous gas-solid flow with a bidisperse distribution (in size or density) of particles is a canonical representation of polydisperse flows. A key feature that distinguishes the bidisperse flow from its monodisperse counterpart is the exchange of momentum and kinetic energy between the particle classes due to collisions, which are important for applications outside the very dilute regime. The average exchange of linear momentum between particle classes due to collisions occurs through the particle-particle drag term. The conservation equations for average momentum corresponding to each particle class can be used to deduce the average slip velocity between the particle size and density classes, which is the signature of particle segregation. In this canonical problem, the steady value of particle mean slip velocity results from a balance between three terms, each in turn involving the body force or the mean fluid pressure gradient, the gas-particle drag, and the particle-particle drag. The particle-particle drag depends on the particle velocity fluctuations in each class [Louge, M. Y. et al., "The role of particle collisions in pneumatic transport," J. Fluid Mech. 231, 345-359 (1991)], thereby coupling the mean and second-moment equations. For monodisperse gas-solid flows the transfer of kinetic energy from the mean to second-moment equations was explained by Subramaniam and co-workers who proposed the conservation of interphase turbulent kinetic energy transfer principle [Xu, Y. and Subramaniam, S., "Consistent modeling of interphase turbulent kinetic energy transfer in particle-laden turbulent flows," Phys. Fluids 19(8), 085101 (2007)], and this was subsequently verified by particle-resolved direct numerical simulation [Mehrabadi

  11. Hydration of Acetylene: A 125th Anniversary

    ERIC Educational Resources Information Center

    Ponomarev, Dmitry A.; Shevchenko, Sergey M.

    2007-01-01

    The year 2006 is the 125th anniversary of a chemical reaction, the discovery of which by Mikhail Kucherov had a profound effect on the development of industrial chemistry in the 19-20th centuries. This was the hydration of alkynes catalyzed by mercury ions that made possible industrial production of acetaldehyde from acetylene. Historical…

  12. Hydration of Acetylene: A 125th Anniversary

    ERIC Educational Resources Information Center

    Ponomarev, Dmitry A.; Shevchenko, Sergey M.

    2007-01-01

    The year 2006 is the 125th anniversary of a chemical reaction, the discovery of which by Mikhail Kucherov had a profound effect on the development of industrial chemistry in the 19-20th centuries. This was the hydration of alkynes catalyzed by mercury ions that made possible industrial production of acetaldehyde from acetylene. Historical…

  13. Hydration rate of obsidian.

    PubMed

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years.

  14. QUANTUM MECHANICAL STUDY OF THE COMPETITIVE HYDRATION BETWEEN PROTONATED QUINAZOLINE AND LI+, NA+, AND CA2+ IONS

    EPA Science Inventory

    Hydration reactions are fundamental to many biological functions and environmental processes. The energetics of hydration of inorganic and organic chemical species influences their fate and transport behavior in the environment. In this study, gas-phase quantum mechanical calcula...

  15. QUANTUM MECHANICAL STUDY OF THE COMPETITIVE HYDRATION BETWEEN PROTONATED QUINAZOLINE AND LI+, NA+, AND CA2+ IONS

    EPA Science Inventory

    Hydration reactions are fundamental to many biological functions and environmental processes. The energetics of hydration of inorganic and organic chemical species influences their fate and transport behavior in the environment. In this study, gas-phase quantum mechanical calcula...

  16. Natural gas hydrate in sediments imaged by cryogenic SEM: Insights from lab experiments on synthetic hydrates as interpretive guides.

    NASA Astrophysics Data System (ADS)

    Stern, L. A.; Kirby, S. H.

    2006-12-01

    . Based on lab experiments, we believe the initial liquid product is frozen as a result of the local temperature reduction accompanying the endothermic dissociation reaction. The porous texture is then preserved by liquid nitrogen quenching. (5) Samples from both marine and permafrost environments also display closely juxtaposed regions of dense and porous hydrate and ice. Although the close association of these regions remains puzzling, lab tests verify that dense hydrate can exhibit such porous appearance along it's surface after even minor decomposition at cold conditions (below 273 K). In turn, companion experiments show that nanoporous hydrate anneals to a densely crystalline habit at conditions within the hydrate stability region above 273 K, suggesting that nanoporous gas hydrate is not stable at most in situ natural conditions.

  17. Combustion of Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Roshandell, Melika

    A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding

  18. Methane Hydrates: Chapter 8

    USGS Publications Warehouse

    Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

    2008-01-01

    Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be

  19. DRIFTS studies on the role of surface water in stabilizing catechol-iron(III) complexes at the gas/solid interface.

    PubMed

    Tofan-Lazar, Julia; Situm, Arthur; Al-Abadleh, Hind A

    2013-10-10

    Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. However, little is known about the role of surface water in the complexation of organic acid molecules to transition metals in multicomponent aerosol systems. We report herein results from real time DRIFTS experiments that show in situ complexation of catechol to Fe(III) under humid conditions. Catechol was schosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It was also detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative, and qualitative information about complexes in the bulk, and potential degradation products in the dark. Under dry conditions, DRIFTS spectra show that gas phase catechol adsorbs molecularly and is fully protonated on samples containing FeCl3 with no evidence of complexation to Fe(III). Upon increasing the relative humidity to a value below the deliquescence of FeCl3, surface water facilitates ionic mobility resulting in the formation of monodentate catechol-Fe complexes. These complexes are stable at the gas/solid interface and do not undergo any further degradation in the dark as shown from bulk UV-vis and HPLC experiments. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin films on buildings, and ocean surfaces containing transition metals are discussed.

  20. Transformations in methane hydrates

    USGS Publications Warehouse

    Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Shu, J.; Mao, Ho-kwang; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

    2000-01-01

    Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

  1. Hydrate morphology: Physical properties of sands with patchy hydrate saturation

    USGS Publications Warehouse

    Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.

    2012-01-01

    The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.

  2. Immobilization conditions of ketoreductase on enantioselective reduction in a gas-solid bioreactor.

    PubMed

    Nagayama, Kazuhito; Spiess, Antje C; Büchs, Jochen

    2010-05-01

    The immobilization conditions of commercial ketoreductase for continuous enantioselective reduction in the gas-phase reaction were investigated with respect to the immobilization efficiency (residual activity and protein loading) and the gas-phase reaction efficiency (initial reaction rate, half-life, and enantioselectivity). For the analyses, ketoreductase was first immobilized by physical deposition on glass supports and the reduction of 2-butanone to (S)-2-butanol with the concomitant regeneration of NADH by 2-propanol was used as a model reaction. The optimal conditions of enzyme immobilization were obtained using an absolute pressure of 100 hPa for drying, a pH between 6.5 and 7.0, and a buffer concentration of 50 mM. The buffer concentration in particular had a strong effect on both the enzyme activity and enantioselectivity. Under optimal immobilization conditions, the thermostability of ketoreductase in the gas-phase system was enhanced compared to the aqueous-phase system, while the enantioselectivity was successfully maintained at a level identical to that of the native enzyme. These results indicate that the gas-phase reaction has a great potential for industrial production of chiral compounds, but requires careful optimization of immobilization conditions for the reaction to progress effectively.

  3. Scanning electron microscopy investigations of laboratory-grown gas clathrate hydrates formed from melting ice, and comparison to natural hydrates

    USGS Publications Warehouse

    Stern, L.A.; Kirby, S.H.; Circone, S.; Durham, W.B.

    2004-01-01

    Scanning electron microscopy (SEM) was used to investigate grain texture and pore structure development within various compositions of pure sI and sII gas hydrates synthesized in the laboratory, as well as in natural samples retrieved from marine (Gulf of Mexico) and permafrost (NW Canada) settings. Several samples of methane hydrate were also quenched after various extents of partial reaction for assessment of mid-synthesis textural progression. All laboratory-synthesized hydrates were grown under relatively high-temperature and high-pressure conditions from rounded ice grains with geometrically simple pore shapes, yet all resulting samples displayed extensive recrystallization with complex pore geometry. Growth fronts of mesoporous methane hydrate advancing into dense ice reactant were prevalent in those samples quenched after limited reaction below and at the ice point. As temperatures transgress the ice point, grain surfaces continue to develop a discrete "rind" of hydrate, typically 5 to 30 ??m thick. The cores then commonly melt, with rind microfracturing allowing migration of the melt to adjacent grain boundaries where it also forms hydrate. As the reaction continues under progressively warmer conditions, the hydrate product anneals to form dense and relatively pore-free regions of hydrate grains, in which grain size is typically several tens of micrometers. The prevalence of hollow, spheroidal shells of hydrate, coupled with extensive redistribution of reactant and product phases throughout reaction, implies that a diffusion-controlled shrinking-core model is an inappropriate description of sustained hydrate growth from melting ice. Completion of reaction at peak synthesis conditions then produces exceptional faceting and euhedral crystal growth along exposed pore walls. Further recrystallization or regrowth can then accompany even short-term exposure of synthetic hydrates to natural ocean-floor conditions, such that the final textures may closely mimic

  4. APPARATUS FOR SHORT TIME MEASUREMENTS IN A FIXED-BED, GAS/SOLID REACTOR

    EPA Science Inventory

    An apparatus for exposure of a solid to reactive process gas is described which makes possible short time (≥ 0.3 to 15 s) exposures in a fixed-bed reactor. Operating conditions for differential reaction with respect to the gas concentration and rapid quench for arresting hi...

  5. APPARATUS FOR SHORT TIME MEASUREMENTS IN A FIXED-BED, GAS/SOLID REACTOR

    EPA Science Inventory

    An apparatus for exposure of a solid to reactive process gas is described which makes possible short time (≥ 0.3 to 15 s) exposures in a fixed-bed reactor. Operating conditions for differential reaction with respect to the gas concentration and rapid quench for arresting hi...

  6. Study By Uv-visible Spectrometry of Gas/solid Interactions In Titan's Simulated Atmosphere, A.k.a. How Aerosols Are Formed On Titan ?

    NASA Astrophysics Data System (ADS)

    Bernard, J.-M.; Coll, P.; Jolly, A.; Bénilan, Y.; Cernogora, G.; Raulin, F.

    The atmospheric chemistry on Titan is reproduced during laboratory simulation ex- periments since several years. The device we developed at LISA leaded to the identi- fication of 70 gaseous compounds (46 hydrocarbons and 24 nitrogenous compounds), while the chemical composition of the solid phase is still not known in spite of IR spectrometry and pyrolysis analysis. These simulations are based on a initial mixture of N2/CH4, submitted to a glow discharge, at continuous flow and at low temperature in order to simulate as well as possible Titan's atmosphere. The highlighting identi- fication of C4N2, detected on Titan but never identified previously in experimental simulations, validates the representativity of the LISA experiment. The aim of the project presented today is a UV-visible spectrometry in situ study of the reactional environment where are produced the solid phase, considered as an analogue of Titan's aerosols. The analysis of the evolution of the compounds (molecules/radicals/ions) present in the reactor will allow the identification of those responsible of the building of the solid phase, at gas/solid interface. A second step will be the modeling of the mechanisms taking place in the reactor, which are very badly known at the present time. The final stage of this work will be to use a full theoretical model of plasma chemistry, still developed. We will present today the first results obtained by emission spectroscopy, during an experimental simulation of Titan's atmosphere, and point out the decreasing of some compounds in parallel to the formation of solid phase.

  7. Erratum to “On the gas-solid difference in stopping power for low energy ions” [Nucl. Instr. and Meth. B 262 (2007) 13

    NASA Astrophysics Data System (ADS)

    Paul, Helmut

    2008-03-01

    Recently, we claimed that the gas-solid difference in stopping powers persists from high down to low ion energies. This claim was based on a comparison between experimental data and the table of ICRU Report 73. We reconsider this claim in view of a recent article by Sigmund and Schinner where the claim was rejected. We find that the apparent gas-solid difference shown in our calculations is an artifact: it really points to an inadequacy of the table of ICRU 73 for low energy ions.

  8. Free energy landscape and molecular pathways of gas hydrate nucleation

    NASA Astrophysics Data System (ADS)

    Bi, Yuanfei; Porras, Anna; Li, Tianshu

    2016-12-01

    Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), pB histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the pB histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

  9. A new type of electrostatic sensor for velocity measurement of gas/solid two-phase flows

    NASA Astrophysics Data System (ADS)

    Deng, Xiang; Gao, Qian; Hu, Jing; Li, Guangyu

    2012-03-01

    Electrostatic sensor is used in gas/solid two-phase flow measurement, because of its simple structure, high sensitivity, low cost, safety, etc. However, there are still some issues need to be further investigated and discussed, such as sensing structural optimization, measuring model simplification and verification, more practical electrostatic sensor research and development, etc. In this paper, a new structure of sensor is designed on the basis of circle electrostatic sensor. Three-dimensional mathematical model of electrostatic sensor is established on the basis of point charge, and its numerical solution is studied. The effects of structural parameters (such as sizes of electrodes, etc) and location distribution of flowing particles in the sensing field of the new electrostatic sensor are investigated systematically. A theoretical basis for the performance improvement and design optimization of the sensor are provided.

  10. Dry Scrubbing of Aluminum Cell Gases: Design and Operating Characteristics of a Novel Gas/Solids Reactor

    NASA Astrophysics Data System (ADS)

    Lamb, W. D.; Reeve, Martin R.; Dethloff, F. H.; Leinum, Magne

    1982-11-01

    Engineering details of a pilot plant reactor are described. It comprises a vertical cylindrical vessel with a tangential bottom gas entry. Countercurrent spiraling gas-solids flow is achieved. Reacted solids can be withdrawn from the bottom or the top using a rising axial gas jet. The reactor was evaluated by testing in a dry scrubber system treating 14,000 m3/h of gas from prebake cells. At inlet concentrations of 30-60 mg/m3 it achieved 99.5% scrubbing efficiency with aluminas of a surface area of 45-80 m2/g at feed rates considerably less than cell requirements. Potential benefits are: 1) control of metal purity by segregation of scrubber catch to selected cells, 2) scrubbing high HF inlet concentrations at full feed rate, and 3) meeting more stringent working environment and stack emission requirements.

  11. Application of electrical capacitance tomography for measurement of gas-solids flow characteristics in a pneumatic conveying system

    NASA Astrophysics Data System (ADS)

    Jaworski, Artur J.; Dyakowski, Tomasz

    2001-08-01

    Transient three-dimensional multiphase flows are a characteristic feature of many industrial processes. The experimental observations and measurements of such flows are extremely difficult, and industrial process tomography has been developed over the last decade into a reliable method for investigating these complex phenomena. Gas-solids flows, such as those in pneumatic conveying systems, exhibit many interesting features and these can be successfully investigated by using electrical capacitance tomography. This paper discusses the current state of the art in this field, advantages and limitations of the technique and required future developments. Various levels of visualization and processing of tomographic data obtained in a pilot-plant-scale pneumatic conveying system are presented. A case study outlining the principles of measuring the mass flow rate of solids in a vertical channel is shown.

  12. Mineral Reaction Buffering of Venus' Atmosphere: Constraints for Terrestrial Exoplanets

    NASA Astrophysics Data System (ADS)

    Treiman, A. H.; Bullock, M. A.

    2011-12-01

    For many years, it has been suggested that the composition of Venus' atmosphere, notably its abundance of CO2, is controlled by gas-solid reactions at its surface. However, the suggested reaction for Venus atmosphere, CaCO3 + SiO2 = CaSiO3 + CO2, cannot act as a buffer - the pressure-temperature trajectory of the reaction and that of the atmosphere (a dry adiabat) do not provide buffering capacity. Instead, perturbations to T or P(CO2) would produce catastrophic expansion or collapse of the atmosphere. This instability can be generalized to all devolatilization reactions that produce a radiatively active gas in a planetary atmosphere dominated by such gases, and gives a simple thermochemical criterion for whether a reaction could buffer such an atmosphere. Simple decarbonation reactions fail this criterion, implying that the abundance of CO2 in a CO2-dominated atmosphere cannot be buffered by chemical reactions with the surface. The same inference holds for the abundance of H2O in an H2O-dominated (steam) atmosphere (e.g., exoplanet GJ 1214b), and for the abundance of methane above a methane-hydrate ice surface (e.g., a Titan-like exoplanet). Buffering of minor gases is more likely; the proposed mineral buffer reaction for SO2 in the Venus atmosphere (FeS2 + CO2 = Fe3O4 + SO2 + CO) passes the thermochemical criterion, as does a reaction involving Ca sulfate (CaSO4 + CO = CaCO3 + SO2). These inferences can be generalized to extrasolar Venus-like planets - those with surfaces hot enough to permit rapid chemical reactions between solids and gas, yet cool enough that their atmospheres contain (are dominated by) gases active in thermal radiative equilibria. On the other hand, it seems likely that abundances of minor atmospheric gas species can be buffered by crust-atmosphere chemical reactions. So, minor species in exoplanet atmospheres may be particularly important for constraining the chemical characteristics of their surfaces.

  13. Blue-colored tert-butylamine clathrate hydrate.

    PubMed

    Tani, Atsushi; Koyama, Satoshi; Urabe, Yusuke; Takato, Kenji; Sugahara, Takeshi; Ohgaki, Kazunari

    2014-11-26

    Clathrate hydrates preserve active species more stably than the other icy materials and investigation of the behavior of the active species elucidates the physicochemical properties of clathrate hydrates like guest-guest interaction. Color of the tert-butylamine clathrate hydrate changes to blue after gamma irradiation and is bleachable with visible light. The electron spin resonance (ESR) spectrum at 120 K mainly consists of a triplet signal of the C-centered radical NH2C(CH3)2CH2• together with a single signal at g = 2.0008. The latter signal disappears after light exposure. These results indicate that both the blue color and the single ESR signal are derived from trapped electrons in the hydrate. They thermally decay around 140-160 K by the first-order reaction, and the activation energy is 27 kJ/mol. Since tert-butylamine molecules can capture protons due to the high proton affinity, electrons may remain in the hydrate without reacting with protons, making the hydrate blue after gamma irradiation. The long-lived trapped electrons in the tert-butylamine hydrate have an advantage to investigate those in icy materials because tert-butylamine hydrate is nonionic and has a tetra-coordinated host water network like crystalline ice without any substitution for water molecules.

  14. HYDRATE CORE DRILLING TESTS

    SciTech Connect

    John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

    2002-11-01

    The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate formation comprised of coarse, large

  15. The effect of polymethylsiloxanes on hydration of clinker phases

    NASA Astrophysics Data System (ADS)

    Stoch, A.; Zdaniewicz, M.; Paluszkiewicz, Cz.

    1999-11-01

    The effect of the polydimethylsiloxane (PDMS) admixture on hydration of pure clinker phases: alite, belite or tricalcium aluminate was studied by means of FTIR spectroscopy. It was shown that PDMS, introduced to a clinker phase paste during the hydration process reduces the carbonation reaction, improves the crystallization of hydrates in tricalcium aluminate and considerably increases water resistance without significantly changing the mechanical parameters. Our FTIR results were also confirmed by XRD, DTA and SEM study of the morphology of the newly formed phases. Introduction of as much as 5 wt.% of the PDMS increases the wetting angle by up to 80-120°.

  16. Hydrated metal ions in the gas phase.

    PubMed

    Beyer, Martin K

    2007-01-01

    Studying metal ion solvation, especially hydration, in the gas phase has developed into a field that is dominated by a tight interaction between experiment and theory. Since the studied species carry charge, mass spectrometry is an indispensable tool in all experiments. Whereas gas-phase coordination chemistry and reactions of bare metal ions are reasonably well understood, systems containing a larger number of solvent molecules are still difficult to understand. This review focuses on the rich chemistry of hydrated metal ions in the gas phase, covering coordination chemistry, charge separation in multiply charged systems, as well as intracluster and ion-molecule reactions. Key ideas of metal ion solvation in the gas phase are illustrated with rare-gas solvated metal ions.

  17. Dynamics of protein hydration water

    NASA Astrophysics Data System (ADS)

    Wolf, M.; Emmert, S.; Gulich, R.; Lunkenheimer, P.; Loidl, A.

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water.

  18. Dynamics of protein hydration water.

    PubMed

    Wolf, M; Emmert, S; Gulich, R; Lunkenheimer, P; Loidl, A

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water.

  19. Hydration process of nuclear-waste glass: an interim report

    SciTech Connect

    Bates, J.K.; Jardine, L.J.; Steindler, M.J.

    1982-07-01

    Aging of simulated nuclear waste glass by contact with a controlled-temperature, humid atmosphere results in the formation of a double hydration layer penetrating the glass, as well as the formation of minerals on the glass surface. The hydration process can be described by Arrhenius behavior between 120 and 240/sup 0/C. Results suggest that simulated aging reactions are necessary for demonstrating that nuclear waste forms can meet projected Nuclear Regulatory Commission regulations. 16 figures, 4 tables.

  20. Formation of nitric acid hydrates - A chemical equilibrium approach

    NASA Technical Reports Server (NTRS)

    Smith, Roland H.

    1990-01-01

    Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

  1. Gas-solid flows - 1986; Proceedings of the Fourth Fluid Mechanics, Plasma Dynamics, and Lasers Conference, Atlanta, GA, May 11-14, 1986

    NASA Astrophysics Data System (ADS)

    Jurewicz, J. T.

    Papers are presented on deposition and resuspension of gas-borne particles in recirculating turbulent flows, particle dispersion in decaying isotropic homogeneous turbulence, turbulent dispersion of droplets for air flow in a pipe, a comparison between Lagrangian and Eulerian model approaches to turbulent particle dispersion, and the effect of turbulent electrohydrodynamics on electrostatic precipitator efficiency. Also considered are errors due to turbidity in particle sizing using laser Doppler velocimetry, particle motion in a fluidically oscillating jet, high pressure steam/water jet measurements using a portable particle sizing laser Doppler system, the effect of particle shape on pressure drop in a turbulent gas/solid suspension, and the experimental study of gas solid flows in pneumatic conveying. Other topics include entropy production and pressure loss in gas-solid flows, a computational study of turbulent gas-particle flow in a Venturi, a numerical analysis of confined recirculating gas-solid turbulent flows, nozzle and free jet flows of gas particle mixtures, and particle separation in pulsed airflow. Papers are also presented on sampling of solid particles in clouds, particle motion near the inlet of a sampling probe, the effects of slot injection on blade erosion in direct coal-fueled gas turbines, bed diameter effects and incipient slugging in gas fluidized beds, and sedimentation of air fluidized fine graphite particles by methanol vapor.

  2. Aluminum Sulfate 18 Hydrate

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  3. Aluminum Sulfate 18 Hydrate

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  4. Effect of a chemical modification on the hydrated adenosine intermediate produced by adenosine deaminase and a model reaction for a potential mechanism of action of 5-aminoimidazole ribonucleotide carboxylase.

    PubMed

    Groziak, M P; Huan, Z W; Ding, H; Meng, Z; Stevens, W C; Robinson, P D

    1997-10-10

    Using the hydrated adenosine intermediate (6R)-6-amino-1, 6-dihydro-6-hydroxy-9-(beta-D-ribofuranosyl)purine (2) produced by adenosine deaminase (ADA, EC 3.5.4.4) as a starting point, the active site probe and inhibitor platform 5-(formylamino)imidazole riboside (FAIRs, 4) was designed by removal of the-C6(OH)(NH2)-molecular fragment of 2 generated by the early events of the enzyme-catalyzed hydrolysis. FAIRs was synthesized directly from the sodium salt of 5-amino-1-(beta-D-ribofuranosyl)imidazole-4-carboxylic acid (CAIR) along a reaction sequence involving a tandem N-formylation/decarboxylation that may have a mechanistic connection to the Escherichia coli purE-catalyzed constitutional isomerization of N5-CAIR to CAIR. The physical and spectral properties of FAIRs were elucidated, its X-ray crystal and NMR solution structures were determined, and its interaction with ADA was investigated. Crystalline FAIRs exists solely as the Z-formamide rotamer and exhibits many of the same intramolecular hydrogen bonding events known to contribute to the association of Ado to ADA. In water and various organic solvents, however, FAIRs exists as NMR-distinct, slowly interconverting Z and E rotamers. This truncated enzymatic tetrahedral intermediate analog was determined to be a competitive inhibitor of ADA with an apparent Ki binding constant of 40 microM, a value quite close to that (33 microM) of the natural substrate's K(m). The actual species selected for binding by ADA, though, is likely the minor hydroxyimino prototropic form of Z-FAIRs possessing a far lower true Ki value. As the structural features of FAIRs appear well-suited to support its use as a template for constructing active site probes of both ADA and AIR carboxylases, a variety of carbohydrate-protected versions of FAIRs suitable for facile aglycon elaborations were synthesized. The N3-alkylation, N3-borane complexation, and C4-iodination of some of these were investigated in order to assess physicochemical

  5. Electrical properties of methane hydrate + sediment mixtures

    NASA Astrophysics Data System (ADS)

    Du Frane, W. L.; Stern, L. A.; Constable, S.; Weitemeyer, K. A.; Roberts, J. J.

    2011-12-01

    Electromagnetic (EM) remote-sensing techniques are demonstrated to be sensitive to gas hydrate concentration and distribution, which complements seismic and other existing resource assessment techniques. Full utilization of EM results requires knowledge of the electrical properties of gas hydrates, mixed phases, and mixing relations. We developed a pressure cell to synthesize gas hydrate while measuring in situ frequency-dependent impedance (Z) and electrical conductivity (σ). Starting samples consisted of either (1) granular ice ( 200 microns grain size) packed to about 25% intergranular porosity, (2) granular ice uniformly mixed with quartz sand (OK#1, 125±50 micron grain size) in various proportions, or (3) ice uniformly mixed with silica glass beads (115±10 micron diameter). The ice was then fully reacted into methane (CH4) hydrate by applying CH4 pore pressure during temperature cycling above and below the ice/water phase boundary. Sediment distribution and grain-scale characterization were determined by post run cryogenic scanning electron microscopy and confirmed no migration of the sediment phase during reaction. Z and σ were measured in samples after hydrate synthesis from -15 to 15 °C, and after dissociation of hydrate into ice from -15 to -2 °C. We determined the σ of unmixed CH4 hydrate to be 10^1.5S/m*exp{(30.6kJ/mol)/RT} and 10^5.0S/m*exp{(45.3kJ/mol)/RT} after dissociation to unmixed ice. For the mixed samples the overall σ measured included significant contribution by surface σ along weathered surfaces of sediments. Samples containing < 30 vol% sand had poorly connected sediment below the percolation threshold, resulting in only a slight increase of up to 0.3 log units in σ and little change in activation energy (Ea) compared to unmixed samples. Conversely, samples containing 47 vol% sand had interconnected sediment above the percolation threshold, with a large increase of 0.7-1.2 log units in σ and a large 80% decrease in Ea. Glass beads

  6. The Methane Hydrate Reservoir System

    NASA Astrophysics Data System (ADS)

    Flemings, P. B.; Liu, X.

    2007-12-01

    We use multi phase flow modeling and field examples (Hydrate Ridge, offshore Oregon and Blake Ridge, offshore North Carolina) to demonstrate that the methane hydrate reservoir system links traditional and non- traditional hydrocarbon system components: free gas flow is a fundamental control on this system. As in a traditional hydrocarbon reservoir, gas migrates into the hydrate reservoir as a separate phase (secondary migration) where it is trapped in a gas column beneath the base of the hydrate layer. With sufficient gas supply, buoyancy forces exceed either the capillary entry pressure of the cap rock or the fracture strength of the cap rock, and gas leaks into the hydrate stability zone, or cap rock. When gas enters the hydrate stability zone and forms hydrate, it becomes a very non traditional reservoir. Free gas forms hydrate, depletes water, and elevates salinity until pore water is too saline for further hydrate formation: salinity and hydrate concentration increase upwards from the base of the regional hydrate stability zone (RHSZ) to the seafloor and the base of the hydrate stability zone has significant topography. Gas chimneys couple the free gas zone to the seafloor through high salinity conduits that are maintained at the three-phase boundary by gas flow. As a result, significant amounts of gaseous methane can bypass the RHSZ, which implies a significantly smaller hydrate reservoir than previously envisioned. Hydrate within gas chimneys lie at the three-phase boundary and thus small increases in temperature or decreases in pressure can immediately transport methane into the ocean. This type of hydrate deposit may be the most economical for producing energy because it has very high methane concentrations (Sh > 70%) located near the seafloor, which lie on the three-phase boundary.

  7. Colorado Plateau Uplift Through Deep Crustal Hydration?

    NASA Astrophysics Data System (ADS)

    Butcher, L. A.; Mahan, K. H.; Jones, C. H.; Farmer, G.

    2013-12-01

    The conventional view of plate tectonics restricts deformation to plate boundaries and does not account for regionally elevated topography in continental interiors. Thermal, mechanical or chemical alteration of ancient continental lithosphere is a mechanism sometimes invoked to explain intracratonic uplift in the western U.S. although the timing, extent and effects of this modification are poorly understood. Here we present new petrological and in situ geochronological data for a hydrated deep crustal xenolith from the Colorado Plateau and investigate the effects of deep crustal hydration on topography. Two distinct mineral assemblages recorded in a garnet biotite schist xenolith from the Navajo Volcanic Field, Four Corners region document hydration subsequent to peak metamorphism in the deep crust whereby the primary metamorphic assemblage (Gt + Bt + Ms + Pl + Kfs + Qtz) is variably replaced by a lower-density, hydrated assemblage (Ab + Ph + Cc + Rt). Results from forward petrological modeling constrain hydration at ≥ 20 km (0.65 GPa, 450 °C) prior to exhumation in the ˜20 Ma volcanic host. In situ Th/Pb dating of secondary monazite grains spatially associated with fluid-related plagioclase and allanite breakdown reveals a significant majority of Late Cretaceous dates from 91 to 58 Ma. These dates are interpreted to reflect a finite period of deep crustal hydration, possibly by fluids sourced from a shallowly subducting Farallon slab. Xenolith data additionally supports crustal hydration as a mechanism for producing regionally elevated topography. Fluid-related reactions in the deep crust may lead to a net density decrease as low-density hydrous phases (e.g. Ms + Amp + Cc) replace high-density, anhydrous minerals (e.g. Gt + Fsp + Opx + Cpx) abundant in high-pressure, high-temperature assemblages preserved in Proterozoic North American lithosphere. If these reactions are sufficiently pervasive and widespread, reductions in lower crustal density would provide a

  8. Synthesis and characterization of a new structure of gas hydrate

    SciTech Connect

    Tulk, Christopher A; Chakoumakos, Bryan C; Ehm, Lars; Klug, Dennis D; Parise, John B; Yang, Ling; Martin, Dave; Ripmeester, John; Moudrakovski, Igor; Ratcliffe, Chris

    2009-01-01

    Atoms and molecules 0.4 0.9 nm in diameter can be incorporated in the cages formed by hydrogen-bonded water molecules making up the crystalline solid clathrate hydrates. There are three structural families of these hydrates , known as sI, sII and sH, and the structure usually depends on the largest guest molecule in the hydrate. Species such as Ar, Kr, Xe and methane form sI or sII hydrate, sH is unique in that it requires both small and large cage guests for stability. All three structures, containing methane, other hydrocarbons, H2S and CO2, O2 and N2 have been found in the geosphere, with sI methane hydrate by far the most abundant. At high pressures (P > 0.7 kbar) small guests (Ar, Kr, Xe, methane) are also known to form sH hydrate with multiple occupancy of the largest cage in the hydrate. The high-pressure methane hydrate of sH has been proposed as playing a role in the outer solar system, including formation models for Titan , and yet another high pressure phase of methane has been reported , although its structure remains unknown. In this study, we report a new and unique hydrate structure that is derived from the high pressure sH hydrate of xenon. After quench recovery at ambient pressure and 77 K it shows considerable stability at low temperatures (T < 160 K) and is compositionally similar to the sI Xe clathrate starting material. This evidence of structural complexity in compositionally similar clathrate compounds indicates that thermodynamic pressure temperature conditions may not be the only important factor in structure determination, but also the reaction path may have an important effect.

