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Sample records for bonding hydration ion

  1. Hydrogen Bonding in Liquid Water and in the Hydration Shell of Salts.

    Science.gov (United States)

    Dagade, Dilip H; Barge, Seema S

    2016-03-16

    A near-IR spectral study on pure water and aqueous salt solutions is used to investigate stoichiometric concentrations of different types of hydrogen-bonded water species in liquid water and in water comprising the hydration shell of salts. Analysis of the thermodynamics of hydrogen-bond formation signifies that hydrogen-bond making and breaking processes are dominated by enthalpy with non-negligible heat capacity effects, as revealed by the temperature dependence of standard molar enthalpies of hydrogen-bond formation and from analysis of the linear enthalpy-entropy compensation effects. A generalized method is proposed for the simultaneous calculation of the spectrum of water in the hydration shell and hydration number of solutes. Resolved spectra of water in the hydration shell of different salts clearly differentiate hydrogen bonding of water in the hydration shell around cations and anions. A comparison of resolved liquid water spectra and resolved hydration-shell spectra of ions highlights that the ordering of absorption frequencies of different kinds of hydrogen-bonded water species is also preserved in the bound state with significant changes in band position, band width, and band intensity because of the polarization of water molecules in the vicinity of ions. PMID:26749515

  2. Ion mixing, hydration, and transport in aqueous ionic systems

    International Nuclear Information System (INIS)

    The enhancement effect on the ion mobility of fluoride (and that of chloride) in a polycationic system, as the chloride content increases, is shown to also exist in other more simple ionic systems with cations such as the cesium ion and an organic ammonium ion. As the chloride content increases, in addition to the finding that there is more unbound water associated with the cation, we also observe that the average lifetime of a hydrogen bond decreases. This change to the hydrogen bonds is correlated to significant changes to both the structural and dynamical properties of water. The more disordered water structure and faster water dynamics are hypothesized to be also responsible for the enhanced ion mobilities. Furthermore, when either the chloride content or hydration level is changed, the self-diffusion constant of each co-ion changes by almost the same factor, implying the existence of a single universal transport mechanism that determines ion mobilities

  3. Ion-water clusters, bulk medium effects, and ion hydration

    CERN Document Server

    Merchant, Safir; Dean, Kelsey R; Asthagiri, D

    2011-01-01

    Thermochemistry of gas-phase ion-water clusters together with estimates of the hydration free energy of the clusters and the water ligands are used to calculate the hydration free energy of the ion. Often the hydration calculations use a continuum model of the solvent. The primitive quasichemical approximation to the quasichemical theory provides a transparent framework to anchor such efforts. Here we evaluate the approximations inherent in the primitive quasichemical approach and elucidate the different roles of the bulk medium. We find that the bulk medium can stabilize configurations of the cluster that are usually not observed in the gas phase, while also simultaneously lowering the excess chemical potential of the ion. This effect is more pronounced for soft ions. Since the coordination number that minimizes the excess chemical potential of the ion is identified as the optimal or most probable coordination number, for such soft ions, the optimum cluster size and the hydration thermodynamics obtained with...

  4. Predicting hydration energies for multivalent ions

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Stipp, Susan Louise Svane

    2014-01-01

    We have predicted the free energy of hydration for 40 monovalent and multivalent cations and anions using density functional theory and the implicit solvent model COnductor like Screening MOdel for Real Solvents (COSMO-RS) at the Becke-Perdew (BP)/Triple zeta valence with polarization functions...... (TZVP) level. Agreement with experimental data for monovalent and divalent ions is good and shows no significant systematic errors. Predictions are noticeably better than with standard COSMO. The agreement with experimental data for trivalent and tetravalent ions is slightly worse and shows systematic...... errors. Our results indicate that quantum chemical calculations combined with COSMO-RS solvent treatment is a reliable method for treating multivalent ions in solution, provided one hydration shell of explicit water molecules is included for metal cations. The accuracy is not high enough to allow...

  5. Range of ion specific effects in the hydration of ions

    CERN Document Server

    Merchant, Safir

    2011-01-01

    Within the quasichemical approach, the hydration free energy of an ion is decomposed into a chemical term accounting for ion specific ion-water interactions within the coordination sphere and nonspecific contributions accounting for packing (excluded volume) and long range interactions. The change in the chemical term with a change in the radius of the coordination sphere is the compressive force exerted by the bulk solvent medium on the surface of the coordination sphere. For the Na+, K+, F-, and Cl- ions considered here this compressive force becomes equal for similarly charged ions for coordination radii of about 0.39 nm, not much larger than a water molecule. These results show that ion specific effects are short ranged and arise primarily due to differences in the local ion-water interactions.

  6. Octa-coordination and the hydrated Ba2+(aq) ion

    CERN Document Server

    Chaudhari, Mangesh I; Rempe, Susan B

    2014-01-01

    The hydration structure of Ba^{2+} ion is important for understanding blocking mechanisms in potassium ion channels. Here, we combine statistical mechanical theory, ab initio molecular dynamics simulations, and electronic structure methods to calculate the hydration free energy and local hydration structure of Ba^{2+}(aq). The predicted hydration free energy (-302.9$\\pm$0.7 kcal/mol) matches the experimental value (-302.56 kcal/mol) when the fully occupied and exclusive inner solvation shell is treated. In the local environment defined by the inner and first shell of hydrating waters, Ba^{2+} is directly coordinated by eight (8) waters. Octa-coordination resembles the structure of Ba^{2+} and K^+ bound in potassium ion channels, but differs from the local hydration structure of K^+(aq) determined earlier.

  7. Friction and Hydration Repulsion Between Hydrogen-Bonding Surfaces

    Science.gov (United States)

    Netz, Roland

    2012-02-01

    The dynamics and statics of polar surfaces are governed by the hydrogen-bonding network and the interfacial water layer properties. Insight can be gained from all-atomistic simulations with explicit water that reach the experimentally relevant length and time scales. Two connected lines of work will be discussed: 1) On surfaces, the friction coefficient of bound peptides is very low on hydrophobic substrates, which is traced back to the presence of a depletion layer between substrate and water that forms a lubrication layer. Conversely, friction forces on hydrophilic substrates are large. A general friction law is presented and describes the dynamics of hydrogen-bonded matter in the viscous limit. 2) The so-called hydration repulsion between polar surfaces in water is studied using a novel simulation technique that allows to efficiently determine the interaction pressure at constant water chemical potential. The hydration repulsion is shown to be caused by a mixture of water polarization effects and the desorption of interfacial water.

  8. Polarization and charge transfer in the hydration of chloride ions

    International Nuclear Information System (INIS)

    A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

  9. Polarization and charge transfer in the hydration of chloride ions

    Science.gov (United States)

    Zhao, Zhen; Rogers, David M.; Beck, Thomas L.

    2010-01-01

    A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

  10. Polarization and Charge Transfer in the Hydration of Chloride Ions

    OpenAIRE

    Zhao, Zhen; Rogers, David M.; Beck, Thomas L.

    2009-01-01

    A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation, and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding...

  11. Interaction of Simple Ions with Water: Theoretical Models for the Study of Ion Hydration

    Science.gov (United States)

    Gancheff, Jorge S.; Kremer, Carlos; Ventura, Oscar N.

    2009-01-01

    A computational experiment aimed to create and systematically analyze models of simple cation hydrates is presented. The changes in the structure (bond distances and angles) and the electronic density distribution of the solvent and the thermodynamic parameters of the hydration process are calculated and compared with the experimental data. The…

  12. Strength and nature of hydrogen bonding interactions in mono- and di-hydrated formamide complexes.

    Science.gov (United States)

    Angelina, Emilio L; Peruchena, Nélida M

    2011-05-12

    In this work, mono- and di-hydrated complexes of the formamide were studied. The calculations were performed at the MP2/6-311++G(d,p) level of approximation. The atoms in molecules theory (AIM), based on the topological properties of the electronic density distribution, was used to characterize the different types of bonds. The analysis of the hydrogen bonds (H-bonds) in the most stable mono- and di-hydrated formamide complexes shows a mutual reinforcement of the interactions, and some of these complexes can be considered as "bifunctional hydrogen bonding hydration complexes". In addition, we analyzed how the strength and the nature of the interactions, in mono-hydrated complexes, are modified by the presence of a second water molecule in di-hydrated formamide complexes. Structural changes, cooperativity, and electron density redistributions demonstrate that the H-bonds are stronger in the di-hydrated complexes than in the corresponding mono-hydrated complexes, wherein the σ- and π-electron delocalization were found. To explain the nature of such interactions, we carried out the atoms in molecules theory in conjunction with reduced variational space self-consistent field (RVS) decomposition analysis. On the basis of the local Virial theorem, the characteristics of the local electron energy density components at the bond critical points (BCPs) (the 1/4∇ (2)ρ(b) component of electron energy density and the kinetic energy density) were analyzed. These parameters were used in conjunction with the electron density and the Laplacian of the electron density to analyze the characteristics of the interactions. The analysis of the interaction energy components for the systems considered indicates that the strengthening of the hydrogen bonds is manifested by an increased contribution of the electrostatic energy component represented by the kinetic energy density at the BCP. PMID:21506592

  13. Benchmark binding energies of ammonium and alkyl-ammonium ions interacting with water. Are ammonium-water hydrogen bonds strong?

    Science.gov (United States)

    Vallet, Valérie; Masella, Michel

    2015-01-01

    Alkyl-ammonium ion/water interactions are investigated using high level quantum computations, yielding thermodynamics data in good agreement with gas-phase experiments. Alkylation and hydration lead to weaken the NHsbnd O hydrogen bonds. Upon complete hydration by four water molecules, their main features are close to those of the OHsbnd O bond in the isolated water dimer. Energy decomposition analyses indicate that hydration of alkyl-ammonium ions are mainly due to electrostatic/polarization effects, as for hard monoatomic cations, but with a larger effect of dispersion.

  14. Hydration and Ion Binding of the Osmolyte Ectoine.

    Science.gov (United States)

    Eiberweiser, Andreas; Nazet, Andreas; Kruchinin, Sergey E; Fedotova, Marina V; Buchner, Richard

    2015-12-10

    Ectoine is a widespread osmolyte enabling halophilic bacteria to withstand high osmotic stress that has many potential applications ranging from cosmetics to its use as a therapeutic agent. In this contribution, combining experiment and theory, the hydration and ion-binding of this zwitterionic compound was studied to gain information on the functioning of ectoine in particular and of osmolytes in general. Dielectric relaxation spectroscopy was used to determine the effective hydration number of ectoine and its effective dipole moment in aqueous solutions with and without added NaCl. The obtained experimental data were compared with structural results from 1D-RISM and 3D-RISM calculations. It was found that ectoine is strongly hydrated, even in the presence of high salt concentrations. Upon addition of NaCl, ions are bound to ectoine but the formed complexes are not very stable. Interestingly, this osmolyte strongly rises the static relative permittivity of its solutions, shielding thus effectively long-range Coulomb interactions among ions in ectoine-containing solutions. We believe that via this effect, which should be common to all zwitterionic osmolytes, ectoine protects against excessive ions within the cell in addition to its strong osmotic activity protecting against ions outside. PMID:26565946

  15. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

    OpenAIRE

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar

    2012-01-01

    The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfo...

