A Fundamental Study of Inorganic Clathrate and Other Open-Framework Materials

Energy Technology Data Exchange (ETDEWEB)

Nolas, George [Univ. of South Florida, Tampa, FL (United States)

2017-08-15

Due to formidable synthetic challenges, many materials of scientific and technological interest are first obtained as microcrystalline powders. High purity, high yield processing techniques are often lacking and thus care must be taken in interpretation of the observed structural, chemical, and physical properties of powder or polycrystalline materials, which can be strongly influenced by extrinsic properties. Furthermore, the preparation of high-quality single crystals for many materials by traditional techniques can be especially challenging in cases where the elemental constituents have greatly differing melting points and/or vapor pressures, when the desired compound is thermodynamically metastable, or where growth with participation of the melt is generally not possible. New processing techniques are therefore imperative in order to investigate the intrinsic properties of these materials and elucidate their fundamental physical properties. Intermetallic clathrates constitute one such class of materials. The complex crystal structures of intermetallic clathrates are characterized by mainly group 14 host frameworks encapsulating guest-ions in polyhedral cages. The unique features of clathrate structures are intimately related to their physical properties, offering ideal systems for the study of structure-property relationships in crystalline solids. Moreover, intermetallic clathrates are being actively investigated due to their potential for application in thermoelectrics, photovoltaics and opto-electronics, superconductivity, and magnetocaloric technologies. We have developed different processing techniques in order to synthesize phase-pure high yield clathrates reproducibly, as well as grow single crystals for the first time. We also employed these techniques to synthesize new “open-framework” compounds. These advances in materials processing and crystal growth allowed for the investigation of the physical properties of a variety of different clathrate

Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation

Science.gov (United States)

Li, Ying; Raghavan, Rahul; Wagner, Nicholas A.; Davidowski, Stephen K.; Baggetto, Loïc; Zhao, Ran; Cheng, Qian; Yarger, Jeffery L.; Veith, Gabriel M.; Ellis‐Terrell, Carol; Miller, Michael A.; Chan, Kwai S.

2015-01-01

Silicon clathrates contain cage‐like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46−y as the anode material for lithium‐ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X‐ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li+ during lithiation and delithiation, respectively, distinct from diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g−1 at a 5 mA g−1 rate were observed for silicon clathrate with composition Ba8Al8.54Si37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium‐ion batteries. PMID:27980951

Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system

Science.gov (United States)

Lunine, J. I.; Stevenson, D. J.

1985-01-01

The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

IR reflectance spectroscopy of carbon dioxide clathrate hydrates. Implications for Saturn's icy moons.

Science.gov (United States)

Oancea, A.; Grasset, O.; Le Menn, E.; Bezacier, L.; Bollengier, O.; Le Mouélic, S.; Tobie, G.

2012-04-01

A CO2 spectral band was discovered by VIMS on the Saturn's satellites Dione, Hyperion, Iapetus and Phoebe [1]. The band position on the three first satellites corresponds to CO2 trapped in a complex material, but no indication exists whether this latter is water ice or some mineral or complex organic compound [1]. On Phoebe, the CO2 spectral band is consistent with solid CO2 or CO2 molecules trapped in the small cages of a clathrate hydrate structure [2]. It is thought that clathrate hydrates could play a significant role in the chemistry of the solar nebula [3] and in the physical evolution of astrophysical objects [4]. But so far, no clathrate hydrate structure has been observed in astrophysical environments. Moreover, identification of molecules trapped in a clathrate hydrate structure is extremely difficult because of the strong IR vibration modes of the water ice matrix. In this work, experimental IR reflectance spectra for CO2 clathrate hydrates are studied on grains and films. Clathrates are synthesized in a high pressure autoclave at low temperatures. IR spectral analysis is made with a low pressure and low temperature cryostat. These experimental conditions - 80 spectrum will be presented. A comparison between the absorption bands of CO2 clathrate hydrates obtained in our lab and CO2 absorption bands as detected by VIMS on the icy satellites of Saturn will be shown. This experimental work confirms that VIMS data are not consistent with the presence of structure I CO2 clathrate hydrates on the surface of the icy moons. Possibility of having metastable structure II still remains unsolved and will be discussed. [1] Dalton et al., Space Sci. Rev. 2010, 153 : 113-154. [2] Cruikshank D.P. et al, Icarus, 2010, 206: 561-572. [3] Mousis O. et al , Ap. J. 2009, 691: 1780-1786. [4] Choukroun M. et al, in Solar System Ices, edited by Castillo-Rogez, J. et al., 2011.

Clathrate Hydrates for Thermal Energy Storage in Buildings: Overview of Proper Hydrate-Forming Compounds

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Beatrice Castellani

2014-09-01

Full Text Available Increasing energy costs are at the origin of the great progress in the field of phase change materials (PCMs. The present work aims at studying the application of clathrate hydrates as PCMs in buildings. Clathrate hydrates are crystalline structures in which guest molecules are enclosed in the crystal lattice of water molecules. Clathrate hydrates can form also at ambient pressure and present a high latent heat, and for this reason, they are good candidates for being used as PCMs. The parameter that makes a PCM suitable to be used in buildings is, first of all, a melting temperature at about 25 °C. The paper provides an overview of groups of clathrate hydrates, whose physical and chemical characteristics could meet the requirements needed for their application in buildings. Simulations with a dynamic building simulation tool are carried out to evaluate the performance of clathrate hydrates in enhancing thermal comfort through the moderation of summer temperature swings and, therefore, in reducing energy consumption. Simulations suggest that clathrate hydrates have a potential in terms of improvement of indoor thermal comfort and a reduction of energy consumption for cooling. Cooling effects of 0.5 °C and reduced overheating hours of up to 1.1% are predicted.

Understanding lattice thermal conductivity in thermoelectric clathrates: A density functional theory study on binary Si-based type-I clathrates

Science.gov (United States)

Euchner, Holger; Pailhès, Stéphane; Giordano, Valentina M.; de Boissieu, Marc

2018-01-01

Despite their crystalline nature, thermoelectric clathrates exhibit a strongly reduced lattice thermal conductivity. While the reason for this unexpected behavior is known to lie in the peculiarities of the complex crystal structure and the interplay of the underlying guest-host framework, their respective roles are still not fully disentangled and understood. Our ab initio study of the most simple type-I clathrate phase, the binary compound Ba8Si46 and its derivatives Ba8 -xSi46 seeks to identify these mechanisms and provides insight into their origin. Indeed, the strongly decreased lattice thermal conductivity in thermoelectric clathrates is a consequence of a reduction of the acoustic phonon bandwidth, a lowering of the acoustic phonon group velocities, and the amplification of three-phonon-scattering processes. While the complexity of the crystal structure is demonstrated not to be the leading factor, the reasons are manifold. A modified Si-Si interaction causes a first decrease of the sound velocity, whereas the presence of flat Ba modes results in an additional lowering. These modes correspond to confined Bloch states that are localized on the Ba atoms and significantly increase the scattering phase space and, together with an increased anharmonicity of the interatomic interactions, strongly affect the phonon lifetimes.

The effect of classical and quantum dynamics on vibrational frequency shifts of H2 in clathrate hydrates

International Nuclear Information System (INIS)

Plattner, Nuria; Meuwly, Markus

2014-01-01

Vibrational frequency shifts of H 2 in clathrate hydrates are important to understand the properties and elucidate details of the clathrate structure. Experimental spectra of H 2 in clathrate hydrates have been measured for different clathrate compositions, temperatures, and pressures. In order to establish reliable relationships between the clathrate structure, dynamics, and observed frequencies, calculations of vibrational frequency shifts in different clathrate environments are required. In this study, a combination of classical molecular dynamics simulations, electronic structure calculations, and quantum dynamical simulation is used to calculate relative vibrational frequencies of H 2 in clathrate hydrates. This approach allows us to assess dynamical effects and simulate the change of vibrational frequencies with temperature and pressure. The frequency distributions of the H 2 vibrations in the different clathrate cage types agree favorably with experiment. Also, the simulations demonstrate that H 2 in the 5 12 cage is more sensitive to the details of the environment and to quantum dynamical effects, in particular when the cage is doubly occupied. We show that for the 5 12 cage quantum effects lead to frequency increases and double occupation is unlikely. This is different for the 5 12 6 4 cages for which higher occupation numbers than one H 2 per cage are likely

Vibrational spectroscopic and quantum theoretical study of host-guest interactions in clathrates: I. Hofmann type clathrates

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VLADIMIR M. PETRUSEVSKI

2000-06-01

Full Text Available Hofmann type clatharates are host-guest compounds with the general formula M(NH32M'(CN4·2G, in which M(NH32M'(CN4 is the host lattice and G is benzene, the guest molecule. In previous studies, host-guest interactions have been investigated by analyzing the RT and LNT vibrational (infrared, far infrared and Raman spectra of these clathrates. All the observed changes in the vibrational spectra of these clathrates are referred to a host-guest interaction originating from weak hydrogen bonding between the ammonia hydrogen atoms from the host lattice and the p electron cloud of the guest (benzene molecules. In order to obtain an insight into the relative importance of the local crystalline field vs. the anharmonicity effects on the spectroscopic properties of the guest species upon enclathration, as well as to explain the observed band shifts and splittings, several quantum theoretical approaches are proposed.

Silicon clathrates for lithium ion batteries: A perspective

International Nuclear Information System (INIS)

Warrier, Pramod; Koh, Carolyn A.

2016-01-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Silicon clathrates for lithium ion batteries: A perspective

Science.gov (United States)

Warrier, Pramod; Koh, Carolyn A.

2016-12-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15-20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Silicon clathrates for lithium ion batteries: A perspective

Energy Technology Data Exchange (ETDEWEB)

Warrier, Pramod, E-mail: pramod.warrier@gmail.com; Koh, Carolyn A. [Center for Hydrate Research, Chemical & Biological Engineering Department, Colorado School of Mines, Golden, Colorado 80401 (United States)

2016-12-15

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

An ir study of M(1-propanethiol)2Ni(CN)4.G (M=Cd,Ni and G=benzene) clathrates

International Nuclear Information System (INIS)

Kartal, Z.; Tuerkoz, D.; Bahceli, S.

2004-01-01

Two Hofmann-propanethiol-type clathrates of the for M(1-propanethiol) 2 Ni(CN) 4 .G (M=Cd or Ni; G = benzene) have been prepared in the powder form. The 1-propanethiol (1-PT) molecules provide the cavities in which the quest benzene molecules in clathrate structure ar accommodated. The infrared investigations of the obtained clathrates indicate that these compounds are similar in structure to the other Hofmann-type clathrates (Authors)

Thermodynamic studies on semi-clathrate hydrates of TBAB + gases containing carbon dioxide

International Nuclear Information System (INIS)

Eslamimanesh, Ali

2012-01-01

CO 2 capture has become an important area of research mainly due to its drastic greenhouse effects. Gas hydrate formation as a separation technique shows tremendous potential, both from a physical feasibility as well as an envisaged lower energy utilization criterion. Briefly, gas (clathrate) hydrates are non-stoichiometric, ice-like crystalline compounds formed through a combination of water and suitably sized guest molecule(s) under low-temperatures and elevated pressures. As the pressure required for gas hydrate formation is generally high, therefore, aqueous solution of tetra-n-butyl ammonium bromide (TBAB) is added to the system as a gas hydrate promoter. TBAB generally reduces the required hydrate formation pressure and/or increases the formation temperature as well as modifies the selectivity of hydrate cages to capture CO 2 molecules. TBAB also takes part in the hydrogen-bonded cages. Such hydrates are called 'semi-clathrate' hydrates. Evidently, reliable and accurate phase equilibrium data, acceptable thermodynamic models, and other thermodynamic studies should be provided to design efficient separation processes using the aforementioned technology. For this purpose, phase equilibria of clathrate/semi-clathrate hydrates of various gas mixtures containing CO 2 (CO 2 + CH 4 /N 2 /H 2 ) in the presence of pure water and aqueous solutions of TBAB have been measured in this thesis. In the theoretical section of the thesis, a thermodynamic model on the basis of the van der Waals and Platteeuw (vdW-P) solid solution theory along with the modified equations for determination of the Langmuir constants of the hydrate formers has been successfully developed to represent/predict equilibrium conditions of semi-clathrate hydrates of CO 2 , CH 4 , and N 2 . Later, several thermodynamic consistency tests on the basis of Gibbs-Duhem equation as well as a statistical approach have been applied on the phase equilibrium data of the systems of mixed/simple clathrate hydrates

High Pressure Properties of a Ba-Cu-Zn-P Clathrate-I

Directory of Open Access Journals (Sweden)

Juli-Anna Dolyniuk

2016-08-01

Full Text Available The high pressure properties of the novel tetrel-free clathrate, Ba8Cu13.1Zn3.3P29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba8Cu13.1Zn3.3P29.6 using a third-order Birch-Murnaghan equation of state is 65(6 GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A8Ga16Ge30 (A = Sr, Ba and Sn19.3Cu4.7P22I8, but lower than those for the transition metal-containing silicon-based clathrates, Ba8TxSi46−x, T = Ni, Cu; 3 ≤ x ≤ 5.

Paraffin molecule mobility in channel clathrates of urea on spectroscopic NMR relaxation data

CERN Document Server

Kriger, Y G; Chekhova, G N

2001-01-01

The temperature dependences of the protons spin-lattice relaxation time (T sub I) in the channel clathrates of urea with paraffins are measured. The data on the T sub I are interpreted within the frames of the model of the paraffins molecules and their fragments orientation in the clathrate channels. The dynamics peculiarities are connected with the disproportion effects of these compounds

Hydrogen storage in clathrate hydrates: Current state of the art and future directions

International Nuclear Information System (INIS)

Veluswamy, Hari Prakash; Kumar, Rajnish; Linga, Praveen

2014-01-01

Hydrogen is looked upon as the next generation clean energy carrier, search for an efficient material and method for storing hydrogen has been pursued relentlessly. Improving hydrogen storage capacity to meet DOE targets has been challenging and research efforts are continuously put forth to achieve the set targets and to make hydrogen storage a commercially realizable process. This review comprehensively summarizes the state of the art experimental work conducted on the storage of hydrogen as hydrogen clathrates both at the molecular level and macroscopic level. It identifies future directions and challenges for this exciting area of research. Hydrogen storage capacities of different clathrate structures – sI, sII, sH, sVI and semi clathrates have been compiled and presented. In addition, promising new approaches for increasing hydrogen storage capacity have been described. Future directions for achieving increased hydrogen storage and process scale up have been outlined. Despite few limitations in storing hydrogen in the form of clathrates, this domain receives prominent attention due to more environmental-friendly method of synthesis, easy recovery of molecular hydrogen with minimum energy requirement, and improved safety of the process

Measurement of Clathrate Hydrate Thermodynamic Stability in the Presence of Ammonia

Science.gov (United States)

Dunham, Marc

2012-01-01

There is a lack of data available for the stability of clathrate hydrates in the presence of ammonia for low-to-moderate pressures in the 0-10 MPa range. Providing such data will allow for a better understanding of natural mass transfer processes on celestial bodies like Titan and Enceladus, on which destabilization of clathrates may be responsible for replenishment of gases in the atmosphere. The experimental process utilizes a custom-built gas handling system (GHS) and a cryogenic calorimeter to allow for the efficient testing of samples under varying pressures and gas species.

Roles of Clathrate Hydrates in Crustal Heating and Volatile Storage/Release on Earth, Mars, and Beyond

Science.gov (United States)

Kargel, J. S.; Beget, J.; Furfaro, R.; Prieto-Ballesteros, O.; Palmero-Rodriguez, J. A.

2007-12-01

Clathrate hydrates are stable through much of the Solar System. These materials and hydrate-like amorphous associations of water with N2, CO, CH4, CO2, O2 and other molecules could, in fact, constitute the bulk of the non-rock components of some icy satellites, comets, and Kuiper Belt Objects. CO2 clathrate is thermodynamically stable at the Martian South Pole surface and could form a significant fraction of both Martian polar caps and icy permafrost distributed across one-third of the Martian surface. CH4 clathrate is the largest clathrate material in Earth's permafrost and cold seafloor regions, and it may be a major volatile reservoir on Mars, too. CO2 clathrate is less abundant on Earth but it might store most of Mars' CO2 inventory and thus may be one of the critical components in the climate system of that planet, just as CH4 clathrate is for Earth. These ice-like phases not only store biologically, geologically, and climatologically important gases, but they also are natural thermal insulators. Thus, they retard the conductive flow of geothermal heat, and thick accumulations of them can modify geotherms, cause brines to exist where otherwise they would not, and induce low-grade metamorphism of upper crustal rocks underlying the insulating bodies. This mechanism of crustal heating may be especially important in assisting hydrogeologic activity on Mars, gas-rich carbonaceous asteroids, icy satellites, and Kuiper Belt Objects. These worlds, compared to Earth, are comparatively energy starved and frozen but may partly make up for their deficit of joules by having large accumulations of joule-conserving hydrates. Thick, continuous layers of clathrate may seal in gases and produce high gas fugacities in aquifers underlying the clathrates, thus producing gas-rich reservoirs capable of erupting violently. This may have happened repeatedly in Earth history, with global climatic consequences for abrupt climate change. We have hypothesized that such eruptions may have

Synthesis and thermoelectric properties of rare earth Yb-doped Ba8−xYbxSi30Ga16 clathrates

International Nuclear Information System (INIS)

Liu, Lihua; Li, Feng; Wei, Yuping; Chen, Ning; Bi, Shanli; Qiu, Hongmei; Cao, Guohui; Li, Yang

2014-01-01

Highlights: • Samples with the chemical formula Ba8− x Yb x Si 30 Ga 16 (x = 0, 0.5, 0.7, 1 and 1.5) were prepared. • Some Yb atoms enter the clathrate lattice to replace Ba, while other Yb atoms are oxidized as Yb 2 O 3 . • The thermal conductivity decreases with Yb-doping. • Thermoelectric figure of merit ZT significantly increased. -- Abstract: The potential thermoelectric and magnetic application of clathrate materials with rare-earth doping is the focus of much of the recent research activity in the synthetic material physics and chemistry. A series of clathrate samples with the chemical formula Ba 8−x Yb x Si 30 Ga 16 (x = 0, 0.5, 0.7, 1 and 1.5) were prepared by combining arc melting, ball milling and spark plasma sintering (SPS) techniques. X-ray diffraction and scanning electronic microscopy combined with energy-dispersive X-ray spectroscopy (EDS) analysis showed the dominant phase to be the type-I clathrate. Whereas, X-ray structural refinement and EDS analysis indicated that some Yb atoms enter the clathrate lattice to replace Ba at 2a sites, while other Yb atoms are oxidized as Yb 2 O 3 precipitated around grain boundaries. The solid solubility of Yb into clathrate lattice yielded x ∼ 0.3. Comparative analysis between Yb-doped and Yb-free clathrates showed that the thermal conductivity decreases with Yb-doping. Consequently, thermoelectric figure of merit ZT significantly increased

Synthesis and thermal conductivity of type II silicon clathrates

Science.gov (United States)

Beekman, M.; Nolas, G. S.

2006-08-01

We have synthesized and characterized polycrystalline Na 1Si 136 and Na 8Si 136, compounds possessing the type II clathrate hydrate crystal structure. Resistivity measurements from 10 to 300 K indicate very large resistivities in this temperature range, with activated temperature dependences indicative of relatively large band gap semiconductors. The thermal conductivity is very low; two orders-of-magnitude lower than that of diamond-structure silicon at room temperature. The thermal conductivity of Na 8Si 136 displays a temperature dependence that is atypical of crystalline solids and more indicative of amorphous materials. This work is part of a continuing effort to explore the many different compositions and structure types of clathrates, a class of materials that continues to be of interest for scientific and technological applications.

Electrochemical stability of ionic clathrate hydrates and their structural consideration

International Nuclear Information System (INIS)

Lee, Wonhee; Lim, Dongwook; Lee, Huen

2013-01-01

Although electrochemical stability is an essential factor in relation to the potential applications of ionic clathrate hydrates to solid electrolytes, most studies regarding the proton conductors have focused on their ionic conductivity and thermal stability. Solid electrolytes in various electrochemical devices have to endure the applied potentials; thus, we examined the linear sweep voltammograms of various tetraalkylammonium hydroxide hydrates in order to shed light on the trend of electrochemical stability depending on the hydrate structure. We revealed that the electrochemical stability of Me 4 NOH hydrates is mainly affected by both their ionic concentration and cage occupancy. In particular, the true clathrate structures of β-Me 4 NOH hydrates are more electrochemically stable than their α-forms that possess partially broken hydrogen bonds. We also observed that the binary THF–Pr 4 NOH and pure Bu 4 NOH clathrate hydrates exhibit greater electrochemical stability than those of pure Me 4 NOH hydrates having lower or similar ionic concentrations. These results are considered to arise from the fact that each of the Pr 4 N + and Bu 4 N + ions occupies an extended space comprising four cages, which leads to stabilization of the larger unit, whereas a Me 4 N + ion is completely included only in one cage

Observation of interstitial molecular hydrogen in clathrate hydrates.

Science.gov (United States)

Grim, R Gary; Barnes, Brian C; Lafond, Patrick G; Kockelmann, Winfred A; Keen, David A; Soper, Alan K; Hiratsuka, Masaki; Yasuoka, Kenji; Koh, Carolyn A; Sum, Amadeu K

2014-09-26

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurements of relevant parameters in the formation of clathrate hydrates by a novel experimental apparatus

Energy Technology Data Exchange (ETDEWEB)

Arca, S.; Di Profio, P.; Germani, R.; Savelli, G. [Perugia Univ., CEMIN, Perugia (Italy). Dept. of Chemistry

2008-07-01

There is a growing interest in understanding the thermodynamics and kinetics of clathrate hydrate formation. This paper presented a study that involved the design, construction, calibration, and testing of a new apparatus that could obtain as many parameters as possible in a single formation batch and that could measure unexplored clathrate hydrate parameters. The apparatus was capable of measuring equilibrium phases involving gaseous components. The paper described the conceptual design as well as the chamber, pressure line, temperature control, liquid addition line, and conductometric probe. The paper also discussed data acquisition, stirring, measurement examples, and internal illumination and video monitoring. It was concluded that refining measurements, particularly those concerning kinetic characterizations, is important in order to clarify several uncertain kinetic behaviors of clathrate hydrates. 6 refs., 16 figs.

Clathrates - An Exploration of the Chemistry of Caged Compounds

Indian Academy of Sciences (India)

also found on the icy moons of our solar system, at Saturn and .... This mineral loses water rapidly on heating and seemed ... The prototype of clathrate-I structure for gas hydrate has a .... Useful for studies of air pollution, process control and.

A spectroscopic study of the structure and occupancies of clathrate hydrates incorporating hydrogen

Science.gov (United States)

Grim, R. Gary

With the ability to store and concentrate gases inside a clean and abundant water framework, clathrate hydrates are considered to be a promising material for many applications related to gas storage, separation, and sequestration. Hydrates of hydrogen are particularly interesting, for in addition to these potential applications, the small molecular size provides an opportunity for use as a model guest in many fundamental studies such as guest diffusion, multiple guest occupancy, and quantum mechanical effects upon confinement. In attempt to study these effects and the viability of H 2 hydrates as an energy storage material, a combined experimental and theoretical approach incorporating Raman spectroscopy, X-ray and neutron diffraction, nuclear magnetic resonance, ab-initio calculations, and molecular dynamic simulations was performed. One of the most significant challenges in the application of H2 clathrate hydrates is the demanding thermodynamic requirements needed for stability. In recent years, a mechanism known as the `tuning' effect had reportedly solved this issue where thermodynamic requirements could be reduced while simultaneously maintaining high storage capacities. In this work, the viability and validity of this technique is explored and alternative explanations in the form of epitaxial hydrate growth under high driving force conditions are discussed. A second, and equally important challenge facing clathrate hydrates as a future storage material is the overall storage capacity of H2. In previous work, H2 has only been experimentally verified to occupy the small 512 and 43566 3 cages and also in the large 51264 cages of the type II clathrate, often with an energy deficient promoter. In order to achieve more robust energy densities, other hydrate cages must be accessible. Herein a new method for increasing overall hydrate energy densities is presented involving the incorporation of H2 in the large cages of the type I clathrate with CH4 as a co

Novel nanotechnology for efficient production of binary clathrate hydrates of hydrogen and other compounds

Energy Technology Data Exchange (ETDEWEB)

Di Profio, P.; Arca, S.; Germani, R.; Savelli, G. [Perugia Univ., Perugia (Italy). Dept. of Chemistry, Center of Excellence on Innovative Nanostructured Materials

2008-07-01

The development of a hydrogen-based economy depends on finding ways to store hydrogen, but current hydrogen storage methods have significant disadvantages. One main challenge in storing sufficient amounts of hydrogen (up to 4 weight per cent) into a clathrate matrix is that of a kinetic origin, in that the mass transfer of hydrogen gas into clathrate structures is significantly limited by the macroscopic scale of the gas-liquid or gas-ice interfaces involved. This paper discussed the possibility of storing hydrogen in clathrate hydrates. It presented a newly developed method for preparing binary hydrogen hydrates that is based on the formation of amphiphile-aided nanoemulsions. Nanotechnology is used to reduce the size of hydrate particles to a few nanometers, thereby minimizing the kinetic hindrance to hydrate formation. This process has potential for increasing the amount of hydrogen stored, as it has provided ca. 1 weight per cent of hydrogen. Two new co-formers were also successfully tested, namely cyclopentane and tetrahydrothiophene. 23 refs., 10 figs.

Hydration of krypton and consideration of clathrate models of hydrophobic effects from the perspective of quasi-chemical theory.

Science.gov (United States)

Ashbaugh, Henry S; Asthagiri, D; Pratt, Lawrence R; Rempe, Susan B

2003-09-01

Ab initio molecular dynamics (AIMD) results on a krypton-water liquid solution are presented and compared to recent XAFS results for the radial hydration structure for a Kr atom in liquid water solution. Though these AIMD calculations have important limitations of scale, the comparisons with the liquid solution results are satisfactory and significantly different from the radial distributions extracted from the data on the solid Kr/H(2)O clathrate hydrate phase. The calculations also produce the coordination number distribution that can be examined for metastable coordination structures suggesting possibilities for clathrate-like organization; none are seen in these results. Clathrate pictures of hydrophobic hydration are discussed, as is the quasi-chemical theory that should provide a basis for clathrate pictures. Outer shell contributions are discussed and estimated; they are positive and larger than the positive experimental hydration free energy of Kr(aq), implying that inner shell contributions must be negative and of comparable size. Clathrate-like inner shell hydration structures on a Kr atom solute are obtained for some, but not all, of the coordination number cases observed in the simulation. The structures found have a delicate stability. Inner shell coordination structures extracted from the simulation of the liquid, and then subjected to quantum chemical optimization, always decomposed. Interactions with the outer shell material are decisive in stabilizing coordination structures observed in liquid solution and in clathrate phases. The primitive quasi-chemical estimate that uses a dielectric model for the influence of the outer shell material on the inner shell equilibria gives a contribution to hydration free energy that is positive and larger than the experimental hydration free energy. The 'what are we to tell students' question about hydrophobic hydration, often answered with structural clathrate pictures, is then considered; we propose an

Polymorphism in Br2 clathrate hydrates.

Science.gov (United States)

Goldschleger, I U; Kerenskaya, G; Janda, K C; Apkarian, V A

2008-02-07

The structure and composition of bromine clathrate hydrate has been controversial for more than 170 years due to the large variation of its observed stoichiometries. Several different crystal structures were proposed before 1997 when Udachin et al. (Udachin, K. A.; Enright, G. D.; Ratcliffe, C. I.; Ripmeester, J. A. J. Am. Chem. Soc. 1997, 119, 11481) concluded that Br2 forms only the tetragonal structure (TS-I). We show polymorphism in Br2 clathrate hydrates by identifying two distinct crystal structures through optical microscopy and resonant Raman spectroscopy on single crystals. After growing TS-I crystals from a liquid bromine-water solution, upon dropping the temperature slightly below -7 degrees C, new crystals of cubic morphology form. The new crystals, which have a limited thermal stability range, are assigned to the CS-II structure. The two structures are clearly distinguished by the resonant Raman spectra of the enclathrated Br2, which show long overtone progressions and allow the extraction of accurate vibrational parameters: omega(e) = 321.2 +/- 0.1 cm(-1) and omega(e)x(e) = 0.82 +/- 0.05 cm(-1) in TS-I and omega(e) = 317.5 +/- 0.1 cm(-1) and omega(e)x(e) = 0.70 +/- 0.1 cm(-1) in CS-II. On the basis of structural analysis, the discovery of the CS-II crystals implies stability of a large class of bromine hydrate structures and, therefore, polymorphism.

Superconductivity of Ba8Si46-xGax clathrates

Science.gov (United States)

Li, Yang; Zhang, Ruihong; Chen, Ning; Ma, Xingqiao; Cao, Guohui; Luo, Z. P.; Hu, C. R.; Ross, Joseph H., Jr.

2007-03-01

We have presented a combined experimental and theoretical study of the effect of Gallium substitution on the superconductivity of the type I clathrate Ba8Si46-xGax. In Ga-doped clathrates, the Ga state is found to be strongly hybridized with the cage conduction-band state. Ga substitution results in a shift toward to a lower energy, a decrease of density of states at Fermi level, a lowering of the carrier concentration and a breakage of integrity of the sp3 hybridized networks. These play key roles in the suppression of superconductivity. For Ba8Si40Ga6, the onset of the superconducting transition occurs at Tc=3.3 K. The investigation of the magnetic superconducting state shows that Ba8Si40Ga6 is a type II superconductor. The critical magnetic fields were measured to be Hc1=35 Oe and Hc2=8.5 kOe. Our estimate of the lectron-phonon coupling reveals that Ba8Si40Ga6 is a moderate phonon-mediated BCS superconductor.

Geochemistry of clathrate-derived methane in Arctic Ocean waters

Energy Technology Data Exchange (ETDEWEB)

Elliott, S.M.; Reagan, M.T.; Moridis, G.J.; Cameron-Smith, P.J.

2010-03-15

Alterations to the composition of seawater are estimated for microbial oxidation of methane from large polar clathrate destabilizations, which may arise in the coming century. Gas fluxes are taken from porous flow models of warming Arctic sediment. Plume spread parameters are then used to bracket the volume of dilution. Consumption stoichiometries for the marine methanotrophs are based on growth efficiency and elemental/enzyme composition data. The nutritional demand implied by extra CH{sub 4} removal is compared with supply in various high latitude water masses. For emissions sized to fit the shelf break, reaction potential begins at one hundred micromolar and falls to order ten a thousand kilometers downstream. Oxygen loss and carbon dioxide production are sufficient respectively to hypoxify and acidify poorly ventilated basins. Nitrogen and the monooxygenase transition metals may be depleted in some locations as well. Deprivation is implied relative to existing ecosystems, along with dispersal of the excess dissolved gas. Physical uncertainties are inherent in the clathrate abundance, patch size, outflow buoyancy and mixing rate. Microbial ecology is even less defined but may involve nutrient recycling and anaerobic oxidizers.

The synthesis and the spectroscopic, thermal, and structural properties of the M2[(fumarate)Ni(CN)4]·2(1,4-Dioxane) clathrate (M = Co, Ni, Cd and Hg)

Science.gov (United States)

Kartal, Zeki; Yavuz, Abdülkerim

2018-03-01

In this study, the clathrates of fumarate-tetracyanonickel-dioxane, given by the formula M2[(fumarate)Ni(CN)4]·2(1,4-Dioxane) (M = Co, Ni, Cd and Hg), have been obtained for the first time through chemical methods. These clathrates have been characterized by elemental, thermal, FT-IR, and FT-Raman spectroscopies. The parameters of structures of clathrates have been determined by X-ray powder diffraction. The thermal behaviors of these clathrates have been also investigated by thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), and derivative thermal gravimetric analysis (DTG) in the range of 20-900 °C. X-ray powder diffraction data have been recorded at ambient temperature in the 2θ range 5-50°. The FT-IR and FT-Raman spectra of clathrates have been recorded in the region of 4000-400 cm-1 and 4000-100 cm-1, respectively. The results of the spectral and thermal analyses of the newly synthesized clathrates of fumarate-tetracyanonickel-dioxane suggest that these clathrates are new examples of the Hofmann-type dioxane clathrates. In our study, the Hofmann-type dioxane clathrates, which are formed by bounding electrons of oxygen-donor atoms of fumarate ion ligand molecule to transition metal atoms, consist of the corrugated |M-Ni(CN)4|∞ polymeric layers, which are held in parallel through the chain of (-M-fumarate-M-).

Clathrate hydrates - the energy of the future an overview and a postulated formation mechanism

International Nuclear Information System (INIS)

Pratt, R.M.

2000-01-01

Clathrate hydrates are non-stoichiometric compounds that form when water and certain low molecular weight hydrocarbons coexist at high pressures and low temperatures. The majority of the earth hydrocarbons are in the hydrate phase and are primarily located along the ocean bottoms and to a lesser degree in the permafrost regions. In addition, hydrate formation is induced in undersea gas transmission lines and causes costly pipeline plugs and requires expensive inhibition measures to be taken. Therefore, both a stick and a carrot motivate hydrate research. They are a costly and dangerous nuisance to the oil and gas industry and represent a tremendous, untapped energy resource of the future. The formation mechanism of clathrate hydrate formation has always been shrouded in mystery, and an ongoing debate has ensued as to whether their formation is a bulk or surface phenomenon. Molecular dynamics simulation and fractal modeling suggest that this may be an irrelevant issue and that two independent factors contribute to the symmetrical ordered structure of clathrate hydrates: hydrophobic hydration of hydrocarbon molecules in water and formation of linked cavities as these small clusters aggregate. (Author)

Raman scattering of type-I clathrate compounds

International Nuclear Information System (INIS)

Takasu, Y.; Hasegawa, T.; Ogita, N.; Udagawa, M.; Avila, M.A.; Takabatake, T.

2006-01-01

Lattice dynamical properties of the type-I clathrate compounds of A 8 Ga 16 Ge 30 (A=Eu, Sr, Ba) have been investigated by Raman scattering. We are successful in the assignment of the observed Raman active phonons to proper symmetry and are able to separate the guest atom origin modes from framework origin modes for the first time experimentally. From the measurements of temperature dependence of the guest origin peaks, we also demonstrate the difference of the behavior of the guest atom at high temperature and low temperature

Pressure-induced phase transformations in the Ba8Si46 clathrate

DEFF Research Database (Denmark)

Yang, Lirong; Ma, Y.M.; Iitaka, T.

2006-01-01

The nature of isostructural transformations of a type-I Ba8Si46 clathrate has been studied by in situ high-pressure angle-dispersive x-ray powder diffraction using liquid He as pressure transmitting medium. The good quality of the diffraction data permitted refinement of structural and thermal...

Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

Energy Technology Data Exchange (ETDEWEB)

Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1N 6N5 (Canada); Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia V6T 1Z3 (Canada)

2016-01-28

Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

Motion of Br2 molecules in clathrate cages. A computational study of the dynamic effects on its spectroscopic behavior.

Science.gov (United States)

Bernal-Uruchurtu, M I; Janda, Kenneth C; Hernández-Lamoneda, R

2015-01-22

This work looks into the spectroscopic behavior of bromine molecules trapped in clathrate cages combining different methodologies. We developed a semiempirical quantum mechanical model to incorporate through molecular dynamics trajectories, the effect movement of bromine molecules in clathrate cages has on its absorption spectra. A simple electrostatic model simulating the cage environment around bromine predicts a blue shift in the spectra, in good agreement with the experimental evidence.

FTIR spectroscopic study on the Hofmann -Td- type clathrates: Ni(benzoic acid)2M(CN)4.aniline (M=Zn, Cd, Hg)

International Nuclear Information System (INIS)

Kesan, G.; Kartal, Z.

2010-01-01

The Hofmann-Td-type clathrates formulated as Ni(L) 2 M(CN) 4 .nG where L is a bidentate or a pair of unidentate ligand molecule, M is Zn, Cd or Hg, G is a guest molecule and n is the number of guest molecule. The host lattice of the Hofmann-Td-type clathrates is formed from endless chains of -Ni-L-L-Ni-L-L-Ni- and M(CN) 4 ions arranged between the consecutive crossing -Ni-L-L-Ni-L-L-Ni- chains with the O-ends bound to the Ni metal atoms. These polymeric layers are held in parallel by Van der Walls interaction between ligand molecules. This structure provides α-type cavity. In this study, Ni(Benzoic Acid ) 2M(CN) 4 .Aniline (M = Zn, Cd, Hg) is obtained for the first time by means of chemical methods in powder form and their infrared spectra are reported in range of (4000-400) cm - 1. The spectral data suggest that the new clathrates are similar in structure to the Hofmann-type clathrates.

Structural and thermoelectric properties of the type-I Sn clathrates Cs8Sn46−n(n=0,2) from Density Functional Theory (DFT)

KAUST Repository

Egbele, Peter O.; Shoko, Elvis; Joubert, Daniel P.

2018-01-01

Sn clathrates are promising phonon glass, electron crystal materials (PGEC), in which the phonon free paths are short and the electron free paths are long. We analysed the relaxed structure of Sn clathrates using four different Density Funtional

Computational characterization of 13C NMR lineshapes of carbon dioxide in structure 1 clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Dornan, P.; Woo, T.K. [Ottawa Univ., ON (Canada). Dept. of Chemistry

2008-07-01

Nonspherical large cages in structure one clathrates impose non-uniform motion of nonspherical guest molecules and anisotropic lineshapes in nuclear magnetic resonance (NMR) spectra of the guest. This paper presented a general method for calculating the chemical shift lineshape anisotropy of guest molecules in clathrate hydrate compounds from molecular dynamics simulations for the case of weak host, guest dipolar coupling. In order to calculate the cage chemical shielding tensors and the NMR lineshape produced by each guest molecule, the study involved the use of orientational distributions from molecular dynamics simulation along with time and powder angle averaging. The total predicted lineshape anisotropy was calculated from the superposition of the lineshapes of all guests. The approach was applied to calculate the temperature dependent 13C NMR lineshape anisotropy of carbon dioxide in structure 1 clathrates. The paper presented the computational methodology and results and discussion. It was concluded that the resulting lineshapes were in good agreement with the experimental 13C NMR spectrum at each temperature. The method provided a uniform procedure to calculate the lineshapes at different temperatures and no prior assumptions about the nature of the motion of the guest in cages was required. 37 refs., 2 tabs., 3 figs.

Structural and thermoelectric properties of the type-I Sn clathrates Cs8Sn46−n(n=0,2) from Density Functional Theory (DFT)

KAUST Repository

Egbele, Peter O.

2018-02-08

Sn clathrates are promising phonon glass, electron crystal materials (PGEC), in which the phonon free paths are short and the electron free paths are long. We analysed the relaxed structure of Sn clathrates using four different Density Funtional Exchange-Correlation functionals. The phonon structures were investigated as a first step in order to determine the phonon contribution to the thermal conductivity. We determined the Seebeck coefficient and electrical conductivity of the clathrate compound and the thermoelectric figure of merit. A glimpse into the dynamics of the system for the evaluation of the thermoelectric and electronic properties is presented.

Snowball Earth termination by destabilization of equatorial permafrost methane clathrate.

Science.gov (United States)

Kennedy, Martin; Mrofka, David; von der Borch, Chris

2008-05-29

The start of the Ediacaran period is defined by one of the most severe climate change events recorded in Earth history--the recovery from the Marinoan 'snowball' ice age, approximately 635 Myr ago (ref. 1). Marinoan glacial-marine deposits occur at equatorial palaeolatitudes, and are sharply overlain by a thin interval of carbonate that preserves marine carbon and sulphur isotopic excursions of about -5 and +15 parts per thousand, respectively; these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise. This abrupt transition records a climate system in profound disequilibrium and contrasts sharply with the cyclical stratigraphic signal imparted by the balanced feedbacks modulating Phanerozoic deglaciation. Hypotheses accounting for the abruptness of deglaciation include ice albedo feedback, deep-ocean out-gassing during post-glacial oceanic overturn or methane hydrate destabilization. Here we report the broadest range of oxygen isotope values yet measured in marine sediments (-25 per thousand to +12 per thousand) in methane seeps in Marinoan deglacial sediments underlying the cap carbonate. This range of values is likely to be the result of mixing between ice-sheet-derived meteoric waters and clathrate-derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater. The equatorial palaeolatitude implies a highly volatile shelf permafrost pool that is an order of magnitude larger than that of the present day. A pool of this size could have provided a massive biogeochemical feedback capable of triggering deglaciation and accounting for the global postglacial marine carbon and sulphur isotopic excursions, abrupt unidirectional warming, cap carbonate deposition, and a marine oxygen crisis. Our findings suggest that methane released from low-latitude permafrost clathrates therefore acted as a trigger and/or strong positive feedback for deglaciation and warming. Methane hydrate

Critical guest concentration and complete tuning pattern appearing in the binary clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Cha, J.H.; Lee, H. [Korea Advanced Inst. of Science and Technology, Yuseong-gu, Daejeon (Korea, Republic of). Dept. of Chemical and Biomolecular Engineering; Kim, D.Y. [SK Engineering and Construction, Jongno-gu, Seoul (Korea, Republic of); Park, J. [Hanwha Chemical R and D Center, Yuseong-gu, Daejeon (Korea, Republic of); Lee, J.W. [Kongju National Univ., Cheonan, Chungnam (Korea, Republic of); Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

2008-07-01

Clathrate hydrates, or gas hydrates, are stabilized by van der Waals interaction between a guest molecule and a host framework. Because of their property, they are a potential resource in the exploitation of natural gas hydrates, as a material for the sequestration of carbon dioxide (CO{sub 2}), as a means of storage and transportation of natural gas, as well as hydrogen storage. Clathrate hydrate research can be divided into two categories that emphasize either macroscopic or microscopic approaches. However, these two approaches need to be closely linked for a better understanding of the structures and processes involving both natural phenomena and hydrates for industrial processes. Details on the molecular scale that concern the less usual properties of clathrate hydrates remain unknown. This paper presented the results of a study that reported on the existence of a critical guest concentration (CGC) and established the complete tuning pattern that occurred in the binary hydrates, including water-soluble hydrate formers (promoters) and water-insoluble guests. The paper presented the experimental procedures, including formation of the methane (CH{sub 4}) and tetrahydrofuran (THF) binary hydrate; a schematic diagram of the experimental apparatus; and formation of the CH{sub 4} and t-BuNH{sub 2} binary hydrate. Nuclear magnetic resonance (NMR) spectroscopic measurements and thermodynamic measurements were also presented. It was concluded that the CGC value appeared to primarily depend on the chemical nature of a liquid guest component participating in the binary hydrate formation. 10 refs., 2 tabs., 9 figs.

Electric double-layer capacitor based on an ionic clathrate hydrate.

Science.gov (United States)

Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

2013-07-01

Herein, we suggest a new approach to an electric double-layer capacitor (EDLC) that is based on a proton-conducting ionic clathrate hydrate (ICH). The ice-like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me4NOH⋅5 H2O show a high specific capacitance, reversible charge-discharge behavior, and a long cycle life. The ionic-hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre-treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more-favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase equilibrium measurements of structure II clathrate hydrates of hydrogen with various promoters

NARCIS (Netherlands)

Torres Trueba, A.; Rovetto, L.J.; Florusse, L.J.; Kroon, M.C.; Peters, C.J.

2011-01-01

Phase equilibrium measurements of single and mixed organic clathrate hydrates with hydrogen were determined within a pressure range of 2.0–14.0 MPa. The organic compounds studied were furan, 2,5-dihydrofuran, tetrahydropyran, 1,3-dioxolane and cyclopentane. These organic compounds are known to form

A statistical method for evaluation of the experimental phase equilibrium data of simple clathrate hydrates

DEFF Research Database (Denmark)

Eslamimanesh, Ali; Gharagheizi, Farhad; Mohammadi, Amir H.

2012-01-01

We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot, and the r......We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot...... in exponential form is used to represent/predict the hydrate dissociation pressures for three-phase equilibrium conditions (liquid water/ice–vapor-hydrate). The investigated hydrate formers are methane, ethane, propane, carbon dioxide, nitrogen, and hydrogen sulfide. It is interpreted from the obtained results...

Exploring the possibility to store the mixed oxygen-hydrogen cluster in clathrate hydrate in molar ratio 1:2 (O2+2H2).

Science.gov (United States)

Qin, Yan; Du, Qi-Shi; Xie, Neng-Zhong; Li, Jian-Xiu; Huang, Ri-Bo

2017-05-01

An interesting possibility is explored: storing the mixture of oxygen and hydrogen in clathrate hydrate in molar ratio 1:2. The interaction energies between oxygen, hydrogen, and clathrate hydrate are calculated using high level quantum chemical methods. The useful conclusion points from this study are summarized as follows. (1) The interaction energies of oxygen-hydrogen mixed cluster are larger than the energies of pure hydrogen molecular cluster. (2) The affinity of oxygen molecules with water molecules is larger than that of the hydrogen molecules with water molecules. (3) The dimension of O 2 -2H 2 interaction structure is smaller than the dimension of CO 2 -2H 2 interaction structure. (4) The escaping energy of oxygen molecules from the hydrate cell is larger than that of the hydrogen molecules. (5) The high affinity of the oxygen molecules with both the water molecules and the hydrogen molecules may promote the stability of oxygen-hydrogen mixture in the clathrate hydrate. Therefore it is possible to store the mixed (O 2 +2H 2 ) cluster in clathrate hydrate. Copyright © 2017 Elsevier Inc. All rights reserved.

Collagen tissue treated with chitosan solution in H2O/CO2 mixtures: Influence of clathrates hydrates on the structure and mechanical properties.

Science.gov (United States)

Chaschin, Ivan S; Bakuleva, Natalia P; Grigoriev, Timofei E; Krasheninnikov, Sergey V; Nikitin, Lev N

2017-03-01

A mixture of water/carbon dioxide is a "green" perspective solvent from the viewpoint of biomedical applications. Clathrate hydrates are formed this solvent under certain conditions and a very interesting question is the impact of clathrates hydrates on the structure and properties of bovine pericardium, which is used in biomedicine, in particular as a main part of biological heart valve prostheses. The aim of the present work is to investigate the influence of clathrates on the structure and mechanical properties of the collagen tissue treated with chitosan in H 2 O/CO 2 mixtures under pressure 3.0-3.5MPa and temperatures 2-4°C. It was first found that the clathrate hydrates in this media due to the strong fluctuations "bomb" collagen tissue of bovine pericardium, which is manifested in the appearance of numerous small gaps (pores) with mean size of 225±25nm and large pores with size of 1-3μ on the surface and within collagen matrices. High porosity leads to averaging characteristics of the organization structure in tissues with different orientation of the collagen fibers. As a result, the mechanical properties of the collagen tissue with a different orientation of the collagen fibrils become similar, which is quite different from their original properties. The structural changes caused by the influence of the environment clathrate hydrates led to a significant decrease of the tensile strength (30-47% in total, p<0.05) and initial elastic moduli (74-83%, p<0.05). However, the final elastic moduli and the maximum tensile virtually unchanged compared to the control. Nevertheless, it was found that the direct deposition of chitosan from the H 2 O/CO 2 mixtures with clathrate improve the mechanical-strength properties of the porous matrices. We believe that these improved mechanical properties are achieved due to particularly deep and uniform impregnation of the collagen matrix with chitosan from its pressurized solutions in H 2 O/CO 2 mixtures. Copyright © 2016

Systematic Studies on Anharmonicity of Rattling Phonons in Type I Clathrates by Low Temperature Heat Capacity Measurements

Science.gov (United States)

Tanigaki, Katsumi; Wu, Jiazhen; Tanabe, Yoichi; Heguri, Satoshi; Shiimotani, Hidekazu; Tohoku University Collaboration

2014-03-01

Clathrates are featured by cage-like polyhedral hosts mainly composed of the IVth group elements of Si, Ge, or Sn and alkali metal or alkaline-earth metal elements can be accommodated inside as a guest atom. One of the most intriguing issues in clathrates is their outstanding high thermoelectric performances thanks to the low thermal conductivity. Being irrespective of good electric conductivity σ, the guest atom motions provide a low-energy lying less-dispersive phonons and can greatly suppress thermal conductivity κ. This makes clathrates close to the concept of ``phonon glass electron crystal: PGEC'' and useful in thermoelectric materials from the viewpoint of the figure of merit. In the present study, we show that the local phonon anharmonicity indicated by the tunneling-term of the endohedral atoms (αT) and the itinerant-electron term (γeT), both of which show T-linear dependences in specific heat Cp, can successfully be separated by employing single crystals with various carrier concentrations in a wide range of temperture experimennts. The factors affecting on the phonon anharmonicity as well as the strength of electron-phonon interactions will be discussed based on our recent experiments. The research was financially supported by Ministry of Education, Science, Sports and Culture, Grant in Aid for Science, and Technology of Japan.

Accurate description of phase diagram of clathrate hydrates on molecular level

Energy Technology Data Exchange (ETDEWEB)

Belosludov, V.; Subbotin, O. [Niklaev Inst. of Inorganic Chemistry, Novosibirsk (Russian Federation). Siberian Branch of Russian Academy of Science; Belosludov, R.; Mizuseki, H.; Kawazoe, Y. [Tohoku Univ., Aoba-ku, Sendai (Japan). Inst. for Materials Research

2008-07-01

A number of experimental and theoretical studies of hydrogen hydrates have been conducted using different methods. In order to accurately estimate the thermodynamic properties of clathrate hydrates that multiply filling the cages, this paper presented a method based on the solid solution theory of van der Waals and Platteeuw with several modifications, including multiple occupancies, host relaxation, and the description of the quantum nature of hydrogen behavior in the cavities. The validity of the proposed approach was verified for argon, methane, and xenon hydrates. The results were in agreement with known experimental data. The model was then used to calculate the curves of monovariant three-phase equilibrium gas-hydrate-ice and the degree of filling of the large and small cavities for pure hydrogen and mixed hydrogen/propane hydrates in a wide range of pressure and at low temperatures. The paper presented the theory, including equations, monovariant equilibria, and computational details. It was concluded that the proposed model accounted for the influence of guest molecules on the host lattice and guest-guest interaction. The model could be used with other inclusion compounds with the same type of composition such as clathrate silicon, zeolites, and inclusion compounds of semiconductor elements. The calculated curves of monovariant equilibrium agree with the experiment. 33 refs., 1 tab., 9 figs.

The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

Science.gov (United States)

Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

2017-10-13

Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

Science.gov (United States)

Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

2015-07-28

The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy.

Iodine capture by Hofmann-type clathrate Ni(II)(pz)[Ni(II)(CN)_4

International Nuclear Information System (INIS)

Massasso, Giovanni; Long, Jerome; Haines, Julien; Devautour-Vinot, Sabine; Maurin, Guillaume; Larionova, Joulia; Guerin, Christian; Guari, Yannick; Grandjean, Agnes; Onida, Barbara; Donnadieu, Bruno

2014-01-01

The thermally stable Hofmann-type clathrate framework Ni(II)(pz)[Ni(II)(CN)_4] (pz = pyrazine) was investigated for the efficient and reversible sorption of iodine (I_2) in the gaseous phase and in solution with a maximum adsorption capacity of 1 mol of I_2 per 1 mol of Ni(II)pz)[Ni(II)(CN)_4] in solution. (authors)

Heat-pump cool storage in a clathrate of freon

Science.gov (United States)

Tomlinson, J. J.

Presented are the analytical description and assessment of a unique heat pump/storage system in which the conventional evaporator of the vapor compression cycle is replaced by a highly efficient direct contract crystallizer. The thermal storage technique requires the formation of a refrigerant gas hydrate (a clathrate) and exploits an enthalpy of reaction comparable to the heat of fusion of ice. Additional system operational benefits include cool storage at the favorable temperatures of 4 to 7 C (40 to 45 F), and highly efficient heat transfer ates afforded by he direct contact mechanism. In addition, the experimental approach underway at ORNL to study such a system is discussed.

NH3 quantum rotators in Hofmann clathrates: intensity and width of rotational transition lines

International Nuclear Information System (INIS)

Vorderwisch, Peter; Sobolev, Oleg; Desmedt, Arnaud

2004-01-01

Inelastic structure factors for rotational transitions of uniaxial NH 3 quantum rotators, measured in a Hofmann clathrate with biphenyl as guest molecule, agree with those calculated for free rotators. A finite intrinsic line width, found for rotational transitions involving the rotational level j=3 at low temperature, supports a recently suggested model based on resonant rotor-rotor coupling

Structure and physical properties of type-I clathrate solid-solution Ba8PtxGe46-x-y□y (□=vacancy)

International Nuclear Information System (INIS)

Melnychenko-Koblyuk, N.; Grytsiv, A.; Rogl, P.; Rotter, M.; Lackner, R.; Bauer, E.; Fornasari, L.; Marabelli, F.; Giester, G.