  9. The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

    NASA Astrophysics Data System (ADS)

    Guan, Jinan; Liang, Deqing; Wu, Nengyou; Fan, Shuanshi

    2009-10-01

    It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m -2 a -1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10 9 m 3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

  10. Transparent organosilica photocatalysts activated by visible light: photophysical and oxidative properties at the gas-solid interface.

    PubMed

    Arzoumanian, Emmanuel; Ronzani, Filippo; Trivella, Aurélien; Oliveros, Esther; Sarakha, Mohamed; Richard, Claire; Blanc, Sylvie; Pigot, Thierry; Lacombe, Sylvie

    2014-01-08

    The photophysical properties of several photosensitizers (PSs) included or grafted in silica monoliths were compared to their properties in solution. The effects of the solid support on their steady-state and transient absorption spectra, on their quantum yields of singlet oxygen ((1)O2) production, and on their ability to photoinduce the oxidation of dimethylsulfide (DMS) were investigated. Two cyanoanthracene derivatives (9,14-dicyanobenzo[b]triphenylene, DBTP, and 9,10-dicyanoanthracene, DCA), as well as three phenothiazine dyes (methylene blue, MB(+), new methylene blue, NMB(+), methylene violet, MV), were encapsulated in silica, analyzed and compared to two reference PSs (perinaphthenone, PN and rose bengal, RB). A DBTP derivative (3-[N-(N″-triethoxysilylpropyl-N'-hexylurea)]carboxamido-9,14-dicyanobenzo[b]triphenylene, 3) was also prepared and grafted onto silica. Thanks to the transparency and the free-standing shape of the monoliths, the complete spectroscopic characterization of the supported PSs was carried out directly at the gas-solid interface. The influence of the silica network, the PS, and the adsorption/grafting link between the PS and silica was investigated. The effects of PS concentration, gaseous atmosphere, humidity, and hydrophobicity on the production of (1)O2 were analyzed. With all PSs, (1)O2 production was very efficient (quantum yields of (1)O2 production, relative to PN, between 0.6 and 1), and this species was the only one involved in the pollutant photooxidation. The influence of the matrix on the PSs' photophysics could be considered as negligible. In contrast, the matrix effect on DMS photooxidation was extremely important: the gas diffusion inside the porous structure, and thus, the photoactivity of the materials, strictly depended on silica's surface area and porosity. Our results highlight the suitability of these silica structures as inert supports for the study of the photosensitizing properties at the gas-solid interface

  11. A pressurized thermogravimetric analyzer for use in studies of gas/solid systems. First technical report

    SciTech Connect

    Mitchell, R.E.

    1993-09-22

    A TG-151 Thermogravimetric Experimental Station, which measures and records weight changes of a solid material over a wide dynamic temperature range at a wide range of pressures in controlled environments, was purchased from Cahn Instruments, Inc. The TG-151 permits temperature to be programmed to follow a precise temperature profile of ramp and/or isothermal segments while monitoring the changes in weight of solid samples exposed to a gaseous environment of specified composition at a preset pressure. Weight and temperature measurements are made at user-specified time intervals and total time (up to 48 hours). Data are stored on the disk of a dedicated computer. The data can be processed by a data analysis program or exported to spreadsheet programs. The pressure vessel is designed to operate in vacuum to 10{sup {minus}5} torr and over a wide range of pressures. At normal room temperature, the TG-151 can operate up to 100 atm and at 1273 K, it can operate up to 70 atm. The null balance has a sensitivity of 10 micrograms, capacity up to 100 grams, and a dynamic range of 10{sup 6}:1. Both reducing and oxidizing environments can be established in the reaction chamber. For our specific needs the instrument had to be slightly modified to allow for two reactant gas streams to enter the pressure vessel at prescribed times. This required the purchase and installation of a gas blending system. The gas blending system permits coal and char samples to be heated at a specified rate to a desired temperature in an inert environment before the sample is exposed to an oxidizing environment.

  12. Volatile organic compound adsorption in a gas-solid fluidized bed.

    PubMed

    Ng, Y L; Yan, R; Tsen, L T S; Yong, L C; Liu, M; Liang, D T

    2004-01-01

    Fluidization finds many process applications in the areas of catalytic reactions, drying, coating, combustion, gasification and microbial culturing. This work aims to compare the dynamic adsorption characteristics and adsorption rates in a bubbling fluidized bed and a fixed bed at the same gas flow-rate, gas residence time and bed height. Adsorption with 520 ppm methanol and 489 ppm isobutane by the ZSM-5 zeolite of different particle size in the two beds enabled the differentiation of the adsorption characteristics and rates due to bed type, intraparticle mass transfer and adsorbate-adsorbent interaction. Adsorption of isobutane by the more commonly used activated carbon provided the comparison of adsorption between the two adsorbent types. With the same gas residence time of 0.79 seconds in both the bubbling bed and fixed bed of the same bed size of 40 mm diameter and 48 mm height, the experimental results showed a higher rate of adsorption in the bubbling bed as compared to the fixed bed. Intraparticle mass transfer and adsorbent-adsorbate interaction played significant roles in affecting the rate of adsorption, with intraparticle mass transfer being more dominant. The bubbling bed was observed to have a steeper decline in adsorption rate with respect to increasing outlet concentration compared to the fixed bed. The adsorption capacities of zeolite for the adsorbates studied were comparatively similar in both beds; fluidizing, and using smaller particles in the bubbling bed did not increase the adsorption capacity of the ZSM-5 zeolite. The adsorption capacity of activated carbon for isobutane was much higher than the ZSM-5 zeolite for isobutane, although at a lower adsorption rate. Fourier transform infra-red (FTIR) spectroscopy was used as an analytical tool for the quantification of gas concentration. Calibration was done using a series of standards prepared by in situ dilution with nitrogen gas, based on the ideal gas law and relating partial pressure to gas

  13. The Hydrated Electron

    NASA Astrophysics Data System (ADS)

    Herbert, John M.; Coons, Marc P.

    2017-05-01

    Existence of a hydrated electron as a byproduct of water radiolysis was established more than 50 years ago, yet this species continues to attract significant attention due to its role in radiation chemistry, including DNA damage, and because questions persist regarding its detailed structure. This work provides an overview of what is known in regards to the structure and spectroscopy of the hydrated electron, both in liquid water and in clusters [Formula: see text], the latter of which provide model systems for how water networks accommodate an excess electron. In clusters, the existence of both surface-bound and internally bound states of the excess electron has elicited much debate, whereas in bulk water there are questions regarding how best to understand the structure of the excess electron's spin density. The energetics of the equilibrium species e-(aq) and its excited states, in bulk water and at the air/water interface, are also addressed.

  14. Hydration of cyanin dyes

    NASA Astrophysics Data System (ADS)

    Calzolari, Arrigo; Monti, Susanna; Ruini, Alice; Catellani, Alessandra

    2010-03-01

    We investigated the hydration properties of the cyanin dye molecule in the ionic flavylium configuration, through massive classical (force field) and ab initio (Car-Parrinello) molecular dynamics simulations at room temperature. Classical and quantum mechanical results coherently describe the structure of the first solvation shell. We discuss the hydrophobicity/hydrophilicity of the molecule in terms of attractive lateral hydroxyl-water and repulsive carbon π-water interactions. The analysis of the electronic structure shows a net polarization and a molecular orbital redistribution induced by the polar solvent on the intrinsic (gas phase) properties of the dye. Changing the properties of the molecule, the hydration effects should be carefully taken into account in the further interactions of cyanin with the external environment.

  15. Modeling and Prediction of the Effects of Collisions in a Gas-Solid Turbulent Channel Flow Using Moment Methods

    NASA Astrophysics Data System (ADS)

    Dunn, Dennis; Squires, Kyle

    2015-11-01

    Modeling dispersions of particles in multiphase flows is especially challenging in gas-solid suspensions. Lagrangian methods are suitable for dilute particle mediums, but are not cost effective at denser concentrations and impose additional modeling challenges. A moderately dense particle phase is neither sufficiently dense for a continuum limit assumption (collisional equilibrium) nor sufficiently dilute for a Lagrangian method, and resides in the intermediate regime under consideration in the current work. A quadrature-based moment method (QBMM) is chosen to simulate a particle-laden turbulent channel flow considering inter-particle collision effects. In quadrature-based approaches similarly behaving particles may be grouped together and treated in a stochastic manner within an Eulerian framework. Specifically, the Conditional Quadrature Method of Moments (CQMOM) is implemented to discretize a fully 3-D velocity space and capture particle trajectory crossing (PTC). This has the potential for large computational savings as compared to Lagrangian methods, especially when dense collisions are prominent. The probability density function is discretized with a two-point-quadrature in each dimension - the minimum requirement to capture PTC and enforce collisions. Predictions of the channel flow demonstrate that the collision treatment leads to the expected effects (e.g., redistribution of kinetic energy) and also offer improved accuracy relative to simpler approaches.

  16. Experimental Study on Gas-Solid Flow Charcteristics in a CFB Riser Of 54M in Height

    NASA Astrophysics Data System (ADS)

    Hu, N.; Yang, H. R.; Zhang, H.; Zhang, R. Q.; Cao, J. N.; Liu, Q.; Lu, J. F.; Yue, G. X.

    Understanding the height effect on the gas-solid flow characteristics in a CFB riser is important as more and more large capacity CFB boilers are used and to be developed. In this study, a cold CFB test rig with a riser of 240mm in LD. and 38m and 54m in height was built. The influences of operating conditions, such as solid inventory and fluidizing gas velocity, on the axial voidage profile along the riser were assessed. When the gas velocity exceeds the transport velocity, the S-shaped profile of voidage in the riser was established. At the same time, the voidage in top-dilute section reached the saturation carrying capacity, and the solids circulation rate did not vary with the height of the riser nor the solids inventory. It was also found the critical solids inventory for the saturation carrying capacity increases as the riser height increases. When the height was changed from 38m to 54m, the critical solids inventory increased about 25% from about 40kg to about 50kg, and pressure drop in the furnace also increased about 25%.

  17. Asymptotic theory of two-phase gas-solid flow through a vertical tube at moderate pressure gradient

    NASA Astrophysics Data System (ADS)

    Sergeev, Y. A.; Zhurov, A. I.

    1997-02-01

    Based on the equations, constitutive relations and boundary conditions of the kinetic theory of colliding particles in a gas-solid suspension, the approximate theory of the steady, developed vertical flow of a gas-particulate mixture is developed for the case of moderate gas pressure gradient in a vertical tube. The basic equations and boundary conditions show a singular behaviour of the solution of the problem at the wall. The method of matched asymptotic expansions is applied to develop a boundary layer-type theory for the flow parameters of the particulate phase. The basic equations in the bulk flow are reduced to a system of two ordinary integrodifferential equations for the particle-phase concentration and mean kinetic energy of particle velocity fluctuations (particle-phase pseudotemperature). The distributions of the particle concentration and velocity are found in both the bulk and the boundary layer. The solutions shows the bifurcation of flow parameters, and an explicit criterion is derived to identify a range of the given macroscopic parameters corresponding to upward or downward particulate flow. The integrated parameters (total fluxes of the gas and particle phase) are calculated.

  18. An Improved Pneumatic Nebulization Gas-Solid Microextraction Device Used to Detect Triazine Herbicides in White Spirit.

    PubMed

    Xu, Hui; Fei, Qiang; Shan, Hongyan; Huan, Yanfu; Mi, Hongyu; Zhang, Hanqi; Li, Guanghua; Feng, Guodong

    2016-01-01

    The pneumatic nebulization gas-solid microextraction device fascinating us is because it directly atomized organic samples to cross a solid-phase microextraction (SPME) cartridge without any pretreatment. In this work, both the spray chamber and SPME column of the extraction device were heated. We found that this would significantly improve the extraction efficiency of this method. Then, this method was used to detect seven triazine herbicides (atraton, desmetryn, atrazine, terbumeton, terbuthylazine, terbutryn, and dipropetryn) in drinking alcohol samples. The experimental results indicated that this extraction procedure could conveniently, efficiently and accurately concentrate any triazine herbicides from drinking alcohol samples. The limits of detection (LODs) were from 0.08 to 0.23 μg L(-1), the limits of quantification (LOQs) were from 0.27 to 0.78 μg L(-1). We used this method to detect triazine herbicides in five white spirit samples. Four concentrations were chosen (5, 25, 50 and 100 μg L(-1)) as the amounts of spikes to investigate the recovery and precision of the present PN-GSME method. The recoveries ranged from 95.91 to 106.67%. The relative standard deviations were not more than 6.51%. Also this method matches the requirement of the maximum residue limits of the European Union.

  19. A Study of the Influence of Numerical Diffusion on Gas-Solid Flow Predictions in Fluidized Beds

    NASA Astrophysics Data System (ADS)

    Ghandriz, Ronak; Sheikhi, Reza

    2015-11-01

    In this work, an investigation is made of the influence of numerical diffusion on the accuracy of gas-solid flow predictions in fluidized beds. This is an important issue particularly in bubbling fluidized beds since numerical error greatly affects the dynamics of bubbles and their associated mixing process. A bed of coal (classified as Geldart A) is considered which becomes fluidized as the velocity of nitrogen stream into the reactor is gradually increased. The fluidization process is simulated using various numerical schemes as well as grid resolutions. Simulations involve Eulerian-Eulerian two-phase flow modeling approach and results are compared with experimental data. It is shown that higher order schemes equipped with flux limiter give favorable prediction of bubble and particle dynamics and hence, the mixing process within the reactor. The excessive numerical diffusion associated with lower order schemes results in unrealistic prediction of bubble shapes and bed height. Comparison is also made of computational efficiency of various schemes. It is shown that the Monotonized Central scheme with down wind factor results in the shortest simulation time because of its efficient parallelization on distributed memory platforms.

  20. Effect of placements (horizontal with vertical) on gas-solid flow and particle impact erosion in gate valve

    NASA Astrophysics Data System (ADS)

    Lin, Zhe; Zhu, Linhang; Cui, Baoling; Li, Yi; Ruan, Xiaodong

    2014-12-01

    Gate valve has various placements in the practical usages. Due to the effect of gravity, particle trajectories and erosions are distinct between placements. Thus in this study, gas-solid flow properties and erosion in gate valve for horizontal placement and vertical placement are discussed and compared by using Euler-Lagrange simulation method. The structure of a gate valve and a simplified structure are investigated. The simulation procedure is validated in our published paper by comparing with the experiment data of a pipe and an elbow. The results show that for all investigated open degrees and Stokes numbers (St), there are little difference of gas flow properties and flow coefficients between two placements. It is also found that the trajectories of particles for two placements are mostly identical when St « 1, making the erosion independent of placement. With the increase of St, the distinction of trajectories between placements becomes more obvious, leading to an increasing difference of the erosion distributions. Besides, the total erosion ratio of surface T for horizontal placement is two orders of magnitudes larger than that for vertical placement when the particle diameter is 250μm.

  1. A novel ECT-EST combined method for gas-solids flow pattern and charge distribution visualization

    NASA Astrophysics Data System (ADS)

    Zhou, B.; Zhang, J. Y.

    2013-07-01

    A non-invasive measurement method of visualizing the flow pattern and charge distribution of gas-solids two-phase flow has been studied and verified using gravity-dropping and pneumatic conveyance rigs with pulverized coal as solids. It has been proven that the permittivity distribution acquired from an electrical capacitance tomography (ECT) system can be used to improve the accuracy in establishing charge sensitivity field of an electrostatic tomography (EST) system, and to reduce the uncertainty of charge distribution reconstruction. The experimental results show that, under the given experimental conditions for the gravity-dropping system, charge density increases with particles' concentration, whilst in the pneumatic conveyance system, charge density decreases in the area where the particles' concentration is higher, and the total charge intensity decreases with the increase of the concentration of pulverized coal in the pipe. The method proposed in this paper is potentially important in pneumatic processes for charge distribution measurement and safe operations. It is envisaged that with further development, this technique can provide information for investigation into the mechanism of inter-particle force on electrostatic attraction and repulsion.

  2. Gas-solid chromatographic analysis of automobile tailpipe emissions as a function of different engine and exhaust system modifications

    SciTech Connect

    Kang, L.; Armstrong, D.W.

    1994-12-31

    The authors developed a single, relatively short gas-solid chromatographic PLOT column and used it to separate aliphatic hydrocarbons, aromatic hydrocarbons and some inorganic gases (O{sub 2}, N{sub 2}, CO and CO{sub 2}) found in automobile exhaust. In the case of hydrocarbons, both aliphatic and aromatic components (up through alkylated-benzenes) were done in one run. Subambient temperature was needed for the oxygen-nitrogen separation, but they were easily resolved from each other and the other compounds present. The effects of different engine and exhaust system modifications on the level of compounds in the exhaust were tested. The concentrations of the emission gases varied considerably with changes in air/fuel ratio, coil voltage, use of catalytic converters and so forth. The results showed that the use of catalytic converter and a higher voltage coil tended to produce the most pronounced decreases in emissions of hydrocarbons and the catalytic converter produced the significant decrease in carbon monoxide concentrations. The results of the GSC analyses were compared to those of a commercial emission analyzer (i.e., sniffer). They showed similar trends and relative concentrations but somewhat different absolute concentrations. This may have been due to differences in the calibration of these methods.

  3. alpha-Terpineol from hydration of crude sulfate turpentine oil.

    PubMed

    Pakdel, H; Sarron, S; Roy, C

    2001-09-01

    Hydration of alpha-pinene under various conditions was studied and compared with the literature. Optimal reaction conditions have been established for the hydration of alpha-pinene and crude turpentine oil in the absence of catalyst and using a low volume of acetone. A detailed reaction product analysis is reported. The main hydration product, alpha-terpineol, was obtained at a yield of 67 wt % of the initial alpha-pinene by reacting with 15% aqueous sulfuric acid and an excess of acetone in an oil bath heated to 80-85 degrees C over the course of 4 h. A progressive transformation of alpha-terpineol to 4-(2-hydroxypropyl)-1-methylcyclohexanol (1,8-terpine) takes place as the hydration time exceeds 4 h. A crude turpentine oil sample was also hydrated under conditions similar to those of alpha-pinene. The alpha-terpineol yield was 77 wt % of the initial alpha-pinene in the crude turpentine oil. The chemical analysis of the crude turpentine oil before and after hydration was carried out, and the distribution of the products was discussed.

  4. Overview: Nucleation of clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

    2016-12-01

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  5. Overview: Nucleation of clathrate hydrates.

    PubMed

    Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

    2016-12-07

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  6. Methane Clathrate Hydrate Prospecting

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2003-01-01

    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  7. Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield

    USGS Publications Warehouse

    Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.

    2010-01-01

    Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.

  8. Synchrotron X-ray computed microtomography study on gas hydrate decomposition in a sedimentary matrix

    NASA Astrophysics Data System (ADS)

    Yang, Lei; Falenty, Andrzej; Chaouachi, Marwen; Haberthür, David; Kuhs, Werner F.

    2016-09-01

    In-situ synchrotron X-ray computed microtomography with sub-micrometer voxel size was used to study the decomposition of gas hydrates in a sedimentary matrix. Xenon-hydrate was used instead of methane hydrate to enhance the absorption contrast. The microstructural features of the decomposition process were elucidated indicating that the decomposition starts at the hydrate-gas interface; it does not proceed at the contacts with quartz grains. Melt water accumulates at retreating hydrate surface. The decomposition is not homogeneous and the decomposition rates depend on the distance of the hydrate surface to the gas phase indicating a diffusion-limitation of the gas transport through the water phase. Gas is found to be metastably enriched in the water phase with a concentration decreasing away from the hydrate-water interface. The initial decomposition process facilitates redistribution of fluid phases in the pore space and local reformation of gas hydrates. The observations allow also rationalizing earlier conjectures from experiments with low spatial resolutions and suggest that the hydrate-sediment assemblies remain intact until the hydrate spacers between sediment grains finally collapse; possible effects on mechanical stability and permeability are discussed. The resulting time resolved characteristics of gas hydrate decomposition and the influence of melt water on the reaction rate are of importance for a suggested gas recovery from marine sediments by depressurization.

  9. Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

    SciTech Connect

    Rutkowski, Philip X; Michelini, Maria C.; Bray, Travis H.; Russo, Nino; Marcalo, Joaquim; Gibson, John K.

    2011-02-11

    Hydration of ytterbium (III) halide/hydroxide ions produced by electrospray ionization was studied in a quadrupole ion trap mass spectrometer and by density functional theory (DFT). Gas-phase YbX{sub 2}{sup +} and YbX(OH){sup +} (X = OH, Cl, Br, or I) were found to coordinate from one to four water molecules, depending on the ion residence time in the trap. From the time dependence of the hydration steps, relative reaction rates were obtained. It was determined that the second hydration was faster than both the first and third hydrations, and the fourth hydration was the slowest; this ordering reflects a combination of insufficient degrees of freedom for cooling the hot monohydrate ion and decreasing binding energies with increasing hydration number. Hydration energetics and hydrate structures were computed using two approaches of DFT. The relativistic scalar ZORA approach was used with the PBE functional and all-electron TZ2P basis sets; the B3LYP functional was used with the Stuttgart relativistic small-core ANO/ECP basis sets. The parallel experimental and computational results illuminate fundamental aspects of hydration of f-element ion complexes. The experimental observations - kinetics and extent of hydration - are discussed in relationship to the computed structures and energetics of the hydrates. The absence of pentahydrates is in accord with the DFT results, which indicate that the lowest energy structures have the fifth water molecule in the second shell.

  10. Hydration of C{sub 3}S thin films

    SciTech Connect

    Rheinheimer, Vanessa; Casanova, Ignasi

    2012-04-15

    Thin films of C{sub 3}S of a few tens of nanometers were produced by electron beam evaporation. After verification that the chemical composition of the bulk material remained unchanged, the samples were hydrated with water vapor in a reaction chamber under saturated pressure and temperature conditions, and were kept isolated from atmospheric exposure throughout the whole duration of the experiment. Analyses by X-ray photoelectron spectroscopy at different stages of hydration evidence a shift of the Si peaks to higher energies and a subsequent decrease of the Ca-Si binding energy distance, indicating silicate polymerization expected upon formation of C-S-H. The measured molar Ca/Si ratio evolves from that of a jennite-like material, of about 1.55, at the beginning of the experiment (attributed to pre-hydration of the thin films), to a tobermorite-like ratio of 0.85 after 3 h of hydration.

  11. Experimental verification of methane-carbon dioxide replacement in natural gas hydrates using a differential scanning calorimeter.

    PubMed

    Lee, Seungmin; Lee, Yohan; Lee, Jaehyoung; Lee, Huen; Seo, Yongwon

    2013-11-19

    The methane (CH4) - carbon dioxide (CO2) swapping phenomenon in naturally occurring gas hydrates is regarded as an attractive method of CO2 sequestration and CH4 recovery. In this study, a high pressure microdifferential scanning calorimeter (HP μ-DSC) was used to monitor and quantify the CH4 - CO2 replacement in the gas hydrate structure. The HP μ-DSC provided reliable measurements of the hydrate dissociation equilibrium and hydrate heat of dissociation for the pure and mixed gas hydrates. The hydrate dissociation equilibrium data obtained from the endothermic thermograms of the replaced gas hydrates indicate that at least 60% of CH4 is recoverable after reaction with CO2, which is consistent with the result obtained via direct dissociation of the replaced gas hydrates. The heat of dissociation values of the CH4 + CO2 hydrates were between that of the pure CH4 hydrate and that of the pure CO2 hydrate, and the values increased as the CO2 compositions in the hydrate phase increased. By monitoring the heat flows from the HP μ-DSC, it was found that the noticeable dissociation or formation of a gas hydrate was not detected during the CH4 - CO2 replacement process, which indicates that a substantial portion of CH4 hydrate does not dissociate into liquid water or ice and then forms the CH4 + CO2 hydrate. This study provides the first experimental evidence using a DSC to reveal that the conversion of the CH4 hydrate to the CH4 + CO2 hydrate occurs without significant hydrate dissociation.

  12. Advances in understanding hydration of Portland cement

    SciTech Connect

    Scrivener, Karen L.; Juilland, Patrick; Monteiro, Paulo J.M.

    2015-12-15

    Progress in understanding hydration is summarized. Evidence supports the geochemistry dissolution theory as an explanation for the induction period, in preference to the inhibiting layer theory. The growth of C–S–H is the principal factor controlling the main heat evolution peak. Electron microscopy indicates that C–S–H “needles” grow from the surface of grains. At the peak, the surface is covered, but deceleration cannot be attributed to diffusion control. The shoulder peak comes from renewed reaction of C{sub 3}A after depletion of sulfate in solution, but release of sulfate absorbed on C–S–H means that ettringite continues to form. After several days space becomes the major factor controlling hydration. The use of new analytical technique is improving our knowledge of the action of superplasticizers and leading to the design of molecules for different applications. Atomistic modeling is becoming a topic of increasing interest. Recent publications in this area are reviewed.

  13. A statistical mechanical description of biomolecular hydration

    SciTech Connect

    1996-02-01

    We present an efficient and accurate theoretical description of the structural hydration of biological macromolecules. The hydration of molecules of almost arbitrary size (tRNA, antibody-antigen complexes, photosynthetic reaction centre) can be studied in solution and in the crystal environment. The biomolecular structure obtained from x-ray crystallography, NMR, or modeling is required as input information. The structural arrangement of water molecules near a biomolecular surface is represented by the local water density analogous to the corresponding electron density in an x-ray diffraction experiment. The water-density distribution is approximated in terms of two- and three-particle correlation functions of solute atoms with water using a potentials-of-mean-force expansion.

  14. Drilling Gas Hydrates on hydrate Ridge, Oregon continental margin

    NASA Astrophysics Data System (ADS)

    Trehu, A. M.; Bohrmann, G.; Leg 204 Science Party

    2002-12-01

    During Leg 204, we cored and logged 9 sites on the Oregon continental margin to determine the distribution and concentration of gas hydrates in an accretionary ridge and adjacent slope basin, investigate the mechanisms that transport methane and other gases into the gas hydrate stability zone (GHSZ), and obtain constraints on physical properties of hydrates in situ. A 3D seismic survey conducted in 2000 provided images of potential subsurface fluid conduits and indicated the position of the GHSZ throughout the survey region. After coring the first site, we acquired Logging-While-Drilling (LWD) data at all but one site to provide an overview of downhole physical properties. The LWD data confirmed the general position of key seismic stratigraphic horizons and yielded an initial estimate of hydrate concentration through the proxy of in situ electrical resistivity. These records proved to be of great value in planning subsequent coring. The second new hydrate proxy to be tested was infrared thermal imaging of cores on the catwalk as rapidly as possible after retrieval. The thermal images were used to identify hydrate samples and to estimate the distribution and texture of hydrate within the cores. Geochemical analyses of interstitial waters and of headspace and void gases provide additional information on the distribution and concentration of hydrate within the stability zone, the origin and pathway of fluids into and through the GHSZ, and the rates at which gas hydrate is forming. Bio- and lithostratigraphic description of cores, measurement of physical properties, and in situ pressure core sampling and thermal measurements complement the data set, providing ground-truth tests of inferred physical and sedimentological properties. Among the most interesting preliminary results are: 1) that gas hydrates are distributed through a broad depth range within the GHSZ and that different physical and chemical proxies for hydrate distribution and concentration give generally

  15. CO2 hydrate: Synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.; Durham, W.B.; Chakoumakos, B.C.; Rawn, C.J.; Rondinone, A.J.; Ishii, Y.

    2003-01-01

    Structure I (sI) carbon dioxide (CO2) hydrate exhibits markedly different dissociation behavior from sI methane (CH4) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H2O melting point (273.15 K). The CO2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO2??nH2O = CO2(g) + nH2O(1 to s) is measurably distinct from the pure H2O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO2 hydrate was synthesized from CO2 liquid and H2O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 ??m diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the

  16. Global occurrences of gas hydrate

    USGS Publications Warehouse

    Kvenvolden, K.A.; Lorenson, T.D.

    2001-01-01

    Natural gas hydrate is found worldwide in sediments of outer continental margins of all oceans and in polar areas with continuous permafrost. There are currently 77 localities identified globally where geophysical, geochemical and/or geological evidence indicates the presence of gas hydrate. Details concerning individual gas-hydrate occurrences are compiled at a new world-wide-web (www) site (http://walrus.wr.usgs.gov/globalhydrate). This site has been created to facilitate global gas-hydrate research by providing information on each of the localities where there is evidence for gas hydrate. Also considered are the implications of gas hydrate as a potential (1) energy resource, (2) factor in global climate change, and (3) geohazard.

  17. Gas hydrate cool storage system

    DOEpatents

    Ternes, M.P.; Kedl, R.J.

    1984-09-12

    The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

  18. The effect of gyrolite additive on the hydration properties of Portland cement

    SciTech Connect

    Eisinas, A. Baltakys, K.; Siauciunas, R.

    2012-01-15

    The influence of gyrolite additive on the hydration properties of ordinary Portland cement was examined. It was found that the additive of synthetic gyrolite accelerates the early stage of hydration of OPC. This compound binds alkaline ions and serves as a nucleation site for the formation of hydration products (stage I). Later on, the crystal lattice of gyrolite becomes unstable and turns into C-S-H, with higher basicity (C/S {approx} 0.8). This recrystallization process is associated with the consumption of energy (the heat of reaction) and with a decrease in the rate of heat evolution of the second exothermic reaction (stage II). The experimental data and theoretical hypothesis were also confirmed by thermodynamic and the apparent kinetic parameters of the reaction rate of C{sub 3}S hydration calculations. The changes occur in the early stage of hydration of OPC samples and do not have a significant effect on the properties of cement stone.