  16. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether):Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether)(PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution functions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain,and there still exists a significant amount(10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentration as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer,which leads to inefficient contacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds,but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry(DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME,which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition,at the concentration of 86%,each ether oxygen atom bonded with water is assigned 1.56 water molecules on average,and ’free’ water molecules emerge at the concentration of around 54%.

  17. Absolute Hydration Free Energies of Ions Under Periodic Boundary Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Won, Youngdo [Hanyang Univ., Seoul (Korea, Republic of)

    2012-12-15

    The additive empirical force field of a monatomic ion is composed of the charge and the Lennard-Jones (LJ) parameters, i. e., the well-depth parameter, ε, and the distance parameter, R{sub min}, at which the potential reaches the minimum. A set of LJ parameters for monocations have been developed by utilizing molecular dynamics simulations under a solvent boundary potential (SBP). A full account of the force field development is in progress and this communication addresses consideration of the air-water phase potential in calculating the absolute free energy of hydration by calculating free energies of hydration, ΔG{sub hyd}, in the presence of periodic boundary conditions (PBC)

  18. Hydration free energies of cyanide and hydroxide ions from molecular dynamics simulations with accurate force fields

    Science.gov (United States)

    Lee, M.W.; Meuwly, M.

    2013-01-01

    The evaluation of hydration free energies is a sensitive test to assess force fields used in atomistic simulations. We showed recently that the vibrational relaxation times, 1D- and 2D-infrared spectroscopies for CN(-) in water can be quantitatively described from molecular dynamics (MD) simulations with multipolar force fields and slightly enlarged van der Waals radii for the C- and N-atoms. To validate such an approach, the present work investigates the solvation free energy of cyanide in water using MD simulations with accurate multipolar electrostatics. It is found that larger van der Waals radii are indeed necessary to obtain results close to the experimental values when a multipolar force field is used. For CN(-), the van der Waals ranges refined in our previous work yield hydration free energy between -72.0 and -77.2 kcal mol(-1), which is in excellent agreement with the experimental data. In addition to the cyanide ion, we also study the hydroxide ion to show that the method used here is readily applicable to similar systems. Hydration free energies are found to sensitively depend on the intermolecular interactions, while bonded interactions are less important, as expected. We also investigate in the present work the possibility of applying the multipolar force field in scoring trajectories generated using computationally inexpensive methods, which should be useful in broader parametrization studies with reduced computational resources, as scoring is much faster than the generation of the trajectories.

  19. Interplay of Ion-Water and Water-Water Interactions within the Hydration Shells of Nitrate and Carbonate Directly Probed with 2D IR Spectroscopy.

    Science.gov (United States)

    Fournier, Joseph A; Carpenter, William; De Marco, Luigi; Tokmakoff, Andrei

    2016-08-01

    The long-range influence of ions in solution on the water hydrogen-bond (H-bond) network remains a topic of vigorous debate. Recent spectroscopic and theoretical studies have, for the most part, reached the consensus that weakly coordinating ions only affect water molecules in the first hydration shell. Here, we apply ultrafast broadband two-dimensional infrared (2D IR) spectroscopy to aqueous nitrate and carbonate in neat H2O to study the solvation structure and dynamics of ions on opposite ends of the Hofmeister series. By exciting both the water OH stretches and ion stretches and probing the associated cross-peaks between them, we are afforded a comprehensive view into the complex nature of ion hydration. We show in aqueous nitrate that weak ion-water H-bonding leads to water-water interactions in the ion solvation shells dominating the dynamics. In contrast, the carbonate CO stretches show significant mixing with the water OH stretches due to strong ion-water H-bonding such that the water and ion modes are intimately correlated. Further, the excitonic nature of vibrations in neat H2O, which spans multiple water molecules, is an important factor in describing ion hydration. We attribute these complex dynamics to the likely presence of intermediate-range effects influenced by waters beyond the first solvation shell. PMID:27404015

  20. Specific ions modulate diffusion dynamics of hydration water on lipid membrane surfaces.

    Science.gov (United States)

    Song, Jinsuk; Franck, John; Pincus, Philip; Kim, Mahn Won; Han, Songi

    2014-02-12

    Effects of specific ions on the local translational diffusion of water near large hydrophilic lipid vesicle surfaces were measured by Overhauser dynamic nuclear polarization (ODNP). ODNP relies on an unpaired electron spin-containing probe located at molecular or surface sites to report on the dynamics of water protons within ~10 Å from the spin probe, which give rise to spectral densities for electron-proton cross-relaxation processes in the 10 GHz regime. This pushes nuclear magnetic resonance relaxometry to more than an order of magnitude higher frequencies than conventionally feasible, permitting the measurement of water moving with picosecond to subnanosecond correlation times. Diffusion of water within ~10 Å of, i.e., up to ~3 water layers around the spin probes located on hydrophilic lipid vesicle surfaces is ~5 times retarded compared to the bulk water translational diffusion. This directly reflects on the activation barrier for surface water diffusion, i.e., how tightly water is bound to the hydrophilic surface and surrounding waters. We find this value to be modulated by the presence of specific ions in solution, with its order following the known Hofmeister series. While a molecular description of how ions affect the hydration structure at the hydrophilic surface remains to be answered, the finding that Hofmeister ions directly modulate the surface water diffusivity implies that the strength of the hydrogen bond network of surface hydration water is directly modulated on hydrophilic surfaces. PMID:24456096

  1. Hydration study of ordinary portland cement in the presence of zinc ions

    Directory of Open Access Journals (Sweden)

    Monica Adriana Trezza

    2007-12-01

    Full Text Available Hydration products of Portland cement pastes, hydrated in water and in the presence of zinc ions were studied comparatively at different ages. Hydration products were studied by X ray diffractions (XRD and infrared spectroscopy (IR. Although IR is not frequently used in cement chemistry, it evidenced a new phase Ca(Zn(OH32. 2H2O formed during cement hydration in the presence of zinc. The significant retardation of early cement hydration in the presence of zinc is assessed in detail by differential calorimetry as a complement to the study carried out by IR and XRD, providing evidence that permits to evaluate the kinetic of the early hydration.

  2. Ab initio molecular dynamics calculations of ion hydration free energies

    International Nuclear Information System (INIS)

    We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or 'λ-path' technique to compute the intrinsic hydration free energies of Li+, Cl-, and Ag+ ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential (φ) contributions, we obtain absolute AIMD hydration free energies (ΔGhyd) within a few kcal/mol, or better than 4%, of Tissandier et al.'s [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model φ predictions. The sums of Li+/Cl- and Ag+/Cl- AIMD ΔGhyd, which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag++Ni+→Ag+Ni2+ in water. The predictions for this reaction suggest that existing estimates of ΔGhyd for unstable radiolysis intermediates such as Ni+ may need to be extensively revised.

  3. Charge density-dependent modifications of hydration shell waters by Hofmeister ions.

    Science.gov (United States)

    Guo, Feng; Friedman, Joel M

    2009-08-12

    Gadolinium (Gd(3+)) vibronic sideband luminescence spectroscopy (GVSBLS) is used to probe, as a function of added Hofmeister series salts, changes in the OH stretching frequency derived from first-shell waters of aqueous Gd(3+) and of Gd(3+) coordinated to three different types of molecules: (i) a chelate (EDTA), (ii) structured peptides (mSE3/SE2) of the lanthanide-binding tags (LBTs) family with a single high-affinity binding site, and (iii) a calcium-binding protein (calmodulin) with four binding sites. The vibronic sideband (VSB) corresponding to the OH stretching mode of waters coordinated to Gd(3+), whose frequency is inversely correlated with the strength of the hydrogen bonding to neighboring waters, exhibits an increase in frequency when Gd(3+) becomes coordinated to either EDTA, calmodulin, or mSE3 peptide. In all of these cases, the addition of cation chloride or acetate salts to the solution increases the frequency of the vibronic band originating from the OH stretching mode of the coordinated waters in a cation- and concentration-dependent fashion. The cation dependence of the frequency increase scales with charge density of the cations, giving rise to an ordering consistent with the Hofmeister ordering. On the other hand, water Raman spectroscopy shows no significant change upon addition of these salts. Additionally, it is shown that the cation effect is modulated by the specific anion used. The results indicate a mechanism of action for Hofmeister series ions in which hydrogen bonding among hydration shell waters is modulated by several factors. High charge density cations sequester waters in a configuration that precludes strong hydrogen bonding to neighboring waters. Under such conditions, anion effects emerge as anions compete for hydrogen-bonding sites with the remaining free waters on the surface of the hydration shell. The magnitude of the anion effect is both cation and Gd(3+)-binding site specific. PMID:19603752

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

    CERN Document Server

    Plumridge, T H

    2001-01-01

    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. 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, ...

  5. Chemical bond properties of rare earth ions in crystals

    International Nuclear Information System (INIS)

    By using the dielectric description theory of ionicity of solids, chemical bond properties of rare earth ions with various ligands are studied. Calculated results show that chemical bond properties of the same rare earth ion and the same ligand in different crystals depend on the crystal structures. In a series of compounds, chemical bond properties of crystals containing different rare earth ions are similar. The magnitude of covalency of chemical bonds of trivalent rare earth ions and various ligands has an order like F< Cl< Br< As< Sb. (orig.)

  6. Modelling the structure and IR spectra of micro-hydrated ions

    OpenAIRE

    Jana, Chandramohan

    2014-01-01

    Ion micro-hydration has been modeled by a combination of classical and quantum methods. The structures, dynamics and IR spectra of micro-hydrated cluster ions ranging from 1 to 216 water molecules have been considered with special emphasis on the comparison to recent experimental data. Quantum modeling has been used to provide reference values against which the polarizable AMOEBA force field could be calibrated. Extension of the parameter set was carried out in some cases, in particular when ...