2007-01-01

Formation, crystal chemistry, and physical properties were investigated for the solid-solution Ba 8 Pt x Ge 46-x-y □ y (□ is a vacancy) deriving from binary clathrate Ba 8 Ge 43 □ 3 with a solubility limit of ∼3.5 Pt atoms/f.u. at T=800 deg. C. Structural investigations throughout the homogeneity region confirm isotypism with the cubic primitive clathrate type-I structure (space group type Pm3n) and lattice parameters ranging from a=1.0657(2) nm for Ba 8 Ge 43 □ 3 to a=1.0752(2) nm for Ba 8 Pt 3.5 Ge 41.5 □ 1.0 . Phase relations for the region concerning the clathrate solution were derived at subsolidus temperatures as well as at 800 deg. C. Transport properties evidence electrons as the majority charge carriers in the system with a slight dependency on the Pt content. The system is located close to a semiconducting regime with a gap in the electronic density of states of a few thousand K. No low temperature maximum is obvious from thermal conductivity which is dominated by the lattice contribution. Thermal conductivity furthermore documents a high efficiency of phonon scattering on vacancies

Phase equilibria, crystal chemistry, electronic structure and physical properties of Ag-Ba-Ge clathrates

Energy Technology Data Exchange (ETDEWEB)

Zeiringer, I.; Chen Mingxing [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Bednar, I.; Royanian, E.; Bauer, E. [Institute of Solid State Physics, Vienna University of Technology, Wiedner Hauptstr. 8-10, 1040 Wien (Austria); Podloucky, R.; Grytsiv, A. [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Rogl, P., E-mail: peter.franz.rogl@univie.ac.at [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Effenberger, H. [Institute of Mineralogy and Crystallography, University of Vienna, A-1090 Wien (Austria)

2011-04-15

In the Ag-Ba-Ge system the clathrate type-{Iota} solid solution, Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y}, extends at 800 deg. C from binary Ba{sub 8}Ge{sub 43{open_square}3} ({open_square} is a vacancy) to Ba{sub 8}Ag{sub 5.3}Ge{sub 40.7}. For the clathrate phase (1 {<=} x {<=} 5.3) the cubic space group Pm3-bar n was established by X-ray powder diffraction and confirmed by X-ray single-crystal analyses of the samples Ba{sub 8}Ag{sub 2.3}Ge{sub 41.9{open_square}1.8} and Ba{sub 8}Ag{sub 4.4}Ge{sub 41.3{open_square}0.3}. Increasing the concentration of Ag causes the lattice parameters of the solid solution to increase linearly from a value of a = 1.0656 (x = 0, y = 3) to a = 1.0842 (x = 4.8, y = 0) nm. Site preference determination using X-ray refinement reveals that Ag atoms preferentially occupy the 6d site randomly mixed with Ge and vacancies, which become filled in the compound Ba{sub 8}Ag{sub 4.8}Ge{sub 41.2} when the Ag content increases. At 600 {sup o}C the phase region of the clathrate solution Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} becomes separated from the Ba-Ge boundary and extends from 6.6 to 9.8 at.% Ag. The compound Ba{sub 6}Ge{sub 25} (clathrate type-{Iota}X) dissolves at 800 {sup o}C a maximum of 1.5 at.% Ag. The homogeneity regions of the two ternary compounds BaAg{sub 2-x}Ge{sub 2+x} (ThCr{sub 2}Si{sub 2}-type, 0.2 {<=} x {<=} 0.7) and Ba(Ag{sub 1-x}Ge{sub x}){sub 2} (AlB{sub 2}-type, 0.65 {<=} x {<=} 0.75) were established at 800 deg. C. Studies of transport properties for the series of Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} compounds evidenced that electrons are the predominant charge carriers with the Fermi energy close to a gap. Its position can be fine-tuned by the substitution of Ge by Ag atoms and by mechanical processing of the starting material, Ba{sub 8}Ge{sub 43}. The proximity of the electronic structure at Fermi energy of Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} to a gap is also corroborated by density

Chemical trends of the band gaps of idealized crystal of semiconducting silicon clathrates, M8Si38A8 (M = Na, K, Rb, Cs; A = Ga, Al, In), predicted by first-principle pseudopotential calculations

International Nuclear Information System (INIS)

Imai, Yoji; Imai, Motoharu

2011-01-01

Research highlights: → This paper reports the results of electronic structural calculations of Si clathrate, M 8 Si 38 Ga 8 (M: the encapsulated guest alkali atom; Na, K, Rb, and Cs). → All of them are found to be indirect semiconductors with the calculated gaps (E g ) from 0.45 to 0.89 eV, which should be compared to the calculated gap of 0.65 eV of crystalline Si with the diamond structure. The gaps become wider with the promotion to the heavier guest alkali atoms and the reasons of gap widening are discussed using the calculated dependence of E g on the cell-volume of guest-free silicon clathrate (Si 46 ). Effect of the substitutional elements in the clathrate framework (Al and In in place of Ga) was also discussed. - Abstract: We have calculated the band structures of Si clathrate, M 8 Si 38 Ga 8 (M = Na, K, Rb, and Cs), using the density-functional theory under the generalized gradient corrected local density approximation, where M is the encapsulated guest alkali atom. They are found to be indirect semiconductors with the calculated gaps (E g ) from 0.45 to 0.89 eV, which should be compared to the calculated gap of 0.65 eV of crystalline Si with the diamond structure. The gaps become wider with the promotion to the heavier guest alkali atoms and the reasons of gap widening are discussed using the calculated dependence of E g on the cell-volume of guest-free silicon clathrate (Si 46 ). Effect of the substitutional elements in the clathrate framework (Al and In in place of Ga) was also discussed.

Pressure-induced amorphization and collapse of magnetic order in the type-I clathrate Eu8Ga16Ge30

Science.gov (United States)

Mardegan, J. R. L.; Fabbris, G.; Veiga, L. S. I.; Adriano, C.; Avila, M. A.; Haskel, D.; Giles, C.

2013-10-01

We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume collapse is observed prior to the crystalline-amorphous phase transition which takes place when the unit cell volume is reduced to 81% of its ambient pressure value. Fits of the pressure-dependent relative volume to a Murnaghan equation of state yield a bulk modulus B0=65±3 GPa and a pressure derivative B0'=3.3±0.5. The Eu L2-edge XMCD data shows quenching of the magnetic order at a pressure coincident with the crystalline-amorphous phase transition. This information along with the persistence of an Eu2+ valence state observed in the XANES spectra up to the highest pressure point (22 GPa) indicates that the suppression of XMCD intensity is due to the loss of long range magnetic order. When compared with other clathrates, the results point to the importance of guest ion-cage interactions in determining the mechanical stability of the framework structure and the critical pressure for amorphization. Finally, the crystalline structure is not found to recover after pressure release, resulting in an amorphous material that is at least metastable at ambient pressure and temperature.

Confining CO2 inside the nanocavities of the sI clathrate: a quantum dynamics study

International Nuclear Information System (INIS)

Prosmiti, R; Arismendi-Arrieta, D J; Valdés, Á

2015-01-01

Clathrate hydrates have been found to occur naturally, and have been extensively studied due to their important industrial applications, such as the storage of the CO 2 from the atmosphere and control climate change. Thus, quantitative understanding of physical and chemical properties, as well as the factors that control the formation of CO 2 hydrates, on both macroscopic and microscopic levels is essential in several areas of physical science. (paper)

Overview: Nucleation of clathrate hydrates.

Science.gov (United States)

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.

Overview: Nucleation of clathrate hydrates

Science.gov (United States)

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.

Lattice dynamics study of low energy guest–host coupling in clathrate hydrate

International Nuclear Information System (INIS)

Yang Yuehai; Dong Shunle; Wang Lin

2008-01-01

Our lattice dynamics simulation of Xe-hydrate with four-site TIP4P oxygen-shell model can accurately reproduce each peak position in the inelastic incoherent neutron scattering spectrum at the acoustic band (below 15meV) and yield correct relative intensity. Based on the results, the uncertain profile at ∼6 meV is assigned to anharmonic guest modes coupled strongly to small cages. Blue shift is proposed in phonon dispersion sheet in the case of anticrossing and found to be an evident signal for guest-host coupling that explains the anomalous thermal conductivity of clathrate hydrate

Lattice Dynamics Study of Phonon Instability and Thermal Properties of Type-I Clathrate K₈Si46 under High Pressure.

Science.gov (United States)

Zhang, Wei; Zeng, Zhao Yi; Ge, Ni Na; Li, Zhi Guo

2016-07-25

For a further understanding of the phase transitions mechanism in type-I silicon clathrates K₈Si 46 , ab initio self-consistent electronic calculations combined with linear-response method have been performed to investigate the vibrational properties of alkali metal K atoms encapsulated type-I silicon-clathrate under pressure within the framework of density functional perturbation theory. Our lattice dynamics simulation results showed that the pressure induced phase transition of K₈Si 46 was believed to be driven by the phonon instability of the calthrate lattice. Analysis of the evolution of the partial phonon density of state with pressure, a legible dynamic picture for both guest K atoms and host lattice, was given. In addition, based on phonon calculations and combined with quasi-harmonic approximation, the specific heat of K₈Si 46 was derived, which agreed very well with experimental results. Also, other important thermal properties including the thermal expansion coefficients and Grüneisen parameters of K₈Si 46 under different temperature and pressure were also predicted.

Crystal structure and thermoelectric properties of clathrate, Ba{sub 8}Ni{sub 3.5}Si{sub 42.0}: Small cage volume and large disorder of the guest atom

Energy Technology Data Exchange (ETDEWEB)

Roudebush, John H., E-mail: jhr@princeton.edu [Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616 (United States); Orellana, Mike [Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616 (United States); Bux, Sabah [Thermal Energy Conversion Technologies Group, Jet Propulsion Laboratory/California Institute of Technology, Pasadena, CA 91109 (United States); Yi Tanghong; Kauzlarich, Susan M. [Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616 (United States)

2012-08-15

Samples with the type-I clathrate composition Ba{sub 8}Ni{sub x}Si{sub 46-x} have been synthesized and their structure and thermoelectric properties characterized. Microprobe analysis indicates the Ni incorporation to be 2.62{<=}x{<=}3.53. The x=3.5 phase crystallizes in the type-I clathrate structure (space group: Pm-3n) with a lattice parameter of 10.2813(3) A. The refined composition was Ba{sub 8}Ni{sub 3.5}Si{sub 42.0}, with small vacancies, 0.4 and 0.5 atoms per formula unit, at the 2a and 6c sites, respectively. The position of the Ba2 atom in the large cage was modeled using a 4-fold split position (24j site), displaced 0.18 A from the cage center (6d site). The volume of the large cage is calculated to be 146 A{sup 3}, smaller than other clathrates with similar cation displacement. The sample shows n-type behavior with a maximum of -50 {mu}V/K at 823 K above which the Seebeck coefficient decreases, suggesting mixed carriers. Lattice thermal conductivity, {kappa}{sub l}, is 55 mW/K above 600 K. - Graphical abstract: Seebeck coefficient and resistivity of the type-I clathrate Ba{sub 8}Ni{sub 3.5}Si{sub 41.0}. Structure show's large displacement of the Ba cation in the large cage (6c site). Highlights: Black-Right-Pointing-Pointer Crystal structure of the Ba{sub 8}Ni{sub 3.5}Si{sub 41.0} reported. Black-Right-Pointing-Pointer Vacancies at the 2a and 6c sites. Black-Right-Pointing-Pointer Large disorder of Ba guest atom, 0.18 A from cage center. Black-Right-Pointing-Pointer Structure is compared to Ba{sub 8}Si{sub 46} and other type-I clathrates. Black-Right-Pointing-Pointer Max Seebeck of -50.7 {mu}V/C at 798.4 K, thermal conductivity {approx}55 mW/K.

Synthesis and Characterization of Novel Copper(II 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

Directory of Open Access Journals (Sweden)

Kayoko Kasai

2011-11-01

Full Text Available Two-dimensional (2D grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyltetrafluorobenzene (bpf with Cu(NO32 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf2(NO32]·(biphenyl2}n (1, {[Cu(bpf2(NO32]·(m-C6H4(OMe22}n (2, {[Cu(bpf2(NO32]·PhtBu}n (3 and {[Cu(bpf2(NO3(H2O]NO3·(bpf0.5}n (4 were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

Study of hydrogen-molecule guests in type II clathrate hydrates using a force-matched potential model parameterised from ab initio molecular dynamics

Science.gov (United States)

Burnham, Christian J.; Futera, Zdenek; English, Niall J.

2018-03-01

The force-matching method has been applied to parameterise an empirical potential model for water-water and water-hydrogen intermolecular interactions for use in clathrate-hydrate simulations containing hydrogen guest molecules. The underlying reference simulations constituted ab initio molecular dynamics (AIMD) of clathrate hydrates with various occupations of hydrogen-molecule guests. It is shown that the resultant model is able to reproduce AIMD-derived free-energy curves for the movement of a tagged hydrogen molecule between the water cages that make up the clathrate, thus giving us confidence in the model. Furthermore, with the aid of an umbrella-sampling algorithm, we calculate barrier heights for the force-matched model, yielding the free-energy barrier for a tagged molecule to move between cages. The barrier heights are reasonably large, being on the order of 30 kJ/mol, and are consistent with our previous studies with empirical models [C. J. Burnham and N. J. English, J. Phys. Chem. C 120, 16561 (2016) and C. J. Burnham et al., Phys. Chem. Chem. Phys. 19, 717 (2017)]. Our results are in opposition to the literature, which claims that this system may have very low barrier heights. We also compare results to that using the more ad hoc empirical model of Alavi et al. [J. Chem. Phys. 123, 024507 (2005)] and find that this model does very well when judged against the force-matched and ab initio simulation data.

Growth mode transition of tetrahydrofuran clathrate hydrates in the guest/host concentration boundary layer.

Science.gov (United States)

Sabase, Yuichiro; Nagashima, Kazushige

2009-11-19

Clathrate hydrates are known to form a thin film along a guest/host boundary. We present here the first report of tetrahydrofuran (THF) clathrate hydrate formation in a THF/water concentration boundary layer. We found that the THF-water system also forms a hydrate film separating the guest/host phases. The lateral growth rate of the film increases as supercooling increases. The thickness of the film at the growth tip decreases as supercooling and the lateral growth rate increase. These tendencies are consistent with reports of experiments for other hydrates and predictions of heat-transfer models. After film formation and slight melting, two types of growth modes are observed, depending on temperature T. At T = 3.0 degrees C, the film slowly thickens. The thickening rate is much lower than the lateral growth rate, as reported for other hydrates. At T agglomerate of small polycrystalline hydrates forms in each phase. Grain boundaries in the film and pore spaces in the agglomerate act as paths for permeation of each liquid. Timing when continuous nucleation starts is dominantly controlled by the time of initiation of liquid permeation through the film. Digital particle image velocimetry analysis of the agglomerate shows that it expands not by growth at the advancing front but rather by continuous nucleation in the interior. Expansion rates of the agglomerate tend to be higher for the cases of multipermeation paths in the film and the thinner film. We suppose that the growth mode transition to continuous nucleation is caused by the memory effect due to slight melting of the hydrate film.

Lattice Dynamics Study of Phonon Instability and Thermal Properties of Type-I Clathrate K8Si46 under High Pressure

Directory of Open Access Journals (Sweden)

Wei Zhang

2016-07-01

Full Text Available For a further understanding of the phase transitions mechanism in type-I silicon clathrates K8Si46, ab initio self-consistent electronic calculations combined with linear-response method have been performed to investigate the vibrational properties of alkali metal K atoms encapsulated type-I silicon-clathrate under pressure within the framework of density functional perturbation theory. Our lattice dynamics simulation results showed that the pressure induced phase transition of K8Si46 was believed to be driven by the phonon instability of the calthrate lattice. Analysis of the evolution of the partial phonon density of state with pressure, a legible dynamic picture for both guest K atoms and host lattice, was given. In addition, based on phonon calculations and combined with quasi-harmonic approximation, the specific heat of K8Si46 was derived, which agreed very well with experimental results. Also, other important thermal properties including the thermal expansion coefficients and Grüneisen parameters of K8Si46 under different temperature and pressure were also predicted.

Competing quantum effects in the free energy profiles and diffusion rates of hydrogen and deuterium molecules through clathrate hydrates.

Science.gov (United States)

Cendagorta, Joseph R; Powers, Anna; Hele, Timothy J H; Marsalek, Ondrej; Bačić, Zlatko; Tuckerman, Mark E

2016-11-30

Clathrate hydrates hold considerable promise as safe and economical materials for hydrogen storage. Here we present a quantum mechanical study of H 2 and D 2 diffusion through a hexagonal face shared by two large cages of clathrate hydrates over a wide range of temperatures. Path integral molecular dynamics simulations are used to compute the free-energy profiles for the diffusion of H 2 and D 2 as a function of temperature. Ring polymer molecular dynamics rate theory, incorporating both exact quantum statistics and approximate quantum dynamical effects, is utilized in the calculations of the H 2 and D 2 diffusion rates in a broad temperature interval. We find that the shape of the quantum free-energy profiles and their height relative to the classical free energy barriers at a given temperature, as well as the rate of diffusion, are strongly affected by competing quantum effects: above 25 K, zero-point energy (ZPE) perpendicular to the reaction path for diffusion between cavities decreases the quantum rate compared to the classical rate, whereas at lower temperatures tunneling outcompetes the ZPE and as a result the quantum rate is greater than the classical rate.

The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates.

Science.gov (United States)

Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M; Bačić, Zlatko

2018-04-14

We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H 2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculations of the coupled translation-rotation eigenstates are performed for H 2 in the v=0 and v=1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H 2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H 2 inside a hydrate domain is assumed to be pairwise additive. The H 2 -H 2 O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H 2 , v=0 or v=1, is derived from the high-quality ab initio full-dimensional (9D) PES of the H 2 -H 2 O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H 2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H 2 change very little with the domain size, unlike the H 2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H 2 O molecules in the first three complete hydration shells around H 2 .

The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates

Science.gov (United States)

Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M.; Bačić, Zlatko

2018-04-01

We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculations of the coupled translation-rotation eigenstates are performed for H2 in the v =0 and v =1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H2 inside a hydrate domain is assumed to be pairwise additive. The H2-H2O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H2, v =0 or v =1 , is derived from the high-quality ab initio full-dimensional (9D) PES of the H2-H2O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H2 change very little with the domain size, unlike the H2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H2O molecules in the first three complete hydration shells around H2.

Squeezing clathrate cages to host trivalent rare-earth guests

Energy Technology Data Exchange (ETDEWEB)

Wang, Jian [Iowa State Univ., Ames, IA (United States). Department of Chemistry; Ames Lab., Ames, IA (United States); He, Yuping [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Mordvinova, Natalia E. [Laboratoire CRISMAT, ENSICAEN, CNRS UMR (France); Lebedev, Oleg [Laboratoire CRISMAT, ENSICAEN, CNRS UMR (France); Kovnir, Kirill [Iowa State Univ., Ames, IA (United States). Department of Chemistry; Ames Lab., Ames, IA (United States)

2017-11-01

Strike difference of the trivalent rare-earth cations from their alkali and alkaline-earth peers is in the presence of localized 4f-electrons and strong spin-orbit coupling. Placing trivalent rare-earth cations inside the fullerene molecules or in between the blocks of itinerant magnetic intermetallics gave rise to plethora of fascinating properties and materials. A long-time missing but hardly desired piece is the semiconducting or metallic compound where rare-earth cations are situated inside the oversized polyhedral cages of three-dimensional framework. In this work we present a synthesis of such compounds, rare-earth containing clathrates Ba_8-xR_xCu₁₆P₃₀. The unambiguous proofs of their composition and crystal structure were achieved by a combination of synchrotron powder diffraction, time-of-flight neutron powder diffraction, scanning-transmission electron microscopy, and electron energy-loss spectroscopy. Our quantum-mechanical calculations and experimental characterizations show that the incorporation of the rare-earth cations significantly enhances the hole mobility and concentration which results in the drastic increase in the thermoelectric performance.

The effect of stirring on the heterogeneous nucleation of water and of clathrates of tetrahydrofuran/water mixtures

Directory of Open Access Journals (Sweden)

P.W. Wilson

2016-03-01

Full Text Available The statistics of liquid-to-crystal nucleation are measured for both water and for clathrate-forming mixtures of tetrahydrofuran (THF and water using an automatic lag time apparatus (ALTA. We measure the nucleation temperature using this apparatus in which a single sample is repeatedly cooled, nucleated and thawed. The effect of stirring on nucleation has been evaluated numerically and is discussed. We find that stirring of the solution makes no difference to the nucleation temperature of a given solution in a given tube.

In situ NMR studies of hydrogen storage kinetics and molecular diffusion in clathrate hydrate at elevated hydrogen pressures

Energy Technology Data Exchange (ETDEWEB)

Okuchi, T. [Okayama Univ., Misasa, Tottori (Japan); Moudrakovski, I.L.; Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

2008-07-01

The challenge of storing high-density hydrogen into compact host media was investigated. The conventional storage scheme where an aqueous solution is frozen with hydrogen gas is too slow for practical use in a hydrogen-based society. Therefore, the authors developed a faster method whereby hydrogen was stored into gas hydrates. The hydrogen gas was directly charged into hydrogen-free, crystalline hydrate powders with partly empty lattices. The storage kinetics and hydrogen diffusion into the hydrate was observed in situ by nuclear magnetic resonance (NMR) in a pressurized tube cell. At pressures up to 20 MPa, the storage was complete within 80 minutes, as observed by growth of stored-hydrogen peak into the hydrate. Hydrogen diffusion within the crystalline hydrate media is the rate-determining step of current storage scheme. Therefore, the authors measured the diffusion coefficient of hydrogen molecules using the pulsed field gradient NMR method. The results show that the stored hydrogen is very mobile at temperatures down to 250 K. As such, the powdered hydrate media should work well even in cold environments. Compared with more prevailing hydrogen storage media such as metal hydrides, clathrate hydrates have the advantage of being free from hydrogen embrittlement, more chemically durable, more environmentally sound, and economically affordable. It was concluded that the powdered clathrate hydrate is suitable as a hydrogen storage media. 22 refs., 4 figs.

Hydrogen storage and carbon dioxide sequestration in TBAF semi-clathrate hydrates: Kinetics and evolution of hydrate-phase composition by in situ raman spectroscopy - Abstract -

NARCIS (Netherlands)

Torres Trueba, A.; Radoviæ, I.R.; Zevenbergen, J.F.; Kroon, M.C.; Peters, C.J.

2012-01-01

Carbon dioxide (CO2) represents almost one third of the emissions from the combustion of fossil fuels additionally, CO2 has been identified as the mayor contributor of global warming. Hydrogen (H2), on the other hand, due to its properties is considered a promising energy carrier. Clathrate hydrates

Weak interactions between water and clathrate-forming gases at low pressures

Energy Technology Data Exchange (ETDEWEB)

Thurmer, Konrad; Yuan, Chunqing; Kimmel, Gregory A.; Kay, Bruce D.; Smith, R. Scott

2015-11-01

Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10-1 mbar methane or 10-5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10-5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water-gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~43 K and isobutane desorbs near ~100 K. Similar desorption temperatures were observed for desorption from amorphous solid water.

Thermoelectric properties of In-substituted Ge-based clathrates prepared by HPHT

Directory of Open Access Journals (Sweden)

Binwu Liu

2018-03-01

Full Text Available Bulk materials Ba8Ga16InxGe30-x (x = 0.5, 1.0, 1.5 were prepared by High-Pressure and High-Temperature (HPHT method and the crystal structure has been confirmed by X-ray diffraction and cell refinement. The actual In composition was much lower than the starting composition, and lattice constants increased with the increase of substitution. As the temperature increased, the Seebeck coefficient and electrical resistivity increased first and then decreased, while the thermal conductivity was the opposite, which leads to significant enhancement on thermoelectric properties of the clathrates. The substitution of indium elements decreased the seebeck coefficient and electrical resistivity, and also changed the microstructure of the compounds. A minimum thermal conductivity of 0.84 Wm−1K−1 was obtained, and a good ZT value of 0.52 was achieved. The grain boundaries and lattice defects generated by high pressure can effectively scatter phonons of different frequencies, which reduce the lattice thermal conductivity.

Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures

Science.gov (United States)

Lueking, Angela [State College, PA; Narayanan, Deepa [Redmond, WA

2011-03-08

A process for making a hydrogenated carbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenated carbon material. A hydrogenated carbon material including a hydrogen carbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.

Lithium-ion induced conformational change of 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene resulting in an egg-shaped dimeric clathrate

DEFF Research Database (Denmark)

Faldt, A.; Krebs, Frederik C; Jørgensen, Mikkel

2000-01-01

Synthesis and structural investigation of a 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene and its lithium complex salt that forms a dimeric clathrate with a molecule of solvent inside a cavity. At least three different interactions were identified as being responsible for the forma...

Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

International Nuclear Information System (INIS)

Cataldo, Franco; Strazzulla, Giovanni; Iglesias-Groth, Susana

2009-01-01

Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization. The host-guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host-guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity - in terms of thermal behaviour - of the PPA from inclusion polymerization with that from stereospecific polymerization

Thermodynamic promotion of carbon dioxide-clathrate hydrate formation by tetrahydrofuran, cyclopentane and their mixtures

DEFF Research Database (Denmark)

Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

2013-01-01

Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....... dioxide (CO2), with 5.0mole percent THF in the initial aqueous phase, are presented in the temperature range from 283.3K to 285.2K. At 283.3K, the three-phase equilibrium pressure is determined to be 0.61MPa (absolute pressure).Four-phase hydrate (H)-aqueous liquid (Lw)-organic liquid (La)-vapour (V...

Enhanced Selectivity of the Separation of CO2 from N2 during Crystallization of Semi-Clathrates from Quaternary Ammonium Solutions

International Nuclear Information System (INIS)

Herri, J.M.; Bouchemoua, A.; Kwaterski, M.; Brantuas, P.; Galfre, A.; Bouillot, B.; Douzet, J.; Ouabbas, Y.; Cameirao, A.

2014-01-01

CO 2 mitigation is crucial environmental problem and a societal challenge for this century. CO 2 capture and sequestration is a route to solve a part of the problem, especially for the industries in which the gases to be treated are well localized. CO 2 capture by using hydrate is a process in which the cost of the separation is due to compression of gases to reach the gas hydrate formation conditions. Under pressure, the water and gas forms a solid that encapsulates preferentially CO 2 . The gas hydrate formation requires high pressures and low temperatures, which explains the use of thermodynamic promoters to decrease the operative pressure. Quaternary ammonium salts represent an interesting family of components because of their thermodynamic effect, but also because they can generate crystals that are easily handled. In this work, we have made experiments concerning the equilibrium of (CO 2 , N 2 ) in presence of Tetra-n-Butyl Ammonium Bromide (TBAB) which form a semi-clathrate hydrate. We propose equilibrium data (pressure, temperature) in presence of TBAB at different concentrations and we compare them to the literature. We have also measured the composition of the hydrate phase in equilibrium with the gas phase at different CO 2 concentrations. We observe that the selectivity of the separation is dramatically increased in comparison to the selectivity of the pure water gas clathrate hydrate. We observe also a benefice on the operative pressure which can be dropped down to the atmospheric pressure. (authors)

Observations of CO{sub 2} clathrate hydrate formation and dissolution under deep-ocean disposal conditions

Energy Technology Data Exchange (ETDEWEB)

Warzinski, R.P.; Cugini, A.V. [Department of Energy, Pittsburgh, PA (United States); Holder, G.D. [Univ. of Pittsburgh, Pittsburgh, PA (United States)

1995-11-01

Disposal of anthropogenic emissions of CO{sub 2} may be required to mitigate rises in atmospheric levels of this greenhouse gas if other measures are ineffective and the worst global warming scenarios begin to occur. Long-term storage of large quantities of CO{sub 2} has been proposed, but the feasibility of large land and ocean disposal options remains to be established. Determining the fate of liquid CO{sub 2} injected into the ocean at depths greater than 500 m is complicated by uncertainties associated with the physical behavior of CO{sub 2} under these conditions, in particular the possible formation of the ice-like CO{sub 2} clathrate hydrate. Resolving this issue is key to establishing the technical feasibility of this option. Experimental and theoretical work in this area is reported.

NMR and computational study of Ba8CuxGe46-x clathrate semiconductors

International Nuclear Information System (INIS)

Chen, Jing-Han; Sirusi Arvij, Ali; Zheng, Xiang; Rodriguez, Sergio Y.; Ross, Joseph H.

2014-01-01

Highlights: • Quadrupole NMR with first-principles calculations probes local site preferences. • Cu/Ge ratio is clarified vs. the ideal Zintl composition. • Modified Becke–Johnson exchange potential agrees well with NMR Knight shifts. - Abstract: Ba 8 Cu x Ge 46-x is a type-I clathrate material that forms as a semiconductor in a narrow composition range corresponding to the electron-balanced Zintl composition, with x = 5.3. We use NMR spectroscopy combined with ab initio electronic structure calculations to probe the electronic and structural behavior of these materials. Computational results based on a superstructure model for the atomic configuration of the alloy provide good agreement with the electric quadrupole-broadened NMR lineshapes. Modeling using the modified Becke–Johnson (TB-mBJ) exchange potential is also shown to agree well with experimental NMR Knight shifts. The results indicate that the Cu–Ge balance is the main factor determining the carrier density, within a narrow stability range near the ideal Zintl composition

A Second Glass Transition in Pressure Collapsed Type II Clathrate Hydrates.

Science.gov (United States)

Andersson, Ove; Häussermann, Ulrich

2018-04-19

Type II clathrate hydrates (CHs) M·17 H 2 O, with M = tetrahydrofuran (THF) or 1,3-dioxolane, are known to collapse, or amorphize, on pressurization to ∼1.3 GPa in the temperature range 77-140 K. On heating at 1 GPa, these pressure-amorphized CH states show a weak, stretched sigmoid-shaped, heat-capacity increase because of a glass transition. Here we use thermal conductivity and heat capacity measurements to show that also type II CH with M = cyclobutanone (CB) collapses on isothermal pressurization and undergoes a similar, weak, glass transition upon heating at 1 GPa. Furthermore, we reveal for both THF CH and CB CH a second, much more pronounced, glass transition at temperatures above the thermally weak glass transition on heating in the 0.2-0.7 GPa range. This result suggests the general occurrence of two glass transitions in water-rich (94 mol %) pressure-collapsed CHs. Because of a large increase in dielectric permittivity concurrently as the weak heat capacity increase, the first glass transition must be due to kinetic unfreezing of water molecules. The thermal features of the second glass transition, measured on isobaric temperature cycling, are typical of a glass-liquid-glass transition, which suggests that pressure-amorphized CHs transform reversibly to liquids.

Cu and Zn substituted silicon clathrates with the cubic type-II structure. Synthesis and characterization of Cs{sub 8}Na{sub 16}Cu{sub 3.8}Si{sub 132.2} and Cs{sub 8}Na{sub 16}Zn{sub 6.9}Si{sub 129.1}

Energy Technology Data Exchange (ETDEWEB)

Schaefer, Marion C.; Bobev, Svilen [Department of Chemistry and Biochemistry, University of Delaware, Newark, DE (United States)

2017-12-13

Studies in the systems Cs-Na-Cu-Si and Cs-Na-Zn-Si yielded the novel clathrates Cs{sub 8}Na{sub 16}(Cu,Si){sub 136} and Cs{sub 8}Na{sub 16}(Zn,Si){sub 136}, both with the cubic type-II structure [space group Fd anti 3m (no. 227), Pearson symbol cF160]. The structures of the title compounds were established from single-crystal X-ray diffraction methods, confirming the complete ordering of the Cs and Na guest atoms. The framework-building Si atoms are found to be randomly substituted by Cu atoms on framework site 96g, exclusively. In the structure of Cs{sub 8}Na{sub 16}(Zn,Si){sub 136}, the refinements indicate that the Zn and Si atoms co-occupy two of the three framework sites with notable preference for site 96g over site 32e. The corresponding refined compositions and unit cell parameters are as follows: Cs{sub 8}Na{sub 16}Cu{sub 3.8}Si{sub 132.2(1)} [a = 14.7583(15) Aa]; Cs{sub 8}Na{sub 16}Zn{sub 6.9}Si{sub 129.1(1)} [a = 14.7682(5) Aa], respectively. The type-II clathrates can be obtained only from experiments employing both Na and Cs, whereas work in the ternary Cs-Cu-Si, Cs-Zn-Si, Na-Cu-Si, and Na-Zn-Si systems failed to yield any clathrate phases. At the same conditions, exploratory studies in the K-Zn-Si and Rb-Zn-Si systems provided evidence that type-I clathrates are favored. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Effects of guest atomic species on the lattice thermal conductivity of type-I silicon clathrate studied via classical molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Kumagai, Tomohisa, E-mail: kumagai@criepi.denken.or.jp; Nakamura, Kaoru; Yamada, Susumu; Ohnuma, Toshiharu [Materials Science Research Laboratory, Central Research Institute of Electric Power Industry, 2-6-1 Nagasaka, Yokosuka, Kanagawa 240-0196 (Japan)

2016-08-14

The effects of guest atomic species in Si clathrates on the lattice thermal conductivity were studied using classical molecular dynamics calculations. The interaction between a host atom and a guest atom was described by the Morse potential function while that between host atoms was described by the Tersoff potential. The parameters of the potentials were newly determined for this study such that the potential curves obtained from first-principles calculations for the insertion of a guest atom into a Si cage were successfully reproduced. The lattice thermal conductivities were calculated by using the Green-Kubo method. The experimental lattice thermal conductivity of Ba{sub 8}Ga{sub 16}Si{sub 30} can be successfully reproduced using the method. As a result, the lattice thermal conductivities of type-I Si clathrates, M{sub 8}Si{sub 46} (M = Na, Mg, K, Ca Rb, Sr, Cs, or Ba), were obtained. It is found that the lattice thermal conductivities of M{sub 8}Si{sub 46}, where M is IIA elements (i.e., M = Mg, Ca, Sr, or Ba) tend to be lower than those of M{sub 8}Si{sub 46}, where M is IA elements (i.e., M = Na, K, Rb, or Cs). Those of {sup m}M{sub 8}Si{sub 46}, where m was artificially modified atomic weight were also obtained. The obtained lattice thermal conductivity can be regarded as a function of a characteristic frequency, f{sub c}. That indicates minimum values around f{sub c}=2-4 THz, which corresponds to the center of the frequencies of the transverse acoustic phonon modes associated with Si cages.

Superconductivity in gallium-substituted Ba8Si46 clathrates

Science.gov (United States)

Li, Yang; Zhang, Ruihong; Liu, Yang; Chen, Ning; Luo, Z. P.; Ma, Xingqiao; Cao, Guohui; Feng, Z. S.; Hu, Chia-Ren; Ross, Joseph H., Jr.

2007-02-01

We report a joint experimental and theoretical investigation of superconductivity in Ga-substituted type-I silicon clathrates. We prepared samples of the general formula Ba8Si46-xGax , with different values of x . We show that Ba8Si40Ga6 is a bulk superconductor, with an onset at TC≈3.3K . For x=10 and higher, no superconductivity was observed down to T=1.8K . This represents a strong suppression of superconductivity with increasing Ga content, compared to Ba8Si46 with TC≈8K . Suppression of superconductivity can be attributed primarily to a decrease in the density of states at the Fermi level, caused by a reduced integrity of the sp3 -hybridized networks as well as the lowering of carrier concentration. These results are corroborated by first-principles calculations, which show that Ga substitution results in a large decrease of the electronic density of states at the Fermi level, which explains the decreased superconducting critical temperature within the BCS framework. To further characterize the superconducting state, we carried out magnetic measurements showing Ba8Si40Ga6 to be a type-II superconductor. The critical magnetic fields were measured to be HC1≈35Oe and HC2≈8.5kOe . We deduce the London penetration depth λ≈3700Å and the coherence length ξc≈200Å . Our estimate of the electron-phonon coupling reveals that Ba8Si40Ga6 is a moderate phonon-mediated BCS superconductor.

Gas hydrates and clathrates. Flow assurance, environmental and economic perspectives and the Nigerian liquefied natural gas project

International Nuclear Information System (INIS)

Gbaruko, B.C.; Igwe, J.C.; Nwokeoma, R.C.; Gbaruko, P.N.

2007-01-01

Gas hydrates are nonstoichiometric crystalline compounds that belong to the inclusion group known as clathrates. They occur when water molecules attach themselves together through hydrogen bonding and form cavities which can be occupied by a single gas or volatile liquid molecule. Gas hydrates, asphaltenes and waxes are three major threats to flow assurance that must be well assessed by design team uptime. Gas hydrates are also looked upon as a future energy source and as a potential climate hazard. The purpose of this review is to show the chemistry and mechanism of gas hydrate formation, the problems they pose, especially to flow assurance, their system implications, their environmental and economic perspectives with respect to their prospects as storage and transport alternative to the liquefied natural gas technology. (author)

Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets.

Science.gov (United States)

Kulkarni, Chidambar; Korevaar, Peter A; Bejagam, Karteek K; Palmans, Anja R A; Meijer, E W; George, Subi J

2017-10-04

Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

Thermoelectric properties of Cu/Ag doped type-III Ba24Ge100 clathrates

Science.gov (United States)

Fu, Jiefei; Su, Xianli; Yan, Yonggao; Liu, Wei; Zhang, Zhengkai; She, Xiaoyu; Uher, Ctirad; Tang, Xinfeng

2017-09-01

Type-III Ba24Ge100 clathrates possess low thermal conductivity and high electrical conductivity at room temperature and, as such, have a great potential as thermoelectric materials for power generation. However, the Seebeck coefficient is very low due to the intrinsically high carrier concentration. In this paper, a series of Ba24CuxGe100-x and Ba24AgyGe100-y specimens were prepared by vacuum melting combined with the subsequent spark plasma sintering (SPS) process. Doping Cu or Ag on the Ge site not only suppresses the concentration of electrons but it also decreases the thermal conductivity. In addition, the carrier mobility and the Seebeck coefficient increase due to the decrease in the carrier concentration. Thus, the power factor is greatly improved, leading to an improvement in the dimensionless figure of merit ZT. Cu-doped Ba24Cu6Ge94 reaches the maximum ZT value of about 0.17 at 873 K, while Ag-doped Ba24Ag6Ge94 attains the dimensionless figure of merit ZT of 0.31 at 873 K, more than 2 times higher value compared to un-doped Ba24Ge100.

Synthesis and first-principle calculations of the structural and electronic properties of Ge-substituted type-VIII Ba{sub 8}Ga{sub 16}Sn{sub 30} clathrate

Energy Technology Data Exchange (ETDEWEB)

Shen, Lanxian [Education Ministry Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology, Yunnan Provincial Renewable Energy Engineering Key Lab, Solar Energy Research Institution, Yunnan Normal University, Kunming 650500 (China); Li, Decong [College of Optoelectronic Engineering, Yunnan Open University, Kunming 650500 (China); Liu, Hongxia; Liu, Zuming [Education Ministry Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology, Yunnan Provincial Renewable Energy Engineering Key Lab, Solar Energy Research Institution, Yunnan Normal University, Kunming 650500 (China); Deng, Shukang, E-mail: skdeng@126.com [Education Ministry Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology, Yunnan Provincial Renewable Energy Engineering Key Lab, Solar Energy Research Institution, Yunnan Normal University, Kunming 650500 (China)

2016-12-01

In this study, the structural and electronic structural properties of Ba{sub 8}Ga{sub 16}Sn{sub 30−x}Ge{sub x} (0≤x≤30) are determined by the first-principle method on the basis of density functional theory. Consistent with experimental findings, calculated results reveal that Ge atoms preferentially occupy the 2a and 24g sites in these compounds. As the content of Ge in Ge-substituted clathrate is increased, the lattice parameter is decreased, and the structural stability is enhanced. The bandgaps of the compound at 1≤x≤10 are smaller than those of Ba{sub 8}Ga{sub 16}Sn{sub 30}. By contrast, the bandgaps of the compound at x>10 are larger than those of Ba{sub 8}Ga{sub 16}Sn{sub 30}. The substitution of Ge for Sn affects p-type conductivity but not n-type conductivity. As Ge content increases, the whole conduction band moves to the direction of high energy, and the density of states of valence-band top decreases. The calculated potential energy versus displacement of Ba indicates that the vibration energy of this atom increases as cage size decreases. Because Ge substitution also affects clathrate structural symmetry, the distance of Ba atom deviation from the center of the cage initially increases and subsequently decreases as the Ge content increases.

High-pressure studies on a new superconducting clathrate: Ba sub 6 Ge sub 2 sub 5

CERN Document Server

Yuan, H Q; Carrillo-Cabrera, W; Paschen, S; Sparn, G; Baenitz, M; Grin, Y; Steglich, F

2002-01-01

The effect of pressure on the low-temperature states of the newly discovered clathrate Ba sub 6 Ge sub 2 sub 5 is investigated by means of measurements of the electrical resistivity. At ambient pressure, Ba sub 6 Ge sub 2 sub 5 undergoes a two-step structural phase transition between 230 and 180 K from metallic behaviour to a high-resistivity state characterized by a mean free path of about 3 A. Interestingly, a Bardeen-Cooper-Schrieffer-like (BCS-like) superconducting transition occurs at T sub C approx 0.24 K from the resulting 'bad metal'. With increasing pressure, the structural phase transition is depressed but T sub C increases drastically. T sub C reaches a maximum value of 3.85 K at the critical pressure p sub C approx 2.8 GPa, where the structural distortion is completely suppressed and the system exhibits metallic behaviour. Higher pressures lead to a slight decrease of T sub C.

“Glass-like” thermal conductivity gradually induced in thermoelectric Sr{sub 8}Ga{sub 16}Ge{sub 30} clathrate by off-centered guest atoms

Energy Technology Data Exchange (ETDEWEB)

Christensen, Sebastian; Schmøkel, Mette Stokkebro; Borup, Kasper Andersen; Christensen, Mogens, E-mail: mch@chem.au.dk, E-mail: bo@chem.au.dk; Iversen, Bo Brummerstedt, E-mail: mch@chem.au.dk, E-mail: bo@chem.au.dk [Department of Inorganic Chemistry & iNANO, Center for Materials Crystallography, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark); Madsen, Georg K. H. [ICAMS, Ruhr-Universität Bochum, Bochum (Germany); McIntyre, Garry J.; Capelli, Silvia C. [Institut Laue-Langevin, 71 Avenue des Martyrs, CS 20156, Grenoble Cedex 9 (France)

2016-05-14

The origin of the “glass-like” plateau in thermal conductivity of inorganic type I clathrates has been debated for more than a decade. Here, it is demonstrated that the low temperature thermal conductivity of Sr{sub 8}Ga{sub 16}Ge{sub 30} can be controlled by the synthesis method: A flux-grown sample has a “glass-like” plateau in thermal conductivity at low temperature, while a zone-melted sample instead has a crystalline peak. A combination of flux-growth and zone-melting produces an intermediate thermal conductivity. In a comprehensive study of three single crystal samples, it is shown by neutron diffraction that the transition from crystalline peak to “glass-like” plateau is related to an increase in Sr guest atom off-centering distance from 0.24 Å to 0.43 Å. By modifying ab initio calculated force constants for the guest atom to an isotropic model, we reproduce both measured heat capacity and inelastic neutron scattering data. The transition from peak to plateau in the thermal conductivity can be modeled by a combined increase of Rayleigh and disorder scattering. Measurement of heat capacity refutes simple models for tunneling of Sr between off-center sites. Furthermore, the electronic properties of the same samples are characterized by Hall carrier density, Seebeck coefficient, and resistivity. The present comprehensive analysis excludes tunneling and charge carrier scattering as dominant contributors to the “glass-like” plateau. The increased guest atom off-centering distance controlled by synthesis provides a possible microscopic mechanism for reducing the low temperature thermal conductivity of clathrates.

Molecular dynamics study on the structure I clathrate-hydrate of methane + ethane mixture

International Nuclear Information System (INIS)

Erfan-Niya, Hamid; Modarress, Hamid; Zaminpayma, Esmaeil

2011-01-01

Molecular dynamics (MD) simulations are used to study the structure I stability of methane + ethane clathrate-hydrates at temperatures 273, 275 and 277 K. NVT- and NPT-ensembles are utilized in MD simulation, and each consists of 3 x 3 x 3 replica unit cells containing 46 water molecules which are considered as the host molecules and up to eight methane + ethane molecules considered as the guest molecules. In MD simulations for host-host interactions, the potential model used was a type of simple point charge (SPC) model, and for guest-guest and host-guest interactions the potential used was Lennard-Jones model. In the process of MD simulation, achieving equilibrium of the studied system was recognized by stability in calculated pressure for NVT-ensemble and volume for NPT-ensemble. To understand the characteristic configurations of the structure I hydrate, the radial distribution functions (RDFs) of host-host, host-guest and guest-guest molecules as well as other properties including kinetic energy, potential energy and total energy were calculated. The results show that guest molecules interaction with host molecules cannot decompose the hydrate structure, and these results are consistent with most previous experimental and theoretical investigations that methane + ethane mixtures form structure I hydrates over the entire mixture composition range.

NMR and computational study of Ba{sub 8}Cu{sub x}Ge{sub 46-x} clathrate semiconductors

Energy Technology Data Exchange (ETDEWEB)

Chen, Jing-Han, E-mail: jhchen@tamu.edu; Sirusi Arvij, Ali; Zheng, Xiang; Rodriguez, Sergio Y.; Ross, Joseph H.

2014-04-01

Highlights: • Quadrupole NMR with first-principles calculations probes local site preferences. • Cu/Ge ratio is clarified vs. the ideal Zintl composition. • Modified Becke–Johnson exchange potential agrees well with NMR Knight shifts. - Abstract: Ba{sub 8}Cu{sub x}Ge{sub 46-x} is a type-I clathrate material that forms as a semiconductor in a narrow composition range corresponding to the electron-balanced Zintl composition, with x = 5.3. We use NMR spectroscopy combined with ab initio electronic structure calculations to probe the electronic and structural behavior of these materials. Computational results based on a superstructure model for the atomic configuration of the alloy provide good agreement with the electric quadrupole-broadened NMR lineshapes. Modeling using the modified Becke–Johnson (TB-mBJ) exchange potential is also shown to agree well with experimental NMR Knight shifts. The results indicate that the Cu–Ge balance is the main factor determining the carrier density, within a narrow stability range near the ideal Zintl composition.

Experimental investigation on TBAB clathrate hydrate slurry flows in a horizontal tube: Forced convective heat transfer behaviors

Energy Technology Data Exchange (ETDEWEB)

Wenji, Song [Guangzhou Institute of Energy Conversion, CAS, No. 2 Nengyuan Road, Tianhe District, Guangzhou 510640 (China); Key Laboratory of Renewable Energy and Gas Hydrate, CAS, No. 2 Nengyuan Road, Tianhe District, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Rui, Xiao; Chong, Huang; Shihui, He; Kaijun, Dong; Ziping, Feng [Guangzhou Institute of Energy Conversion, CAS, No. 2 Nengyuan Road, Tianhe District, Guangzhou 510640 (China); Key Laboratory of Renewable Energy and Gas Hydrate, CAS, No. 2 Nengyuan Road, Tianhe District, Guangzhou 510640 (China)

2009-11-15

Tetra-n-butyl-ammonium bromide (TBAB) clathrate hydrate slurry (CHS) is one kind of secondary refrigerants, which is promising to be applied into air-conditioning or latent-heat transportation systems as a thermal storage or cold carrying medium for energy saving. It is a solid-liquid two phase mixture which is easy to produce and has high latent heat and good fluidity. In this paper, the heat transfer characteristics of TBAB slurry were investigated in a horizontal stainless steel tube under different solid mass fractions and flow velocities with constant heat flux. One velocity region of weakened heat transfer was found. Moreover, TBAB CHS was treated as a kind of Bingham fluids, and the influences of the solid particles, flow velocity and types of flow on the forced convective heat transfer coefficients of TBAB CHS were investigated. At last, criterial correlations of Nusselt number for laminar and turbulent flows in the form of power function were summarized, and the error with experimental results was within {+-}20%. (author)

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

Science.gov (United States)

Weinsten, A.; Navarrete, L; Ruppel, Carolyn D.; Weber, T.C.; Leonte, M.; Kellermann, M.; Arrington, E.; Valentine, D.L.; Scranton, M.L; Kessler, John D.

2016-01-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern US Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady-state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6 – 24 kmol methane per day). These analyses suggest this methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH. This article is protected by copyright. All rights reserved.

Thermoelectric material including a multiple transition metal-doped type I clathrate crystal structure

Science.gov (United States)

Yang, Jihui [Lakeshore, CA; Shi, Xun [Troy, MI; Bai, Shengqiang [Shanghai, CN; Zhang, Wenqing [Shanghai, CN; Chen, Lidong [Shanghai, CN; Yang, Jiong [Shanghai, CN

2012-01-17

A thermoelectric material includes a multiple transition metal-doped type I clathrate crystal structure having the formula A.sub.8TM.sub.y.sub.1.sup.1TM.sub.y.sub.2.sup.2 . . . TM.sub.y.sub.n.sup.nM.sub.zX.sub.46-y.sub.1.sub.-y.sub.2.sub.- . . . -y.sub.n.sub.-z. In the formula, A is selected from the group consisting of barium, strontium, and europium; X is selected from the group consisting of silicon, germanium, and tin; M is selected from the group consisting of aluminum, gallium, and indium; TM.sup.1, TM.sup.2, and TM.sup.n are independently selected from the group consisting of 3d, 4d, and 5d transition metals; and y.sub.1, y.sub.2, y.sub.n and Z are actual compositions of TM.sup.1, TM.sup.2, TM.sup.n, and M, respectively. The actual compositions are based upon nominal compositions derived from the following equation: z=8q.sub.A-|.DELTA.q.sub.1|y.sub.1-|.DELTA.q.sub.2|y.sub.2- . . . -|.DELTA.q.sub.n|y.sub.n, wherein q.sub.A is a charge state of A, and wherein .DELTA.q.sub.1, .DELTA.q.sub.2, .DELTA.q.sub.n are, respectively, the nominal charge state of the first, second, and n-th TM.

Free NH3 quantum rotations in Hofmann clathrates: structure factors and line widths studied by inelastic neutron scattering

International Nuclear Information System (INIS)

Sobolev, O.; Vorderwisch, P.; Desmedt, A.

2005-01-01

Quantum rotations of NH 3 groups in Hofmann clathrates Ni-Ni-C 6 H 6 and Ni-Ni-C 12 H 10 have been studied using inelastic neutron scattering. Calculations of the dynamical structure factor for a free uniaxial quantum rotor reproduce the neutron scattering data with respect to their Q- and T-dependence as well as the relative intensities for the 0 → 1, 0 → 2 and 1 → 2 transitions. Though the effective NH 3 rotation constant is different from the gas phase value, the effective radius of rotation (i.e., the average distance of protons from the rotation axis) is equal or very close to the geometrical value r = 0.94 A for a NH 3 group. Comparing the experimental data with the calculated dynamical structure factor for the 0 → 3 transition it could be shown, that the corresponding transition line, in contrast to transitions between j = 0,1,2 levels measured so far, has a finite width at T = 0 K

Energy consumption estimation for greenhouse gas separation processes by clathrate hydrate formation

International Nuclear Information System (INIS)

Tajima, Hideo; Yamasaki, Akihiro; Kiyono, Fumio

2004-01-01

The process energy consumption was estimated for gas separation processes by the formation of clathrate hydrates. The separation process is based on the equilibrium partition of the components between the gaseous phase and the hydrate phase. The separation and capturing processes of greenhouse gases were examined in this study. The target components were hydrofluorocarbon (HFC-134a) from air, sulfur hexafluoride (SF 6 ) from nitrogen, and CO 2 from flue gas. Since these greenhouse gases would form hydrates under much lower pressure and higher temperature conditions than the accompanying components, the effective capturing of the greenhouse gases could be achieved by using hydrate formation. A model separation process for each gaseous mixture was designed from the basis of thermodynamics, and the process energy consumption was estimated. The obtained results were then compared with those for conventional separation processes such as liquefaction separation processes. For the recovery of SF 6 , the hydrate process is preferable to liquefaction process in terms of energy consumption. On the other hand, the liquefaction process consumes less energy than the hydrate process for the recovery of HFC-134a. The capturing of CO 2 by the hydrate process from a flue gas will consume a considerable amount of energy; mainly due to the extremely high pressure conditions required for hydrate formation. The influences of the operation conditions on the heat of hydrate formation were elucidated by sensitivity analysis. The hydrate processes for separating these greenhouse gases were evaluated in terms of reduction of global warming potential (GWP)

Coloration and darkening of methane clathrate and other ices by charged particle irradiation - Applications to the outer solar system

Science.gov (United States)

Thompson, W. Reid; Murray, B. G. J. P. T.; Khare, B. N.; Sagan, Carl

1987-01-01

The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

An effect of surface properties on detachment of adhered solid to cooling surface for formation of clathrate hydrate slurry

Science.gov (United States)

Daitoku, Tadafumi; Utaka, Yoshio

In air-conditioning systems, it is desirable that the liquid-solid phase change temperature of a cool energy storage material is approximately 10 °C from the perspective of improving coefficient of performance (COP). Moreover, a thermal storage material that forms slurry can realize large heat capacity of working fluids. Since the solid that adheres to the heat transfer surface forms a thermal resistance layer and remarkably reduces the rate of cold storage, it is important to avoid the adhesion of a thick solid layer on the surface so as to realize efficient energy storage. Considering a harvest type cooling unit, the force required for removing the solid phase from the heat transfer surface was studied. Tetra-n-butylammonium Bromide (TBAB) clathrate hydrate was used as a cold storage material. The effect of the heat transfer surface properties on the scraping force for detachment of adhered solid of TBAB hydrate to the heat transfer surface was examined experimentally.