  19. Cross-correlation focus method with an electrostatic sensor array for local particle velocity measurement in dilute gas-solid two-phase flow

    NASA Astrophysics Data System (ADS)

    Wang, Chao; Zhang, Jingyu; Gao, Wenbin; Ding, Hongbing; Wu, Weiping

    2015-11-01

    The gas-solid two-phase flow has been widely applied in the power, chemical and metallurgical industries. It is of great significance in the research of gas-solid two-phase flow to measure particle velocity at different locations in the pipeline. Thus, an electrostatic sensor array comprising eight arc-shaped electrodes was designed. The relationship between the cross-correlation (CC) velocity and the distribution of particle velocity, charge density and electrode spatial sensitivity was analysed. Then the CC sensitivity and its calculation method were proposed. According to the distribution of CC sensitivity, it was found that, between different electrode pairs, it had different focus areas. The CC focus method was proposed for particle velocity measurement at different locations and validated by a belt-style electrostatic induction experiment facility. Finally, the particle velocities at different locations with different flow conditions were measured to research the particle velocity distribution in a dilute horizontal pneumatic conveying pipeline.

  20. Water molecules in clay minerals: Thermodynamic functions and hydration

    NASA Astrophysics Data System (ADS)

    Gailhanou, Helène; Amouric, Marc; Olives, Juan; Rogez, Jacques; van Miltenburg, J. C.; van der Berg, G. J. K.; de Weireld, G.; Gaucher, E.; Blanc, P.

    2010-05-01

    Thermodynamic functions and adsorption of water molecules are very important properties for clay minerals. Smectite MX-80 and mixed-layer illite-smectite ISCz-1 were selected. They were first carefully characterized (HRTEM with EDX analysis), revealing original results. Then, the thermodynamic properties of water in clay were obtained by (i) comparison of the thermodynamic properties of anhydrous and hydrated minerals, between 0 and 350 K (adiabatic calorimetry, solution isothermal calorimetry), and (ii) water vapor adsorption isotherms, between 300 and 380 K (magnetic suspension thermobalance). Solution isothermal calorimetry is used to determine the enthalpies of formation of the minerals (1 bar and 298 K). Comparison of the results, for the anhydrous and the hydrated minerals, leads to the enthalpies of hydration at 298 K. Adiabatic calorimetry measurements give the heat capacities of the minerals from 5 to 350 K. Entropies, enthalpies of formation and Gibbs free energies of formation, for the anhydrous and the hydrated minerals, and then, entropies of hydration, enthalpies of hydration and Gibbs free energies of hydration, between 0 and 350 K, are finally obtained. Comparison of two close hydration states leads to the entropy, the enthalpy and the Gibbs free energy of the adsorption reaction: H2O free - H2O adsorbed. The Cp(T) curve, for the heat capacity of water in clay - i.e., the difference between the heat capacities of the hydrated and the anhydrous minerals -, shows that water in clay is a glass at low temperature, undergoes one or two continuous glass transitions between 150 and 270 K, and behaves as free liquid water above 273 K. The two glass transitions might correspond to two types of water molecules: (i) first adsorbed water molecules, bound to the interlayer cations of the clay mineral; (ii) last adsorbed water molecules, not bound to the interlayer cations. In addition, water vapor adsorption isotherms are obtained from 298 to 378 K (magnetic

  1. Elevating salinity and temperature with hydrate formation at deepwater Gulf of Mexico vents

    NASA Astrophysics Data System (ADS)

    Smith, Andrew J.; Flemings, Peter B.; Liu, Xiaoli

    2013-04-01

    We study the Ursa vent in ~1070 meters water depth at lease blocks MC852/853 in the northern Gulf of Mexico. Elevated salinities and temperatures at the vent shift the base of the hydrate stability zone (HSZ) to the seafloor (Paull et al., 2005; Ruppel et al., 2005). We model the coexistence of high salinities, high temperatures, and an uplifted hydrate phase boundary with a one-dimensional, multicomponent, multiphase, fluid- and heat-flow model of hydrate formation. In this model, free gas supplied from depth migrates vertically through a high-permeability conduit to the regional hydrate stability zone (RHSZ). Once reaching the base of the RHSZ, gas combines with water to form hydrate, salt is excluded, and heat is released. Hydrate formation continues until water is too warm and saline for further hydrate formation. This process self generates three-phase (gas, liquid, hydrate) equilibrium through the RHSZ and allows gas to vent from the base of the RHSZ to the seafloor. Once the reaction front breaches the seafloor, a pseudo steady state is reached in which a continuous salt flux diffuses from the seafloor, and further hydrate formation occurs at a rate necessary to replace the diffuse salt loss. This continued hydrate formation has the potential to produce large, steady fluxes of salt and heat from the seafloor. Such gas-hydrate and fluid-flow systems are important because they are especially sensitive to global ocean warming due to the large concentrations of hydrate that exist at three-phase equilibrium near the seafloor. References: Paull, C., Ussler, W., Lorenson, T., Winters, W., Dougherty, J., 2005. Geochemical constraints on the distribution of gas hydrates in the Gulf of Mexico. Geo-Marine Letters 25, 273-280. Ruppel, C., Dickens, G.R., Castellini, D.G., Gilhooly, W., Lizarralde, D., 2005. Heat and salt inhibition of gas hydrate formation in the northern Gulf of Mexico. Geophys. Res. Lett. 32, L04605.

  2. Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

    NASA Astrophysics Data System (ADS)

    White, M. D.

    2011-12-01

    Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and

  3. Controllable perovskite crystallization at a gas-solid interface for hole conductor-free solar cells with steady power conversion efficiency over 10%.

    PubMed

    Hao, Feng; Stoumpos, Constantinos C; Liu, Zhao; Chang, Robert P H; Kanatzidis, Mercouri G

    2014-11-19

    Depositing a pinhole-free perovskite film is of paramount importance to achieve high performance perovskite solar cells, especially in a heterojunction device format that is free of hole transport material (HTM). Here, we report that high-quality pinhole-free CH3NH3PbI3 perovskite film can be controllably deposited via a facile low-temperature (<150 °C) gas-solid crystallization process. The crystallite formation process was compared with respect to the conventional solution approach, in which the needle-shaped solvation intermediates (CH3NH3PbI3·DMF and CH3NH3PbI3·H2O) have been recognized as the main cause for the incomplete coverage of the resultant film. By avoiding these intermediates, the films crystallized at the gas-solid interface offer several beneficial features for device performance including high surface coverage, small surface roughness, as well as controllable grain size. Highly efficient HTM-free perovskite solar cells were constructed with these pinhole-free CH3NH3PbI3 films, exhibiting significant enhancement of the light harvesting in the long wavelength regime with respect to the conventional solution processed one. Overall, the gas-solid method yields devices with an impressive power conversion efficiency of 10.6% with high reproducibility displaying a negligible deviation of 0.1% for a total of 30 cells.

  4. Multiple H2 occupancy of cages of clathrate hydrate under mild conditions.

    PubMed

    Lu, Hailong; Wang, Jianwei; Liu, Changling; Ratcliffe, Christopher I; Becker, Udo; Kumar, Rajnish; Ripmeester, John

    2012-06-06

    Experiments were carried out by reacting H(2) gas with N(2) hydrate at a temperature of 243 K and a pressure of 15 MPa. The characterizations of the reaction products indicated that multiple H(2) molecules can be loaded into both large and small cages of structure II clathrate hydrates. The realization of multiple H(2) occupancy of hydrate cages under moderate conditions not only brings new insights into hydrogen clathrates but also refreshes the perspective of clathrate hydrates as hydrogen storage media.

  5. The role of water in gas hydrate dissociation

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.

    2004-01-01

    When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

  6. Kinetics of the Osmotic Hydration of Chickpeas

    NASA Astrophysics Data System (ADS)

    Pinto, Gabriel; Esin, Ali

    2004-04-01

    An experiment examining the swelling of chickpeas as they are soaked in water is presented to introduce students to topics such as osmotic flow, mass transfer, diffusion, kinetics of hydration, modeling, and estimation of activation energy. The experiment may be performed by students at home, at the laboratory, or directly by the professor. Experimental data are analyzed using an empirical model (Peleg equation) for the description of moisture sorption curves for different foods soaked in water. The proposed experiment needs inexpensive hardware. The equations that fit adequately with experimental data allow the calculation of initial hydration rates at different temperatures, and subsequently, the estimation of the activation energy, E a , of the process. The obtained value of E a (19.5 ± 0.9 kJ/mol) shows a process controlled by diffusion and not by chemical reaction. It was also observed that, for a given temperature, the increase in concentration of NaCl in the immersion solution results in the decrease of hydration kinetics.

  7. Ductile flow of methane hydrate

    USGS Publications Warehouse

    Durham, W.B.; Stern, L.A.; Kirby, S.H.

    2003-01-01

    Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

  8. Some thermodynamical aspects of protein hydration water.

    PubMed

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H Eugene; Chen, Sow-Hsin

    2015-06-07

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

  9. Some thermodynamical aspects of protein hydration water

    SciTech Connect

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene; Chen, Sow-Hsin

    2015-06-07

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

  10. Gas Hydrate Petroleum System Analysis

    NASA Astrophysics Data System (ADS)

    Collett, T. S.

    2012-12-01

    In a gas hydrate petroleum system, the individual factors that contribute to the formation of gas hydrate accumulations, such as (1) gas hydrate pressure-temperature stability conditions, (2) gas source, (3) gas migration, and (4) the growth of the gas hydrate in suitable host sediment can identified and quantified. The study of know and inferred gas hydrate accumulations reveal the occurrence of concentrated gas hydrate is mostly controlled by the presence of fractures and/or coarser grained sediments. Field studies have concluded that hydrate grows preferentially in coarse-grained sediments because lower capillary pressures in these sediments permit the migration of gas and nucleation of hydrate. Due to the relatively distal nature of the deep marine geologic settings, the overall abundance of sand within the shallow geologic section is usually low. However, drilling projects in the offshore of Japan, Korea, and in the Gulf of Mexico has revealed the occurrence of significant hydrate-bearing sand reservoirs. The 1999/2000 Japan Nankai Trough drilling confirmed occurrence of hydrate-bearing sand-rich intervals (interpreted as turbidite fan deposits). Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. A multi-well drilling program titled "METI Toaki-oki to Kumano-nada" also identified sand-rich reservoirs with pore-filling hydrate. The recovered hydrate-bearing sand layers were described as very-fine- to fine-grained turbidite sand layers measuring from several centimeters up to a meter thick. However, the gross thickness of the hydrate-bearing sand layers were up to 50 m. In 2010, the Republic of Korea conducted the Second Ulleung Basin Gas Hydrate (UBGH2) Drilling Expedition. Seismic data clearly showed the development of a thick, potential basin wide, sedimentary sections characterized by mostly debris flows. The downhole LWD logs and core data from Site UBGH2-5 reveal that each debris flows is

  11. Diurnally-Varying Lunar Hydration

    NASA Astrophysics Data System (ADS)

    Hendrix, A. R.; Hurley, D.; Retherford, K. D.; Mandt, K.; Greathouse, T. K.; Farrell, W. M.; Vilas, F.

    2016-12-01

    Dayside, non-polar lunar hydration signatures have been observed by a handful of instruments and present insights into the lunar water cycle. In this study, we utilize the unique measurements from the current Lunar Reconnaissance Orbiter (LRO) mission to study the phenomenon of diurnally-varying dayside lunar hydration. The Lyman Alpha Mapping Project (LAMP) onboard LRO senses a strong far-ultraviolet water absorption edge indicating hydration in small abundances in the permanently shadowed regions as well as on the lunar dayside. We report on diurnal variability in hydration in different terrain types. We investigate the importance of different sources of hydration, including solar wind bombardment and meteoroid bombardment, by observing trends during magnetotail and meteor stream crossings.

  12. Chemical vs. Physical Acceleration of Cement Hydration

    PubMed Central

    Bentz, Dale P.; Zunino, Franco; Lootens, Didier

    2016-01-01

    Cold weather concreting often requires the use of chemical accelerators to speed up the hydration reactions of the cement, so that setting and early-age strength development will occur in a timely manner. While calcium chloride (dihydrate – CaCl2·2H2O) is the most commonly used chemical accelerator, recent research using fine limestone powders has indicated their high proficiency for physically accelerating early-age hydration and reducing setting times. This paper presents a comparative study of the efficiency of these two approaches in accelerating hydration (as assessed via isothermal calorimetry), reducing setting times (Vicat needle), and increasing early-age mortar cube strength (1 d and 7 d). Both the CaCl2 and the fine limestone powder are used to replace a portion of the finest sand in the mortar mixtures, while keeping both the water-to-cement ratio and volume fractions of water and cement constant. Studies are conducted at 73.4 °F (23°C) and 50 °F (10 °C), so that activation energies can be estimated for the hydration and setting processes. Because the mechanisms of acceleration of the CaCl2 and limestone powder are different, a hybrid mixture with 1 % CaCl2 and 20 % limestone powder (by mass of cement) is also investigated. Both technologies are found to be viable options for reducing setting times and increasing early-age strengths, and it is hoped that concrete producers and contractors will consider the addition of fine limestone powder to their toolbox of techniques for assuring performance in cold weather and other concreting conditions where acceleration may be needed. PMID:28077884

  13. Hydration kinetics of cementitious materials composed of red mud and coal gangue

    NASA Astrophysics Data System (ADS)

    Zhang, Na; Li, Hong-xu; Liu, Xiao-ming

    2016-10-01

    To elucidate the intrinsic reaction mechanism of cementitious materials composed of red mud and coal gangue (RGC), the hydration kinetics of these cementitious materials at 20°C was investigated on the basis of the Krstulović-Dabić model. An isothermal calorimeter was used to characterize the hydration heat evolution. The results show that the hydration of RGC is controlled by the processes of nucleation and crystal growth (NG), interaction at phase boundaries (I), and diffusion (D) in order, and the pozzolanic reactions of slag and compound-activated red mud-coal gangue are mainly controlled by the I process. Slag accelerates the clinker hydration during NG process, whereas the compound-activated red mud-coal gangue retards the hydration of RGC and the time required for I process increases with increasing dosage of red mud-coal gangue in RGC.

  14. Shifting Focus: From Hydration for Performance to Hydration for Health.

    PubMed

    Perrier, Erica T

    2017-01-01

    Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the

  15. Water, Hydration and Health

    PubMed Central

    Popkin, Barry M.; D’Anci, Kristen E.; Rosenberg, Irwin H.

    2010-01-01

    This review attempts to provide some sense of our current knowledge of water including overall patterns of intake and some factors linked with intake, the complex mechanisms behind water homeostasis, the effects of variation in water intake on health and energy intake, weight, and human performance and functioning. Water represents a critical nutrient whose absence will be lethal within days. Water’s importance for prevention of nutrition-related noncommunicable diseases has emerged more recently because of the shift toward large proportions of fluids coming from caloric beverages. Nevertheless, there are major gaps in knowledge related to measurement of total fluid intake, hydration status at the population level, and few longer-term systematic interventions and no published random-controlled longer-term trials. We suggest some ways to examine water requirements as a means to encouraging more dialogue on this important topic. PMID:20646222

  16. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  17. Value of periangiography hydration.

    PubMed

    Kerstein, M D; Puyau, F A

    1984-11-01

    The value of contrast dye to the planning and evaluation of cardiovascular disease cannot be overestimated. However, adverse renal sequellae may cause the surgeon to hesitate in obtaining an arteriogram, especially in patients with compromised renal function. The purpose of this study was to evaluate the incidence of renal dysfunction in patients requiring angiography. Standard contrast angiography for cerebral or peripheral vascular disease was administered to 150 consecutive patients (89 men and 61 women), with an average age of 63.3 years (range 49 to 89 years). All patients received 100 to 150 ml of dye, with a concentration of approximately 50% iodine. Patients were hydrated with 0.5 N saline/5% dextrose, intravenously, for 8 hours before the procedure (1 to 3 ml/kg/hr). In 31 patients (11 women and 20 men) the serum BUN and/or creatinine levels were elevated (mean BUN value of 48 +/- 9 mg/dl; mean creatinine level of 2.8 +/- 0.6 mg/dl). The patients with abnormal renal function received an additional 300 to 500 ml of intravenous fluid, plus 20 to 40 mg intravenous furosemide, 1 hour before roentgenography to establish a diuresis. All patients were hydrated for 6 hours after angiography with the same solution at the same rate (1 to 3 ml/kg/hr). There were no episodes of compromised renal or cardiopulmonary dysfunction because of contrast angiography. In no patient did the BUN or creatinine level rise, nor was there evidence of acute tubular necrosis, as documented by oliguria and abnormal cells in the urine. Angiography is a safe procedure, even with patients who may have compromised renal function, if appropriate prehydration/posthydration and diuretic measures are undertaken.

  18. Alcohol cosurfactants in hydrate antiagglomeration.

    PubMed

    York, J Dalton; Firoozabadi, Abbas

    2008-08-28

    Because of availability, as well as economical and environmental considerations, natural gas is projected to be the premium fuel of the 21st century. Natural gas production involves risk of the shut down of onshore and offshore operations because of blockage from hydrates formed from coproduced water and hydrate-forming species in natural gas. Industry practice has been usage of thermodynamic inhibitors such as alcohols often in significant amounts, which have undesirable environmental and safety impacts. Thermodynamic inhibitors affect bulk-phase properties and inhibit hydrate formation. An alternative is changing surface properties through usage of polymers and surfactants, effective at 0.5 to 3 weight % of coproduced water. One group of low dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are antiagglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, work on hydrate antiagglomeration is very limited. This work centers on the effect of small amounts of alcohol cosurfactant in mixtures of two vastly different antiagglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. Results show that alcohol cosurfactants may help with antiagglomeration when traditional antiagglomerants alone are ineffective. Specifically, as low as 0.5 wt. % methanol cosurfactant used in this study is shown to be effective in antiagglomeration. Without the cosurfactant there will be agglomeration independent of the AA concentration. To our knowledge, this is the first report of alcohol cosurfactants in hydrate antiagglomerants. It is also shown that a rhamnolipid biosurfactant is effective down to only 0.5 wt. % in such mixtures, yet a quaternary ammonium chloride salt, i. e., quat, results in hydrate slurries down to 0.01 wt. %. However, biochemical surfactants are less toxic and biodegradable, and thus their use may prove beneficial even if at

  19. Gas-Solid Interactions During Nonisothermal Heat Treatment of a High-Strength CrMnCN Austenitic Steel Powder: Influence of Atmospheric Conditions and Heating Rate on the Densification Behavior

    NASA Astrophysics Data System (ADS)

    Krasokha, Nikolaj; Weber, Sebastian; Huth, Stephan; Zumsande, Kathrin; Theisen, Werner

    2012-11-01

    This work deals with gas-solid interactions between a high-alloyed steel powder and the surrounding atmosphere during continuous heating. It is motivated by the recently developed corrosion-resistant CrMnCN austenitic cast steels. Here, powder metallurgical processing would be desirable to manufacture highly homogeneous parts and/or novel corrosion-resistant metal-matrix composites. However, the successful use of this new production route calls for a comprehensive investigation of interactions between the sintering atmosphere and the metallic powder to prevent undesirable changes to the chemical composition, e.g., degassing of nitrogen or evaporation of manganese. In this study, dilatometric measurements combined with residual gas analysis, high-temperature X-ray diffraction (XRD) measurements, and thermodynamic equilibrium calculations provided detailed information about the influence of different atmospheric conditions on the microstructure, constitution, and densification behavior of a gas-atomized CrMnCN steel powder during continuous heating. Intensive desorption of nitrogen led to the conclusion that a vacuum atmosphere is not suitable for powder metallurgical (PM) processing. Exposure to an N2-containing atmosphere resulted in the formation of nitrides and lattice expansion. Experimental findings have shown that the N content can be controlled by the nitrogen partial pressure. Furthermore, the reduction of surface oxides because of a carbothermal reaction at elevated temperatures and the resulting enhancement of the powder's densification behavior are discussed in this work.

  20. Hydrothermal preparation of diatomaceous earth combined with calcium silicate hydrate gels.

    PubMed

    Maeda, Hirotaka; Ishida, Emile Hideki

    2011-01-30

    A novel composite for the removal of color in waste water was prepared by subjecting slurries consisting diatomaceous earth and slaked lime to a hydrothermal reaction at 180 °C. Subsequently, calcium silicate hydrate gels covered the surface of diatomaceous earth due to the reaction between the amorphous silica of diatomaceous earth and slaked lime. The formation of calcium silicate hydrate gels led to an increase in the specific surface area. The composites showed higher methylene blue adsorption capacity compared with diatomaceous earth. The improved adsorption capacity of the composites depended on the amount of the calcium silicate hydrate gels and their silicate anion chain-lengths.

  1. CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

    NASA Astrophysics Data System (ADS)

    Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

    2013-04-01

    the reservoir is minimized. Our results clearly indicate that the formation of mixed CH4-CO2-hydrates is an important aspect in the conversion process. The experimental studies have shown that the injection of heated CO2 into the hydrate reservoir induces a variety of spatial and temporal processes which result in substantial bulk heterogeneity. Current numerical simulators are not able to predict these process dynamics and it is important to improve available transport-reaction models (e.g. to include the effect of bulk sediment permeability on the conversion dynamics). Our results confirm that experimental studies are important to better understand the mechanisms of hydrate dissociation and conversion at CO2-injection conditions as a basis towards the development of a suitable hydrate conversion technology. The application of non-invasive analytical methods such as Magnetic Resonance Imaging (MRI) and Raman microscopy are important tools, which were applied to resolve process dynamics on the pore scale. Additionally, the NESSI system is being modified to allow high-pressure flow-through experiments under triaxial loading to better simulate hydrate-sediment mechanics. This aspect is important for overall process development and evaluation of process safety issues.

  2. Direct numerical simulation of gas-solid-liquid flows with capillary effects: An application to liquid bridge forces between spherical particles.

    PubMed

    Sun, Xiaosong; Sakai, Mikio

    2016-12-01

    In this study, a numerical method is developed to perform the direct numerical simulation (DNS) of gas-solid-liquid flows involving capillary effects. The volume-of-fluid method employed to track the free surface and the immersed boundary method is adopted for the fluid-particle coupling in three-phase flows. This numerical method is able to fully resolve the hydrodynamic force and capillary force as well as the particle motions arising from complicated gas-solid-liquid interactions. We present its application to liquid bridges among spherical particles in this paper. By using the DNS method, we obtain the static bridge force as a function of the liquid volume, contact angle, and separation distance. The results from the DNS are compared with theoretical equations and other solutions to examine its validity and suitability for modeling capillary bridges. Particularly, the nontrivial liquid bridges formed in triangular and tetrahedral particle clusters are calculated and some preliminary results are reported. We also perform dynamic simulations of liquid bridge ruptures subject to axial stretching and particle motions driven by liquid bridge action, for which accurate predictions are obtained with respect to the critical rupture distance and the equilibrium particle position, respectively. As shown through the simulations, the strength of the present method is the ability to predict the liquid bridge problem under general conditions, from which models of liquid bridge actions may be constructed without limitations. Therefore, it is believed that this DNS method can be a useful tool to improve the understanding and modeling of liquid bridges formed in complex gas-solid-liquid flows.

  3. Development of Millimeter-Wave Velocimetry and Acoustic Time-of-Flight Tomography for Measurements in Densely Loaded Gas-Solid Riser Flow

    SciTech Connect

    Fort, James A.; Pfund, David M.; Sheen, David M.; Pappas, Richard A.; Morgen, Gerald P.

    2007-04-01

    The MFDRC was formed in 1998 to advance the state-of-the-art in simulating multiphase turbulent flows by developing advanced computational models for gas-solid flows that are experimentally validated over a wide range of industrially relevant conditions. The goal was to transfer the resulting validated models to interested US commercial CFD software vendors, who would then propagate the models as part of new code versions to their customers in the US chemical industry. Since the lack of detailed data sets at industrially relevant conditions is the major roadblock to developing and validating multiphase turbulence models, a significant component of the work involved flow measurements on an industrial-scale riser contributed by Westinghouse, which was subsequently installed at SNL. Model comparisons were performed against these datasets by LANL. A parallel Office of Industrial Technology (OIT) project within the consortium made similar comparisons between riser measurements and models at NETL. Measured flow quantities of interest included volume fraction, velocity, and velocity-fluctuation profiles for both gas and solid phases at various locations in the riser. Some additional techniques were required for these measurements beyond what was currently available. PNNL’s role on the project was to work with the SNL experimental team to develop and test two new measurement techniques, acoustic tomography and millimeter-wave velocimetry. Acoustic tomography is a promising technique for gas-solid flow measurements in risers and PNNL has substantial related experience in this area. PNNL is also active in developing millimeter wave imaging techniques, and this technology presents an additional approach to make desired measurements. PNNL supported the advanced diagnostics development part of this project by evaluating these techniques and then by adapting and developing the selected technology to bulk gas-solids flows and by implementing them for testing in the SNL riser

  4. Direct numerical simulation of gas-solid-liquid flows with capillary effects: An application to liquid bridge forces between spherical particles

    NASA Astrophysics Data System (ADS)

    Sun, Xiaosong; Sakai, Mikio

    2016-12-01

    In this study, a numerical method is developed to perform the direct numerical simulation (DNS) of gas-solid-liquid flows involving capillary effects. The volume-of-fluid method employed to track the free surface and the immersed boundary method is adopted for the fluid-particle coupling in three-phase flows. This numerical method is able to fully resolve the hydrodynamic force and capillary force as well as the particle motions arising from complicated gas-solid-liquid interactions. We present its application to liquid bridges among spherical particles in this paper. By using the DNS method, we obtain the static bridge force as a function of the liquid volume, contact angle, and separation distance. The results from the DNS are compared with theoretical equations and other solutions to examine its validity and suitability for modeling capillary bridges. Particularly, the nontrivial liquid bridges formed in triangular and tetrahedral particle clusters are calculated and some preliminary results are reported. We also perform dynamic simulations of liquid bridge ruptures subject to axial stretching and particle motions driven by liquid bridge action, for which accurate predictions are obtained with respect to the critical rupture distance and the equilibrium particle position, respectively. As shown through the simulations, the strength of the present method is the ability to predict the liquid bridge problem under general conditions, from which models of liquid bridge actions may be constructed without limitations. Therefore, it is believed that this DNS method can be a useful tool to improve the understanding and modeling of liquid bridges formed in complex gas-solid-liquid flows.

  5. Quantifying methane hydrate distribution in worldwide sediments: Comparison between observations and numerical simulations

    NASA Astrophysics Data System (ADS)

    Bhatnagar, G.; Chapman, W. G.; Dickens, G. D.; Dugan, B.; Hirasaki, G. J.

    2006-12-01

    Models for studying methane hydrate accumulation in marine sediments have previously been developed for specific locations and are valid only for the numerous parameters characteristic of these sites. To understand the general distribution of hydrates and explain the variability of hydrate saturations in different geologic settings, we develop a one-dimensional model that simulates accumulation of hydrates over time. We use results from our numerical model and dimensionless scalings to generate average gas hydrate saturation maps that are valid over a wide range of transport parameters. It is shown that just two saturation contour maps suffice in explaining gas hydrate distributions resulting from methane generated either via in-situ methanogenic reactions or transported through upward fluxes from deeper sources. These contour maps are also relatively insensitive to changes in seafloor properties (like seafloor depth, bottom water temperature and geothermal gradient), making them applicable to any general geologic setting. To test and validate our model, we have evaluated where known and well characterized gas hydrate systems such as Blake Ridge (offshore southeastern USA), Cascadia Margin (offshore northwestern USA), Peru Margin (offshore Peru), Costa Rica Margin and Nankai Trough (offshore Japan) lie on our simulated saturation maps. Average gas hydrate saturations at these locations are predicted to be about 4%, 9%, 8%, 1% and 3%, respectively. These saturations match values inferred from proxy data for most of the ODP Sites. Hence, our contour plots provide an approximate, yet accurate, estimate of gas hydrate saturations at the regional scale.

  6. Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces

    PubMed Central

    Smith, Benjamin J.; Rawal, Aditya; Funkhouser, Gary P.; Roberts, Lawrence R.; Gupta, Vijay; Israelachvili, Jacob N.; Chmelka, Bradley F.

    2011-01-01

    Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state 1H, 13C, 29Si, and 27Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications. PMID:21562207

  7. Improved evidence for the existence of an intermediate phase during hydration of tricalcium silicate

    SciTech Connect

    Bellmann, Frank; Damidot, Denis; Moeser, Bernd; Skibsted, Jorgen

    2010-06-15

    Tricalcium silicate (Ca{sub 3}SiO{sub 5}) with a very small particle size of approximately 50 nm has been prepared and hydrated for a very short time (5 min) by two different modes in a paste experiment, using a water/solid-ratio of 1.20, and by hydration as a suspension employing a water/solid-ratio of 4000. A phase containing uncondensed silicate monomers close to hydrogen atoms (either hydroxyl groups or water molecules) was formed in both experiments. This phase is distinct from anhydrous tricalcium silicate and from the calcium-silicate-hydrate (C-S-H) phase, commonly identified as the hydration product of tricalcium silicate. In the paste experiment, approximately 79% of silicon atoms were present in the hydrated phase containing silicate monomers as determined from {sup 29}Sileft brace{sup 1}Hright brace CP/MAS NMR. This result is used to show that the hydrated silicate monomers are part of a separate phase and that they cannot be attributed to a hydroxylated surface of tricalcium silicate after contact with water. The phase containing hydrated silicate monomers is metastable with respect to the C-S-H phase since it transforms into the latter in a half saturated calcium hydroxide solution. These data is used to emphasize that the hydration of tricalcium silicate proceeds in two consecutive steps. In the first reaction, an intermediate phase containing hydrated silicate monomers is formed which is subsequently transformed into C-S-H as the final hydration product in the second step. The introduction of an intermediate phase in calculations of the early hydration of tricalcium silicate can explain the presence of the induction period. It is shown that heterogeneous nucleation on appropriate crystal surfaces is able to reduce the length of the induction period and thus to accelerate the reaction of tricalcium silicate with water.

  8. Obsidian Hydration: A New Paleothermometer

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Riciputi, Lee R; Cole, David R; Fayek, Mostafa; Elam, J. Michael

    2006-01-01

    The natural hydration of obsidian was first proposed as a dating technique for young geological and archaeological specimens by Friedman and Smith (1960), who noted that the thickness of the hydrated layer on obsidian artifacts increases with time. This approach is, however, sensitive to temperature and humidity under earth-surface conditions. This has made obsidian hydration dating more difficult, but potentially provides a unique tool for paleoclimatic reconstructions. In this paper we present the first successful application of this approach, based on combining laboratory-based experimental calibrations with archaeological samples from the Chalco site in the Basin of Mexico, dated using stratigraphically correlated 14C results and measuring hydration depths by secondary ion mass spectrometry. The resultant data suggest, first, that this approach is viable, even given the existing uncertainties, and that a cooling trend occurred in the Basin of Mexico over the past 1450 yr, a result corroborated by other paleoclimatic data.

  9. Obsidian hydration dates glacial loading?

    USGS Publications Warehouse

    Friedman, I.; Pierce, K.L.; Obradovich, J.D.; Long, W.D.