  7. Effects of electronic structure on the hydration of PbNO3(+) and SrNO3(+) ion pairs.

    Science.gov (United States)

    Cooper, Richard J; Heiles, Sven; Williams, Evan R

    2015-06-28

    Hydration of PbNO3(+) and SrNO3(+) with up to 30 water molecules was investigated with infrared photodissociation (IRPD) spectroscopy and with theory. These ions are the same size, yet the IRPD spectra of these ion pairs for n = 2-8 are significantly different. Bands in the bonded O-H region (∼3000-3550 cm(-1)) indicate that the onset of a second hydration shell begins at n = 5 for PbNO3(+) and n = 6 for SrNO3(+). Spectra for [PbNO3](+)(H2O)2-5 and [SrNO3](+)(H2O)3-6 indicate that the structures of clusters with Pb(ii) are hemidirected with a void in the coordinate sphere. A natural bond orbital analysis of [PbNO3](+)(H2O)5 indicates that the anisotropic solvation of the ion is due to a region of asymmetric electron density on Pb(ii) that can be explained by charge transfer from the nitrate and water ligands into unoccupied p-orbitals on Pb(ii). There are differences in the IRPD spectra of PbNO3(+) and SrNO3(+) with up to 25 water molecules attached. IR intensity in the bonded O-H region is blue-shifted by ∼50 cm(-1) in nanodrops containing SrNO3(+) compared to those containing PbNO3(+), indicative of a greater perturbation of the water H-bond network by strontium. The free O-H stretches of surface water molecules in nanodrops containing 10, 15, 20, and 25 water molecules are red-shifted by ∼3-8 cm(-1) for PbNO3(+) compared to those for SrNO3(+), consistent with more charge transfer between water molecules and Pb(ii). These results demonstrate that the different electronic structure of these ions significantly influences how they are solvated. PMID:26028325

  8. Hydration number of alkali metal ions determined by insertion in a conducting polymer

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2008-01-01

    In aqueous solutions, the alkali metals ions are associated with a number of H2O molecules. A distinction is made between a primary solvent shell, (or inner solvation shell), consisting of H2O molecules directly coordinated to the metal ion, and a secondary (or outer) solvation shell, consisting of...... all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile...

  9. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state.

    Science.gov (United States)

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar

    2012-09-17

    The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen-donor solvents water, dimethyl sulfoxide (DMSO), and N,N'-dimethylpropyleneurea (DMPU) has been studied in solution by extended X-ray absorption fine structure (EXAFS) and large-angle X-ray scattering (LAXS) and in the solid state by single-crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and DMSO-solvated oxovanadium(IV) ions, vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O═V-O(perp) bond angle is ca. 98°. In the DMPU-solvated oxovanadium(IV) ion, the space-demanding properties of the DMPU molecule leave no solvent molecule in the trans position to the oxo group, which reduces the coordination number to 5. The O═V-O bond angle is consequently much larger, 107°, and the mean V═O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and DMSO-solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in the cis position with a mean V═O bond distance of 1.6 Å and a O═V═O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen-donor ligands. PMID:22950803

  10. Hydration Free Energies of Molecular Ions from Theory and Simulation.

    Science.gov (United States)

    Misin, Maksim; Fedorov, Maxim V; Palmer, David S

    2016-02-11

    We present a theoretical/computational framework for accurate calculation of hydration free energies of ionized molecular species. The method is based on a molecular theory, 3D-RISM, combined with a recently developed pressure correction (PC+). The 3D-RISM/PC+ model can provide ∼3 kcal/mol hydration free energy accuracy for a large variety of ionic compounds, provided that the Galvani potential of water is taken into account. The results are compared with direct atomistic simulations. Several methodological aspects of hydration free energy calculations for charged species are discussed. PMID:26756333

  11. Irradiation effect of gas-hydrate cluster ions on solid surfaces

    International Nuclear Information System (INIS)

    In our newly developed gas-hydrate cluster ion source, a vapor of water bubbling with carbon dioxide (CO2) gas was ejected through a nozzle into a vacuum region, and mixed beams of water clusters and carbon dioxide-hydrate clusters were produced by adiabatic expansion. According to time-of-flight measurements, the largest water clusters consisted of approximately 2800 molecules at a vapor pressure of 0.3 MPa. Also, the largest mixed clusters contained approximately 2000 molecules. Copper and silicon substrates were irradiated by the water cluster ions as well as carbon dioxide-hydrate cluster ions. X-ray photoelectron spectroscopy measurements showed that carbon was included in the Cu and Si substrates irradiated by the carbon dioxide-hydrate cluster ions, and a chemical shift owing to the formation of carboxyl radicals occurred on the Cu surface. Furthermore, the Cu surface was sputtered, and the sputtering depth was larger than the distance penetrated by the water cluster ion irradiation. Therefore, the formation of carboxyl radicals played an important role in the sputtering of the Cu surface, which occurred effectively in carbon dioxide-hydrate cluster ion irradiation

  12. Determination of membrane hydration numbers of alkali metal ions by insertion in a conducting polymer

    DEFF Research Database (Denmark)

    Skaarup, Steen; Junaid Mohamed Jafeen, Mohamed; Careem, M.A.

    2010-01-01

    In aqueous solutions, the alkali metals ions, Li+, Na+, K+, Rb+ and Cs+ are known to be associated with a number of H2O molecules. Traditionally, a distinction is made between a primary solvent shell, (or inner solvation shell), consisting of H2O molecules directly coordinated to the metal ion, and...... a secondary (or outer) solvation shell, consisting of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different...... necessarily define the same hydration shell. This work presents a systematic study of one special variant of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS-). The technique of...

  13. Cementation of ILW ion exchange resins: Impact of sulfate ions released by radiolysis on hydrated matrix

    Science.gov (United States)

    Frizon, F.; Cau-dit-Coumes, C.

    2006-12-01

    Some of the ion exchange resins used during treatment of spent nuclear fuels are intermediate level radioactive wastes which may be damaged by radiolysis process, releasing sulfate ions directly into the cement-based encapsulating material. This work consists in an experimental study of the resulting sulfate attack on the properties of the hydrated matrix: dimensional stability, mineralogy and microstructure of the samples, as well as variations in the chemical composition of the curing solution, were studied during six months. Three sites of delayed ettringite formation were detected: into the cement matrix near the surface exposed to solution, localized in the interfacial transition zone between cement matrix and resins, or progressively replacing the portlandite that initially fulfilled the cracks of anionic resins. During the experiment period, the ettringite precipitation and the expansion detected were moderate, and did not lead to cracking. The material involved was considered as having a good resistance to sulfate attack.

  14. Individual and combined effects of chloride, sulfate, and magnesium ions on hydrated Portland-cement paste

    International Nuclear Information System (INIS)

    Ground water with a high concentration of magnesium ion is known to cause deterioration to portland cement concretes. A proposed mechanism for this deterioration process published previously involves an approximate 1:1 replacement of Ca ions by Mg ions in the crystalline phases of hydrated cement. The current study was undertaken to determine which ions, among magnesium, chloride, and sulfate, cause deterioration; whether their deleterious action is individual or interdependent; and to relate this mechanism of deterioration to the outlook for a 100-yr service life of concretes used in mass placements at the Waste Isolation Pilot Plant. Loss of Ca ion by cement pastes was found to be strongly related to the concentration of Mg ion in simulated ground-water solutions in which the paste samples were aged. This was true of both salt- containing and conventional cement pastes. No other ion in the solutions exerted a strong effect on Ca loss. Ca ion left first from calcium hydroxide in the pastes, depleting all calcium hydroxide by 60 days. Some calcium silicate hydrate remained even after 90 days in the solutions with the highest concentration of Mg ion, while the paste samples deteriorated noticeably. The results indicated a mechanism that involves dissolution of Ca phases and transport of Ca ions to the surface of the sample, followed by formation of Mg-bearing phases at this reaction surface rather than directly by substitution within the microstructure of hydrated cement. Given that calcium hydroxide and calcium silicate hydrate are the principal strength-giving phases of hydrated cement, this mechanism indicates the likelihood of significant loss of integrity of a concrete exposed to Mg-bearing ground water at the WIPP. The rate of deterioration ultimately will depend on Mg-ion concentration, the microstructure materials of the concrete exposed to that groundwater, and the availability of brine

  15. Solvated Positron Chemistry. The Reaction of Hydrated Positrons with Chloride Ions

    DEFF Research Database (Denmark)

    Mogensen, O. E.; Shantarovich, V. P.

    1974-01-01

    The reaction of hydrated positrons (caq+ with cloride ions in aqueous solutions has been studied by means of positron annihilation angular correlation measurements. A rate constant of k = (2.5 ± 0.5) × 1010 M−1 s−1 was found. Probably the reacting positrons annihilated from an e+ Cl− bound state ...... resulting in an angular correlation curve 8% narrower than for the hydrated positron. Carbontetrachloride in benzene seems to give similar, but smaller effect....

  16. Crystal structure and hydrogen bonding in the water-stabilized proton-transfer salt brucinium 4-amino­phenyl­arsonate tetra­hydrate

    Science.gov (United States)

    Smith, Graham; Wermuth, Urs D.

    2016-01-01

    In the structure of the brucinium salt of 4-amino­phenyl­arsonic acid (p-arsanilic acid), systematically 2,3-dimeth­oxy-10-oxostrychnidinium 4-amino­phenyl­ar­son­ate tetra­hydrate, (C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O, the brucinium cations form the characteristic undulating and overlapping head-to-tail layered brucine substructures packed along [010]. The arsanilate anions and the water mol­ecules of solvation are accommodated between the layers and are linked to them through a primary cation N—H⋯O(anion) hydrogen bond, as well as through water O—H⋯O hydrogen bonds to brucinium and arsanilate ions as well as bridging water O-atom acceptors, giving an overall three-dimensional network structure. PMID:27308034

  17. Crystal structure and hydrogen bonding in the water-stabilized proton-transfer salt brucinium 4-amino-phenyl-arsonate tetra-hydrate.

    Science.gov (United States)

    Smith, Graham; Wermuth, Urs D

    2016-05-01

    In the structure of the brucinium salt of 4-amino-phenyl-arsonic acid (p-arsanilic acid), systematically 2,3-dimeth-oxy-10-oxostrychnidinium 4-amino-phenyl-ar-son-ate tetra-hydrate, (C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O, the brucinium cations form the characteristic undulating and overlapping head-to-tail layered brucine substructures packed along [010]. The arsanilate anions and the water mol-ecules of solvation are accommodated between the layers and are linked to them through a primary cation N-H⋯O(anion) hydrogen bond, as well as through water O-H⋯O hydrogen bonds to brucinium and arsanilate ions as well as bridging water O-atom acceptors, giving an overall three-dimensional network structure. PMID:27308034

  18. Complex formation constant and hydration number change of aqua-rare earth ions

    International Nuclear Information System (INIS)

    Full text: It is now well established that the inner-sphere hydration number of aqua-rare earth ions changes from nine to eight in the middle of the rare earth series. This hydration number change greatly affects the complex formation of rare earth ions as we observe irregular variations in most series behaviours of the complex formation constant (K) in aqueous solution systems when K being plotted against 1/r or r (r is ionic radius of rare earth ion). Furthermore, it shows very anomalous concentration dependence in the sense that nona-aqua Ln3+ ion increases in number with increase in salt concentration in aqueous rare earth salt solution (salt chloride, perchlorate). In this report, a theoretical derivation of the formation constant (K) for the inner-sphere complex formation of rare earth ions with a monodentate ligand was made by taking account of both the hydration number change in the middle of the series and its anomalous salt concentration dependence. The series behaviour of the formation constant against 1/r (or r) is successfully explained with using the empirical finding that K varies almost linearly with 1/r (or r) in the region where only one hydration number dominates. This success is also taken as evidence that the anomalous salt concentration dependence of the hydration number change is caused by the outer-sphere complex formation of rare earth ions with the condition that nona-aqua rare earth ions form outer-sphere complexes more easily than octa-aqua ions

  19. Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: the case of the halide ions F-, Cl-, and Br-.