Major occurrences and reservoir concepts of marine clathrate hydrates: Implications of field evidence

Science.gov (United States)

Booth, J.S.; Winters, W.J.; Dillon, William P.; Clennell, M.B.; Rowe, M.M.

1998-01-01

This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert). Questions concerning clathrate hydrate as an energy resource, as a factor in modifying global climate and as a triggering mechanism for mass movements invite consideration of what factors promote hydrate concentration, and what the quintessential hydrate-rich sediment may be. Gas hydrate field data, although limited, provide a starting point for identifying the environments and processes that lead to more massive concentrations. Gas hydrate zones are up to 30 m thick and the vertical range of occurrence at a site may exceed 200 m. Zones typically occur more than 100m above the phase boundary. Thicker zones are overwhelmingly associated with structural features and tectonism, and often contain sand. It is unclear whether an apparent association between zone thickness and porosity represents a cause-and-effect relationship. The primary control on the thickness of a potential gas hydrate reservoir is the geological setting. Deep water and low geothermal gradients foster thick gas hydrate stability zones (GHSZs). The presence of faults, fractures, etc. can favour migration of gas-rich fluids. Geological processes, such as eustacy or subsidence, may alter the thickness of the GHSZ or affect hydrate concentratiion. Tectonic forces may promote injection of gas into the GHSZ. More porous and permeable sediment, as host sediment properties, increase storage capacity and fluid conductivity, and thus also enhance reservoir potential.

Dielectric relaxation of guest molecules in a clathrate structure of syndiotactic polystyrene.

Science.gov (United States)

Urakawa, Osamu; Kaneko, Fumitoshi; Kobayashi, Hideo

2012-12-13

Structure and dynamics of semicrystalline polymer films composed of syndiotactic polystyrene (sPS) and 2-butanone were examined through X-ray diffraction, polarized FTIR, and dielectric relaxation measurements. The X-ray and FTIR measurements revealed its crystal structure to be δ-clathrate containing 2-butanone molecules inside. The carbonyl group of 2-butanone in the crystal was found to orient preferentially parallel to the ac plane of the crystal through the polarized ATR FTIR measurements. Dielectric measurements were also conducted on these film samples to see only the relaxation dynamics of 2-butanone thanks to the high dielectric intensity of 2-butanone compared to sPS. Two relaxation modes denoted by slow and fast modes appeared. The former was assigned to the motion of 2-butanone molecules entrapped in the cavities of the crystalline (δ-form) and the latter to those in the amorphous region. We focused on the slow mode in order to elucidate the specific dynamics of the guest molecule confined in the crystalline region. The relaxation time of the slow mode was about 4 orders of magnitude longer than that of liquid 2-butanone. This suggests that the dynamics of guest molecules is highly restricted due to the high barrier to conformational and/or orientational change of the guest molecule in the cavity of δ-crystal. Furthermore, the dielectric intensity Δε of the slow mode was much smaller than the one calculated from that of bulk liquid 2-butanone and the guest concentration in the crystalline region (the intensity was only 10% of the estimated value from the bulk liquid data). This result also indicates that the free rotational motion of 2-butanone molecules is restricted inside the crystal. This will be consistently related to the weak uniplanar orientation of the carbonyl group of 2-butanone parallel to the ac plane revealed by the X-ray and polarized ATR FTIR measurements.

Pre-combustion capture of carbon dioxide in a fixed bed reactor using the clathrate hydrate process

International Nuclear Information System (INIS)

Babu, Ponnivalavan; Kumar, Rajnish; Linga, Praveen

2013-01-01

Hydrate based gas separation (HBGS) process with silica sand and silica gel as contact medium was employed to capture CO 2 from fuel gas mixture. Gas uptake measurement at three different pressures (7.5, 8.5 and 9.0 MPa) and 274.15 K were conducted for hydrate formation kinetics and overall conversion of water to hydrate, rate of hydrate formation were determined. Water conversion of up to 36% was achieved with silica sand bed compared to 13% conversion in the silica gel bed. Effect of driving force on the rate of hydrate formation and gas consumption was significant in silica sand bed whereas it was found to be insignificant in silica gel bed. Hydrate dissociation experiments by thermal stimulation (at constant pressure) alone and a combination of depressurization and thermal stimulation were carried out for complete recovery of the hydrated gas. A driving force of 23 K was found to be sufficient to recover all the hydrated gas within 1 h. This study indicates that silica sand can be an effective porous media for separation of CO 2 from fuel gas when compared to silica gel. - Highlights: ► The clathrate process for pre-combustion capture of carbon dioxide in a novel fixed bed reactor is presented. ► Performance of two contact media (silica gel and silica sand) was investigated. ► Water to hydrate conversion was higher in a silica sand column. ► A pressure reduction and thermal stimulation approach is presented for a complete recovery of the hydrated gas

M(4-PridinkarboksialdehidNi(CN4.nG Hofmann Tipi Konak-Konuk Bileşiklerinin Kırmızıaltı Spektroskopik Özelliklerinin İncelenmesi (M = Ni, Cd ve G = 1,4-Dioksan

Directory of Open Access Journals (Sweden)

Zeki KARTAL

2014-12-01

M(4-PyridinecarboxaldehydeNi(CN4.nG Hofmann Type Clathrates (M = Ni, Cd and G = 1,4-Dioxane Abstract: In this study, clathrate of 4-pyridinecarboxaldehyde tetracyanonickel-dioxane, given by the formula M(4-PyridinecarboxaldehydeNi(CN4 nG (m = Ni, Cd and G = 1,4-dioxane, is obtained for the first time through chemical methods. The FT-IR spectroscopic data in the region of (3000–400 cm-1 was recorded and the IR vibrational modes frequencies were given and explained in detail. The spectral analyzes results of the newly synthesized clathrate of 4-pyridinecarboxaldehyde tetracyanonickel- dioxane suggests that these clathrates are new examples of the Hofmann-type dioxane clathrates. In our study, the Hofmann-type dioxane clathrates formed by bounding electrons of nitrogen-donor atom of pyridine ring and electrons of oxygen-donor atom of aldehyde group (-CH=O of 4-pyridinecarboxaldehyde ligand molecule to transition metal atoms consist of the corrugated |M–Ni(CN4|ï‚¥ polymeric layers which are held in parallel through the chain of (–M–4PCA–M–. Key words: Infrared Spectroscopy, Hofmann Types Clathrates, Tetracyanonickelate, 4-pyridinecarboxaldehyde, 1,4-dioxane

Crystallization of tetra-n-butyl ammonium bromide clathrate hydrate slurry and the related heat transfer characteristics

International Nuclear Information System (INIS)

Shi, X.J.; Zhang, P.

2014-01-01

Highlights: • Crystallization characteristics of TBAB CHS under different thermal conditions were clarified. • Overall heat transfer coefficients before and during the crystallization were obtained. • The crystallization characteristics of TBAB CHS mainly depend on the status of supercooled solution. • Dropping of TBAB CHS can accelerate the supercooling release and crystallization. - Abstract: Tetra-n-butyl ammonium bromide (TBAB) clathrate hydrate slurry (CHS) is a promising phase change material slurry for cold storage and transport in air-conditioning system. This slurry can be generated from the supercooled TBAB aqueous solution. In the present study, TBAB CHS was generated under different thermal conditions, i.e. different initial mass concentrations of TBAB aqueous solution and different supercooling degrees. The crystallization of TBAB CHS and the overall heat transfer coefficient under different thermal conditions were clarified. It was concluded that the crystallization characteristics of TBAB hydrate crystals mainly depended upon the thermal condition of the supercooled TBAB aqueous solution. In addition, the dropping of pre-produced TBAB CHS into supercooled TBAB aqueous solution could immediately induce the crystallization of TBAB hydrate crystals, and the initial type of TBAB hydrate crystals was only related to the status of the supercooled TBAB aqueous solution regardless of the type of the dropped TBAB CHS. Furthermore, the overall heat transfer coefficients before crystallization and during crystallization were also measured. It was found that more hydrate crystals would adhere to the vessel wall at larger supercooling degree and higher mass concentration of aqueous solution, which would deteriorate the heat transfer significantly. Moreover, images of TBAB hydrate crystals under different thermal conditions were recorded in order to help clarifying the crystallization characteristics

Two-component, ab initio potential energy surface for CO2-H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both.

Science.gov (United States)

Wang, Qingfeng Kee; Bowman, Joel M

2017-10-28

We report an ab initio, full-dimensional, potential energy surface (PES) for CO 2 -H 2 O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D 0 , of 787 cm -1 is obtained using that ZPE, D e , and the rigorous ZPEs of the monomers. Using a benchmark D e , D 0 is 758 cm -1 . Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO 2 hydrate clathrate CO 2 (H 2 O) 20 (5 12 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO 2 .

Effect of Transition Metal Substitution on the Structure and Properties of a Clathrate-Like Compound Eu7Cu44As23

Directory of Open Access Journals (Sweden)

Igor V. Plokhikh

2016-07-01

Full Text Available A series of substitutional solid solutions—Eu7Cu44−xTxAs23 (T = Fe, Co, Ni—based on a recently discovered clathrate-like compound (Eu7Cu44As23 were synthesized from the elements at 800 °C. Almost up to 50% of Cu can be substituted by Ni, resulting in a linear decrease of the cubic unit cell parameter from a = 16.6707(1 Å for the ternary compound to a = 16.3719(1 Å for the sample with the nominal composition Eu7Cu24Ni20As23. In contrast, Co and Fe can only substitute less than 20% of Cu. Crystal structures of six samples of different composition were refined from powder diffraction data. Despite very small differences in scattering powers of Cu, Ni, Co, and Fe, we were able to propose a reasonable model of dopant distribution over copper sites based on the trends in interatomic distances as well as on Mössbauer spectra for the iron-substituted compound Eu7Cu36Fe8As23. Ni doping increases the Curie temperature to 25 K with respect to the parent compound, which is ferromagnetically ordered below 17.5 K, whereas Fe doping suppresses the ferromagnetic ordering in the Eu sublattice.

Performance of local correlation methods for halogen bonding: The case of Br2-(H2O)n,n = 4,5 clusters and Br2@5(12)6(2) clathrate cage.

Science.gov (United States)

Batista-Romero, Fidel A; Pajón-Suárez, Pedro; Bernal-Uruchurtu, Margarita I; Hernández-Lamoneda, Ramón

2015-09-07

The performance of local correlation methods is examined for the interactions present in clusters of bromine with water where the combined effect of hydrogen bonding (HB), halogen bonding (XB), and hydrogen-halogen (HX) interactions lead to many interesting properties. Local methods reproduce all the subtleties involved such as many-body effects and dispersion contributions provided that specific methodological steps are followed. Additionally, they predict optimized geometries that are nearly free of basis set superposition error that lead to improved estimates of spectroscopic properties. Taking advantage of the local correlation energy partitioning scheme, we compare the different interaction environments present in small clusters and those inside the 5(12)6(2) clathrate cage. This analysis allows a clear identification of the reasons supporting the use of local methods for large systems where non-covalent interactions play a key role.

Experimental study and thermodynamic modelling of methane clathrate hydrate dissociation conditions in silica gel porous media in the presence of methanol aqueous solution

International Nuclear Information System (INIS)

Hashemi, Hamed; Javanmardi, Jafar; Zarifi, Mojdeh; Eslamimanesh, Ali; Mohammadi, Amir H.

2012-01-01

Highlights: ► Phase equilibria of hydrates of methane in confined silica gel pores are reported. ► Dissociation data in the presences of methanol aqueous solution are also measured. ► A thermodynamic model is developed for prediction of the obtained data. ► Acceptable agreement is found between the obtained data and the predicted results. - Abstract: In this work, the phase equilibria of clathrate hydrates of methane in the presence of pure water and 0.035 mass fraction of methanol aqueous solution in confined silica gel pores with (10 and 15) nm mean diameters are measured and reported. A thermodynamic model is also developed for prediction of the obtained experimental hydrate dissociation data. The Valderrama–Patel–Teja (VPT-EoS) equation of state (EoS) accompanied with the non-density dependent (NDD) mixing rules coupled with a previously developed activity model are applied to evaluate the fugacity of the species present and the activity coefficient of water in methanol aqueous solution. Acceptable agreement between the reported data and the predicted results using the proposed model and an existing method reported in the literature demonstrates the reliability of the presented model.

Two-component, ab initio potential energy surface for CO2—H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both

Science.gov (United States)

Wang, Qingfeng Kee; Bowman, Joel M.

2017-10-01

We report an ab initio, full-dimensional, potential energy surface (PES) for CO2—H2O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D0, of 787 cm-1 is obtained using that ZPE, De, and the rigorous ZPEs of the monomers. Using a benchmark De, D0 is 758 cm-1. Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO2 hydrate clathrate CO2(H2O)20(512 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO2.

Crystal structure, characterization and thermoelectric properties of the type-I clathrate Ba8-ySryAl14Si32 (0.6≤y≤1.3) prepared by aluminum flux

International Nuclear Information System (INIS)

Roudebush, John H.; Toberer, Eric S.; Hope, Hakon; Jeffrey Snyder, G.; Kauzlarich, Susan M.

2011-01-01

The title compound was prepared as single crystals using an aluminum flux technique. Single crystal and powder X-ray diffraction indicate that this composition crystallizes in the clathrate type-I structure, space group Pm3-bar n. Electron microprobe characterization indicates the composition to be Ba 8-y Sr y Al 14.2(2) Si 31.8(2) (0.77 1 =0.0233, wR 2 =0.0441) on a crystal of compositions Ba. The Sr atom preferentially occupies the 2a position; mixed Al/Si occupancy was found on all framework sites. These refinements are consistent with a fully occupied framework and nearly fully occupied cation guest sites as found by microprobe analysis. Temperature dependent electrical resistivity and thermal conductivity have been measured from room temperature to 1200 K on a hot-pressed pellet. Electrical resistivity reveals metallic behavior. The negative Seebeck coefficient indicates transport processes dominated by electrons as carriers. Thermal conductivity is between 22 and 25 mW/cm K. The sample shows n-type conductivity with a maximum figure of merit, zT of 0.3 at 1200 K. A single parabolic band model predicts a five-fold increase in zT at 800 K if carrier concentration is lowered. -- Graphical abstract: The inorganic type-I clathrate phase with nominal composition Ba 7 Sr 1 Al 14 Si 32 has been prepared by Al flux. Single crystal diffraction at 90 and 12 K reveal that the framework is fully occupied with the cation sites nearly fully occupied. The lattice thermal conductivity is low thereby suggesting further optimization of the carrier concentration will lead to a high zT. Display Omitted Highlights: → Ba 7 Sr 1 Al 14 Si 32 is a light element phase ideal for thermoelectric power generation. → Ba 7 Sr 1 Al 14 Si 32 is a high melting point cubic structure ideal for efficient power generation. → The framework is fully occupied with the cation sites nearly fully occupied. → Further optimization of the carrier concentration is expected to lead to a high zT.

Phase equilibrium condition measurements in nitrogen and air clathrate hydrate forming systems at temperatures below freezing point of water

International Nuclear Information System (INIS)

Yasuda, Keita; Oto, Yuya; Shen, Renkai; Uchida, Tsutomu; Ohmura, Ryo

2013-01-01

Highlights: • Phase equilibrium conditions in the nitrogen and modelled air hydrate forming systems are measured. • Measurements are conducted at temperatures below the freezing point of water. • Results have relevance to the air hydrate formation in the ice sheets. • Measured data are quantitatively compared with the previously reported values. • Range of the equilibrium measurements was from (242 to 268) K. -- Abstract: Contained in this paper are the three phase equilibrium conditions of the (ice + clathrate hydrate + guest-rich) vapour in the (nitrogen + water) and the modelled (air + water) systems at temperatures below the freezing point of water. The precise determination of the equilibrium conditions in those systems are of importance for the analysis of the past climate change using the cored samples from the ice sheets at Antarctica and Greenland because the air hydrates keep the ancient climate signals. The mole ratio of the modelled air composed of nitrogen and oxygen is 0.790:0.210. The equilibrium conditions were measured by the batch, isochoric procedure. The temperature range of the measurements in the nitrogen hydrate forming system is (244.05 < T < 266.55) K and the corresponding equilibrium pressure range is (7.151 < p < 12.613) MPa. The temperature range of the measurements in the modelled air hydrate forming system is (242.55 < T < 267.85) K, and the corresponding equilibrium pressure range is (6.294 < p < 12.144) MPa. The data obtained quantitatively compared with the previously reported data

Clathrate hydrate dissociation conditions of refrigerants R404A, R406A, R408A and R427A: Experimental measurements and thermodynamic modeling

International Nuclear Information System (INIS)

Hashemi, Hamed; Babaee, Saeedeh; Mohammadi, Amir H.; Naidoo, Paramespri; Ramjugernath, Deresh

2015-01-01

Highlights: • The application of refrigerant hydrates in cold storage systems is investigated. • Hydrate dissociation conditions of various refrigerants have been measured. • A correlative thermodynamic model was applied to the data. • Enthalpy of dissociation for the refrigerants studied calculated. • Experimental measurements performed over a wide range of pressures. - Abstract: Clathrate hydrate dissociation conditions were measured for four “alternative” refrigerants, viz. R404A, R406A, R408A and R427A. The experimental measurements were performed within the pressure range of (0.079 to 9.995) MPa and temperatures ranging from (272.7 to 288.7) K. An isochoric pressure-search method was used to perform the measurements. A thermodynamic model based on the van der Waals–Platteeuw (vdW–P) model was applied for the prediction of the dissociation conditions which were compared to the experimental measurements. The fluid phase was modeled using the MHV2 G E -EoS mixing rule along with the UNIFAC (original) activity model. The van der Waals–Platteeuw (vdW–P) model was used for the modeling of the hydrate phase. There was reasonable agreement between the experimental and predicted values

Thermodynamic model for predicting equilibrium conditions of clathrate hydrates of noble gases + light hydrocarbons: Combination of Van der Waals–Platteeuw model and sPC-SAFT EoS

International Nuclear Information System (INIS)

Abolala, Mostafa; Varaminian, Farshad

2015-01-01

Highlights: • Applying sPC-SAFT for phase equilibrium calculations. • Determining Kihara potential parameters for hydrate formers. • Successful usage of the model for systems with hydrate azeotropes. - Abstract: In this communication, equilibrium conditions of clathrate hydrates containing mixtures of noble gases (Argon, Krypton and Xenon) and light hydrocarbons (C 1 –C 3 ), which form structure I and II, are modeled. The thermodynamic model is based on the solid solution theory of Van der Waals–Platteeuw combined with the simplified Perturbed-Chain Statistical Association Fluid Theory equation of state (sPC-SAFT EoS). In dispersion term of sPC-SAFT EoS, the temperature dependent binary interaction parameters (k ij ) are adjusted; taking advantage of the well described (vapor + liquid) phase equilibria. Furthermore, the Kihara potential parameters are optimized based on the P–T data of pure hydrate former. Subsequently, these obtained parameters are used to predict the binary gas hydrate dissociation conditions. The equilibrium conditions of the binary gas hydrates predicted by this model agree well with experimental data (overall AAD P ∼ 2.17)

Method for solid state crystal growth

Science.gov (United States)

Nolas, George S.; Beekman, Matthew K.

2013-04-09

A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

Study of biogas storage; Biogas no chozo ni kansuru kenkyu

Energy Technology Data Exchange (ETDEWEB)

Fujii, I; Kimura, T; Umeda, H [Meiji University, Tokyo (Japan)

1997-11-25

Study was made on the storage method of a methane component in biogas mainly composed of CO2 and methane gases. Methane clathrate as molecular complex is one kind of clathrate compounds. Eight methane gas molecules are absorbed into 46 water molecules, or methane gas of 216 l is absorbed into water of 1 l, resulting in considerable compact methane storage. Although methane clathrate is usually stable only under a condition of low temperature and high pressure, its formation equilibrium shifts toward a low pressure/high temperature side by adding additives such as amine, ether and ketone. Acetone can shift formation pressure from 30 to 10atm at 1degC, and formation temperature from 1 to 10degC at 30atm. Although methane liquefaction is also an efficient storage method, it requires liquefaction temperature and pressure of -83degC and 45.6atm, respectively. The distance between methane molecules in clathrate lattice can be more shortened than that in high- pressure charged gas, suggesting higher storage efficiency. The study result showed that the handling of methane clathrate is possible around room temperature and pressure. 7 refs., 5 figs.

Performance of local correlation methods for halogen bonding: The case of Br{sub 2}–(H{sub 2}O){sub n},n = 4,5 clusters and Br{sub 2}@5{sup 12}6{sup 2} clathrate cage

Energy Technology Data Exchange (ETDEWEB)

Batista-Romero, Fidel A.; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón, E-mail: ramon@uaem.mx [Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209 (Mexico); Pajón-Suárez, Pedro [Instituto Superior de Tecnologías y Ciencias Aplicadas (InSTEC), Habana 6163 (Cuba)

2015-09-07

The performance of local correlation methods is examined for the interactions present in clusters of bromine with water where the combined effect of hydrogen bonding (HB), halogen bonding (XB), and hydrogen-halogen (HX) interactions lead to many interesting properties. Local methods reproduce all the subtleties involved such as many-body effects and dispersion contributions provided that specific methodological steps are followed. Additionally, they predict optimized geometries that are nearly free of basis set superposition error that lead to improved estimates of spectroscopic properties. Taking advantage of the local correlation energy partitioning scheme, we compare the different interaction environments present in small clusters and those inside the 5{sup 12}6{sup 2} clathrate cage. This analysis allows a clear identification of the reasons supporting the use of local methods for large systems where non-covalent interactions play a key role.

Mechanisms of Xenon Effect on Skin and Red Blood Cells

DEFF Research Database (Denmark)

Ponomarev, Alexander; Rodin, V.; Gurevich, Leonid

2017-01-01

The usage of Xenon (Xe) is known in anesthesia and biobanking areas. It is considered preservation effect of Xe is associated either with clathrate formation - solid gaseous structures or dissolution of Xe molecules in liquid phase without physical state modification (so-called hyperbarium) [1......]. This study is addressed to establish differences between hyberbarium or clathrate Xe actions as well as its applications on various bioobjects with anaerobic - red blood cells (RBCs) and aerobic (skin fragments) metabolism. Xe clathrates and hyperbarium storage were simulated under 277 K and 620-725 k...... to control (15.68 ± 1.11, CI95%). Skin fragments were harvested from rat tails and divided on hyberbarium, clathrate and dimetylsulfoxide cryopreserved as control group and stored for 7 days. Assessment was performed by point-score method including epidermal-dermal integrity various assays and engraftment...

Phase Behaviour of Methane Hydrate Under Conditions Relevant to Titan's Interior

Science.gov (United States)

Sclater, G.; Fortes, A. D.; Crawford, I. A.

2018-06-01

The high-pressure behaviour Clathrate hydrates, thought to be abundant in the outer solar system, underpins planetary modelling efforts of the interior of Titan, where clathrates are hypothesised to be the source of the dense N2, CH4 atmosphere.

Intermolecular Interactions at high pressure

DEFF Research Database (Denmark)

Eikeland, Espen Zink

2016-01-01

In this project high-pressure single crystal X-ray diffraction has been combined with quantitative energy calculations to probe the energy landscape of three hydroquinone clathrates enclosing different guest molecules. The simplicity of the hydroquinone clathrate structures together with their st...

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: Energetics, occupancy, and vibrationally averaged cluster structures

Science.gov (United States)

Sebastianelli, Francesco; Xu, Minzhong; Bačić, Zlatko

2008-12-01

We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H2 (p-H2) and ortho-D2 (o-D2) molecules inside the large hexakaidecahedral (51264) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H2)n and (o-D2)n clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H2)4. At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H2 or D2 molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D2 molecules, their mean distance from the cage center, the D2-D2 separation, and the specific orientation and localization of the tetrahedral (D2)4 cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D2 occupancy.

Inelastic neutron scattering and spectral measurements of advanced cold moderator materials

International Nuclear Information System (INIS)

Conrad, H.; Prager, M.; Nuenighoff, K.; Pohl, C.; Kuhs, W.F.

2004-01-01

Inelastic neutron scattering with emphasis on energetically low lying modes as well as cold neutron leakage measurements have been performed on four prospective advanced cold moderator materials. Employing the time-of-flight instrument SV29 at the Juelich FRJ-2 reactor, spectra have been obtained from synthetic methane clathrate, tetrahydro-furane (THF) clathrate, 1,3,5-trimethyl-benzene (mesitylene) and light water ice at several temperatures between 2 K and 70 K. Clearly separated excitations at energy transfers of ±1 meV, +2 meV and +3 meV have been observed with synthetic methane clathrate. In mesitylene a wealth of low lying excitations have been observed. In the quenched phase we found lines at 4.7, 7.2, 9.6, 13.6, 15.4, 18.4, 19.0, 23.0, 29.5 and 34.3 meV, respectively. In the annealed phase, we observed significant shifts with the majority of lines. The lowest lying lines now are located at 7.0, 8.5 and 10.5 meV, respectively. In hexagonal ice at T=2 K up to now unreported low lying energy levels were found at energy transfers of 1.8 meV and 2.8 meV. An additional line at about 10 meV could be detected in THF clathrate. Mesitylene, synthetic methane clathrate and water ice, all at T=20 K, have been tested as moderators at the Juelich spallation mock-up JESSICA. The expected gain in neutron leakage current at energies around 2 meV as compared to conventional liquid hydrogen moderators has been observed for methane clathrate and mesitylene. (orig.)

Tracking "apolar" NMe4+ ions within two polyoxothiomolybdates that have the same pores: smaller clathrate and larger highly porous clusters in action.

Science.gov (United States)

Korenev, Vladimir S; Boulay, Antoine G; Haouas, Mohamed; Bannani, Fatma; Fedin, Vladimir P; Sokolov, Maxim N; Terazzi, Emmanuel; Garai, Somenath; Müller, Achim; Taulelle, Francis; Marrot, Jérôme; Leclerc, Nathalie; Floquet, Sébastien; Cadot, Emmanuel

2014-03-10

Two nanosized polyoxothiometalates were synthesized based on linking oxomolybdate building blocks with {Mo2O2S2}(2+) groups. Remarkably, both compounds are formed selectively primarily upon changing the related concentrations in a logical way; they exhibit common structural features based on the same {Mo9O6S3}-type pores, which result in connections between {Mo6O21} pentagons and {Mo2O2S2}(2+) linkers. Whereas the much larger spherical Mo132-type Keplerate contains twenty pores, the smaller Mo63 -type cluster remarkably contains only two. The two compounds and a similar Keplerate exhibit interesting supramolecular properties related to interactions with the unusual predominantly apolar NMe4(+) cations. Structural characterization of the Mo63 -type compound reveals in the solid state a clathrate-like species that contains four NMe4(+) cations embedded in two types of structurally well-adapted pockets. Related NMR spectroscopic investigations in solution using NMe4(+) as the NMR spectroscopic probe are in agreement with the solid-state description. (1)H NMR spectroscopic experiments (1D variable-temperature, 2D total correlation spectroscopy (TOCSY), exchange spectroscopy (EXSY), and diffusion-ordered spectroscopy (DOSY)) feature firmly immobilized and mobile NMe4(+) ions in relationship with the type of host-guest arrangements. The use of the (1)H NMR DOSY spectroscopic methodology has been successfully applied to track the interactions of the NMe4(+) cations with the {Mo9O6S3} pores of a sulfurated Keplerate, thereby allowing the first quantitative analysis of this type of plugging process. The stability constant K=(210±20) mol(-1)  L is discussed related to the character of the process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A comparative study of different methods for the generation of tetra-n-butyl ammonium bromide clathrate hydrate slurry in a cold storage air-conditioning system

International Nuclear Information System (INIS)

Shi, X.J.; Zhang, P.

2013-01-01

Highlights: ► Four kinds of TBAB CHS generation methods are experimentally investigated. ► Accession of CHS into supercooled solution can be helpful to the generation. ► Higher flow rate results in higher energy efficiency of CHS generation. - Abstract: A cold storage air-conditioning system using tetra-n-butyl ammonium bromide (TBAB) clathrate hydrate slurry (CHS) as cold storage medium was built to investigate the high-efficiency method of TBAB CHS generation. In the present study, four kinds of different TBAB CHS generation methods were experimentally investigated and compared, and these methods included continuously cooling, turning off refrigerator while crystals appearing, supercooling release and accession of TBAB CHS into supercooled TBAB aqueous solution. The results showed that continuously cooling would lead to severe adhesion of crystal to the heat exchanger wall, and supercooling release took place with a big stochastic characteristic, hence the first and third method were concluded not reliable. Both the second and fourth methods could maintain the temperature of heat exchanger wall at a relatively higher level, therefore the crystal adhesion to the heat exchanger wall would be reduced significantly, which led to higher coefficient of performance (COP). In addition, accession of TBAB CHS into TBAB supercooled solution could shorten the time of supercooling release, resulting in about 21.8–35.4% shorter generation time than other methods. Moreover, the influence of flow rate on the CHS generation process was investigated, and the results showed that higher flow rate generally resulted in higher system COP

Atmospheric modeling of Mars CH4 subsurface clathrates releases mimicking SAM and 2003 Earth-based detections

Science.gov (United States)

Pla-García, J.; Rafkin, S. C.

2017-12-01

The aim of this work is to establish the amount of mixing during all martian seasons to test whether CH4 releases inside or outside of Gale crater are consistent with MSL-SAM observations. Several modeling scenarios were configured, including instantaneous and steady releases, both inside and outside the crater. A simulation to mimic the 2003 Earth-based detections (Mumma et al. 2009 or M09) was also performed. In the instantaneous release inside Gale experiments, Ls270 was shown to be the faster mixing season when air within and outside the crater was well mixed: all tracer mass inside the crater is diluted after just 8 hours. The mixing of near surface crater air with the external environment in the rest of the year is potentially rapid but slower than Ls270.In the instantaneous release outside Gale (NW) experiment, in just 12 hours the CH4 that makes it to the MSL landing location is diluted by six orders of magnitude. The timescale of mixing in MRAMS experiments is on the order of 1 sol regardless of season. The duration of the CH4 peak observed by SAM is 100 sols. Therefore there is a steady release inside the crater, or there is a very large magnitude steady release outside the crater. In the steady release Gale experiments, CH4 flux rate from ground is 1.8 kg m-2 s-1 (derived from Gloesener et al. 2017 clathrates fluxes) and it is not predictive. In these experiments, 200 times lower CH4 values detected by SAM are modeled around MSL location. There are CH4 concentration variations of orders of magnitude depending on the hour, so timing of SAM measurements is important. With a larger (but further away) outside crater release area compared to inside, similar CH4 values around MSL are modeled, so distance to source is important. In the steady experiments mimicking M09 detection release area, only 12 times lower CH4 values detected by SAM are modeled around MSL. The highest value in the M09 modeled scenario (0.6 ppbv) is reached in Ls270. This value is the

Probing the Subtle Structure Modifications of Thermoelectric Materials by Variable Temperature Total Scattering

DEFF Research Database (Denmark)

Reardon, Hazel; Iversen, Bo Brummerstedt; Blichfeld, Anders Bank

The complex host-guest structure of Type-I inorganic clathrates has been studied fervently within the CMC based on their low thermal conductivity and promising thermoelectric Figure of Merit (zT). We have recently been focused on understanding unusual features in the high temperature diffraction...... data collected over a number of years on Ba8Ga16Ge30 (BGG), where numerous samples have been prepared in-house using various synthesis methods. This led to a comprehensive thermal stability study of clathrate powders, where PXRD revealed amorphous components in the samples treated at high temperature...... in air. PDF measurements were performed on data collected from ex situ annealed BGG samples. This ex situ study (to be submitted), reveals that the seemingly subtle change in the clathrate structure and the emergence of a significant amorphous phase observed from PXRD data is likely to be the result...

Phase equilibria of carbon dioxide and methane gas-hydrates predicted with the modified analytical S-L-V equation of state

Directory of Open Access Journals (Sweden)

Span Roland

2012-04-01

Full Text Available Gas-hydrates (clathrates are non-stoichiometric crystallized solutions of gas molecules in the metastable water lattice. Two or more components are associated without ordinary chemical union but through complete enclosure of gas molecules in a framework of water molecules linked together by hydrogen bonds. The clathrates are important in the following applications: the pipeline blockage in natural gas industry, potential energy source in the form of natural hydrates present in ocean bottom, and the CO2 separation and storage. In this study, we have modified an analytical solid-liquid-vapor equation of state (EoS [A. Yokozeki, Fluid Phase Equil. 222–223 (2004] to improve its ability for modeling the phase equilibria of clathrates. The EoS can predict the formation conditions for CO2- and CH4-hydrates. It will be used as an initial estimate for a more complicated hydrate model based on the fundamental EoSs for fluid phases.

Precise structural analysis of methane hydrate by neutron diffraction

International Nuclear Information System (INIS)

Igawa, Naoki; Hoshikawa, Akinori; Ishii, Yoshinobu

2006-01-01

Methane hydrate has attracted great interest as an energy resource to replace natural gas since this material is deposited in the seafloor and the deposits are estimated to exceed those of natural gas. Understanding the physical proprieties, such as the temperature dependence of the crystal structure, helps to specify the optimum environmental temperature and pressure during drilling, transport, and storage of methane hydrate. Clathrate hydrates consisted of encaging atomic and/or molecular species as a guest and host water formed by a hydrogen bonding. Although many studies on the clathrate hydrate including methane hydrate were reported, no detailed crystallographic property has yet been cleared. We focused on the motion of methane in the clathrate hydrate by the neutron diffraction. The crystal structure of the methane hydrate was analyzed by the applying the combination of the Rietveld refinement and the maximum entropy method (MEM) to neutron powder diffraction. Temperature dependence of the scattering-length density distribution maps revealed that the motion of methane molecules differs between the shapes of dodecahedron and tetrakaidecahedron. (author)

Composition and method for hydrogen storage

Science.gov (United States)

Mao, Wendy L. (Inventor); Mao, Ho-Kwang (Inventor)

2004-01-01

A method for hydrogen storage includes providing water and hydrogen gas to a containment volume, reducing the temperature of the water and hydrogen gas to form a hydrogen clathrate at a first cryogenic temperature and a first pressure and maintaining the hydrogen clathrate at second cryogenic temperature within a temperature range of up to 250 K to effect hydrogen storage. The low-pressure hydrogen hydrate includes H.sub.2 O molecules, H.sub.2 molecules and a unit cell including polyhedron cages of hydrogen-bonded frameworks of the H.sub.2 O molecules built around the H.sub.2 molecules.

Finding New Thermoelectric Compounds Using Crystallographic Data: Atomic Displacement Parameters

International Nuclear Information System (INIS)

Chakoumakos, B.C.; Mandrus, D.G.; Sales, B.C.; Sharp, J.W.

1999-01-01

A new structure-property relationship is discussed which links atomic displacement parameters (ADPs) and the lattice thermal conductivity of clathrate-like compounds. For many clathrate-like compounds, in which one of the atom types is weakly bound and ''rattles'' within its atomic cage, room temperature ADP information can be used to estimate the room temperature lattice thermal conductivity, the vibration frequency of the ''rattler'', and the temperature dependence of the heat capacity. Neutron data and X-ray crystallography data, reported in the literature, are used to apply this analysis to several promising classes of thermoelectric materials

Geodetic data support trapping of ethane in Titan's polar crust

Science.gov (United States)

Sotin, Christophe; Rambaux, Nicolas

2016-04-01

Titan's surface is characterized by polar depressions that strongly influence interpretations of the gravity data. This study investigates several geodynamical models that can explain these depressions. For each model, the values of the three moments of inertia are computed numerically by discretizing the interior in spherical coordinates. The study shows that a Pratt model where the polar subsurface is made of ethane clathrates can explain the polar depression, the abrupt jump in altitude at about 60 degrees latitude, and the values of the degree 2 gravity coefficients. This model, proposed by Choukroun and Sotin [1], is based on the stability of ethane clathrate hydrates relative to methane clathrate hydrates. In addition to fitting the geodetic data, it explains the absence of ethane in Titan's atmosphere although ethane is the main product of the photolysis of methane. Other geophysical models based on latitudinal variations in the tidal heating production or in the heat flux at the base of the icy crust do not provide such a good match to the gravity and topographic observations. The ethane-clathrate model predicts that all the ethane produced by photolysis of methane at the present rate during the last billion years could be stored in the polar subsurface. It is consistent with the age of Titan's surface and that of Titan's atmospheric methane inferred from geological and geochemical observations by the Cassini/Huygens mission. The present study also emphasizes the role of mass anomalies on the interpretation of the degree 2 gravity coefficients. It shows that for Titan, a slow rotator, the values of the two equatorial moments of inertia (MoI) are largely affected by the polar depressions whereas the value of polar MoI is not. Therefore, as pointed out by previous calculations [2], calculating the moment of inertia (MoI) factor from the value of J2 could lead to major errors. This is not the case for our preferred Titan's model for which the negative polar

Early Mars serpentinization-derived CH4 reservoirs, H2 induced warming and paleopressure evolution

Science.gov (United States)

Lasue, J.; Chassefiere, E.; Langlais, B.; Quesnel, Y.

2016-12-01

CH4 has been observed on Mars both by remote sensing and in situ during the past 15 years. Early Mars serpentinization is one possible abiotic mechanism that could not only produce methane, but also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH4 as clathrates in stable form at depth. We recently estimated the maximum storage capacity of such clathrate layer to be about 2x1019 to 2x1020 moles of methane. Such reservoirs may be stable or unstable, depending on many factors that are poorly constrained: major and sudden geological events such as the Tharsis bulge formation, the Hellas impact or the martian polar wander, could have destabilized the clathrates early in the history of the planet and released large quantities of gas in the atmosphere. Here we estimate the associated amounts of serpentinization-derived CH4 stored in the cryosphere that have been released to the atmosphere at the end of the Noachian and the beginning of the Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH4 to H2, these episodes of massive CH4 release may have resulted in transient H2-rich atmospheres, at typical levels of 10-20% in a background 1-2 bar CO2 atmosphere. We propose that the early Mars cryosphere had a sufficient CH4 storage capacity to have maintained H2-rich transient atmospheres during a total time period up to several Myr or tens of Myr, having potentially contributed - by collision-induced heating effect of atmospheric H2 - to the formation of valley networks during the late Noachian and early Hesperian.

Advanced heat pumps and their economic aspects. The case for super heat pump

International Nuclear Information System (INIS)

Yabe, Akira; Akiya, Takaji

1996-01-01

The results of the economic evaluation of the Super Heat Pump Energy Accumulation System project in Japan are reviewed. It is reported that although the initial costs of super heat pumps are higher than those of conventional systems, the calculated operating costs of a unit thermal energy produced by a super heat pump is reduced considerably. All the various system concepts with thermal/chemical storage were evaluated economically with the exception of the high temperature thermal storage systems using salt ammonia complexes and solvation. These latter systems were not further developed as pilot plants. It is advocated to accelerate the introduction of super heat pumps by facilitating their market introduction. Actual clathrate chemical storage systems have shown that the annual costs are comparable to those of an ice storage system. Clathrate systems will find their way in the market. It is concluded that most of the super heat pump systems and clathrate storage systems will be economic in the future. A big challenge however still exists in further improving the cost effectiveness of heat storage in tanks by reducing their size dramatically (to 1/10th)

astrophysical significance

Directory of Open Access Journals (Sweden)

Dartois E.

2014-02-01

Full Text Available Clathrate hydrates, ice inclusion compounds, are of major importance for the Earth’s permafrost regions and may control the stability of gases in many astrophysical bodies such as the planets, comets and possibly interstellar grains. Their physical behavior may provide a trapping mechanism to modify the absolute and relative composition of icy bodies that could be the source of late-time injection of gaseous species in planetary atmospheres or hot cores. In this study, we provide and discuss laboratory-recorded infrared signatures of clathrate hydrates in the near to mid-infrared and the implications for space-based astrophysical tele-detection in order to constrain their possible presence.

Finding New Thermoelectric Compounds Using Crystallographic Data: Atomic Displacement Parameters

Energy Technology Data Exchange (ETDEWEB)

Chakoumakos, B.C.; Mandrus, D.G.; Sales, B.C.; Sharp, J.W.

1999-08-29

A new structure-property relationship is discussed which links atomic displacement parameters (ADPs) and the lattice thermal conductivity of clathrate-like compounds. For many clathrate-like compounds, in which one of the atom types is weakly bound and ''rattles'' within its atomic cage, room temperature ADP information can be used to estimate the room temperature lattice thermal conductivity, the vibration frequency of the ''rattler'', and the temperature dependence of the heat capacity. Neutron data and X-ray crystallography data, reported in the literature, are used to apply this analysis to several promising classes of thermoelectric materials.

The mysteries of memory effect and its elimination with antifreeze proteins

Energy Technology Data Exchange (ETDEWEB)

Walker, V.; Gordienko, R.; Kuiper, M.; Huva, E.; Wu, Z. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology; Zeng, H.; Ripmeester, J. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology]|[National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

2008-07-01

With the decline in easily accessible and conventional hydrocarbon supplies, exploration will focus on hydrocarbons in deep offshore waters, in permafrost or in crystalline water as gas hydrates. Crystallization of water or water-encaged gas molecules takes place when nuclei reach a critical size, but the crystal growth may be inhibited by certain antifreeze proteins (AFPs). In this study, the authors hypothesized that the crystal lattice of gas hydrates may act as an alternative for substrate antifreeze proteins (AFPs). AFP-mediated inhibition of ice and clathrate hydrate crystallization was examined. Since the AFPs had a notable ability to eliminate the memory effect (ME) or the faster reformation of clathrate hydrates after melting, the authors were prompted to examine heterogeneous nucleation. Silica, served as a model nucleator hydrophilic surface. Quartz crystal microbalance-dissipation (QCM-D) experiments showed that an active AFP was tightly adsorbed to the silica surface. However, polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap), 2 commercial hydrate kinetic inhibitors that do not eliminate ME, were not as tightly adsorbed. A mutant AFP inhibited tetrahydrofuran clathrate hydrate growth, but not ME. QCM-D analysis showed that adsorption of the mutant AFP was more similar to PVCap than the active AFP. It was concluded that although there is no evidence for memory in ice reformation, the crystallization of ice and hydrates, and the elimination of the more rapid recrystallization of hydrates, can be mediated by the same proteins. The properties of adsorbed layers can be effectively monitored by QCM-D. These study results provided useful information about the inhibition mechanism of heterogeneous nucleation of clathrate hydrate. The technique facilitates the screening of potential low dose hydrate inhibitors and residues in AFPs that are involved in silica adsorption. 24 refs., 1 tab., 4 figs.

Characterisation of poly(methacrylates) formed inside zeolites by gamma irradiation

International Nuclear Information System (INIS)

Kwiatkowski, J.; Whittaker, A.K.

1996-01-01

Full text: Inclusion polymerisation was first developed in the second half of the 50's as an alternative to Ziegler-Natta co-ordination polymerisation to obtain highly stereo-regular polymers. Inclusion polymerisation was performed in organic clathrates such as thio-urea channels. However the channels are only stable when formed around the monomer. This means there is a specific concentration of monomer, namely saturation, for which the host/channel system can exist. There is also a limited number of monomers which are suitable for use with a given clathrate and the channel dimension is not usually a variable parameter for a given monomer/clathrate system. One exception is Tris(o-phenolenedioxy)cycotriphosphazene. Initiation of the monomer can be easily achieved by high energy irradiation and many of the polymers obtained show considerable chemical and steric regularity. For example poly (2,3 -dimethylbutadiene) obtained by polymerisation in a thio-urea inclusion compound has only the 1,4 trans structure and is highly crystalline. The restriction on the number of clathrate and monomer systems has lead us to investigate the use of zeolites as hosts for inclusion compounds. Zeolites exist independently of any included guest compound. They are aluminosilicate compounds whose structures form molecular-dimension channels and belong to a class of materials known as molecular sieves. Channel structures can be in 1,2 or 3 dimensions. The structural aluminium in the zeolite creates a negative charge on the lattice which is balanced by cations. In this study we have diffused methyl and ethyl methacrylate into Na-ZSM5, Beta, Y and Mordenite zeolites. The samples where irradiated under vacuum and then extracted. The structures of the exrtracted polymer have been characterized by GPC, NMR and DSC The results will be correlated as a function of the channel size of the zeolite and compared to the bulk system

ORIGIN OF MOLECULAR OXYGEN IN COMET 67P/CHURYUMOV–GERASIMENKO

Energy Technology Data Exchange (ETDEWEB)

Mousis, O.; Ronnet, T.; Brugger, B.; Vernazza, P. [Aix Marseille Université, CNRS, LAM (Laboratoire d’Astrophysique de Marseille) UMR 7326, F-13388, Marseille (France); Ozgurel, O.; Pauzat, F.; Ellinger, Y.; Markovits, A. [Laboratoire de Chimie Théorique, Sorbonne Universités, UPMC Univ. Paris 06, CNRS UMR 7616, F-75252 Paris CEDEX 05 (France); Maggiolo, R. [Royal Institute for Space Aeronomy, 3 Avenue Circulaire, Brussels (Belgium); Wurz, P.; Altwegg, K.; Bieler, A.; Rubin, M. [Physikalisches Institut, University of Bern, Sidlerstrasse 5, CH-3012 Bern (Switzerland); Lunine, J. I. [Department of Astronomy and Carl Sagan Institute, Space Sciences Building Cornell University, Ithaca, NY 14853 (United States); Luspay-Kuti, A.; Mandt, K. E., E-mail: olivier.mousis@lam.fr [Department of Space Research, Southwest Research Institute, 6220 Culebra Rd., San Antonio, TX 78228 (United States)

2016-06-01

Molecular oxygen has been detected in the coma of comet 67P/Churyumov–Gerasimenko with abundances in the 1%–10% range by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis-Double Focusing Mass Spectrometer instrument on board the Rosetta spacecraft. Here we find that the radiolysis of icy grains in low-density environments such as the presolar cloud may induce the production of large amounts of molecular oxygen. We also show that molecular oxygen can be efficiently trapped in clathrates formed in the protosolar nebula (PSN), and that its incorporation as crystalline ice is highly implausible, because this would imply much larger abundances of Ar and N{sub 2} than those observed in the coma. Assuming that radiolysis has been the only O{sub 2} production mechanism at work, we conclude that the formation of comet 67P/Churyumov–Gerasimenko is possible in a dense and early PSN in the framework of two extreme scenarios: (1) agglomeration from pristine amorphous icy grains/particles formed in ISM and (2) agglomeration from clathrates that formed during the disk’s cooling. The former scenario is found consistent with the strong correlation between O{sub 2} and H{sub 2}O observed in comet 67P/Churyumov-Gerasimenko’s coma while the latter scenario requires that clathrates formed from ISM icy grains that crystallized when entering the PSN.

ORIGIN OF MOLECULAR OXYGEN IN COMET 67P/CHURYUMOV–GERASIMENKO

International Nuclear Information System (INIS)

Mousis, O.; Ronnet, T.; Brugger, B.; Vernazza, P.; Ozgurel, O.; Pauzat, F.; Ellinger, Y.; Markovits, A.; Maggiolo, R.; Wurz, P.; Altwegg, K.; Bieler, A.; Rubin, M.; Lunine, J. I.; Luspay-Kuti, A.; Mandt, K. E.

2016-01-01

Molecular oxygen has been detected in the coma of comet 67P/Churyumov–Gerasimenko with abundances in the 1%–10% range by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis-Double Focusing Mass Spectrometer instrument on board the Rosetta spacecraft. Here we find that the radiolysis of icy grains in low-density environments such as the presolar cloud may induce the production of large amounts of molecular oxygen. We also show that molecular oxygen can be efficiently trapped in clathrates formed in the protosolar nebula (PSN), and that its incorporation as crystalline ice is highly implausible, because this would imply much larger abundances of Ar and N_2 than those observed in the coma. Assuming that radiolysis has been the only O_2 production mechanism at work, we conclude that the formation of comet 67P/Churyumov–Gerasimenko is possible in a dense and early PSN in the framework of two extreme scenarios: (1) agglomeration from pristine amorphous icy grains/particles formed in ISM and (2) agglomeration from clathrates that formed during the disk’s cooling. The former scenario is found consistent with the strong correlation between O_2 and H_2O observed in comet 67P/Churyumov-Gerasimenko’s coma while the latter scenario requires that clathrates formed from ISM icy grains that crystallized when entering the PSN.

Morphology studies on gas hydrates interacting with silica gel

Energy Technology Data Exchange (ETDEWEB)

Beltran, J.; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering

2008-07-01

Clathrate hydrates or gas hydrates are non-stoichiometric, crystalline compounds that form when small molecules come in contact with water at certain temperatures and pressures. Natural gas hydrates are found in the ocean bottom and in permafrost regions. It is thought that the amount of energy stored in natural hydrates is at least twice that of all other fossil fuels combined. In addition, trapping carbon dioxide as a hydrate in the bottom of the ocean has been suggested as an alternative means of reducing atmospheric carbon dioxide levels. Naturally occurring clathrates are found in close interaction with fine grained particles of very small mean pore diameters. Even though an increasing amount of hydrate equilibrium data for small diameter porous media has become available, the morphological behavior of hydrates subject to such conditions is yet to be explored. This paper presented a study that visually examined hydrate formation and decomposition of gas hydrates while interacting with fine grains of silica gel. The study showed still frames from high-resolution video recordings for hydrate formation and decomposition. The paper discussed the experiment including the apparatus as well as the results of hydrate formation and hydrate dissociation. This study enabled for the first time to observe clathrate morphology while hydrates interacted closely with fine grain particles with small mean pore diameters. 9 refs., 8 figs.

Description of gas hydrates equilibria in sediments using experimental data of soil water potential

Energy Technology Data Exchange (ETDEWEB)

Istomin, V. [NOVATEK, Moscow (Russian Federation); Chuvilin, E. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology; Makhonina, N.; Kvon, V. [VNIIGAZ, Moscow (Russian Federation); Safonov, S. [Schlumberger Moscow Research, Moscow (Russian Federation)

2008-07-01

Analytical relationships have been developed between hydrate dissociation pressure and vapor pressure above the pore water surface. In addition, experiments have been discussed in numerous publications on the effect of narrow interconnected throats between pores on clathrate dissociation conditions in porous media. This paper presented an approach that improved upon the available thermodynamic methods for calculation of hydrate phase equilibria. The approach took into account the properties of pore water in natural sediments including three-phase equilibrium of gas-pore water-gas hydrate in a similar way as for unfrozen water in geocryology science. The purpose of the paper was to apply and adapt geocryology and soil physics method to the thermodynamic calculation of non-clathrated water content in sediments. It answered the question of how to estimate the non-clathrated water content if pore water potential was known. The paper explained the thermodynamics of water phase in porous media including the thermodynamic properties of supercooled water, the thermodynamic properties of pore water and pore ice in sediments, and the phase equilibria of pore water. The paper also discussed the quantitative techniques that were utilized for determination of unfrozen water content in sediments and its dependence on temperature variation. These included contact-saturation, calorimetric, dielectric, nuclear magnetic resonance, and others. The thermodynamic calculations of pore water phase equilibria were also presented. 30 refs., 5 tabs., 8 figs.