    1973-01-01

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming . The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  10. Obsidian hydration: A new paleothermometer

    NASA Astrophysics Data System (ADS)

    Anovitz, Lawrence M.; Riciputi, Lee R.; Cole, David R.; Fayek, Mostafa; Elam, J. Michael

    2006-07-01

    The natural hydration of obsidian was first proposed as a dating technique for young geological and archaeological specimens by Friedman and Smith (1960), who noted that the thickness of the hydrated layer on obsidian artifacts increases with time. This approach is, however, sensitive to temperature and humidity under earth-surface conditions. This has made obsidian hydration dating more difficult, but potentially provides a unique tool for paleoclimatic reconstructions. In this paper we present the first successful application of this approach, based on combining laboratory-based experimental calibrations with archaeological samples from the Chalco site in the Basin of Mexico, dated using stratigraphically correlated 14C results and measuring hydration depths by secondary ion mass spectrometry. The resultant data suggest, first, that this approach is viable, even given the existing uncertainties, and that a cooling trend occurred in the Basin of Mexico over the past 1450 yr, a result corroborated by other paleoclimatic data.

  11. Obsidian hydration dates glacial loading?

    PubMed

    Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

    1973-05-18

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  12. Hydration of ground granulated blast-furnace slag

    NASA Astrophysics Data System (ADS)

    Song, Sujin

    1998-12-01

    The hydration of ground granulated blast-furnace slag (GGBFS) has been studied for 28 days of hydration at 25sp°C. The reaction between GGBFS and DI water is slow, however, activated hydration was observed for GGBFS pastes mixed with NaOH solutions. When NaOH was added into the mixing solution to control the pH, the rate of reaction was dependent on the pH of the starting solution and it was quantified using heat evolution characteristics. The main hydration product was identified as C-S-H, and hydrotalcite was observed when the paste reached high degree of hydration. The non-evaporable water content of fully hydrated GGBFS pastes was determined to be 0.162 g Hsb2O/g of slag, indicating that the stoichiometry of C-S-H formed in GGBFS paste is close to Csb{1.7}SHsb{1.5}. GGBFS paste showed microstructure consisted of poorly crystalline, homogeneous solid and highly disconnected pores. Highly disconnected capillary pore structure was responsible for low conductivity as well as low water transport through GGBFS pastes. C-S-H formed on the surface of GGBFS particles had honeycomb-like morphology close to Type II C-S-H. Pore solution chemistry of GGBFS paste provided important understanding with respect to the role of pH in alkali-activated hydration of GGBFS. pH was concluded to be a very important variable controlling the aqueous solubility, the equilibrium between C-S-H and aqueous phase, and the alkali-activation of GGBFS. At early stages of hydration, the pH was determined by the amount of NaOH added into initial mixing solution. High pH in the pore solution increases the solubilities of Si and Al, but decreases the solubilities of Ca and Mg. This pH-dependent solubility behavior is well explained using solubility equations from thermodynamics. The solubility of Si is the most important variable affecting alkali-activation of GGBFS since it is hard to solubilize Si from solid into aqueous phase due to the low Si solubility at pH < 11.5, which is the critical p

  13. Controversies about the occurrence of chloral hydrate in drinking water.

    PubMed

    Dabrowska, Agata; Nawrocki, Jacek

    2009-05-01

    Besides trihalomethanes (THMs) and haloacetic acids (HAAs), chloral hydrate (CH) is the next most prevalent disinfection by-product (DBP) in drinking water, formed as a result of the reaction between chlorine and natural organic matter (NOM). Chloral hydrate (trichloroacetaldehyde) should be limited in drinking water because of its adverse health effect. The controversies concerning the appearance of CH in disinfected water found in literature are discussed in the present paper. According to some authors the CH yield during chlorination of water depends only on TOC. However, there are other data available that do not confirm this relationship. Another fact requiring clarification is the dependence of CH formation on pH. In the present study, CH formation is analysed in different types of water disinfected with different doses of chlorine. Formation of CH is correlated with the dose of Cl(2) and the contact time. The formation of chloral hydrate takes place as long as chlorine is available in the water. Total organic carbon (TOC) is not considered the main factor influencing the production of chloral hydrate in water treated with Cl(2) as the production depends also on the nature of NOM. Higher levels of CH are observed at alkaline conditions (pH>7). A significant correlation (R(2)>0.9) between the concentrations of chloral hydrate and chloroform has been observed. The preozonation increases significantly the chloral hydrate formation potential in the water treated. Biofiltration process does not remove all of CH precursors and its efficiency depends strongly on the contact time. Chloral hydrate was analyzed by gas chromatography with electron capture detector with the detection limit 0.1 microg L(-1).

  14. Hydrate formation and growth in pores

    NASA Astrophysics Data System (ADS)

    Jung, Jong-Won; Santamarina, J. Carlos

    2012-04-01

    Gas hydrates consist of guest gas molecules encaged in water cages. Methane hydrate forms in marine and permafrost sediments. In this study, we use optical, mechanical and electrical measurements to monitor hydrate formation and growth in small pores to better understand the hydrate pore habit in hydrate-bearing sediments. Hydrate formation in capillary tubes exposes the complex and dynamic interactions between nucleation, gas diffusion and gas solubility. The observation of hydrate growth in a droplet between transparent plates shows that the hydrate shell does not grow homogeneously but advances in the form of lobes that invade the water phase; in fact, the hydrate shell must be discontinuous and possibly cracked to justify the relatively fast growth rates observed in these experiments. Volume expansion during hydrate formation causes water to flow out of menisci; expelled water either spreads on the surface of water-wet substrates and forms a thin hydrate sheet, or remains next to menisci when substrates are oil-wet. Hydrate formation is accompanied by ion exclusion, yet, there is an overall increase in electrical resistance during hydrate formation. Hydrate growth may become salt-limited in trapped water conditions; in this case, aqueous brine and gas CH4 may be separated by hydrate and the three-phase system remains stable within the pore space of sediments.

  15. Crystallization of a polymorphic hydrate system.

    PubMed

    Tian, F; Qu, H; Louhi-Kultanen, M; Rantanen, J

    2010-02-01

    Nitrofurantoin can form two monohydrates, which have the same chemical composition and molar ratio of water, but differ in the crystal arrangements. The two monohydrates (hydrates I and II) could be produced independently via evaporative crystallization, where supersaturation and solvent composition were both found to have an effect. Hydrate I showed much slower crystallization than hydrate II. During cooling crystallization, the nucleation and growth of hydrate II was again dominant, consuming all supersaturation and leading to no hydrate I formation. Seeding of hydrate I during cooling crystallization was also applied, but the hydrate I seeds were not able to initiate its nucleation rather than dissolving into crystallizing solution. Although solubility tests revealed that hydrate II is more stable than hydrate I due to its lower solubility (110 +/- 4 and 131 +/- 12 microg/mL for hydrates II and I, respectively), this difference is rather small. Therefore, the small free energy difference between the two hydrates, together with the slow crystallization of hydrate I, both lead to a hindrance of hydrate I formation. Furthermore, the crystal structure of hydrate II demonstrated a higher H-bonding extent than hydrate I, suggesting its more favorable crystallization. This is in good agreement with experimental results.

  16. Airway Hydration and COPD

    PubMed Central

    Ghosh, Arunava; Boucher, R.C.; Tarran, Robert

    2015-01-01

    Chronic obstructive pulmonary disease (COPD) is one of the prevalent causes of worldwide mortality and encompasses two major clinical phenotypes, i.e., chronic bronchitis (CB) and emphysema. The most common cause of COPD is chronic tobacco inhalation. Research focused on the chronic bronchitic phenotype of COPD has identified several pathological processes that drive disease initiation and progression. For example, the lung’s mucociliary clearance (MCC) system performs the critical task of clearing inhaled pathogens and toxic materials from the lung. MCC efficiency is dependent on: (i) the ability of apical plasma membrane ion channels such as the cystic fibrosis transmembrane conductance regulator (CFTR) and the epithelial Na+ channel (ENaC) to maintain airway hydration; (ii) ciliary beating; and, (iii) appropriate rates of mucin secretion. Each of these components is impaired in CB and likely contributes to the mucus stasis/accumulation seen in CB patients. This review highlights the cellular components responsible for maintaining MCC and how this process is disrupted following tobacco exposure and with CB. We shall also discuss existing therapeutic strategies for the treatment of chronic bronchitis and how components of the MCC can be used as biomarkers for the evaluation of tobacco or tobacco-like-product exposure. PMID:26068443

  17. Catalytic hydration of terminal alkenes to primary alcohols.

    PubMed

    Jensen, C M; Trogler, W C

    1986-09-05

    Direct catalytic hydration of terminal alkenes to primary alcohols would be an inexpensive route to industrially useful alcohols and a convenient synthetic route for the synthesis of terminal alcohols in general. The reaction between trans- PtHCl(PMe(3))(2) (where Me = CH(3)) and sodium hydroxide in a one-to-one mixture of water and 1-hexene yields a species that, at 60 degrees C and in the presence of the phasetransfer catalyst benzyltriethylammonium chloride, catalyzes selective hydration of 1-hexene to n-hexanol at a rate of 6.9 +/- 0.2 turnovers per hour. Hydration of 1-dodecene to n-dodecanol occurs at a rate of 8.3 +/- 0.4 turnovers per hour at 100 degrees C. Deuterium labeling experiments with trans-PtDCl(PMe(3))(2) show that hydration involves reductive elimination of a C-H bond. At low hydroxide concentrations (<8 equivalents), hydration of the water-soluble olefin 3-butene-1-ol to 1,4-butanediol exhibited a first-order dependence on hydroxide concentration for loss of catalytic activity. This suggests that hydroxide attacks the coordinated alkene slowly. At high hydroxide concentrations, the rate of catalysis was hydroxide-independent and first order in alkene. Substitution of coordinated water (k(1) = 9.3 +/- 0.5 x 10(-3) liters per mol per second) appears to be limitng under these conditions.

  18. Tetrahydrofuran hydrate decomposition characteristics in porous media

    NASA Astrophysics Data System (ADS)

    Song, Yongchen; Wang, Pengfei; Wang, Shenglong; Zhao, Jiafei; Yang, Mingjun

    2016-12-01

    Many tetrahydrofuran (THF) hydrate properties are similar to those of gas hydrates. In the present work THF hydrate dissociation in four types of porous media is studied. THF solution was cooled to 275.15 K with formation of the hydrate under ambient pressure, and then it dissociated under ambient conditions. THF hydrate dissociation experiments in each porous medium were conducted three times. Magnetic resonance imaging (MRI) was used to obtain images. Decomposition time, THF hydrate saturation and MRI mean intensity (MI) were measured and analyzed. The experimental results showed that the hydrate decomposition time in BZ-4 and BZ-3 was similar and longer than that in BZ-02. In each dissociation process, the hydrate decomposition time of the second and third cycles was shorter than that of the first cycle in BZ-4, BZ-3, and BZ-02. The relationship between THF hydrate saturation and time is almost linear.

  19. Energy resource potential of natural gas hydrates

    USGS Publications Warehouse

    Collett, T.S.

    2002-01-01

    The discovery of large gas hydrate accumulations in terrestrial permafrost regions of the Arctic and beneath the sea along the outer continental margins of the world's oceans has heightened interest in gas hydrates as a possible energy resource. However, significant to potentially insurmountable technical issues must be resolved before gas hydrates can be considered a viable option for affordable supplies of natural gas. The combined information from Arctic gas hydrate studies shows that, in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors, known as bottom-simulating reflectors, that have been mapped at depths below the sea floor ranging from about 100 to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas hydrate accumulations are in rough accord at about 20,000 trillion m3. Disagreements over fundamental issues such as the volume of gas stored within delineated gas hydrate accumulations and the concentration of gas hydrates within hydrate-bearing strata have demonstrated that we know little about gas hydrates. Recently, however, several countries, including Japan, India, and the United States, have launched ambitious national projects to further examine the resource potential of gas hydrates. These projects may help answer key questions dealing with the properties of gas hydrate reservoirs, the design of production systems, and, most important, the costs and economics of gas hydrate production.

  20. Gas-phase hydration thermochemistry of sodiated and potassiated nucleic acid bases.

    PubMed

    Wincel, Henryk

    2012-09-01

    Hydration reactions of sodiated and potassiated nucleic acid bases (uracil, thymine, cytosine, and adenine) produced by electrospray have been studied in a gas phase using the pulsed ion-beam high-pressure mass spectrometer. The thermochemical properties, ΔH(o)(n), ΔS(o)(n), and ΔG(o)(n), for the hydrated systems were obtained from hydration equilibrium measurement. The structural aspects of the hydrated complexes are discussed in conjunction with available literature data. The correlation between water binding energies in the hydrated complexes and the corresponding metal ion affinities of nucleobases suggests that a significant (if not dominant) amount of the canonical structure of cytosine undergoes tautomerization during electrospray ionization, and the thermochemical values for cationized cytosine probably correspond to a mixture of tautomeric complexes.

  1. Gas-Phase Hydration Thermochemistry of Sodiated and Potassiated Nucleic Acid Bases

    NASA Astrophysics Data System (ADS)

    Wincel, Henryk

    2012-09-01

    Hydration reactions of sodiated and potassiated nucleic acid bases (uracil, thymine, cytosine, and adenine) produced by electrospray have been studied in a gas phase using the pulsed ion-beam high-pressure mass spectrometer. The thermochemical properties, ΔH o n , ΔS o n , and ΔG o n , for the hydrated systems were obtained from hydration equilibrium measurement. The structural aspects of the hydrated complexes are discussed in conjunction with available literature data. The correlation between water binding energies in the hydrated complexes and the corresponding metal ion affinities of nucleobases suggests that a significant (if not dominant) amount of the canonical structure of cytosine undergoes tautomerization during electrospray ionization, and the thermochemical values for cationized cytosine probably correspond to a mixture of tautomeric complexes.

  2. Hydration water in dynamics of a hydrated beta-lactoglobulin

    NASA Astrophysics Data System (ADS)

    Yoshida, K.; Yamaguchi, T.; Bellissent-Funel, M.-C.; Longeville, S.

    2007-02-01

    Incoherent spin-echo signals of a hydrated β-lactoglobulin protein were investigated, at 275 and 293 K. The intermediate scattering functions I(Q,t) were divided in two contributions from surface water and protein, respectively. On one hand, the dynamics of the surface water follows a KWW stretched exponential function (the exponent is ~0.5), on the other hand, that of the protein follows a single exponential. The present results are consistent with our previous results of hydrated C-phycocyanin combining elastic and quasielastic neutron scattering and by molecular dynamics simulation.

  3. Comparison of stromal hydration techniques for clear corneal cataract incisions: conventional hydration versus anterior stromal pocket hydration.

    PubMed

    Mifflin, Mark D; Kinard, Krista; Neuffer, Marcus C

    2012-06-01

    Anterior stromal pocket hydration was compared with conventional hydration for preventing wound leak after 2.8 mm uniplanar clear corneal incisions (CCIs) in patients having routine cataract surgery. Conventional hydration involves hydration of the lateral walls of the main incision with visible whitening of the stroma. The anterior stromal pocket hydration technique involves creation of an additional supraincisional stromal pocket overlying the main incision, which is then hydrated instead of the main incision. Sixty-six eyes of 48 patients were included in the data analysis with 33 assigned to each study group. The anterior stromal pocket hydration technique was significantly better than conventional hydration in preventing wound leak due to direct pressure on the posterior lip of the incision. Copyright © 2012 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

  4. High temperature corrosion studies. A. Iron: based superalloy in SO/sub 2//O/sub 2/ atmospheres. B. Gas: solid reaction with formation of volatile species

    SciTech Connect

    Liu, T.K.

    1980-03-01

    The thermogravimetric method was used to study high temperature corrosion under SO/sub 2//O/sub 2/ atmosphere applied to Armco 18SR alloys with different heat treatment histories, Armco T310 and pure chromium between 750 and 1100/sup 0/C. The weight gain follows the parabolic rate law. The volatilization of the protective Cr/sub 2/O/sub 3/ layer via formation of CrO/sub 3/ was taken into account above 900/sup 0/C for long time runs. The parabolic rate and the volatilization rate, derived from fitting the experimental data to the modified Tedmon's non-linear model, were correlated using the Arrhenius equation. Armco 18SR-C has the best corrosion resistance of the Armco 18SR alloys. Armco T310 is not protective at high temperatures. The available rate data on the oxidation of chromium oxide, chlorination of chromium, oxidation-chlorination of chromium oxide, chlorination of nickel and chlorination of iron were found to be predictable. The calculation of high temperature volatilization rate was performed using the available fluid correlation equations and the Lennard-Jones parameters derived from the molecule with similar structure and from the low temperature viscosity measurement. The lower predicted volatilization rate is due to the use of the Chapman-Enskog equation with the Lennard-Jones parameters mostly derived from the low temperature viscosity measurement. This was substantiated by comparing the reliable high temperature diffusion rate in the literature with the above mentioned calculational method. The experimental volatilization rates of this study are compared with the other related studies and the mass transfer predictions.

  5. REVIEW - Graphical Displays of the Thermodynamics of High-Temperature Gas-Solid Reactions and Their Application to Oxidation of Metals and Evaporation of Oxides

    DTIC Science & Technology

    1985-02-01

    point of -20’C) and for the C0 2 /CO scale 05 Fig. H1. Ellingham-type diagram for the AI-O system. 0 -100 2 1’-300 X - -300 - 70 -4 -~ -i -60 10 10- 0...AH,) - (S7/AH 7) tures.- J. Appl. Plays.. 29. 1295 (1958).’K. Blegen . ~Equilibria and Kinetics in the Systems Si-N and Si-N-0. Spec. According to Eq

  6. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  7. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence? Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  8. Dissociation heat transfer characteristics of methane hydrates

    SciTech Connect

    Kamath, V.A.; Holder, G.D.

    1987-02-01

    Knowledge of the interfacial heat transfer phenomenon during the dissociation of gas hydrates is essential in modeling the hydrate dissociation process. Such knowledge has applications in natural gas processing, storage, or transportation; in the drilling and recovery of oil and gas in the presence of gas hydrates; in the desalination of sea water; and in the production of natural gas from hydrate reservoirs. The process of hydrate dissociation is a unique phenomenon in which gas and water are simultaneously produced at the dissociated hydrate surface and play an important role in the mechanism of heat transfer to hydrates. An earlier study of propane hydrate dissociation showed that hydrate dissociation is a heat-transfer-limited process and somewhat similar to the nucleate boiling of liquids. In the present study, heat transfer limitations for methane hydrate dissociation were studied for two reasons. First, a comparison of the results of this study with propane hydrate was desired. Second, the effect of hydrate structure and gas molecule type on the rate of heat transfer during hydrate dissociation was sought.

  9. The characteristics of methane hydrates synthesized in sand and clay sediments

    NASA Astrophysics Data System (ADS)

    Lu, H.; Wright, F.; Okui, T.; Zheng, J.; Ripmeester, J. A.; Dallimore, S.

    2003-04-01

    The investigation of the formation of gas hydrate in natural sediments not only can give important information on the mechanism and kinetics of hydrate formation in sediments, but also will help to establish methodology for preparing samples suitable for elucidating the changes in physical properties of sediments upon hydrate formation. So far, few results are available in this important area of research. The present work addresses this deficiency by monitoring the methane hydrate formation processes in water-saturated sediments (clayey sand, silty sand and clay) and specifying the distribution of synthetic methane hydrate in the test sediments. The clayey sand and silty sand sediment samples are molded into columns of 49 mm in diameter and about 50 mm in length, while the clay columns are 49 mm, 38 mm, 33 mm in diameter and ˜50 mm in length. The measurement of water content on samples prepared with the same materials and methods as the test specimen confirmed that water saturated the test specimens and that they were homogeneously distributed. The formation of methane hydrate in the sediments was carried out in a pressure vessel at 3^oC with an initial gas pressure of 10 MPa. For specifying the distribution of synthetic gas hydrate in sediment, the amount of gas released by hydrate dissociation was measured on samples taken from 10 mm thick slices cut from the test sediment column. As indicated by the pressure and time trajectory, methane hydrate had been kept after forming over a reaction period of even more than one month in clayey sand and silty sand. However the reaction looked like it stopped after only about 2 days in clay columns with diameters of 49 mm and 38 mm, while it still continued after 2 weeks in the clay column with a diameter of 33 mm. According to the amounts of released gas upon decomposition, methane hydrates have different distribution features in silty sand and in clay. In silty sand, methane hydrate has a very high saturation rate (>80% of

  10. Dependence of molecular hydrogen formation in water on scavengers of the precursor to the hydrated electron

    SciTech Connect

    Pastina, B. |; LaVerne, J.A.; Pimblott, S.M.

    1999-07-22

    Early studies on the radiolysis of water suggested a wide variety of precursors, and mechanisms, for the formation of the observed yield of molecular hydrogen. Molecular hydrogen yields have been measured in the {gamma} radiolysis of aqueous solutions with a wide variety of scavengers of the hydrated electron and its precursors. A decrease in molecular hydrogen yield with increasing scavenging capacity of the hydrated electron is found with all solutes. Scavengers with particularly high rate coefficients for reaction with the precursors to the hydrated electron compared to the hydrated electron, such as selenate and to a lesser extent molybdate, show a more rapid decrease in hydrogen yields with increasing scavenging capacity than is observed with the other solutes. The yield of molecular hydrogen is better parameterized by the scavenging capacity for the precursors to the hydrated electron than by the scavenging capacity for the hydrated electron. Good scavengers of precursors to the hydrated electrons do not exhibit a nonscavengable hydrogen yield in the high scavenging capacity limit. These results suggest that the previously accepted nonscavengable yield of molecular hydrogen is due to precursors of the hydrated electron and it can be lowered with appropriate scavengers.

  11. Rates and mechanisms of conversion of ice nanocrystals to hydrates of HCl and HBr: acid diffusion in the ionic hydrates.

    PubMed

    Devlin, J Paul; Gulluru, Dheeraj B; Buch, Victoria

    2005-03-03

    This FTIR study focuses on solid-state chemistry associated with formation and interconversion of the ionic HX (X = Cl, Br) hydrates. Kinetic data are reported for conversions of ice nanocrystal arrays exposed to the saturation pressure of the acids in the 110 approximately 125 K range. The product is amorphous acid dihydrate in the case of HBr, and amorphous monohydrate for HCl. The rate-determining step is identified as HX diffusion through the hydrate product crust toward the interfacial reaction zone, rather than diffusion through ice, as commonly believed. Slowing of the conversion process is thus observed with increasing thickness of the crust. The diffusion coefficient (D(e)) and activation energy values for HX diffusion through the hydrates were evaluated with the help of the shrinking-core model. Hydrate crystallization occurs as a separate step, upon heating above 130 K. Subsequently, rates of reversible transitions between crystal di- and monohydrates were observed upon exposure to acid vapor and acid evacuation. In conversion from di- to monohydrate, the rate slows after fast formation of several layers; subsequently, diffusion through the product crust appears to be the rate-controlling step. The activation energy for HBr diffusion through crystal dihydrate is found to be significantly higher than that for the amorphous analogue. Conjecture is offered for a molecular mechanism of HX transport through the crystal hydrate, based on (i) spectroscopic/computational evidence for the presence of molecular HX bonded to X(-) in each of the ionic hydrate phases and (ii) the relative E(a) values found for HBr and HCl diffusion. Monte Carlo modeling suggests acid transport to the reaction zone along boundaries between "nanocrystallites" generated by multiple hydrate nucleation events at the particle surfaces. The reverse conversion, of crystalline monohydrate particles to the dihydrate phase, as well as dihydrate to trihydrate, displays nearly constant rate

  12. Gas Hydrate and Pore Pressure

    NASA Astrophysics Data System (ADS)

    Tinivella, Umberta; Giustiniani, Michela

    2014-05-01

    Many efforts have been devoted to quantify excess pore pressures related to gas hydrate dissociation in marine sediments below the BSR using several approaches. Dissociation of gas hydrates in proximity of the BSR, in response to a change in the physical environment (i.e., temperature and/or pressure regime), can liberate excess gas incrising the local pore fluid pressure in the sediment, so decreasing the effective normal stress. So, gas hydrate dissociation may lead to excess pore pressure resulting in sediment deformation or failure, such as submarine landslides, sediment slumping, pockmarks and mud volcanoes, soft-sediment deformation and giant hummocks. Moreover, excess pore pressure may be the result of gas hydrate dissociation due to continuous sedimentation, tectonic uplift, sea level fall, heating or inhibitor injection. In order to detect the presence of the overpressure below the BSR, we propose two approachs. The fist approach models the BSR depth versus pore pressure; in fact, if the free gas below the BSR is in overpressure condition, the base of the gas hydrate stability is deeper with respect to the hydrostatic case. This effect causes a discrepancy between seismic and theoretical BSR depths. The second approach models the velocities versus gas hydrate and free gas concentrations and pore pressure, considering the approximation of the Biot theory in case of low frequency, i.e. seismic frequency. Knowing the P and S seismic velocity from seismic data analysis, it is possibile to jointly estimate the gas hydrate and free gas concentrations and the pore pressure regime. Alternatively, if the S-wave velocity is not availbale (due to lack of OBS/OBC data), an AVO analysis can be performed in order to extract information about Poisson ratio. Our modeling suggests that the areas characterized by shallow waters (i.e., areas in which human infrastructures, such as pipelines, are present) are significantly affected by the presence of overpressure condition

  13. Hydration of highly charged ions.

    PubMed

    Hofer, Thomas S; Weiss, Alexander K H; Randolf, Bernhard R; Rode, Bernd M

    2011-08-01

    Based on a series of ab initio quantum mechanical charge field molecular dynamics (QMCF MD) simulations, the broad spectrum of structural and dynamical properties of hydrates of trivalent and tetravalent ions is presented, ranging from extreme inertness to immediate hydrolysis. Main group and transition metal ions representative for different parts of the periodic system are treated, as are 2 threefold negatively charged anions. The results show that simple predictions of the properties of the hydrates appear impossible and that an accurate quantum mechanical simulation in cooperation with sophisticated experimental investigations seems the only way to obtain conclusive results.

  14. The Penetration Behavior of an Annular Gas-Solid Jet Impinging on a Liquid Bath: The Effects of the Density and Size of Solid Particles

    NASA Astrophysics Data System (ADS)

    Chang, J. S.; Sohn, H. Y.

    2012-08-01

    Top-blow injection of a gas-solid jet through a circular lance is used in the Mitsubishi Continuous Smelting Process. One problem associated with this injection is the severe erosion of the hearth refractory below the lances. A new configuration of the lance to form an annular gas-solid jet rather than the circular jet was designed in this laboratory. With this new configuration, the solid particles fed through the center tube leave the lance at a much lower velocity than the gas, and the penetration behavior of the jet is significantly different from that with a circular lance where the solid particles leave the lance at the same high velocity as the gas. In previous cold-model investigations in this laboratory, the effects of the gas velocity, particle feed rate, lance height of the annular lance, and the cross-sectional area of the gas jet were studied and compared with the circular lance. This study examined the effect of the density and size of the solid particles on the penetration behavior of the annular gas-solid jet, which yielded some unexpected results. The variation in the penetration depth with the density of the solid particles at the same mass feed rate was opposite for the circular lance and the annular lance. In the case of the circular lance, the penetration depth became shallower as the density of the solid particles increased; on the contrary, for the annular lance, the penetration depth became deeper with the increasing density of particles. However, at the same volumetric feed rate of the particles, the density effect was small for the circular lance, but for the annular lance, the jets with higher density particles penetrated more deeply. The variation in the penetration depth with the particle diameter was also different for the circular and the annular lances. With the circular lance, the penetration depth became deeper as the particle size decreased for all the feed rates, but with the annular lance, the effect of the particle size was

  15. Natural Gas Hydrates Update 1998-2000

    EIA Publications

    2001-01-01

    Significant events have transpired on the natural gas hydrate research and development front since "Future Supply Potential of Natural Gas Hydrates" appeared in Natural Gas 1998 Issues and Trends and in the Potential Gas Committee's 1998 biennial report.

  16. Effect of hydrophilic walls on the hydration of sodium cations in planar nanopores

    NASA Astrophysics Data System (ADS)

    Shevkunov, S. V.

    2016-09-01

    A computer simulation of the structure of Na+ ion hydration shells with sizes in the range of 1 to 100 molecules in a planar model nanopore 0.7 nm wide with structureless hydrophilic walls is performed using the Monte Carlo method at a temperature of 298 K. A detailed model of many-body intermolecular interactions, calibrated with reference to experimental data on the free energy and enthalpy of reactions after gaseous water molecules are added to a hydration shell, is used. It is found that perturbations produced by hydrophilic walls cause the hydration shell to decay into two components that differ in their spatial arrangement and molecular orientational order.

  17. Methods to determine hydration states of minerals and cement hydrates

    SciTech Connect

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars

    2014-11-15

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  18. Molecular Dynamics Modeling of Hydrated Calcium-Silicate-Hydrate (CSH) Cement Molecular Structure

    DTIC Science & Technology

    2014-08-30

    properties of key hydrated cement constituent calcium-silicate-hydrate (CSH) at the molecular, nanometer scale level. Due to complexity, still unknown...public release; distribution is unlimited. Molecular Dynamics Modeling of Hydrated Calcium-Silicate- Hydrate (CSH) Cement Molecular Structure The views... Cement Molecular Structure Report Title Multi-scale modeling of complex material systems requires starting from fundamental building blocks to

  19. Natural gas hydrates; vast resource, uncertain future

    USGS Publications Warehouse

    Collett, T.S.

    2001-01-01

    Gas hydrates are naturally occurring icelike solids in which water molecules trap gas molecules in a cagelike structure known as a clathrate. Although many gases form hydrates in nature, methane hydrate is by far the most common; methane is the most abundant natural gas. The volume of carbon contained in methane hydrates worldwide is estimated to be twice the amount contained in all fossil fuels on Earth, including coal.

  20. Hydration and Thermal Expansion in Anatase Nanoparticles.

    PubMed

    Zhu, He; Li, Qiang; Ren, Yang; Fan, Longlong; Chen, Jun; Deng, Jinxia; Xing, Xianran

    2016-08-01

    A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

  1. Hydration and Thermal Expansion in Anatase Nanoparticles

    SciTech Connect

    Zhu, He; Li, Qiang; Ren, Yang; Fan, Longlong; Chen, Jun; Deng, Jinxia; Xing, Xianran

    2016-06-06

    A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

  2. De novo synthesis of natural products via the asymmetric hydration of polyenes.

    PubMed

    Wang, Yanping; Xing, Yalan; Zhang, Qi; O'Doherty, George A

    2011-08-14

    For the last ten years our group has been working toward the development of an asymmetric hydration approach to polyketide natural products based on the regioselective hydration of di- and tri-enoates. Key to the success of this approach is the recognition that both high regiocontrol and asymmetric induction could be obtained by the use of a Sharpless asymmetric dihydroxylation reaction. Herein we describe the development of the method and its application to natural product total synthesis.