    OpenAIRE

    Trumm, Michael; Guerrero Martínez, Yansel Omar; Réal, Florent; Masella, Michel; Vallet, Valérie; Schimmelpfennig, Bernd

    2012-01-01

    In this work, we investigate the hydration of the halide ions fluoride, chloride, and bromide using classical molecular dynamics simulations at the 10 ns scale and based on a polarizable force-field approach, which treats explicitly the cooperative bond character of strong hydrogen bond networks. We have carried out a thorough analysis of the ab initio data at the MP2 or CCSD(T) level concerning anion/water clusters in gas phase to adjust the force-field parameters. In particular, we consider...

  20. Adsorption of sodium ions and hydrated sodium ions on a hydrophobic graphite surface via cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    Shi Guo-Sheng; Wang Zhi-Gang; Zhao Ji-Jun; Hu Jun; Fang Hai-Ping

    2011-01-01

    Using density functional theory computation, we show that sodium ions and hydrated sodium ions can be strongly adsorbed onto a hydrophobic graphite surface via cation-π interactions. The key to this cation-π interaction is the coupling of the delocalized π states of graphite and the empty orbitals of sodium ions. This finding implies that the property of the graphite surface is extremely dependent on the existence of the ions on the surface, suggesting that the hydrophobic property of the graphite surface may be affected by the existence of the sodium ions.

  1. Role of the H bond network in the radiation chemistry of hydrated systems

    International Nuclear Information System (INIS)

    Introduction: In the present contribution, we want to address the influence of the H bond network on the observed reactivity of hydrated system. In radiation chemistry the primary species appear extremely simple and at the same time are very reactive. The comprehension of their dynamics is rather difficult since their reactivity involves the solvent molecules as reactant. Some of those species like the hydrated electron and the proton are highly hydrophilic, while others like the hydroxide radical and the H atom are rather hydrophobic. Both the hydrated electron and the H atom locate near a defect of the H bond network i.e. a cavity. As an example of the role of the environment in radical chemistry, when studying the radiation chemistry of porous media we noticed that the interface play a crucial role in the outcome of that chemistry. More particularly we observed that the silanol band of the silica/water interface was strongly affected by the irradiation even so no energy is directly absorbed by an interface. In this contribution, we will first review the recent work on the H bond dynamics, in absence of any reactant. We will then present recent results on the radiation chemistry of nanoporous media and its influence on the H bond network of an interface and will also present recent results obtained on the H bond dynamics at an alumina-water interface. All those results will be discussed in light of the H bonded nature of neat water. Radiation chemistry of an H bonded interface: A Fourier transformed infrared detection associated to an electron accelerator was developed so as to characterise in situ the effects of irradiation on various systems. The FT-IR spectrometer and the detector were moved out of the accelerator room to be protected against radiation. The infrared beam was guided on a distance of 6 meters by optical conduits and mirrors. The spectra were obtained from 100 scans accumulated with a Bruker Vertex 70 equipment operating with a 4 cm-1 resolution

  2. Hydration to the poly(oxyethylene) derivative complexes of alkali metal ions and barium ion in 1,2-dichloroethane

    International Nuclear Information System (INIS)

    A series of poly(oxyethylene) derivatives (POE compound) complexes of alkali metal and barium ions were extracted into 1,2-dichloroethane (1,2-DCE) by forming ion-pairs with picrate ion. Water molecules were coextracted into 1,2-DCE with the ion-pairs. The mean number of water molecules bound to the POE compound, XH2O,S, and its complex, XH2O,comp, in water saturated with 1,2-DCE was determined by means of aquametry. The XH2O,S value increases with the increase in the number of the oxyethylene units (EO unit) of the POE compound. The XH2O,comp value decreases in the order Li+>Na+>K+≅Rb+≅Cs+ in any POE compound systems, and increases with the number of EO units of the POE compounds for a given metal ion. These results are interpreted by the hypothesis that the water molecules bound to the complex are those hydrated to the central metal ion, and the hydrated metal ion is surrounded by the EO chain with a helical conformation in the complex. The large number of water molecules are coordinating to the lithium ion complexes and bring about a serious distortion in the helical structure of the complexes. Because of the ion-pair formation with two picrate ions, the XH2O,comp values of barium ion complexes are smaller than those of potassium ion complexes. (author)

  3. Hydration studies of electrospray ions from amino acids and small peptides

    Science.gov (United States)

    Nguyen, Chuong (Steve)

    This project was undertaken to gain a better understanding of the hydration behaviors of gas phase ions from solutions containing amino acids and peptides. In order to characterize their hydration behavior, the molecules of interest in solutions were first converted into gas phase ions by electrospray ionization (ESI). The completely desolvated ions were then deliberately dispersed into an inert bath gas, usually nitrogen, containing accurately known concentrations of solvent vapor. The resulting mixtures of ions and bath gas were subsequently passed into a vacuum chamber by way of an adiabatic supersonic free jet expansion. The cooling during that expansion caused solvation of the ions, the extent of which was determined by a quadrupole mass analyzer. Mass analysis of the solute ions in the absence of vapor showed peaks with the mass to charge ratios corresponding to the desolvated ions. On the other hand, mass spectrometric analyses of ions in the presence of solvent vapor showed sequences of peaks corresponding to the solvated ions with varying numbers of water molecules. The extent of the ion solvation was controlled by varying the concentration of solvent vapor in the bath gas. Two different scales were proposed for the evaluation of the relative affinities of amino acids for water molecules. One was based primarily on the assumption that the affinities of amino acids for water molecules are directly proportional to their gas phase solvation rate constants ( k). An alternative approach produced an affinity scale based on the extent of ion hydration occurred during the free jet expansion. It was found that the addition of a polar solvent vapor to the bath gas at low concentrations substantially enhanced the production of the bare solute ions from the evaporating charged droplets. This remarkable result not only provided a means to increase the ion production and thus detection sensitivity of mass spectrometric analyses, but also yielded important information

  4. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

    Science.gov (United States)

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

  5. Hydration properties and ionic radii of actinide(III) ions in aqueous solution

    International Nuclear Information System (INIS)

    Ionic radii of actinide(III) cations (from U(III) to Cf(III)) in aqueous solution have been derived for the first time starting from accurate experimental determination of the ion-water distances obtained by combining extended X-ray absorption fine structure (EXAFS) results and molecular dynamics (MD) structural data. A strong analogy has been found between the lanthanide and actinide series concerning hydration properties. The existence of a contraction of the An-O distance along the series has been highlighted, while no decrease of the hydration number is evident up to Cf(III). (authors)

  6. Assessment of antimicrobial activity of polyazolidinammonium modified by iodine hydrate ions depending on its physical and chemical characteristics.

    OpenAIRE

    Vakaraeva M.M.; Uljanov V.Yu.; Nechaeva O.V.; Luneva I.0.; Tikhomirova E.l.; Shapoval O.G.; Zayarskiy D.A.

    2015-01-01

    Aim: to study antimicrobial activity of variants of polymeric compound polyazolidinammonium modified by iodine hydrate-ions (PAAG-M), depending on the polymeric chain length and concentration of the iodine hydrate-ions against standard strains of gram-positive and gram-negative bacteria as well as microscopic fungi. Materials and methods. Minimum inhibitory concentrations of all variants of the polymeric compound for tested microbial strains have been determined by using serial dilution metho...

  7. Hydration of magnesia cubes: a helium ion microscopy study.

    Science.gov (United States)

    Schwaiger, Ruth; Schneider, Johannes; Bourret, Gilles R; Diwald, Oliver

    2016-01-01

    Physisorbed water originating from exposure to the ambient can have a strong impact on the structure and chemistry of oxide nanomaterials. The effect can be particularly pronounced when these oxides are in physical contact with a solid substrate such as the ones used for immobilization to perform electron or ion microscopy imaging. We used helium ion microscopy (HIM) and investigated morphological changes of vapor-phase-grown MgO cubes after vacuum annealing and pressing into foils of soft and high purity indium. The indium foils were either used as obtained or, for reference, subjected to vacuum drying. After four days of storage in the vacuum chamber of the microscope and at a base pressure of p definition specific to the MgO cubes. Comparison of different regions within one sample before and after exposure to liquid water reveals different transformation processes, such as the formation of Mg(OH)2 shells that act as diffusion barriers for MgO dissolution or the evolution of brucite nanosheets organized in characteristic flower-like microstructures. The findings underline the significant metastability of nanomaterials under both ambient and high-vacuum conditions and show the dramatic effect of ubiquitous water films during storage and characterization of oxide nanomaterials. PMID:27335725

  8. Fluidity of water and of hydrated ions confined between solid surfaces to molecularly thin films

    International Nuclear Information System (INIS)

    In contrast to non-associating liquids such as oils or organic solvents, whose viscosity diverges when they are confined by solid surfaces to films thinner than about ten molecular diameters, recent studies reveal that salt-free water remains fluid, with a viscosity close to its bulk value, even when confined to films down to only one or two monolayers thick. For the case of high concentration aqueous salt solutions compressed down to subnanometre films between confining planar surfaces, the hydration sheaths about the ions (trapped between the oppositely charged surfaces) also remain extremely fluid: this behaviour is attributed to the tenacity of water molecules in the hydration layers together with their rapid relaxation/exchange time. Related experiments on highly compressed, polyelectrolyte brushes in aqueous media reveal a remarkable lubricity which is in large measure attributed to similar hydration layers about the charged segments: this water of hydration strongly resists being squeezed out, but at the same time it may rapidly exchange with adjacent water molecules, thereby remaining quite fluid and acting as a molecular lubricant

  9. Polymerization contraction stress in resin-tooth bonds under hydrated and dehydrated conditions

    NARCIS (Netherlands)

    M. Hashimoto; K. Nakamura; A.J. Feilzer

    2009-01-01

    Objective: This study hypothesizes that, with enamel or dentin as a bonding substrate, intrinsic water affects the development of polymerization contraction stress in the bonds of self-etching adhesives during bonding. Materials and methods: The influence of the water content in dentin and enamel (w

  10. Capture CO2 from Ambient Air Using Nanoconfined Ion Hydration.

    Science.gov (United States)

    Shi, Xiaoyang; Xiao, Hang; Lackner, Klaus S; Chen, Xi

    2016-03-14

    Water confined in nanoscopic pores is essential in determining the energetics of many physical and chemical systems. Herein, we report a recently discovered unconventional, reversible chemical reaction driven by water quantities in nanopores. The reduction of the number of water molecules present in the pore space promotes the hydrolysis of CO3 (2-) to HCO3 (-) and OH(-) . This phenomenon led to a nano-structured CO2 sorbent that binds CO2 spontaneously in ambient air when the surrounding is dry, while releasing it when exposed to moisture. The underlying mechanism is elucidated theoretically by computational modeling and verified by experiments. The free energy of CO3 (2-) hydrolysis in nanopores reduces with a decrease of water availability. This promotes the formation of OH(-) , which has a high affinity to CO2 . The effect is not limited to carbonate/bicarbonate, but is extendable to a series of ions. Humidity-driven sorption opens a new approach to gas separation technology. PMID:26914978

  11. Ion Pairs or Neutral Molecule Adducts? Cooperativity in Hydrogen Bonding

    Science.gov (United States)

    DeKock, Roger L.; Schipper, Laura A.; Dykhouse, Stephanie C.; Heeringa, Lee P.; Brandsen, Benjamin M.