Application of gas hydrate formation in separation processes: A review of experimental studies

International Nuclear Information System (INIS)

Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique; Naidoo, Paramespri; Ramjugernath, Deresh

2012-01-01

Highlights: ► Review of gas hydrate technology applied to separation processes. ► Gas hydrates have potential to be a future sustainable separation technology. ► More theoretical, simulation, and economic studies needed. - Abstract: There has been a dramatic increase in gas hydrate research over the last decade. Interestingly, the research has not focussed on only the inhibition of gas hydrate formation, which is of particular relevance to the petroleum industry, but has evolved into investigations on the promotion of hydrate formation as a potential novel separation technology. Gas hydrate formation as a separation technology shows tremendous potential, both from a physical feasibility (in terms of effecting difficult separations) as well as an envisaged lower energy utilization criterion. It is therefore a technology that should be considered as a future sustainable technology and will find wide application, possibly replacing a number of current commercial separation processes. In this article, we focus on presenting a brief description of the positive applications of clathrate hydrates and a comprehensive survey of experimental studies performed on separation processes using gas hydrate formation technology. Although many investigations have been undertaken on the positive application of gas hydrates to date, there is a need to perform more theoretical, experimental, and economic studies to clarify various aspects of separation processes using clathrate/semi-clathrate hydrate formation phenomena, and to conclusively prove its sustainability.

Tracking all-vapor instant gas-hydrate formation and guest molecule populations: A possible probe for molecules trapped in water nanodroplets

Czech Academy of Sciences Publication Activity Database

Uras-Aytemiz, N.; Cwiklik, Lukasz; Devlin, J. P.

2012-01-01

Roč. 137, č. 20 (2012), s. 204501 ISSN 0021-9606 Institutional support: RVO:61388955 Keywords : Fourier transform infrared emission spectra * clathrate hydrate * simulations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.164, year: 2012

The Dual Origin Of The Nitrogen Deficiency In Comets: Selective Volatile Trapping In The Nebula And Postaccretion Radiogenic Heating

Science.gov (United States)

Mousis, Olivier; Guilbert-Lepoutre, A.; Lunine, J. I.; Cochran, A. L.; Waite, J. H.; Petit, J.; Rousselot, P.

2012-10-01

We propose a scenario that explains the apparent nitrogen deficiency in comets in a way consistent with the presence of this molecule in the atmospheres of Pluto and Triton. We use a statistical thermodynamic model to investigate the composition of the successive multiple guest clathrates that may have formed during the cooling of the primordial nebula from the most abundant volatiles present in the gas phase. These clathrates agglomerated with the other ices (pure condensates or stoechiometric hydrates) and formed the building blocks of comets. We report that molecular nitrogen is a poor clathrate former, when we consider a plausible gas phase composition of the primordial nebula. This implies that its trapping into cometesimals requires a low disk temperature (about 20 K) in order to allow the formation of its pure condensate. We find that it is possible to explain the lack of molecular nitrogen in comets as a consequence of their postformation internal heating engendered by the decay of radiogenic nuclides. This scenario is found to be consistent with the presence of nitrogen-rich atmospheres around Pluto and Triton. Our model predicts that comets should present xenon-to-water and krypton-to-water ratios close to solar xenon-to-oxygen and krypton-to-oxygen ratios, respectively. In contrast, the argon-to-water ratio is predicted to be depleted by a factor of about 300 in comets compared to solar argon-to-oxygen, as a consequence of the nitrogen outgassing.

Process optimization for the enrichment of α-linolenic acid from ...

African Journals Online (AJOL)

USER

2010-05-17

May 17, 2010 ... medicine, food and cosmetic industries. Extraction technology of crude .... Crude MFAs in desilked silkworm pupae determined by HPLC-UV. On the .... process of urea clathration reaction lead to a low purity of. ALA. Therefore ...

Phase equilibrium conditions of semi-calthrate hydrates of (tetra-n-butyl ammonium chloride + carbon dioxide)

International Nuclear Information System (INIS)

Sun, Zhi-Gao; Jiao, Li-Jun; Zhao, Zhi-Gui; Wang, Gong-Liang; Huang, Hai-Feng

2014-01-01

Highlights: • Carbon dioxide hydrate stability zone was enlarged with the help of TBAC. • Carbon dioxide uptake into TBAC semi-clathrate hydrates is confirmed. • Equilibrium pressure of hydrate decreased with the increase of TBAC mass concentration. • The addition of TBAC reduces the formation pressures of carbon dioxide hydrate by 2.5 MPa. - Abstract: In the present work, hydrate equilibrium conditions for (tetra-n-butyl ammonium chloride (TBAC) + carbon dioxide + water) mixtures were investigated. Tetra-n-butyl ammonium chloride was reported to form a semi-clathrate hydrate. The experiments were carried out within the TBAC mass fraction range of (0.05 to 0.3). The experimental results showed that the presence of TBAC decreased the formation pressure of carbon dioxide double hydrate within the experimental temperature range. Moreover, pressure reduction was dependent on the TBAC concentration

Pentagonal dodecahedron methane hydrate cage and methanol ...

Indian Academy of Sciences (India)

methane hydrate in sea bed near continental margin and underneath of permafrost ... clathrate structure,6,7 IR spectroscopy analysis of vibra- tional form of guest .... Hydrogen (H71) of the hydroxyl group of methanol is found to have formed ...

Probing Amorphous Components in High Temperature TE Materials by in situ Total Scattering and the Pair Distribution Function (PDF) Method

DEFF Research Database (Denmark)

Reardon, Hazel; Iversen, Bo Brummerstedt; Blichfeld, Anders Bank

-I clathrate Ba8Ga16Ge30. This suggests that local structure reorientations in the cage are likely to be the root cause of the degradation of the structure. This deepens our understanding of disordered clathrates, and provides evidence that the PDF technique is an effective method for probing local structure.......e., by measuring both the Bragg and diffuse scattering from a sample. This method has rarely been exploited by the non-oxide thermoelectrics community. , , Treating total scattering data by the Pair Distribution Function method is a logical approach to understanding defects, disorder and amorphous components...... to heating cycles, then we are closer to distinguishing how we may generate materials that do not undergo specific structure reorientation processes, and/or how we may mitigate them before they occur. Here, we will present a total scattering and PDF study that probes the local structure of the Type...

Marine methane cycle simulations for the period of early global warming

Energy Technology Data Exchange (ETDEWEB)

Elliott, S.; Maltrud, M.; Reagan, M.T.; Moridis, G.J.; Cameron-Smith, P.J.

2011-01-02

Geochemical environments, fates, and effects are modeled for methane released into seawater by the decomposition of climate-sensitive clathrates. A contemporary global background cycle is first constructed, within the framework of the Parallel Ocean Program. Input from organics in the upper thermocline is related to oxygen levels, and microbial consumption is parameterized from available rate measurements. Seepage into bottom layers is then superimposed, representing typical seabed fluid flow. The resulting CH{sub 4} distribution is validated against surface saturation ratios, vertical sections, and slope plume studies. Injections of clathrate-derived methane are explored by distributing a small number of point sources around the Arctic continental shelf, where stocks are extensive and susceptible to instability during the first few decades of global warming. Isolated bottom cells are assigned dissolved gas fluxes from porous-media simulation. Given the present bulk removal pattern, methane does not penetrate far from emission sites. Accumulated effects, however, spread to the regional scale following the modeled current system. Both hypoxification and acidification are documented. Sensitivity studies illustrate a potential for material restrictions to broaden the perturbations, since methanotrophic consumers require nutrients and trace metals. When such factors are considered, methane buildup within the Arctic basin is enhanced. However, freshened polar surface waters act as a barrier to atmospheric transfer, diverting products into the deep return flow. Uncertainties in the logic and calculations are enumerated including those inherent in high-latitude clathrate abundance, buoyant effluent rise through the column, representation of the general circulation, and bacterial growth kinetics.

Marine methane cycle simulations for the period of early global warming

Science.gov (United States)

Elliott, Scott; Maltrud, Mathew; Reagan, Matthew; Moridis, George; Cameron-Smith, Philip

2011-03-01

Geochemical environments, fates, and effects are modeled for methane released into seawater by the decomposition of climate-sensitive clathrates. A contemporary global background cycle is first constructed, within the framework of the Parallel Ocean Program. Input from organics in the upper thermocline is related to oxygen levels, and microbial consumption is parameterized from available rate measurements. Seepage into bottom layers is then superimposed, representing typical seabed fluid flow. The resulting CH4 distribution is validated against surface saturation ratios, vertical sections, and slope plume studies. Injections of clathrate-derived methane are explored by distributing a small number of point sources around the Arctic continental shelf, where stocks are extensive and susceptible to instability during the first few decades of global warming. Isolated bottom cells are assigned dissolved gas fluxes from porous-media simulation. Given the present bulk removal pattern, methane does not penetrate far from emission sites. Accumulated effects, however, spread to the regional scale following the modeled current system. Both hypoxification and acidification are documented. Sensitivity studies illustrate a potential for material restrictions to broaden the perturbations, since methanotrophic consumers require nutrients and trace metals. When such factors are considered, methane buildup within the Arctic basin is enhanced. However, freshened polar surface waters act as a barrier to atmospheric transfer, diverting products into the deep return flow. Uncertainties in the logic and calculations are enumerated including those inherent in high-latitude clathrate abundance, buoyant effluent rise through the column, representation of the general circulation, and bacterial growth kinetics.

Design concepts for improved thermoelectric materials

Energy Technology Data Exchange (ETDEWEB)

Slack, G A

1997-07-01

Some new guidelines are given that should be useful in the search for thermoelectric materials that are better than those currently available. In particular, clathrate and cryptoclathrate compounds with filler atoms in their cages offer the ability to substantially lower the lattice thermal conductivity.

The Synthesis of Novel Enclathration Compounds : Bis(9-amino-9 ...

African Journals Online (AJOL)

The stability of the clathrate complexes has been investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Competition experiments were carried out with the compounds that successfully hosted solvent molecules in order to determine their relative affinity for these solvents. One of the ...

A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

Directory of Open Access Journals (Sweden)

H. Fischer

2011-07-01

Full Text Available In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2 from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS. In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used. A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

The formation of gas hydrates and the effect of inhibitiors on their ...

African Journals Online (AJOL)

Natural gas hydrate is a solid crystalline compound produced by combining water and gas and it is considered as the clathrates. Guest gas molecules are stuck insider the pores of water networks produced by hydrogen bonds between molecules of water. There are different ways to analyze the hydrate formation operating ...

A two component model for thermal emission from organic grains in Comet Halley

Science.gov (United States)

Chyba, Christopher; Sagan, Carl

1988-01-01

Observations of Comet Halley in the near infrared reveal a triple-peaked emission feature near 3.4 micrometer, characteristic of C-H stretching in hydrocarbons. A variety of plausible cometary materials exhibit these features, including the organic residue of irradiated candidate cometary ices (such as the residue of irradiated methane ice clathrate, and polycyclic aromatic hydrocarbons. Indeed, any molecule containing -CH3 and -CH2 alkanes will emit at 3.4 micrometer under suitable conditions. Therefore tentative identifications must rest on additional evidence, including a plausible account of the origins of the organic material, a plausible model for the infrared emission of this material, and a demonstration that this conjunction of material and model not only matches the 3 to 4 micrometer spectrum, but also does not yield additional emission features where none is observed. In the case of the residue of irradiated low occupancy methane ice clathrate, it is argued that the lab synthesis of the organic residue well simulates the radiation processing experienced by Comet Halley.

Superconducting Open-Framework Allotrope of Silicon at Ambient Pressure

Science.gov (United States)

Sung, Ha-Jun; Han, W. H.; Lee, In-Ho; Chang, K. J.

2018-04-01

Diamond Si is a semiconductor with an indirect band gap that is the basis of modern semiconductor technology. Although many metastable forms of Si were observed using diamond anvil cells for compression and chemical precursors for synthesis, no metallic phase at ambient conditions has been reported thus far. Here we report the prediction of pure metallic Si allotropes with open channels at ambient pressure, unlike a cubic diamond structure in covalent bonding networks. The metallic phase termed P 6 /m -Si6 can be obtained by removing Na after pressure release from a novel Na-Si clathrate called P 6 /m -NaSi6 , which is predicted through first-principles study at high pressure. We identify that both P 6 /m -NaSi6 and P 6 /m -Si6 are stable and superconducting with the critical temperatures of about 13 and 12 K at ambient pressure, respectively. The prediction of new Na-Si and Si clathrate structures presents the possibility of exploring new exotic allotropes useful for Si-based devices.

4-Bromoanilinium perchlorate 18-crown-6 clathrate

Directory of Open Access Journals (Sweden)

Min Guo

2010-11-01

Full Text Available The reaction of 4-bromoaniline, 18-crown-6, and perchloric acid in methanol yields the title compound, C6H7BrN+·ClO4−·C12H24O6, in which the protonated –NH3+ group forms three bifurcated N—H...O hydrogen bonds to the O atoms of the crown ether.

Energetic and economic evaluations on hydrogen storage technologies

Energy Technology Data Exchange (ETDEWEB)

Arca, S.; Di Profio, P.; Germani, R. [Perugia Univ., Perugia (Italy). Centro di Eccellenza Materiali Innovativi Nanostrutturati, Dip. Chimica; Savelli, G.; Cotana, F.; Rossi, F.; Amantini, M. [Universita degli Studi di Perugia, Perugia (Italy). Dipartimento di Ingegneria Industriale, Sezione di Fisica Tecnica

2008-07-01

With the development of the hydrogen economy and fuel cell vehicles, a major technological issue has emerged regarding the storage and delivery of large amounts of hydrogen. Several hydrogen storage methodologies are available while other technologies are being developed aside from the classical compression and liquefaction of hydrogen. A novel technology is also in rapid process, which is based on clathrate hydrates of hydrogen. The features and performances of available storage systems were evaluated in an effort to determine the best technology throughout the hydrogen chain. For each of the storage solutions presented, the key parameters were compared. These key parameters included interaction energy between hydrogen and support; real and practical storage capacity; and specific energy consumption. The paper presented the study methods and discussed hydrogen storage technologies using compressed hydrogen; metal hydrides; liquefied hydrogen; carbon nanotubes; ammonia; and gas hydrates. Carbon dioxide emissions were also evaluated for each storage system analyzed. The paper also presented the worst scenario. It was concluded that a technology based on clathrate hydrates of hydrogen, while being far from optimized, was highly competitive with the classical approaches. 21 refs., 9 figs.

Methane bursts as a trigger for intermittent lake-forming climates on post-Noachian Mars

Science.gov (United States)

Kite, Edwin S.; Gao, Peter; Goldblatt, Colin; Mischna, Michael A.; Mayer, David P.; Yung, Yuk L.

2017-10-01

Lakes existed on Mars later than 3.6 billion years ago, according to sedimentary evidence for deltaic deposition. The observed fluviolacustrine deposits suggest that individual lake-forming climates persisted for at least several thousand years (assuming dilute flow). But the lake watersheds’ little-weathered soils indicate a largely dry climate history, with intermittent runoff events. Here we show that these observational constraints, although inconsistent with many previously proposed triggers for lake-forming climates, are consistent with a methane burst scenario. In this scenario, chaotic transitions in mean obliquity drive latitudinal shifts in temperature and ice loading that destabilize methane clathrate. Using numerical simulations, we find that outgassed methane can build up to atmospheric levels sufficient for lake-forming climates, if methane clathrate initially occupies more than 4% of the total volume in which it is thermodynamically stable. Such occupancy fractions are consistent with methane production by water-rock reactions due to hydrothermal circulation on early Mars. We further estimate that photochemical destruction of atmospheric methane curtails the duration of individual lake-forming climates to less than a million years, consistent with observations. We conclude that methane bursts represent a potential pathway for intermittent excursions to a warm, wet climate state on early Mars.

Gas Hydrate Research Database and Web Dissemination Channel

Energy Technology Data Exchange (ETDEWEB)

Micheal Frenkel; Kenneth Kroenlein; V Diky; R.D. Chirico; A. Kazakow; C.D. Muzny; M. Frenkel

2009-09-30

To facilitate advances in application of technologies pertaining to gas hydrates, a United States database containing experimentally-derived information about those materials was developed. The Clathrate Hydrate Physical Property Database (NIST Standard Reference Database {number_sign} 156) was developed by the TRC Group at NIST in Boulder, Colorado paralleling a highly-successful database of thermodynamic properties of molecular pure compounds and their mixtures and in association with an international effort on the part of CODATA to aid in international data sharing. Development and population of this database relied on the development of three components of information-processing infrastructure: (1) guided data capture (GDC) software designed to convert data and metadata into a well-organized, electronic format, (2) a relational data storage facility to accommodate all types of numerical and metadata within the scope of the project, and (3) a gas hydrate markup language (GHML) developed to standardize data communications between 'data producers' and 'data users'. Having developed the appropriate data storage and communication technologies, a web-based interface for both the new Clathrate Hydrate Physical Property Database, as well as Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program was developed and deployed at http://gashydrates.nist.gov.

Thermodynamic Stability of Structure H Hydrates Based on the Molecular Properties of Large Guest Molecules

OpenAIRE

Tezuka, Kyoichi; Taguchi, Tatsuhiko; Alavi, Saman; Sum, Amadeu K.; Ohmura, Ryo

2012-01-01

This paper report analyses of thermodynamic stability of structure-H clathrate hydrates formed with methane and large guest molecules in terms of their gas phase molecular sizes and molar masses for the selection of a large guest molecule providing better hydrate stability. We investigated the correlation among the gas phase molecular sizes, the molar masses of large molecule guest substances, and the equilibrium pressures. The results suggest that there exists a molecular-size value for the ...

State of the art on phase change material slurries

International Nuclear Information System (INIS)

Youssef, Ziad; Delahaye, Anthony; Huang Li; Trinquet, François; Fournaison, Laurence; Pollerberg, Clemens; Doetsch, Christian

2013-01-01

Highlights: ► A bibliographic study on PCM slurries. ► Clathrate Hydrate slurry, Microencapsulated PCM Slurry, shape-stabilized PCM slurries and Phase Change Material Emulsions. ► Formation, thermo-physical, rheological, heat transfers properties and applications of these four PCS systems. ► The use of thermal energy storage and distribution based on PCM slurries can improve the refrigerating machine performances. - Abstract: The interest in using phase change slurry (PCS) media as thermal storage and heat transfer fluids is increasing and thus leading to an enhancement in the number of articles on the subject. In air-conditioning and refrigeration applications, PCS systems represent a pure benefit resulting in the increase of thermal energy storage capacity, high heat transfer characteristics and positive phase change temperatures which can occur under low pressures. Hence, they allow the increase of energy efficiency and reduce the quantity of thermal fluids. This review describes the formation, thermo-physical, rheological, heat transfer properties and applications of four PCS systems: Clathrate hydrate slurry (CHS), Microencapsulated Phase Change Materials Slurry (MPCMS), shape-stabilized PCM slurries (SPCMSs) and Phase Change Material Emulsions (PCMEs). It regroups a bibliographic summary of important information that can be very helpful when such systems are used. It also gives interesting and valuable insights on the choice of the most suitable PCS media for laboratory and industrial applications.

Inter-cage dynamics in structure I, II, and H fluoromethane hydrates as studied by NMR and molecular dynamics simulations

International Nuclear Information System (INIS)

Trueba, Alondra Torres; Kroon, Maaike C.; Peters, Cor J.; Moudrakovski, Igor L.; Ratcliffe, Christopher I.; Ripmeester, John A.; Alavi, Saman

2014-01-01

Prospective industrial applications of clathrate hydrates as materials for gas separation require further knowledge of cavity distortion, cavity selectivity, and defects induction by guest-host interactions. The results presented in this contribution show that under certain temperature conditions the guest combination of CH 3 F and a large polar molecule induces defects on the clathrate hydrate framework that allow intercage guest dynamics. 13 C NMR chemical shifts of a CH 3 F/CH 4 /TBME sH hydrate and a temperature analysis of the 2 H NMR powder lineshapes of a CD 3 F/THF sII and CD 3 F/TBME sH hydrate, displayed evidence that the populations of CH 4 and CH 3 F in the D and D ′ cages were in a state of rapid exchange. A hydrogen bonding analysis using molecular dynamics simulations on the TBME/CH 3 F and TBME/CH 4 sH hydrates showed that the presence of CH 3 F enhances the hydrogen bonding probability of the TBME molecule with the water molecules of the cavity. Similar results were obtained for THF/CH 3 F and THF/CH 4 sII hydrates. The enhanced hydrogen bond formation leads to the formation of defects in the water hydrogen bonding lattice and this can enhance the migration of CH 3 F molecules between adjacent small cages

Competition between intermolecular interaction and configuration entropy as the structure-determining factor for inclusion compounds

Energy Technology Data Exchange (ETDEWEB)

Subbotin, O.; Belosludov, V.; Adamova, T. [Russian Academy of Science, Novosibirsk (Russian Federation). Nikolaev Inst. of Inorganic Chemistry; Belosludov, R.; Kawazoe, Y. [Tohoku Univ., Aoba-ku, Sendai (Japan). Inst. for Materials Research; Kudoh, J.I. [Tohoku Univ., Aoba-ku, Sendai (Japan). Center for Northeast Asia Studies

2008-07-01

This paper presented a newly developed method to accurately predict the thermodynamic properties of clathrate hydrates, particularly their structural phase transitions under pressure. The method is based on the theory of Van-der-Waals and Platteeuw with some modifications that include the influence of guest molecules on the host lattice. The model was used to explain the exception from the established rule that small guest molecules form structure s1 and large molecules form structure s2 hydrates. In this study, the thermodynamic properties of argon (Ar) hydrate and methane hydrate, each in both cubic structure s1 and s2 were modelled. The model showed that two competing factors play a role in the formation of inclusions, notably the intermolecular interaction of guest molecules with water molecules, and the configuration entropy. Competition of these 2 factors determines the structure of hydrate formed at different pressures. The model provides an accurate description of the thermodynamic properties of gas hydrates and how they behave under pressure. For the argon hydrates, the structural phase transition from structure s2 to s1 at high pressure was predicted, while methane hydrates were predicted to be metastable in the s2 structure. The model can be used for other inclusion compounds with the same type of composition such as clathrate silicon, zeolites, and inclusion compounds of semiconductor elements. 17 refs., 5 figs.

Feasibility of Large-Scale Ocean CO2 Sequestration

Energy Technology Data Exchange (ETDEWEB)

Peter Brewer

2008-08-31

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 CO{sub 2}. 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. In this report we detail research carried out in the period October 1, 2007 through September 30, 2008. The primary body of work is contained in a formal publication attached as Appendix 1 to this report. In brief we have surveyed the recent literature with respect to the natural occurrence of clathrate hydrates (with a special emphasis on methane hydrates), the tools used to investigate them and their potential as a new source of natural gas for energy production.

Methods of gas hydrate concentration estimation with field examples

Digital Repository Service at National Institute of Oceanography (India)

Kumar, D.; Dash, R.; Dewangan, P.

physics and seismic inversion: examples from the northern deepwater Gulf of Mexico: The Leading Edge, 23, 60-66. Dash R., 2007, Crustal structure and marine gas hydrate studies near Vancouver Island using seismic tomography: PhD thesis, University...-resistivity logs: Examples from Green Canyon, Gulf of Mexico: SEG expanded abstracts, 26, 1579-1583. Singh, S. C., Minshull, T. A., and Spence, G. D., 1993, Velocity structure of a gas hydrate reflector: Science, 260, 204-207. Sloan, E. D. Jr., 1998, Clathrate...

Methane Storage in Biosilica-Supported Semiclathrates at Ambient Temperature and Pressure

Science.gov (United States)

Li, Liang; Wang, Suying; Wang, Weixing

2018-01-01

Two key issues regarding the use of clathrates and semiclathrates for practical gas storage and transport is the pressure-temperature stability of the material and very low formation kinetics. For many practical applications, the avoidance of cooling, gas overpressure, and mechanical mixing would be very desirable. Here, we show that biosilica supports from rice husks greatly enhance gases uptake kinetics in tetra-iso-amyl ammonium bromide semiclathrates without introducing complex mixing technologies. These systems show excellent thermal stability and good recyclability.

How to oxidize atmospheric CH4? - A challenge for the future

International Nuclear Information System (INIS)

Chazelas, Bruno; Leger, Alain; Ollivier, Marc

2006-01-01

Methane is an active Greenhouse effect gas whose concentration will likely increase in the future. The possible destabilisation of CH 4 clathrates (hydrates) due to anthropogenic climate warming, and the resulting outgasing of methane, could lead to a major increase of the global Greenhouse effect, with dramatic consequences for Humanity. For these reasons, the study of possible countermeasures should be actively considered. Here, we suggest taking advantage of the thermodynamic instability of CH 4 in air, and search for ways to oxidize it

Model for gas hydrates applied to CCS systems part I. Parameter study of the van der Waals and Platteeuw model

Czech Academy of Sciences Publication Activity Database

Vinš, Václav; Jäger, A.; Span, R.; Hrubý, Jan

2016-01-01

Roč. 427, November (2016), s. 268-281 ISSN 0378-3812 R&D Projects: GA MŠk(CZ) 7F14466 Grant - others:Rada Programu interní podpory projektů mezinárodní spolupráce AV ČR(CZ) M100761201 Institutional support: RVO:61388998 Keywords : carbon capture and storage * clathrate * lattice parameter * reference equation of state * langmuir constant Subject RIV: BJ - Thermodynamics Impact factor: 2.473, year: 2016 http://www.sciencedirect.com/science/article/pii/S0378381216303442

Clathrates and beyond: Low-density allotropy in crystalline silicon

Energy Technology Data Exchange (ETDEWEB)

Beekman, Matt [Department of Physics, California Polytechnic State University, San Luis Obispo, California 93407 (United States); Wei, Kaya; Nolas, George S., E-mail: gnolas@usf.edu [Department of Physics, University of South Florida, Tampa, Florida 33620 (United States)

2016-12-15

In its common, thermodynamically stable state, silicon adopts the same crystal structure as diamond. Although only a few alternative allotropic structures have been discovered and studied over the past six decades, advanced methods for structure prediction have recently suggested a remarkably rich low-density phase space that has only begun to be explored. The electronic properties of these low-density allotropes of silicon, predicted by first-principles calculations, indicate that these materials could offer a pathway to improving performance and reducing cost in a variety of electronic and energy-related applications. In this focus review, we provide an introduction and overview of recent theoretical and experimental results related to low-density allotropes of silicon, highlighting the significant potential these materials may have for technological applications, provided substantial challenges to their experimental preparation can be overcome.

Self-Organization of +-Crown Ether Derivatives into Double-Columnar Arrays Controlled by Supramolecular Isomers of Hydrogen-Bonded Anionic Biimidazolate Ni Complexes

Directory of Open Access Journals (Sweden)

Makoto Tadokoro

2012-01-01

Full Text Available Anionic tris (biimidazolate nickelate (II ([Ni(Hbim3]−, which is a hydrogen-bonding (H-bonding molecular building block, undergoes self-organization into honeycomb-sheet superstructures connected by complementary intermolecular H-bonds. The crystal obtained from the stacking of these sheets is assembled into channel frameworks, approximately 2 nm wide, that clathrate two cationic K+-crown ether derivatives organised into one-dimensional (1D double-columnar arrays. In this study, we have shown that all five cationic guest-included crystals form nanochannel structures that clathrate the 1-D double-columnar arrays of one of the four types of K+-crown ether derivatives, one of which induces a polymorph. This is accomplished by adaptably fitting two types of anionic [Ni(Hbim3]− host arrays. One is a ΔΛ−ΔΛ−ΔΛ⋯ network with H-bonded linkages alternating between the two different optical isomers of the Δ and Λ types with flexible H-bonded [Ni(Hbim3]−. The other is a ΔΔΔ−ΛΛΛ⋯ network of a racemate with 1-D H-bonded arrays of the same optical isomer for each type. Thus, [Ni(Hbim3]− can assemble large cations such as K+ crown-ether derivatives into double-columnar arrays by highly recognizing flexible H-bonding arrangements with two host networks of ΔΛ−ΔΛ−ΔΛ⋯ and ΔΔΔ−ΛΛΛ⋯.

Xenon-Water Interaction in Bacterial Suspensions as Studied by NMR

DEFF Research Database (Denmark)

Rodin, V.; Ponomarev, Alexander; Gerasimov, Maxim

2017-01-01

suspensions of Escherichia coli in the presence of xenon using nuclear magnetic resonance (NMR). The work studied how the spin-lattice relaxation times of water protons in suspension change under xenon conditions. Xenon is able to form clathrate hydrates with water molecules at a temperature above the melting...... point of ice. The work studied NMR relaxation times which reflect the rotation freedom of water molecules in suspension. Lower relaxation times indicate reduced rotational freedom of water. Single exponential behavior of spin-lattice relaxation of protons in the suspensions of microorganisms has been...

Novel silicon phases and nanostructures for solar energy conversion

Energy Technology Data Exchange (ETDEWEB)

Wippermann, Stefan; He, Yuping; Vörös, Márton; Galli, Giulia

2016-12-01

Silicon exhibits a large variety of different bulk phases, allotropes, and composite structures, such as, e.g., clathrates or nanostructures, at both higher and lower densities compared with diamond-like Si-I. New Si structures continue to be discovered. These novel forms of Si offer exciting prospects to create Si based materials, which are non-toxic and earth-abundant, with properties tailored precisely towards specific applications. We illustrate how such novel Si based materials either in the bulk or as nanostructures may be used to significantly improve the efficiency of solar energy conversion devices.

LIQUID CLATHRATE FORMATION IN IONIC LIQUIDS/AROMATIC MIXTURES. (R828257)

Science.gov (United States)

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

A PROTOSOLAR NEBULA ORIGIN FOR THE ICES AGGLOMERATED BY COMET 67P/CHURYUMOV–GERASIMENKO

Energy Technology Data Exchange (ETDEWEB)

Mousis, O.; Vernazza, P. [Aix Marseille Université, CNRS, LAM (Laboratoire d’Astrophysique de Marseille) UMR 7326, F-13388 Marseille (France); Lunine, J. I. [Center For Radiophysics And Space Research, Space Sciences Building Cornell University, Ithaca, NY 14853 (United States); Luspay-Kuti, A.; Hässig, M.; Waite, J. H. [Department of Space Research, Southwest Research Institute, 6220 Culebra Road, San Antonio, TX 78228 (United States); Guillot, T. [Laboratoire J.-L. Lagrange, Université de Nice-Sophia Antipolis, CNRS, Observatoire de la Côte d’Azur, BP 4229, F-06304 Nice (France); Marty, B. [CRPG-CNRS, Nancy-Université, 15 rue Notre Dame des Pauvres, F-54501 Vandoeuvre-lès-Nancy (France); Ali-Dib, M. [Université de Franche-Comté, Institut UTINAM, CNRS/INSU, UMR 6213, Besançon Cedex (France); Wurz, P.; Altwegg, K.; Bieler, A.; Rubin, M., E-mail: olivier.mousis@lam.fr [Physikalisches Institut, University of Bern, Sidlerstrasse 5, CH-3012 Bern (Switzerland)

2016-03-10

The nature of the icy material accreted by comets during their formation in the outer regions of the protosolar nebula (PSN) is a major open question in planetary science. Some scenarios of comet formation predict that these bodies agglomerated from crystalline ices condensed in the PSN. Concurrently, alternative scenarios suggest that comets accreted amorphous ice originating from the interstellar cloud or from the very distant regions of the PSN. On the basis of existing laboratory and modeling data, we find that the N{sub 2}/CO and Ar/CO ratios measured in the coma of the Jupiter-family comet 67P/Churyumov–Gerasimenko by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis instrument on board the European Space Agency’s Rosetta spacecraft match those predicted for gases trapped in clathrates. If these measurements are representative of the bulk N{sub 2}/CO and Ar/CO ratios in 67P/Churyumov–Gerasimenko, it implies that the ices accreted by the comet formed in the nebula and do not originate from the interstellar medium, supporting the idea that the building blocks of outer solar system bodies have been formed from clathrates and possibly from pure crystalline ices. Moreover, because 67P/Churyumov–Gerasimenko is impoverished in Ar and N{sub 2}, the volatile enrichments observed in Jupiter’s atmosphere cannot be explained solely via the accretion of building blocks with similar compositions and require an additional delivery source. A potential source may be the accretion of gas from the nebula that has been progressively enriched in heavy elements due to photoevaporation.

On the production of positive molecular ions in cometary comas

International Nuclear Information System (INIS)

Tarafdar, S.P.; Wickramasinghe, N.C.

1977-01-01

Positively charged molecular ions, such as H 2 O + , which have been observed in cometary comas, may be efficiently produced by the evaporation of positively charged clathrate grains of radii in the range approximately 10 -6 -10 -3 cm. Such grains may be expelled from nuclei of comets, along with gaseous molecules. Grain charging occurs via interaction with solar ultraviolet photons and/or solar wind protons. Observational data on the total quantities as well as the distributions of H 2 O and H 2 O + in cometary comas are shown to be in accord with detailed model calculations. (Auth.)

Structure of cometary atmospheres. II. Ion distribution

Energy Technology Data Exchange (ETDEWEB)

Shimizu, M [Tokyo Univ. (Japan). Inst. of Space and Aeronautical Science

1976-04-01

The distributions of various kinds of molecular ions in the atmospheres of new and old comets made up from dirty ice of the second kind (H/sub 2/O ice and hydrate clathrates of CO and N/sub 2/) have been computed at various heliocentric distances, by taking into account photoionization, ion-molecular reactions, electron-ion recombinations, and some transport effects. The results have been compared with observations and other computations. It is argued that dirty ice of the second kind model will impose a restriction on the theory of the origin of the solar system.

Long term storage techniques for 85Kr

International Nuclear Information System (INIS)

Foster, B.A.; Pence, D.T.; Staples, B.A.

1975-01-01

As new nuclear fuel reprocessing plants go on stream, the collection of fission product 85 Kr will be required to avoid potential local release problems and long-term atmospheric buildup. Storage of the collected 85 Kr for a period of at least 100 years will be necessary to allow approximately 99.9 percent decay before it is released. A program designed to develop and evaluate proposed methods for long-term storage of 85 Kr is discussed, and the results of a preliminary evaluation of three methods, high pressure steel cylinders, zeolite encapsulation, and clathrate inclusion are presented. (U.S.)

Overview of the physical-chemical properties of the noble gases

International Nuclear Information System (INIS)

McKinley, C.

1973-01-01

This paper lists the concentrations of noble gases in the atmosphere and the relative abundance of the stable isotopes. Selected physical properties are tabulated; solubilities of noble gases in water and other liquids, and liquid-vapor equilibria data for binary systems containing a noble gas are presented. Adsorption data are tabulated for illustrative conventional adsorbents and are also presented by a Polanyi correlation. Clathration, biochemical effects, and chemical reactivity are highlighted. Analytical procedures are briefly described. Other relatively non-reactive gases present in the atmosphere in trace quantities are mentioned: methane, carbon tetrafluoride, and sulfur hexafluoride.

Model for gas hydrates applied to CCS systems part II. Fitting of parameters for models of hydrates of pure gases

Czech Academy of Sciences Publication Activity Database

Vinš, Václav; Jäger, A.; Hrubý, Jan; Span, R.

2017-01-01

Roč. 435, March (2017), s. 104-117 ISSN 0378-3812 R&D Projects: GA MŠk(CZ) 7F14466; GA ČR(CZ) GJ15-07129Y Institutional support: RVO:61388998 Keywords : carbon capture and storage * clathrate * parameter fitting Subject RIV: BJ - Thermodynamics Impact factor: 2.473, year: 2016 http://ac.els-cdn.com/S0378381216306069/1-s2.0-S0378381216306069-main.pdf?_tid=7b6bf82c-2f22-11e7-8661-00000aab0f02&acdnat=1493721260_17561db239dd867f17c2ad3bda9a5540

Natural gas: A bridge to the future?

International Nuclear Information System (INIS)

Andriesse, C.D.

1991-01-01

Natural gas is the cleanest fossil fuel, but never got the chance to develop its use. The reason for that is the notion that the natural gas supplies would last for only some decennia. That is only right for the conventional gas supplies. In ice crystals, some hundreds of meters deep in the oceans, enormous methane reserves, many times larger than the conventional supplies, are enclosed in so-called clathrates. From the literature it appears that other sources of natural gas or methane and new options to use these energy sources are considered or to be developed. Attention is paid to the methane reserves in geologic formations, methane produced by microbes, and methane in clathrates. It is estimated that the methane reserve is 8 x 10 2 3 Joule. By using natural gas as a fuel CO 2 emission will be reduced considerably. Methane emission however must be limited, because of the reducing effect of methane on the oxygen production in the troposphere. The large reserves of methane also offer good prospects for the production of hydrogen, large-scale applications to generate electric power or the use of CH 4 as a fuel in the transportation sector. New techniques and economic, social and institutional factors determine how fast the use of natural gas will increase. It is expected that 0.54 Tm 3 of natural gas will be needed for the twelve countries of the European Community. Main users in the year 2030 will be the electric power industry (39%), industry (26%), households and trade (18%), and transportation sector and supply (15%). In 2030 63% of natural gas has to be imported. 3 refs

Methane storage capacity of the early martian cryosphere

Science.gov (United States)

Lasue, Jeremie; Quesnel, Yoann; Langlais, Benoit; Chassefière, Eric

2015-11-01

Methane is a key molecule to understand the habitability of Mars due to its possible biological origin and short atmospheric lifetime. Recent methane detections on Mars present a large variability that is probably due to relatively localized sources and sink processes yet unknown. In this study, we determine how much methane could have been abiotically produced by early Mars serpentinization processes that could also explain the observed martian remanent magnetic field. Under the assumption of a cold early Mars environment, a cryosphere could trap such methane as clathrates in stable form at depth. The extent and spatial distribution of these methane reservoirs have been calculated with respect to the magnetization distribution and other factors. We calculate that the maximum storage capacity of such a clathrate cryosphere is about 2.1 × 1019-2.2 × 1020 moles of CH4, which can explain sporadic releases of methane that have been observed on the surface of the planet during the past decade (∼1.2 × 109 moles). This amount of trapped methane is sufficient for similar sized releases to have happened yearly during the history of the planet. While the stability of such reservoirs depends on many factors that are poorly constrained, it is possible that they have remained trapped at depth until the present day. Due to the possible implications of methane detection for life and its influence on the atmospheric and climate processes on the planet, confirming the sporadic release of methane on Mars and the global distribution of its sources is one of the major goals of the current and next space missions to Mars.

SUBSURFACE CHARACTERIZATION OF 67P/CHURYUMOV–GERASIMENKO’S ABYDOS SITE

Energy Technology Data Exchange (ETDEWEB)

Brugger, B.; Mousis, O.; Jorda, L.; Lamy, P.; Vernazza, P. [Aix Marseille Université, CNRS, LAM (Laboratoire d’Astrophysique de Marseille) UMR 7326, F-13388, Marseille (France); Morse, A.; Andrews, D.; Barber, S.; Morgan, G.; Sheridan, S.; Wright, I. P. [Planetary and Space Sciences, Department of Physics, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom); Marboeuf, U. [Physikalishes Institut, Center for Space and Habitability, University of Bern (Switzerland); Guilbert-Lepoutre, A. [Institut UTINAM, UMR 6213 CNRS-Université de Franche-Comté, Besançon (France); Luspay-Kuti, A.; Mandt, K., E-mail: bastien.brugger@lam.fr [Department of Space Science, Southwest Research Institute, 6220 Culebra Road, San Antonio, TX 78228 (United States)

2016-05-10

On 2014 November 12, the ESA/ Rosetta descent module Philae landed on the Abydos site of comet 67P/Churyumov–Gerasimenko. Aboard this module, the Ptolemy mass spectrometer measured a CO/CO{sub 2} ratio of 0.07 ± 0.04, which differs substantially from the value obtained in the coma by the Rosetta /ROSINA instrument, suggesting a heterogeneity in the comet nucleus. To understand this difference, we investigated the physicochemical properties of the Abydos subsurface, leading to CO/CO{sub 2} ratios close to that observed by Ptolemy at the surface of this region. We used a comet nucleus model that takes into account different water ice phase changes (amorphous ice, crystalline ice, and clathrates) as well as diffusion of molecules throughout the pores of the matrix. The input parameters of the model were optimized for the Abydos site, and the ROSINA CO/CO{sub 2} measured ratio is assumed to correspond to the bulk value in the nucleus. We find that all considered structures of water ice are able to reproduce the Ptolemy observation with a time difference not exceeding ∼50 days, i.e., lower than ∼2% on 67P/Churyumov–Gerasimenko’s orbital period. The suspected heterogeneity of 67P/Churyumov–Gerasimenko’s nucleus is also found possible only if it is constituted of crystalline ices. If the icy phase is made of amorphous ice or clathrates, the difference between Ptolemy and ROSINA’s measurements would rather originate from the spatial variations in illumination on the nucleus surface. An eventual new measurement of the CO/CO{sub 2} ratio at Abydos by Ptolemy could be decisive to distinguish between the three water ice structures.

Structure of catenary complex bis(trimethylamine)cadmium(2)-tetra-μ-cyanonickelate(2) and contact self-stabilization of molecules

International Nuclear Information System (INIS)

Ivamoto, T.; Nishikiori, Sh.; Dyadin, Yu.A.; Soldatov, D.V.

1999-01-01

Complex [Cd(N(CH 3 ) 3 ) 2 Ni(CN) 4 ] is synthesized and studied by x-ray diffraction method. Complex studied is crystallized in tetragonal system in space group I4/mmm. There are parallel polymeric layers in the structure which are consisted from coordinately bound metal atoms and bridge cyanides. Octahedral Cd(2) surrounding is formed by six atoms of nitrogen of the cyanide groups in laminar plate and by two trimethylamine ligands in trans-position. Layers are stacked in the correspondence with Van-der-Waals type of packing. Space complementation of layers results in dense packing of complexes and explains the absence of clathrate-forming ability [ru

Radioactive tracer system to indicate drill bit wear or failure

International Nuclear Information System (INIS)

Fries, B.A.

1975-01-01

A radioactive tracer system for indicating drill bit wear or failure utilizing radioactive krypton 85 in clathrate form, in the form of water-soluble kryptonates, or dissolved grease, is described. Preferably the radioactive krypton is placed so that when drill bit wear or failure occurs, the radioactive krypton 85 is relased and effectively becomes diffused in the circulating drilling fluid. At the surface, the radioactive krypton 85 gas is separated from the circulating drilling fluid by gas-mud separating means and is transported as a gas to a counting chamber where an accurate radioactivity count of beta rays released from the krypton is obtained. (Patent Office Record)

Considering multiple occupancy of cavities in clathrate hydrate phase equilibrium calculations

Energy Technology Data Exchange (ETDEWEB)

Asiaee, Alireza; Raeissi, Sona [Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of); Shariati, Alireza, E-mail: shariati@shirazu.ac.i [Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of)

2011-05-15

Research highlights: A model is presented to predict dissociation pressures of gas hydrates at various temperatures. The present model is applicable on a wide range of equilibrium conditions. The simple calculation procedure presented here saves considerably the calculation time. - Abstract: One of the major assumptions of the original van der Waals-Platteeuw (vdWP) model is the single occupancy of hydrate cavities. In this work, the vdWP model is modified to also account for multiple occupancies of hydrate cavities by small molecules. The developed model is evaluated by calculating the hydrate equilibrium conditions with either oxygen or nitrogen as guest molecules in pure form, as well as mixtures of nitrogen and propane (molecules of these pure gases and those in (nitrogen + propane) have double occupancy in large cavities of structure II up to a certain concentration of propane). The results of this modified model show good agreement with the experimental data reported in the literature.

Considering multiple occupancy of cavities in clathrate hydrate phase equilibrium calculations

International Nuclear Information System (INIS)

Asiaee, Alireza; Raeissi, Sona; Shariati, Alireza

2011-01-01

Research highlights: → A model is presented to predict dissociation pressures of gas hydrates at various temperatures. → The present model is applicable on a wide range of equilibrium conditions. → The simple calculation procedure presented here saves considerably the calculation time. - Abstract: One of the major assumptions of the original van der Waals-Platteeuw (vdWP) model is the single occupancy of hydrate cavities. In this work, the vdWP model is modified to also account for multiple occupancies of hydrate cavities by small molecules. The developed model is evaluated by calculating the hydrate equilibrium conditions with either oxygen or nitrogen as guest molecules in pure form, as well as mixtures of nitrogen and propane (molecules of these pure gases and those in (nitrogen + propane) have double occupancy in large cavities of structure II up to a certain concentration of propane). The results of this modified model show good agreement with the experimental data reported in the literature.

Capillary pressure controlled methane hydrate and ice growth-melting patterns in porous media : synthetic silica versus natural sandstone

Energy Technology Data Exchange (ETDEWEB)

Anderson, R.; Tohidi, B.; Webber, B. [Heriot-Watt Univ., Centre for Gas Research, Edinburgh (United Kingdom). Inst. of Petroleum Engineering

2008-07-01

Although naturally-occurring gas hydrates (or clathrate hydrates) in marine sediments can pose a hazard to deepwater hydrocarbon production operations, they represent a potential strategic energy reserve. Gas hydrates can also provide a means for deep ocean carbon dioxide disposal through sequestration/storage. They have long-term importance with respect to ocean margin stability, methane release, and global climate change. However, fundamental knowledge is still lacking regarding the mechanisms of hydrate growth, accumulation and distribution within the subsurface. Marine sediments which host gas hydrates are commonly fine-grained silts, muds, and clays with narrow mean pore diameters, leading to speculation that capillary phenomena could play a significant role in controlling hydrate distribution in the seafloor, and may be partly responsible for discrepancies between observed and predicted hydrate stability zone thicknesses. A close relationship between hydrate inhibition and pore size has been confirmed through previous laboratory studies. Clathrate stability has been significantly reduced in narrow pores. However, the focus of investigations has generally been hydrate dissociation conditions in porous media, with capillary controls on the equally important process of hydrate growth being largely overlooked. This paper presented the results of an experimental investigation into methane hydrate growth and dissociation equilibria in natural medium grained sandstone. The study also compared data with that previously measured for mesoporous silica glasses. The paper discussed solid-liquid phase behaviour in confined geometries including hysteresis in porous media. It also discussed the experimental equipment and method. It was concluded that, as for synthetic silicas, hydrate growth and dissociation in the sandstone were characterised by a measurable hysteresis between opposing transitions, notably hydrate (or ice) formation occurring at temperatures lower than

Revealing Surface Waters on an Antifreeze Protein by Fusion Protein Crystallography Combined with Molecular Dynamic Simulations.

Science.gov (United States)

Sun, Tianjun; Gauthier, Sherry Y; Campbell, Robert L; Davies, Peter L

2015-10-08

Antifreeze proteins (AFPs) adsorb to ice through an extensive, flat, relatively hydrophobic surface. It has been suggested that this ice-binding site (IBS) organizes surface waters into an ice-like clathrate arrangement that matches and fuses to the quasi-liquid layer on the ice surface. On cooling, these waters join the ice lattice and freeze the AFP to its ligand. Evidence for the generality of this binding mechanism is limited because AFPs tend to crystallize with their IBS as a preferred protein-protein contact surface, which displaces some bound waters. Type III AFP is a 7 kDa globular protein with an IBS made up two adjacent surfaces. In the crystal structure of the most active isoform (QAE1), the part of the IBS that docks to the primary prism plane of ice is partially exposed to solvent and has clathrate waters present that match this plane of ice. The adjacent IBS, which matches the pyramidal plane of ice, is involved in protein-protein crystal contacts with few surface waters. Here we have changed the protein-protein contacts in the ice-binding region by crystallizing a fusion of QAE1 to maltose-binding protein. In this 1.9 Å structure, the IBS that fits the pyramidal plane of ice is exposed to solvent. By combining crystallography data with MD simulations, the surface waters on both sides of the IBS were revealed and match well with the target ice planes. The waters on the pyramidal plane IBS were loosely constrained, which might explain why other isoforms of type III AFP that lack the prism plane IBS are less active than QAE1. The AFP fusion crystallization method can potentially be used to force the exposure to solvent of the IBS on other AFPs to reveal the locations of key surface waters.

Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines.

Science.gov (United States)

Kucheriv, Olesia I; Shylin, Sergii I; Ksenofontov, Vadim; Dechert, Sebastian; Haukka, Matti; Fritsky, Igor O; Gural'skiy, Il'ya A

2016-05-16

Discovery of spin-crossover (SCO) behavior in the family of Fe(II)-based Hofmann clathrates has led to a "new rush" in the field of bistable molecular materials. To date this class of SCO complexes is represented by several dozens of individual compounds, and areas of their potential application steadily increase. Starting from Fe(2+), square planar tetracyanometalates M(II)(CN)4(2-) (M(II) = Ni, Pd, Pt) and 2-substituted pyrazines Xpz (X = Cl, Me, I) as coligands we obtained a series of nine new Hofmann clathrate-like coordination frameworks. X-ray diffraction reveals that in these complexes Fe(II) ion has a pseudo-octahedral coordination environment supported by four μ4-tetracyanometallates forming its equatorial coordination environment. Depending on the nature of X and M, axial positions are occupied by two 2X-pyrazines (X = Cl and M(II) = Ni (1), Pd (2), Pt (3); X = Me and M(II) = Ni (4), Pd (5)) or one 2X-pyrazine and one water molecule (X = I and M(II) = Ni (7), Pd (8), Pt (9)), or, alternatively, two distinct Fe(II) positions with either two pyrazines or two water molecules (X = Me and M(II) = Pt (6)) are observed. Temperature behavior of magnetic susceptibility indicates that all compounds bearing FeN6 units (1-6) display cooperative spin transition, while Fe(II) ions in N5O or N4O2 surrounding are high spin (HS). Structural changes in the nearest Fe(II) environment upon low-spin (LS) to HS transition, which include ca. 10% Fe-N distance increase, lead to the cell expansion. Mössbauer spectroscopy is used to characterize the spin state of all HS, LS, and intermediate phases of 1-9 (see abstract figure). Effects of a pyrazine substituent and M(II) nature on the hyperfine parameters in both spin states are established.

Hydrolysis in the organic phase during the extraction of alkali metal halides and water by copper bis(2-ethylhexyl)phosphate

International Nuclear Information System (INIS)

Golovanov, V.I.; Kuznetsov, S.M.

2001-01-01

Experimental data on extraction of halides, among which are LiCl and CsCl, and water by copper di-(2-ethylhexyl)phosphate solutions in respect to hydrolysis mechanism of reaction are generalized. Copper di-(2-ethylhexyl)phosphate manifests properties of ionogen colloidal surfactant in water. Extraction of halides by copper di-(2-ethylhexyl)phosphate was shown to be visualized by the process of capsule formation in MHal molecules, as well as in hydrolyzed MOH and HHal forms of electrolyte by Cu 4 (D2EHF) 8 · hH 2 O clathrate-like micellar associates. The model of hydrolysis mechanism is not different from proposed earlier model of electrolyte extraction with their partial dissociation in organic phase [ru

Molecular dynamics study of the hydration of Lennard-Jones solutes

International Nuclear Information System (INIS)

Geiger, A.; Rahman, A.; Stillinger, F.H.

1979-01-01

In order to clarify the nature of hydrophobic interactions in water, we have used the molecular dynamics simulation method to study a system comprising two Lennard-Jones solute particles and 214 water molecules. Although the solutes were placed initially in contact, forces in the system drive them slightly apart to permit formation of vertex-sharing solvent ''cages.'' Definite orientational preferences have been observed for water molecules in the first solvation layer around the Lennard-Jones solutes; these preferences are loosely reminiscent of structure in clathrates. Nevertheless, substantial local disorder is obviously present. The dynamical data show that translational and rotational motions of solvation--sheath water molecules are perceptibly slower (by at least 20%) than those in pure bulk water

Solid organic residues produced by irradiation of hydrocarbon-containing H2O and H2O/NH3 ices - Infrared spectroscopy and astronomical implications

International Nuclear Information System (INIS)

Khare, B.N.; Thompson, W.R.; Murray, B.G.J.P.T.; Chyba, C.F.; Sagan, C.

1989-01-01

Plasma-discharge irradiations were conducted for the methane clathrate expected in outer solar system satellites and cometary nuclei; also irradiated were ices prepared from other combinations of H 2 O with CH 4 , C 2 H 6 , or C 2 H 2 . Upon evaporation of the yellowish-to-tan irradiated ices, it is found that a colored solid film adheres to the walls of the reaction vessel at room temperature. These organic films are found to exhibit IR band identifiable with alkane, aldehide, alcohol, and perhaps alkene, as well as substituted aromatic functional groups. These spectra are compared with previous studies of UV- or photon-irradiated nonclathrated hydrocarbon-containing ices. 73 refs

Review of Solid State Hydrogen Storage Methods Adopting Different Kinds of Novel Materials

Directory of Open Access Journals (Sweden)

Renju Zacharia

2015-01-01

Full Text Available Overview of advances in the technology of solid state hydrogen storage methods applying different kinds of novel materials is provided. Metallic and intermetallic hydrides, complex chemical hydride, nanostructured carbon materials, metal-doped carbon nanotubes, metal-organic frameworks (MOFs, metal-doped metal organic frameworks, covalent organic frameworks (COFs, and clathrates solid state hydrogen storage techniques are discussed. The studies on their hydrogen storage properties are in progress towards positive direction. Nevertheless, it is believed that these novel materials will offer far-reaching solutions to the onboard hydrogen storage problems in near future. The review begins with the deficiencies of current energy economy and discusses the various aspects of implementation of hydrogen energy based economy.