  3. Calculation of multicomponent chemical equilibria in gas-solid- liquid systems: calculation methods, thermochemical data, and applications to studies of high-temperature volcanic gases with examples from Mount St. Helens

    USGS Publications Warehouse

    Symonds, R.B.; Reed, M.H.

    1993-01-01

    This paper documents the numerical formulations, thermochemical data base, and possible applications of computer programs, SOLVGAS and GASWORKS, for calculating multicomponent chemical equilibria in gas-solid-liquid systems. SOLVGAS and GASWORKS compute simultaneous equilibria by solving simultaneously a set of mass balance and mass action equations written for all gas species and for all gas-solid or gas-liquid equilibria. Examples of gas-evaporation-from-magma and precipitation-with-cooling calculations for volcanic gases collected from Mount St. Helens are shown. -from Authors

  4. Acid-Catalyzed Hydration of anti-Sesquinorbornene.

    PubMed

    Slebocka-Tilk, H.; Brown, R. S.

    1996-11-15

    The acid-catalyzed hydration of anti-sesquinorbornene (1) has been studied at 25 degrees C in 20% DME/H(2)O from 0.001 M < [HC1] < 0.05 M. The second-order rate constant for hydration is 5.35 +/- 0.07 M(-)(1) s(-)(1) which can be compared with a value of 1.38 +/- 0.06 M(-)(1) s(-)(1) for ethyl vinyl ether determined under the same conditions. The solvent deuterium kinetic isotope effect for hydration of 1 is 2.7, and a plot of the observed second-order rate constant for the hydration in a mixed solvent system of H(2)O/D(2)O against the atom fraction of deuterium (n) is bowed upward. The reaction also shows marked buffer catalysis by formic, chloroacetic, and dichloroacetic acids, the Brønsted alpha being 1 for these three carboxylic acids: H(3)O(+) does not fit on this Brønsted line. A mechanism for the reaction is presented which is consistent with the generally accepted one for acid-catalyzed hydration of an alkene in which the rate-limiting step involves proton transfer from H(3)O(+) to the double bond. Whether attack of a second water on the developing carbocation occurs simultaneously with protonation cannot be ascertained from the data for 1, but if so, the extent of its C-OH(2) bond formation must be small enough that there is little change in the bonding of these O-H bonds.

  5. Why alite stops hydrating below 80% relative humidity

    SciTech Connect

    Flatt, Robert J.; Scherer, George W.; Bullard, Jeffrey W.

    2011-09-15

    It has been observed that the hydration of cement paste stops when the relative humidity drops below about 80%. A thermodynamic analysis shows that the capillary pressure exerted at that RH shifts the solubility of tricalcium silicate, so that it is in equilibrium with water. This is a reflection of the chemical shrinkage in this system: according to Le Chatelier's principle, since the volume of the products is less than that of the reactants, a negative (capillary) pressure opposes the reaction.

  6. Direct measurement of vertical binding energy of a hydrated electron.

    PubMed

    Tang, Ying; Shen, Huan; Sekiguchi, Kentaro; Kurahashi, Naoya; Mizuno, Tomoya; Suzuki, Yoshi-ichi; Suzuki, Toshinori

    2010-04-21

    We present the first measurement of the vertical binding energy (VBE) of a hydrated electron in bulk water by the time-resolved photoelectron spectroscopy (TRPES) of the charge-transfer-to-solvent (CTTS) reaction in aqueous NaI solution. Our best estimate of VBE is 3.27 +/- 0.10 eV for H(2)O and 3.20 +/- 0.10 eV for D(2)O.

  7. Kinetics of methane hydrate replacement with carbon dioxide and nitrogen gas mixture using in situ NMR spectroscopy.

    PubMed

    Cha, Minjun; Shin, Kyuchul; Lee, Huen; Moudrakovski, Igor L; Ripmeester, John A; Seo, Yutaek

    2015-02-03

    In this study, the kinetics of methane replacement with carbon dioxide and nitrogen gas in methane gas hydrate prepared in porous silica gel matrices has been studied by in situ (1)H and (13)C NMR spectroscopy. The replacement process was monitored by in situ (1)H NMR spectra, where about 42 mol % of the methane in the hydrate cages was replaced in 65 h. Large amounts of free water were not observed during the replacement process, indicating a spontaneous replacement reaction upon exposing methane hydrate to carbon dioxide and nitrogen gas mixture. From in situ (13)C NMR spectra, we confirmed that the replacement ratio was slightly higher in small cages, but due to the composition of structure I hydrate, the amount of methane evolved from the large cages was larger than that of the small cages. Compositional analysis of vapor and hydrate phases was also carried out after the replacement reaction ceased. Notably, the composition changes in hydrate phases after the replacement reaction would be affected by the difference in the chemical potential between the vapor phase and hydrate surface rather than a pore size effect. These results suggest that the replacement technique provides methane recovery as well as stabilization of the resulting carbon dioxide hydrate phase without melting.

  8. Gas hydrate hunting in China seas

    NASA Astrophysics Data System (ADS)

    Yang, J.; Zhang, X.; Chen, J.; Xiang, Q.; Ye, Y.; Gong, J.

    2003-04-01

    Gas hydrate research is a hotspot now in geosciences. Many countries have carried on gas hydrate survey and research for many years. China, as a country with large sea areas unfolded gas hydrate research work in its marine areas in 1999 and tries to keep pace with the advanced countries on gas hydrate study. Substantial funds were launched by various governmental and non-governmental funding agencies to support gas hydrate research. Many institutions on marine geosciences are involved in. China Geological Survey (CGS) has launched several research projects in the sea. So far, some fieldwork such as seismic survey, sampling, profiling, underwater video imaging have been done in South China Sea and East China Sea areas. Some preliminary results have been achieved. BSRs are found in many seismic profiles. Some potential gas hydrate bearing areas are marked and potential amount of gas hydrate resources is calculated. At the same time, gas hydrate laboratory was founded and successful experiments have been carried out to model the gas hydrate synthesis in accordance with the geological condition of the China seas. Now, gas hydrate detecting techniques such as sampling equipment (PCS), seismic data processing, interpretation and the formation mechanism study as well as environmental effect research are undergoing. Though China's gas hydrate research work is still at its initial stage, China is willing to be an active member in the international society of gas hydrate study and hopes to contribute its effort.

  9. 77 FR 40032 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-06

    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee.... SUPPLEMENTARY INFORMATION: Purpose of the Committee: The purpose of the Methane Hydrate Advisory Committee is...

  10. 75 FR 9886 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-04

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... Methane Hydrate Advisory Committee is to provide advice on potential applications of methane hydrate...

  11. Stability of prostacyclin analogues: an unusual lack of reactivity in acid-catalyzed alkene hydration.

    PubMed

    Magill, A; O'Yang, C; Powell, M F

    1988-04-01

    Prostacyclin analogue 5 undergoes specific acid-catalyzed hydration (kH+ = 1.9 x 10(-7)M-1 sec-1 at 25 degrees C) and a pH-independent oxidation reaction (k0 = 1.2 x 10(-10) sec-1 at 25 degrees C) above pH approximately 5. The hydration reaction for 5 is much slower than for other structurally similar exocyclic alkenes, even though the rate-determining step is proton transfer. This slowness of reaction and an analysis of the pH-rate profile show that 5 does not exhibit significant intramolecular general acid catalysis, as does prostacyclin.

  12. In-line continuous sizing of biomass particles in gas-solid two-phase flow at a biomass-fired power plant

    NASA Astrophysics Data System (ADS)

    Gao, L.; Yan, Y.; Sun, D.; Qian, X.; Xu, C. L.

    2014-04-01

    Gas-solid two-phase flows are widely seen in many industrial processes. A good exampleis the pneumatically conveyed pulverised fuel flow in the power generation industry. As a significant renewable fuel source, biomass has been widely adopted in electrical power generation. The particle size distribution of pneumatically conveyed biomass correlates closely with combustion efficiency and pollutant emissions and should therefore be monitored on anin-line, continuous basis. In this paper an integrated instrumentation system using both a piezoelectric sensorand anelectrostatic sensor arrayis proposed to measure the size distribution and flow velocity of biomass particles. A prototype system was tested on a 250mm bore pipe at a biomass-fired power plantand its performance has been evaluated under industrial conditions.

  13. Engineering models for the gas-solid motion and interaction in the return loop of circulating fluidized beds. Topical report, January 1992--June 1992

    SciTech Connect

    Celik, I.; Zhang, G.Q.

    1992-08-01

    It is reported on development, testing and verification of engineering models for predicting the pressure drop, the solids flow rate, and the downcoming gas flow rate through an L-valve for a given aeration flow rate. The models are, in particular, applicable for studying the one-dimensional gas-solids motion through the return loop of a circulating fluidized bed. A literature review is presented in a comparative manner. One-dimensional transient equations governing the dense two-phase flows are derived. Those equations are then used to deduce relevant characteristic dimensionless parameters. Experimental data from literature have been analyzed and empirical correlations are suggested. A calculation procedure is proposed for predicting relevant gas and solid flow parameters. The model is based on integrated conservation equations for mass and momentum for both phases. Some experiments of our own have been performed and the data have been analyzed. The model is calibrated against experimental data.

  14. Analysis of pressure drop characteristics and methods for calculating gas and gas-solid flow in horizontal pipes for dilute coal conveying system

    SciTech Connect

    Weiguo Pan; Zuohe Chi; Yongjing Liao

    1997-07-01

    This article reported pressure drop characteristics and methods for calculating friction factors {lambda} 0 and {lambda}{sub {mu}} for gas and gas-solids flows, respectively, in straight horizontal pipes are summarized advantages seed. The and disadvantages of calculating friction factor {lambda}{sub {mu}} through dimensional analysis in comparison with model simulation are analyzed. It is pointed out that model simulation is more suitable to engineering use than dimensional analysis. According to experimental results of dilute gas-coal powder flow in straight horizontal pipes of the coal pulverization system in a power plant; an empirical formula and a theoretical formula for calculating friction factor {lambda}{sub {mu}} in straight horizontal pipes transporting dilute coal powder are obtained.

  15. Terahertz sensing of corneal hydration.

    PubMed

    Singh, Rahul S; Tewari, Priyamvada; Bourges, Jean Louis; Hubschman, Jean Pierre; Bennett, David B; Taylor, Zachary D; Lee, H; Brown, Elliott R; Grundfest, Warren S; Culjat, Martin O

    2010-01-01

    An indicator of ocular health is the hydrodyanmics of the cornea. Many corneal disorders deteriorate sight as they upset the normal hydrodynamics of the cornea. The mechanisms include the loss of endothelial pump function of corneal dystophies, swelling and immune response of corneal graft rejection, and inflammation and edema, which accompany trauma, burn, and irritation events. Due to high sensitivity to changes of water content in materials, a reflective terahertz (300 GHz and 3 THz) imaging system could be an ideal tool to measure the hydration level of the cornea. This paper presents the application of THz technology to visualize the hydration content across ex vivo porcine corneas. The corneas, with a thickness variation from 470 - 940 µm, were successfully imaged using a reflective pulsed THz imaging system, with a maximum SNR of 50 dB. To our knowledge, no prior studies have reported on the use of THz in measuring hydration in corneal tissues or other ocular tissues. These preliminary findings indicate that THz can be used to accurately sense hydration levels in the cornea using a pulsed, reflective THz imaging system.

  16. Hydration rind dates rhyolite flows

    USGS Publications Warehouse

    Friedman, I.

    1968-01-01

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  17. Attraction between hydrated hydrophilic surfaces

    NASA Astrophysics Data System (ADS)

    Kanduč, Matej; Schneck, Emanuel; Netz, Roland R.

    2014-08-01

    According to common knowledge, hydrophilic surfaces repel via hydration forces while hydrophobic surfaces attract, but mounting experimental evidence suggests that also hydrophilic surfaces can attract. Using all-atom molecular dynamics simulations at prescribed water chemical potential we study the crossover from hydration repulsion to hydrophobic attraction for planar polar surfaces of varying stiffness and hydrogen-bonding capability. Rescaling the partial charges of the polar surface groups, we cover the complete spectrum from very hydrophobic surfaces (characterized by contact angles θ ≃ 135°) to hydrophilic surfaces exhibiting complete wetting (θ = 0°). Indeed, for a finite range θadh < θ < 90°, we find a regime where hydrophilic surfaces attract at sub-nanometer separation and stably adhere without intervening water. The adhesive contact angle θadh depends on surface type and lies in the range 65° < θadh < 80°, in good agreement with experiments. Analysis of the total number of hydrogen bonds (HBs) formed by water and surface groups rationalizes this crossover between hydration repulsion and hydrophilic attraction in terms of a subtle balance: Highly polar surfaces repel because of strongly bound hydration water, less polar hydrophilic surfaces attract because water-water HBs are preferred over surface-water HBs. Such solvent reorganization forces presumably underlie also other important phenomena, such as selective ion adsorption to interfaces as well as ion pair formation.

  18. Hydration rind dates rhyolite flows.

    PubMed

    Friedman, I

    1968-02-23

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  19. Is Br2 hydration hydrophobic?

    NASA Astrophysics Data System (ADS)

    Alcaraz-Torres, A.; Gamboa-Suárez, A.; Bernal-Uruchurtu, M. I.

    2017-02-01

    The spectroscopic properties of bromine in aqueous systems suggest it can behave as either hydrophilic or hydrophobic solute. In small water clusters, the halogen bond and the hydrogen-halogen interaction are responsible for its specific way of binding. In water hydrates, it is efficiently hosted by two different cages forming the crystal structure and it has been frequently assumed that there is little or no interaction between the guest and the host. Bromine in liquid solution poses a challenging question due to its non-negligible solubility and the large blue shift measured in its absorption spectra. Using a refined semi-empirical force field, PM3-PIF, we performed a Born-Oppenheimer molecular dynamics study of bromine in liquid water. Here we present a detailed study in which we retrieved the most representative hydration structures in terms of the most frequent positions around bromine and the most common water orientations. Albeit being an approximate description of the total hydration phenomenon, it captures the contribution of the leading molecular interactions in form of the recurrent structures. Our findings confirm that the spectroscopic signature is mainly caused by the closest neighbors. The dynamics of the whole first hydration shell strongly suggests that the external molecules in that structure effectively isolate the bulk from the presence of bromine. The solvation structure fluctuates from a hydrophilic to a hydrophobic-like environment along the studied trajectory.

  20. Model of Methane Hydrate Formation in Mid-ocean Ridges

    NASA Astrophysics Data System (ADS)

    Dmitrievsky, A. N.; Balanyuk, I. E.; Sorokhtin, O. G.; Matveenkov, V. V.; Dongaryan, L. Sh.

    2003-04-01

    MODEL OF METHANE HYDRATE FORMATION IN MID-OCEAN RIDGES A.N. Dmitrievsky, I.E. Balanyuk, O.G.Sorokhtin, V.V. Matveenkov, and L.Sh. Dongaryan P.P.Shirshov Institute of Oceanology Russian Academy of Sciences Moscow, Russia, balanyuk@sio.rssi.ru One among the most perspective direction in studying the ocean floor is the research of hydrothermal fields within the most active zones — rift valleys, where the processes of spreading of the ocean floor, uplift of the deep matter to the surface of the ocean floor, and creation of the new oceanic crust occur. Volcanic activity in these zones is accompanied with the formation of the hydrothermal system executing separation, transfer, and precipitation of a series of chemical elements. It is known that ore deposits with high concentration of iron, manganese, copper, nickel, cobalt are formed as a result of hydrothermal activity. It is much less known that hydrothermal activity in these zones has important but not so evident result — the formation of hydrocarbons in the form of methane hydrates. We propose the hypothesis of formation of methane hydrate deposits over the shallow slopes of the mid-oceanic ridges as an outcome of the action of two factors: the thermal convection of water in fractured-porous rocks of the crust and the reaction of serpentinization of the crust. The intensive exhalation of hydrocarbons takes place in the process of serpentinization. The conditions of water convection in the porous media are favorable for the formation and accumulation of methane hydrates in the near-surface layers of the oceanic crust. The carbonic-acid gas dissolved in the seawater is involved into the process of methane hydrate formation. It was established that the most favorable conditions for this mechanism are over the slopes of the Mid-Atlantic Ridge. All types of water areas where gas hydrates occur can be conditionally subdivided into following geodynamic zones: the abyssal basins of the inner and marginal seas, the

  1. Enhanced Photoreduction of Nitro-aromatic Compounds by Hydrated Electrons Derived from Indole on Natural Montmorillonite.

    PubMed

    Tian, Haoting; Guo, Yong; Pan, Bo; Gu, Cheng; Li, Hui; Boyd, Stephen A

    2015-07-07

    A new photoreduction pathway for nitro-aromatic compounds (NACs) and the underlying degradation mechanism are described. 1,3-Dinitrobenzene was reduced to 3-nitroaniline by the widely distributed aromatic molecule indole; the reaction is facilitated by montmorillonite clay mineral under both simulated and natural sunlight irradiation. The novel chemical reaction is strongly affected by the type of exchangeable cation present on montmorillonite. The photoreduction reaction is initiated by the adsorption of 1,3-dinitrobenzene and indole in clay interlayers. Under light irradiation, the excited indole molecule generates a hydrated electron and the indole radical cation. The structural negative charge of montmorillonite plausibly stabilizes the radical cation hence preventing charge recombination. This promotes the release of reactive hydrated electrons for further reductive reactions. Similar results were observed for the photoreduction of nitrobenzene. In situ irradiation time-resolved electron paramagnetic resonance and Fourier transform infrared spectroscopies provided direct evidence for the generation of hydrated electrons and the indole radical cations, which supported the proposed degradation mechanism. In the photoreduction process, the role of clay mineral is to both enhance the generation of hydrated electrons and to provide a constrained reaction environment in the galley regions, which increases the probability of contact between NACs and hydrated electrons.

  2. Thermal properties of methane gas hydrates

    USGS Publications Warehouse

    Waite, William F.

    2007-01-01

    Gas hydrates are crystalline solids in which molecules of a “guest” species occupy and stabilize cages formed by water molecules. Similar to ice in appearance (fig. 1), gas hydrates are stable at high pressures and temperatures above freezing (0°C). Methane is the most common naturally occurring hydrate guest species. Methane hydrates, also called simply “gas hydrates,” are extremely concentrated stores of methane and are found in shallow permafrost and continental margin sediments worldwide. Brought to sea-level conditions, methane hydrate breaks down and releases up to 160 times its own volume in methane gas. The methane stored in gas hydrates is of interest and concern to policy makers as a potential alternative energy resource and as a potent greenhouse gas that could be released from sediments to the atmosphere and ocean during global warming. In continental margin settings, methane release from gas hydrates also is a potential geohazard and could cause submarine landslides that endanger offshore infrastructure. Gas hydrate stability is sensitive to temperature changes. To understand methane release from gas hydrate, the U.S. Geological Survey (USGS) conducted a laboratory investigation of pure methane hydrate thermal properties at conditions relevant to accumulations of naturally occurring methane hydrate. Prior to this work, thermal properties for gas hydrates generally were measured on analog systems such as ice and non-methane hydrates or at temperatures below freezing; these conditions limit direct comparisons to methane hydrates in marine and permafrost sediment. Three thermal properties, defined succinctly by Briaud and Chaouch (1997), are estimated from the experiments described here: - Thermal conductivity, λ: if λ is high, heat travels easily through the material. - Thermal diffusivity, κ: if κ is high, it takes little time for the temperature to rise in the material. - Specific heat, cp: if cp is high, it takes a great deal of heat to

  3. Physical activity, hydration and health.

    PubMed

    Marcos, Ascensión; Manonelles, Pedro; Palacios, Nieves; Wärnberg, Julia; Casajús, José A; Pérez, Margarita; Aznar, Susana; Benito, Pedro J; Martínez-Gomez, David; Ortega, Francisco B; Ortega, Eduardo; Urrialde, Rafael

    2014-06-01

    Since the beginning of mankind, man has sought ways to promote and preserve health as well as to prevent disease. Hydration, physical activity and exercise are key factors for enhancing human health. However, either a little dose of them or an excess can be harmful for health maintenance at any age. Water is an essential nutrient for human body and a major key to survival has been to prevent dehydration. However, there is still a general controversy regarding the necessary amount to drink water or other beverages to properly get an adequate level of hydration. In addition, up to now the tools used to measure hydration are controversial. To this end, there are several important groups of variables to take into account such as water balance, hydration biomarkers and total body water. A combination of methods will be the most preferred tool to find out any risk or situation of dehydration at any age range. On the other hand, physical activity and exercise are being demonstrated to promote health, avoiding or reducing health problems, vascular and inflammatory disea ses and helping weight management. Therefore, physical activity is also being used as a pill within a therapy to promote health and reduce risk diseases, but as in the case of drugs, dose, intensity, frequency, duration and precautions have to be evaluated and taken into account in order to get the maximum effectiveness and success of a treatment. On the other hand, sedentariness is the opposite concept to physical activity that has been recently recognized as an important factor of lifestyle involved in the obesogenic environment and consequently in the risk of the non-communicable diseases. In view of the literature consulted and taking into account the expertise of the authors, in this review a Decalogue of global recommendations is included to achieve an adequate hydration and physical activity status to avoid overweight/obesity consequences.

  4. Mesoscale texture of cement hydrates

    PubMed Central

    Ioannidou, Katerina; Krakowiak, Konrad J.; Bauchy, Mathieu; Hoover, Christian G.; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J.-M.; Del Gado, Emanuela

    2016-01-01

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium–silicate–hydrates (C–S–H) during cement hydration. Controlling structure and properties of the C–S–H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C–S–H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C–S–H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C–S–H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C–S–H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  5. Chloral hydrate for sedation of children with asthma during dental treatment.

    PubMed

    Abdulhamid, I; Tremblay, M; Stenger, J; Tutag Lehr, V

    2016-06-01

    We hypothesised that chloral hydrate is safe and effective for sedation during dental treatments for children with mild asthma. We evaluated the safety and efficacy of chloral hydrate by measuring changes in heart rate (HR), transcutaneous oxygen saturation, (SpO2), asthma score, behaviour, types and frequency of adverse reactions associated with chloral hydrate were assessed throughout treatment. Children (<10 years old) with mild asthma undergoing dental treatments received a single 65 mg/kg oral dose of chloral hydrate liquid 1 hour prior to treatment in an open label trial. Heart rate (HR), SpO2, asthma score, behaviour, types and frequency of adverse reactions associated with chloral hydrate were assessed throughout treatment. Asthma score was obtained before and after treatment. Thirty minutes after treatment, SpO2, HR, and level of consciousness was assessed. Twenty four children were enrolled and 92% (22/24) recovered from sedation without respiratory depression. Two experienced mild respiratory depression related to chloral hydrate. Asthma was not a contributing factor as they did not experience wheezing, cough, tachypnoea, or retractions. Inhaled nitrous oxide supplemented chloral hydrate sedation in 63% (15/24) children to achieve effective cooperation. Three children had a SpO2 <95% (2 during treatment, 1 during recovery). Chloral hydrate 65 mg/kg administered a as single oral dose appears to be safe with respect to disease exacerbation for children with mild asthma undergoing dental treatment. Due to ineffective sedation and mild respiratory depression associated with chloral hydrate, newer, easily titrated medications, such as midazolam, may offer advantages.

  6. Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

    USGS Publications Warehouse

    Stern, L.A.; Kirby, S.H.; Durham, W.B.

    1998-01-01

    We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s???1) ??? CH4??6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25-30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140-200 K, Pc = 50-100 MPa, and ?? = 10-4 10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing

  7. Lactate Dehydrogenase Catalysis: Roles of Keto, Hydrated, and Enol Pyruvate

    NASA Astrophysics Data System (ADS)

    Meany, J. E.

    2007-09-01

    Many carbonyl substrates of oxidoreductase enzymes undergo hydration and enolization so that these substrate systems are partitioned between keto, hydrated (gem-diol), and enol forms in aqueous solution. Some oxidoreductase enzymes are subject to inhibition by high concentrations of substrate. For such enzymes, two questions arise pertaining to enzyme "substrate" interactions: (i) which form of the substrate system serves as the preferential substrate and (ii) which form acts to inhibit the enzyme? Thus the relative concentrations of the forms of these substrate systems (keto, hydrated, enol) may provide a form of metabolic control. In this light, the present article considers the reduction of pyruvate by lactate dehydrogenase in the presence of NADH. This reaction is inhibited by relatively high concentrations of pyruvate and the physiological significance of this inhibition has been a subject of controversy for many years. Summarized in this article are data from the literature pertaining to the interactions of keto, hydrated, and enol pyruvate with lactate dehydrogenase. Biochemistry instructors and their students are invited to review such pertinent articles so that they also may evaluate the possibility that the "substrate" inhibition of the isoenzymes in the heart muscle may be, under certain conditions, relevant as a form of metabolic control.

  8. Gas hydrate reservoir characteristics and economics

    SciTech Connect

    Collett, T.S.; Bird, K.J.; Burruss, R.C.; Lee, Myung W.

    1992-06-01

    The primary objective of the DOE-funded USGS Gas Hydrate Program is to assess the production characteristics and economic potential of gas hydrates in northern Alaska. The objectives of this project for FY-1992 will include the following: (1) Utilize industry seismic data to assess the distribution of gas hydrates within the nearshore Alaskan continental shelf between Harrison Bay and Prudhoe Bay; (2) Further characterize and quantify the well-log characteristics of gas hydrates; and (3) Establish gas monitoring stations over the Eileen fault zone in northern Alaska, which will be used to measure gas flux from destabilized hydrates.

  9. Gas hydrate reservoir characteristics and economics

    SciTech Connect

    Collett, T.S.; Bird, K.J.; Burruss, R.C.; Lee, Myung W.

    1992-01-01

    The primary objective of the DOE-funded USGS Gas Hydrate Program is to assess the production characteristics and economic potential of gas hydrates in northern Alaska. The objectives of this project for FY-1992 will include the following: (1) Utilize industry seismic data to assess the distribution of gas hydrates within the nearshore Alaskan continental shelf between Harrison Bay and Prudhoe Bay; (2) Further characterize and quantify the well-log characteristics of gas hydrates; and (3) Establish gas monitoring stations over the Eileen fault zone in northern Alaska, which will be used to measure gas flux from destabilized hydrates.

  10. Surface reactions of natural glasses

    SciTech Connect

    White, A.F.

    1986-12-31

    Reactions at natural glass surfaces are important in studies involving nuclear waste transport due to chemical control on ground water in host rocks such as basalt and tuff, to potential diffusion into natural hydrated glass surfaces and as natural analogs for waste glass stability. Dissolution kinetics can be described by linear surface reaction coupled with cation interdiffusion with resulting rates similar to those of synthetic silicate glasses. Rates of Cs diffusion into hydrated obsidian surfaces between 25{sup 0} and 75{sup 0}C were determined by XPS depth profiles and loss rates from aqueous solutions. Calculated diffusion coefficients were ten others of magnitude more rapid than predicted from an Arrhenius extrapolation of high temperature tracer diffusion data due to surface hydration reactions.

  11. Well log evaluation of gas hydrate saturations

    USGS Publications Warehouse

    Collett, T.S.

    1998-01-01

    The amount of gas sequestered in gas hydrates is probably enormous, but estimates are highly speculative due to the lack of previous quantitative studies. Gas volumes that may be attributed to a gas hydrate accumulation within a given geologic setting are dependent on a number of reservoir parameters; one of which, gas-hydrate saturation, can be assessed with data obtained from downhole well logging devices. The primary objective of this study was to develop quantitative well-log evaluation techniques which will permit the calculation of gas-hydrate saturations in gas-hydrate-bearing sedimentary units. The "standard" and "quick look" Archie relations (resistivity log data) yielded accurate gas-hydrate and free-gas saturations within all of the gas hydrate accumulations assessed in the field verification phase of the study. Compressional wave acoustic log data have been used along with the Timur, modified Wood, and the Lee weighted average acoustic equations to calculate accurate gas-hydrate saturations in all of the gas hydrate accumulations assessed in this study. The well log derived gas-hydrate saturations calculated in the field verification phase of this study, which range from as low as 2% to as high as 97%, confirm that gas hydrates represent a potentially important source of natural gas.

  12. Handbook of gas hydrate properties and occurrence

    SciTech Connect

    Kuustraa, V.A.; Hammershaimb, E.C.

    1983-12-01

    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  13. Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

    USGS Publications Warehouse

    Stern, L.A.; Kirby, S.H.; Durham, W.B.

    1997-01-01

    Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

  14. Growth kinetics and microstructure of methane hydrates formed in porous media

    NASA Astrophysics Data System (ADS)

    Falenty, A.; Klapproth, A.; Techmer, K.; Murshed, M. M.; Kuhs, W. F.

    2007-12-01

    The occurrence of natural gas hydrates within sediments is known from a large number of locations. They commonly occupy pore spaces cementing sedimentary deposits. Yet, detailed information about the influence of mineral composition on the formation process in porous media is still very limited. Laboratory investigations of the microstructure of gas hydrate in porous media, as a function of p-T conditions, mineral composition and water/gas supersaturation are therefore of considerable interest. Such studies may allow a better understanding of the formation process and even the prediction of accumulation /decomposition rates of some natural gas hydrates in a given geological setting. As a model study, we carried out various reactions with methane gas and water in three types of media: 1) quartz, 2) quartz + kaolinite, 3) quartz + montmorillonite. The progress of the reactions was recorded by gas consumption (pressure drop) at 3°C. Samples recovered at various stages of the formation or decomposition reactions were investigated using field-emission scanning electron microscopes (FE-SEM) equipped with a cryo-stage [1]. In the SEM investigations, methane hydrates appeared between the quartz grains acting as cement. Kaolinite particles were observed as a filigree network on the surface of hydrate cement, while montmorillonite form flakes or crust like features. Each of the minerals may play individual/coupled interaction with water and gas hydrate, and thereby display a characteristic configuration in the SEM images. Dissimilar kinetic features, using different porous media at the investigated conditions, confirm that mineral composition directly influences the progress of gas hydrate formation. Medium 3 shows the fastest hydrate saturation. With increasing water content of the porous media the formation tends to proceed in a multi-stage process with a slower diffusion-limited later stage. Reference: [1] A. Klapproth, K. Techmer, S.A. Klapp, M.M. Murshed and W.F. Kuhs

  15. Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1997-01-01

    The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.

  16. Well log characterization of natural gas hydrates

    USGS Publications Warehouse

    Collett, Timothy S.; Lee, Myung W.