    2009-01-01

    We performed theoretical studies on the systems NH[subscript 3] times HF times mH[subscript 2]O, NH[subscript 3] times HCl times mH[subscript 2]O, with m = 0, 1, 2, and 6. The molecules with m = 0 form hydrogen-bonded adducts with little tendency to form an ion-pair structure. The molecule NH[subscript 3] times HCl times H[subscript 2]O cannot be…

  12. Heavy ion collisions and the site-bond percolation

    Energy Technology Data Exchange (ETDEWEB)

    Desbois, J.

    1987-05-01

    Site-bond percolation on a lattice is used for the investigation of heavy ions reactions. A model characterized by two parameters, p and q, is worked out and a critical zone in the p, q plane is shown up. Analytical expressions for various quantities concerning percolation and evaporation are established. Calculations of energy spectra, linear momentum transfer, fragment multiplicities and mass yields at various bombarding energies are compared with experimental data. Different possibilities for the attainment of the multifragmentation regime are discussed.

  13. Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: The case of the halide ions F-, Cl-, and Br-

    Science.gov (United States)

    Trumm, Michael; Martínez, Yansel Omar Guerrero; Réal, Florent; Masella, Michel; Vallet, Valérie; Schimmelpfennig, Bernd

    2012-01-01

    In this work, we investigate the hydration of the halide ions fluoride, chloride, and bromide using classical molecular dynamics simulations at the 10 ns scale and based on a polarizable force-field approach, which treats explicitly the cooperative bond character of strong hydrogen bond networks. We have carried out a thorough analysis of the ab initio data at the MP2 or CCSD(T) level concerning anion/water clusters in gas phase to adjust the force-field parameters. In particular, we consider the anion static polarizabilities computed in gas phase using large atomic basis sets including additional diffuse functions. The information extracted from trajectories in solution shows well structured first hydration shells formed of 6.7, 7.0, and 7.6 water molecules at about 2.78 Å, 3.15 Å, and 3.36 Å for fluoride, chloride, and bromide, respectively. These results are in excellent agreement with the latest neutron- and x-ray diffraction studies. In addition, our model reproduces several other properties of halide ions in solution, such as diffusion coefficients, description of hydration processes, and exchange reactions. Moreover, it is also able to reproduce the electrostatic properties of the anions in solution (in terms of anion dipole moment) as reported by recent ab initio quantum simulations. All the results show the ability of the proposed model in predicting data, as well as the need of accounting explicitly for the cooperative character of strong hydrogen bonds to reproduce ab initio potential energy surfaces in a mean square sense and to build up a reliable force field.

  14. Hydration of some trivalent metal ions extracted as perchlorates with trioctylphosphine oxide in hexane

    International Nuclear Information System (INIS)

    Perchlorates of Sc3+, Y3+, La3+, and Eu3+ have each been extracted from 0.1 mol x dem-3 aqueous solution of μ=1 with trioctylphosphine oxide (TOPO) in hexane. The hydration number of the extracted salts has been determined by Karl Fischer titration. Sc3+, Y3+, and Eu3+ are extracted as the tetra- and hexa-solvates of TOPO but the assumption of octa-solvate on addition to the tetra-solvate explains the extraction data of La3+ well. The hydration number of tetra-solvates is 2(Sc3+ and Eu3+), 3(Y3+) and probably 4 for La3+ ion. That of hexa-and octa-solvates is 4-5. (author)

  15. Carbonation of wollastonite(001) competing hydration: microscopic insights from ion spectroscopy and density functional theory.

    Science.gov (United States)

    Longo, Roberto C; Cho, Kyeongjae; Brüner, Philipp; Welle, Alexander; Gerdes, Andreas; Thissen, Peter

    2015-03-01

    In this paper, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as a model surface of cement and concrete. Total energy calculations based on density functional theory combined with kinetic barrier predictions based on nudge elastic band method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO3(2-)) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (also called early stage hydration) and Ca(2+) ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca(2+) reacts again with CO2 and forms carbonate complexes, ending in a delocalized layer. By means of high-resolution time-of-flight secondary-ion mass spectrometry images, we confirm that hydration can lead to a partially delocalization of Ca(2+) ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by the meaning of low-energy ion-scattering spectroscopy combined with careful discussion about the competing reactions of carbonation vs hydration. PMID:25648453

  16. Effect of preparation conditions on porous structure and ion exchange properties of hydrated tantalum pentoxide

    International Nuclear Information System (INIS)

    Ion-exchange properties and physical parameters of porous hydrated tantalum pentoxide (TPO) have been studied in connection with the conditions of preparation. TPO hydrogel has been precipitated from Ta solutions in hydrochloric acid with the acid concentration 0.12, 0.24 and 0.48 N and from aqueous potassium tantalate. The increase in Ta concentration in hydrochloric acid solution from 5 to 20 g/l by Ta2O5 results in the decrease in specific surface of the xerogels from 130 to 23 m2/g, in the 3 time increase of the specific volume of the pores, sharp increase in the pore neck diameter and in the skeleton particle size, whereas the ion-exchange capacity decreases. These variations in the porous structure of the xerogels are due to the influence of the Ta ions state in the solution, i.e. the extent of their hydrolysis and polymerization

  17. Shape and size of simple cations in aqueous solutions: A theoretical reexamination of the hydrated ion via computer simulations

    Science.gov (United States)

    Martínez, José M.; Pappalardo, Rafael R.; Marcos, Enrique Sánchez

    1999-01-01

    The simplest representation of monoatomic cations in aqueous solutions by means of a sphere with a radius chosen on the basis of a well-defined property (that of the bare ion or its hydrate) is reexamined considering classical molecular dynamics simulations. Two charged sphere-water interaction potentials were employed to mimic the bare and hydrated cation in a sample of 512 water molecules. Short-range interactions of trivalent cations were described by Lennard-Jones potentials which were fitted from ab initio calculations. Five statistically independent runs of 150 ps for each of the trivalent spheres in water were carried out in the microcanonical ensemble. A comparison of structural and dynamical properties of these simple ion models in solution with those of a system containing the Cr3+ hydrate ([Cr(H2O)6]3+) is made to get insight into the size and shape definition of simple ions in water, especially those that are highly charged. Advantages and shortcomings of using simple spherical approaches are discussed on the basis of reference calculations performed with a more rigorous hydrated ion model [J. Phys. Chem. B 102, 3272 (1998)]. The importance of nonspherical shape for the hydrate of highly charged ions is stressed and it is paradoxically shown that when spherical shape is retained, the big sphere representing the hydrate leads to results of ionic solution worse than those obtained with the small sphere. A low-cost method to generate hydrated ion-water interaction potentials taking into account the shape of the ionic aggregate is proposed.

  18. Lutetium(iii) aqua ion: On the dynamical structure of the heaviest lanthanoid hydration complex

    Science.gov (United States)

    Sessa, Francesco; Spezia, Riccardo; D'Angelo, Paola

    2016-05-01

    The structure and dynamics of the lutetium(iii) ion in aqueous solution have been investigated by means of a polarizable force field molecular dynamics (MD). An 8-fold square antiprism (SAP) geometry has been found to be the dominant configuration of the lutetium(iii) aqua ion. Nevertheless, a low percentage of 9-fold complexes arranged in a tricapped trigonal prism (TTP) geometry has been also detected. Dynamic properties have been explored by carrying out six independent MD simulations for each of four different temperatures: 277 K, 298 K, 423 K, 632 K. The mean residence time of water molecules in the first hydration shell at room temperature has been found to increase as compared to the central elements of the lanthanoid series in agreement with previous experimental findings. Water exchange kinetic rate constants at each temperature and activation parameters of the process have been determined from the MD simulations. The obtained structural and dynamical results suggest that the water exchange process for the lutetium(iii) aqua ion proceeds with an associative mechanism, in which the SAP hydration complex undergoes temporary structural changes passing through a 9-fold TTP intermediate. Such results are consistent with the water exchange mechanism proposed for heavy lanthanoid atoms.

  19. Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case

    Energy Technology Data Exchange (ETDEWEB)

    Den Auwer, Ch.; Guillaumont, D. [CEA Marcoule, Nucl Energy Div, Radiochem Proc Dept, SCPS LILA, 30 (France); Galbis, E.; Pappalardo, Rafael R.; Marcos Sanchez, E. [Univ Seville, Dept Quim Fis, E-41012 Seville (Spain); Hernandez-Cobos, J. [Inst Ciencias Fis, Cuernavaca 62251, Morelos (Mexico); Le Naour, C.; Simoni, E. [Univ Paris Sud, Inst Phys Nucl Orsay, Paris (France)

    2010-07-01

    In summary, the first MC simulation of the trivalent cation of californium, based on an exchangeable hydrated ion-water intermolecular potential, has been shown to extend and improve the hydrated ion model. Likewise, the CfL{sub III}-edge EXAFS spectrum of an acidic 1 mm Cf(ClO{sub 4}){sub 3} aqueous solution recorded under optimized experimental conditions has greatly improved the signal/noise ratio of the only previously recorded spectrum. The comparison of the experimental EXAFS spectrum with the two computed ones, obtained from two different intermolecular potentials that predict eight (BP86) or nine (MP2) water molecules in the first coordination shell, leads to the conclusion that the lowest hydration number is preferred. Then, as Cf{sup III} is the heaviest actinide aqua ion for which there is experimental information, the actinide contraction is supported by the present study. (For U{sup III}, R{sub U-O}=2.56 Angstroms, and CN=9{+-}1; for Pu{sup III}, R{sub Pu-O}=2.51 Angstroms and CN=9{+-}1; for Cm{sup III}, R{sub Cm-O}=2.47 Angstroms and CN=9{+-}1). The role of the second hydration shell is important in defining the structure and dynamics of the Cf{sup III} aqua ion, but the contribution of second-shell water molecules to the EXAFS signal as back-scatters is marginal. Finally, this work gives an illustrative example of the benefits which can be achieved from the combination of experimental X-ray absorption spectroscopy and computer simulations. The usefulness of the simultaneous analysis of the results as well as the importance of the structural statistical average has been clearly demonstrated herein. Each technique independently was not adequate. We believe that this study traces out a still poorly explored combined methodology which may be extremely useful for many other complexes and chemical problems. A systematic theoretical and experimental examination of the other known actinide cations on the same basis should be undertaken to confirm the

  20. Kr-86 Ion-Beam Irradiation of Hydrated DNA: Free Radical and Unaltered Base Yields

    OpenAIRE

    Becker, David; Adhikary, Amitava; Tetteh, Smedley T.; Bull, Arthur W.; Sevilla, Michael D.