Structure and dynamics of cold water super-Earths: the case of occluded CH4 and its outgassing

International Nuclear Information System (INIS)

Levi, A.; Podolak, M.; Sasselov, D.

2014-01-01

In this work, we study the transport of methane in the external water envelopes surrounding water-rich super-Earths. We investigate the influence of methane on the thermodynamics and mechanics of the water mantle. We find that including methane in the water matrix introduces a new phase (filled ice), resulting in hotter planetary interiors. This effect renders the super-ionic and reticulating phases accessible to the lower ice mantle of relatively low-mass planets (∼5 M E ) lacking a H/He atmosphere. We model the thermal and structural profile of the planetary crust and discuss five possible crustal regimes which depend on the surface temperature and heat flux. We demonstrate that the planetary crust can be conductive throughout or partly confined to the dissociation curve of methane clathrate hydrate. The formation of methane clathrate in the subsurface is shown to inhibit the formation of a subterranean ocean. This effect results in increased stresses on the lithosphere, making modes of ice plate tectonics possible. The dynamic character of the tectonic plates is analyzed and the ability of this tectonic mode to cool the planet is estimated. The icy tectonic plates are found to be faster than those on a silicate super-Earth. A mid-layer of low viscosity is found to exist between the lithosphere and the lower mantle. Its existence results in a large difference between ice mantle overturn timescales and resurfacing timescales. Resurfacing timescales are found to be 1 Ma for fast plates and 100 Ma for sluggish plates, depending on the viscosity profile and ice mass fraction. Melting beneath spreading centers is required in order to account for the planetary radiogenic heating. The melt fraction is quantified for the various tectonic solutions explored, ranging from a few percent for the fast and thin plates to total melting of the upwelled material for the thick and sluggish plates. Ice mantle dynamics is found to be important for assessing the composition of the

Gas hydrate phase equilibria measurement techniques and phase rule considerations

International Nuclear Information System (INIS)

Beltran, Juan G.; Bruusgaard, Hallvard; Servio, Phillip

2012-01-01

Highlights: → Inconsistencies found in hydrate literature. → Clarification to the number of variables needed to satisfy and justify equilibrium data. → Application of phase rule to mixed hydrate systems. → Thermodynamically consistent format to present data. - Abstract: A brief review of the Gibbs phase rule for non-reacting systems and its correct application to clathrate hydrates is presented. Clarification is provided for a common mistake found in hydrate phase-equilibria literature, whereby initial compositions are used as intensive variables to satisfy the Gibbs phase rule instead of the equilibrium values. The system of (methane + carbon dioxide + water) under (hydrate + liquid + vapor) equilibrium is used as a case study to illustrate key points and suggestions to improve experimental techniques are proposed.

Martian Methane From a Cometary Source: A Hypothesis

Science.gov (United States)

Fries, M.; Christou, A.; Archer, D.; Conrad, P.; Cooke, W.; Eigenbrode, J.; ten Kate, I. L.; Matney, M.; Niles, P.; Sykes, M.;

Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes

DEFF Research Database (Denmark)

Herslund, Peter Jørgensen

A novel gas separation technique based on gas hydrate formation (solid precipitation) is investigated by means of thermodynamic modeling and experimental investigations. This process has previously been proposed for application in post-combustion carbon dioxide capture from power station flue gases...... formation may be performed at pressures of approximately 20 MPa and temperatures below 280 K. Thermodynamic promoters are needed, to reduce the pressure requirement of the process, thereby making it competitive to existing capture technologies. A literature study is presented focusing mainly...... on thermodynamic gas hydrate promotion by hydrate formers stabilising the classical gas clathrate hydrate structures (sI, sII and sH) at low to moderate pressures. Much literature is available on this subject. Both experimental and theoretical studies presented in the literature have pointed out cyclopentane...

Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates

Science.gov (United States)

Saad Khan, Muhammad; Yaqub, Sana; Manner, Naathiya; Ani Karthwathi, Nur; Qasim, Ali; Mellon, Nurhayati Binti; Lal, Bhajan

2018-04-01

Clathrate hydrates are eminent structures regard as a threat to the gas and oil industry in light of their irritating propensity to subsea pipelines. For natural gas transmission and processing, the formation of gas hydrate is one of the main flow assurance delinquent has led researchers toward conducting fresh and meticulous studies on various aspects of gas hydrates. This paper highlighted the thermodynamic analysis on pure CH4 and CO2 gas hydrates on the custom fabricated equipment (Sapphire cell hydrate reactor) for experimental validation. CO2 gas hydrate formed at lower pressure (41 bar) as compared to CH4 gas hydrate (70 bar) while comparison of thermodynamic properties between CH4 and CO2 also presented in this study. This preliminary study could provide pathways for the quest of potent hydrate inhibitors.

Global Energy Issues and Alternate Fueling

Science.gov (United States)

Hendricks, Robert C.

2007-01-01

This viewgraph presentation describes world energy issues and alternate fueling effects on aircraft design. The contents include: 1) US Uses about 100 Quad/year (1 Q = 10(exp 15) Btu) World Energy Use: about 433 Q/yr; 2) US Renewable Energy about 6%; 3) Nuclear Could Grow: Has Legacy Problems; 4) Energy Sources Primarily NonRenewable Hydrocarbon; 5) Notes; 6) Alternate Fuels Effect Aircraft Design; 7) Conventional-Biomass Issue - Food or Fuel; 8) Alternate fuels must be environmentally benign; 9) World Carbon (CO2) Emissions Problem; 10) Jim Hansen s Global Warming Warnings; 11) Gas Hydrates (Clathrates), Solar & Biomass Locations; 12) Global Energy Sector Response; 13) Alternative Renewables; 14) Stratospheric Sulfur Injection Global Cooling Switch; 15) Potential Global Energy Sector Response; and 16) New Sealing and Fluid Flow Challenges.

Thermal expansion and magnetostriction of clathrate compound Pr3Pd20Ge6

Science.gov (United States)

Matsumoto, K.; Sekiguchi, Y.; Iwakami, O.; Ono, T.; Abe, S.; Ano, G.; Akatsu, M.; Mitsumoto, K.; Nemoto, Y.; Goto, T.; Takeda, N.; Kitazawa, H.

2018-03-01

In Pr3Pd20Ge6, the Pr ions are located at two different crystallographic sites, 4a and 8c site. Antiferro-quadrupole ordering (AFQ) of the 8c site occurs at 250 mK. Ac susceptibility measurement indicated that antiferromagnetic ordering (AFM) of the 4a site and Hyperfine-enhanced Pr nuclear magnetic ordering of the 8c site occur at 77 and 9 mK, respectively. To clarify the magnetic and quadrupole properties of Pr3Pd20Ge6, thermal expansion and magnetostriction measurements on single crystal sample were carried out along the [001] direction up to 8 T down to 500 μK using a capacitive dilatometer. In zero field, relative length change ΔL/L in [001] direction had a dip at AFQ and abrupt decrease at AFM ordering. From thermal expansion and isothermal magnetostriction measurements, magnetic phase diagram of Pr3Pd20Ge6 along [001] direction was obtained.

Large methane releases lead to strong aerosol forcing and reduced cloudiness

DEFF Research Database (Denmark)

Kurten, T.; Zhou, L.; Makkonen, R.

2011-01-01

forcing that is comparable in magnitude to the long-wave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O-3 and CH4-OHaerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously......The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller...... contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4) levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations...

Defining the Thermal Stability of Ba8Ga16Ge30 and its Future in Thermoelectrics

DEFF Research Database (Denmark)

Reardon, Hazel; Iversen, Bo Brummerstedt; Blichfeld, Anders Bank

The majority of research on the auspicious n/p-Ba8Ga16-xGe30+x (BGG) Type-I thermoelectric clathrates has been focused on property measurements at low temperature. High temperature property measurements have also been reported for BGG, although they have not yet been fully explained. Therefore...... to evaluate the underlying chemistry of the anomalies seen in thermoelectric property measurements. Using X-ray diffraction and DTA-TG, we have discovered that BGG is not chemically stable at high temperatures over a range of thermal treatment periods. Our variable temperature synchrotron XRD measurements...... and longer term annealing experiments reveal that Ge evolution is the first indicator of BGG decomposition. This presentation summarizes the results from these research activities and highlight that the slow decomposition kinetics of BGG have been overlooked on the timescales typically used...

VOLATILE TRANSPORT INSIDE SUPER-EARTHS BY ENTRAPMENT IN THE WATER-ICE MATRIX

Energy Technology Data Exchange (ETDEWEB)

Levi, A.; Podolak, M. [Department of Geophysics and Planetary Science, Tel Aviv University, Tel Aviv 69978 (Israel); Sasselov, D., E-mail: amitlevi.planetphys@gmail.com [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

2013-05-20

Whether volatiles can be entrapped in a background matrix composing planetary envelopes and be dragged via convection to the surface is a key question in understanding atmospheric fluxes, cycles, and composition. In this paper, we consider super-Earths with an extensive water mantle (i.e., water planets), and the possibility of entrapment of methane in their extensive water-ice envelopes. We adopt the theory developed by van der Waals and Platteeuw for modeling solid solutions, often used for modeling clathrate hydrates, and modify it in order to estimate the thermodynamic stability field of a new phase called methane filled ice Ih. We find that in comparison to water ice VII the filled ice Ih structure may be stable not only at the high pressures but also at the high temperatures expected at the core-water mantle transition boundary of water planets.

Structural Relaxations and Thermodynamic Properties of Molecular Amorphous Solids by Mechanical Milling

Science.gov (United States)

Tsukushi, I.; Yamamuro, O.; Matsuo, T.

The organic crystals of tri-O-methyl-β-cyclodextrin (TMCD) and its three clathrate compounds containing benzoic acid (BA), p-nitrobenzoic acid (NBA) and p-hydroxybenzoic acid (HBA), sucrose (SUC), salicin (SAL), phenolphthalein (PP), 1,3,5-tri-α-naphthylbenzene (TNB) were amorphized by milling with a vibrating mill for 2 ˜ 16 hours at room temperature. The amorphization was checked by differential scanning calorimetry (DSC) and X-ray powder diffraction. The heat capacities of crystals, liquid quenched glasses (LQG), and mechanically-milled amorphous solid (MMAS) of TMCD and TNB were measured with an adiabatic calorimeter in the temperature range between 12 and 375 K. For both compounds, the enthalpy relaxation of MMAS appeared in the wide temperature range below Tg and the released configurational enthalpy was much larger than that of LQG, indicating that MMAS is more disordered and strained than LQG.

Glycine Betaine Recognition through Cation−π Interactions in Crystal Structures of Glycine Betaine Complexes with C-Ethyl-pyrogallol[4]arene and C-Ethyl-resorcin[4]arene as Receptors

Directory of Open Access Journals (Sweden)

Ikuhide Fujisawa

2013-04-01

Full Text Available The glycine betaine (betaine, interacts with several types of proteins with diverse structures in vivo, and in the contact regions, the aromatic rings of protein residues are frequently found beside the trimethylammonium group of betaine, implying the importance of the cation−π interactions in recognition of this molecule. The crystal structures determined by X-ray crystallography of the complexes of betaine and C-ethyl-pyrogallol[4]arene (pyrogallol cyclic tetramer: PCT and betaine and C-ethyl-resorcin[4]arene (resorcinol cyclic tetramer: RCT mimic the conformations of betaine and protein complexes and show that the clathrate conformations are retained by the cation−π interactions. The difference of the conformation feature of betaine in the Protein Data Bank and in the Cambridge Structural Database was found by chance during the research and analyzed with the torsion angles.

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Science.gov (United States)

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.

Thermal transport property of Ge34 and d-Ge investigated by molecular dynamics and the Slack's equation

International Nuclear Information System (INIS)

Han-Fu, Wang; Wei-Guo, Chu; Yan-Jun, Guo; Hao, Jin

2010-01-01

In this study, we evaluate the values of lattice thermal conductivity κ L of type II Ge clathrate (Ge 34 ) and diamond phase Ge crystal (d-Ge) with the equilibrium molecular dynamics (EMD) method and the Slack's equation. The key parameters of the Slack's equation are derived from the thermodynamic properties obtained from the lattice dynamics (LD) calculations. The empirical Tersoff's potential is used in both EMD and LD simulations. The thermal conductivities of d-Ge calculated by both methods are in accordance with the experimental values. The predictions of the Slack's equation are consistent with the EMD results above 250 K for both Ge 34 and d-Ge. In a temperature range of 200–1000 K, the κ L value of d-Ge is about several times larger than that of Ge 34 . (condensed matter: structure, thermal and mechanical properties)

Large methane releases lead to strong aerosol forcing and reduced cloudiness

DEFF Research Database (Denmark)

Kurten, T.; Zhou, L.; Makkonen, R.

2011-01-01

The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller...... is predicted to significantly decrease hydroxyl radical (OH) concentrations, while moderately increasing ozone (O-3). These changes lead to a 70% increase in the atmospheric lifetime of methane, and an 18% decrease in global mean cloud droplet number concentrations (CDNC). The CDNC change causes a radiative...... forcing that is comparable in magnitude to the long-wave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O-3 and CH4-OHaerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously...

Investigating Molecular Interactions

DEFF Research Database (Denmark)

Clausen, Henrik Fanø

2010-01-01

···π interactions are accommodated by electrostatic complementarity. The crystal structure of both the α- and the β-polymorph of hydroquinone is presented in Chapter 6 with focus on close intermolecular contacts between the molecules via Hirshfeld surface analysis. The charge density distribution of the empty β....... The last chapter of this dissertation presents the analysis of intermolecular interaction using both the Hirshfeld surface and charge density distribution of the acetonitrile β-hydroquinone clathrate. The local packing and related close contacts are examined by breakdown of the fingerprint plots revealing......, are also introduced, as a goal of the analysis of charge density distributions is to obtain further understanding of these macroscopic properties. Neutron diffraction will be used as a complementary tool to the X-ray diffraction experiment, as positional and thermal parameters of hydrogen atoms can...

The genetic source and timing of hydrocarbon formation in gas hydrate reservoirs in Green Canyon, Block GC955

Science.gov (United States)

Moore, M. T.; Darrah, T.; Cook, A.; Sawyer, D.; Phillips, S.; Whyte, C. J.; Lary, B. A.

2017-12-01

Although large volumes of gas hydrates are known to exist along continental slopes and below permafrost, their role in the energy sector and the global carbon cycle remains uncertain. Investigations regarding the genetic source(s) (i.e., biogenic, thermogenic, mixed sources of hydrocarbon gases), the location of hydrocarbon generation, (whether hydrocarbons formed within the current reservoir formations or underwent migration), rates of clathrate formation, and the timing of natural gas formation/accumulation within clathrates are vital to evaluate economic potential and enhance our understanding of geologic processes. Previous studies addressed some of these questions through analysis of conventional hydrocarbon molecular (C1/C2+) and stable isotopic (e.g., δ13C-CH4, δ2H-CH4, δ13C-CO2) composition of gases, water chemistry and isotopes (e.g., major and trace elements, δ2H-H2O, δ18O-H2O), and dissolved inorganic carbon (δ13C-DIC) of natural gas hydrate systems to determine proportions of biogenic and thermogenic gas. However, the effects from contributions of mixing, transport/migration, methanogenesis, and oxidation in the subsurface can complicate the first-order application of these techniques. Because the original noble gas composition of a fluid is preserved independent of microbial activity, chemical reactions, or changes in oxygen fugacity, the integration of noble gas data can provide both a geochemical fingerprint for sources of fluids and an additional insight as to the uncertainty between effects of mixing versus post-genetic modification. Here, we integrate inert noble gases (He, Ne, Ar, and associated isotopes) with these conventional approaches to better constrain the source of gas hydrate formation and the residence time of fluids (porewaters and natural gases) using radiogenic 4He ingrowth techniques in cores from two boreholes collected as part of the University of Texas led UT-GOM2-01 drilling project. Pressurized cores were extracted from

Thermodynamics of a post combustion hydrate-based carbon dioxide capture process

International Nuclear Information System (INIS)

Ben Attouche Sfaxi, I.

2011-07-01

Hydrates selectivity towards carbon dioxide is offering a promising route for carbon dioxide removal from flue gases. Hydrate-based CO 2 capture process could substitute amine facilities widely implemented in gas treatment plants but suffering from oxidative degradation problems and high energy demand. In the framework of this thesis, we focus on phase equilibria that are involved in such process. Experimental dissociation conditions for clathrate hydrates of carbon dioxide and nitrogen, in the presence of some promoting molecules (Tetrahydrofuran, Tetrabutyl ammonium bromide and Tetrabutyl ammonium Fluoride ) are reported in the experimental section of this work. The data generated in this work along with literature data are compared to the model predictions. The developed model is based on the Cubic Plus Association (CPA) equation of state (EoS) for fluid phases combined to the van der Waals and Platteeuw's theory for the hydrate phase. (author)

Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

Science.gov (United States)

Prasad, Pinnelli S R; Sugahara, Takeshi; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-10-22

Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

(CH4)-C-14 Measurements in Greenland Ice: Investigating Last Glacial Termination CH4 Sources

DEFF Research Database (Denmark)

Petrenko, V. V.; Smith, A. M.; Brook, E. J.

2009-01-01

by direct cosmogenic C-14 production in ice. C-14 of CO was measured to better understand this process and correct the sample (CH4)-C-14. Corrected results suggest that wetland sources were likely responsible for the majority of the Younger Dryas-Preboreal CH4 rise.......The cause of a large increase of atmospheric methane concentration during the Younger Dryas-Preboreal abrupt climatic transition (similar to 11,600 years ago) has been the subject of much debate. The carbon-14 (C-14) content of methane ((CH4)-C-14) should distinguish between wetland and clathrate...... contributions to this increase. We present measurements of (CH4)-C-14 in glacial ice, targeting this transition, performed by using ice samples obtained from an ablation site in west Greenland. Measured (CH4)-C-14 values were higher than predicted under any scenario. Sample (CH4)-C-14 appears to be elevated...

Synthesis and Stability of Lanthanum Superhydrides

Energy Technology Data Exchange (ETDEWEB)

Geballe, Zachary M. [Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; Liu, Hanyu [Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; Mishra, Ajay K. [Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; Permanent address: HP& SRPD, Bhabha Atomic Research Center, Mumbai-85 India; Ahart, Muhtar [Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; Somayazulu, Maddury [Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; Meng, Yue [HPCAT, Geophysical Laboratory, Carnegie Institution of Washington, Argonne IL 60439 USA; Baldini, Maria [Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; Hemley, Russell J. [Institute of Materials Science and Department of Civil and Environmental Engineering, The George Washington University, Washington DC 20052 USA

2017-12-15

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH10 having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1 Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.

Physicochemically modified peat by thermal and oxidation processes as an active material for purification of wastewaters from certain hazardous pollutants

Directory of Open Access Journals (Sweden)

Purenović Jelena M.

2017-01-01

Full Text Available The physicochemical modification of peat through thermal and oxidation processes was carried out, in order to obtain new, inexpensive and active material for purification of different types of waters. During the modification, surface chemical compounds of Shilov type were formed. Batch adsorption properties and suitability of physicochemically modified peat (PCMP for odor removal were tested in aqueous solutions of H2S and colloidal sulphur. Additionally, PCMP was tested in the removal of As(V which is hazardous ingredient in contaminated waters. Possible mechanisms of pollutants binding include interactions, which lead to formation of adducts and clathrates. All these processes are elucidated in detail. The results showed that the obtained material can be used for the removal of sulphide, colloidal sulphur and As(V from different types of waters. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III 45012

Macroscopic investigation of water volume effects on interfacial dynamic behaviors between clathrate hydrate and water.

Science.gov (United States)

Cha, Minjun; Couzis, Alexander; Lee, Jae W

2013-05-14

This study investigated the effects of the water volume on the interfacial dynamics between cyclopentane (CP) hydrate and water droplet in a CP/n-decane oil mixture. The adhesion force between CP hydrate and various water droplets was determined using the z-directional microbalance. Through repetition of precise measurements over several cycles from contact to detachment, we observed abnormal wetting behaviors in the capillary bridge during the retraction process when the water drop volume is larger than 100 μL. With the increase in water droplet volumes, the contact force between CP hydrate and water also increases up to 300 μL. However, there is a dramatic reduction of increasing rate in the contact forces over 300 μL of water droplet. With the addition of the surfactants of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) to the water droplet, the contact force between CP hydrate and solution droplet exhibits a lower value and a transition volume of the contact force comes with a smaller solution volume of 200 μL. The water volume effects on the liquid wetting of the probe and the size of capillary bridges provide important insight into hydrate growth and aggregation/agglomeration in the presence of free water phase inside gas/oil pipelines.

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ

Energy Technology Data Exchange (ETDEWEB)

Wang, Hsiu-Wen; Fanelli, Victor R.; Reiche, Helmut M.; Larson, Eric; Taylor, Mark A.; Siewenie, Joan [Lujan Neutron Scattering Center, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Xu, Hongwu [Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Zhu, Jinlong [High Pressure Science and Engineering Center, Department of Physics and Astronomy, The University of Nevada, Las Vegas, Nevada 89154, USA and National Lab for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Page, Katharine, E-mail: pagekl@ornl.gov [Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

2014-12-15

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO{sub 2} measurements. The new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO{sub 2} sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H{sub 2} and natural gas uptake/storage.

The infrared spectral properties of frozen volatiles. [in cometary nuclei

Science.gov (United States)

Fink, U.; Sill, G. T.

1982-01-01

Since Whipple's dirty snowball model of comet nuclei, it has been generally accepted that volatile ices help to explain cometary phenomena. The infrared spectral properties of many substances that are potential candidates for frozen volatiles in the solar system are being pursued; indeed some of these frozen materials have been found in the solar system: H2O, CO2, and SO2. A review of laboratory spectra in the range 1 to 20 microns of H2O, CO2, SO2, CH4, NH3, H2S, CO, NH4HS and NH3.H2O is presented. Both reflection spectra of thick frosts and transmission spectra of thin films are shown, and their main characteristics are described. Hydrates, clathrates, and composite spectra are discussed. When it is possible to observe the nuclei of comets at close range, it may be possible to identify frozen volatiles by their infrared spectra.

Synthesis and stability of lanthanum superhydrides

Energy Technology Data Exchange (ETDEWEB)

Geballe, Zachary M.; Liu, Hanyu; Mishra, Ajay K.; Ahart, Muhtar; Somayazulu, Maddury; Baldini, Maria [Geophysical Laboratory, Carnegie Institution, Washington, DC (United States); Meng, Yue [HPCAT, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL (United States); Hemley, Russell J. [Institute of Materials Science and Department of Civil and Environmental Engineering, The George Washington University, Washington, DC (United States)

2018-01-15

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH{sub 10} having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1 Aa, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Action of acoustical oscillations and hydrodynamic factors on the chemical activity of iodne in solution

International Nuclear Information System (INIS)

Nikolaev, L.A.; Fadeev, G.N.

1984-01-01

Investigation results on the effect of acoustic oscillations within the frequency range of 1-500 Hz on aqueous iodine solutions and dark blue iodide-starch complex have been presented. Experiments were carried out within the range of action of acoustical and hydrodynamic oscillations without visual formation of bubbles. Form of kinetic dependences corresponds to the first order reaction in respect to iodine. Sharp increase of solution electric conductivity and noticeable increase of medium acidity were observed after the action of oscillations. It has been shown that low-frequency oscillations strengthen iodine hydrolysis and lead to iodate atom formation. Effect of oscillations with 25-30 Hz upon the iodide-starch complex results in the complex destruction, i. e. iodide atom chains removal out of clathrate starch cavities. Formation of iodide-starch complexes is promoted under the action of 250 Hz frequency, as such oscillations lead to the change of starch structure, but do not effect upon iodide

Production of Xenon Compounds by the Beta Decay of Iodine in Iodine Compounds; Production de Composes du Xenon par Desintegration Beta de l'Iode dans les Composes Iodes; 041f 0420 041e 0418 0417 0412 041e 0414 0421 0422 0412 041e 0421 041e 0415 0414 0418 041d 0415 041d 0418 0419 041a 0421 0415 041d 041e 041d 0410 041f 041e 0421 0420 0415 0414 0421 0422 0412 041e 041c 0411 0415 0422 0410 - 0420 0410 0421 041f 0410 0414 0410 0419 041e 0414 0410 0412 0419 041e 0414 0418 0421 0422 042b 0425 0421 041e 0415 0414 0418 041d 0415 041d 0418 042f 0425 ; Produccion de Compuestos de Xenon por Desintegracion Beta del Yodo de Compuestos Yodados

Energy Technology Data Exchange (ETDEWEB)

Perlow, G. J.; Perlow, M. R. [Argonne National Laboratory, Argonne, IL (United States)

1965-04-15

It is known that most beta decays cause no change in the electron number of the atom containing the decaying nucleus. In the beta decay I{sup 129} -Xe{sup 129} in an iodine compound the electronic structure and geometry are often appropriate for formation of a xenon compound with the same ligands. This process has been discovered and studied by use of the Moessbauer effect in Xe{sup 129}. The first-excited state in Xe{sup 129} has J{sup {pi}} = 3+/2, T{sub Vulgar-Fraction-One-Half} = 10{sup -9} * s, and lies 40 keV above the Vulgar-Fraction-One-Half {sup +} ground state. It is populated by decay from 1,6 x 10{sup 6} y. I{sup 129}. The Moessbauer effect of the 40-keV gamma ray may readily be observed with a variety of sources and absorbers in experiments done at 4.2 Degree-Sign K. The electric quadrupole splitting of the excited state results in two absorption lines when the Doppler shift is used to scan the spectrum. The separation between lines characterizes the electronic configuration on the xenon and often unequivocally identifies the structure. In the first experiments a source of Nal{sup 129} was used with absorbers of hydroquinone clathrate, Na{sub 4}XeO{sub 6}, XeF{sub 4}, and XeF{sub 2}. Single-line spectra were observed for the clathrate and pexenate, and two-line spectra for the fluorides. The single line indicates that in the source I{sup -} -{yields} Xe{sup 0}, its iso-electronic daughter. When Na{sub 3}H{sub 2}IO{sub 6} was used as source, with clathrate absorber, the recoil-less fraction increased by a factor of 3, implying stronger bonding. KIO{sub 4} also gave a single but somewhat less intense line. With NalO{sub 3} as source and clathrate absorber, splitting was observed suggesting that IO{sub 3}{sup -} -{yields} XeO{sub 6}. This was verified by the observation of identical splitting in an XeO{sub 3} absorber used with KIO{sub 4} source. An experiment with KIC1{sub 4} * H{sub 2}O as source and clathrate absorber showed splitting somewhat smaller

Enceladus' near-surface CO2 gas pockets and surface frost deposits

Science.gov (United States)

Matson, Dennis L.; Davies, Ashley Gerard; Johnson, Torrence V.; Combe, Jean-Philippe; McCord, Thomas B.; Radebaugh, Jani; Singh, Sandeep

2018-03-01

Solid CO2 surface deposits were reported in Enceladus' South Polar Region by Brown et al. (2006). They noted that such volatile deposits are temporary and posited ongoing replenishment. We present a model for this replenishment by expanding on the Matson et al. (2012) model of subsurface heat and chemical transport in Enceladus. Our model explains the distributions of both CO2 frost and complexed CO2 clathrate hydrate as seen in the Cassini Visual and Infrared Mapping Spectrometer (VIMS) data. We trace the journey of CO2 from a subsurface ocean. The ocean-water circulation model of Matson et al. (2012) brings water up to near the surface where gas exsolves to form bubbles. Some of the CO2 bubbles are trapped and form pockets of gas in recesses at the bottom of the uppermost ice layer. When fissures break open these pockets, the CO2 gas is vented. Gas pocket venting is episodic compared to the more or less continuous eruptive plumes, emanating from the "tiger stripes", that are supported by plume chambers. Two styles of gas pocket venting are considered: (1) seeps, and (2) blowouts. The presence of CO2 frost patches suggests that the pocket gas slowly seeped through fractured, cold ice and when some of the gas reached the surface it was cold enough to condense (i.e., T ∼70 to ∼119 K). If the fissure opening is large, a blowout occurs. The rapid escape of gas and drop in pocket pressure causes water in the pocket to boil and create many small aerosol droplets of seawater. These may be carried along by the erupting gas. Electrically charged droplets can couple to the magnetosphere, and be dragged away from Enceladus. Most of the CO2 blowout gas escapes from Enceladus and the remainder is distributed globally. However, CO2 trapped in a clathrate structure does not escape. It is much heavier and slower moving than the CO2 gas. Its motion is ballistic and has an average range of about 17 km. Thus, it contributes to deposits in the vicinity of the vent. Local heat

The carbon budget in the outer solar nebula.

Science.gov (United States)

Simonelli, D P; Pollack, J B; McKay, C P; Reynolds, R T; Summers, A L

1989-01-01

Detailed models of the internal structures of Pluto and Charon, assuming rock and water ice as the only constituents, indicate that the mean silicate mass fraction of this two-body system is on the order of 0.7; thus the Pluto/Charon system is significantly "rockier" than the satellites of the giant planets (silicate mass fraction approximately 0.55). This compositional contrast reflects different formation mechanisms: it is likely that Pluto and Charon formed directly from the solar nebula, while the circumplanetary nebulae that produced the giant planet satellites were derived from envelopes that surrounded the forming giant planets (envelopes in which icy planetesimals dissolved more readily than rocky planetesimals). Simple cosmic abundance calculations, and the assumption that the Pluto/Charon system formed directly from solar nebula condensates, strongly suggest that the majority of the carbon in the outer solar nebula was in the form of carbon monoxide; these results are consistent with (1) inheritance from the dense molecular clouds in the interstellar medium (where CH4/CO nebula chemistry. Theoretical predictions of the C/H enhancements in the atmospheres of the giant planets, when compared to the actual observed enhancements, suggest that 10%, or slightly more, of the carbon in the outer solar nebula was in the form of condensed materials (although the amount of condensed C may have dropped slightly with increasing heliocentric distance). Strict compositional limits computed for the Pluto/Charon system using the densities of CH4 and CO ices indicate that these pure ices are at best minor components in the interiors of these bodies, and imply that CH4 and CO ices were not the dominant C-bearing solids in the outer nebula. Clathrate-hydrates could not have appropriated enough CH4 or CO to be the major form of condensed carbon, although such clathrates may be necessary to explain the presence of methane on Pluto after its formation from a CO-rich nebula

Megafauna and frozen soil: the drivers of atmospheric CH4 dynamics

Science.gov (United States)

Zimov, N.; Zimov, S. A.

2010-12-01

During the last deglaciation (LD) a strong increase in atmospheric methane (CH4) concentrations occurred simultaneously with a rise in Greenland temperatures indicating that in the north, during this time period, strong CH4 sources “awakened”, as additionally documented by the appearance of a strong gradient between northern (Greenland) and southern (Antarctica) hemisphere atmospheric CH4 concentrations. This rise could not be caused by wetland expansion. A reconstruction of peatland formation dynamics has indicated that wetlands on Earth were few in LD and only actively expanded 10,000 yr BP, after atmospheric CH4 concentrations began to decline. Destabilization of methane clathrates also could not be the source for atmospheric CH4 increase. Geological CH4 (including methane clathrates) has the highest deuterium content (δD) among all of the known sources of CH4 while atmospheric CH4 δD values determined for the LD were record low. To explain recorded atmospheric CH4 and its isotopic dynamics required a strong northern source, which was active only during the LD and that provided very low δD CH4 values. Such a source is permafrost thawing under anaerobic conditions (or better stated soils of mammoth steppe-tundra ecosystems). Permafrost thawing is the strongest, among known, wetland sources (usually over 100g CH4/m2yr) and has a unique isotopic signature (δD = -400 per mil (-338 to -479 per mil), δ13C = -73 per mil (-58 to -99 per mil)). The main sources of atmospheric CH4 have different isotopic signatures (δ13C, δD). The isotopic content of atmospheric CH4 is a simple function of the weight average for all of the sources. Inclusion of permafrost source into a budget model of the atmospheric methane and its isotopes allowed us to reconstruct the dynamics of methane’s main sources. Model indicated geological source to be negligible as in LGM so and in LD and Holocene. During the glaciation, the largest methane source was megafauna, whose 1

Molecular storage of ozone in a clathrate hydrate: an attempt at preserving ozone at high concentrations.

Directory of Open Access Journals (Sweden)

Takahiro Nakajima

Full Text Available This paper reports an experimental study of the formation of a mixed O(3+ O(2+ CO(2 hydrate and its frozen storage under atmospheric pressure, which aimed to establish a hydrate-based technology for preserving ozone (O(3, a chemically unstable substance, for various industrial, medical and consumer uses. By improving the experimental technique that we recently devised for forming an O(3+ O(2+ CO(2 hydrate, we succeeded in significantly increasing the fraction of ozone contained in the hydrate. For a hydrate formed at a system pressure of 3.0 MPa, the mass fraction of ozone was initially about 0.9%; and even after a 20-day storage at -25°C and atmospheric pressure, it was still about 0.6%. These results support the prospect of establishing an economical, safe, and easy-to-handle ozone-preservation technology of practical use.

Water for energy and fuel production

CERN Document Server

Shah, Yatish T

2014-01-01

Water, in all its forms, may be the key to an environmentally friendly energy economy. Water is free, there is plenty of it, plus it carries what is generally believed to be the best long-term source of green energy-hydrogen. Water for Energy and Fuel Production explores the many roles of water in the energy and fuel industry. The text not only discusses water's use as a direct source of energy and fuel-such as hydrogen from water dissociation, methane from water-based clathrate molecules, hydroelectric dams, and hydrokinetic energy from tidal waves, off-shore undercurrents, and inland waterways-but also: Describes water's benign application in the production of oil, gas, coal, uranium, biomass, and other raw fuels, and as an energy carrier in the form of hot water and steam Examines water's role as a reactant, reaction medium, and catalyst-as well as steam's role as a reactant-for the conversion of raw fuels to synthetic fuels Explains how supercritical water can be used to convert fossil- and bio-based feed...

Tetra-n-butylammonium borohydride semiclathrate: a hybrid material for hydrogen storage.

Science.gov (United States)

Shin, Kyuchul; Kim, Yongkwan; Strobel, Timothy A; Prasad, P S R; Sugahara, Takeshi; Lee, Huen; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-06-11

In this study, we demonstrate that tetra-n-butylammonium borohydride [(n-C(4)H(9))(4)NBH(4)] can be used to form a hybrid hydrogen storage material. Powder X-ray diffraction measurements verify the formation of tetra-n-butylammonium borohydride semiclathrate, while Raman spectroscopic and direct gas release measurements confirm the storage of molecular hydrogen within the vacant cavities. Subsequent to clathrate decomposition and the release of physically bound H(2), additional hydrogen was produced from the hybrid system via a hydrolysis reaction between the water host molecules and the incorporated BH(4)(-) anions. The additional hydrogen produced from the hydrolysis reaction resulted in a 170% increase in the gravimetric hydrogen storage capacity, or 27% greater storage than fully occupied THF + H(2) hydrate. The decomposition temperature of tetra-n-butylammonium borohydride semiclathrate was measured at 5.7 degrees C, which is higher than that for pure THF hydrate (4.4 degrees C). The present results reveal that the BH(4)(-) anion is capable of stabilizing tetraalkylammonium hydrates.

Proceedings of the 6. international conference on gas hydrates : ICGH 2008

Energy Technology Data Exchange (ETDEWEB)

Englezos, P. (ed.) [British Columbia Univ., Vancouver, BC (Canada); Ripmeester, J. (ed.) [National Research Council of Canada, Ottawa, ON (Canada); Dallimore, S.R. [Natural Resources Canada, Ottawa, ON (Canada). Geological Survey of Canada; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering; Austvik, T. [Statoil, Trondheim (Norway); Collett, T.S. [United States Geological Survey, Denver, CO (United States); Mehta, A. [Shell E and P Asia Pacific, Sarawak (Malaysia); Paull, C.K. [Monterey Bay Aquarium Research Inst., CA (United States); Sloan, E.D.Jr. [Colorado School of Mines, Golden, CO (United States); Uchida, T. [Hokkaido Univ., Sapporo (Japan)] (comps.)

2008-07-01

This international conference provided a forum to highlight gas hydrate research that is underway at academic institutions as well as government and industrial laboratories around the world. The gas or clathrate hydrate research community includes chemical, petroleum and mechanical engineers, geologists, geophysicists, marine biologists, chemists and physicists. The conference was attended by more than 500 delegates who presented their professional knowledge in all areas of the gas hydrates field, emphasizing new aspects. The topics of discussion included resource delineation, reservoir simulation modeling and production technology. Environmental considerations involving natural gas hydrates and global climate change were also highlighted along with carbon dioxide disposal in aquifers and deep oceans. Issues facing oil and gas operations were also discussed, with reference to flow assurance in pipelines, safety issues, permafrost and marine geohazards. Novel technologies involving hydrogen storage, carbon dioxide capture and sequestration were also highlighted along with basic science and engineering aspects of gas hydrate systems. All 417 presentations from the conference have been catalogued separately for inclusion in this database. refs., tabs., figs.

Natural Gas Hydrate as a Storage Mechanism for Safe, Sustainable and Economical Production from Offshore Petroleum Reserves

Directory of Open Access Journals (Sweden)

Michael T. Kezirian

2017-06-01

Full Text Available Century Fathom presents an innovative process to utilize clathrate hydrates for the production, storage and transportation of natural gas from off-shore energy reserves in deep ocean environments. The production scheme was developed by considering the preferred state of natural gas in the deep ocean and addressing the hazards associated with conventional techniques to transport natural gas. It also is designed to mitigate the significant shipping cost inherent with all methods. The resulting proposed scheme restrains transport in the hydrate form to the ocean and does not attempt to supply energy to the residential consumer. Instead; the target recipients are industrial operations. The resulting operational concept is intrinsically safer by design; environmentally sustainable and significantly cost-effective compared with currently proposed schemes for the use of natural gas hydrates and has the potential to be the optimal solution for new production of reserves; depending on the distance to shore and capacity of the petroleum reserve. A potential additional benefit is the byproduct of desalinated water.

Application of two-dimensional crystallography and image processing to atomic resolution Z-contrast images.

Science.gov (United States)

Morgan, David G; Ramasse, Quentin M; Browning, Nigel D

2009-06-01

Zone axis images recorded using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM or Z-contrast imaging) reveal the atomic structure with a resolution that is defined by the probe size of the microscope. In most cases, the full images contain many sub-images of the crystal unit cell and/or interface structure. Thanks to the repetitive nature of these images, it is possible to apply standard image processing techniques that have been developed for the electron crystallography of biological macromolecules and have been used widely in other fields of electron microscopy for both organic and inorganic materials. These methods can be used to enhance the signal-to-noise present in the original images, to remove distortions in the images that arise from either the instrumentation or the specimen itself and to quantify properties of the material in ways that are difficult without such data processing. In this paper, we describe briefly the theory behind these image processing techniques and demonstrate them for aberration-corrected, high-resolution HAADF-STEM images of Si(46) clathrates developed for hydrogen storage.

The phase diagram of water at negative pressures: virtual ices.

Science.gov (United States)

Conde, M M; Vega, C; Tribello, G A; Slater, B

2009-07-21

The phase diagram of water at negative pressures as obtained from computer simulations for two models of water, TIP4P/2005 and TIP5P is presented. Several solid structures with lower densities than ice Ih, so-called virtual ices, were considered as possible candidates to occupy the negative pressure region of the phase diagram of water. In particular the empty hydrate structures sI, sII, and sH and another, recently proposed, low-density ice structure. The relative stabilities of these structures at 0 K was determined using empirical water potentials and density functional theory calculations. By performing free energy calculations and Gibbs-Duhem integration the phase diagram of TIP4P/2005 was determined at negative pressures. The empty hydrates sII and sH appear to be the stable solid phases of water at negative pressures. The phase boundary between ice Ih and sII clathrate occurs at moderate negative pressures, while at large negative pressures sH becomes the most stable phase. This behavior is in reasonable agreement with what is observed in density functional theory calculations.

Proceedings of the 6. international conference on gas hydrates : ICGH 2008

International Nuclear Information System (INIS)

Englezos, P.; Ripmeester, J.; Dallimore, S.R.; Collett, T.S.; Mehta, A.; Paull, C.K.; Sloan, E.D.Jr.; Uchida, T.

2008-01-01

This international conference provided a forum to highlight gas hydrate research that is underway at academic institutions as well as government and industrial laboratories around the world. The gas or clathrate hydrate research community includes chemical, petroleum and mechanical engineers, geologists, geophysicists, marine biologists, chemists and physicists. The conference was attended by more than 500 delegates who presented their professional knowledge in all areas of the gas hydrates field, emphasizing new aspects. The topics of discussion included resource delineation, reservoir simulation modeling and production technology. Environmental considerations involving natural gas hydrates and global climate change were also highlighted along with carbon dioxide disposal in aquifers and deep oceans. Issues facing oil and gas operations were also discussed, with reference to flow assurance in pipelines, safety issues, permafrost and marine geohazards. Novel technologies involving hydrogen storage, carbon dioxide capture and sequestration were also highlighted along with basic science and engineering aspects of gas hydrate systems. All 417 presentations from the conference have been catalogued separately for inclusion in this database. refs., tabs., figs

Conference on Continental margin mass wasting and Pleistocene sea-level changes, August 13-15, 1980

Science.gov (United States)

Folger, David W.; Hathaway, J.C.

1987-01-01

A conference on Continental Margin Mass Wasting and Pleistocene Sea-Level Changes was held in Woods Hole, Mass., August 13-15, 1980. Forty-seven participants, representing many government, academic, and industrial organizations, discussed the current state of knowledge of the features of marine mass wasting and of the interrelations of factors influencing them. These factors include sediment source, composition, textures, sedimentation rates, climatic and sea-level changes, gas and gas hydrate (clathrate) contents of sediments, geotechnical characteristics, oceanographic and morphological factors, ground-water processes, and seismic events. The part played by these factors in the processes and features of mass movement and the engineering considerations imposed by the emplacement of manmade structures on the sea floor were considered vital to the evaluation of hazards involved in offshore exploration and development. The conference concluded with a call for bold programs to establish the probability of occurrence and the quantitative importance of these factors and to devise more reliable means of measurement, particularly in place, of the characteristics of the sediment and features involved.

Thermoelectric transport in rare-earth compounds

International Nuclear Information System (INIS)

Koehler, Ulrike

2007-01-01

This work focuses on the thermoelectric transport in rare-earth compounds. The measurements of the thermal conductivity, thermopower, and Nernst coefficient are supplemented by investigations of other quantities as magnetic susceptibility and specific heat. Chapter 2 provides an introduction to the relevant physical concepts. Section 1 of that chapter summarizes the characteristic properties of rare-earth systems; section 2 gives an overview on thermoelectric transport processes in magnetic fields. The applied experimental techniques as well as the new experimental setup are described in detail in Chapter 3. The experimental results are presented in Chapter 4-6, of which each concentrates on a different subject. In Chapter 4, various Eu clathrates and the skutterudite-like Ce 3 Rh 4 Sn 13 are presented, which have been investigated as potential thermoelectric materials for applications. Chapter 5 focusses on the study of the energy scales in the heavy-fermion series Lu 1-x Yb x Rh 2 Si 2 and Ce x La 1-x Ni 2 Ge 2 by means of thermopower investigations. Chapter 6 is dedicated to the thermoelectric transport properties of the correlated semimetal CeNiSn with special emphasis on the Nernst coefficient of this compound. (orig.)

High-pressure synchrotron infrared spectroscopy at the National Synchrotron Light Source

International Nuclear Information System (INIS)

Hemley, R.J.; Goncharov, A.F.; Lu, R.; Struzhkin, V.V.; Li, M.; Mao, H.K.

1998-01-01

The paper describes a synchrotron infrared facility for high-pressure spectroscopy and microspectroscopy at the National Synchrotron Light-Source (NSLS). Located at beamline U2B on the VUV ring of the NSLS, the facility utilizes a commercial FT-IR together with custom-built microscope optics designed for a variety of diamond anvil cell experiments, including low- and high- temperature studies. The system contains an integrated laser optical/grating spectrometer for concurrent optical experiments. The facility has been used to characterize a growing number of materials to ultrahigh pressure and has been instrumental of new high-pressure phenomena. Experiments on dense hydrogen to >200 GPa have led to the discovery of numerous unexpected properties of this fundamental system. The theoretically predicted molecular-atomic transition of H 2 O ice to the symmetric hydrogen-bonded structure has been identified, and new classes of high-density clathrates and molecular compounds have been characterized. Experiments on natural and synthetic mineral samples have been performed to study hydrogen speciation, phase transformations, and microscopic inclusions in multiphase assemblages. Detailed information on the behavior of new materials, including novel high-pressure glasses and ceramics, has also been obtained

FY 1991 Report on research and development of super heat pump energy accumulation system. Material for explanation (Construction and operation of the prototype system - researches on elementary techniques and construction and operation of the pilot system); Super heat pump energy shuseki system no kenkyu kaihatsu 1991 nendo seika hokokusho. Setsumei shiryo (system shisaku unten kenkyu (yoso gijutsu no kenkyu / pilot system no shisaku unten kenkyu))

Energy Technology Data Exchange (ETDEWEB)

NONE

1982-05-01

Summarized herein are R and D results of the researches on the super heat pump energy accumulation system, obtained from FY 1985 to 1991. For R and D of the super high performance compression heat pumps, the R and D results of the elementary techniques and bench and pilot plant operation are summarized for the highly efficient type (for heating) and highly efficient type (for cooling and heating), and high temperature type (utilizing high temperature heat source) and high temperature type (utilizing low temperature heat source). Described are patent application list, designated know-hows, and conclusions. For the elementary equipment and working fluids, the R and D results are summarized for the evaporators for mixed solvents, EHD condensers, and working fluids (alcohol-based fluids and application characteristics of new fluids) and working fluids (nonalcohol-based fluids and basic properties of new fluids). For the chemical heat storage techniques, the R and D results are summarized for the high temperature heat storage type (utilizing metathesis reactions, ammonia complexes and hydration reactions), and low temperature heat storage type (utilizing clathrates, hydration by solute mixing and solvation). (NEDO)

On the Phase Separation in n-Type Thermoelectric Half-Heusler Materials

Directory of Open Access Journals (Sweden)

Michael Schwall

2018-04-01

Full Text Available Half-Heusler compounds have been in focus as potential materials for thermoelectric energy conversion in the mid-temperature range, e.g., as in automotive or industrial waste heat recovery, for more than ten years now. Because of their mechanical and thermal stability, these compounds are advantageous for common thermoelectric materials such as Bi 2 Te 3 , SiGe, clathrates or filled skutterudites. A further advantage lies in the tunability of Heusler compounds, allowing one to avoid expensive and toxic elements. Half-Heusler compounds usually exhibit a high electrical conductivity σ , resulting in high power factors. The main drawback of half-Heusler compounds is their high lattice thermal conductivity. Here, we present a detailed study of the phase separation in an n-type Heusler materials system, showing that the Ti x Zr y Hf z NiSn system is not a solid solution. We also show that this phase separation is key to the thermoelectric high efficiency of n-type Heusler materials. These results strongly underline the importance of phase separation as a powerful tool for designing highly efficient materials for thermoelectric applications that fulfill the industrial demands of a thermoelectric converter.

Public subscription project for international joint research proposals in fiscal 2000 - public subscription of international proposal (substitution No.3). Report on achievements in research related to industrial utilization and social systematization of gas hydrate technologies - Separate volume; 2000 nendo kokusai kyodo kenkyu teian kobo jigyo - kokusai teian kobo (daitai No.3). Gas hydrate gijutsu no sangyo riyo shakai system ka ni kansuru kenkyu kaihatsu seika hokokusho (bessatsu)

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

Investigations were performed on important properties when utilization of gas hydrates to industries is discussed, such as production and decomposition speeds and storage stability. Activities have been taken in the following two fields: 1) experimental studies on production and decomposition of gas hydrates, and 2) summarized view on research related to gas hydrate self-retention effect. In Item 1), a production device of stirring system using rotating blades with gas circulation holes (self-suction type) was fabricated to have discussed the production and decomposition speeds. It was made clear that the production speed is governed by the over-cooling degree under the appropriate gas circulation and appropriate stirring conditions, and that the decomposition speed becomes abnormally high unless the self-retention status is maintained. In Item 2), following the introduction, seven researches were introduced, including the first observation of abnormal reaction of gas hydrate under the decreased pressure condition, the research by Yu. P. Handa related to gas hydrate decomposition below zero degree C, and the research by E. Mayer and A. Hall Brucker related to unexpectedly stable nitrogen, oxygen, carbon monoxide and argon clathrate gas hydrate formed from amorphous solid water. (NEDO)

Composition and structure of the shallow subsurface of Ceres revealed by crater morphology

Science.gov (United States)

Bland, Michael T.; Carol A. Raymond,; Schenk, Paul M.; Roger R. Fu,; Thomas Kneisl,; Hendrick Pasckert, Jan; Hiesinger, Harald; Frank Preusker,; Ryan S. Park,; Simone Marchi,; Scott King,; Castillo-Rogez, Julie C.; Christopher T. Russell,

2016-01-01

Before NASA’s Dawn mission, the dwarf planet Ceres was widely believed to contain a substantial ice-rich layer below its rocky surface. The existence of such a layer has significant implications for Ceres’s formation, evolution, and astrobiological potential. Ceres is warmer than icy worlds in the outer Solar System and, if its shallow subsurface is ice-rich, large impact craters are expected to be erased by viscous flow on short geologic timescales. Here we use digital terrain models derived from Dawn Framing Camera images to show that most of Ceres’s largest craters are several kilometres deep, and are therefore inconsistent with the existence of an ice-rich subsurface. We further show from numerical simulations that the absence of viscous relaxation over billion-year timescales implies a subsurface viscosity that is at least one thousand times greater than that of pure water ice. We conclude that Ceres’s shallow subsurface is no more than 30% to 40% ice by volume, with a mixture of rock, salts and/or clathrates accounting for the other 60% to 70%. However, several anomalously shallow craters are consistent with limited viscous relaxation and may indicate spatial variations in subsurface ice content.

Report on the investigational study on the technical trend of temperature control materials for high efficiency LED lighting use; Kokoritsu LED shomeiyo no ondo seigyo zairyo no gijutsu doko ni kansuru chosa kenkyu hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

For the purpose of the innovative conservation of lighting use energy, a project is being promoted with the aim of developing light emitted diode (LED) and commercializing lighting use light source substituting for fluorescent light. In this study, the following were conducted: literature survey on Peltier materials as temperature control materials for high efficiency LED lighting and the making of them as elements, extraction of technical subjects in the commercialization of LED cooling use Peltier element materials, market surveys/analyses were made of the fields of application including the LED cooling use field. As a result, for the commercialization of temperature control use Peltier elements of lighting use LED, the desirable performance index is 5x10{sup -5}/K or more. Bi{sub 2}Te{sub 3} elements which are now commercially available as Peltier elements are not good in performance and have the toxicity problem. As a candidate of temperature control use materials of lighting use LED, Mg{sub 2} (Sn, Si) or clathrate system are regarded, but the point, etc. were pointed out that it is necessary to improve thermoelectric characteristics. (NEDO)

Modeling thermodynamic properties of propane or tetrahydrofuran mixed with carbon dioxide or methane in structure-II clathrate hydrates

NARCIS (Netherlands)

Fang, Bin; Ning, Fulong; Cao, Pinqiang; Peng, Li; Wu, Jianyang; Zhang, Zhun; Vlugt, T.J.H.; Kjelstrup, Signe

2017-01-01

A sound knowledge of thermodynamic properties of sII hydrates is of great importance to understand the stability of sII gas hydrates in petroleum pipelines and in natural settings. Here, we report direct molecular dynamics (MD) simulations of the thermal expansion coefficient, the

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

Science.gov (United States)

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Large methane releases lead to strong aerosol forcing and reduced cloudiness

Directory of Open Access Journals (Sweden)

T. Kurtén

2011-07-01

Full Text Available The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH₄ levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is predicted to significantly decrease hydroxyl radical (OH concentrations, while moderately increasing ozone (O₃. These changes lead to a 70 % increase in the atmospheric lifetime of methane, and an 18 % decrease in global mean cloud droplet number concentrations (CDNC. The CDNC change causes a radiative forcing that is comparable in magnitude to the longwave radiative forcing ("enhanced greenhouse effect" of the added methane. Together, the indirect CH₄-O₃ and CH₄-OH-aerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously large temperature changes associated with historic methane releases.