    2011-01-01

    In the last 25 years we have seen significant advancements in the use of downhole well logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From an early start of using wireline electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells drilled in Arctic permafrost environments to today where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. The most established and well known use of downhole log data in gas hydrate research is the use of electrical resistivity and acoustic velocity data (both compressional- and shear-wave data) to make estimates of gas hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. New downhole logging tools designed to make directionally oriented acoustic and propagation resistivity log measurements have provided the data needed to analyze the acoustic and electrical anisotropic properties of both highly inter-bedded and fracture dominated gas hydrate reservoirs. Advancements in nuclear-magnetic-resonance (NMR) logging and wireline formation testing have also allowed for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids (i.e., free-water along with clay and capillary bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas hydrate reservoir properties (i.e., permeabilities) needed to accurately predict gas production rates for various gas hydrate

  17. Thermal conductivity of hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn

    2009-11-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

  18. Experimental hydration studies of natural and synthetic glasses

    SciTech Connect

    Bates, J.K.; Abrajano, T.A. Jr.; Ebert, W.L.; Mazer, J.J.; Gerding, T.J.

    1988-01-01

    The results of a series of hydration experiments on natural glasses (Hawaiian basalt, obsidian) and the nuclear waste glass WV-44 done to examine laboratory methods of accelerating reaction processes are summarized. The glasses were reacted in hydrothermal solution and in saturated vapor water. It was found that different reaction rates and processes were found using the differing conditions, and that laboratory efforts to accelerate and duplicate natural processes must amount for the physical processes that occur naturally. 18 refs., 5 figs., 1 tab.

  19. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Sultan, N.; Bohrmann, G.; Ruffine, L.; Pape, T.; Riboulot, V.; Colliat, J.-L.; De Prunelé, A.; Dennielou, B.; Garziglia, S.; Himmler, T.; Marsset, T.; Peters, C. A.; Rabiu, A.; Wei, J.

    2014-04-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

  20. Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition.

    PubMed

    Buchanan, Piers; Soper, Alan K; Thompson, Helen; Westacott, Robin E; Creek, Jefferson L; Hobson, Greg; Koh, Carolyn A

    2005-10-22

    Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.

  1. Improvement of gas hydrate preservation by increasing compression pressure to simple hydrates of methane, ethane, and propane

    NASA Astrophysics Data System (ADS)

    Kida, Masato; Jin, Yusuke; Watanabe, Mizuho; Murayama, Tetsuro; Nagao, Jiro

    2017-09-01

    In this report, we describe the dissociation behavior of gas hydrate grains pressed at 1 and 6 MPa. Certain simple gas hydrates in powder form show anomalous preservation phenomenon under their thermodynamic unstable condition. Investigation of simple hydrates of methane, ethane, and propane reveals that high pressure applied to the gas hydrate particles enhances their preservation effects. Application of high pressure increases the dissociation temperature of methane hydrate and has a restrictive effect against the dissociation of ethane and propane hydrate grains. These improvements of gas hydrate preservation by increasing pressure to the initial gas hydrate particles imply that appropriate pressure applied to gas hydrate particles enhances gas hydrate preservation effects.

  2. How Sodium Chloride Salt Inhibits the Formation of CO2 Gas Hydrates.

    PubMed

    Holzammer, Christine; Finckenstein, Agnes; Will, Stefan; Braeuer, Andreas S

    2016-03-10

    We present an experimental Raman study on how the addition of sodium chloride to CO2-hydrate-forming systems inhibits the hydrate formation thermodynamically. For this purpose, the molar enthalpy of reaction and the molar entropy of reaction for the reaction of weakly hydrogen-bonded water molecules to strongly hydrogen bonded water molecules are determined for different salinities from the Raman spectrum of the water-stretching vibration. Simultaneously, the influence of the salinity on the solubility of CO2 in the liquid water-rich phase right before the start of hydrate formation is analyzed. The results demonstrate that various mechanisms contribute to the inhibition of gas hydrate formation. For the highest salt concentration of 20 wt % investigated, the temperature of gas hydrate formation is lowered by 12 K. For this concentration the molar enthalpy and entropy of reaction become smaller by 50 and 20%, respectively. Concurrently, the solubility of carbon dioxide is reduced by 70%. These results are compared with data in literature for systems of sodium chloride in water (without carbon dioxide).

  3. Uranyl p-toluenesulphonate and its crystal hydrates. Synthesis and dehydration-hydration processes

    NASA Astrophysics Data System (ADS)

    Baluev, A. V.; Mityakhina, V. S.; Bogachev, S. V.; Suglobova, I. G.

    2003-01-01

    Lowest hydrates of uranyl p-toluenesulphonate (UPTS) and anhydrous salt were synthesised. The dehydration-hydration processes were studied by thermal gravimetric analysis. It has been established that the hydrate shell of UPTS has a layered structure. The IR spectra of UPTS and its hydrates were recorded. It was found that the IR spectra of UPTS crystal hydrates of the same composition, produced in dehydration-hydration, noticeably differ in the range of water vibrations and are the same in the range corresponding to vibrations of sulphonate groups.

  4. Soda Incorporation During Hydrate Precipitation

    NASA Astrophysics Data System (ADS)

    Vernon, Chris; Loh, Joanne; Lau, Daniel; Stanley, Andrew

    The economic necessity to achieve high precipitation yields and tough alumina must be balanced against another important quality consideration — occluded soda. Although there are a number of publications that develop hypotheses for the mechanism of soda incorporation, and some that give mathematical relationships to describe the rate of soda incorporation, none attempt to do this with any reference to known physical and chemical phenomena associated with the hydrate (gibbsite) growth mechanism.

  5. Gas hydrate cool storage system

    DOEpatents

    Ternes, Mark P.; Kedl, Robert J.

    1985-01-01

    This invention is a process for formation of a gas hydrate to be used as a cool storage medium using a refrigerant in water. Mixing of the immiscible refrigerant and water is effected by addition of a surfactant and agitation. The difficult problem of subcooling during the process is overcome by using the surfactant and agitation and performance of the process significantly improves and approaches ideal.

  6. Gas hydrate resources of northern Alaska

    USGS Publications Warehouse

    Collett, T.S.

    1997-01-01

    Large amounts of natural gas, composed mainly of methane, can occur in arctic sedimentary basins in the form of gas hydrates under appropriate temperature and pressure conditions. Gas hydrates are solids, composed of rigid cages of water molecules that trap molecules of gas. These substances are regarded as a potential unconventional source of natural gas because of their enormous gas-storage capacity. Most published gas hydrate resource estimates are highly simplified and based on limited geological data. The gas hydrate resource assessment for northern Alaska presented in this paper is based on a "play analysis" scheme, in which geological factors controlling the accumulation and preservation of gas hydrates are individually evaluated and risked for each hydrate play. This resource assessment identified two gas hydrate plays; the in-place gas resources within the gas hydrates of northern Alaska are estimated to range from 6.7 to 66.8 trillion cubic metres of gas (236 to 2,357 trillion cubic feet of gas), at the 0.50 and 0.05 probability levels respectively. The mean in-place hydrate resource estimate for northern Alaska is calculated to be 16.7 trillion cubic metres of gas (590 trillion cubic feet of gas). If this assessment is valid, the amount of natural gas stored as gas hydrates in northern Alaska could be almost seven times larger then the estimated total remaining recoverable conventional natural gas resources in the entire United States.

  7. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, H.K. Jr.

    1983-05-31

    An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means for separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means. 7 figs.

  8. Well log evaluation of gas hydrate saturations

    USGS Publications Warehouse

    Collett, Timothy S.

    1998-01-01

    The amount of gas sequestered in gas hydrates is probably enormous, but estimates are highly speculative due to the lack of previous quantitative studies. Gas volumes that may be attributed to a gas hydrate accumulation within a given geologic setting are dependent on a number of reservoir parameters; one of which, gas-hydrate saturation, can be assessed with data obtained from downhole well logging devices. The primary objective of this study was to develop quantitative well-log evaluation techniques which will permit the calculation of gas-hydrate saturations in gas-hydrate-bearing sedimentary units. The `standard' and `quick look' Archie relations (resistivity log data) yielded accurate gas-hydrate and free-gas saturations within all of the gas hydrate accumulations assessed in the field verification phase of the study. Compressional wave acoustic log data have been used along with the Timur, modified Wood, and the Lee weighted average acoustic equations to calculate accurate gas-hydrate saturations in this study. The well log derived gas-hydrate saturations calculated in the field verification phase of this study, which range from as low as 2% to as high as 97%, confirm that gas hydrates represent a potentially important source of natural gas.

  9. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, Jr., Harry K.

    1983-05-31

    An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means or separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means.

  10. Gas hydrates: Technology status report

    SciTech Connect

    Not Available

    1987-01-01

    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  11. Identification of the hydrate gel phases present in phosphate-modified calcium aluminate binders

    SciTech Connect

    Chavda, Mehul A.; Bernal, Susan A.; Apperley, David C.; Kinoshita, Hajime; Provis, John L.

    2015-04-15

    The conversion of hexagonal calcium aluminate hydrates to cubic phases in hydrated calcium aluminate cements (CAC) can involve undesirable porosity changes and loss of strength. Modification of CAC by phosphate addition avoids conversion, by altering the nature of the reaction products, yielding a stable amorphous gel instead of the usual crystalline hydrate products. Here, details of the environments of aluminium and phosphorus in this gel were elucidated using solid-state NMR and complementary techniques. Aluminium is identified in both octahedral and tetrahedral coordination states, and phosphorus is present in hydrous environments with varying, but mostly low, degrees of crosslinking. A {sup 31}P/{sup 27}Al rotational echo adiabatic passage double resonance (REAPDOR) experiment showed the existence of aluminium–phosphorus interactions, confirming the formation of a hydrated calcium aluminophosphate gel as a key component of the binding phase. This resolves previous disagreements in the literature regarding the nature of the disordered products forming in this system.

  12. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

    USGS Publications Warehouse

    Circone, S.; Kirby, S.H.; Stern, L.A.

    2006-01-01

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

  13. Assessing hydration disturbances from concrete aggregates with radiation shielding properties by isothermal calorimetry

    NASA Astrophysics Data System (ADS)

    Wadsö, Lars; Cooper-Jensen, Carsten P.; Bentley, Phillip M.

    2017-04-01

    Spallation sources create a large amount of neutrons with energies up to the GeV range. To shield for these neutrons, steel and concrete are important materials. By adding different aggregates to normal concrete, one can improve the shielding effect of the concrete. Some of these aggregates can influence the rate of hydration (reaction) of the cement or even completely inhibit the hydration. It is thus good practice to start the investigation of new shielding concretes by assessing the rate of cement hydration in the presence of new aggregates. This is preferably made with isothermal (heat conduction) calorimetry. In this paper we describe such tests made with a large number of different potential aggregates for a shielding concrete. We found a full range of influence on the hydration, from no influence to severely disturbed. In some cases smaller particles gave more disturbance.

  14. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria.

    PubMed

    Circone, Susan; Kirby, Stephen H; Stern, Laura A

    2006-04-27

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within +/-2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol(-1) K(-1) for 1/nCH4.H2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled.

  15. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

    DOE PAGES

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; ...

    2016-07-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high asmore » 301 mAh g–1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g–1 still remains without any obvious decay in voltage. Lastly, this study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.« less

  16. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

    SciTech Connect

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley; Hy, Sunny

    2016-07-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g–1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g–1 still remains without any obvious decay in voltage. Lastly, this study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

  17. Characterization of non-stoichiometric hydration and the dehydration behavior of sitafloxacin hydrate.

    PubMed

    Suzuki, Tetsuya; Araki, Tetsuya; Kitaoka, Hiroaki; Terada, Katsuhide

    2012-01-01

    Sitafloxacin (STFX) hydrate is a non-stoichiometric hydrate. The hydration state of STFX hydrate varies non-stoichiometrically depending on the relative humidity and temperature, though X-ray powder diffraction (XRPD) of STFX hydrate was not affected by storing at low and high relative humidities. The detailed properties of crystalline water of STFX hydrate were estimated in terms of hygroscopicity, thermal analysis combined with X-ray powder diffractometry, crystallography and density functional theory (DFT) calculation. STFX hydrate changed the water contents continuously and reversibly from an equivalent amount of dihydrate through that of sesquihydrate depending on the relative humidity at 25°C. Thermal analysis and X-ray powder diffraction (XRPD) simultaneous measurement also revealed that STFX hydrate dehydrated into a hydrated state equivalent to monohydrate by heating up to 100°C, whereas XRPD patterns were slightly affected. This indicated that the crystal structure of STFX hydrate was retained at the dehydration level of monohydrate. Single-crystal X-ray structural analysis showed that two STFX molecules and four water molecule sites were contained in an asymmetric unit. STFX molecules formed a channel structure where water molecules were included. At the partially dehydrated state, at least two of four water molecules were considered to be disordered in occupancy and/or coordinates. Insight into the crystal structure of STFX hydrate stored at low and high relative humidities and geometry of the hydrogen bond were helpful to estimate the origin of non-stoichiometric hydration of STFX hydrate.

  18. Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

    USGS Publications Warehouse

    Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.; McFarlane, J.; Kirkwood, W.

    1997-01-01

    We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROY) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free sea-water occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the Filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

  19. Fundamentals and applications of gas hydrates.

    PubMed

    Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

    2011-01-01

    Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties.

  20. Development of Alaskan gas hydrate resources

    SciTech Connect

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

  1. Structural characteristics of hydration sites in lysozyme.

    PubMed

    Soda, Kunitsugu; Shimbo, Yudai; Seki, Yasutaka; Taiji, Makoto

    2011-06-01

    A new method is presented for determining the hydration site of proteins, where the effect of structural fluctuations in both protein and hydration water is explicitly considered by using molecular dynamics simulation (MDS). The whole hydration sites (HS) of lysozyme are composed of 195 single HSs and 38 clustered ones (CHS), and divided into 231 external HSs (EHS) and 2 internal ones (IHS). The largest CHSs, 'Hg' and 'Lβ', are the IHSs having 2.54 and 1.35 mean internal hydration waters respectively. The largest EHS, 'Clft', is located in the cleft region. The real hydration structure of a CHS is an ensemble of multiple structures. The transition between two structures occurs through recombinations of some H-bonds. The number of the experimental X-ray crystal waters is nearly the same as that of the estimated MDS hydration waters for 70% of the HSs, but significantly different for the rest of HSs.

  2. Hydrogen speciation in hydrated layers on nuclear waste glass

    SciTech Connect

    Aines, R.D.; Weed, H.C.; Bates, J.K.

    1987-01-15

    The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 & 165, and PNL 76-68), which were leached at 90{sup 0}C (all glasses) or hydrated in a vapor-saturated atmosphere at 202{sup 0}C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was found in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 {mu}m layer on SRL-131 glass formed by leaching at 90{sup 0}C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H{sup +} interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups.

  3. Dynamics in the methane hydrate system of the Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Mienert, Jurgen; Andreassen, Karin; Knies, Jochen; Carroll, JoLynn; Bünz, Stephan; Ferre, Benedicte; Rasmussen, Tine; Panieri, Giuliana; Myhre, Catherine Lund

    2014-05-01

    Methane hydrate formed in abundance in deep permafrost regions but little documentation exists about resource accumulation in shallow Arctic subsea areas and its evolution in time and space. Today's sub-seabed methane hydrate reservoirs remain elusive targets as a natural methane emitter that influences ocean environments and ecosystems. Rising Arctic Ocean temperatures are causing a destabilization of these reservoirs which in turn releases methane leading to geo-hazards, ocean acidification, and marine benthic reaction at unknown rates and response times. CAGE - Centre for Arctic Gas Hydrate, Environment, and Climate initiates a ten year interdisciplinary research and education program aimed at achieving a quantitative understanding of feedbacks between methane sub-seabed reservoirs, the seabed and the ocean. The Centre addresses how the coupled (reservoirs-seabed-ocean) system in the Arctic reacts and affects the future ocean, its environment and possibly the climate with focus on high resolution geophysics; seabed gas-emissions; environmental reactions; and benthic-response times. The project MOCA (Methane emissions from the Arctic Ocean to the Atmosphere) concentrates on the atmospheric component and present as well as future climate effects. Details on the CAGE research plan and organization will be presented to foster opportunities for cross-disciplinary collaboration. Based in Tromsø, at the world's northernmost University, CAGE establishes the intellectual and infrastructure resources for studying the amount of methane hydrate and magnitude of methane release in Arctic Ocean environments on time scales from the Neogene to the present (www.cage.uit.no). The Centre of Excellence is funded by the Norwegian Research Council ((grant No. 223259) over a period of ten years.

  4. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

    Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn

    2009-01-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

  5. Gas hydrates of outer continental margins

    SciTech Connect

    Kvenvolden, K.A. )

    1990-05-01

    Gas hydrates are crystalline substances in which a rigid framework of water molecules traps molecules of gas, mainly methane. Gas-hydrate deposits are common in continental margin sediment in all major oceans at water depths greater than about 300 m. Thirty-three localities with evidence for gas-hydrate occurrence have been described worldwide. The presence of these gas hydrates has been inferred mainly from anomalous lacoustic reflectors seen on marine seismic records. Naturally occurring marine gas hydrates have been sampled and analyzed at about tensites in several regions including continental slope and rise sediment of the eastern Pacific Ocean and the Gulf of Mexico. Except for some Gulf of Mexico gas hydrate occurrences, the analyzed gas hydrates are composed almost exclusively of microbial methane. Evidence for the microbial origin of methane in gas hydrates includes (1) the inverse relation between methane occurence and sulfate concentration in the sediment, (2) the subparallel depth trends in carbon isotopic compositions of methane and bicarbonate in the interstitial water, and (3) the general range of {sup 13}C depletion ({delta}{sub PDB}{sup 13}C = {minus}90 to {minus}60 {per thousand}) in the methane. Analyses of gas hydrates from the Peruvian outer continental margin in particular illustrate this evidence for microbially generated methane. The total amount of methane in gas hydrates of continental margins is not known, but estimates of about 10{sup 16} m{sup 3} seem reasonable. Although this amount of methane is large, it is not yet clear whether methane hydrates of outer continental margins will ever be a significant energy resource; however, these gas hydrates will probably constitute a drilling hazard when outer continental margins are explored in the future.

  6. Potential geologic hazards of Arctic gas hydrates

    SciTech Connect

    Collett, T.S. )

    1990-05-01

    Sediments of the Arctic region may contain enormous quantities of natural gas in the form of gas hydrates, which are crystalline substances composed of water and mostly methane gas. These ice-like substances are generally found in two distinct environments: (1) offshore in sediments of outer continental margins and (2) nearshore and onshore in areas associated with the occurrence of permafrost. Recently, US, Canadian, and Soviet researchers have described numerous drilling and production problems attributed to the presence of gas hydrates, including uncontrolled gas releases during drilling, collapsed casings, and gas leakage to the surface. When the drill bit penetrates a gas hydrate, the drilling mud, unless cooled significantly by the operator, will become highly gasified as the hydrate decomposes. The hydrate adjacent to the well bore will continue to decompose and gasify the drilling mud as long as drilling and/or production introduces heat into the hydrate-bearing interval. The production of hot fluids from depth through the permafrost and gas hydrate-bearing intervals adversely raises formation temperatures, thus decomposing the gas hydrates. If the disassociated, free gas is trapped behind the casing, reservoir pressures may substantially increase and cause the casing to collapse. In several wells in northern Alaska, the disassociated free gas has leaked to the surface outside the conductor casing. An additional drilling hazard associated with gas hydrates results from the sealing attributes of hydrates, which may trap large volumes of over pressured free gas at shallow depths. Even though documented problems attributed to the presence of gas hydrates have been relatively few, it is likely that as exploration and development activity moves farther offshore into deeper water (>300 m) and to higher latitudes in the Arctic, the frequency of gas hydrate-related problems will increase.

  7. Natural gas hydrate occurrence and issues

    USGS Publications Warehouse

    Kvenvolden, K.A.

    1994-01-01

    Naturally occurring gas hydrate is found in sediment of two regions: (1) continental, including continental shelves, at high latitudes where surface temperatures are very cold, and (2) submarine outer continental margins where pressures are very high and bottom-water temperatures are near 0??C. Continental gas hydrate is found in association with onshore and offshore permafrost. Submarine gas hydrate is found in sediment of continental slopes and rises. The amount of methane present in gas hydrate is thought to be very large, but the estimates that have been made are more speculative than real. Nevertheless, at the present time there has been a convergence of ideas regarding the amount of methane in gas hydrate deposits worldwide at about 2 x 1016 m3 or 7 x 1017 ft3 = 7 x 105 Tcf [Tcf = trillion (1012) ft3]. The potentially large amount of methane in gas hydrate and the shallow depth of gas hydrate deposits are two of the principal factors driving research concerning this substance. Such a large amount of methane, if it could be commercially produced, provides a potential energy resource for the future. Because gas hydrate is metastable, changes of surface pressure and temperature affect its stability. Destabilized gas hydrate beneath the sea floor leads to geologic hazards such as submarine mass movements. Examples of submarine slope failures attributed to gas hydrate are found worldwide. The metastability of gas hydrate may also have an effect on climate. The release of methane, a 'greenhouse' gas, from destabilized gas hydrate may contribute to global warming and be a factor in global climate change.

  8. Some aspects of hydrate formation and wetting.

    PubMed

    Fotland, P; Askvik, K M

    2008-05-01

    Experimental observations of gas hydrate formation have shown that, in the initial nucleation and crystallization process, water-oil emulsions may be generated, destabilized or even inverted. These phenomena are consistent with the effects of particles on emulsions. In this work we relate experimental observations of hydrate formation to the phenomenon of wettability. It is shown that details of hydrate wetting are important for both the morphology and the kinetics of the formed hydrates. For the cases of hydrate lenses and spheres, it is shown that the various wetting states can be illustrated and analyzed by using wetting diagrams. Metastability is a function of the surface energies of the hydrate formation, i.e., the wetting state, and it is shown that in some cases metastability vanishes, and thus hydrates nucleates instantly at all positive driving forces. The magnitude of buoyancy and turbulence forces acting on a hydrate sphere are compared to the capillary force and it is concluded that capillary energy dominates when the hydrate spheres is less than 1 mm.

  9. Physical Properties of Gas Hydrates: A Review

    SciTech Connect

    Gabitto, Jorge; Tsouris, Costas

    2010-01-01

    Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

  10. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  11. Physical Properties of Gas Hydrates: A Review

    DOE PAGES

    Gabitto, Jorge F.; Tsouris, Costas

    2010-01-01

    Memore » thane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 10 16   m 3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.« less

  12. In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

    SciTech Connect

    Álvarez-Pinazo, G.; Cuesta, A.; García-Maté, M.; Santacruz, I.; Losilla, E.R.; Fauth, F.; Aranda, M.A.G.; De la Torre, A.G.

    2014-02-15

    Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (α ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.

  13. Extension of Toth function from gas-solid to liquid-solid equilibria and application to reversed-phase liquid chromatography systems

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-03-01

    The extension of the {Psi} function developed by Toth from equilibria taking place at gas-solid interfaces to those taking place at liquid-solid interfaces was investigated. The results were applied to conventional liquid-solid systems used in reversed-phase liquid chromatography (RPLC). The adsorbents in these systems are made of porous silica having a hydrophobic solid surface obtained by chemically bonding C{sub 18} alkyl chains to a porous silica gel then endcapping the surface with trimethylsilyl groups. The liquid is an aqueous solution of an organic solvent, most often methanol or acetonitrile. The probe compound used here is phenol. Adsorption data of phenol were measured using the dynamic frontal analysis (FA) method. The excess adsorption of the organic solvent was measured using the minor disturbance (MD) method. Activity coefficients in the bulk were estimated through the UNIFAC group contributions. The results show that the {Psi} function predicts 90% of the total free energy of immersion, {Delta}F, of the solid when the concentration of phenol is moderate (typically less than 10 g/L). At higher concentrations, the nonideal behavior of the bulk liquid phase becomes significant and it may contribute up to about 30% of {Delta}F. The high concentration of adsorbed molecules of phenol at the interface decreases the interfacial tension, {sigma}, by about 18 mN/m, independently of the structure of the adsorbed phase and of the nature of the organic solvent.

  14. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  15. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  16. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    USGS Publications Warehouse

    Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

    2007-01-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  17. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Lee, J. Y.; Yun, T. S.; Santamarina, J. C.; Ruppel, C.

    2007-06-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  18. Catastrophic growth of gas hydrates in the presence of kinetic hydrate inhibitors.

    PubMed

    Cha, Minjun; Shin, Kyuchul; Seo, Yutaek; Shin, Ju-Young; Kang, Seong-Pil

    2013-12-27

    The effect of the concentration of kinetic hydrate inhibitors, polyvinylpyrrolidone (PVP), and polyvinylcaprolactam (PVCap) on the onset and growth of synthetic natural gas hydrates is investigated by measuring the hydrate onset time and gas consumption rate. Although the hydrate onset time is extended by increasing the concentration from 0.5 to 3.0 wt % for both PVP and PVCap, the growth rate of hydrates shows that the different tendency depends on the type of kinetic hydrate inhibitor and its concentration. For PVCap solution, the hydrate growth was slow for more than 1000 min after the onset at the concentration of 0.5 and 1.5 wt %. However, the growth rate becames almost 8 times faster at the concentration of 3.0 wt %, representing the catastrophic growth of hydrate just after the hydrate onset. (13)C NMR spectra of hydrates formed at 3.0 wt % of PVP and PVCap indicate the existence of both structures I and II. Cage occupancy of methane in large cages of structure II decreases significantly when compared to that for pure water. These results suggest that increasing the concentration of KHI up to 3.0 wt % may induce the earlier appearance of catastrophic hydrate growth and the existence of metastable structure I; thus, there needs to be an upper limit for using KHI to manage the formation of gas hydrates.

  19. Salt hydrates for in situ water activity control have acid-base effects on enzymes in nonaqueous media.

    PubMed

    Fontes, Nuno; Harper, Neil; Halling, Peter J; Barreiros, Susana

    2003-06-30

    Salt hydrates very frequently are utilized as in situ water activity buffers in reaction mixtures of enzymes in nonaqueous media. In addition to buffering water activity, there is evidence that salt hydrates also often affect initial rates in other ways. This has been generally overlooked or thought to be related to water transfer effects. Here we show that salt hydrates can have important acid-base effects on enzymes in nonaqueous media. We performed transesterification reactions in n-hexane and in supercritical ethane catalyzed by cross-linked crystals of subtilisin, differing in the method used to set a(W), and confirmed that the presence of salt hydrate pairs significantly affected the catalytic performance of the enzyme. However, in the presence of a solid-state acid-base buffer, salt hydrates had no effect on enzymatic activity. Direct evidence for the acid-base effects of salt hydrates was obtained by testing their effect on the protonation state of an organo-soluble H(+)/Na(+) indicator. The four salt hydrate pairs tested affected the indicator to very different extents. By promoting the exchange of H(+) for Na(+), salt hydrates will tend to affect the ionization state of acidic residues in the protein and, hence, enzymatic activity. In fact, salt hydrates were able to affect the pH memory of subtilisin lyophilized from different aqueous pHs, bringing about up to 20-fold enhancements and up to 5-fold decreases in catalytic activity. The possibility of such acid-base effects need to be considered in all experiments using salt hydrates to control water activity.

  20. Steps Towards Understanding Large-scale Deformation of Gas Hydrate-bearing Sediments

    NASA Astrophysics Data System (ADS)

    Gupta, S.; Deusner, C.; Haeckel, M.; Kossel, E.

    2016-12-01

    Marine sediments bearing gas hydrates are typically characterized by heterogeneity in the gas hydrate distribution and anisotropy in the sediment-gas hydrate fabric properties. Gas hydrates also contribute to the strength and stiffness of the marine sediment, and any disturbance in the thermodynamic stability of the gas hydrates is likely to affect the geomechanical stability of the sediment. Understanding mechanisms and triggers of large-strain deformation and failure of marine gas hydrate-bearing sediments is an area of extensive research, particularly in the context of marine slope-stability and industrial gas production. The ultimate objective is to predict severe deformation events such as regional-scale slope failure or excessive sand production by using numerical simulation tools. The development of such tools essentially requires a careful analysis of thermo-hydro-chemo-mechanical behavior of gas hydrate-bearing sediments at lab-scale, and its stepwise integration into reservoir-scale simulators through definition of effective variables, use of suitable constitutive relations, and application of scaling laws. One of the focus areas of our research is to understand the bulk coupled behavior of marine gas hydrate systems with contributions from micro-scale characteristics, transport-reaction dynamics, and structural heterogeneity through experimental flow-through studies using high-pressure triaxial test systems and advanced tomographical tools (CT, ERT, MRI). We combine these studies to develop mathematical model and numerical simulation tools which could be used to predict the coupled hydro-geomechanical behavior of marine gas hydrate reservoirs in a large-strain framework. Here we will present some of our recent results from closely co-ordinated experimental and numerical simulation studies with an objective to capture the large-deformation behavior relevant to different gas production scenarios. We will also report on a variety of mechanically relevant

  1. Gas hydrate decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

    NASA Astrophysics Data System (ADS)

    Kasten, Sabine; Nöthen, Kerstin; Hensen, Christian; Spieß, Volkhard; Blumenberg, Martin; Schneider, Ralph R.

    2012-12-01

    The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to

  2. Methane hydrate research at NETL: Research to make methane production from hydrates a reality

    SciTech Connect

    Taylor, C.E.; Link, D.D.; English, N.

    2007-03-01

    Research is underway at NETL to understand the physical properties of methane hydrates. Five key areas of research that need further investigation have been identified. These five areas, i.e. thermal properties of hydrates in sediments, kinetics of natural hydrate dissociation, hysteresis effects, permeability of sediments to gas flow and capillary pressures within sediments, and hydrate distribution at porous scale, are important to the production models that will be used for producing methane from hydrate deposits. NETL is using both laboratory experiments and computational modeling to address these five key areas. The laboratory and computational research reinforce each other by providing feedback. The laboratory results are used in the computational models and the results from the computational modeling is used to help direct future laboratory research. The data generated at NETL will be used to help fulfill The National Methane Hydrate R&D Program of a “long-term supply of natural gas by developing the knowledge and technology base to allow commercial production of methane from domestic hydrate deposits by the year 2015” as outlined on the NETL Website [NETL Website, 2005. http://www.netl.doe.gov/scngo/Natural%20Gas/hydrates/index.html]. Laboratory research is accomplished in one of the numerous high-pressure hydrate cells available ranging in size from 0.15 mL to 15 L in volume. A dedicated high-pressure view cell within the Raman spectrometer allows for monitoring the formation and dissociation of hydrates. Thermal conductivity of hydrates (synthetic and natural) at a certain temperature and pressure is performed in a NETL-designed cell. Computational modeling studies are investigating the kinetics of hydrate formation and dissociation, modeling methane hydrate reservoirs, molecular dynamics simulations of hydrate formation, dissociation, and thermal properties, and Monte Carlo simulations of hydrate formation and dissociation.