    2012-01-01

    This work reports an ESR and product analysis investigation of Kr-86 ion-beam irradiation of hydrated DNA at 77 K. The irradiation results in the formation and trapping of both base radicals and sugar phosphate radicals (DNA backbone radicals). The absolute yields (G, μmol/J) of the base radicals are smaller than the yields found in similarly prepared γ-irradiated DNA samples, and the relative yields of backbone radicals relative to base radicals are much higher than that found in γ-irradiate...

  1. Stability of Hydrated Methylamine: Structural Characteristics and H2N···H–O Hydrogen Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Sha-Sha; Liu, Yi-Rong; Huang, Teng; Feng, Ya-Juan; Jiang, Shuai; Huang, Wei

    2015-04-23

    Methylamine is the simplest aliphatic amine found in human urine, blood, and tissues. It is thought to play a significant part in central nervous system disturbances observed during renal and hepatic disease. In this work we have investigated the methylamine hydration clusters using a basin hopping (BH) algorithm with the density functional theory (DFT). The results presented herein yield a detailed understanding of the structure and stability for a system consisting of one methylamine molecule and up to seven waters: the most stable geometries arise from a fusion of tetramer or pentamer rings; by the geometrical parameters and topological parameters analysis, the strengths of the H2N···H–O hydrogen bonds of the global minima increase as the sizes of clusters increase, except for n = 5 where there is a slight fluctuation. This work may shed light on the form mechanism of methylamine existing in organisms and the hydration structures of larger molecules containing amino functional groups and their interaction with the water molecules nearby.

  2. Heavy ions collisions and the site-bond percolation

    International Nuclear Information System (INIS)

    Site-bond percolation on a lattice is used for the investigation of heavy ions reactions. A model characterized by two parameters, p and q, is worked out and a critical zone in the p-q plane is shown up. Analytical expressions for various quantities concerning percolation and evaporation are established. Calculations of energy spectra, linear momentum transfer, fragment multiplicities and mass yields at various bombarding energies are compared with experimental data. Different possibilities for the attainment of the multifragmentation regime are discussed. 17 figs; 43 refs

  3. Heavy ion collisions and the site-bond percolation

    International Nuclear Information System (INIS)

    Site-bond percolation on a lattice is used for the investigation of heavy ions reactions. A model characterized by two parameters, p and q, is worked out and a critical zone in the p, q plane is shown up. Analytical expressions for various quantities concerning percolation and evaporation are established. Calculations of energy spectra, linear momentum transfer, fragment multiplicities and mass yields at various bombarding energies are compared with experimental data. Different possibilities for the attainment of the multifragmentation regime are discussed. (orig.)

  4. Assessment of antimicrobial activity of polyazolidinammonium modified by iodine hydrate ions depending on its physical and chemical characteristics.

    Directory of Open Access Journals (Sweden)

    Vakaraeva M.M.

    2015-09-01

    Full Text Available Aim: to study antimicrobial activity of variants of polymeric compound polyazolidinammonium modified by iodine hydrate-ions (PAAG-M, depending on the polymeric chain length and concentration of the iodine hydrate-ions against standard strains of gram-positive and gram-negative bacteria as well as microscopic fungi. Materials and methods. Minimum inhibitory concentrations of all variants of the polymeric compound for tested microbial strains have been determined by using serial dilution method. Results. High sensitivity of Eschehchia coli 113-13 and Pseudomonas aeruginosa ATCC 27853 was shown to the variants of PAAG-M with molecular weight <100 and 100-200 kD. Staphylococcus aureus 209 P was more sensitive to the variants with molecular weight 200-350 and 400-500 kD. Direct relation of sensitivity was demonstrated for all microbial strains on the increase of iodine hydrate-ions concentration in the polymeric compound. Standard strain Candida albicans 13108 was sensitive to variants of the polymer with maximum iodine hydrate-ions concentration. Conclusion. The received results allow to carry out a choice of the most effective chemotherapeutic antimicrobic preparations depending on biological properties of the activator of infectious process.

  5. Structure and dynamics of the hydrated magnesium ion and of the solvated magnesium carbonates: insights from first principles simulations.

    Science.gov (United States)

    Di Tommaso, Devis; de Leeuw, Nora H

    2010-01-28

    We report first principles molecular dynamics simulations based on the density functional theory and the Car-Parrinello method to study the structures and dynamics of the hydrated Mg(2+) ion and of the solvated MgHCO(3)(+) and MgCO(3) complexes in aqueous solution. According to these simulations, the first hydration shell of the hydrated magnesium ion consists of six water molecules, whereas in the solvated magnesium bicarbonate and magnesium carbonate complexes the Mg(2+) is mostly five-coordinated, which indicates that when coordinated to magnesium the HCO(3)(-) and CO(3)(2-) anions reduce its the coordination sphere. Our simulations show that the structures of the most stable monomers of magnesium bi-carbonate and magnesium carbonate in solution are Mg[eta(1)-HCO(3)](H(2)O)(4)(+) and Mg[eta(1)-CO(3)](H(2)O)(4), i.e. the preferred hydration number is four, while the (bi-)carbonate is coordinated to the magnesium in a monodentate mode. The analysis of the exchange processes of the water molecules in the first and second hydration shell of Mg(2+) shows that the HCO(3)(-) or CO(3)(2-) ligands affect the dynamics of the magnesium coordination spheres by making its hydration shell more "labile". Furthermore, molecular dynamics simulations of the non-associated Mg(2+)/Cl(-) pair in water suggest that, despite negligible differences in the coordination spheres of Mg(2+), the chloride anion has a significant influence on the water exchange rates in the second hydration shell of Mg(2+). PMID:20066374

  6. Immobilization of Co (Ⅱ) Ions in Cement Pastes and Their Effects on the Hydration Characteristics

    Institute of Scientific and Technical Information of China (English)

    Eisa Hekal; Essam Kishar; Wafaa Hegazi; Maha Mohamed

    2011-01-01

    The immobilization of Co (Ⅱ) in various cement matrices was investigated by using the solidification/stabilization (S/S) technique. The different cement pastes used in this study were ordinary Portland cement in absence and presence of water reducing- and water repelling-admixtures as well as blended cement with kaolin. Two ratios of Co (Ⅱ) were used (0.5% and 1.0% by weight of the solid binder). The hydration characteristics of the used cement pastes were tested uia the determination of the combined water content, phase composition and compressive strength at different time intervals up to 180 d. The degree of immobilization of the added heavy metal ions was evaluated by determining the leached ion concentration after time intervals extended up to 180 d. The leachability experiments were carried out by using two modes: the static and the semi-dynamic leaching processes. It was noticed that the concentration of the leached Co2+ ions in the static mode of leachability was lower than the solubility of its hydroxide in all the investigated cement pastes.

  7. Improved model of hydrated calcium ion for molecular dynamics simulations using classical biomolecular force fields.

    Science.gov (United States)

    Yoo, Jejoong; Wilson, James; Aksimentiev, Aleksei

    2016-10-01

    Calcium ions (Ca(2+) ) play key roles in various fundamental biological processes such as cell signaling and brain function. Molecular dynamics (MD) simulations have been used to study such interactions, however, the accuracy of the Ca(2+) models provided by the standard MD force fields has not been rigorously tested. Here, we assess the performance of the Ca(2+) models from the most popular classical force fields AMBER and CHARMM by computing the osmotic pressure of model compounds and the free energy of DNA-DNA interactions. In the simulations performed using the two standard models, Ca(2+) ions are seen to form artificial clusters with chloride, acetate, and phosphate species; the osmotic pressure of CaAc2 and CaCl2 solutions is a small fraction of the experimental values for both force fields. Using the standard parameterization of Ca(2+) ions in the simulations of Ca(2+) -mediated DNA-DNA interactions leads to qualitatively wrong outcomes: both AMBER and CHARMM simulations suggest strong inter-DNA attraction whereas, in experiment, DNA molecules repel one another. The artificial attraction of Ca(2+) to DNA phosphate is strong enough to affect the direction of the electric field-driven translocation of DNA through a solid-state nanopore. To address these shortcomings of the standard Ca(2+) model, we introduce a custom model of a hydrated Ca(2+) ion and show that using our model brings the results of the above MD simulations in quantitative agreement with experiment. Our improved model of Ca(2+) can be readily applied to MD simulations of various biomolecular systems, including nucleic acids, proteins and lipid bilayer membranes. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 752-763, 2016. PMID:27144470

  8. Hydrogen-Bond Dynamics of Water in Ionic Solutions

    Science.gov (United States)

    Bakker, H. J.; Kropman, M. F.; Omta, A. W.; Woutersen, S.

    We study the effects of ions on the structure and dynamics of the hydrogen bonds in liquid water. As a technique we use femtosecond two-color mid-infrared spectroscopy, since this technique allows a clear distinction of the dynamics of the first solvation (hydration) shell of water molecules from the dynamics of bulk water. We find that water molecules in the first hydration shell of the halogenic anions Cl, and I show much slower hydrogen-bond dynamics than water molecules in the pure liquid. We also observe that the first hydration shell shows very slow collective orientational dynamics, and forms a rigid, long-living structure. Finally, we find that ions have surprisingly little effect on the hydrogen-bond dynamics of water molecules outside the first hydration shell, which implies that ions do not enhance or weaken the hydrogen-bond network of liquid water.

  9. Ion aggregation in high salt solutions. IV. Graph-theoretical analyses of ion aggregate structure and water hydrogen bonding network.

    Science.gov (United States)

    Choi, Jun-Ho; Cho, Minhaeng

    2015-09-14

    Ions in high salt solutions form a variety of ion aggregates, from ion pairs to clusters and networks. Their influences on water hydrogen bonding (H-bonding) network structures have long been of great interest. Recently, we have shown that the morphological structures of ion aggregates can be analyzed by using a spectral graph analysis theory, where each ion cluster or ion network is represented by a properly defined graph with edges and vertices. Here, to further examine the network properties of ion aggregates and water H-bonding networks in high salt solutions, we consider a few representative graph-theoretical descriptors: clustering coefficient, minimum path length, global efficiency, and degree distribution of ion aggregates. From the molecular dynamics trajectories, these graph theoretical properties of ion aggregates and water structures in NaCl and kosmotropic solutions are calculated and shown to be strongly dependent on the two types of ion aggregate structures, i.e., ion cluster and ion network. Ion clusters in high NaCl solutions exhibit typical behaviors of scale free network. The corresponding graph theoretical properties of ion networks in high KSCN solutions are notably different from those of NaCl ion clusters and furthermore they are very similar to those of water hydrogen-bonding network. The present graph-theoretical analysis results indicate that the high solubility limits of KSCN and other ion-network-forming salts might originate from their ability to form a large scale morphological network that can be intertwined with co-existing water H-bonding network. Furthermore, it is shown that the graph-theoretical properties of water H-bonding network structures do not strongly depend on the nature of dissolved ions nor on the morphological structures of ion aggregates, indicating that water's H-bonding interaction and network-forming capability are highly robust. We anticipate that the present graph-theoretical analysis results of high salt

  10. Molecular and environmental factors governing non-covalent bonding interactions and conformations of phosphorous functionalized γ-cyclodextrin hydrate systems.