Thermoelectric transport in rare-earth compounds

Energy Technology Data Exchange (ETDEWEB)

Koehler, Ulrike

2007-07-01

This work focuses on the thermoelectric transport in rare-earth compounds. The measurements of the thermal conductivity, thermopower, and Nernst coefficient are supplemented by investigations of other quantities as magnetic susceptibility and specific heat. Chapter 2 provides an introduction to the relevant physical concepts. Section 1 of that chapter summarizes the characteristic properties of rare-earth systems; section 2 gives an overview on thermoelectric transport processes in magnetic fields. The applied experimental techniques as well as the new experimental setup are described in detail in Chapter 3. The experimental results are presented in Chapter 4-6, of which each concentrates on a different subject. In Chapter 4, various Eu clathrates and the skutterudite-like Ce{sub 3}Rh{sub 4}Sn{sub 13} are presented, which have been investigated as potential thermoelectric materials for applications. Chapter 5 focusses on the study of the energy scales in the heavy-fermion series Lu{sub 1-x}Yb{sub x}Rh{sub 2}Si{sub 2} and Ce{sub x}La{sub 1-x}Ni{sub 2}Ge{sub 2} by means of thermopower investigations. Chapter 6 is dedicated to the thermoelectric transport properties of the correlated semimetal CeNiSn with special emphasis on the Nernst coefficient of this compound. (orig.)

Low temperature X-ray diffraction studies of natural gas hydrate samples from the Gulf of Mexico

Energy Technology Data Exchange (ETDEWEB)

Rawn, C.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Materials Science and Technology Div.; Sassen, R. [Texas A and M Univ., College Station, TX (United States). Geochemical and Environmental Research Group; Ulrich, S.M.; Phelps, T.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Biosciences Div.; Chakoumakos, B.C. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Neutron Scattering Science Div.; Payzant, E.A. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Center for Nanophase Materials Science

2008-07-01

Quantitative studies of natural clathrate hydrates are hampered by the difficulties associated with obtaining pristine samples for the sea floor without comprising their integrity. This paper discussed X-ray power diffraction studies conducted to measure natural gas hydrate samples obtained from the Green Canyon in the Gulf of Mexico. Data on the hydrate deposits were initially collected in 2002. The X-ray diffraction data were collected in order to examine the structure 2 (s2) gas hydrates as functions of temperature and time. A diffractometer with a theta-theta goniometer modified with a helium closed cycle refrigerator and temperature controller was used. Aragonite, quartz and halite phases were determined in the decomposed sample. Refined phase fractions for both the ice and the s2 hydrate were obtained as a function of temperature. Results of the study demonstrated that the amount of hydrates decreased with increasing temperatures and amounts of time. Large pieces of the hydrate showed heterogenous ice content. Dissociation rates were higher at lower temperatures. It was concluded that unusual trends observed for the smaller lattice parameter of the hydrates resulted from the formation of ice layers that acted as barriers to the released gases and caused increased isostatic pressures around the hydrate core. 9 refs., 6 figs.

Hydration of amino acids: FTIR spectra and molecular dynamics studies.

Science.gov (United States)

Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

2015-11-01

The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

Frost at the Viking Lander 2 Site

Science.gov (United States)

1977-01-01

Photo from Viking Lander 2 shows late-winter frost on the ground on Mars around the lander. The view is southeast over the top of Lander 2, and shows patches of frost around dark rocks. The surface is reddish-brown; the dark rocks vary in size from 10 centimeters (four inches) to 76 centimeters (30 inches) in diameter. This picture was obtained Sept. 25, 1977. The frost deposits were detected for the first time 12 Martian days (sols) earlier in a black-and-white image. Color differences between the white frost and the reddish soil confirm that we are observing frost. The Lander Imaging Team is trying to determine if frost deposits routinely form due to cold night temperatures, then disappear during the warmer daytime. Preliminary analysis, however, indicates the frost was on the ground for some time and is disappearing over many days. That suggests to scientists that the frost is not frozen carbon dioxide (dry ice) but is more likely a carbon dioxide clathrate (six parts water to one part carbon dioxide). Detailed studies of the frost formation and disappearance, in conjunction with temperature measurements from the lander's meteorology experiment, should be able to confirm or deny that hypothesis, scientists say.

Effects of high-pressure argon and nitrogen treatments on respiration, browning and antioxidant potential of minimally processed pineapples during shelf life.

Science.gov (United States)

Wu, Zhi-shuang; Zhang, Min; Wang, Shao-jin

2012-08-30

High-pressure (HP) inert gas processing causes inert gas and water molecules to form clathrate hydrates that restrict intracellular water activity and enzymatic reactions. This technique can be used to preserve fruits and vegetables. In this study, minimally processed (MP) pineapples were treated with HP (∼10 MPa) argon (Ar) and nitrogen (N) for 20 min. The effects of these treatments on respiration, browning and antioxidant potential of MP pineapples were investigated after cutting and during 20 days of storage at 4 °C. Lower respiration rate and ethylene production were found in HP Ar- and HP N-treated samples compared with control samples. HP Ar and HP N treatments effectively reduced browning and loss of total phenols and ascorbic acid and maintained antioxidant capacity of MP pineapples. They did not cause a significant decline in tissue firmness or increase in juice leakage. HP Ar treatments had greater effects than HP N treatments on reduction of respiration rate and ethylene production and maintenance of phenolic compounds and DPPH(•) and ABTS(•+) radical-scavenging activities. Both HP Ar and HP N processing had beneficial effects on MP pineapples throughout 20 days of storage at 4 °C. Copyright © 2012 Society of Chemical Industry.

Advanced research and development of gas hydrate resources. R and D of exploration and others - R and D of excavation technologies and others - surveys/researches on methods of evaluating environmental effects - surveys/researches on application systems; Gas hydrate shigenka gijutsu sendo kenkyu kaihatsu. Tansa nado ni kansuru kenkyu kaihatsu / kussaku gijutsu nado ni kansuru kenkyu kaihatsu / kankyo eikyo hyokaho no chosa kenkyu / riyo system ni kansuru chosa kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

Gas hydrate is a clathrate compound in a gaseous molecule as the host, stable under relatively mild environments. It is deposited in the 600m or deeper sea bottoms to form the gas hydrate deposit and massively occurring in the sea areas around Japan. This deposit has been studied viewed from natural gas resources, causes for natural hazards and contribution to the global warming. This project excavates a well in the deposit, to study possibilities of the technologies for decomposing, fluidizing and lifting the hydrate as the gas source, and for establishing the natural gas transporting/mooring systems in which its characteristics are utilized. The R and D activities are directed to the 4 areas, (1) development of the exploration technologies to determine the deposit sea area, quantity and conditions, (2) development of the stable well-excavation technologies, (3) studies on the effects of gas production on the environments, and development of the system for predicting the effects, (4) and studies on the application systems. The item (3) finds out the transportation/storage system possibly more economical than the current freezing/liquefaction technologies. The item (3) has the development themes of evaluating the geohazards caused by excavation and gas production, and their effects on the ecological systems. (NEDO)

Rattling of Ba-atoms in Ba8ZnxGe43-5x/8([]3-3x/8)

International Nuclear Information System (INIS)

Melnychenko, N.; Grytsiv, A.; Rotter, M.; Rogl, P.; Devishvili, A.

2006-01-01

Full text: In order to improve the figure of merit of thermoelectric materials, one of the key parameters to be minimized is the lattice thermal conductivity. It is thus essential for the design of new thermoelectric materials to understand the lattice dynamics, especially the scattering mechanism of low energy phonons. The present paper describes formation, phase relations at subsolidus temperatures as well as at 800 o C, crystal chemistry and physical properties of a series of ternary clathrates as part of the solid solution, Ba 8 Zn x (Ge 43-5x/8[]3-3x/8 ), deriving from binary Ba 8 Ge 43 []3 with a solubility limit of 8 Zn per formula unit at 800 o C. Structural investigations in all cases confirm cubic primitive symmetry with a lattice parameter a ∼ 1.1 nm consistent with the space group type Pm-3n. Studies of transport coefficients evidence electrons as the majority charge carriers in the systems. Thermal conductivity exhibits a pronounced low temperature maximum, dominated by the lattice contribution, while at higher temperatures the electronic part gains weight. Inelastic neutron scattering experiments are used to study the phonon spectrum for Ba 8 Zn 8 Ge 38 . (author)

Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

KAUST Repository

Savage, Mathew; da Silva, Ivan; Johnson, Mark; Carter, Joseph H.; Newby, Ruth; Suetin, Mikhail; Besley, Elena; Manuel, Pascal; Rudić, Svemir; Fitch, Andrew N.; Murray, Claire; David, William I. F.; Yang, Sihai; Schrö der, Martin

2016-01-01

The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.

FY 1991 Report on research and development of super heat pump energy accumulation system. Part 2. Construction and operation of the prototype system (researches on elementary techniques and construction and operation of the pilot system); Super heat pump energy shuseki system no kenkyu kaihatsu 1991 nendo seika hokokusho. 2. System shisaku unten kenkyu (yoso gijutsu no kenkyu / pilot system no shisaku unten kenkyu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1982-05-01

Summarized herein are R and D results of the researches on the chemical heat storage systems, plant simulation techniques and combined systems, and international technical exchanges, for R and D of the super heat pump energy accumulation system. For the high temperature heat storage type (utilizing ammonia complexes), the initial research targets are almost attained, as a result of the designs of a chemical heat storage unit having heat storage capacity of 1,000 kWh. For the high temperature heat storage type (utilizing hydration reactions), a 25 Mcal-scale pilot partial test unit is operated, to study applicability of the practical materials and other operation-related themes. For the low temperature heat storage type (utilizing hydration reactions by solute mixing), a pilot system is operated, to attain heat recovery of 75% or more, heat storage density of 30 kcal/kg or more, and output temperature of 7 degrees C. For the low temperature heat storage type (utilizing clathrates), the evaluation tests by a pilot plant produce heat recovery of 93.2% and heat storage density of 32.0 kcal/kg. In addition, the R and D efforts are directed to, e.g., researches on plant simulation techniques and combined systems. (NEDO)

Methane eddy covariance flux measurements from a low flying aircraft: Bridging the scale gap between local and regional emissions estimates

Science.gov (United States)

Sayres, D. S.; Dobosy, R.; Dumas, E. J.; Kochendorfer, J.; Wilkerson, J.; Anderson, J. G.

2017-12-01

The Arctic contains a large reservoir of organic matter stored in permafrost and clathrates. Varying geology and hydrology across the Arctic, even on small scales, can cause large variability in surface carbon fluxes and partitioning between methane and carbon dioxide. This makes upscaling from point source measurements such as small flux towers or chambers difficult. Ground based measurements can yield high temporal resolution and detailed information about a specific location, but due to the inaccessibility of most of the Arctic to date have only made measurements at very few sites. In August 2013, a small aircraft, flying low over the surface (5-30 m), and carrying an air turbulence probe and spectroscopic instruments to measure methane, carbon dioxide, nitrous oxide, water vapor and their isotopologues, flew over the North Slope of Alaska. During the six flights multiple comparisons were made with a ground based Eddy Covariance tower as well as three region surveys flights of fluxes over three areas each approximately 2500 km2. We present analysis using the Flux Fragment Method and surface landscape classification maps to relate the fluxes to different surface land types. We show examples of how we use the aircraft data to upscale from a eddy covariance tower and map spatial variability across different ecotopes.

Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

KAUST Repository

Savage, Mathew

2016-07-27

The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.

A consistent and verifiable macroscopic model for the dissolution of liquid CO2 in water under hydrate forming conditions

International Nuclear Information System (INIS)

Radhakrishnan, R.; Demurov, A.; Trout, B.L.; Herzog, H.

2003-01-01

Direct injection of liquid CO 2 into the ocean has been proposed as one method to reduce the emission levels of CO 2 into the atmosphere. When liquid CO 2 is injected (normally as droplets) at ocean depths >500 m, a solid interfacial region between the CO 2 and the water is observed to form. This region consists of hydrate clathrates and hinders the rate of dissolution of CO 2 . It is, therefore, expected to have a significant impact on the injection of liquid CO 2 into the ocean. Up until now, no consistent and predictive model for the shrinking of droplets of CO 2 under hydrate forming conditions has been proposed. This is because all models proposed to date have had too many unknowns. By computing rates of the physical and chemical processes in hydrates via molecular dynamics simulations, we have been able to determine independently some of these unknowns. We then propose the most reasonable model and use it to make independent predictions of the rates of mass transfer and thickness of the hydrate region. These predictions are compared to measurements, and implications to the rates of shrinkage of CO 2 droplets under varying flow conditions are discussed. (author)

Paul Hagenmüller's contribution to solid state chemistry: A scientometric analysis

Science.gov (United States)

El Aichouchi, Adil; Gorry, Philippe

2018-06-01

Paul Hagenmüller (1921-2017) is an important figure of French solid-state chemistry, who enjoyed scientific and institutional recognition. He published 796 papers and has been cited more than 16,000 times. This paper explores Hagenmüller's work using scientometric analysis to reveal the impact of his work, his main research topics and his collaborations. Although Hagenmüller was a recognized scientist, a subset of his work, now highly cited, attracted little attention at the time of publication. To understand this phenomenon, we detect and study papers with delayed recognition, also called 'Sleeping Beauties' (SBs). In scientometrics, SBs are publications that go unnoticed, or 'sleep' for a long time before suddenly attracting a lot of attention in terms of citations. We identify 7 SBs published between 1965 and 1985, and awakened between 1993 and 2010. The first SB reports the discovery of the clathrate structure of silicon. The second reports the isolation of four new phases with the formula NaxCoO2 (x < =1). The five other SBs investigate the electrochemical intercalation and deintercalation of sodium, and the structure and properties of layered oxides. Through interviews with his coworkers, we attempt to identify the reasons for the delayed recognition and the context of the renewed interest in those papers.

Inferred gas hydrate and permafrost stability history models linked to climate change in the Beaufort-Mackenzie Basin, Arctic Canada

Directory of Open Access Journals (Sweden)

J. Majorowicz

2012-03-01

Full Text Available Atmospheric methane from episodic gas hydrate (GH destabilization, the "clathrate gun" hypothesis, is proposed to affect past climates, possibly since the Phanerozoic began or earlier. In the terrestrial Beaufort-Mackenzie Basin (BMB, GHs occur commonly below thick ice-bearing permafrost (IBP, but they are rare within it. Two end-member GH models, where gas is either trapped conventionally (Case 1 or where it is trapped dynamically by GH formation (Case 2, were simulated using profile (1-D models and a 14 Myr ground surface temperature (GST history based on marine isotopic data, adjusted to the study setting, constrained by deep heat flow, sedimentary succession conductivity, and observed IBP and Type I GH contacts in Mallik wells. Models consider latent heat effects throughout the IBP and GH intervals. Case 1 GHs formed at ~0.9 km depth only ~1 Myr ago by in situ transformation of conventionally trapped natural gas. Case 2 GHs begin to form at ~290–300 m ~6 Myr ago in the absence of lithological migration barriers. During glacial intervals Case 2 GH layers expand both downward and upward as the permafrost grows downward through and intercalated with GHs. The distinctive model results suggest that most BMB GHs resemble Case 1 models, based on the observed distinct and separate occurrences of GHs and IBP and the lack of observed GH intercalations in IBP. Case 2 GHs formed >255 m, below a persistent ice-filled permafrost layer that is as effective a seal to upward methane migration as are Case 1 lithological seals. All models respond to GST variations, but in a delayed and muted manner such that GH layers continue to grow even as the GST begins to increase. The models show that the GH stability zone history is buffered strongly by IBP during the interglacials. Thick IBP and GHs could have persisted since ~1.0 Myr ago and ~4.0 Myr ago for Cases 1 and 2, respectively. Offshore BMB IBP and GHs formed terrestrially during Pleistocene sea level low

Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale

Science.gov (United States)

Cruikshank, D.P.; Meyer, A.W.; Brown, R.H.; Clark, R.N.; Jaumann, R.; Stephan, K.; Hibbitts, C.A.; Sandford, S.A.; Mastrapa, R.M.E.; Filacchione, G.; Ore, C.M.D.; Nicholson, P.D.; Buratti, B.J.; McCord, T.B.; Nelson, R.M.; Dalton, J.B.; Baines, K.H.; Matson, D.L.

2010-01-01

Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO2) at or near the nominal solid-phase laboratory wavelength of 4.2675 ??m (2343.3 cm-1), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO2 absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO2, CO2 clathrates, ternary mixtures of CO2 with other volatiles, implanted and adsorbed CO2 in non-volatile materials, and ab initio theoretical calculations of CO2 * nH2O. At the wavelength resolution of VIMS, the CO2 on Phoebe is indistinguishable from pure CO2 ice (each molecule's nearby neighbors are also CO2) or type II clathrate of CO2 in H2O. In contrast, the CO2 band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ???4.255 ??m (???2350.2 cm-1)) and broadened. These wavelengths are characteristic of complexes of CO2 with different near-neighbor molecules that are encountered in other volatile mixtures such as with H2O and CH3OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe's CO2 is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO2 on the other three satellites results at least in part from particle or UV irradiation of native H2O plus a source of C, implantation or accretion from external sources, or redistribution of native CO2 from the interior. The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 ??m, apparently as a consequence of telluric CO2 gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector

Neutron spectra and cross sections for ice and clathrate generated from the synthetic spectrum and synthetic model for molecular solids

International Nuclear Information System (INIS)

Petriw, S; Cantargi, F; Granada, R

2006-01-01

We present here a Synthetic Model for Molecular Solids, aimed at the description of the interaction of thermal neutrons with this kind of systems.Simple representations of the molecular dynamical modes are used, in order to produce a fair description of neutron scattering kernels and cross sections with a minimum set of input data. Using those spectra, we have generated thermal libraries for M C N P [es

Modeling the methane hydrate formation in an aqueous film submitted to steady cooling

Energy Technology Data Exchange (ETDEWEB)

Avendano-Gomez, J.R. [ESIQIE, Laboratorio de Ingenieria Quimica Ambiental, Mexico (Mexico). Inst. Politecnico Nacional; Garcia-Sanchez, F. [Laboratorio de Termodinamica, Mexico (Mexico). Inst. Mexicano del Petroleo; Gurrola, D.V. [UPIBI, Laboratorio de Diseno de Plantas, Mexico (Mexico). Inst. Politecnico Nacional

2008-07-01

Gas hydrates, or clathrate hydrates, are ice-like compounds that results from the kinetic process of crystallization of an aqueous solution supersaturated with a dissolved gas. This paper presented a model that took into account two factors involved in the hydrate crystallization, notably the stochastic nature of crystallization that causes sub-cooling and the heat resulting from the exothermic enthalpy of hydrate formation. The purpose of this study was to model the thermal evolution inside a hydrate forming system which was submitted to an imposed steady cooling. The study system was a cylindrical thin film of aqueous solution at 19 Mpa. The study involved using methane as the hydrate forming molecule. It was assumed that methane was homogeneously dissolved in the aqueous phase. Ethane hydrate was formed through a kinetic process of nucleation and crystallization. In order to predict the onset time of nucleation, the induction time needed to be considered. This paper discussed the probability of nucleation as well as the estimation of the rate of nucleation. It also presented the mathematical model and boundary conditions. These included assumptions and derivation of the model; boundary conditions; initial conditions; and numerical solution of the model equation. It was concluded that the heat source must be considered when investigating crystallization effects. 34 refs., 2 tabs., 2 figs.

FY 1986 Report on research and development of super heat pump energy accumulation system. Part 2. Development of elementary techniques; 1986 nendo super heat pump energy shuseki system no kenkyu kaihatsu seika hokokusho. 2. Yoso gijutsu no kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1987-04-01

Summarized in detail herein are R and D results of the chemical heat storage techniques and plant simulation, for R and D of the super heat pump energy accumulation system. For R and D of the chemical heat storage techniques, the R and D efforts are directed to the researches on the fundamental reactions and continuous exothermic reactions involved for the high temperature heat storage type (utilizing the metathesis reactions); researches on the physical properties, heat storage systems, solid-phase reactions, liquid-phase reactors, corrosion of the materials, and so on for the high temperature heat storage type (utilizing ammonia complex); collection of the data related to media and structural materials, tests of the elementary equipment for the absorption and hydration reactions, and so on for the high temperature heat storage type (chemical heat storage utilizing hydration); researches on the media properties and system performance, tests of equipment, and so on for the high temperature heat storage type (heat storage/heating utilizing solvation); researches on the heat storage media, heat storage techniques, corrosion of the materials, systems, and so on for the low temperature heat storage type (utilizing the hydration reactions by mixing solutes); and researches on the media, corrosion and elementary equipment, optimization of the system, and so on for the low temperature heat storage type (clathrate low temperature heat storage systems). (NEDO)

Experiments indicating a second hydrogen ordered phase of ice VI.

Science.gov (United States)

Gasser, Tobias M; Thoeny, Alexander V; Plaga, Lucie J; Köster, Karsten W; Etter, Martin; Böhmer, Roland; Loerting, Thomas

2018-05-14

In the last twelve years five new ice phases were experimentally prepared. Two of them are empty clathrate hydrates and three of them represent hydrogen ordered counterparts of previously known disordered ice phases. Here, we report on hydrogen ordering in ice VI samples produced by cooling at pressures up to 2.00 GPa. Based on results from calorimetry, dielectric relaxation spectroscopy, Raman spectroscopy, and powder X-ray diffraction the existence of a second hydrogen ordered polymorph related to ice VI is suggested. Powder X-ray data show the oxygen network to be the one of ice VI. For the 1.80 GPa sample the activation energy from dielectric spectroscopy is 45 kJ mol -1 , which is much larger than for the known hydrogen ordered proxy of ice VI, ice XV. Raman spectroscopy indicates the 1.80 GPa sample to be more ordered than ice XV. It is further distinct from ice XV in that it experiences hydrogen disordering above ≈103 K which is 26 K below the ice XV to ice VI disordering transition. Consequently, below 103 K it is thermodynamically more stable than ice XV, adding a stability region to the phase diagram of water. For the time being we suggest to call this new phase ice β-XV and to relabel it ice XVIII once its crystal structure is known.

Concentrations and carbon isotope compositions of methane in the cored sediments from offshore SW Taiwan

Energy Technology Data Exchange (ETDEWEB)

Chuang, P.C.; Yang, T.F.; Hong, W.L. [National Taiwan Univ., Taipei, Taiwan (China). Dept. of Geosciences; Lin, S.; Chen, J.C. [National Taiwan Univ., Taipei, Taiwan (China). Inst. of Oceanography; Sun, C.H. [CPC Corp., Wen Shan, Miaoli, Taiwan (China). Exploration and Development Research Inst.; Wang, Y. [Central Geological Survey, MOEA, Taipei, Taiwan (China)

2008-07-01

Gas hydrates are natural occurring solids that contain natural gases, mainly methane, within a rigid lattice of water molecules. They are a type of non-stoichiometric clathrates and metastable crystal products in low temperature and high pressure conditions and are widely distributed in oceans and in permafrost regions around the world. Gas hydrates have been considered as potential energy resources for the future since methane is the major gas inside gas hydrates. Methane is also a greenhouse gas that might affect the global climates from the dissociations of gas hydrates. Bottom simulating reflections (BSRs) have been found to be widely distributed in offshore southwestern Taiwan therefore, inferring the existence of potential gas hydrates underneath the seafloor sediments. This paper presented a study that involved the systematic collection of sea waters and cored sediments as well as the analysis of the gas composition of pore-space of sediments through ten cruises from 2003 to 2006. The paper discussed the results in terms of the distribution of methane concentrations in bottom waters and cored sediments; methane fluxes in offshore southwestern Taiwan; and isotopic compositions of methane in pore spaces of cored sediments. It was concluded that the carbon isotopic compositions of methane demonstrated that biogenic gas source was dominated at shallower depth. However, some thermogenic gases might be introduced from deeper source in this region. 15 refs., 5 figs.

NASA Tech Briefs, December 2003

Science.gov (United States)

2003-01-01

Topics covered include: Organic/Inorganic Hybrid Polymer/Clay Nanocomposites; Less-Toxic Coatings for Inhibiting Corrosion of Aluminum; Liquid Coatings for Reducing Corrosion of Steel in Concrete; Processable Polyimides Containing APB and Reactive End Caps; Rod/Coil Block Copolyimides for Ion-Conducting Membranes; Techniques for Characterizing Microwave Printed Antennas; Cylindrical Antenna With Partly Adaptive Phased-Array Feed; Command Interface ASIC - Analog Interface ASIC Chip Set; Predicting Accumulations of Ice on Aerodynamic Surfaces; Analyzing Aeroelasticity in Turbomachines; Software for Allocating Resources in the Deep Space Network; Expert Seeker; High-Speed Recording of Test Data on Hard Disks; Functionally Graded Nanophase Beryllium/Carbon Composites; Thin Thermal-Insulation Blankets for Very High Temperatures; Aerostructures Test Wing; Flight-Test Evaluation of Flutter-Prediction Methods; Piezoelectrically Actuated Microvalve for Liquid Effluents; Larger-Stroke Piezoelectrically Actuated Microvalve; Innovative, High-Pressure, Cryogenic Control Valve: Short Face-to-Face, Reduced Cost; Safer Roadside Crash Walls Would Limit Deceleration; Improved Interactive Medical-Imaging System; Scanning Microscopes Using X Rays and Microchannels; Slotting Fins of Heat Exchangers to Provide Thermal Breaks; Methane Clathrate Hydrate Prospecting; Automated Monitoring with a BSP Fault-Detection Test; Automated Monitoring with a BCP Fault-Decision Test; Vector-Ordering Filter Procedure for Data Reduction; Remote Sensing and Information Technology for Large Farms; Developments at the Advanced Design Technologies Testbed; Spore-Forming Bacteria that Resist Sterilization; and Acoustical Applications of the HHT Method.

Use of chemically treated carbon dioxide. ; Separation, recovery and fixation of carbon dioxide from large scale origination. Nisanka tanso no kagaku teki shori riyo; Nisanka tanso no daikibo hasseigen kara no bunri kaishu to koteika

Energy Technology Data Exchange (ETDEWEB)

Saito, M. (National Research Inst. for Pollution and Resources, Tsukuba (Japan))

1991-02-15

Tehcnology for separation, recovery and fixation of CO {sub 2} was stated. In an absorption method used as a separating recovery method, CO {sub 2} in the waste gas is absorbed into a solution such as amine, heated and recovered. In an adsorption method, the CO {sub 2} is adsorbed by adsorbent such as zeolite, and recovered either by reduction of pressure or by heating. In a distillation method, the CO {sub 2} is distilled under low temperature and high pressure. In a membrane separation method, the difference of the membrane transmisison speed is used. In a fixation technology, the CO {sub 2} disposed into the ocean is liquefied by compression and forced into the deep sea through pipings. The liquid CO {sub 2} has greater density than water under 200 to 300 atmospheric pressure and clathrate is produced over the interface between the sea water and the liquid CO {sub 2} but the influence on the environment should be evaluated. As a means of recycling, synthesis of methanol or hydrocarbon with hydrogen contacting can be considered, and if such synthesis is used, fossil fuel can be reduced. As the source of the hydrogen, a method for combining the electrolysis of water and energy such as the sun and hydraulic power which do not generate CO {sub 2}. 16 refs., 3 figs.

Survey of solar thermal energy storage subsystems for thermal/electric applications

Energy Technology Data Exchange (ETDEWEB)

Segaser, C. L.

1978-08-01

A survey of the current technology and estimated costs of subsystems for storing the thermal energy produced by solar collectors is presented. The systems considered were capable of producing both electricity and space conditioning for three types of loads: a single-family detached residence, an apartment complex of 100 units, and a city of 30,000 residents, containing both single-family residences and apartments. Collector temperatures will be in four ranges: (1) 100 to 250/sup 0/F (used for space heating and single-cycle air conditioners and organic Rankine low-temperature turbines); (2) 300 to 400/sup 0/F (used for dual-cycle air conditioners and low-temperature turbines); (3) 400 to 600/sup 0/F (using fluids from parabolic trough collectors to run Rankine turbines); (4) 800 to 1000/sup 0/F (using fluids from heliostats to run closed-cycle gas turbines and steam Rankine turbines). The solar thermal energy subsystems will require from 60 to 36 x 10/sup 5/ kWhr (2.05 x 10/sup 5/ to 1.23 x 10/sup 10/ Btu) of thermal storage capacity. In addition to sensible heat and latent heat storage materials, several other media were investigated as potential thermal energy storage materials, including the clathrate and semiclathrate hydrates, various metal hydrides, and heat storage based on inorganic chemical reactions.

The interior structure of Ceres as revealed by surface topography

Science.gov (United States)

Fu, Roger R.; Ermakov, Anton; Marchi, Simone; Castillo-Rogez, Julie C.; Raymond, Carol A.; Hager, Bradford; Zuber, Maria; King, Scott D.; Bland, Michael T.; De Sanctis, Maria Cristina; Preusker, Frank; Park, Ryan S.; Russell, Christopher T.

2017-01-01

Ceres, the largest body in the asteroid belt (940 km diameter), provides a unique opportunity to study the interior structure of a volatile-rich dwarf planet. Variations in a planetary body's subsurface rheology and density affect the rate of topographic relaxation. Preferential attenuation of long wavelength topography (≥150 km) on Ceres suggests that the viscosity of its crust decreases with increasing depth. We present finite element (FE) geodynamical simulations of Ceres to identify the internal structures and compositions that best reproduce its topography as observed by the NASA Dawn mission. We infer that Ceres has a mechanically strong crust with maximum effective viscosity ∼1025 Pa s. Combined with density constraints, this rheology suggests a crustal composition of carbonates or phyllosilicates, water ice, and at least 30 volume percent (vol.%) low-density, high-strength phases most consistent with salt and/or clathrate hydrates. The inference of these crustal materials supports the past existence of a global ocean, consistent with the observed surface composition. Meanwhile, we infer that the uppermost ≥60 km of the silicate-rich mantle is mechanically weak with viscosity <1021 Pa s, suggesting the presence of liquid pore fluids in this region and a low temperature history that avoided igneous differentiation due to late accretion or efficient heat loss through hydrothermal processes.

A HOT GAP AROUND JUPITER'S ORBIT IN THE SOLAR NEBULA

Energy Technology Data Exchange (ETDEWEB)

Turner, N. J.; Choukroun, M.; Castillo-Rogez, J.; Bryden, G., E-mail: neal.turner@jpl.nasa.gov [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States)

2012-04-01

The Sun was an order of magnitude more luminous during the first few hundred thousand years of its existence, due in part to the gravitational energy released by material accreting from the solar nebula. If Jupiter was already near its present mass, the planet's tides opened an optically thin gap in the nebula. Using Monte Carlo radiative transfer calculations, we show that sunlight absorbed by the nebula and re-radiated into the gap raised temperatures well above the sublimation threshold for water ice, with potentially drastic consequences for the icy bodies in Jupiter's feeding zone. Bodies up to a meter in size were vaporized within a single orbit if the planet was near its present location during this early epoch. Dust particles lost their ice mantles, and planetesimals were partially to fully devolatilized, depending on their size. Scenarios in which Jupiter formed promptly, such as those involving a gravitational instability of the massive early nebula, must cope with the high temperatures. Enriching Jupiter in the noble gases through delivery trapped in clathrate hydrates will be more difficult, but might be achieved by either forming the planet much farther from the star or capturing planetesimals at later epochs. The hot gap resulting from an early origin for Jupiter also would affect the surface compositions of any primordial Trojan asteroids.

Methane hydrates in quaternary climate change

International Nuclear Information System (INIS)

Kennett, J. P.; Hill, T. M.; Behl, R. J.

2005-01-01

The hydrate reservoir in marine sediments is known to contain a large volume of exchangeable carbon stored as solid methane hydrate and associated free gas. This reservoir has been shown to be potentially unstable in response to changing intermediate water temperature and sea level (pressure). Evidence continues to grow for past episodes of major methane release at times of climatic warming. Yet few studies of late Quaternary climate change include methane hydrates as an integral part of the global climate system, in spite of the largest known oscillations at this time in sea level and upper ocean temperature changes for the Cenozoic or earlier, conditions that favor instability of the methane hydrate reservoir. Abrupt increases in atmospheric methane recorded in polar ice cores are widely believed to have resulted, not from ocean-floor methane degassing, but instead from continental wetland activation, a hypothesis thus far unsupported by geological data. Furthermore, as part of this Wetland Methane Hypothesis, the abrupt methane increases have been seen as a response to climatic warming rather than contributing significantly to the change. An alternative view (formulated as the Clathrate Gun Hypothesis) is that the speed, magnitude and timing of abrupt climate change in the recent geologic past are consistent with the process of major degassing of methane hydrates. We summarize aspects of this hypothesis here and needs to test this hypothesis. (Author)

Titan and habitable planets around M-dwarfs.

Science.gov (United States)

Lunine, Jonathan I

2010-01-01

The Cassini-Huygens mission discovered an active "hydrologic cycle" on Saturn's giant moon Titan, in which methane takes the place of water. Shrouded by a dense nitrogen-methane atmosphere, Titan's surface is blanketed in the equatorial regions by dunes composed of solid organics, sculpted by wind and fluvial erosion, and dotted at the poles with lakes and seas of liquid methane and ethane. The underlying crust is almost certainly water ice, possibly in the form of gas hydrates (clathrate hydrates) dominated by methane as the included species. The processes that work the surface of Titan resemble in their overall balance no other moon in the solar system; instead, they are most like that of the Earth. The presence of methane in place of water, however, means that in any particular planetary system, a body like Titan will always be outside the orbit of an Earth-type planet. Around M-dwarfs, planets with a Titan-like climate will sit at 1 AU--a far more stable environment than the approximately 0.1 AU where Earth-like planets sit. However, an observable Titan-like exoplanet might have to be much larger than Titan itself to be observable, increasing the ratio of heat contributed to the surface atmosphere system from internal (geologic) processes versus photons from the parent star.

Carbon dioxide storage in marine sediments - dissolution, transport and hydrate formation kinetics from high-pressure experiments

Science.gov (United States)

Bigalke, N. K.; Savy, J. P.; Pansegrau, M.; Aloisi, G.; Kossel, E.; Haeckel, M.

2009-12-01

By satisfying thermodynamic framework conditions for CO2 hydrate formation, pressures and temperatures of the deep marine environment are unique assets for sequestering CO2 in clathrates below the seabed. However, feasibility and safety of this storage option require an accurate knowledge of the rate constants governing the speed of physicochemical reactions following the injection of the liquefied gas into the sediments. High-pressure experiments designed to simulate the deep marine environment open the possibility to obtain the required parameters for a wide range of oceanic conditions. In an effort to constrain mass transfer coefficients and transport rates of CO2 in(to) the pore water of marine sediments first experiments were targeted at quantifying the rate of CO2 uptake by de-ionized water and seawater across a two-phase interface. The nature of the interface was controlled by selecting p and T to conditions within and outside the hydrate stability field (HSF) while considering both liquid and gaseous CO2. Concentration increase and hydrate growth were monitored by Raman spectroscopy. The experiments revealed anomalously fast transport rates of dissolved CO2 at conditions both inside and outside the HSF. While future experiments will further elucidate kinetics of CO2 transport and hydrate formation, these first results could have major significance to safety-related issues in the discussion of carbon storage in the marine environment.

An innovative approach to enhance methane hydrate formation kinetics with leucine for energy storage application

International Nuclear Information System (INIS)

Veluswamy, Hari Prakash; Kumar, Asheesh; Kumar, Rajnish; Linga, Praveen

2017-01-01

Highlights: • Innovative combinatorial hybrid approach to reduce nucleation stochasticity and enhance hydrate growth. • Methane hydrate growth curves are similar in UTR and STR configurations in presence of leucine. • Amalgamation of stirred (STR) and unstirred (UTR) configuration is demonstrated. • Reliable method for scale up and commercial production of Solidified Natural Gas (SNG). - Abstract: Natural gas storage in clathrate hydrates or solidified natural gas (SNG) offers the safest, cleanest and the most compact mode of storage aided by the relative ease in natural gas (NG) recovery with minimal cost compared to known conventional methods of NG storage. The stochastic nature of hydrate nucleation and the slow kinetics of hydrate growth are major challenges that needs to be addressed on the SNG production side. A deterministic and fast nucleation coupled with rapid crystallization kinetics would empower this beneficial technology for commercial application. We propose a hybrid combinatorial approach of methane hydrate formation utilizing the beneficial aspect of environmentally benign amino acid (leucine) as a kinetic promoter by combining stirred and unstirred reactor operation. This hybrid approach is simple, can easily be implemented and scaled-up to develop an economical SNG technology for efficient storage of natural gas on a large scale. Added benefits include the minimal energy requirement during hydrate growth resulting in overall cost reduction for SNG technology.

Influence of fluorosurfactants on hydrate formation rates

Energy Technology Data Exchange (ETDEWEB)

Kim, C.U.; Jeong, K.E.; Chae, H.J.; Jeong, S.Y. [Korea Reasearch Inst. of Chemical Technology, Alternative Chemicals/Fuel Research Center, Yuseong-Gu, Daejon (Korea, Republic of)

2008-07-01

Gas hydrates, or clathrates, are ice-like solids that forms when natural gas is in contact with liquid water or ice under high pressure and low temperature. There is significant interest in studying the storage and transportation of gas in the form of hydrates. However, a critical problem impacting the industrial application of gas hydrates for storage and transportation of natural gas is the slow formation rate of natural gas hydrate. Researchers have previously reported on the promotion effect of some additives on gas hydrate formation and hydrate gas content. Fluorosurfactants are significantly superior to nonfluorinated surfactants in wetting action, as well as stability in harsh environments, both thermal and chemical. This paper discussed an experimental investigation into the effects of fluorosurfactants with different ionic types on the formation of methane hydrate. The surfactants used were FSN-100 of DuPont Zonyl as non-ionic surfactant and FC-143 of DuPont as anionic surfactant. The paper discussed the experimental apparatus for methane hydrate formation. It also discussed hydrate formation kinetics and the series of hydrate formation experiments that were conducted in the presence of fluorosurfactants. Last, the paper explored the results of the study. It was concluded that anionic fluorosurfactant of FC-143 had a better promoting effect on methane hydrate formation compared with nonionic surfactant of FSN-100. 8 refs., 2 tabs., 2 figs.

Achievement report for fiscal 1998. Research and development of new technologies for storing farm products utilizing low-temperature energy (2nd fiscal year); 1998 nendo seika hokokusho. Teion energy wo riyoshita nosanbutsu no shinki chozo gijutsu no kenkyu kaihatsu (dai 2 nendo)

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

The aim of the work was to create new industrial technologies utilizing low-temperature energy satisfying local needs through developing new technologies, including air conditioning technologies high in reliability and excellent in energy efficiency. The objectives of the effort were to elucidate the behavior of moisture in the atmosphere below the freezing point and to develop farm product preserving technologies, to develop highly efficient energy conversion technologies for use in the low-temperature zone, latent heat storing cold heat technologies, and system evaluation. Constructed in connection with the last-said system evaluation were three technologies, which were a below-zero high-humidity air conditioning technology based on the outcome of agricultural verification of farm product storage, energy-efficient low-temperature storage of farm products which was a combination of a low-temperature oriented energy-efficient energy conversion technology and a clathrate hydrate-aided cold heat storing technology, and a technology applicable to business in the low-temperature processing field accessorial to the said technologies. They were compared with the conventional technologies, and then it was found that the most energy-efficient system, as endorsed by a 40-50% reduction it caused in electricity rate, was a combination of a low-temperature storage, frozen food storage, hydrate cold heat storage tank, recovery facility for farm waste incineration-produced waste heat, and a pulse tube freezer. (NEDO)

In situ investigations on the formation and decomposition of KSiH{sub 3} and CsSiH{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Auer, Henry; Kohlmann, Holger [Department of Inorganic Chemistry, Leipzig University (Germany)

2017-08-03

The system KSi-KSiH{sub 3} stores 4.3 wt % of hydrogen and shows a very good reversibility at mild conditions of 0.1 MPa hydrogen pressure and 414 K.[] We followed the reaction pathways of the hydrogenation reactions of KSi and its higher homologue CsSi by in situ methods in order to check for possible intermediate hydrides. In situ diffraction at temperatures up to 500 K and gas pressures up to 5.0 MPa hydrogen gas for X-ray and deuterium gas for neutron reveal that both KSi and CsSi react in one step to the hydrides KSiH{sub 3} and CsSiH{sub 3} and the respective deuterides. Neither do the Zintl phases dissolve hydrogen (deuterium), nor do the hydrides (deuterides) show any signs for non-stoichiometry, i.e. all phases involved in the formation are line phases. Heating to temperatures above 500 K shows that at 5.0 MPa hydrogen pressure only the reaction 2CsSi + 3H{sub 2} = 2CsSiH{sub 3} is reversible. Under these conditions, KSiH{sub 3} decomposes to a clathrate and potassium hydride according to 46KSiH{sub 3} = K{sub 8}Si{sub 46} + 38KH + 50H{sub 2}. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

Science.gov (United States)

Vlasic, Thomas M.; Servio, Phillip; Rey, Alejandro D.

2016-08-01

This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

Using zeolites for fixation and long-term storage of krypton

International Nuclear Information System (INIS)

Pirogova, G.N.; Voronin, Yu.V.; Pribylov, A.A.; Serpinskii, V.V.; Mirskii, Ya.V.; Almazova, B.B.; Golitsina, V.V.

1993-01-01

It is known that large quantities of 85 Kr are liberated during the operation of nuclear power plants and, in particular, during the processing of nuclear fuel. At the present time, there are several methods of its fixation (accumulation), viz., storage in high-pressure gas balloons, adsorption, plasma-aided implantation into metals, introduction into clathrate compounds, and obtaining kryptonates. Encapsulation in zeolites is one of the most promising methods. The merits of this method include safety during storage, a favorable volume-to-mass ratio, the possibility of separating krypton from a mixture of different gases, and purity of the encapsulated gas. The encapsulation technique has been developed quite recently. Several recent reports established the possibility of encapsulating krypton in the 3A-type zeolites. However, most of the investigators observed leakage during the storage of the zeolite-gas system and complete liberation of krypton from the zeolite during prolonged storage. This paper deals with a study of the encapsulation process of krypton in the zeolites obtained by cation exchange from NaA. The experimental specimens were characterized by the degree of exchange of sodium into potassium and cesium. It is known that the introduction of cesium into the structure (body) of a zeolite reduces the size of the window of entrance. All the synthesized specimens were used in their granulated form. The aim of this study was to develop zeolite specimens for carrying out long-term storage of krypton

Nuclear data generation for cryogenic moderators and high temperature moderators

International Nuclear Information System (INIS)

Petriw, Sergio

2007-01-01

The commonly used processing codes for nuclear data only allow the generation of cross section data for a limited number of materials and physical conditions.At present, one of the most used computer codes for the generation of neutron cross sections is N J O Y, which is based on a phonon expansion of the scattering function starting from the frequency spectrum.Therefore, the information related to the system's density of states is crucial to produce the required data of interest. In this work the formalism of the Synthetic Model for Molecular Solids (S M M S) was implemented, which is in turn based on the Synthetic Frequency Spectrum (S F S) concept.The synthetic spectrum is central in the present work, and it is built from simple, relevant parameters of the moderator, thus conforming an alternative tool when no information on the actual frequency spectrum of the moderator material is available.S F S 's for several material of interest where produced in this work, for both cryogenic and high temperature moderators.We studied some materials of special interest, like solid methane, ice, methyl clathrate and two which are of special interest in the nuclear industry: graphite and beryllium.The libraries generated in the present work for the materials considered, in spite of their synthetic origin, are able to produce results that are even in better agreement with available information [es

Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

Directory of Open Access Journals (Sweden)

Thomas M. Vlasic

2016-08-01

Full Text Available This work uses density functional theory (DFT to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane, at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

Titan's Methane Cycle is Closed

Science.gov (United States)

Hofgartner, J. D.; Lunine, J. I.

2013-12-01

Doppler tracking of the Cassini spacecraft determined a polar moment of inertia for Titan of 0.34 (Iess et al., 2010, Science, 327, 1367). Assuming hydrostatic equilibrium, one interpretation is that Titan's silicate core is partially hydrated (Castillo-Rogez and Lunine, 2010, Geophys. Res. Lett., 37, L20205). These authors point out that for the core to have avoided complete thermal dehydration to the present day, at least 30% of the potassium content of Titan must have leached into an overlying water ocean by the end of the core overturn. We calculate that for probable ammonia compositions of Titan's ocean (compositions with greater than 1% ammonia by weight), that this amount of potassium leaching is achievable via the substitution of ammonium for potassium during the hydration epoch. Formation of a hydrous core early in Titan's history by serpentinization results in the loss of one hydrogen molecule for every hydrating water molecule. We calculate that complete serpentinization of Titan's core corresponds to the release of more than enough hydrogen to reconstitute all of the methane atoms photolyzed throughout Titan's history. Insertion of molecular hydrogen by double occupancy into crustal clathrates provides a storage medium and an opportunity for ethane to be converted back to methane slowly over time--potentially completing a cycle that extends the lifetime of methane in Titan's surface atmosphere system by factors of several to an order of magnitude over the photochemically-calculated lifetime.

Solvation dynamics through Raman spectroscopy: hydration of Br2 and Br3(-), and solvation of Br2 in liquid bromine.

Science.gov (United States)

Branigan, Edward T; Halberstadt, N; Apkarian, V A

2011-05-07

Raman spectroscopy of bromine in the liquid phase and in water illustrates uncommon principles and yields insights regarding hydration. In liquid Br(2), resonant excitation over the B((3)Π(0u)(+)) ← X((1)Σ(g)(+)) valence transition at 532 nm produces a weak resonant Raman (RR) progression accompanied by a five-fold stronger non-resonant (NR) scattering. The latter is assigned to pre-resonance with the C-state, which in turn must be strongly mixed with inter-molecular charge transfer states. Despite the electronic resonance, RR of Br(2) in water is quenched. At 532 nm, the homogeneously broadened fundamental is observed, as in the NR case at 785 nm. The implications of the quenching of RR scattering are analyzed in a simple, semi-quantitative model, to conclude that the inertial evolution of the Raman packet in aqueous Br(2) occurs along multiple equivalent water-Br(2) coordinates. In distinct contrast with hydrophilic hydration in small clusters and hydrophobic hydration in clathrates, it is concluded that the hydration shell of bromine in water consists of dynamically equivalent fluxional water molecules. At 405 nm, the RR progression of Br(3)(-) is observed, accompanied by difference transitions between the breathing of the hydration shell and the symmetric stretch of the ion. The RR scattering process in this case can be regarded as the coherent photo-induced electron transfer to the solvent and its radiative back-transfer.

Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

Energy Technology Data Exchange (ETDEWEB)

Vlasic, Thomas M.; Servio, Phillip; Rey, Alejandro D., E-mail: alejandro.rey@mcgill.ca [Department of Chemical Engineering, McGill University, Montreal H3A 0C5 (Canada)

2016-08-15

This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

What is Neptune's D/H ratio really telling us about its water abundance?

Science.gov (United States)

Ali-Dib, Mohamad; Lakhlani, Gunjan

2018-05-01

We investigate the deep-water abundance of Neptune using a simple two-component (core + envelope) toy model. The free parameters of the model are the total mass of heavy elements in the planet (Z), the mass fraction of Z in the envelope (fenv), and the D/H ratio of the accreted building blocks (D/Hbuild).We systematically search the allowed parameter space on a grid and constrain it using Neptune's bulk carbon abundance, D/H ratio, and interior structure models. Assuming solar C/O ratio and cometary D/H for the accreted building blocks are forming the planet, we can fit all of the constraints if less than ˜15 per cent of Z is in the envelope (f_{env}^{median} ˜ 7 per cent), and the rest is locked in a solid core. This model predicts a maximum bulk oxygen abundance in Neptune of 65× solar value. If we assume a C/O of 0.17, corresponding to clathrate-hydrates building blocks, we predict a maximum oxygen abundance of 200× solar value with a median value of ˜140. Thus, both cases lead to oxygen abundance significantly lower than the preferred value of Cavalié et al. (˜540× solar), inferred from model-dependent deep CO observations. Such high-water abundances are excluded by our simple but robust model. We attribute this discrepancy to our imperfect understanding of either the interior structure of Neptune or the chemistry of the primordial protosolar nebula.

Kinetic studies of methane-ethane mixed gas hydrates by neutron diffraction and Raman spectroscopy.

Science.gov (United States)

Murshed, M Mangir; Kuhs, Werner F

2009-04-16

In situ formations of CH(4)-C(2)H(6) mixed gas hydrates were made using high flux neutron diffraction at 270 K and 5 MPa. For this purpose, a feed gas composition of CH(4) and C(2)H(6) (95 mol% CH(4)) was employed. The rates of transformation of spherical grains of deuterated ice Ih into hydrates were measured by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. Phase fractions of the crystalline constituents were obtained from Rietveld refinements. A concomitant formation of structure type I (sI) and structure type II (sII) hydrates were observed soon after the gas pressure was applied. The initial fast formation of sII hydrate reached its maximum volume and started declining very slowly. The formation of sI hydrate followed a sigmoid growth kinetics that slowed down due to diffusion limitation. This observation has been interpreted in terms of a kinetically favored nucleation of the sII hydrate along with a slow transformation into sI. Both powder diffraction and Raman spectroscopic results suggest that a C(2)H(6)-rich sII hydrate was formed at the early part of the clathration, which slowly decreased to approximately 3% after a reaction of 158 days as confirmed by synchrotron XRD. The final persistence of a small portion of sII hydrate points to a miscibility gap between CH(4)-rich sI and C(2)H(6)-rich sII hydrates.

Study on gas hydrate as a new energy resource in the twenty first century

Energy Technology Data Exchange (ETDEWEB)

Ryu, Byung Jae; Kim, Won Sik; Oh, Jae Ho [Korea Institute of Geology Mining and Materials, Taejon (Korea)] [and others

1998-12-01

Methane hydrate, a special type of clathrate hydrates, is a metastable solid compound mainly consisted of methane and water and generally called as gas hydrate. It is stable in the specific low- temperature/high-pressure conditions. Very large amount of methane that is the main component of natural gas, is accumulated in the form of methane hydrate subaquatic areas. Methane hydrate are the major reservoir of methane on the earth. On the other hand, the development and transmission through pipeline of oil and natural gas in the permafrost and deep subaquatic regions are significantly complicated by formation and dissociation of methane hydrate. The dissociation of natural methane hydrates caused by increasing temperature and decreasing pressure could cause the atmospheric pollution and geohazard. The formation, stable existence and dissociation of natural methane hydrates depend on the temperature, pressure, and composition of gas and characteristics of the interstitial waters. For the study on geophysical and geological conditions for the methane hydrate accumulation and to find BSR in the East Sea, Korea, the geophysical surveys using air-gun system, multibeam echo sounder, SBP were implemented in last September. The water temperature data vs. depth were obtained to determine the methane hydrate stability zone in the study area. The experimental equilibrium condition of methane hydrate was also measured in 3 wt.% sodium chloride solution. The relationship between Methane hydrate formation time and overpressure was analyzed through the laboratory work. (author). 49 refs., 6 tabs., 26 figs.

Methane emissions from oceans, coasts, and freshwater habitats: New perspectives and feedbacks on climate

Science.gov (United States)

Hamdan, Leila J.; Wickland, Kimberly P.

2016-01-01

Methane is a powerful greenhouse gas, and atmospheric concentrations have risen 2.5 times since the beginning of the Industrial age. While much of this increase is attributed to anthropogenic sources, natural sources, which contribute between 35% and 50% of global methane emissions, are thought to have a role in the atmospheric methane increase, in part due to human influences. Methane emissions from many natural sources are sensitive to climate, and positive feedbacks from climate change and cultural eutrophication may promote increased emissions to the atmosphere. These natural sources include aquatic environments such as wetlands, freshwater lakes, streams and rivers, and estuarine, coastal, and marine systems. Furthermore, there are significant marine sediment stores of methane in the form of clathrates that are vulnerable to mobilization and release to the atmosphere from climate feedbacks, and subsurface thermogenic gas which in exceptional cases may be released following accidents and disasters (North Sea blowout and Deepwater Horizon Spill respectively). Understanding of natural sources, key processes, and controls on emission is continually evolving as new measurement and modeling capabilities develop, and different sources and processes are revealed. This special issue of Limnology and Oceanography gathers together diverse studies on methane production, consumption, and emissions from freshwater, estuarine, and marine systems, and provides a broad view of the current science on methane dynamics of aquatic ecosystems. Here, we provide a general overview of aquatic methane sources, their contribution to the global methane budget, and key uncertainties. We then briefly summarize the contributions to and highlights of this special issue.