  3. Hydration energies of deprotonated amino acids from gas phase equilibria measurements.

    PubMed

    Wincel, Henryk

    2008-08-01

    Singly hydrated clusters of deprotonated amino acids were studied using an electrospray high-pressure mass spectrometer equipped with a pulsed ion-beam reaction chamber. Thermochemical data, DeltaH(o), DeltaS(o), and DeltaG(o), for the hydration reaction [AA - H](-) + H(2)O = [AA - H](-).(H(2)O) were obtained from gas-phase equilibria determinations for AA = Gly, Ala, Val, Pro, Phe, Lys, Met, Trp, Gln, Arg, and Asp. The hydration free-energy changes are found to depend significantly on the side-chain substituents. The water binding energy in [AA - H](-).(H(2)O) increases with the gas-phase acidity of AA. The anionic hydrogen bond strengths in [AA - H](-).(H(2)O) are compared with those of the cationic bonds in the corresponding AAH(+).(H(2)O) systems.

  4. Gas hydrate formation in the deep sea: In situ experiments with controlled release of methane, natural gas, and carbon dioxide

    USGS Publications Warehouse

    Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.

    1998-01-01

    We have utilized a remotely operated vehicle (ROV) to initiate a program of research into gas hydrate formation in the deep sea by controlled release of hydrocarbon gases and liquid CO2 into natural sea water and marine sediments. Our objectives were to investigate the formation rates and growth patterns of gas hydrates in natural systems and to assess the geochemical stability of the reaction products over time. The novel experimental procedures used the carrying capacity, imaging capability, and control mechanisms of the ROV to transport gas cylinders to depth and to open valves selectively under desired P-T conditions to release the gas either into contained natural sea water or into sediments. In experiments in Monterey Bay, California, at 910 m depth and 3.9??C water temperature we find hydrate formation to be nearly instantaneous for a variety of gases. In sediments the pattern of hydrate formation is dependent on the pore size, with flooding of the pore spaces in a coarse sand yielding a hydrate cemented mass, and gas channeling in a fine-grained mud creating a veined hydrate structure. In experiments with liquid CO2 the released globules appeared to form a hydrate skin as they slowly rose in the apparatus. An initial attempt to leave the experimental material on the sea floor for an extended period was partially successful; we observed an apparent complete dissolution of the liquid CO2 mass, and an apparent consolidation of the CH4 hydrate, over a period of about 85 days.

  5. Investigation of the hydration and bioactivity of radiopacified tricalcium silicate cement, Biodentine and MTA Angelus.

    PubMed

    Camilleri, Josette; Sorrentino, François; Damidot, Denis

    2013-05-01

    Novel root-end filling materials are composed of tricalcium silicate (TCS) and radiopacifier as opposed to the traditional mineral trioxide aggregate (MTA) which is made up of clinker derived from Portland cement and bismuth oxide. The aim of this research was to characterize and investigate the hydration of a tricalcium silicate-based proprietary brand cement (Biodentine™) and a laboratory manufactured cement made with a mixture of tricalcium silicate and zirconium oxide (TCS-20-Z) and compare their properties to MTA Angelus™. The materials investigated included a cement containing 80% of TCS and 20% zirconium oxide (TCS-20-Z), Biodentine™ and MTA Angelus™. The specific surface area and the particle size distribution of the un-hydrated cements and zirconium oxide were investigated using a gas adsorption method and scanning electron microscopy. Un-hydrated cements and set materials were tested for mineralogy and microstructure, assessment of bioactivity and hydration. Scanning electron microscopy, X-ray energy dispersive analysis, X-ray fluorescence spectroscopy, X-ray diffraction, Rietveld refined X-ray diffraction and calorimetry were employed. The radiopacity of the materials was investigated using ISO 6876 methods. The un-hydrated cements were composed of tricalcium silicate and a radiopacifier phase; zirconium oxide for both Biodentine™ and TCS-20-Z whereas bismuth oxide for MTA Angelus™. In addition Biodentine™ contained calcium carbonate particles and MTA Angelus™ exhibited the presence of dicalcium silicate, tricalcium aluminate, calcium, aluminum and silicon oxides. TCS and MTA Angelus™ exhibited similar specific surface area while Biodentine™ had a greater specific surface area. The cements hydrated and produced some hydrates located either as reaction rim around the tricalcium silicate grain or in between the grains at the expense of volume containing the water initially present in the mixture. The rate of reaction of tricalcium

  6. Hydration and Nanoconfined Water: Insights from Computer Simulations.

    PubMed

    Alarcón, Laureano M; Rodríguez Fris, J A; Morini, Marcela A; Sierra, M Belén; Accordino, S A; Montes de Oca, J M; Pedroni, Viviana I; Appignanesi, Gustavo A

    2015-01-01

    The comprehension of the structure and behavior of water at interfaces and under nanoconfinement represents an issue of major concern in several central research areas like hydration, reaction dynamics and biology. From one side, water is known to play a dominant role in the structuring, the dynamics and the functionality of biological molecules, governing main processes like protein folding, protein binding and biological function. In turn, the same principles that rule biological organization at the molecular level are also operative for materials science processes that take place within a water environment, being responsible for the self-assembly of molecular structures to create synthetic supramolecular nanometrically-sized materials. Thus, the understanding of the principles of water hydration, including the development of a theory of hydrophobicity at the nanoscale, is imperative both from a fundamental and an applied standpoint. In this work we present some molecular dynamics studies of the structure and dynamics of water at different interfaces or confinement conditions, ranging from simple model hydrophobic interfaces with different geometrical constraints (in order to single out curvature effects), to self-assembled monolayers, proteins and phospholipid membranes. The tendency of the water molecules to sacrifice the lowest hydrogen bond (HB) coordination as possible at extended interfaces is revealed. This fact makes the first hydration layers to be highly oriented, in some situations even resembling the structure of hexagonal ice. A similar trend to maximize the number of HBs is shown to hold in cavity filling, with small subnanometric hydrophobic cavities remaining empty while larger cavities display an alternation of filled and dry states with a significant inner HB network. We also study interfaces with complex chemical and geometrical nature in order to determine how different conditions affect the local hydration properties. Thus, we show some

  7. Hydration Characteristics of Low-Heat Cement Substituted by Fly Ash and Limestone Powder

    PubMed Central

    Kim, Si-Jun; Yang, Keun-Hyeok; Moon, Gyu-Don

    2015-01-01

    This study proposed a new binder as an alternative to conventional cement to reduce the heat of hydration in mass concrete elements. As a main cementitious material, low-heat cement (LHC) was considered, and then fly ash (FA), modified FA (MFA) by vibrator mill, and limestone powder (LP) were used as a partial replacement of LHC. The addition of FA delayed the induction period at the hydration heat curve and the maximum heat flow value (qmax) increased compared with the LHC based binder. As the proportion and fineness of the FA increased, the induction period of the hydration heat curve was extended, and the qmax increased. The hydration production of Ca(OH)2 was independent of the addition of FA or MFA up to an age of 7 days, beyond which the amount of Ca(OH)2 gradually decreased owing to their pozzolanic reaction. In the case of LP being used as a supplementary cementitious material, the induction period of the hydration heat curve was reduced by comparison with the case of LHC based binder, and monocarboaluminate was observed as a hydration product. The average pore size measured at an age of 28 days was smaller for LHC with FA or MFA than for 100% LHC. PMID:28793538

  8. Hydrated Electrons at the Plasma-Water Interface

    NASA Astrophysics Data System (ADS)

    Graves, David; Gopalakrishnan, Ranga; Kawamura, Emi; Lieberman, Michael

    2015-09-01

    When atmospheric pressure plasma interacts with liquid water surfaces, complex processes involving both charged and neutral species generally occur but the details of the processes are not well understood. One plasma-generated specie of considerable interest that can enter an adjacent liquid water phase is the electron. Hydrated electrons are well known to be important in radiation chemistry as initiating precursors for a variety of other reactive compounds. Recent experimental evidence for hydrated electrons near the atmospheric pressure plasma-water interface was reported by Rumbach et al.. We present results from a model of a dc argon plasma coupled to an anodic adjacent water layer that aims to simulate this experiment. The coupled plasma-electrolyte model illustrates the nature of the plasma-water interface and reveals important information regarding the self-consistent electric fields on each side of the interface as well as time- and space-resolved rates of reaction of key reactive species. We suggest that the reducing chemistry that results from electron hydration may be useful therapeutically in countering local excess oxidative stress. Supported by the Department of Energy, Office of Fusion Science Plasma Science Center

  9. X-ray microanalysis of hydrated biological specimens

    SciTech Connect

    Makita, T.; Ueda, H.; Hirose, H.; Idegomori, T.

    1982-01-01

    Using a wide angle backscattered electron detector (BED), glutaraldehyde fixed or unfixed specimens of biological soft tissues such as hen oviduct, kidney, liver, duodenum of mouse as well as mitochondrial fraction from rat liver were observed under low vacuum (0.3 to 0.5 torr) at magnifications from x300 to 10,000. The backscattered electron images (BEI) of glutaraldehyde fixed hen oviduct were correlated to X-ray microanalysis. Intracellular secretion granules in such unhydrated, uncoated and unstained slices of hen oviduct preserved Ca even after glutaraldehyde fixation. Backscattered electron images of unfixed duodenum and kidney of mice were not satisfactory for observing intracellular structures, though X-ray microanalysis could detect P,S,Cl and K over cut surfaces of such hydrated unfixed tissue. Compared with frozen dehydrated specimen, the hydrated unfixed tissue tends to preserve more potassium and less chlorine. Cytochemical reaction product of succinate dehydrogenase (SDH-ase) activity in isolated mitochondria from rat liver was detectable in hydrated condition. Quick and easy assessment of localized elements in surgical specimens by combination of wet-SEM and X-ray microanalysis will be a new tool for clinical application of SEM. In spite of obvious limitations of this method, especially of its spatial resolution both in backscattered electron image and in bulk specimen X-ray microanalysis, the combination of wet-SEM and X-ray microanalysis provides information which has not been available in the past.

  10. Activation energy of methyl radical decay in methane hydrate.

    PubMed

    Takeya, Kei; Nango, Kouhei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

    2005-11-10

    The thermal stability of gamma-ray-induced methyl radicals in methane hydrate was studied using the ESR method at atmospheric pressure and 210-260 K. The methyl radical decay proceeded with the second-order reaction, and ethane molecules were generated from the dimerization process. The methyl radical decay proceeds by two different temperature-dependent processes, that is, the respective activation energies of these processes are 20.0 +/- 1.6 kJ/mol for the lower temperature region of 210-230 K and 54.8 +/- 5.7 kJ/mol for the higher temperature region of 235-260 K. The former agrees well with the enthalpy change of methane hydrate dissociation into ice and gaseous methane, while the latter agrees well with the enthalpy change into liquid water and gaseous methane. The present findings reveal that methane hydrates dissociate into liquid (supercooled) water and gaseous methane in the temperature range of 235-260 K.

  11. Gas hydrates in the ocean environment

    USGS Publications Warehouse

    Dillon, William P.

    2002-01-01

    A GAS HYDRATE, also known as a gas clathrate, is a gas-bearing, icelike material. It occurs in abundance in marine sediments and stores immense amounts of methane, with major implications for future energy resources and global climate change. Furthermore, gas hydrate controls some of the physical properties of sedimentary deposits and thereby influences seafloor stability.

  12. 78 FR 26337 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-06

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  13. 78 FR 37536 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-21

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  14. 76 FR 59667 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-27

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... of the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice...

  15. New gas-hydrate phase: Synthesis and stability of clay methane hydrate intercalate

    NASA Astrophysics Data System (ADS)

    Guggenheim, Stephen; Koster van Groos, August F.

    2003-07-01

    Intercalated Na-rich montmorillonite methane hydrate was synthesized for the first time. The upper limit of stability for the intercalate in pressure and temperature is parallel to that of methane hydrate but at temperatures that are ˜0.5 1 °C lower than for methane hydrate. The low-temperature stability of the intercalate is at -11.5 ± 3 °C at ˜40 bar, where methane and some H2O are expelled from the region between the silicate layers (interlayer). In contrast, methane hydrates do not dissociate at these low temperatures. We conclude that at conditions similar to where methane hydrate is stable, smectite may intercalate with methane hydrate and provide additional sinks for methane. The limitation in the stability of smectite methane hydrate intercalate at low temperatures suggests that, if present in large quantities, it may release at decreasing temperatures sufficient methane to ameliorate a planetary cooling event.

  16. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the revolutionary and new

  17. In-situ characterization of gas hydrates

    NASA Astrophysics Data System (ADS)

    Moerz, T.; Brueckmann, W.; Linke, P.; Tuerkay, M.

    2003-04-01

    Gas hydrates are a dynamic reservoir in the marine carbon cycle and a periodically large and focussed source of methane probably constituting the largest carbon reservoir on earth. Therefore an important issue in gas hydrate research is the need for better tools to remotely estimate the volume and stability conditions of marine gas hydrate in the near sub-surface. It is also crucial to precisely determine the hydrate stability conditions in the near sub-surface, where gas hydrates are most susceptible to dissolution under changing P/T conditions. Our knowledge about the occurrence, spatial distribution, and life-cycle of gas hydrates in marine sediments is mainly derived from indirect geophysical and geochemical evidence. In a few instances gas hydrates have also been directly observed and sampled at the sea floor. For regional or global estimates of hydrate volumes and stability conditions however, new techniques for ground-truthing and calibration of geophysical, biological and geochemical methods are needed. During the OTEGA cruise with RV SONNE to Hydrate Ridge off Oregon a new device for in-situ characterization of gas hydrates was deployed and tested for the first time. The tool, HDSD (Hydrate Detection and Stability Determination) is being developed as part of Cooperative Research Center (SFB) 574 "Volatiles and Fluids in Subduction Zones". It is designed to identify and quantify small volumes of near-surface gas hydrate through continuous in-situ thermal and resistivity monitoring in a defined volume of sediment while it is slowly heated to destabilize gas hydrates embedded in it. In its current configuration HDSD is delivered to the seafloor by a video-guided GEOMAR BC Lander system. The sediment volume to be tested for the presence and abundance of gas hydrates is first isolated by a rectangular experiment chamber that is pushed into the upper 30cm of sediment. A "stinger", centrally mounted in the chamber and equipped with two arrays of sensors, provides

  18. Solubility of hematite revisited: effects of hydration.

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2007-11-01

    Measured pH and dissolved ferric iron concentration ([Fe(III)diss]) in contact with well-characterized hematite indicated an equilibrium with hematite immediately after synthesis, but [Fe(III)diss] increased with hydration time to be consistent with the predicted solubility of goethite or hydrous ferric oxide (HFO), hydrated analogues of hematite. X-ray diffraction did not detect structural modification of hematite after 190 days of hydration, but Mössbauer spectroscopy detected hydration that penetrated several crystalline layers. When the hematite suspension was diluted with water, solids were invariably identified as hematite, but [Fe(III)diss] and pH indicated an equilibrium with goethite or HFO. This is the first experimental confirmation that the interfacial hydration of anhydrous hematite results in higher solubility than predicted by bulk thermodynamic properties of hematite. Correspondence of the results with previously published measurements and implications for environmental chemistry of ferric oxides are also discussed.

  19. A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

    NASA Astrophysics Data System (ADS)

    White, M. D.

    2012-12-01

    The potential energy resource of natural gas hydrates held in geologic accumulations, using lower volumetric estimates, is sufficient to meet the world demand for natural gas for nearly eight decades, at current rates of increase. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. The thermodynamic complexity of gas hydrate systems makes numerical simulation a particularly attractive research tool for understanding production strategies and experimental observations. Simply stated, producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. Alternatively, the guest-molecule exchange technology releases CH4 by replacing it with more thermodynamically stable molecules (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it potentially releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, nonaqueous liquid, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulations that predict

  20. Hydration of Two Cisplatin Aqua-Derivatives Studied by Quantum Mechanics and Molecular Dynamics Simulations.

    PubMed

    Melchior, Andrea; Tolazzi, Marilena; Martínez, José Manuel; Pappalardo, Rafael R; Sánchez Marcos, Enrique

    2015-04-14

    The hydration of the cisplatin aqua-derivatives, cis-[PtCl(H2O)(NH3)2](+) (w-cisplatin) and cis-[Pt(H2O)2(NH3)2](2+) (w2-cisplatin), has been studied by means of classical molecular dynamics simulations. The new platinum complex-water interaction potential, w-cisplatin-W, has been built on the basis of the already obtained cisplatin-water interaction potential (cisplatin-W) [J. Chem. Theory Comput. 2013 9, 4562]. That potential has been then transferred to the w2-cisplatin-W potential. The w-cisplatin and w2-cisplatin atomic charges were specifically derived from their solute's wave functions. Bulk solvent effects on the complex-water interactions have been included by means of a continuum model. Classical MD simulations with 1 platinum complex and 1000 SPC/E water molecules have been carried out. Angle-solved radial distribution functions and spatial distribution functions have been used to provide detailed pictures of the local hydration structure around the ligands (water, chloride, and ammine) and the axial region. A novel definition of a multisite cavity has been employed to compute the hydration number of complexes in order to provide a consistent definition of their first-hydration shell. Interestingly, the hydration number decreases with the increase of the complex net charge from 27 for cisplatin to 23 and 18 for w-cisplatin and w2-cisplatin, respectively. In parallel to this hydration number behavior, the compactness of the hydration shell increases when going from the neutral complex, i.e. cisplatin, to the doubly charged complex, w2-cisplatin. Quantum mechanics estimation of the hydration energies for the platinum complexes allows the computation of the reaction energy for the first- and second-hydrolysis of cisplatin in water. The agreement with experimental data is satisfactory.

  1. CO2 Injection Into CH4 Hydrate Reservoirs: Quantifying Controls of Micro-Scale Processes

    NASA Astrophysics Data System (ADS)

    Bigalke, N. K.; Deusner, C.; Kossel, E.; Haeckel, M.

    2014-12-01

    The exchangeability of methane for carbon dioxide in gas hydrates opens the possibility of producing emission-neutral hydrocarbon energy. Recent field tests have shown that the production of natural gas from gas hydrates is feasible via injection of carbon dioxide into sandy, methane-hydrate-bearing sediment strata. Industrial-scale application of this method requires identification of thermo- and fluid-dynamic as well as kinetic controls on methane yield from and carbon dioxide retention within the reservoir. Extraction of gas via injection of carbon dioxide into the hydrate reservoir triggers a number of macroscopic effects, which are revealed for example by changes of the hydraulic conductivity and geomechanical stability. Thus far, due to analytical limitations, localized reactions and fluid-flow phenomena held responsible for these effects remain unresolved on the microscale (1 µm - 1 mm) and at near-natural reservoir conditions. We address this deficit by showing results from high-resolution, two-dimensional Raman spectroscopy mappings of an artificial hydrate reservoir during carbon dioxide injection under realistic reservoir conditions. The experiments allow us to resolve hydrate conversion rate and efficiency as well as activation of fluid pathways in space and time and their effect on methane yield, carbon-dioxide retention and hydraulic conductivity of the reservoir. We hypothesize that the conversion of single hydrate grains is a diffusion-controlled process which starts at the grain surface before continuing into the grain interior and show that the conversion can be modeled simply by using published permeation coefficients for CO2 and CH4 in hydrate and grain size as only input parameters.

  2. Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

    PubMed

    Uddin, M; Coombe, D

    2014-03-20

    Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to

  3. Compound Natural Gas Hydrate: A Natural System for Separation of Hydrate-Forming Gases

    NASA Astrophysics Data System (ADS)

    Max, M. D.; Osegovic, J. P.

    2007-12-01

    Natural processes that separate materials from a mixture may exert a major influence on the development of the atmospheres and surfaces of planets, moons, and other planetary bodies. Natural distillation and gravity separation, amongst others, are well known means of differentiating materials through liquid-gas partitioning. One of the least known attributes of clathrate (gas) hydrates is their potential effect on the evolution of planetary system oceans and atmospheres. Gas hydrates separate gases from mixtures of gases by concentrating preferred hydrate-forming materials (HFM) guests within the water-molecule cage structure of crystalline hydrate. Different HFMs have very different fields of stability. When multiple hydrate formers are present, a preference series based on their selective uptake exists. Compound hydrate, which is formed from two or more species of HFM, extract preferred HFM from a mixture in very different proportions to their relative percentages of the original mixture. These compound hydrates can have different formation and dissociation conditions depending on the evolution of the environment. That is, the phase boundary of the compound hydrate that is required for dissociation lies along a lower pressure - higher temperature course. Compound hydrates respond to variations in temperature, pressure, and HFM composition. On Earth, the primary naturally occurring hydrate of interest to global climate modeling is methane hydrate. Oceanic hydrate on Earth is the largest store of carbon in the biosphere that is immediately reactive to environmental change, and is capable of releasing large amounts of methane into the atmosphere over a short geological time span. Hydrate formation is essentially metastable and is very sensitive to environmental change and to gas flux. Where natural variations in temperature and pressure varies so that hydrate will form and dissociate in some cyclical manner, such as in oceans where sea level is capable of rising and

  4. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-06-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-07-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  6. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated and is

  7. Overview on Hydrate Coring, Handling and Analysis

    SciTech Connect

    Jon Burger; Deepak Gupta; Patrick Jacobs; John Shillinglaw

    2003-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Worldwide, gas hydrate is estimated to hold about 1016 kg of organic carbon in the form of methane (Kvenvolden et al., 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In June 2002, Westport Technology Center was requested by the Department of Energy (DOE) to prepare a ''Best Practices Manual on Gas Hydrate Coring, Handling and Analysis'' under Award No. DE-FC26-02NT41327. The scope of the task was specifically targeted for coring sediments with hydrates in Alaska, the Gulf of Mexico (GOM) and from the present Ocean Drilling Program (ODP) drillship. The specific subjects under this scope were defined in 3 stages as follows: Stage 1: Collect information on coring sediments with hydrates, core handling, core preservation, sample transportation, analysis of the core, and long term preservation. Stage 2: Provide copies of the first draft to a list of experts and stakeholders designated by DOE. Stage 3: Produce a second draft of the manual with benefit of input from external review for delivery. The manual provides an overview of existing information available in the published literature and reports on coring, analysis, preservation and transport of gas hydrates for laboratory analysis as of June 2003. The manual was delivered as draft version 3 to the DOE Project Manager for distribution in July 2003. This Final Report is provided for records purposes.

  8. Correlation of Sulfuric Acid Hydrate Abundance with Charged Particle Flux at the Surface of Europa

    NASA Astrophysics Data System (ADS)

    Dalton, James B.; Paranicas, C. P.; Cassidy, T. A.; Shirley, J. H.

    2010-10-01

    The trailing hemisphere of Jupiter's moon Europa is bombarded by charged particles trapped within Jupiter's magnetosphere. Sulfur ion implantation and impacting energetic electrons strongly affect the surface chemistry of Europa. Understanding these processes is important for disentangling the extrinsic and intrinsic components of Europa's surface chemistry. In the sulfur cycle model of Carlson et al. (Science 286, 97, 1999), hydrated sulfuric acid represents the dominant reaction product of radiolytic surface modification processes on Europa. In recent compositional investigations employing linear mixture modeling, Dalton et al. (LPSC XV, #2511, 2009) and Shirley et al. (Icarus, in press, 2010) document a well-defined gradient of hydrated sulfuric acid abundance for a study area spanning the leading side - trailing side boundary in Argadnel Regio. Sulfuric acid hydrate abundance in this region increases toward the trailing side apex. Here we compare the derived sulfuric acid hydrate abundances at 41 locations on Europa's surface with independent model results describing 1) the sulfur ion flux (Hendrix et al., 2010, in preparation), and 2) the energetic electron flux, at the same locations. We improve upon the prior calculation of electron energy into the surface of Paranicas et al. (2009, in Europa, U. Arizona, p529; Pappalardo, McKinnon, & Khurana eds.) by incorporating a realistic pitch angle dependence of the distribution. While the sulfur ion implantation and electron energy deposition model distributions differ in important details, both show trailing side gradients similar to that found for the sulfuric acid hydrate. Correlation coefficients exceed 0.9 in comparisons of each of these models with the sulfuric acid hydrate distribution. Our results support models in which the electron energy flux drives reactions that utilize implanted sulfur to produce sulfuric acid hydrate. This work was performed at the California Institute of Technology-Jet Propulsion

  9. Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

    SciTech Connect

    Mendoza, Oscar; Giraldo, Carolina; Camargo, Sergio S.

    2015-08-15

    This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure.

  10. Understanding the formation of Titan's aerosols : Study by UV-visible spectrometry of gas/solid interactions in Titan's simulated atmosphere.

    NASA Astrophysics Data System (ADS)

    Bernard, J.-M.; Coll, P.; Jolly, A.; Bénilan, Y.; Cernogora, G.; Raulin, F.

    2003-04-01

    The atmospheric chemistry on Titan is reproduced during laboratory simulation experiments since several years. In order to simulate as well as possible Titan's atmosphere, these simulations are done by initiating a glow discharge in a continuously flowing N2/CH4 mixture at low temperature. Cold plasma at low pressure are used to simulate the photochemistry because the Electron Energy Distribution Function (EEDF) is close to the solar spectrum. The aim of the presented work is the in situ plasma study by a UV-visible Optical Emission Spectrometry and electrostatic probe measurements. The gas temperature is deduced from rotational nitrogen spectra, and the electric field from probe measurements. From the ratio E/N0 it is possible to calculate the EEDF. Moreover, the compounds (molecules/radicals/ions) evolution analysis in the reactor will allow the identification of those at the origin of the building of the solid phase, at gas/solid interface. From this work it could be possible to have a better knowledge of the formation of "tholins" considered to be an analogue of Titan's aerosols. We will present the first results obtained by emission spectroscopy, during experimental simulations of Titan's atmosphere. We will point out the detection of all the possible diatomic species made of C, N or H. We will also show the variation of their abundance as a function of the physico-chemical parameters of the discharge (temperature, pressure, percentage of methane in the initial gas mixture...). For example, the reactor immersion in a cryogenic fluid (liquid nitrogen) implies a noticeable change on the gas temperature and proves also the impact of this immersion to better simulate Titan's environment.

  11. Mass transfer and trace element redistribution during hydration of granulites in the Bergen Arcs, Norway

    NASA Astrophysics Data System (ADS)

    Centrella, Stephen; Austrheim, Håkon; Putnis, Andrew

    2016-10-01

    The Bergen Arcs, located on the western coast of Norway, are characterized by Precambrian granulite facies rocks partially hydrated at amphibolite and eclogite facies conditions. At Hilland Radöy, granulite displays sharp hydration fronts across which the granulite facies assemblage composed of garnet (55%) and clinopyroxene (45%) is replaced by an amphibolite facies mineralogy defined by chlorite, epidote, and amphibole. The replacement of both phases is pseudomorphic and the overall reaction is isovolumetric. In the present study, LA ICPMS has been used to determine the trace element redistribution during the hydration. Although the bulk concentrations of the trace elements do not change, the LILE, HFSE, and REE losses and gains in replacing the garnet are qualitatively balanced by the opposite gains and losses associated with the replacement of clinopyroxene. From the REE compositions of the parent granulite and the product amphibolite, measured in μg/cm3, we conclude that the mass of rock lost to the fluid phase during the hydration is approximately 20%. This suggests a mechanism for coupling between the local stress generated by hydration reactions and mass transfer, dependent on the spatial scale over which the system is open.

  12. Adsorption of hydrated hydroxide and hydronium ions on Ag(1 1 1). A quantum mechanical investigation

    NASA Astrophysics Data System (ADS)

    Patrito, E. M.; Paredes-Olivera, P.

    2003-03-01

    In this paper we have studied comparatively the adsorption of hydroxide and hydronium ions, extending our previous study on hydronium adsorption [J. Phys. Chem. B. 105 (2001) 7227] and emphasizing the adsorption of hydroxide. The calculations were performed on the 111 surface of silver using ab initio quantum mechanical methods (Hartree-Fock+Moller-Plesset second order perturbation theory). The adsorption was investigated for the bare and the hydrated ions (up to three water molecules). Binding energies, equilibrium structures and charge transfer processes were investigated. While the successive hydration of hydronium detaches the ion from the surface, the hydrated hydroxide anion remains specifically adsorbed. Charge transfer processes between the adsorbates and the surface were studied using electron density difference plots and effective charges obtained from Mulliken populations and from surface-dipole moment curves. The energetics of the surface reactions leading to the formation of the hydrated hydronium and hydroxide ions from the bare adsorbed ions and water molecules was also investigated. Both reactions are exothermic mainly due to the formation of strong hydrogen bonds. The effect of an external homogeneous electric field perpendicular to the surface on different adsorbate properties was investigated for the bare and hydrated hydroxide ion in order to model the environment of the electrical double layer. The electric field affects the orientation of the water molecules on the surface and the hydroxide surface distance.

  13. The mechanism of the dehydration of alcohols and the hydration of alkenes in acid solution

    NASA Astrophysics Data System (ADS)

    Vinnik, M. I.; Obraztsov, P. A.

    1990-01-01

    Kinetic data for the hydration of unsaturated compounds, the dehydration of alcohols, and the isotope exchange of the oxygen atom in alcohols and aqueous solutions of strong acids are analysed to establish the detailed mechanisms of these reactions. The catalytic action of the acid is caused not only by its ability to protonate the reactant but also by the possibility of the formation of reactive complexes of the reactant with the acid hydrates or the molecules of the undissociated acids. Equations are presented whereby the influence of the ionising capacity of the medium on the effective rate constants for the reactions indicated can be taken into account quantitatively. The question of the involvement of carbonium ions as reactive intermediates in reactions involving the dehydration of alcohols, the hydration of unsaturated compounds, and the isotope exchange of the oxygen atom in alcohols is examined. Complexes of the reactant with a solvated proton, the acid molecules, and the acid hydrates are the intermediates in these reactions. The relative contributions of the complexes to the effective rate constant depend on the acid concentration in the aqueous solution. The bibliography includes 65 references

  14. Pattern formation at liquid interfaces II. The KI/chloral hydrate/starch system

    NASA Astrophysics Data System (ADS)

    Liu, Cliff Zeh-Wen; Knobler, Charles M.

    1992-02-01

    Measurements are reported of pattern formation at a liquid interface produced by a photochemical reaction involving the system KI/chloral hydrate/ starch. The dependence of the wavelength on the concentrations of the reactants, the viscosity, and the height of the sample has been examined. It is concluded that the pattern is produced by a hydrodynamic mechanism.

  15. PRODUCTION OF HYDRATED ELECTRONS FROM PHOTOIONIZATION OF DISSOLVED ORGANIC MATTER IN NATURAL WATERS

    EPA Science Inventory

    Under UV irradiation, an important primary photochemical reaction of colored dissolved organic matter (CDOM) is electron ejection, producing hydrated electrons (e-aq). The efficiency of this process has been studied in both fresh and seawater samples with both steady-state scave...

  16. PRODUCTION OF HYDRATED ELECTRONS FROM PHOTOIONIZATION OF DISSOLVED ORGANIC MATTER IN NATURAL WATERS

    EPA Science Inventory

    Under UV irradiation, an important primary photochemical reaction of colored dissolved organic matter (CDOM) is electron ejection, producing hydrated electrons (e-aq). The efficiency of this process has been studied in both fresh and seawater samples with both steady-state scave...