    Science.gov (United States)

    Ivanova, Bojidarka; Spiteller, Michael

    2016-06-01

    Recent strategies in molecular drugs-design shift efforts to nanomedicine. Large supra-molecular inclusion systems are implemented as therapeutics. The sophistication of design is based on major advances of cyclodextrins (CDs) as host molecules. They are friendly towards biological environment. CDs have good (bio)compatibility as well. CDs can form host-guest macromolecular systems incorporating small molecules with suitable shapes due to non-covalent interactions. Innovative strategies yield to polymeric nano-particles; micelles; linear polymers and/or CDs-functionalized dendrimeric nanostructures; nanofibers as well as hydrogels. Attractive are phosphorous containing (bio)matrerials, having high selectivity toward biological active molecules. The non-covalent interactions in aquatic CD-systems contribute to stability of host-guest systems under physiological conditions, determining conformational preferences of host-CD macromolecule and guest small molecular template. In this paper we have reported complementation application of mass spectrometric (MS) and quantum chemical analysis of phosphorous chemically substituted γ-cyclodextrin hydrates γ-CDPO/nH2O (n ∊ [0-14]), studying neutral and polynegatively charged molecules as an effort to describe realistic a representative scale of physiological conditions. The binding affinity and molecular conformations are discussed. The 250 neutral and charged systems (γ-CDPOHm/nH2O, n ∊ [10][0,14], m ∊ [0,15], γ-CDPOH-8/nH2O.8Na(+), and γ-CDPOH-16/nH2O.16Na(+)) in four main domains of non-covalent hydrogen bonding interactions are studied. PMID:26944657

  11. Negligible effect of ions on the hydrogen-bond structure in liquid water.

    Science.gov (United States)

    Omta, Anne Willem; Kropman, Michel F; Woutersen, Sander; Bakker, Huib J

    2003-07-18

    The effects of ions on bulk properties of liquid water, such as viscosity, have suggested that ions alter water's hydrogen-bonding network. We measured the orientational correlation time of water molecules in Mg(ClO4)2, NaClO4, and Na2SO4 solutions by means of femtosecond pump-probe spectroscopy. The addition of ions had no influence on the rotational dynamics of water molecules outside the first solvation shells of the ions. This result shows that the presence of ions does not lead to an enhancement or a breakdown of the hydrogen-bond network in liquid water. PMID:12869755

  12. Negligible Effect of Ions on the Hydrogen-Bond Structure in Liquid Water

    Science.gov (United States)

    Omta, Anne Willem; Kropman, Michel F.; Woutersen, Sander; Bakker, Huib J.

    2003-07-01

    The effects of ions on bulk properties of liquid water, such as viscosity, have suggested that ions alter water's hydrogen-bonding network. We measured the orientational correlation time of water molecules in Mg(ClO4)2, NaClO4, and Na2SO4 solutions by means of femtosecond pump-probe spectroscopy. The addition of ions had no influence on the rotational dynamics of water molecules outside the first solvation shells of the ions. This result shows that the presence of ions does not lead to an enhancement or a breakdown of the hydrogen-bond network in liquid water.

  13. Hydrated copper ion chemistry: guided ion beam and computational investigation of Cu2+(H2O)n (n = 7-10) complexes.

    Science.gov (United States)

    Armentrout, Peter B; Sweeney, Andrew F

    2015-01-01

    Cross sections for the threshold collision-induced dissociation of Cu(2+)(H(2)O)(n), where n = 8 - 10, are measured using a guided ion beam tandem mass spectrometer. The primary dissociation pathway is found to be loss of a single water molecule followed by the sequential loss of additional water molecules until n = 8, at which point charge separation to form CuOH(+)(H(2)O)(4) (+) H(+)(H(2)O)(3) is observed to occur at a slightly lower energy than loss of a water molecule. Competition from charge separation prohibits the formation of appreciable amounts of the n = 7 or smaller complexes as reactants in the source. These findings indicate that Cu(2+) has a critical size of 8. Analysis of the data using statistical modeling techniques that account for energy distributions and lifetime effects yields primary and sequential bond dissociation energies (BDEs) for loss of one and two water molecules from n = 8 - 10 complexes as well as the barrier for charge separation from n = 8. More speculative analysis extends the thermochemistry obtained down to n = 5 and 6. Theoretical BDEs are determined from quantum chemical calculations using structures optimized at the B3LYP/6 311(+)G(d,p) level along with the lowest-energy isomers suggested by single point energies at the MP2(full), M06, B3LYP, and B3P86 levels of theory using a 6- 311(+)G(2d,2p) basis set. BDEs at 0K are converted to 298 K thermodynamic values using a rigid rotor/harmonic oscillator approximation. Experimental and theoretical entropies of activation suggest that a third solvent shell forms at n = 9, in accord with previous findings. The present work represents the first experimentally determined hydration enthalpies for the Cu(2+)(H(2)O)n system. PMID:26307731

  14. Thermodynamics of water dimer dissociation in the primary hydration shell of the iodide ion with temperature-dependent vibrational predissociation spectroscopy.

    Science.gov (United States)

    Wolke, Conrad T; Menges, Fabian S; Tötsch, Niklas; Gorlova, Olga; Fournier, Joseph A; Weddle, Gary H; Johnson, Mark A; Heine, Nadja; Esser, Tim K; Knorke, Harald; Asmis, Knut R; McCoy, Anne B; Arismendi-Arrieta, Daniel J; Prosmiti, Rita; Paesani, Francesco

    2015-03-12

    The strong temperature dependence of the I(-)·(H2O)2 vibrational predissociation spectrum is traced to the intracluster dissociation of the ion-bound water dimer into independent water monomers that remain tethered to the ion. The thermodynamics of this process is determined using van't Hoff analysis of key features that quantify the relative populations of H-bonded and independent water molecules. The dissociation enthalpy of the isolated water dimer is thus observed to be reduced by roughly a factor of three upon attachment to the ion. The cause of this reduction is explored with electronic structure calculations of the potential energy profile for dissociation of the dimer, which suggest that both reduction of the intrinsic binding energy and vibrational zero-point effects act to weaken the intermolecular interaction between the water molecules in the first hydration shell. Additional insights are obtained by analyzing how classical trajectories of the I(-)·(H2O)2 system sample the extended potential energy surface with increasing temperature. PMID:25647222

  15. Ion aggregation in high salt solutions. V. Graph entropy analyses of ion aggregate structure and water hydrogen bonding network

    Science.gov (United States)

    Choi, Jun-Ho; Cho, Minhaeng

    2016-05-01

    Dissolved ions in water tend to form polydisperse ion aggregates such as ion pairs, relatively compact ion clusters, and even spatially extended ion networks with increasing salt concentration. Combining molecular dynamics simulation and graph theoretical analysis methods, we recently studied morphological structures of ion aggregates with distinctively different characteristics. They can be distinguished from each other by calculating various spectral graph theoretical properties such as eigenvalues and eigenvectors of adjacency matrices of ion aggregates and water hydrogen-bonding networks, minimum path lengths, clustering coefficients, and degree distributions. Here, we focus on percolation and graph entropic properties of ion aggregates and water hydrogen-bonding networks in high salt solutions. Ion network-forming K+ and SCN- ions at high concentrations show a percolating behavior in their aqueous solutions, but ion cluster-forming ions in NaCl solutions do not show such a transition from isolated ion aggregates to percolating ion-water mixture morphology. Despite that the ion aggregate structures are strikingly different for either cluster- or network-forming ions in high salt solutions, it is interesting that the water structures remain insensitive to the electrostatic properties, such as charge densities and polydentate properties, of dissolved ions, and morphological structures of water H-bonding networks appear to be highly robust regardless of the nature and concentration of salt. We anticipate that the present graph entropy analysis results would be of use in understanding a variety of anomalous behaviors of interfacial water around biomolecules as well as electric conductivities of high electrolyte solutions.

  16. Study of the action of phosphate ions contained in the mixing water on the hydration of a Portland cement

    International Nuclear Information System (INIS)

    Cementation is considered as the most attractive solution for the conditioning of low and intermediate radioactive wastes. The species contained in these wastes can strongly influence the reactivity of the cement pastes, it is in particular the case of the ortho-phosphate ions which are found in the evaporation concentrates. The aim of our work was to determine the influence of these ions on the hydration and the rheological properties of the cement pastes at early age as well as the mechanical and physical properties on the hardened material. (author)

  17. Ion Mobility-Mass Spectrometry as a Tool for the Structural Characterization of Peptides Bearing Intramolecular Disulfide Bond(s)

    Science.gov (United States)

    Massonnet, Philippe; Haler, Jean R. N.; Upert, Gregory; Degueldre, Michel; Morsa, Denis; Smargiasso, Nicolas; Mourier, Gilles; Gilles, Nicolas; Quinton, Loïc; De Pauw, Edwin

    2016-08-01

    Disulfide bonds are post-translationnal modifications that can be crucial for the stability and the biological activities of natural peptides. Considering the importance of these disulfide bond-containing peptides, the development of new techniques in order to characterize these modifications is of great interest. For this purpose, collision cross cections (CCS) of a large data set of 118 peptides (displaying various sequences) bearing zero, one, two, or three disulfide bond(s) have been measured in this study at different charge states using ion mobility-mass spectrometry. From an experimental point of view, CCS differences (ΔCCS) between peptides bearing various numbers of disulfide bonds and peptides having no disulfide bonds have been calculated. The ΔCCS calculations have also been applied to peptides bearing two disulfide bonds but different cysteine connectivities (Cys1-Cys2/Cys3-Cys4; Cys1-Cys3/Cys2-Cys4; Cys1-Cys4/Cys2-Cys3). The effect of the replacement of a proton by a potassium adduct on a peptidic structure has also been investigated.

  18. Hydration structure and dynamics of a hydroxide ion in water clusters of varying size and temperature: Quantum chemical and ab initio molecular dynamics studies

    International Nuclear Information System (INIS)

    Highlights: ► A theoretical study of hydroxide ion-water clusters is carried for varying cluster size and temperature. ► The structures of OH−(H2O)n are found out through quantum chemical calculations for n = 4, 8, 16 and 20. ► The finite temperature behavior of the clusters is studied through ab initio dynamical simulations. ► The spectral features of OH modes (deuterated) and their dependence on hydrogen bonding states of water are discussed. ► The mechanism and kinetics of proton transfer processes in these anionic clusters are also investigated. - Abstract: We have investigated the hydration structure and dynamics of OH−(H2O)n clusters (n = 4, 8, 16 and 20) by means of quantum chemical and ab initio molecular dynamics calculations. Quantum chemical calculations reveal that the solvation structure of the hydroxide ion transforms from three and four-coordinated surface states to five-coordinated interior state with increase in cluster size. Several other isomeric structures with energies not very different from the most stable isomer are also found. Ab initio simulations show that the most probable configurations at higher temperatures need not be the lowest energy isomeric structure. The rates of proton transfer in these clusters are found to be slower than that in bulk water. The vibrational spectral calculations reveal distinct features for free OH (deuterated) stretch modes of water in different hydrogen bonding states. Effects of temperature on the structural and dynamical properties are also investigated for the largest cluster considered here.