Solid and gaseous inclusions in the EDML deep ice core: origins and implications for the physical properties of polar ice

Science.gov (United States)

Faria, S. H.; Kipfstuhl, S.; Garbe, C. S.; Bendel, V.; Weikusat, C.; Weikusat, I.

2010-12-01

The great value of polar deep ice cores stems mainly from two essential features of polar ice: its crystalline structure and its impurities. They determine the physical properties of the ice matrix and provide proxies for the investigation of past climates. Experience shows that these two essential features of polar ice manifest themselves in a multiscale diversity of dynamic structures, including dislocations, grain boundaries, solid particles, air bubbles, clathrate hydrates and cloudy bands, among others. The fact that these structures are dynamic implies that they evolve with time through intricate interactions between the crystalline structure, impurities, and the ice flow. Records of these interactions have been carefully investigated in samples of the EPICA deep ice core drilled in Dronning Maud Land, Antarctica (75°S, 0°E, 2882 m elevation, 2774.15 m core length). Here we show how the distributions of sizes and shapes of air bubbles correlate with impurities and the crystalline structure, how the interaction between moving grain boundaries and micro-inclusions changes with ice depth and temperature, as well as the possible causes for the abrupt change in ice rheology observed in the MIS6-MIS5e transition. We also discuss how these observations may affect the flow of the ice sheet and the interpretation of paleoclimate records. Micrograph of an EDML sample from 555m depth. One can identify air bubbles (dark, round objects), microinclusions (tiny defocused spots), and a grain boundary pinned by a bubble. The width of the image is 700 micrometers.

Experimental solid state NMR of gas hydrates : problems and solutions

Energy Technology Data Exchange (ETDEWEB)

Moudrakovski, I.; Lu, H.; Ripmeester, J. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Kumar, R.; Susilo, R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Luzi, M. [GeoForschungsZentrum Potsdam, Potsdam (Germany)

2008-07-01

Solid State NMR is a suitable spectroscopic technique for hydrate research for several reasons, including its capability to distinguish between different structural types of hydrates, its quantitative nature and potential for both in-situ and time resolved experiments. This study illustrated the applications of solid state NMR for compositional and structural studies of clathrate hydrates, with particular emphasis on experimental techniques and potential ways to overcome technical difficulties. In order to use the method to its full capacity, some instrumental developments are needed to adapt it to the specific experimental requirements of hydrate studies, such as very low temperatures and high pressures. This presentation discussed the quantification of the Carbon-13 spectra with examples from natural and synthetic hydrates prepared from multi-component mixtures of hydrocarbons. The main approach used for the first two examples was Carbon-13 NMR with Magic Angle Spinning (MAS) at -100 degrees C. The detailed characterization of mixed hydrogen hydrates required low temperature hydrogen MAS. The quantification problems encountered during these experiments were also discussed. The purpose of these recent experimental developments was to prompt wider application of Solid State NMR in hydrate research. NMR proved to be a viable method for analyzing the composition and structure of multi-component mixed gas hydrates; characterizing natural gas hydrates; and, evaluating the formation conditions and properties of mixed hydrogen hydrates. The limitations of the method were highlighted and sensible choices of experimental conditions and techniques that ensure accurate results were discussed. 34 refs., 10 figs.

Fire extinction utilizing carbon dioxide hydrate

Energy Technology Data Exchange (ETDEWEB)

Hatakeyama, T.; Aida, E.; Yokomori, T.; Ohmura, R.; Ueda, T. [Keio Univ., Hiyoshi, Kohoku-ku, Yokohama (Japan)

2008-07-01

Clathrate hydrates formed with nonflammable gases may be suitable for use as fire extinguishing agents because dissociation of the hydrates results in the temperature decrease in the combustion field and the nonflammable gases released from the dissociated hydrates prevent the supply of the oxygen to the combustion field. This paper discussed experiments in which ordinary ice and dry ice were used to evaluate the performance of CO{sub 2} hydrate as a fire extinguishing agent. The paper described the apparatus and procedure for the preparation of CO{sub 2} hydrate crystals. A schematic of the reactor to form CO{sub 2} hydrate and a photograph of CO{sub 2} hydrate crystal formed in the study were also presented. Other illustrations, photographs, and tables that were presented included a schematic diagram of the experimental apparatus used for the flame extinction experiments; a photograph of CO{sub 2} hydrate powder; sequential video graphs of the flame extinction by the supply of CO{sub 2} hydrate crystals to the methanol pool flame and the relevant illustration; and heat of CO{sub 2} hydrate dissociation, water vaporization and sublimation of dry ice. It was concluded that the critical mass of the CO{sub 2} hydrate required to extinguish a flame was much less than that of ordinary ice, indicating the superiority of CO{sub 2} hydrate to the ice. In addition, the experiments also revealed that the size of the CO{sub 2} hydrate particles had a significant effect on the performance of flame extinction. 5 refs., 2 tabs., 7 figs.

Effect of temperature on mixing thermodynamics of a new ionic liquid: {2-Hydroxy ethylammonium formate (2-HEAF) + short hydroxylic solvents}

International Nuclear Information System (INIS)

Iglesias, M.; Torres, A.; Gonzalez-Olmos, R.; Salvatierra, D.

2008-01-01

Density and ultrasonic velocity of the mixtures of the new ionic liquid 2-hydroxy ethylammonium formate (2-HEAF) and short hydroxylic solvents (water, methanol, and ethanol) have been measured at the range of temperature (288.15 to 323.15) K and atmospheric pressure. The corresponding apparent molar volume and the apparent molar isentropic compressibility values have been evaluated from the experimental data and fitted to a temperature dependent Redlich-Mayer equation. From these correlations, the limiting infinite dilution values of the apparent magnitudes have also been computed. Derived properties such as isobaric expansibility and isothermal coefficient of pressure excess molar enthalpy were computed due to their importance in the study of specific molecular interactions. The new experimental data were used to test the capability of prediction of the modified Heller temperature dependent equation (MHE) and collision factor theory (CFT). The obtained results indicate that ionic liquid interactions in water are weaker than in the studied alcoholic solutions. An intersection point in isotherms of isentropic compressibility was observed for aqueous solutions which may be an indication of the clathrate structural interactions at high solvent composition. The observed inverse dependence on temperature for aqueous or alcoholic mixtures points out the special trend of packing of this ionic liquid into hydroxylic solvents and its strong dependence on steric hindrance of aliphatic residues. As previously observed, the increase in van der Waals forces due to the presence of long alkyl chain (into ionic liquid and alcohols) leads to higher interactions on mixing

Constraints on Ceres' Internal Structure and Evolution From Its Shape and Gravity Measured by the Dawn Spacecraft

Science.gov (United States)

Ermakov, A. I.; Fu, R. R.; Castillo-Rogez, J. C.; Raymond, C. A.; Park, R. S.; Preusker, F.; Russell, C. T.; Smith, D. E.; Zuber, M. T.

2017-11-01

Ceres is the largest body in the asteroid belt with a radius of approximately 470 km. In part due to its large mass, Ceres more closely approaches hydrostatic equilibrium than major asteroids. Pre-Dawn mission shape observations of Ceres revealed a shape consistent with a hydrostatic ellipsoid of revolution. The Dawn spacecraft Framing Camera has been imaging Ceres since March 2015, which has led to high-resolution shape models of the dwarf planet, while the gravity field has been globally determined to a spherical harmonic degree 14 (equivalent to a spatial wavelength of 211 km) and locally to 18 (a wavelength of 164 km). We use these shape and gravity models to constrain Ceres' internal structure. We find a negative correlation and admittance between topography and gravity at degree 2 and order 2. Low admittances between spherical harmonic degrees 3 and 16 are well explained by Airy isostatic compensation mechanism. Different models of isostasy give crustal densities between 1,200 and 1,400 kg/m3 with our preferred model giving a crustal density of 1,287+70-87 kg/m3. The mantle density is constrained to be 2,434+5-8 kg/m3. We compute isostatic gravity anomaly and find evidence for mascon-like structures in the two biggest basins. The topographic power spectrum of Ceres and its latitude dependence suggest that viscous relaxation occurred at the long wavelengths (>246 km). Our density constraints combined with finite element modeling of viscous relaxation suggests that the rheology and density of the shallow surface are most consistent with a rock, ice, salt and clathrate mixture.

Vasodilative effects of prostaglandin E1 derivate on arteries of nerve roots in a canine model of a chronically compressed cauda equina

Directory of Open Access Journals (Sweden)

Konno Shin-ichi

2008-04-01

Full Text Available Abstract Background Reduction of blood flow is important in the induction of neurogenic intermittent claudication (NIC in lumbar spinal canal stenosis. PGE1 improves the mean walking distance in patients with NIC type cauda equina compression. PGE1 derivate might be effective in dilating blood vessels and improving blood flow in nerve roots with chronically compressed cauda equina. The aim of this study was to assess whether PGE1 derivate has vasodilatory effects on both arteries and veins in a canine model of chronic cauda equina compression. Methods Fourteen dogs were used in this study. A plastic balloon inflated to 10 mmHg was placed under the lamina of the 7th lumbar vertebra for 1 week. OP-1206-cyclodextrin clathrate (OP-1206-CD: prostaglandin E1 derivate was administered orally. The blood vessels of the second or third sacral nerve root were identified using a specially designed surgical microscope equipped with a video camera. The diameter of the blood vessels was measured on video-recordings every 15 minutes until 90 minutes after the administration of the PGE1 derivate. Results We observed seven arteries and seven veins. The diameter and blood flow of the arteries was significantly increased compared with the veins at both 60 and 75 minutes after administration of the PGE1 derivate (p Discussion The PGE1 derivate improved blood flow in the arteries but did not induce blood stasis in the veins. Our results suggest that the PGE1 derivate might be a potential therapeutic agent, as it improved blood flow in the nerve roots in a canine model of chronic cauda equina compression.

Climate sensitivity to Arctic seaway restriction during the early Paleogene

Science.gov (United States)

Roberts, Christopher D.; LeGrande, Allegra N.; Tripati, Aradhna K.

2009-09-01

The opening and closing of ocean gateways affects the global distribution of heat, salt, and moisture, potentially driving climatic change on regional to global scales. Between 65 and 45 million years ago (Ma), during the early Paleogene, exchange between the Arctic and global oceans occurred through two narrow and shallow seaways, the Greenland-Norway seaway and the Turgai Strait. Sediments from the Arctic Ocean suggest that, during this interval, the surface ocean was warm, brackish, and episodically enabled the freshwater fern Azolla to bloom. The precise mechanisms responsible for the development of these conditions in the Paleogene Arctic remain uncertain. Here we show results from an isotope-enabled, atmosphere-ocean general circulation model, which indicate that Northern Hemisphere climate would have been very sensitive to the degree of oceanic exchange through the Arctic seaways. We also present modelled estimates of seawater and calcite δ18O for the Paleogene. By restricting these seaways, we simulate freshening of the surface Arctic Ocean to ~ 6 psu and warming of sea-surface temperatures by 2 °C in the North Atlantic and 5-10 °C in the Labrador Sea. Our results may help explain the occurrence of low-salinity tolerant taxa in the Arctic Ocean during the Eocene and provide a mechanism for enhanced warmth in the north western Atlantic. We propose that the formation of a volcanic land-bridge between Greenland and Europe could have caused increased ocean convection and warming of intermediate waters in the Atlantic. If true, this result is consistent with the theory that bathymetry changes may have caused thermal destabilisation of methane clathrates and supports a tectonic trigger hypothesis for the Paleocene Eocene Thermal Maximum (PETM).

Modeling dissociation behaviour of methane hydrate in porous soil media

Energy Technology Data Exchange (ETDEWEB)

Jayasinghe, A.G.; Grozic, J.L.H. [Calgary Univ., AB (Canada). Dept. of Civil Engineering

2008-07-01

Gas hydrates, or clathrates, exist in the form of crystalline solid structures of hydrogen bonded water molecules where the lattice cages are occupied by guest gas molecules. Methane gas hydrates are the most common. As such, hydrate bearing sediments are considered to be a potential future energy resource. Gas hydrates also function as a source or sink for atmospheric methane, which may influence global warming. The authors emphasized that an understanding of the behaviour of soils containing gas hydrates is necessary in order to develop ways of recovering the vast gas resources that exist in the form of hydrates, particularly since hydrates are also suspected to be a potential factor in the initiation and propagation of submarine slope failures. Gas hydrate dissociation occurs when water and gas are released, resulting in an increase in pore fluid pressure, thereby causing significant reductions in effective stress leading to sediment failure. Dissociation may occur as a result of pressure reductions or increases in temperature. This study focused on the strength and deformation behaviour of hydrate bearing soils associated with temperature induced dissociation. Modeling the dissociation behavior of hydrates in porous soil media involves an understanding of the geomechanics of hydrate dissociation. This paper addressed the issue of coupling the hydrate dissociation problem with the soil deformation problem. A mathematical framework was constructed in which the thermally stimulated hydrate dissociation process in porous soil media under undrained conditions was considered with conduction heat transfer. It was concluded that a knowledge of geomechanical response of hydrate bearing sediments will enable better estimates of benefits and risks associated with the recovery process, thereby ensuring safe and economical exploration. 20 refs., 1 fig., 1 appendix.

Apparent Km of mitochondria for oxygen computed from Vmax measured in permeabilized muscle fibers is lower in water enriched in oxygen by electrolysis than injection.

Science.gov (United States)

Zoll, Joffrey; Bouitbir, Jamal; Sirvent, Pascal; Klein, Alexis; Charton, Antoine; Jimenez, Liliana; Péronnet, François R; Geny, Bernard; Richard, Ruddy

2015-01-01

It has been suggested that oxygen (O2) diffusion could be favored in water enriched in O2 by a new electrolytic process because of O2 trapping in water superstructures (clathrates), which could reduce the local pressure/content relationships for O2 and facilitate O2 diffusion along PO2 gradients. Mitochondrial respiration was compared in situ in saponin-skinned fibers isolated from the soleus muscles of Wistar rats, in solution enriched in O2 by injection or the electrolytic process 1) at an O2 concentration decreasing from 240 µmol/L to 10 µmol/L (132 mmHg to 5 mmHg), with glutamate-malate or N, N, N', N'-tetramethyl-p-phenylenediamine dihydrochloride (TMPD)-ascorbate (with antimycin A) as substrates; and 2) at increasing adenosine diphosphate (ADP) concentration with glutamate-malate as substrate. As expected, maximal respiration decreased with O2 concentration and, when compared to glutamate-malate, the apparent Km O2 of mitochondria for O2 was significantly lower with TMPD-ascorbate with both waters. However, when compared to the water enriched in O2 by injection, the Km O2 was significantly lower with both electron donors in water enriched in O2 by electrolysis. This was not associated with any increase in the sensitivity of mitochondria to ADP; no significant difference was observed for the Km ADP between the two waters. In this experiment, a higher affinity of the mitochondria for O2 was observed in water enriched in O2 by electrolysis than by injection. This observation is consistent with the hypothesis that O2 diffusion can be facilitated in water enriched in O2 by the electrolytic process.

The Ice Cap Zone: A Unique Habitable Zone for Ocean Worlds

Science.gov (United States)

Ramirez, Ramses M.; Levi, Amit

2018-03-01

Traditional definitions of the habitable zone assume that habitable planets contain a carbonate-silicate cycle that regulates CO2 between the atmosphere, surface, and the interior. Such theories have been used to cast doubt on the habitability of ocean worlds. However, Levi et al (2017) have recently proposed a mechanism by which CO2 is mobilized between the atmosphere and the interior of an ocean world. At high enough CO2 pressures, sea ice can become enriched in CO2 clathrates and sink after a threshold density is achieved. The presence of subpolar sea ice is of great importance for habitability in ocean worlds. It may moderate the climate and is fundamental in current theories of life formation in diluted environments. Here, we model the Levi et al. mechanism and use latitudinally-dependent non-grey energy balance and single-column radiative-convective models and find that this mechanism may be sustained on ocean worlds that rotate at least 3 times faster than the Earth. We calculate the circumstellar region in which this cycle may operate for G-M-stars (Teff = 2,600-5,800 K), extending from ˜1.23 - 1.65, 0.69 - 0.873, 0.38-0.528 AU, 0.219-0.308 AU, 0.146-0.206 AU, and 0.0428-0.0617 AU for G2, K3, M0, M3, M5, and M8 stars, respectively. However, unless planets are very young and not tidally-locked, our mechanism would be unlikely to apply to stars cooler than a ˜M3. We predict C/O ratios for our atmospheres (˜0.5) that can be verified by the JWST mission.

Big Impacts and Transient Oceans on Titan

Science.gov (United States)

Zahnle, K. J.; Korycansky, D. G.; Nixon, C. A.

2014-01-01

We have studied the thermal consequences of very big impacts on Titan [1]. Titan's thick atmosphere and volatile-rich surface cause it to respond to big impacts in a somewhat Earth-like manner. Here we construct a simple globally-averaged model that tracks the flow of energy through the environment in the weeks, years, and millenia after a big comet strikes Titan. The model Titan is endowed with 1.4 bars of N2 and 0.07 bars of CH4, methane lakes, a water ice crust, and enough methane underground to saturate the regolith to the surface. We assume that half of the impact energy is immediately available to the atmosphere and surface while the other half is buried at the site of the crater and is unavailable on time scales of interest. The atmosphere and surface are treated as isothermal. We make the simplifying assumptions that the crust is everywhere as methane saturated as it was at the Huygens landing site, that the concentration of methane in the regolith is the same as it is at the surface, and that the crust is made of water ice. Heat flow into and out of the crust is approximated by step-functions. If the impact is great enough, ice melts. The meltwater oceans cool to the atmosphere conductively through an ice lid while at the base melting their way into the interior, driven down in part through Rayleigh-Taylor instabilities between the dense water and the warm ice. Topography, CO2, and hydrocarbons other than methane are ignored. Methane and ethane clathrate hydrates are discussed quantitatively but not fully incorporated into the model.

To other worlds via the laboratory (Invited)

Science.gov (United States)

Lorenz, R. D.

2009-12-01

Planetary science is fun, largely by virtue of the wide range of disciplines and techniques it embraces. Progress relies not only on spacecraft observation and models, but also on laboratory work to provide reference data with which to interpret observations and to provide quantitative constraints on model parameters. An important distinction should be drawn between two classes of investigation. The most familiar, pursued by those who make laboratory studies the focus of their careers, is the construction of well-controlled experiments, typically to determine the functional dependence of some desired physical property upon one or two controlled parameters such as temperature, pressure or concentration. Another class of experiment is more exploratory - to 'see what happens'. This exercise often reveals that models may be based on entirely false assumptions. In some cases laboratory results also have value as persuasive tools in providing graphic support for unfamiliar properties or processes - the iconic image of 'flaming ice' makes the exotic notion of methane clathrate immediately accessible. This talk will review the role of laboratory work in planetary science and especially the outer solar system. A few of the author's personal forays into laboratory measurements will be discussed in the talk; These include the physical properties of dessicated icy loess in the US Army Permafrost tunnel in Alaska (as a Mars analog), the use of a domestic microwave oven to measure radar absorptivity (in particular of ammonia-rich water ice) and the generation of waves - and ice - on the surface of a liquid by wind with fluid and air parameters appropriate to Mars and Titan rather than Earth using the MARSWIT wind tunnel at NASA Ames.

A geometry-based simulation of the hydration of ions and small molecules

International Nuclear Information System (INIS)

Plumridge, T.H.

2001-01-01

The behaviour of solutes in water is of universal significance, but still not fully understood. This thesis provides details of a new computer simulation technique used to investigate the hydration of ions and small molecules. In contrast to conventional techniques such as molecular dynamics, this is a purely geometric method involving no forcefield or energy terms. Molecules of interest are modelled using crystallographic data to ensure that the structures are accurate. Water molecules are added randomly at any hydrogen bonding site in chains. At each addition the chain is rotated through all available space testing for the possibility of ring formation. The constraints used by the program to decide whether a ring should be conserved, i.e. whether the ring-forming hydrogen bond is viable were derived from a survey of (i) all available ice and clathrate hydrate structures and (ii) the hydrates of small biological molecules from the Cambridge Crystallographic Data Centre. If a ring forms, it is conserved and the process restarted with the addition of another random water. If the chain reaches a certain length and no hydrogen bonding opportunities are detected, the water chain is dissolved, and the process restarted. Using these techniques structure makers such as sulfate will readily allow structured water to form around them leading to large networks, whereas structure breakers such as urea will not allow any water chains to bridge the hydrogen bonding groups. The software has been tested with a set of twenty widely varying solutes and has produced results which generally agree with experimental data for structure makers and breakers, and also agrees well with traditional techniques such as molecular dynamics and Monte Carlo techniques. (author)

Novel rattling of K atoms in aluminium-doped defect pyrochlore tungstate

International Nuclear Information System (INIS)

Shoko, Elvis; Kearley, Gordon J; Peterson, Vanessa K; Thorogood, Gordon J; Mutka, Hannu; Koza, Michael M; Yamaura, Jun-ichi; Hiroi, Zenji

2014-01-01

Rattling dynamics have been identified as fundamental to superconductivity in defect pyrochlore osmates and aluminium vanadium intermetallics, as well as low thermal conductivity in clathrates and filled skutterudites. Combining inelastic neutron scattering (INS) measurements and ab initio molecular dynamics (MD) simulations, we use a new approach to investigate rattling in the Al-doped defect pyrochlore tungstates: AAl 0.33 W 1.67 O 6 (A = K, Rb, Cs). We find that although all the alkali metals rattle, the rattling of the K atoms is unique, not only among the tungstates but also among the analogous defect osmates, KOs 2 O 6 and RbOs 2 O 6 . Detailed analysis of the MD trajectories reveals that two unique features set the K dynamics apart from the rest, namely, (1) quasi one-dimensional local diffusion within a cage, and (2) vibration at a range of frequencies. The local diffusion is driven by strongly anharmonic local potentials around the K atoms exhibiting a double-well structure in the direction of maximum displacement, which is also the direction of local diffusion. On the other hand, vibration at a range of frequencies is a consequence of the strong anisotropy in the local potentials around the K atoms as revealed by directional magnitude spectra. We present evidence to show that it is the smaller size rather than the smaller mass of the K rattler which leads to the unusual dynamics. Finally, we suggest that the occurrence of local diffusion and vibration at a range of frequencies in the dynamics of a single rattler, as found here for the K atoms, may open new possibilities for phonon engineering in thermoelectric materials. (paper)

Incorporating public priorities in the Ocean Health Index: Canada as a case study.

Directory of Open Access Journals (Sweden)

Rémi M Daigle

Full Text Available The Ocean Health Index (OHI is a framework to assess ocean health by considering many benefits (called 'goals' provided by the ocean provides to humans, such as food provision, tourism opportunities, and coastal protection. The OHI framework can be used to assess marine areas at global or regional scales, but how various OHI goals should be weighted to reflect priorities at those scales remains unclear. In this study, we adapted the framework in two ways for application to Canada as a case study. First, we customized the OHI goals to create a national Canadian Ocean Health Index (COHI. In particular, we altered the list of iconic species assessed, added methane clathrates and subsea permafrost as carbon storage habitats, and developed a new goal, 'Aboriginal Needs', to measure access of Aboriginal people to traditional marine hunting and fishing grounds. Second, we evaluated various goal weighting schemes based on preferences elicited from the general public in online surveys. We quantified these public preferences in three ways: using Likert scores, simple ranks from a best-worst choice experiment, and model coefficients from the analysis of elicited choice experiment. The latter provided the clearest statistical discrimination among goals, and we recommend their use because they can more accurately reflect both public opinion and the trade-offs faced by policy-makers. This initial iteration of the COHI can be used as a baseline against which future COHI scores can be compared, and could potentially be used as a management tool to prioritise actions on a national scale and predict public support for these actions given that the goal weights are based on public priorities.

Thermodynamic and kinetic verification of tetra-n-butyl ammonium nitrate (TBANO3) as a promoter for the clathrate process applicable to precombustion carbon dioxide capture.

Science.gov (United States)

Babu, Ponnivalavan; Yao, Minghuang; Datta, Stuti; Kumar, Rajnish; Linga, Praveen

2014-03-18

In this study, tetra-n-butyl ammonium nitrate (TBANO3) is evaluated as a promoter for precombustion capture of CO2 via hydrate formation. New hydrate phase equilibrium data for fuel gas (CO2/H2) mixture in presence of TBANO3 of various concentrations of 0.5, 1.0, 2.0, 3.0, and 3.7 mol % was determined and presented. Heat of hydrate dissociation was calculated using Clausius-Clapeyron equation and as the concentration of TBANO3 increases, the heat of hydrate dissociation also increases. Kinetic performance of TBANO3 as a promoter at different concentrations was evaluated at 6.0 MPa and 274.2 K. Based on induction time, gas uptake, separation factor, hydrate phase CO2 composition, and rate of hydrate growth, 1.0 mol % TBANO3 solution was found to be the optimum concentration at the experimental conditions of 6.0 MPa and 274.2 K for gas hydrate formation. A 93.0 mol % CO2 rich stream can be produced with a gas uptake of 0.0132 mol of gas/mol of water after one stage of hydrate formation in the presence of 1.0 mol % TBANO3 solution. Solubility measurements and microscopic images of kinetic measurements provide further insights to understand the reason for 1.0 mol % TBANO3 to be the optimum concentration.

NMR investigations of surfaces and interfaces using spin-polarized xenon

International Nuclear Information System (INIS)

Gaede, H.C.; Lawrence Berkeley Lab., CA

1995-07-01

129 Xe NMR is potentially useful for the investigation of material surfaces, but has been limited to high surface area samples in which sufficient xenon can be loaded to achieve acceptable signal to noise ratios. In Chapter 2 conventional 129 Xe NMR is used to study a high surface area polymer, a catalyst, and a confined liquid crystal to determine the topology of these systems. Further information about the spatial proximity of different sites of the catalyst and liquid crystal systems is determined through two dimensional exchange NMR in Chapter 3. Lower surface area systems may be investigated with spin-polarized xenon, which may be achieved through optical pumping and spin exchange. Optically polarized xenon can be up to 10 5 times more sensitive than thermally polarized xenon. In Chapter 4 highly polarized xenon is used to examine the surface of poly(acrylonitrile) and the formation of xenon clathrate hydrates. An attractive use of polarized xenon is as a magnetization source in cross polarization experiments. Cross polarization from adsorbed polarized xenon may allow detection of surface nuclei with drastic enhancements. A non-selective low field thermal mixing technique is used to enhance the 13 C signal of CO 2 of xenon occluded in solid CO 2 by a factor of 200. High-field cross polarization from xenon to proton on the surface of high surface area polymers has enabled signal enhancements of ∼1,000. These studies, together with investigations of the efficiency of the cross polarization process from polarized xenon, are discussed in Chapter 5. Another use of polarized xenon is as an imaging contrast agent in systems that are not compatible with traditional contrast agents. The resolution attainable with this method is determined through images of structured phantoms in Chapter 6

Phase diagram of the Ge-rich of the Ba–Ge system and characterisation of single-phase BaGe4

International Nuclear Information System (INIS)

Prokofieva, Violetta K.; Pavlova, Lydia M.

2014-01-01

Highlights: • The Ba-Ge phase diagram for the range 50–100 at.% Ge was constructed. • Single-phase BaGe 4 grown by the Czochralski method was characterised. • A phenomenological model for a liquid-liquid phase transition is proposed. - Abstract: The Ba–Ge binary system has been investigated by several authors, but some uncertainties remain regarding phases with Ba/Ge ⩽ 2. The goal of this work was to resolve the uncertainty about the current phase diagram of Ba–Ge by performing DTA, X-ray powder diffraction, metallographic and chemical analyses, and measurements of the electrical conductivity and viscosity. The experimental Ba–Ge phase diagram over the composition range of 50–100 at.% Ge was constructed from the cooling curves and single-phase BaGe 4 grown by the Czochralski crystal pulling method was characterised. Semiconducting BaGe 4 crystallised peritectically from the liquid phase near the eutectic. In the liquid state, the caloric effects were observed in the DTA curves at 1050 °C where there are no definite phase lines in the Ba–Ge phase diagram. These effects are confirmed by significant changes in the viscosity and electrical conductivity of a Ba–Ge alloy with eutectic composition at this temperature. A phenomenological model based on two different approaches, a phase approach and a chemical approach, is proposed to explain the isothermal liquid–liquid phase transition observed in the Ba–Ge system from the Ge side. Our results suggest that this transition is due to the peritectic reactions in the liquid phase. This reversible phase transition results in the formation of precursors of various metastable clathrate phases and is associated with sudden changes in the structure of Ba–Ge liquid alloys. Characteristics of both first- and second-order phase transitions are observed. Charge transfer appears to play an important role in this transition

Thermodynamic and structural signatures of water-driven methane-methane attraction in coarse-grained mW water.

Science.gov (United States)

Song, Bin; Molinero, Valeria

2013-08-07

Hydrophobic interactions are responsible for water-driven processes such as protein folding and self-assembly of biomolecules. Microscopic theories and molecular simulations have been used to study association of a pair of methanes in water, the paradigmatic example of hydrophobic attraction, and determined that entropy is the driving force for the association of the methane pair, while the enthalpy disfavors it. An open question is to which extent coarse-grained water models can still produce correct thermodynamic and structural signatures of hydrophobic interaction. In this work, we investigate the hydrophobic interaction between a methane pair in water at temperatures from 260 to 340 K through molecular dynamics simulations with the coarse-grained monatomic water model mW. We find that the coarse-grained model correctly represents the free energy of association of the methane pair, the temperature dependence of free energy, and the positive change in entropy and enthalpy upon association. We investigate the relationship between thermodynamic signatures and structural order of water through the analysis of the spatial distribution of the density, energy, and tetrahedral order parameter Qt of water. The simulations reveal an enhancement of tetrahedral order in the region between the first and second hydration shells of the methane molecules. The increase in tetrahedral order, however, is far from what would be expected for a clathrate-like or ice-like shell around the solutes. This work shows that the mW water model reproduces the key signatures of hydrophobic interaction without long ranged electrostatics or the need to be re-parameterized for different thermodynamic states. These characteristics, and its hundred-fold increase in efficiency with respect to atomistic models, make mW a promising water model for studying water-driven hydrophobic processes in more complex systems.

Eocene climate and Arctic paleobathymetry: A tectonic sensitivity study using GISS ModelE-R

Science.gov (United States)

Roberts, C. D.; Legrande, A. N.; Tripati, A. K.

2009-12-01

The early Paleogene (65-45 million years ago, Ma) was a ‘greenhouse’ interval with global temperatures warmer than any other time in the last 65 Ma. This period was characterized by high levels of CO2, warm high-latitudes, warm surface-and-deep oceans, and an intensified hydrological cycle. Sediments from the Arctic suggest that the Eocene surface Arctic Ocean was warm, brackish, and episodically enabled the freshwater fern Azolla to bloom. The precise mechanisms responsible for the development of these conditions remain uncertain. We present equilibrium climate conditions derived from a fully-coupled, water-isotope enabled, general circulation model (GISS ModelE-R) configured for the early Eocene. We also present model-data comparison plots for key climatic variables (SST and δ18O) and analyses of the leading modes of variability in the tropical Pacific and North Atlantic regions. Our tectonic sensitivity study indicates that Northern Hemisphere climate would have been very sensitive to the degree of oceanic exchange through the seaways connecting the Arctic to the Atlantic and Tethys. By restricting these seaways, we simulate freshening of the surface Arctic Ocean to ~6 psu and warming of sea-surface temperatures by 2°C in the North Atlantic and 5-10°C in the Labrador Sea. Our results may help explain the occurrence of low-salinity tolerant taxa in the Arctic Ocean during the Eocene and provide a mechanism for enhanced warmth in the north western Atlantic. We also suggest that the formation of a volcanic land-bridge between Greenland and Europe could have caused increased ocean convection and warming of intermediate waters in the Atlantic. If true, this result is consistent with the theory that bathymetry changes may have caused thermal destabilisation of methane clathrates in the Atlantic.

Effect of administration of water enriched in O2 by injection or electrolysis on transcutaneous oxygen pressure in anesthetized pigs.

Science.gov (United States)

Charton, Antoine; Péronnet, François; Doutreleau, Stephane; Lonsdorfer, Evelyne; Klein, Alexis; Jimenez, Liliana; Geny, Bernard; Diemunsch, Pierre; Richard, Ruddy

2014-01-01

Oral administration of oxygenated water has been shown to improve blood oxygenation and could be an alternate way for oxygen (O2) supply. In this experiment, tissue oxygenation was compared in anesthetized pigs receiving a placebo or water enriched in O2 by injection or a new electrolytic process. Forty-two pigs randomized in three groups received either mineral water as placebo or water enriched in O2 by injection or the electrolytic process (10 mL/kg in the stomach). Hemodynamic parameters, partial pressure of oxygen in the arterial blood (PaO2), skin blood flow, and tissue oxygenation (transcutaneous oxygen pressure, or TcPO2) were monitored during 90 minutes of general anesthesia. Absorption and tissue distribution of the three waters administered were assessed using dilution of deuterium oxide. Mean arterial pressure, heart rate, PaO2, arteriovenous oxygen difference, and water absorption from the gut were not significantly different among the three groups. The deuterium to protium ratio was also similar in the plasma, skin, and muscle at the end of the protocol. Skin blood flow decreased in the three groups. TcPO2 slowly decreased over the last 60 minutes of the experiment in the three groups, but when compared to the control group, the values remained significantly higher in animals that received the water enriched in O2 by electrolysis. In this protocol, water enriched in O2 by electrolysis lessened the decline of peripheral tissue oxygenation. This observation is compatible with the claim that the electrolytic process generates water clathrates which trap O2 and facilitate O2 diffusion along pressure gradients. Potential applications of O2-enriched water include an alternate method of oxygen supply.

Carbon and energy footprint of the hydrate-based biogas upgrading process integrated with CO2 valorization.

Science.gov (United States)

Castellani, Beatrice; Rinaldi, Sara; Bonamente, Emanuele; Nicolini, Andrea; Rossi, Federico; Cotana, Franco

2018-02-15

The present paper aims at assessing the carbon and energy footprint of an energy process, in which the energy excess from intermittent renewable sources is used to produce hydrogen which reacts with the CO 2 previously separated from an innovative biogas upgrading process. The process integrates a hydrate-based biogas upgrading section and a CO 2 methanation section, to produce biomethane from the biogas enrichment and synthetic methane from the CO 2 methanation. Clathrate hydrates are crystalline compounds, formed by gas enclathrated in cages of water molecules and are applied to the selective separation of CO 2 from biogas mixtures. Data from the experimental setup were analyzed in order to evaluate the green-house gas emissions (carbon footprint CF) and the primary energy consumption (energy footprint EF) associated to the two sections of the process. The biosynthetic methane production during a single-stage process was 0.962Nm 3 , obtained mixing 0.830Nm 3 of methane-enriched biogas and 0.132Nm 3 of synthetic methane. The final volume composition was: 73.82% CH 4 , 19.47% CO 2 , 0.67% H 2 , 1.98% O 2 , 4.06% N 2 and the energy content was 28.0MJ/Nm 3 . The functional unit is the unitary amount of produced biosynthetic methane in Nm 3 . Carbon and energy footprints are 0.7081kgCO 2eq /Nm 3 and 28.55MJ/Nm 3 , respectively, when the electric energy required by the process is provided by photovoltaic panels. In this scenario, the overall energy efficiency is about 0.82, higher than the worldwide average energy efficiency for fossil methane, which is 0.75. Copyright © 2017 Elsevier B.V. All rights reserved.

The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study.

Science.gov (United States)

Zhang, Zhengcai; Guo, Guang-Jun

2017-07-26

Although ice powders are widely used in gas hydrate formation experiments, the effects of ice on hydrate nucleation and what happens in the quasi-liquid layer of ice are still not well understood. Here, we used high-precision constant energy molecular dynamics simulations to study methane hydrate nucleation from vapor-liquid mixtures exposed to the basal, prismatic, and secondary prismatic planes of hexagonal ice (ice Ih). Although no significant difference is observed in hydrate nucleation processes for these different crystal planes, it is found, more interestingly, that methane hydrate can nucleate either on the ice surface heterogeneously or in the bulk solution phase homogeneously. Several factors are mentioned to be able to promote the heterogeneous nucleation of hydrates, including the adsorption of methane molecules at the solid-liquid interface, hydrogen bonding between hydrate cages and the ice structure, the stronger ability of ice to transfer heat than that of the aqueous solution, and the higher occurrence probability of hydrate cages in the vicinity of the ice surface than in the bulk solution. Meanwhile, however, the other factors including the hydrophilicity of ice and the ice lattice mismatch with clathrate hydrates can inhibit heterogeneous nucleation on the ice surface and virtually promote homogeneous nucleation in the bulk solution. Certainly, the efficiency of ice as a promoter and as an inhibitor for heterogeneous nucleation is different. We estimate that the former is larger than the latter under the working conditions. Additionally, utilizing the benefit of ice to absorb heat, the NVE simulation of hydrate formation with ice can mimic the phenomenon of ice shrinking during the heterogeneous nucleation of hydrates and lower the overly large temperature increase during homogeneous nucleation. These results are helpful in understanding the nucleation mechanism of methane hydrate in the presence of ice.

Role of Megafauna and Frozen Soil in the Atmospheric CH4 Dynamics

Science.gov (United States)

Zimov, Sergey; Zimov, Nikita

2014-01-01

Modern wetlands are the world’s strongest methane source. But what was the role of this source in the past? An analysis of global 14C data for basal peat combined with modelling of wetland succession allowed us to reconstruct the dynamics of global wetland methane emission through time. These data show that the rise of atmospheric methane concentrations during the Pleistocene-Holocene transition was not connected with wetland expansion, but rather started substantially later, only 9 thousand years ago. Additionally, wetland expansion took place against the background of a decline in atmospheric methane concentration. The isotopic composition of methane varies according to source. Owing to ice sheet drilling programs past dynamics of atmospheric methane isotopic composition is now known. For example over the course of Pleistocene-Holocene transition atmospheric methane became depleted in the deuterium isotope, which indicated that the rise in methane concentrations was not connected with activation of the deuterium-rich gas clathrates. Modelling of the budget of the atmospheric methane and its isotopic composition allowed us to reconstruct the dynamics of all main methane sources. For the late Pleistocene, the largest methane source was megaherbivores, whose total biomass is estimated to have exceeded that of present-day humans and domestic animals. This corresponds with our independent estimates of herbivore density on the pastures of the late Pleistocene based on herbivore skeleton density in the permafrost. During deglaciation, the largest methane emissions originated from degrading frozen soils of the mammoth steppe biome. Methane from this source is unique, as it is depleted of all isotopes. We estimated that over the entire course of deglaciation (15,000 to 6,000 year before present), soils of the mammoth steppe released 300–550 Pg (1015 g) of methane. From current study we conclude that the Late Quaternary Extinction significantly affected the global

Sequestering carbon dioxide in industrial polymers: Building materials for the 21st century

Energy Technology Data Exchange (ETDEWEB)

Molton, P.M.; Nelson, D.A.

1993-06-01

This study was undertaken to determine the possibility of developing beneficial uses for carbon dioxide as a key component for a large-volume building product. Such a use may provide an alternative to storing the gas in oceanic sinks or clathrates as a way to slow the rate of global warming. The authors investigated the concept that carbon dioxide might be used with other chemicals to make carbon-dioxide-based polymers which would be lightweight, strong, and economical alternatives to some types of wood and silica-based building materials. As a construction-grade material, carbon dioxide would be fixed in a solid, useful form where it would not contribute to global warming. With the probable imposition of a fuel carbon tax in industrialized countries, this alternative would allow beneficial use of the carbon dioxide and could remove it from the tax basis if legislation were structured appropriately. Hence, there would be an economic driver towards the use of carbon-dioxide-based polymers which would enhance their future applications. Information was obtained through literature searches and personal contacts on carbon dioxide polymers which showed that the concept (1) is technically feasible, (2) is economically defensible, and (3) has an existing industrial infrastructure which could logically develop it. The technology exists for production of building materials which are strong enough for use by industry and which contain up to 90% by weight of carbon dioxide, both chemically and physically bound. A significant side-benefit of using this material would be that it is self-extinguishing in case of fire. This report is the first stage in the investigation. Further work being proposed will provide details on costs, specific applications and volumes, and potential impacts of this technology.

THE IMPRINT OF EXOPLANET FORMATION HISTORY ON OBSERVABLE PRESENT-DAY SPECTRA OF HOT JUPITERS

Energy Technology Data Exchange (ETDEWEB)

Mordasini, C.; Van Boekel, R.; Mollière, P.; Henning, Th. [Max-Planck-Institut für Astronomie, Königstuhl 17, D-69117 Heidelberg (Germany); Benneke, Björn, E-mail: christoph.mordasini@space.unibe.ch, E-mail: boekel@mpia.de, E-mail: molliere@mpia.de, E-mail: henning@mpia.de, E-mail: bbenneke@caltech.edu [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 (United States)

2016-11-20

The composition of a planet’s atmosphere is determined by its formation, evolution, and present-day insolation. A planet’s spectrum therefore may hold clues on its origins. We present a “chain” of models, linking the formation of a planet to its observable present-day spectrum. The chain links include (1) the planet’s formation and migration, (2) its long-term thermodynamic evolution, (3) a variety of disk chemistry models, (4) a non-gray atmospheric model, and (5) a radiometric model to obtain simulated spectroscopic observations with James Webb Space Telescope and ARIEL. In our standard chemistry model the inner disk is depleted in refractory carbon as in the Solar System and in white dwarfs polluted by extrasolar planetesimals. Our main findings are: (1) envelope enrichment by planetesimal impacts during formation dominates the final planetary atmospheric composition of hot Jupiters. We investigate two, under this finding, prototypical formation pathways: a formation inside or outside the water iceline, called “dry” and “wet” planets, respectively. (2) Both the “dry” and “wet” planets are oxygen-rich (C/O < 1) due to the oxygen-rich nature of the solid building blocks. The “dry” planet’s C/O ratio is <0.2 for standard carbon depletion, while the “wet” planet has typical C/O values between 0.1 and 0.5 depending mainly on the clathrate formation efficiency. Only non-standard disk chemistries without carbon depletion lead to carbon-rich C/O ratios >1 for the “dry” planet. (3) While we consistently find C/O ratios <1, they still vary significantly. To link a formation history to a specific C/O, a better understanding of the disk chemistry is thus needed.

Fluid Evolution During Mineralization of Atashkuh Fluorite-Barite (±Sulfide Deposit, South of Delijan

Directory of Open Access Journals (Sweden)

Seyed Javad Moghaddasi

2016-07-01

the Atashkuh deposit. Fluid inclusions are of several types: (1 two-phase, liquid-vapor (LV, two- phase aqueous with hydrohalite (LVHH, multiphase (SH, H2O-CO2 with clathrate (C1 and without clathrate (C2 were recognized and analyzed. The first ice melting temperature (Te of fluorite, barite and quartz two-phase aqueous (LV inclusions varies between -22°C and -25°C, representing a H2O ± NaCl ± KCl multiphase solution (Van den Kerkhof and Hein, 2001. The last ice melting temperatures of three samples (Tmice vary between -4.9°C to -9.7°C, -3.2°C to -7.2°C and -2°C to -4.8°C which indicate salinities of 7.7-13.6, 5.2-10.7 and 3.2-7.5 wt% NaCl equivalent for fluorite, barite and quartz. The final homogenization temperatures (Thtotal of these inclusions vary between 90 and 205 °C for fluorite, 130 to 270 °C for barite and 110 to 193 °C for quartz. The CO2 melting temperatures (TmCO2 of fluorite and quartz C1 inclusions show ranges of -57.1 to -58.5 °C which suggest the presence of CH4 and/or N2 impurities (Burruss, 1981. The clathrate melting temperature (Tmclath varies between 4.8 and 8.5 °C representing a salinity of 5.3 to 9.2 and 3 to 6.7 wt% NaCl equivalent for fluorite and quartz. The CO2 homogenization temperature (ThCO2 in these inclusions is 7.4 to 18.8 °C for fluorite and 13.4 to 27.5 °C for quartz. The homogenization temperature (Thtotal for these inclusions is 170-210 °C for fluorite and 195-280 °C for quartz. References Burruss, R.C., 1981. Analysis of phase equilibria in C–O–H–S fluid inclusions. Mineralogical Association of Canada Short Course, 6(3: 39-74. Ghorbani, M., 2013. The economic geology of Iran, mineral deposits and natural resources. Springer Netherlands, 569 pp. Thiele, O., Alavi, M., Assefi, R., Hushmand-zadeh, A., Seyed-Emami, K. and Zahedi, M., 1968. Explanatory text of the Golpaygan quadrangle map, scale 1:250,000. Geological Survey of Iran. Geological quadrangle E7, 24 pp. Van den Kerkhof, A.M. and Hein, U.F., 2001

Thermodynamic modeling of phase equilibria of semi-clathrate hydrates of CO₂, CH₄, or N₂+tetra-n-butylammonium bromide aqueous solution

DEFF Research Database (Denmark)

Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique

2012-01-01

, the Non-Random Two-Liquid (NRTL) activity model is used. To calculate the mean activity coefficients of the electrolyte portion, a correlation on the basis of existing osmotic coefficient and activity coefficient values is employed. It is shown that the presented model results are in acceptable agreement...

Modeling the Acceleration of Global Surface Temperture

Science.gov (United States)

Jones, B.

2017-12-01

A mathematical projection focusing on the changing rate of acceleration of Global Surface Temperatures. Using historical trajectory and informed expert near-term prediction, it is possible to extend this further forward drawing a reference arc of acceleration. Presented here is an example of this technique based on data found in the Summary of Findings of A New Estimate of the Average Earth Surface Land Temperature Spanning 1753 to 2011 and that same team's stated prediction to 2050. With this, we can project a curve showing future acceleration: Decade (midpoint) Change in Global Land Temp Degrees C Known Slope Projected Trend 1755 0.000 1955 0.600 0.0030 2005 1.500 0.0051 2045 3.000 0.0375 2095 5.485 0.0497 2145 8.895 0.0682 2195 13.488 0.0919 Observations: Slopes are getting steeper and doing so faster in an "acceleration of the acceleration" or an "arc of acceleration". This is consistent with the non-linear accelerating feedback loops of global warming. Such projected temperatures threaten human civilization and human life. This `thumbnail' projection is consistent with the other long term predictions based on anthropogenic greenhouse gases. This projection is low when compared to those whose forecasts include greenhouse gases released from thawing permafrost and clathrate hydrates. A reference line: This curve should be considered a point of reference. In the near term and absent significant drawdown of greenhouse gases, my "bet" for this AGU session is that future temperatures will generally be above this reference curve. For example, the decade ending 2020 - more than 1.9C and the decade ending 2030 - more than 2.3C - again measured from the 1750 start point. *Caveat: The long term curve and prediction assumes that mankind does not move quickly away from high cost fossil fuels and does not invent, mobilize and take actions drawing down greenhouse gases. Those seeking a comprehensive action plan are directed to drawdown.org

Frost on Utopia Planitia

Science.gov (United States)

1977-01-01

This Viking Lander 2 picture from Utopia Planitia shows the first clear indication of frost accumulation on the Martian surface seen by lander cameras. The picture, looking due north, was obtained with a blue filter at 12:59 p.m. local lander time, Sept. 13, 1977. The season is late winter. Frost appears as a white accumulation around the bottom of rocks, in a trench dug by the lander sampler arm, and in scattered patches on the darker surface. The shadow of the lander, including the camera (center) and the meteorology boom (left), appears in foreground. As the sun moves, the shadow is moving from left to right, exposing areas covered by frost and previously protected from the sun by the lander shadow. (Another image taken one-half hour later suggests the frost patches have become smaller.) Apparently frost, formed during the Martian night, at least partially disappears during the warmer daytime. The composition of the frost, whether carbon dioxide or water or a mixture of the two (CO2 clathrate), is not known. Measurements from the meteorology instrument indicate minimum nighttime temperatures of 160 Kelvin (-171 Fahrenheit). At the time the image was taken, the temperature had risen to 175 Kelvin (-144 Fahrenheit). The atmospheric pressure was 8.835 millibars. This combination of pressure and temperature are inconsistent with carbon dioxide frost formation, but plausible near-surface mechanisms might have resulted in conditions favorable for CO2 frost formation. Viking orbiter thermal mapping and water vapor instruments indicate temperatures might have been slightly lower than measured by the lander, suggesting that the frost is more likely CO2 than H20. A remote, but possible, explanation is that the material is an extremely bright dust deposit. Color images to be taken will be able to discount this interpretation. The mechanism for frost deposition is unknown. Possibilities include formation directly on the surface, precipitation as snow, or material blown to

Seismic Modeling Of Reservoir Heterogeneity Scales: An Application To Gas Hydrate Reservoirs

Science.gov (United States)

Huang, J.; Bellefleur, G.; Milkereit, B.

2008-12-01

Natural gas hydrates, a type of inclusion compound or clathrate, are composed of gas molecules trapped within a cage of water molecules. The occurrence of gas hydrates in permafrost regions has been confirmed by core samples recovered from the Mallik gas hydrate research wells located within Mackenzie Delta in Northwest Territories of Canada. Strong vertical variations of compressional and shear sonic velocities and weak surface seismic expressions of gas hydrates indicate that lithological heterogeneities control the distribution of hydrates. Seismic scattering studies predict that typical scales and strong physical contrasts due to gas hydrate concentration will generate strong forward scattering, leaving only weak energy captured by surface receivers. In order to understand the distribution of hydrates and the seismic scattering effects, an algorithm was developed to construct heterogeneous petrophysical reservoir models. The algorithm was based on well logs showing power law features and Gaussian or Non-Gaussian probability density distribution, and was designed to honor the whole statistical features of well logs such as the characteristic scales and the correlation among rock parameters. Multi-dimensional and multi-variable heterogeneous models representing the same statistical properties were constructed and applied to the heterogeneity analysis of gas hydrate reservoirs. The petrophysical models provide the platform to estimate rock physics properties as well as to study the impact of seismic scattering, wave mode conversion, and their integration on wave behavior in heterogeneous reservoirs. Using the Biot-Gassmann theory, the statistical parameters obtained from Mallik 5L-38, and the correlation length estimated from acoustic impedance inversion, gas hydrate volume fraction in Mallik area was estimated to be 1.8%, approximately 2x108 m3 natural gas stored in a hydrate bearing interval within 0.25 km2 lateral extension and between 889 m and 1115 m depth

Measurements of 14C in ancient ice from Taylor Glacier, Antarctica constrain in situ cosmogenic 14CH4 and 14CO production rates

Science.gov (United States)

Petrenko, Vasilii V.; Severinghaus, Jeffrey P.; Schaefer, Hinrich; Smith, Andrew M.; Kuhl, Tanner; Baggenstos, Daniel; Hua, Quan; Brook, Edward J.; Rose, Paul; Kulin, Robb; Bauska, Thomas; Harth, Christina; Buizert, Christo; Orsi, Anais; Emanuele, Guy; Lee, James E.; Brailsford, Gordon; Keeling, Ralph; Weiss, Ray F.

2016-03-01

Carbon-14 (14C) is incorporated into glacial ice by trapping of atmospheric gases as well as direct near-surface in situ cosmogenic production. 14C of trapped methane (14CH4) is a powerful tracer for past CH4 emissions from ;old; carbon sources such as permafrost and marine CH4 clathrates. 14C in trapped carbon dioxide (14CO2) can be used for absolute dating of ice cores. In situ produced cosmogenic 14C in carbon monoxide (14CO) can potentially be used to reconstruct the past cosmic ray flux and past solar activity. Unfortunately, the trapped atmospheric and in situ cosmogenic components of 14C in glacial ice are difficult to disentangle and a thorough understanding of the in situ cosmogenic component is needed in order to extract useful information from ice core 14C. We analyzed very large (≈1000 kg) ice samples in the 2.26-19.53 m depth range from the ablation zone of Taylor Glacier, Antarctica, to study in situ cosmogenic production of 14CH4 and 14CO. All sampled ice is >50 ka in age, allowing for the assumption that most of the measured 14C originates from recent in situ cosmogenic production as ancient ice is brought to the surface via ablation. Our results place the first constraints on cosmogenic 14CH4 production rates and improve on prior estimates of 14CO production rates in ice. We find a constant 14CH4/14CO production ratio (0.0076 ± 0.0003) for samples deeper than 3 m, which allows the use of 14CO for correcting the 14CH4 signals for the in situ cosmogenic component. Our results also provide the first unambiguous confirmation of 14C production by fast muons in a natural setting (ice or rock) and suggest that the 14C production rates in ice commonly used in the literature may be too high.