  17. Capillary gas-solid chromatography

    NASA Astrophysics Data System (ADS)

    Berezkin, Viktor G.

    1996-11-01

    The current state of gas adsorption chromatography on open tubular capillary columns is analysed. The history of the development of this method and its role in gas chromatography are considered. The preparation of open tubular adsorption capillary columns, fundamentals of the theory of retention and of broadening of chromatographic zones, and the use of columns of this type in practical analytical chemistry are discussed. The bibliography includes 148 references.

  18. Hydration and mobility of HO-(aq)

    PubMed Central

    Asthagiri, D.; Pratt, Lawrence R.; Kress, J. D.; Gomez, Maria A.

    2004-01-01

    The hydroxide anion plays an essential role in many chemical and biochemical reactions. But a molecular-scale description of its hydration state, and hence also its transport, in water is currently controversial. The statistical mechanical quasichemical theory of solutions suggests that \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} \\begin{equation*}{\\mathrm{HO}}{\\cdot}[{\\mathrm{H}}_{2}{\\mathrm{O}}]_{3}^{-}\\end{equation*}\\end{document} is the predominant species in the aqueous phase under standard conditions. This result agrees with recent spectroscopic studies on hydroxide water clusters and with the available thermodynamic hydration free energies. In contrast, a recent ab initio molecular dynamics simulation has suggested that \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} \\begin{equation*}{\\mathrm{HO}}{\\cdot}[{\\mathrm{H}}_{2}{\\mathrm{O}}]_{4}^{-}\\end{equation*}\\end{document} is the only dominant aqueous solution species. We apply adiabatic ab initio molecular dynamics simulations and find good agreement with both the quasichemical theoretical predictions and experimental results. The present results suggest a picture that is simpler, more traditional, but with additional subtlety. These coordination structures are labile but the tricoordinate species is the prominent case. This conclusion is unaltered with changes in the electronic density functional. No evidence is found for rate-determining activated interconversion of a \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\setlength

  19. Clathrate hydrate tuning for technological purposes

    NASA Astrophysics Data System (ADS)

    di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco

    2010-05-01

    Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006

  20. Methane Recovery from Hydrate-bearing Sediments

    SciTech Connect

    J. Carlos Santamarina; Costas Tsouris

    2011-04-30

    Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with

  1. Gas Hydrate Storage of Natural Gas

    SciTech Connect

    Rudy Rogers; John Etheridge

    2006-03-31

    Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

  2. Diffusion of CO2 During Hydrate Formation and Dissolution

    SciTech Connect

    Franklin M. Orr, Jr.

    2002-08-20

    Experiments were performed to measure the rate of diffusion of CO2 through hydrate films. Hydrate films were created in a capillary tube, and the growth of the hydrate film was measured. Difficulties were encountered in creating hydrate repeatedly, and some non-uniform growth of the films was observed. Sufficient observations were obtained to demonstrate that hydrate growth occurs preferentially on the hydrate/water side of the interface, rather than at the hydrate/CO2 interface. Diffusion coefficients were estimated from observations of the rate of growth of the hydrate film along with estimates of the solubility of CO2 in water and of the concentration gradient across the hydrate layer. The experimental observations indicate that hydrate formation occurs much more rapidly at the hydrate water interface than at the hydrate/CO2 interface. Any growth of hydrate at the CO2/hydrate interface was too slow to be observed at the time scale of the experiments. That observation is consistent with the idea that CO2 can move more easily through the hydrate, presumably by hopping between hydrate cages, than water can move through the hydrate, presumably by lattice hopping. Estimated diffusion coefficients were in the range 1-3E-06 cm2/sec. Those values are about an order of magnitude lower than the diffusion coefficient for CO2 in liquid water, but four orders of magnitude larger than the value for diffusion of CO2 in a solid. The rate of diffusion through the hydrate controls both the creation of new hydrate at the hydrate/water interface and the rate at which CO2 dissolves in the liquid water and diffuses away from the hydrate layer. Formation of a hydrate layer reduces the rate at which CO2 dissolves in liquid water.

  3. Abundance and texture of gas hydrate beneath Hydrate Ridge, offshore Oregon, USA from infrared imaging

    NASA Astrophysics Data System (ADS)

    Long, P.; Riedel, M.; Trehu, A.; Collett, T.; Weinberger, J.; Torres, M.; Rack, F.; Bohrmann, G.; Liu, C.; Odp Leg 204 Shipboard Scientific Party

    2003-04-01

    The strongly endothermic dissociation of gas hydrate cools sediment samples containing gas hydrates once they are out of hydrate stability conditions. Previously, multiple thermistors have been used on cores to detect such cooling as a proxy for gas hydrate occurrence. On Leg 204 of the Ocean Drilling Program (ODP), infrared (IR) imaging cameras (FLIR SC-2000, 320 x 240 pixels) were used make continuous images of cores while they were still in plastic liners. Resulting images facilitated on-catwalk identification and sampling of core sections likely to contain hydrate. Temperature data extracted from the images were used to map hydrate occurrence as a function of depth at each of 9 sites on or near southern Hydrate Ridge (ODP Sites 1244-1252). Down-core temperature anomalies ranging from -0.3 to -9^oC were compared to other proxies for hydrate occurrence such as resistivity logs using the Archie Relationship to estimate pore water saturation (Sw), chloride concentration of interstitial water, and gas composition. The IR images also provide information on cm-scale textures of hydrate occurrences. Observed textures include lenses or veins (conformable and cross-cutting), nodular, and disseminated features. Dissection of selected samples revealed that individual hydrate lenses commonly have adjacent fine (<1 mm) veinlets oriented in 2 to 3 mutually orthogonal directions.

  4. Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

    USGS Publications Warehouse

    Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

    2013-01-01

    As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

  5. Pore water anomalies of submarine gas-hydrate zones as tool to assess hydrate abundance and distribution in the subsurface - What have we learned in the past decade?

    NASA Astrophysics Data System (ADS)

    Hesse, Reinhard

    2003-04-01

    δ 18O increase [Hesse and Harrison, 1981, Earth Planet. Sci. Lett. 55 (1981) 453.]—need not occur together in the presence of hydrates because the isotope effect may be overprinted by the effects of other reactions such as volcanic ash alteration or by the advection of low-δ 18O fluids. However, if the anomalies show up, hydrates are present almost invariably (with the exception of advected low-Cl -/high-δ 18O waters). Coming to terms with the effects of advection and diffusion has allowed successful modeling of the simpler hydrate-affected pore water profiles at passive margins. Instrumental for modeling are chlorine isotopes, which provide an effective tool to assess advection rates. The Egeberg and Dickens model allows estimation of hydrate concentration and distribution in the subsurface because it separates the effects of advection, diffusion and hydrate dissociation but critically depends on samples taken under in situ pressure and temperature conditions. Modeling the more complex pore water profiles of active margins is a challenge for the future. Compared to geophysical methods to estimate hydrate concentration, the geochemical method gives minimum amounts.

  6. Extensive decarbonation of continuously hydrated subducting slabs

    NASA Astrophysics Data System (ADS)

    Arzilli, Fabio; Burton, Mike; La Spina, Giuseppe; Macpherson, Colin G.

    2017-04-01

    CO2 release from subducting slabs is a key element of Earth's carbon cycle, consigning slab carbon either to mantle burial or recycling to the surface through arc volcanism, however, what controls subducted carbon's fate is poorly understood. Fluids mobilized by devolatilization of subducting slabs play a fundamental role in the melting of mantle wedges and in global geochemical cycles [1]. The effect of such fluids on decarbonation in subducting lithologies has been investigated recently [2-5], but several thermodynamic models [2-3], and experimental studies [6] suggest that carbon-bearing phases are stable at sub-arc depths (80-140 km; 2.6-4.5 GPa), implying that this carbon can be carried to mantle depths of >140 km. This is inconsistent with observations of voluminous CO2 release from arc volcanoes [7-10], located above slabs that are at 2.6-4.5 GPa pressure. The aim of this study is to re-evaluate the role of metamorphic decarbonation, showing if decarbonation reactions could be feasible at sub-arc depths combined with a continuous hydration scenario. We used the PerpleX software combined with a custom-designed algorithm to simulate a pervasive fluid infiltration characterized by "continuous hydration" combined with a distillation model, in which is possible to remove CO2 when decarbonation occurs, to obtain an open-system scenario. This is performed by repeatedly flushing the sediment with pure H2O at 0.5, 1.0 or 5 wt.% until no further decarbonation occurs. Here we show that continuous hydrated of sediment veneers on subducting slabs by H2O released from oceanic crust and serpentinised mantle lithosphere [11-13], produces extensive slab decarbonation over a narrow, sub-arc pressure range, even for low temperature subduction pathways. This explains the location of CO2-rich volcanism, quantitatively links the sedimentary composition of slab material to the degree of decarbonation and greatly increases estimates for the magnitude of carbon flux through the arc

  7. Modeling the Formation of Hydrate-Filled Veins in Fine-Grained Sediments from in Situ Microbial Methane

    NASA Astrophysics Data System (ADS)

    Malinverno, A.; Cook, A.; Daigle, H.

    2016-12-01

    Continental margin sediments are dominantly fine-grained silt and clay, and methane hydrates in these sediments are often found in semi-vertical veins and fractures. In several instances, these hydrate veins occupy discrete depth intervals that are a few tens of meters thick and are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the gas hydrate stability zone (GHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. To investigate the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, compaction, solute diffusion, and microbial methane generation. Microbial methane generation depends on the amount of metabolizable organic carbon deposited at the seafloor, whose progressive degradation produces methane beneath the sulfate reduction zone. If the amount of organic carbon entering the methanogenic zone is kept constant in time, we found that the computed amounts of hydrate formed in discrete intervals within the GHSZ are well below those estimated from observations. On the other hand, if the deposition of organic carbon is higher in a given time interval, methane generation during burial is more intense in the corresponding sediment interval, resulting in enhanced hydrate formation. With variations in organic carbon deposition comparable to those generally observed in continental margins, our model was able to reproduce the methane hydrate contents that were estimated from drilling. These results support the suggestion that in situ microbial generation associated with transient organic carbon deposition is the source of methane that forms isolated intervals of hydrate-filled veins in fine-grained sediments.

  8. Detection and Production of Methane Hydrate

    SciTech Connect

    George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

    2011-12-31

    This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand processes

  9. [The outcome of hydration in functional dysphonia].

    PubMed

    García Real, T; García Real, A; Díaz Román, T; Cañizo Fernández Roldán, A

    2002-01-01

    Functional dysphonia has high prevalence among professional voice users. Different aspects should be considered in vocal therapy. One of them is hydration. The aim of the present study is to assess the effect of hydration on a few aspect of vocal dysfunction. 75 subjects were distributed into three different groups. 23 participated as a control group, 27 received hydration treatment and 25 received hydration treatment plus voice training. Dryness, mucosity, phonatory effort, hoarseness, fundamental frequency (Fo), maximum phonatory time (MPT), time of speech and laryngeal status were the variables evaluated at time 0 and 14 days later, immediately after the completion of the treatment of each group. Statistical differences regarding dryness (p = 0.003) and hoarseness (p = 0.033) were found between the control group and the groups receiving treatment. There were no statistical differences in severity and frequency of variables measured at time 0 at 14 days later in the control group. However, all variables except laryngeal status, improved significantly in the groups receiving hydration alone. Only clinical variables improved in the combined group. These findings indicated a therapeutic benefit of hydration, with or without voice training, for functional dysphonia. Further studies using acoustic and stroboscopic analysis are required in order to define the effect of hydration on the compliance of glottic sphincter.

  10. Influence of temperature on methane hydrate formation.

    PubMed

    Zhang, Peng; Wu, Qingbai; Mu, Cuicui

    2017-08-11

    During gas hydrate formation process, a phase transition of liquid water exists naturally, implying that temperature has an important influence on hydrate formation. In this study, methane hydrate was formed within the same media. The experimental system was kept at 1.45, 6.49, and 12.91 °C respectively, and then different pressurization modes were applied in steps. We proposed a new indicator, namely the slope of the gas flow rates against time (dν g /dt), to represent the intrinsic driving force for hydrate formation. The driving force was calculated as a fixed value at the different stages of formation, including initial nucleation/growth, secondary nucleation/growth, and decay. The amounts of gas consumed at each stage were also calculated. The results show that the driving force during each stage follows an inverse relation with temperature, whereas the amount of consumed gas is proportional to temperature. This opposite trend indicates that the influences of temperature on the specific formation processes and final amounts of gas contained in hydrate should be considered separately. Our results also suggest that the specific ambient temperature under which hydrate is formed should be taken into consideration, when explaining the formation of different configurations and saturations of gas hydrates in natural reservoirs.

  11. Prospecting for marine gas hydrate resources

    USGS Publications Warehouse

    Boswell, Ray; Shipp, Craig; Reichel, Thomas; Shelander, Dianna; Saeki, Tetsuo; Frye, Matthew; Shedd, William; Collett, Timothy S.; McConnell, Daniel R.

    2016-01-01

    As gas hydrate energy assessment matures worldwide, emphasis has evolved away from confirmation of the mere presence of gas hydrate to the more complex issue of prospecting for those specific accumulations that are viable resource targets. Gas hydrate exploration now integrates the unique pressure and temperature preconditions for gas hydrate occurrence with those concepts and practices that are the basis for conventional oil and gas exploration. We have aimed to assimilate the lessons learned to date in global gas hydrate exploration to outline a generalized prospecting approach as follows: (1) use existing well and geophysical data to delineate the gas hydrate stability zone (GHSZ), (2) identify and evaluate potential direct indications of hydrate occurrence through evaluation of interval of elevated acoustic velocity and/or seismic events of prospective amplitude and polarity, (3) mitigate geologic risk via regional seismic and stratigraphic facies analysis as well as seismic mapping of amplitude distribution along prospective horizons, and (4) mitigate further prospect risk through assessment of the evidence of gas presence and migration into the GHSZ. Although a wide range of occurrence types might ultimately become viable energy supply options, this approach, which has been tested in only a small number of locations worldwide, has directed prospect evaluation toward those sand-hosted, high-saturation occurrences that were presently considered to have the greatest future commercial potential.

  12. Gas Hydrates Research Programs: An International Review

    SciTech Connect

    Jorge Gabitto; Maria Barrufet

    2009-12-09

    Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

  13. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by Maurer Technology, Noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition. We plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. We also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. We are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. We hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, our goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  14. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2003-12-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the US have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by maurer Technology, noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R and D in the area of onshore hydrate deposition. They plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. They also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. They are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. They hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, the goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  15. Tapping methane hydrates for unconventional natural gas

    USGS Publications Warehouse

    Ruppel, Carolyn

    2007-01-01

    Methane hydrate is an icelike form of concentrated methane and water found in the sediments of permafrost regions and marine continental margins at depths far shallower than conventional oil and gas. Despite their relative accessibility and widespread occurrence, methane hydrates have never been tapped to meet increasing global energy demands. With rising natural gas prices, production from these unconventional gas deposits is becoming economically viable, particularly in permafrost areas already being exploited for conventional oil and gas. This article provides an overview of gas hydrate occurrence, resource assessment, exploration, production technologies, renewability, and future challenges.

  16. Carbon dioxide hydrate and floods on Mars.

    PubMed

    Milton, D J

    1974-02-15

    Ground ice on Mars probably consists largely of carbon dioxide hydrate, CO(2) . 6H(2)O. This hydrate dissociates upon release of pressure at temperatures between 0 degrees and 10 degrees C. The heat capacity of the ground would be sufficient to produce up to 4 percent (by volume) of water at a rate equal to that at which it can be drained away. Catastrophic dissociation of carbon dioxide hydrate during some past epoch when the near surface temperature was in this range would have produced chaotic terrain and flood channels.

  17. Dynamics of hydration water in protein

    NASA Astrophysics Data System (ADS)

    Bellissent-Funel, M.-C.; Teixeira, J.; Bradley, K. F.; Chen, S. H.

    1992-06-01

    Incoherent quasi-elastic neutron scattering studies of in vivo deuterated C-phycocyanin, at different levels of hydration, have been made. We show that the mobility at high temperature, (sim 300 K) of the water molecules near the protein surface can be described by relatively simple models. At full hydration the high temperature data can be interpreted using a model where each water molecule is diffusing in a confined space of 3 Å in radius. At low hydration, and 298 K, the diffusional behaviour is typical of jump diffusion with a residence time 10 times larger than the one in bulk water at the same temperature.

  18. Carbon dioxide hydrate and floods on Mars

    NASA Technical Reports Server (NTRS)

    Milton, D. J.

    1974-01-01

    Ground ice on Mars probably consists largely of carbon dioxide hydrate. This hydrate dissociates upon release of pressure at temperatures between 0 and 10 C. The heat capacity of the ground would be sufficient to produce up to 4% (by volume) of water at a rate equal to that at which it can be drained away. Catastrophic dissociation of carbon dioxide hydrate during some past epoch when the near-surface temperature was in this range would have produced chaotic terrain and flood channels.

  19. Transition-metal-free hydration of nitriles using potassium tert-butoxide under anhydrous conditions.

    PubMed

    Midya, Ganesh Chandra; Kapat, Ajoy; Maiti, Subhadip; Dash, Jyotirmayee

    2015-04-17

    Potassium tert-butoxide acts as a nucleophilic oxygen source during the hydration of nitriles to give the corresponding amides under anhydrous conditions. The reaction proceeds smoothly for a broad range of substrates under mild conditions, providing an efficient and economically affordable synthetic route to the amides in excellent yields. This protocol does not need any transition-metal catalyst or any special experimental setup and is easily scalable to bulk scale synthesis. A single-electron-transfer radical mechanism as well as an ionic mechanism have been proposed for the hydration process.

  20. Three-dimensional distribution of gas hydrate beneath southern Hydrate Ridge: Constraints from ODP Leg 204

    USGS Publications Warehouse

    Trehu, A.M.; Long, P.E.; Torres, M.E.; Bohrmann, G.; Rack, F.R.; Collett, T.S.; Goldberg, D.S.; Milkov, A.V.; Riedel, M.; Schultheiss, P.; Bangs, N.L.; Barr, S.R.; Borowski, W.S.; Claypool, G.E.; Delwiche, M.E.; Dickens, G.R.; Gracia, E.; Guerin, G.; Holland, M.; Johnson, J.E.; Lee, Y.-J.; Liu, C.-S.; Su, X.; Teichert, B.; Tomaru, H.; Vanneste, M.; Watanabe, M. E.; Weinberger, J.L.

    2004-01-01

    Large uncertainties about the energy resource potential and role in global climate change of gas hydrates result from uncertainty about how much hydrate is contained in marine sediments. During Leg 204 of the Ocean Drilling Program (ODP) to the accretionary complex of the Cascadia subduction zone, we sampled the gas hydrate stability zone (GHSZ) from the seafloor to its base in contrasting geological settings defined by a 3D seismic survey. By integrating results from different methods, including several new techniques developed for Leg 204, we overcome the problem of spatial under-sampling inherent in robust methods traditionally used for estimating the hydrate content of cores and obtain a high-resolution, quantitative estimate of the total amount and spatial variability of gas hydrate in this structural system. We conclude that high gas hydrate content (30-40% of pore space or 20-26% of total volume) is restricted to the upper tens of meters below the seafloor near the summit of the structure, where vigorous fluid venting occurs. Elsewhere, the average gas hydrate content of the sediments in the gas hydrate stability zone is generally <2% of the pore space, although this estimate may increase by a factor of 2 when patchy zones of locally higher gas hydrate content are included in the calculation. These patchy zones are structurally and stratigraphically controlled, contain up to 20% hydrate in the pore space when averaged over zones ???10 m thick, and may occur in up to ???20% of the region imaged by 3D seismic data. This heterogeneous gas hydrate distribution is an important constraint on models of gas hydrate formation in marine sediments and the response of the sediments to tectonic and environmental change. ?? 2004 Published by Elsevier B.V.

  1. Three-dimensional distribution of gas hydrate beneath southern Hydrate Ridge: constraints from ODP Leg 204

    NASA Astrophysics Data System (ADS)

    Tréhu, A. M.; Long, P. E.; Torres, M. E.; Bohrmann, G.; Rack, F. R.; Collett, T. S.; Goldberg, D. S.; Milkov, A. V.; Riedel, M.; Schultheiss, P.; Bangs, N. L.; Barr, S. R.; Borowski, W. S.; Claypool, G. E.; Delwiche, M. E.; Dickens, G. R.; Gracia, E.; Guerin, G.; Holland, M.; Johnson, J. E.; Lee, Y.-J.; Liu, C.-S.; Su, X.; Teichert, B.; Tomaru, H.; Vanneste, M.; Watanabe, M.; Weinberger, J. L.

    2004-06-01

    Large uncertainties about the energy resource potential and role in global climate change of gas hydrates result from uncertainty about how much hydrate is contained in marine sediments. During Leg 204 of the Ocean Drilling Program (ODP) to the accretionary complex of the Cascadia subduction zone, we sampled the gas hydrate stability zone (GHSZ) from the seafloor to its base in contrasting geological settings defined by a 3D seismic survey. By integrating results from different methods, including several new techniques developed for Leg 204, we overcome the problem of spatial under-sampling inherent in robust methods traditionally used for estimating the hydrate content of cores and obtain a high-resolution, quantitative estimate of the total amount and spatial variability of gas hydrate in this structural system. We conclude that high gas hydrate content (30-40% of pore space or 20-26% of total volume) is restricted to the upper tens of meters below the seafloor near the summit of the structure, where vigorous fluid venting occurs. Elsewhere, the average gas hydrate content of the sediments in the gas hydrate stability zone is generally <2% of the pore space, although this estimate may increase by a factor of 2 when patchy zones of locally higher gas hydrate content are included in the calculation. These patchy zones are structurally and stratigraphically controlled, contain up to 20% hydrate in the pore space when averaged over zones ˜10 m thick, and may occur in up to ˜20% of the region imaged by 3D seismic data. This heterogeneous gas hydrate distribution is an important constraint on models of gas hydrate formation in marine sediments and the response of the sediments to tectonic and environmental change.

  2. Hydration of C{sub 3}A-gypsum systems

    SciTech Connect

    Quennoz, Alexandra Scrivener, Karen L.

    2012-07-15

    Hydration of C{sub 3}A-gypsum systems with different gypsum additions was investigated in terms of the phase assemblage, kinetics and microstructural development. The second stage of the reaction, which begins after the depletion of gypsum, was of particular interest. From in-situ X-ray diffraction results, it was seen that the dissolution of ettringite and C{sub 3}A to form monosulfoaluminate and/or hydroxy-AFm phases is a rapid reaction that occurs right after the depletion of gypsum. The observation of the calorimetric curves obtained for the different gypsum additions leads us to the conclusion that the mechanism controlling the hydration rate during this period is the nucleation and growth of the AFm phases. The microstructural study showed that the formation of AFm phases occurs in the space between the C{sub 3}A grains but also within the boundaries of the original C{sub 3}A grains. Hydrogarnet was observed growing as a shell around the C{sub 3}A grains.

  3. Ab initio molecular dynamics calculations of ion hydration free energies.

    PubMed

    Leung, Kevin; Rempe, Susan B; von Lilienfeld, O Anatole

    2009-05-28

    We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or "lambda-path" technique to compute the intrinsic hydration free energies of Li(+), Cl(-), and Ag(+) ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential (phi) contributions, we obtain absolute AIMD hydration free energies (DeltaG(hyd)) within a few kcal/mol, or better than 4%, of Tissandier et al.'s [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model phi predictions. The sums of Li(+)/Cl(-) and Ag(+)/Cl(-) AIMD DeltaG(hyd), which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag(+)+Ni(+)-->Ag+Ni(2+) in water. The predictions for this reaction suggest that existing estimates of DeltaG(hyd) for unstable radiolysis intermediates such as Ni(+) may need to be extensively revised.

  4. Methane hydrate formation in partially water-saturated Ottawa sand

    USGS Publications Warehouse

    Waite, W.F.; Winters, W.J.; Mason, D.H.

    2004-01-01

    Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

  5. Methane hydrate formation in partially water-saturated Ottawa sand

    USGS Publications Warehouse

    Waite, W.F.; Winters, W.J.; Mason, D.H.

    2004-01-01

    Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

  6. Partitioning of particle velocities in gas-solid turbulent flows into a continuous field and a spatially uncorrelated random distribution: theoretical formalism and numerical study

    NASA Astrophysics Data System (ADS)

    Février, Pierre; Simonin, Olivier; Squires, Kyle D.

    2005-06-01

    The velocity distribution of dilute suspensions of heavy particles in gas-solid turbulent flows is investigated. A statistical approach - the mesoscopic Eulerian formalism (MEF) - is developed in which an average conditioned on a realization of the turbulent carrier flow is introduced and enables a decomposition of the instantaneous particle velocity into two contributions. The first is a contribution from an underlying continuous turbulent velocity field shared by all the particles - the mesoscopic Eulerian particle velocity field (MEPVF) - that accounts for all particle-particle and fluid-particle two-point correlations. The second contribution corresponds to a distribution - the quasi-Brownian velocity distribution (QBVD) - that represents a random velocity component satisfying the molecular chaos assumption that is not spatially correlated and identified with each particle of the system. The MEF is used to investigate properties of statistically stationary particle-laden isotropic turbulence. The carrier flow is computed using direct numerical simulation (DNS) or large-eddy simulation (LES) with discrete particle tracking employed for the dispersed phase. Particle material densities are much larger than that of the fluid and the force of the fluid on the particle is assumed to reduce to the drag contribution. Computations are performed in the dilute regime for which the influences of inter-particle collisions and fluid-turbulence modulation are neglected. The simulations show that increases in particle inertia increase the contribution of the quasi-Brownian component to the particle velocity. The particle velocity field is correlated at larger length scales than the fluid, with the integral length scales of the MEPVF also increasing with particle inertia. Consistent with the previous work of Abrahamson (1975), the MEF shows that in the limiting case of large inertia, particle motion becomes stochastically equivalent to a Brownian motion with a random spatial

  7. Free gas in the regional hydrate stability zone: Implications for hydrate distribution and fracturing behavior

    NASA Astrophysics Data System (ADS)

    Daigle, H.; Dugan, B.

    2010-12-01

    We show that hydrate distribution and fracture genesis in the hydrate stability zone are largely governed by the phase of methane supply. In systems where methane is supplied primarily as free gas, hydrate saturation increases upwards in the hydrate stability zone, and fractures nucleate in the middle of the stability zone where hydrate saturation is highest. In systems where methane is supplied primarily as a dissolved phase in the pore water, hydrate saturation decreases upwards in the stability zone, and fractures nucleate at the base of the stability zone. These interpretations are based on our one-dimensional model that incorporates multiphase flow and free gas within the regional hydrate stability zone (RHSZ). The RHSZ is defined as the interval in which methane hydrate may occur at seawater salinity (3.35% by mass). As hydrate forms and excludes salt from the crystal structure, the porewater salinity increases. Free gas enters the RHSZ when the porewater salinity increases to the value required for three-phase (dissolved methane + gas hydrate + free gas) equilibrium. Our model also incorporates changes to capillary pressure as hydrate forms and occludes the pore system. We model the system until the excess pore pressure exceeds the vertical effective stress in the domain due to capillary effects and pore occlusion, at which point we assume fractures nucleate. We test our model at Hydrate Ridge, where methane supply is dominantly in the gas phase, and show that hydrate saturation increases upwards and fractures nucleate high within the stability zone, eventually allowing gas to vent to the seafloor. We also model Blake Ridge, where methane supply is dominantly in the dissolved phase, and show that hydrate saturation is greatest at the base of the stability zone; fractures nucleate here and in some cases could propagate through the regional hydrate stability zone, allowing methane-charged water to vent to the seafloor. These two systems represent endmembers of

  8. Understanding effect of structure and stability on transformation of CH4 hydrate to CO2 hydrate

    NASA Astrophysics Data System (ADS)

    Liu, Jinxiang; Yan, Yujie; Liu, Haiying; Xu, Jiafang; Zhang, Jun; Chen, Gang

    2016-03-01

    Understanding the transformation process of CH4 hydrate to CO2 hydrate is crucial to develop the CH4sbnd CO2 replacement technique for CH4 production and CO2 sequestration. Ab initio calculations show that the transformation will slightly distort the host lattice and decrease the binding strength of guest molecules, but it is a thermodynamically spontaneous process dominated by the entropic contribution. Moreover, ab initio molecular dynamics simulations suggest that the dynamics of the host lattice is independent on the guest molecules, while CO2 in hydrate exhibits slower translational and rotational motion than CH4 in hydrate.

  9. Map of Hydrated Minerals on Vesta

    NASA Image and Video Library

    2012-09-26

    This map from NASA Dawn mission indicates the presence of hydrated minerals on the giant asteroid Vesta about 30 degrees north latitude, in August 2011. At the time, it was winter in Vesta northern hemisphere.

  10. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Thomas Williams; Bjorn Paulsson; Alexander Goertz

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a drilling hazard by the oil and gas industry for years. Drilling engineers working in Russia, Canada and the USA have documented numerous problems, including drilling kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates as a potential energy source agree that the resource potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained from physical samples taken from actual hydrate-bearing rocks. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The project team drilled and continuously cored the Hot Ice No. 1 well on Anadarko-leased acreage beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and used for determining physical characteristics of hydrates and surrounding rock. After the well was logged, a 3D vertical seismic profile (VSP) was recorded to calibrate the shallow geologic section with seismic data and to investigate techniques to better resolve lateral subsurface variations of potential hydrate-bearing strata. Paulsson Geophysical Services, Inc. deployed their 80 level 3C clamped borehole seismic receiver array in the wellbore to record samples every 25 ft. Seismic vibrators were successively positioned at 1185 different surface positions in a circular pattern around the wellbore. This technique generated a 3D image of the subsurface. Correlations were

  11. Hydrate Control for Gas Storage Operations

    SciTech Connect

    Jeffrey Savidge

    2008-10-31

    The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

  12. Gas hydrate formation in reversed micelles

    SciTech Connect

    Nguyen, H.; Rao, A.M.; Phillips, J.B.; John, V.T.; Reed, W.F.

    1991-12-31

    We describe a technique to modify protein solubility and optimize enzyme activity in reversed micellar solutions. The technique is based on the ability of hydrates of natural gas to form in the microaqueous phase. Clathrate hydrates are crystalline inclusions of water and gas, and their formation in bulk water has traditionally been studied with relevance to natural gas recovery. We have found that hydrates can form in the environment of the microaqueous pools of reversed micelles, and that their extent of formation can be well controlled through the thermodynamic variables of temperature and pressure. Additionally, formation of hydrates affects the size and aggregation number of the micelles, and thus influences the solubility and conformation of encapsulated proteins. We demonstrate how the concept can be used in two applications: (1) protein extraction into reversed micelles and subsequent recovery, and (2) optimization of enzyme activit