Material Exchange and Migration between Pore Fluids and Sandstones during Diagenetic Processes in Rift Basins: A Case Study Based on Analysis of Diagenetic Products in Dongying Sag, Bohai Bay Basin, East China

Directory of Open Access Journals (Sweden)

W. Meng

2018-01-01

Full Text Available The exchange and migration of basin materials that are carried by pore fluids are the essence of diagenesis, which can alter physical properties of clastic rocks as well as control formation and distribution of favorable reservoirs of petroliferous basins. Diagenetic products and pore fluids, resulting from migration and exchange of basin materials, can be used to deduce those processes. In this study, 300 core samples from 46 wells were collected for preparation of casting thin sections, SEM, BSE, EDS, inclusion analysis, and isotope analysis in Dongying Sag, Bohai Bay Basin, East China. Combined with geochemical characteristics of pore fluids and geological background of the study area, the source and exchange mechanisms of materials in the pore fluids of rift basins were discussed. It was revealed that the material exchange of pore fluids could be divided into five stages. The first stage was the evaporation concentration stage during which mainly Ca2+, Mg2+, and CO32- precipitated as high-Mg calcites. Then came the shale compaction stage, when mainly Ca2+ and CO32- from shale compaction water precipitated as calcites. The third stage was the carboxylic acid dissolution stage featured by predominant dissolution of plagioclases, during which Ca2+ and Na+ entered pore fluids, and Si and Al also entered pore fluids and then migrated as clathrates, ultimately precipitating as kaolinites. The fourth stage was the organic CO2 stage, mainly characterized by the kaolinization of K-feldspar as well as dissolution of metamorphic lithic fragments and carbon cements. During this stage, K+, Fe2+, Mg2+, Ca2+, HCO3-, and CO32- entered pore fluids. The fifth stage was the alkaline fluid stage, during which the cementation of ferro-carbonates and ankerites as well as illitization or chloritization of kaolinites prevailed, leading to the precipitation of K+, Fe2+, Mg2+, Ca2+, and CO32- from pore fluids.

Methane Seepage on Mars: Where to Look and Why.

Science.gov (United States)

Oehler, Dorothy Z; Etiope, Giuseppe

2017-12-01

Words: Mars-Methane-Seepage-Clathrate-Fischer-Tropsch-Serpentinization. Astrobiology 17, 1233-1264.

Study on gas hydrate as a new energy resource in the 21th century

Energy Technology Data Exchange (ETDEWEB)

Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

1999-12-01

Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

Tracking Early Jurassic marine (de)oxygenation

Science.gov (United States)

Them, T. R., II; Caruthers, A. H.; Gill, B. C.; Gröcke, D. R.; Marroquín, S. M.; Owens, J. D.

2017-12-01

It has been suggested that the carbon cycle was perturbed during the Toarcian OAE (T-OAE) as observed in the carbon isotope record, and more recently other elemental cycles (e.g., Hg, Mo, Os, S). The most widely accepted hypothesis focuses on the emplacement of the Karoo-Ferrar large igneous province, outgassing of greenhouse gases, and subsequent feedbacks in the Earth system, which caused severe environmental change and biological turnover. Feedbacks to elevated atmospheric pCO2 include enhanced weathering rates, dissociation of methane clathrates, increased terrestrial methanogenesis, and widespread marine anoxia. The sequence of events related to the development and duration of marine anoxia are not well constrained for this time interval due to a lack of open-ocean geochemical records. In order to reconstruct the timing of marine deoxygenation during the Early Jurassic T-OAE, we have utilized thallium isotopes, a novel geochemical proxy from multiple anoxic basins in North America and Germany. Three sites representing a basin transect from the Western Canada Sedimentary Basin, and one site from the South German Basin, were chosen to reconstruct the thallium isotopic composition (ɛ205Tl) of the ocean. The ɛ205Tl composition of sediments deposited under anoxic and euxinic water columns records the global seawater ɛ205Tl composition, a function of the amount of manganese oxides that are precipitated. Increased geographic extent of marine anoxia will cause a decrease in manganese oxide precipitation and perturb the thallium system. Importantly, the inputs of thallium are nearly identical, thus changes in these fluxes cannot drive the observed perturbation. Our new Early Jurassic ɛ205Tl records suggest that the onset of marine deoxygenation occurred concurrently with Karoo-Ferrar magmatism in the late Pliensbachian and continued until after the T-OAE. These new data support a Karoo-Ferrar trigger of the T-OAE. However, thallium isotopes also suggest that

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

Science.gov (United States)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and

The 2006 Eruption of Raoul Volcano (Kermadecs): A Phreato-magmatic Event From a Hydrothermally-Sealed Volcanic Conduit System.

Science.gov (United States)

Christenson, B. W.; Reyes, A. G.; Werner, C. A.

2006-12-01

The March 17, 2006 eruption from Raoul volcano (Kermadec Islands, NZ), which tragically claimed the life of NZ Department of Conservation staff member Mark Kearney, is being interpreted as a magmatic-hydrothermal event triggered by shaking associated with regional earthquake swarm activity. Although the eruption released ca. 200 T of SO2, thus confirming its magmatic nature, it occurred without significant precursory volcanic seismicity, and without any of the precursory responses of the volcanic hydrothermal system which were observed prior to the last eruption in 1964. Raoul Island has a long and varied eruption history dating back > 1.4 ma, and has been hydrothermally active throughout historic time. Present day fumarolic and hotspring discharges within Raoul caldera point to the existence of a small but well established, mixed meteoric - seawater hydrothermal system within the volcano. Magmatic signatures are apparent in fumarolic gas discharges, but are heavily masked by their interaction with hydrothermal system fluids (eg. near complete scrubbing of sulphur and halogen gases from the boiling point fumarolic discharges). A diffuse degassing study conducted in 2004 revealed that ca. 80 T/d CO2 is passively discharged from the volcano, suggesting that ongoing (albeit low level) convective degassing of magma occurs at depth. Interestingly, vent locations from the 2006 eruption correspond to areas of relatively low CO2 discharge on the crater floor in 2004. This, in conjunction with the preliminary findings of abundant hydrothermal mineralisation (calcite, anhydrite, quartz) in eruption ejecta, suggests that the main volcanic conduits had become effectively sealed during the interval since the last eruption. Calcite-hosted fluid inclusions are CO2 clathrate-bearing, and have relatively low homogenisation temperatures (165-180 °C), suggesting that the seal environment was both gas-charged and shallowly seated (< 200 m). Shaking associated with the regional

Ceres’ Evolution and Potential Habitability

Science.gov (United States)

Raymond, Carol Anne; Ammannito, Eleonora; Bland, Michael T.; Castillo-Rogez, Julie; De Sanctis, Maria Cristina; Ermakov, Anton; Fu, Roger; McCord, Thomas; Park, Ryan; Prettyman, Thomas H.; Ruesch, Ottaviano; Russell, Christopher T.; Dawn Team

2017-10-01

Dawn’s observations at Ceres confirm it is a volatile-rich body that has undergone ice-rock differentiation and global alteration [1-4], indicating that, as predicted by pre-Dawn thermochemical models, Ceres harbored an ancient subsurface ocean [5,6]. Density and shape data indicate that at present, Ceres has a crust composed of silicate, salts, clathrates and ≤ 35% water ice, overlying a denser core of hydrated silicates [7,8,9,10], whereas the original ice-dominated outer shell was likely lost to impact-induced sublimation early in Ceres’ history [11]. The interior structure constrains the maximum internal temperature to have been only a few hundred degrees [9]; however, rather than indicating a late formation for Ceres, it may indicate that circulation of fluids within Ceres modulated the temperature [12].The extent and longevity of the ocean are debatable; however, the modern surface of Ceres shows evidence of brine extrusion [e.g., 13], indicating at least pockets of subsurface liquid remain. Carbonates are found to dominate the composition of the brightest deposits on the surface, attesting to transport of crystallized brine material to the surface [14]. These multiple lines of evidence point to a warm aqueous subsurface environment with complex chemistry early in Ceres’ history and processes that exchanged material between the muddy ocean layer and the surface. Such history and the presence of organic material in localized deposits [15, 16] make Ceres an enticing target for future exploration. [1] Russell et al., Science, 2016 [2] Prettyman et al., Science, 2017 [3] De Sanctis et al., 2015 10.1038/nature18290 [4] Ammannito et al., Science, 2016 [5] McCord and Sotin, JGR, 2005 [6] Castillo-Rogez and McCord, Icarus, 2010 [7] Park et al., Nature, 2016 [8] Ermakov et al., JGR, 2017 [9] Fu et al., EPSL, 2017 [10] Bland et al., Nat. GeoSci., 2016 [11] Castillo-Rogez et al., LPSC, 2016 [12] Travis et al., Icarus, subm. [13] Ruesch et al., Science, 2106 [14

Ternary systems Sr-{Ni,Cu}-Si: Phase equilibria and crystal structure of ternary phases

International Nuclear Information System (INIS)

Nasir, Navida; Melnychenko-Koblyuk, Nataliya; Grytsiv, Andriy; Rogl, Peter; Giester, Gerald; Wosik, Jaroslaw; Nauer, Gerhard E.

2010-01-01

Phase relations were established in the Sr-poor part of the ternary systems Sr-Ni-Si (900 deg. C) and Sr-Cu-Si (800 deg. C) by light optical microscopy, electron probe microanalysis and X-ray diffraction on as cast and annealed alloys. Two new ternary compounds SrNiSi 3 (BaNiSn 3 -type) and SrNi 9-x Si 4+x (own-type) were found in the Sr-Ni-Si system along with previously reported Sr(Ni x Si 1-x ) 2 (AlB 2 -type). The crystal structure of SrNi 9-x Si 4+x (own-type, x=2.7, a=0.78998(3), c=1.1337(2) nm; space group P4/nbm) was determined from X-ray single crystal counter to be a low symmetry derivative of the cubic, parent NaZn 13 -type. At higher Si-content X-ray Rietveld refinements reveal the formation of a vacant site (□) corresponding to a formula SrNi 5.5 Si 6.5 □ 1.0 . Phase equilibria in the Sr-Cu-Si system are characterized by the compounds SrCu 2-x Si 2+x (ThCr 2 Si 2 -type), Sr(Cu x Si 1-x ) 2 (AlB 2 -type), SrCu 9-x Si 4+x (0≤x≤1.0; CeNi 8.5 Si 4.5 -type) and SrCu 13-x Si x (4≤x≤1.8; NaZn 13 -type). The latter two structure types appear within a continuous solid solution. Neither a type-I nor a type-IX clathrate compound was encountered in the Sr-{Cu,Ni}-Si systems. Structural details are furthermore given for about 14 new ternary compounds from related alloy systems with Ba. - Graphical abstract: The crystal structure of SrNi 9-x Si 4+x (own-type, x=2.7, a=0.78998(3), c=1.1337(2) nm; space group P4/nbm) was determined from X-ray single crystal counter to be a low symmetry derivative of the cubic, parent NaZn 13 -type and is related to CeNi 8.5 Si 4.5 -type.

Constraining the cause of the end-Guadalupian extinction with coupled records of carbon and calcium isotopes

Science.gov (United States)

Jost, A. B.; Mundil, R.; He, B.; Brown, S. T.; Altiner, D.; Sun, Y.; DePaolo, D. J.; Payne, J.

2013-12-01

A negative δ13C excursion in carbonate sediments from Guadalupian (Middle Permian) and Lopingian (Late Permian) stratigraphic sections has been interpreted to result from a large carbon cycle disturbance during end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbations to the global carbon cycle. The carbon and calcium cycles are coupled via CaCO3 burial, so changes in calcium isotopes can be used to constrain the cause of a carbon isotope excursion. In this study, we present coupled carbon and calcium isotope records from three Guadalupian-Lopingian (G/L) sections in China and Turkey. Isotope records among our studied sections are inconsistent in both their δ13C and δ44/40Ca records. Similar inconsistencies in δ13C among sections occur across previously published datasets. Sections with large (>3‰) changes in δ13C either show evidence for diagenetic alteration or do not show δ13C and δ44/40Ca changes consistent with severe volcanic degassing from Emeishan or methane clathrate destabilization. We conclude that the large isotopic changes are more likely the result of local burial conditions or diagenetic effects, rather than a large carbon cycle disturbance. Perturbations to the global carbon and calcium cycles appear to have been much smaller across the G/L transition than across the subsequent Permian-Triassic boundary. This finding is consistent with recent paleobiological data showing that the end-Guadalupian extinction was much less severe than previously believed, and was indistinguishable in magnitude from background intervals. However, selective extinction of marine animals with passive respiratory physiology indicates that the G/L extinction cannot simply be due to background extinction or sampling failure, and that it was triggered by some environmental event. Therefore, any environmental event must have been small enough to not generate large

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

Science.gov (United States)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the

Na{sub 8}Au{sub 9.8(4)}Ga{sub 7.2} and Na{sub 17}Au{sub 5.87(2)}Ga{sub 46.63}: The diversity of pseudo 5-fold symmetries in the Na–Au–Ga system

Energy Technology Data Exchange (ETDEWEB)

Smetana, Volodymyr; Corbett, John D., E-mail: jcorbett@iastate.edu; Miller, Gordon J.

2013-11-15

The Na-rich part (∼30% Na) of the Na–Au–Ga system between NaAu{sub 2}, NaGa{sub 4}, and Na{sub 22}Ga{sub 39} has been found to contain the ternary phases Na{sub 8}Au{sub 9.8(4)}Ga{sub 7.2} (I) and Na{sub 17}Au{sub 5.87(2)}Ga{sub 46.63} (II), according to the results of single crystal X-ray diffraction measurements. I is orthorhombic, Cmcm, a=5.3040(1), b=24.519(5), c=14.573(3) Å, and contains a network of clusters with local 5-fold symmetry along the a-axis. Such clusters are frequent building units in decagonal quasicrystals and their approximants. II is rhombohedral, R3{sup ¯}m, a=16.325(2), c=35.242(7) Å, and contains building blocks that are structurally identical to the Bergman-type clusters as well as fused icosahedral units known with active metals, triels and late transition elements. II also contains a polycationic network with elements of the clathrate V type structure. Tight-binding electronic structure calculations using linear muffin–tin-orbital (LMTO) methods on idealized models of I and II indicate that both compounds are metallic with evident pseudogaps at the corresponding Fermi levels. The overall Hamilton bond populations are generally dominated by Au–Ga and Au–Au bonds in I and by Ga–Ga bonds in II; moreover, the Na–Au and Na–Ga contributions in I are unexpectedly large, ∼20% of the total. A similar involvement of sodium in covalent bonding has also been found in the electron-richer i-Na{sub 13}Au{sub 12}Ga{sub 15} quasicrystal approximant. - Graphical abstract: Multiply-endohedral Bergman-related clusters in the structure of Na{sub 17}Au{sub 5.9(1)}Ga{sub 46.6.} Display Omitted - Highlights: • Two new compounds with the local 5-fold symmetry have been investigated. • Na{sub 8}Au{sub 9.8(4)}Ga{sub 7.2} is an orthorhombic approximant of the Na{sub 13}Au{sub 12}Ga{sub 15} quasicrystal. • Na{sub 17}Au{sub 5.87(2)}Ga{sub 46.63} represents a rhombohedral distortion of the Bergman-type phases.

H{sub 2} storage in microporous materials: a comparison between zeolites and Mos

Energy Technology Data Exchange (ETDEWEB)

Ricchiardi, G.; Regli, L.; Vitillo, J. G.; Cocina, D.; Bordiga, S.; Lamberti, C.; Spoto, G.; Zecchina, A.; Bjorgen, M.; Lillerud, K. P.

2005-07-01

One of the main concerns about a hydrogen-based energy economy is the efficient storage and transport of this highly flammable gas. Many strategies have been followed or suggested in recent years to solve this problem. The most important ones are: 1) storage in metals and alloys; 2) storage in complex hydrides (alanates, borides); 3) storage by trapping in clathrates (ice and others); 4) storage in microporous materials (carbons, zeolitic materials, metal-organic frameworks, polymers). [1, 2] In this work we have focused our attention on microporous materials, where the crucial point is the strength of the interaction between the molecular hydrogen and the internal surfaces of micropores and/ or of cages of entrapping materials. It is known from fundamental studies that H2 strongly interacts with ions in the gas but that the presence of counterions decreases the interaction energy substantially. The most prominent class of microporous materials, which contains isolated and exposed cations, are zeolites and zeotypes: ideal systems to investigate the interaction of H2 with both dispersive and electrostatic forces [3]. So, even if they are not sufficiently light to represent the final solution to H2 storage, the availability of a large variety of frameworks and chemical compositions combined with low cost and superior mechanical and thermal stabilities increases the interest in these materials. In this work we have studied in detail, by means of volumetric and spectroscopic measurements, zeolites with CHA topology (as they are characterized by a strong acidity and by a big surface area). H-SSZ-13 zeolite, characterized by a low Al content (Si/Al = 11), has shown the best properties in hydrogen storage in respect to all the other zeolites and zeotypes with different compositions and topologies [4]. The results have been compared with those obtained for MOF-5 [5], a well known Metal-Organic Framework, indicated as a very good material for molecular hydrogen storage [6

Davisson-Germer Prize Talk: Hydrogen storage in nanoporous materials

Science.gov (United States)

Chabal, Yves

2009-03-01

To develop a hydrogen-based energy technology, several classes of materials are being considered to achieve the DOE targets for gravimetric and volumetric hydrogen densities for hydrogen storage, including liquids (e.g. ammonium borohydrides), clathrate structures, complex metal hydrides, nanostructured (e.g. carbon) an nanoporous materials. Fundamental studies are necessary to determine the ultimate hydrogen capacity of each system. Nanoporous Metal-organic Framework (MOF) materials are promising candidates for hydrogen storage because the chemical nature and size of their unit cell can be tailored to weakly attract and incorporate H2 molecules, with good volumetric and mass density. In this talk, we consider the structure M2(BDC)2(TED), where M is a metal atom (Zn, Ni, Cu), BDC is benzenedicarboxylate and TED triethylenediamine, to determine the location and interaction of H2 molecules within the MOF. These compounds are isostructural and crystallize in the tetragonal phase (space group P4/ncc), they construct 3D porous structures with relatively large pore size (˜7-8 A ), pore volume (˜0.63-0.84 cc/g) and BET surface area (˜1500-1900 m^2/g). At high pressures (300-800 psi), the perturbation of the H-H stretching mode can be measured with IR absorption spectroscopy, showing a 35 cm-1 redshift from the unperturbed ortho (4155 cm-1 ) and para (4161 cm-1 ) frequencies. Using a newly developed non empirical van der Waals DFT method vdW-DFT),ootnotetextJ.Y. Lee, D.H. Olson, L. Pan, T.J. Emge, J. Li, Adv. Func. Mater. 17, 1255 (2007) it can be shown that the locus of the deepest H2 binding positions lies within to types of narrow channels. The energies of the most stable binding sites, as well as the number of such binding sites, are consistent with the values obtained from experimental adsorption isotherms, and heat of adsorption) data.ootnotetextM. Dion, H. Ryberg, E. Schroder, D. C. Langreth, B.I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004). Importantly, the

Titan's geoid and hydrology: implications for Titan's geological evolution

Science.gov (United States)

Sotin, Christophe; Seignovert, Benoit; Lawrence, Kenneth; MacKenzie, Shannon; Barnes, Jason; Brown, Robert

2014-05-01

A 1x1 degree altitude map of Titan is constructed from the degree 4 gravity potential [1] and Titan's shape [2] determined by the Radio Science measurements and RADAR observations of the Cassini mission. The amplitude of the latitudinal altitude variations is equal to 300 m compared to 600 m for the amplitude of the latitudinal shape variations. The two polar caps form marked depressions with an abrupt change in topography at exactly 60 degrees at both caps. Three models are envisaged to explain the low altitude of the polar caps: (i) thinner ice crust due to higher heat flux at the poles, (ii) fossil shape acquired if Titan had higher spin rate in the past, and (iii) subsidence of the crust following the formation of a denser layer of clathrates as ethane rain reacts with the H2O ice crust [3]. The later model is favored because of the strong correlation between the location of the cloud system during the winter season and the latitude of the abrupt change in altitude. Low altitude polar caps would be the place where liquids would run to and eventually form large seas. Indeed, the large seas of Titan are found at the deepest locations at the North Pole. However, the lakes and terrains considered to be evaporite candidates due to their spectral characteristics in the infrared [4,5] seem to be perched. Lakes may have been filled during Titan's winter and then slowly evaporated leaving material on the surface. Interestingly, the largest evaporite deposits are located at the equator in a deep depression 150 m below the altitude of the northern seas. This observation seems to rule out the presence of a global subsurface hydrocarbon reservoir unless the evaporation rate at the equator is faster than the transport of fluids from the North Pole to the equator. This work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. [1] Iess L. et al. (2012) Science, doi 10.1126/science.1219631. [2] Lorenz R.D. (2013

Polarimetry of Solar System Objects: Observations vs. Models

Science.gov (United States)

Yanamandra-Fisher, P. A.

2014-04-01

The overarching goals for the remote sensing and robotic exploration of planetary systems are: (1) understanding the formation of planetary systems and their diversity; and (2) search for habitability. Since all objects have unique polarimetric signatures inclusion of spectrophotopolarimetry as a complementary approach to standard techniques of imaging and spectroscopy, provides insight into the scattering properties of the planetary media. Specifically, linear and circular polarimetric signatures of the object arise from different physical processes and their study proves essential to the characterization of the object. Linear polarization of reflected light by various solar system objects provides insight into the scattering characteristics of atmospheric aerosols and hazes? and surficial properties of atmosphereless bodies. Many optically active materials are anisotropic and so their scattering properties differ with the object's principal axes (such as dichroic or birefringent materials) and are crystalline in structure instead of amorphous, (eg., the presence of olivines and silicates in cometary dust and circumstellar disks? Titan, etc.). Ices (water and other species) are abundant in the system indicated in their near - infrared spectra. Gas giants form outside the frost line (where ices condense), and their satellites and ring systems exhibit signature of water ice? clathrates, nonices (Si, C, Fe) in their NIR spectra and spectral dependence of linear polarization. Additionally, spectral dependence of polarization is important to separate the macroscopic (bulk) properties of the scattering medium from the microscopic (particulate) properties of the scattering medium. Circular polarization, on the other hand, is indicative of magnetic fields and biologically active molecules, necessary for habitability. These applications suffer from lack of detailed observations, instrumentation, dedicated missions and numericalretrieval methods. With recent discoveries and

Mapping basin-wide subaquatic slope failure susceptibility as a tool to assess regional seismic and tsunami hazards

Science.gov (United States)

Strasser, Michael; Hilbe, Michael; Anselmetti, Flavio S.

2010-05-01

With increasing awareness of oceanic geohazards, submarine landslides are gaining wide attention because of their catastrophic impacts on both offshore infrastructures (e.g. pipelines, cables and platforms) and coastal areas (e.g. landslide-induced tsunamis). They also are of great interest because they can be directly related to primary trigger mechanisms including earthquakes, rapid sedimentation, gas release, glacial and tidal loading, wave action, or clathrate dissociation, many of which represent potential geohazards themselves. In active tectonic environments, for instance, subaquatic landslide deposits can be used to make inferences regarding the hazard derived from seismic activity. Enormous scientific and economic efforts are thus being undertaken to better determine and quantify causes and effects of natural hazards related to subaquatic landslides. In order to achieve this fundamental goal, the detailed study of past events, the assessment of their recurrence intervals and the quantitative reconstruction of magnitudes and intensities of both causal and subsequent processes and impacts are key requirements. Here we present data and results from a study using fjord-type Lake Lucerne in central Switzerland as a "model ocean" to test a new concept for the assessment of regional seismic and tsunami hazard by basin-wide mapping of critical slope stability conditions for subaquatic landslide initiation. Previously acquired high-resolution bathymetry and reflection seismic data as well as sedimentological and in situ geotechnical data, provide a comprehensive data base to investigate subaquatic landslides and related geohazards. Available data are implemented into a basin-wide slope model. In a Geographic Information System (GIS)-framework, a pseudo-static limit equilibrium infinite slope stability equation is solved for each model point representing reconstructed slope conditions at different times in the past, during which earthquake-triggered landslides

An atmosphere-ocean GCM modelling study of the climate response to changing Arctic seaways in the early Cenozoic.

Science.gov (United States)

Roberts, C. D.; Legrande, A. N.; Tripati, A. K.

2008-12-01

previous findings on the potential influence of Arctic gateways on ocean overturning and also suggests that Northern Hemisphere climate, particularly in the North Atlantic, was very sensitive to changes in Arctic seaways. This result is of particular significance when considered in the context of the Paleocene Eocene Thermal Maximum (PETM). Volcanic activity prior to the PETM may have been responsible for the formation of a sub-aerial barrier in the North Atlantic, and consequently may have driven warming of intermediate waters sufficient to destabilize methane clathrates. Evidence for freshening of Arctic ocean waters prior to the PETM would support this hypothesis.

Apparent Km of mitochondria for oxygen computed from Vmax measured in permeabilized muscle fibers is lower in water enriched in oxygen by electrolysis than injection

Directory of Open Access Journals (Sweden)

Zoll J

2015-07-01

Full Text Available Joffrey Zoll,1 Jamal Bouitbir,1 Pascal Sirvent,2 Alexis Klein,3 Antoine Charton,1,4 Liliana Jimenez,3 François R Péronnet,5 Bernard Geny,1 Ruddy Richard61Physiology Department, Faculty of Medicine and EA3072, Université de Strasbourg, Strasbourg, 2Clermont Université, Université Blaise Pascal, EA 3533, Laboratoire des Adaptations Métaboliques à l’Exercice en Conditions Physiologiques et Pathologiques, Clermont-Ferrand, 3Danone Research, Centre Daniel Carasso, Palaiseau, 4Department of Anesthesia and Critical Care and EA3072, Hôpital de Hautepierre, Université de Strasbourg, France; 5Kinesiology Department, Université de Montréal, Montréal, QC, Canada; 6Department of Sport Medicine and Functional Explorations and INRA UMR 1019, Faculty of Medicine, Université d’Auvergne, Clermont-Ferrand, FranceBackground: It has been suggested that oxygen (O2 diffusion could be favored in water enriched in O2 by a new electrolytic process because of O2 trapping in water superstructures (clathrates, which could reduce the local pressure/content relationships for O2 and facilitate O2 diffusion along PO2 gradients.Materials and methods: Mitochondrial respiration was compared in situ in saponin-skinned fibers isolated from the soleus muscles of Wistar rats, in solution enriched in O2 by injection or the electrolytic process 1 at an O2 concentration decreasing from 240 µmol/L to 10 µmol/L (132 mmHg to 5 mmHg, with glutamate–malate or N, N, N', N'-tetramethyl-p-phenylenediamine dihydrochloride (TMPD–ascorbate (with antimycin A as substrates; and 2 at increasing adenosine diphosphate (ADP concentration with glutamate–malate as substrate.Results: As expected, maximal respiration decreased with O2 concentration and, when compared to glutamate–malate, the apparent Km O2 of mitochondria for O2 was significantly lower with TMPD–ascorbate with both waters. However, when compared to the water enriched in O2 by injection, the Km O2 was

Computational Recreation of Carbon Dioxide Hydrates at Habitable Planetary Conditions

Science.gov (United States)

Recio, J. M.; Izquierdo-Ruiz, F.; Prieto-Ballesteros, O.

2017-12-01

Gas clathrate hydrates are proposed as constituents of the icy moons of the giant planets in the Solar System [1]. Carbon dioxide has been detected on the surface of the moons of Jupiter, supposedly originated by internal degasification. In Ganymede, an aqueous ocean is proposed to exist under a thick ice crust in coexistence with several forms of ice, with pressure reaching up to 1.3 GPa [2]. Due to the limited available data on these systems under these conditions, we propose a combination of computational and experimental studies to describe microscopically and macroscopically the structural and chemical behavior of CO2@H2O polymorphs. This will allow us to understand how their presence affects the geophysical structure and activity and their impact on the habitability of the icy moon. A transition from the sI cubic structure to a high pressure phase at around 0.7 GPa has been found for CO2@H2O. In spite of different attempts to characterize the new structure, a definite answer has not been provided yet. A MH-III Filled Ice Structure type was proposed after neutron diffraction experiments in contrast with an alternative structure similar to the hexagonal C0 type for H2 hydrates [3]. It has an estimated hydration level ratio up to 2H2O:1CO2 and 6 water molecules per unit cell. In the figure below, our optimized unit cell based on this hexagonal C0 structure is displayed. Ab initio calculations using the XDM approximation to include van der Waals effects are performed in our search for the pressure evolution of the equilibrium geometries of the C0-CO2@H2O phase and those of a close related structure to this one called Ih-C0, with 8 water molecules per unit cell. We obtain occupation energies at different hydration ratios, densities, equations of state parameters, and stability energies with respect to decomposition. Raman and IR frequencies are also computed in the 0-2 GPa range. High pressure experiments are also being done in a newly designed chamber able to

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field, Central Mexico

International Nuclear Information System (INIS)

Gonzalez-Partida, E.; Carrillo-Chavez, A.; Levresse, G.; Tello-Hinojosa, E.; Venegas-Salgado, S.; Ramirez-Silva, G.; Pal-Verma, M.; Tritlla, J.; Camprubi, A.

2005-01-01

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T mi ) near zero (0 deg C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T h ) = 325 ± 5 deg C. The boiling zone shows T h = ±300 deg C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO 2 . Positive clathrate melting temperatures (fusion) with T h = 150 deg C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 deg C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO 2 (80-98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir. The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ 18 O-δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ 18

Effect of gas hydrates melting on seafloor slope stability

Science.gov (United States)

Sultan, N.; Cochonat, P.; Foucher, J. P.; Mienert, J.; Haflidason, H.; Sejrup, H. P.

2003-04-01

Henriet, J.-P.; Mienert, J. (Ed.): Gas hydrates: relevance to world margin stability and climate change. Geological Society Special Publication, 137. The Geological Society: London, UK, p. 267-274. Handa,Y.P., 1989. Effect of Hydrostatic Pressure and Salinity on the Stability of Gas Hydrates. J.Phys.Chem., Vol.94, p.2652-2657. Henry, P., Thomas, M.; Clennell, M.B., 1999. Formation of Natural Gas Hydrates in Marine Sediments 2. Thermodynamic Calculations of Stability Conditions in Porous Sediments,” J. Geophys. Res., 104, p. 23005. Sloan, E.D. Jr., 1998. Clathrate hydrates of natural gases. Marcel Dekker Inc., 2nd edition, New York, pp. 705. Soave G, 1972. Equilibrium

Timing and thermochemical constraints on multi-element mineralisation at the Nori/RA Cu-Mo-U prospect, Great Bear magmatic zone, Northwest Territories, Canada

Science.gov (United States)

Ootes, Luke; Goff, Steve; Jackson, Valerie A.; Gleeson, Sarah A.; Creaser, Robert A.; Samson, Iain M.; Evensen, Norman; Corriveau, Louise; Mumin, A. Hamid

2010-08-01

clathrates or CH4 was not observed or detected. Quartz grains only host secondary fluid inclusions, which fluoresce under ultraviolet light, indicating trapped hydrocarbons. We speculate that these resulted from Phanerozoic fluid circulation through the Proterozoic basement. The collective interpretation of the age, hydrothermal character and associated metals, high temperature and variable salinity suggests that the Nori/RA Cu-Mo-U mineralisation can be linked with the earliest stages of plutonism in the Great Bear magmatic zone. From a regional perspective, the mineralisation may pre-date the extensive multi-element mineralisation now recognised as part of the iron oxide copper-gold (IOCG) spectrum of deposits. As IOCG provinces generally contain a variety of mineralisation styles, we interpret this as the earliest phase of the extensive mineralising system.

Local structure analysis of materials for increased energy efficiency

Science.gov (United States)

Medling, Scott

adjacent to a S vacancy. In Chapter 5, I present a study into thermoelectric clathrates to determine how differences in size of one of the cage atoms affects the local structure and, therefore, the thermoelectric properties. I then discuss the effect of additional cage disorder on the scattering of phonons and the scattering of electrons, and thus the thermoelectric figure of merit. In Chapter 6, I present an XMCD study of La1 --xSrxCoO 3, finding results that are consistent with Sr-induced formation of ferromagnetic clusters within the non-magnetic, insulating matrix. We also show that not only are the O states spin-polarized, but a significant fraction of holes from Sr-doping go onto the O sites. Further, experimental results are compared to density functional calculations and discussed.

Investigation of the role of water-structured conditions in forming physics-chemical and biological features of the natural and model systems exposed to the energy influences (ecological and technological problems)

International Nuclear Information System (INIS)

Eremin, Y.; Belyashov, D.; Yuskov, A.; Kupchishin, A.; Polyakov, A.; Abishev, D.; Bekturov, E.; Adashkin, O.; Sultanbaev, E.; Davydov, G.; Aliev, M.; Verbolovich, V.; Kleinbok, I.; Fryazinova, T.

1996-01-01

The project is devoted to solve ecological and technological goals of Semipalatinsk Nuclear Testing Site and uranium industry of Kazakstan. Its anticipated basic results include: - Creation of common systemic research methodology using the spectral, physical-chemical and biological tests; - Development of new testing methods for molecular-structural variations in water systems; evaluation of effect of water and water systems after radiation irradiation upon physical-chemical and biological properties of subjects, which are contacted with these systems; - Determination of a pattern of interaction between the water and the coarse- and fine-dispersions as well as effect of molecular-structural variations in systems upon physical-chemical and biological processes occurred in these systems; - Determination of water role in radiation-chemical reactions by means of electron, gamma- and ion irradiation of water-mineral model systems. There are following basic goals to be solved to reach a general objective of Project: In Water-Mineralogical Section: - To determine a pattern of interaction between the radiant energy and ion and dispersed (hydrophilic and hydrophobic) components; - To clarify a relationship between physical-chemical properties of water with its isotope composition; - To establish a transfer mechanism of micro dispersed radionuclides in geological and soil conditions of SNTS and a role of water structures in hydrophobic interactions between micro dispersions and non-polar radicals of chemical agents; - To determine the water-molecular structure in acid and alkaline water fractions and interspersion interactions within these fractions; - To establish the interaction with water minerals in ice-like and clathrate-like conditions. - In Biological Section: - To study a role of water structure formation and hydrophobic interactions in the modification of humor immunity components for biological liquids being effected by electron and gamma rays beams; - To study the

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field, Central Mexico

Energy Technology Data Exchange (ETDEWEB)

Gonzalez-Partida, E. [Centro de Geociencias, UNAM, Campus Juriquilla, A.P. 15, Juriquilla, Qro., 76230 (Mexico)]. E-mail: egp@geociencias.unam.mx; Carrillo-Chavez, A. [Centro de Geociencias, UNAM, Campus Juriquilla, A.P. 15, Juriquilla, Qro., 76230 (Mexico); Levresse, G. [Centro de Geociencias, UNAM, Campus Juriquilla, A.P. 15, Juriquilla, Qro., 76230 (Mexico); Tello-Hinojosa, E. [Comision Federal de Electricidad, A.P. 31-7, C.P. 58090 Morelia, Mich. (Mexico); Venegas-Salgado, S. [Comision Federal de Electricidad, A.P. 31-7, C.P. 58090 Morelia, Mich. (Mexico); Ramirez-Silva, G. [Comision Federal de Electricidad, A.P. 31-7, C.P. 58090 Morelia, Mich. (Mexico); Pal-Verma, M. [Instituto de Investigaciones Electricas, A.P. 1-475, C.P. 62001 Cuernavaca, Morelos (Mexico); Tritlla, J. [Centro de Geociencias, UNAM, Campus Juriquilla, A.P. 15, Juriquilla, Qro., 76230 (Mexico); Camprubi, A. [Centro de Geociencias, UNAM, Campus Juriquilla, A.P. 15, Juriquilla, Qro., 76230 (Mexico)

2005-01-01

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T{sub mi}) near zero (0 deg C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T{sub h}) = 325 {+-} 5 deg C. The boiling zone shows T{sub h} = {+-}300 deg C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO{sub 2}. Positive clathrate melting temperatures (fusion) with T{sub h} = 150 deg C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 deg C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO{sub 2} (80-98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir. The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions ({delta}{sup 18}O-{delta}D) of the geothermal brine indicate mixing between meteoric water and a

Analysis of Mineral Assemblages Containing Unstable Hydrous Phases

Science.gov (United States)

Vaniman, D. T.; Wilson, S. A.; Bish, D. L.; Chipera, S.

2011-12-01

for sampling cold-environment deposits at the lunar poles, at the poles of Mercury, on icy satellites, and on many other bodies that may host hydrous minerals. The problem of adequate in situ analysis of such mutable assemblages extends to Earth as well, for example in the need for improved understanding of polar and permafrost regions, deep sea clathrates, cave minerals, and mine dump efflorescence. Advanced methods of in situ analysis are needed, including but not limited to contact instruments and instrumentation that can be inserted by probe or operated within a borehole that could be advanced with minimal thermal disturbance. One of the lessons of robotic analysis is that field instruments, which by necessity are less capable than laboratory equivalents, provide greatly improved interpretations if data from several different instruments can be compared.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

Science.gov (United States)

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural

On the Discovery of CO Nighttime Emissions on Titan by Cassini/VIMS: Derived Stratospheric Abundances and Geological Implications

Science.gov (United States)

Bainesa, Kevin H.; Drossart, Pierre; Lopez-Valverde, Miguel A.; Atreya, Sushil K.; Sotin, Christophe; Momary, Thomas W.; Brown, Robert H.; Buratti, Bonnie J.; Clark, Roger N.; Nicholson, Philip D.

2006-01-01

atmosphere and ionosphere. J. Geophys. Res. 109, E06002 Doi: 10.1029/2003JE002181]. This low CO/CH4 ratio is much lower than expected for the sub-nebular formation region of Titan and supports the hypothesis [e.g., Atreya et al., 2005. Methane on Titan: photochemical-meteorological-hydrogeochemical cycle. Bull. Am. Astron. Soc. 37, 735] that the conversion of primordial CO and other carbon-bearing materials into CH4-enriched clathrate-hydrates occurs within the deep interior of Titan via the release of hydrogen through the serpentinization process followed by Fischer-Tropsch catalysis. The time-averaged predicted emission rate of methane-rich surface materials is approximately 0.02 km(exp 3) yr (exp -1), a value significantly lower than the rate of silicate lava production for the Earth and Venus, but nonetheless indicative of significant geological processes reshaping the surface of Titan.

Global Assessment of Methane Gas Hydrates: Outreach for the public and policy makers

Science.gov (United States)

Beaudoin, Yannick

2010-05-01

The United Nations Environment Programme (UNEP), via its official collaborating center in Norway, GRID-Arendal, is in the process of implementing a Global Assessment of Methane Gas Hydrates. Global reservoirs of methane gas have long been the topic of scientific discussion both in the realm of environmental issues such as natural forces of climate change and as a potential energy resource for economic development. Of particular interest are the volumes of methane locked away in frozen molecules known as clathrates or hydrates. Our rapidly evolving scientific knowledge and technological development related to methane hydrates makes these formations increasingly prospective to economic development. In addition, global demand for energy continues, and will continue to outpace supply for the foreseeable future, resulting in pressure to expand development activities, with associated concerns about environmental and social impacts. Understanding the intricate links between methane hydrates and 1) natural and anthropogenic contributions to climate change, 2) their role in the carbon cycle (e.g. ocean chemistry) and 3) the environmental and socio-economic impacts of extraction, are key factors in making good decisions that promote sustainable development. As policy makers, environmental organizations and private sector interests seek to forward their respective agendas which tend to be weighted towards applied research, there is a clear and imminent need for a an authoritative source of accessible information on various topics related to methane gas hydrates. The 2008 United Nations Environment Programme Annual Report highlighted methane from the Arctic as an emerging challenge with respect to climate change and other environmental issues. Building upon this foundation, UNEP/GRID-Arendal, in conjunction with experts from national hydrates research groups from Canada, the US, Japan, Germany, Norway, India and Korea, aims to provide a multi-thematic overview of the key

Oceanic ecosystem dynamics during gigantic volcanic episodes: the Ontong Java and Manihiki Plateaus recorded by calcareous nannoplankton. (Invited)

Science.gov (United States)

Erba, E.

2010-12-01

Earth's volcanic activity introduces environmental stress that biota are forced to survive. There is a general consensus on the role of volcanogenic carbon dioxide increases, and implicit tectonic-igneous events, triggering major climate changes and profound variations in chemical, physical and trophic characteristics of the oceans through the Phanerozoic. Cretaceous geological records indicate conditions of excess atmCO2 (up to 2000-3000 ppm) derived from construction of Large Igneous Provinces (LIPs). In such “high CO2 world” and greenhouse conditions, the deep ocean became depleted of oxygen promoting the accumulation and burial of massive amounts of organic matter; such episodes are recognized as Oceanic Anoxic Events (OAEs) and their geological records merit careful examination of how the Earth system, and Life in particular, can overcome extreme experiments of global change. The Early Aptian (˜ 120 million years ago) OAE1a is a complex example of volcanicCO2-induced environmental stress. There is a general consensus on the causes of this case-history, namely excess CO2 derived from the construction of the Ontong Java-Manihiki LIP. Multi- and inter-disciplinary studies of the OAE1a have pointed out C, O, Os, Sr isotopic anomalies, a biocalcification crisis in pelagic and neritic settings, enhanced fertility and primary productivity, as well as ocean acidification. Available cyclochronology allows high-resolution dating of biotic and environmental fluctuations, providing the precision necessary for understanding the role of volcanogenic CO2 on nannoplankton biocalcification, adaptations, evolutionary innovation and/or extinctions. The reconstructed sequence of volcanogenic CO2 pulses, and perhaps some clathrate melting, triggered a climate change to supergreenhouse conditions, anoxia and ocean acidification. The demise of heavily calcified nannoconids and reduced calcite paleofluxes marks beginning of the pre-OAE1a calcification crisis. Ephemeral coccolith

Thermal Conductive Heat Transfer and Partial Melting of Volatiles in Icy Moons, Asteroids, and Kuiper Belt Objects (Invited)

Science.gov (United States)

Kargel, J. S.; Furfaro, R.

2013-12-01

Thermal gradients within conductive layers of icy satellite and asteroids depend partly on heat flow, which is related to the secular decay of radioactive isotopes, to heat released by chemical phase changes, by conversion of gravitational potential energy to heat during differentiation, tidal energy dissipation, and to release of heat stored from prior periods. Thermal gradients are also dependent on the thermal conductivity of materials, which in turn depends on their composition, crystallinity, porosity, crystal fabric anisotropy, and details of their mixture with other materials. Small impurities can produce lattice defects and changes in polymerization, and thereby have a huge influence on thermal conductivity, as can cage-inclusion (clathrate) compounds. Heat flow and thermal gradients can be affected by fluid phase advection of mass and heat (in oceans or sublimating upper crusts), by refraction related to heterogeneities of thermal conductivity due to lateral variations and composition or porosity. Thermal profiles depend also on the surface temperature controlled by albedo and climate, surface relief, and latitude, orbital obliquity and surface insolation, solid state greenhouses, and endogenic heating of the surface. The thermal state of icy moon interiors and thermal gradients can be limited at depth by fluid phase advection of heat (e.g., percolating meteoric methane or gas emission), by the latent heat of phase transitions (melting, solid-state transitions, and sublimation), by solid-state convective or diapiric heat transfer, and by foundering. Rapid burial of thick volatile deposits can also affect thermal gradients. For geologically inactive or simple icy objects, most of these controls on heat flow and thermal gradients are irrelevant, but for many other icy objects they can be important, in some cases causing large lateral and depth variations in thermal gradients, large variations in heat flow, and dynamically evolving thermal states. Many of

The thermal evolution of large water-rich asteroids

Science.gov (United States)

Schmidt, B. E.; Castillo, J. C.

2009-12-01

the asteroid belt to several hundred kilometers (Morbidelli et al, in press, Icarus), so that even the water-rich asteroids accreted a volume of short-lived radionuclides significant enough to create substantial internal heat. As an alternative to the classical model of formation in the inner solar system, it has been hypothesized that some water-rich asteroids could have formed in the transneptunian region before migration inward. In such a context the accretion timescale for objects 100-300 km radius is several hundred My, limiting the role of 26Al as a major heat source. However, formation in the outer solar system implies a different composition of the volatile and refractory phases, such as the possible accretion of clathrate hydrates, ammonia hydrates, etc. We will quantify the degree of differentiation achieved for the different formation scenarios envisioned for these objects and investigate the endogenic activity (e.g., hydrothermal, core warming) promoted by the accompanying geophysical conditions. Part of this work has been carried out at the Jet Propulsion Laboratory, California Institute of Technology. Government sponsorship acknowledged.

Radiation Polymerization in the Solid Phase; Polymerisation radiochimique en phase solide; Radiatsionnaya polimerizatsiya v tverdoj faze; Radiopolimerizacion en fase solida

Energy Technology Data Exchange (ETDEWEB)

Barkalov, I. M.; Gol' danskij, V. I.; Enikolopov, N. S.; Terekhova, S. F.; Trofimova, G. M.

1963-11-15

The radiation polymerization of solid and frozen monomers has recently attracted a great deal of attention because of its theoretical and practical importance in chemical kinetics and radiation chemistry. The strict spacing of monomer units in a polymer brings about a sharp improvement in the physico-chemical properties without any change of chemicai composition. In the synthesis of stereo-regular polymers, the matrix principle is used, i.e. the monomer unit is strictly oriented spatially by the formation of a complex with a catalyst or some other compound. In the radiation polymerization of a number of monomers oriented in clathrate complexes of urea and thio-urea, for instance, crystal stereo-regular polymers were obtained. The simplest variation, however, is the orientation of a monomer in its own crystal lattice. Although many of the theoretical questions involved remain obscure, the technique is extremely promising. Thus, highly crystalline polyoxymethylene has already been obtained by the radiation polymerization of crystalline trioxane. Nevertheless, a more detailed theoretical investigation of the technique is required. For each separate monomer, the contribution to the general picture made by the different types of reaction taking place during irradiation and the subsequent fusion of the solid monomers (specific radiation reaction, post-polymerization and polymerization at phase transition points) needs clarification. Recent detailed research at the Institute of Chemical Physics, USSR, into the solid-phase radiation-polymerization kinetics of a number of monomers, using the calorimetric method and an EPR signal, has revealed the essential role of the specific radiation reaction during the irradiation. The polymerization process for acrylonitrile (from -196{sup o}C to -140{sup o}C) and vinyl acetate (-196{sup o}C to -100{sup o}C) ceases when irradiation is discontinued despite the retention of the shape and intensity of the EPR signal and despite the long

Highly efficient molecular simulation methods for evaluation of thermodynamic properties of crystalline phases

Science.gov (United States)

Moustafa, Sabry Gad Al-Hak Mohammad

Molecular simulation (MS) methods (e.g. Monte Carlo (MC) and molecular dynamics (MD)) provide a reliable tool (especially at extreme conditions) to measure solid properties. However, measuring them accurately and efficiently (smallest uncertainty for a given time) using MS can be a big challenge especially with ab initio-type models. In addition, comparing with experimental results through extrapolating properties from finite size to the thermodynamic limit can be a critical obstacle. We first estimate the free energy (FE) of crystalline system of simple discontinuous potential, hard-spheres (HS), at its melting condition. Several approaches are explored to determine the most efficient route. The comparison study shows a considerable improvement in efficiency over the standard MS methods that are known for solid phases. In addition, we were able to accurately extrapolate to the thermodynamic limit using relatively small system sizes. Although the method is applied to HS model, it is readily extended to more complex hard-body potentials, such as hard tetrahedra. The harmonic approximation of the potential energy surface is usually an accurate model (especially at low temperature and large density) to describe many realistic solid phases. In addition, since the analysis is done numerically the method is relatively cheap. Here, we apply lattice dynamics (LD) techniques to get the FE of clathrate hydrates structures. Rigid-bonds model is assumed to describe water molecules; this, however, requires additional orientation degree-of-freedom in order to specify each molecule. However, we were able to efficiently avoid using those degrees of freedom through a mathematical transformation that only uses the atomic coordinates of water molecules. In addition, the proton-disorder nature of hydrate water networks adds extra complexity to the problem, especially when extrapolating to the thermodynamic limit is needed. The finite-size effects of the proton disorder contribution is

Global Methane Biogeochemistry

Science.gov (United States)

Reeburgh, W. S.

2003-12-01

impact of CH4 on climate. The Intergovernmental Panel on Climate Change (IPCC) has published periodic updates (see, e.g., IPCC, 2001).Substantial advances have resulted from research aimed at understanding the global CH4 mixing ratio increase. Time-series measurements of atmospheric CH4 have continued, new CH4 flux measurements in a range of environments have been reported, and data allowing use of the stable isotope (13C/12C, 2H/1H) composition of CH4 as an independent budget constraint have increased. The importance of microbial oxidation of CH4 has been recognized and modeled; the possible role of CH4 clathrate hydrates in the global budget has been clarified with the introduction of new technology. Studies of CH4 trapped in ice cores from the Greenland and Antarctic ice caps have continued, resulting in higher-resolution records and new interpretations of past conditions. There have been few recent changes in our understanding of the atmospheric chemistry of CH4, and since this is covered in Cicerone and Oremland (1988) it will not be covered here. The aim here is not to repeat information contained in the reviews mentioned above, but to present results that have appeared in the literature since their publication, to outline major questions, and to point to promising new approaches.

Tracking the MSL-SAM methane detection source location Through Mars Regional Atmospheric Modeling System (MRAMS)

Science.gov (United States)

Pla-García, Jorge

2016-04-01

1. Introduction: The putative in situ detection of methane by Sample Analysis at Mars (SAM) instrument suite on Curiosi-ty at Gale crater has garnered significant attention because of the potential implications for the presence of geological methane sources or indigenous Martian organisms [1, 2]. SAM reported detection of back-ground levels of atmospheric methane of mean value 0.69±0.25 parts per billion by volume (ppbv) at the 95% confidence interval (CI). Additionally, in four sequential measurements spanning a 60-sol period, SAM observed elevated levels of methane of 7.2±2.1 ppbv (95% CI), implying that Mars is episodically producing methane from an additional unknown source. There are many major unresolved questions regard-ing this detection: 1) What are the potential sources of the methane release? 2) What causes the rapid decrease in concentration? and 3) Where is the re-lease location? 4) How spatially extensive is the re-lease? 5) For how long is CH4 released? Regarding the first question, the source of methane, is so far not identified. It could be related with geo-logical process like methane release from clathrates [3], serpentinisation [4] and volcanism [5]; or due to biological activity from methanogenesis [6]. To answer the second question, the rapid decrease in concentration, it is important to note that the photo-chemical lifetime of methane is of order 100 years, much longer than the atmospheric mixing time scale, and thus the gas should tend to be well mixed except near a source or shortly after an episodic release. The observed spike of 7 ppb from the background of System (MRAMS). The model was focused on rover locations using nested grids with a spacing of 330 meters on the in-nermost grid that is centered over the landing [8, 9]. MRAMS is ideally suited for this investigation; the model is explicitly designed to simulate Mars' at-mospheric circulations at the mesoscale and smaller with realistic, high-resolution surface properties [10, 11

EDITORIAL: Van der Waals interactions in advanced materials, in memory of David C Langreth Van der Waals interactions in advanced materials, in memory of David C Langreth

Science.gov (United States)

Hyldgaard, Per; Rahman, Talat S.

2012-10-01

forces by examining the impact their inclusion has on predictions of material properties. On the other hand, the experimental and theoretical study of Casimir forces also plays a vital role in the exploration of material behavior. vdW forces are related to the Casimir force but lack retardation effects. While the vdW bonding depends on additional effects (for example, the multipole contributions that reflect image-plane effects), the study of Casimir forces provides direct (and not indirect) measurements of the nature of interactions. Klimchitskaya et al note that to reconcile explicit measurements of the Casmir forces between semiconductor fragments within the Lifshitz description, it is relevant to question the Drude-like description of the contributions from free carriers and instead proceed with a formulation based only on optical observations of the permittivity. This optical response can be seen as a reflection of a more plasmon-like behavior. The authors suggest an experiment involving the study of the impact on the Casimir forces by a Mott transition in doped semiconductors. Such an experiment would permit explicit testing of the validity of the present model for Casimir forces and hence provide additional perspectives on the nature of dispersive interactions. There is an effort to store energy, e.g. H2 or CO2, inside a range of open cage-like structures, such as metal organics frameworks (MOF) or clathrates. The fact that the internal molecular adhesion is dominated by vdW forces suggests that the storage and retrieval costs could perhaps be lowered as compared to an approach that involves more traditional chemical compounds. Nijem et al have provided spectroscopic characterization of vdW interactions of both hydrogen molecules and CO in a specific MOF. The study includes a vdW-DF calculation of structure and a theoretical prediction of expected infrared activity. The potential applications to energy materials have motivated more theoretical characterizations