  19. Multi-layered, chemically bonded lithium-ion and lithium/air batteries

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

    2014-05-13

    Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

  20. Influence of ions on the hydrogen-bond structure in liquid water

    Science.gov (United States)

    Omta, Anne Willem; Kropman, Michel F.; Woutersen, Sander; Bakker, Huib J.

    2003-12-01

    The orientational-correlation time of water molecules in ionic solutions has been measured with femtosecond pump-probe spectroscopy. It is found that the addition of ions has no influence on the rotational dynamics of water molecules outside the first solvation shells of the ions. This shows that the presence of ions does not lead to an enhancement or a breakdown of the hydrogen-bond network in liquid water.

  1. Structure and Spectroscopy of Hydrated Sodium Ions at Different Temperatures and the Cluster Stability Rules.

    Science.gov (United States)

    Fifen, Jean Jules; Agmon, Noam

    2016-04-12

    The sodium cation plays an important role in several physiological processes. Understanding its solvation may help understanding ion selectivity in sodium channels that are pivotal for nerve impulses. This paper presents a thorough investigation of over 75 isomers of gas-phase Na(+)(H2O)(n=1-8) clusters, whose optimized structures, energies, and (harmonic) vibrational frequencies were computed quantum mechanically at the full MP2/6-31++G(d,p) level of theory. From these data, we have calculated the temperature effects on the cluster thermodynamic functions, and thus the equilibrium Boltzmann distribution for each n. For a selected number of isomers, we have corrected the calculations for basis set superposition error (BSSE) to obtain accurate clustering energies, in excellent agreement with experiment. The computed clusters are overwhelmingly 4-coordinated, as opposed to bulk liquid water, where sodium cations are believed to be mostly 5- or 6-coordinated. To explain this, we suggest the "cluster stability rules", a set of coordination-number-dependent hydrogen-bond (HB) strengths that can be obtained using a single BSSE correction. Assuming additivity and transferability, these reproduce the relative stability of most of our computed isomers. These rules enable us to elucidate the trends in HB strengths, outlining the major determinants of cluster stability. For n = 4 and 5, we have also performed anharmonic vibrational calculations (VPT2) to compare with available photodissociation infrared spectra of these gas-phase clusters. The comparison suggests that the experiments actually monitor a mixture of predominantly 3-coordinated isomers, which is quite remote from the computed Boltzmann distribution, particularly at low temperatures. Surprisingly, for these experiments, water evaporation pathways can rationalize the non-equilibrium isomer distribution. The equilibrium isomer distribution is, in turn, rationalized by the entropy of internal rotations of "dangling

  2. Effect of Graded Hydration on the Dynamics of an Ion Channel Peptide: A Fluorescence Approach

    OpenAIRE

    Kelkar, Devaki A.; Chattopadhyay, Amitabha

    2004-01-01

    Water plays an important role in determining the folding, structure, dynamics, and, in turn, the function of proteins. We have utilized a combination of fluorescence approaches such as the wavelength-selective fluorescence approach to monitor the effect of varying degrees of hydration on the organization and dynamics of the functionally important tryptophan residues of gramicidin in reverse micelles formed by sodium bis(2-ethylhexyl) sulfosuccinate. Our results show that tryptophans in gramic...

  3. Ion-Specific Long-Range Correlations on Interfacial Water Driven by Hydrogen Bond Fluctuations

    OpenAIRE

    Enami, Shinichi; Colussi, Agustín J.

    2014-01-01

    Some of the most important processes in nature involve interfacial water. It has long been conjectured that specific ion effects therein are associated with the unique properties of interfacial water. Here we reveal the mechanism of such association by showing that the strength of ion-specific long-range correlations tracks the amplification of fluctuations on the surface of water-alcohol mixtures at the percolation thresholds of their hydrogen-bonded water networks. We used in situ online el...

  4. Effect of aging on surface chemical bonds of PTFE irradiated by low energy Ti ion

    International Nuclear Information System (INIS)

    Polytetrafluoroethylene (PTFE) was irradiated by low energy titanium ion in a metal vapor vacuum arc (MEVVA) implanter. The samples were irradiated with 80 keV Ti ion with fluences from 5x1015 to 5x1017 Ti/cm2, respectively. Transportation of Ion in Matters (TRIM) code was employed to simulate Ti ion irradiation. The as-irradiated samples were investigated by ESCA, SEM and wettability. As increasing ion fluence, various chemical bonds and irradiation-damaged surfaces were observed. The water droplet contact angel of PTFE samples increased gradually with ion fluence. All the as-irradiated PTFE samples were aged in air for 1 year. After aging the surface-restructuring behavior was observed on the surfaces of the samples irradiated with ion fluence equal to or less than 5x1016 Ti/cm2, which resulted in decrease of the droplet contact angle of these samples. The surface roughness change of the aged samples, which were measured by atomic force microscopy (AFM), was consistent with the droplet contact angle change. The experimental results revealed that Ti ion fluence closely affected the surface chemical bond, morphology and wettability, as well as the aging stability of the as-irradiated PTFE samples

  5. Integrated optics Bragg filters made by ion exchange and wafer bonding

    Science.gov (United States)

    Gardillou, F.; Bastard, L.; Broquin, J.-E.

    2006-09-01

    A polarization-insensitive Bragg filter has been realized on a glass substrate thanks to the epoxy-free wafer bonding technique. This device is based on the combined embedding of a corrugated grating and a surface ion-exchanged waveguide, both realized on a silicate glass. With this configuration, the grating patterns are also protected from external degradation of the environment.

  6. Modelling of Ion Transport in Solids with a General Bond Valence Based Force-Field

    Directory of Open Access Journals (Sweden)

    S. Adams

    2010-12-01

    Full Text Available Empirical bond length - bond valence relations provide insight into the link between structure of and ion transport in solid electrolytes. Building on our earlier systematic adjustment of bond valence (BV parameters to the bond softness, here we discuss how the squared BV mismatch can be linked to the absolute energy scale and used as a general Morse-type interaction potential for analyzing low-energy pathways in ion conducting solid or mixed conductors either by an energy landscape approach or by molecular dynamics (MD simulations. For a wide range of Lithium oxides we could thus model ion transport revealing significant differences to an earlier geometric approach. Our novel BV-based force-field has also been applied to investigate a range of mixed conductors, focusing on cathode materials for lithium ion battery (LIB applications to promote a systematic design of LIB cathodes that combine high energy density with high power density. To demonstrate the versatility of the new BV-based force-field it is applied in exploring various strategies to enhance the power performance of safe low cost LIB materials (LiFePO4, LiVPO4F, LiFeSO4F, etc..

  7. Electrochemical stability of ionic clathrate hydrates and their structural consideration

    International Nuclear Information System (INIS)

    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 Me4NOH hydrates is mainly affected by both their ionic concentration and cage occupancy. In particular, the true clathrate structures of β-Me4NOH hydrates are more electrochemically stable than their α-forms that possess partially broken hydrogen bonds. We also observed that the binary THF–Pr4NOH and pure Bu4NOH clathrate hydrates exhibit greater electrochemical stability than those of pure Me4NOH hydrates having lower or similar ionic concentrations. These results are considered to arise from the fact that each of the Pr4N+ and Bu4N+ ions occupies an extended space comprising four cages, which leads to stabilization of the larger unit, whereas a Me4N+ ion is completely included only in one cage

  8. Heterogeneous collision velocity for hydrated ions in aqueous solutions is nearly 10{sup 4} cm/s

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, O.S. [Cornell Univ. Medical College, New York, NY (United States); Feldberg, S.W. [Brookhaven National Lab., Upton, NY (United States)

    1996-03-14

    The heterogeneous collision velocity (v{sub o}, units of centimeters/second) is the average velocity of a solution particle toward a surface. V{sub o} thus defines the maximum flux of the particles to the surface. Einstein argued that v{sub o} in condensed phases and in gases may be deduced in a precisely analogous manner and that v{sub o} in aqueous solution therefore should be nearly 10{sup 4} cm/s (for particles with a mass of 100 Da). Values of v{sub o} for several aqueous monovalent cations (Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +} and NH{sub 4}{sup +}) were estimated from steady-state limiting current measurements through single gramicidin A channels spanning lipid bilayer membranes. The collisional and diffusional current components were separated by making use of the different viscosities of H{sub 2}O and D{sub 2}O solutions. The transfer of ions from the bulk solution to the channel entrance is modeled using a hemispherical entrance and an extension of the classical analysis of diffusion to a (hemi)sphere in which we relax the assumption that the jump distance (associated with three-dimensional diffusion of an ion in the bulk phase) be small compared to the hemispherical capture radius. Our estimate of v{sub o} agrees well with the prediction of Einstein. We therefore conclude that ion dehydration (only partially hydrated ions can pass through the gramicidin A channel) cannot be a rate-controlling step - a conclusion that is consistent with known rate constants for water exchange for these ions. 36 refs., 7 figs., 1 tab.

  9. The effect of multivalent ions on the thermal transition of hydrated polyelectrolyte multilayers

    Science.gov (United States)

    Reid, Dariya; Lutkenhaus, Jodie

    2015-03-01

    Layer-by-layer (LbL) assembly is a commonly studied technique in the production of uniform thin films. Hydrate LbL assemblies made of model polyelectrolytes, poly(diallyldimethylammonium chloride) (PDAC) and poly(styrene sulfonate) (PSS), exhibit a thermal transition with features of a glass transition and a lower critical solution temperature transition when assembled in the presence of sodium chloride. The question remains as to how multivalent cations affect the nature of the transition. Here, we present results on the thermal transition of PDAC/PSS LbL assemblies exposed to various multivalent salts. Quartz crystal microbalance (QCM-D) and modulated differential scanning calorimetry (MDSC) is used to assess the transition.

  10. Effects of ion concentration on the hydrogen bonded structure of water in the vicinity of ions in aqueous NaCl solutions

    Indian Academy of Sciences (India)

    A Nag; D Chakraborty; A Chandra

    2008-01-01

    Molecular dynamics simulations of dilute and concentrated aqueous NaCl solutions are carried out to investigate the changes of the hydrogen bonded structures in the vicinity of ions for different ion concentrations. An analysis of the hydrogen bond population in the first and second solvation shells of the ions and in the bulk water is done. Although essentially no effect of ions on the hydrogen bonding is observed beyond the first solvation shell of the ions for the dilute solutions, for the concentrated solutions a noticeable change in the average number of water-water hydrogen bonds is observed in the second solvation shells of the ions and even beyond. However, the changes in the average number of hydrogen bonds are found to be relatively less when both water-water and ion-water hydrogen bonds are counted. Thus, the changes in the total number of hydrogen bonds per water are not very dramatic beyond the first solvation shell even for concentrated solutions.

  11. Molecular dynamics simulation study of ionic hydration and ion association in dilute and 1 molal aqueous sodium chloride solutions from ambient to supercritical conditions

    Science.gov (United States)

    Driesner, T.; Seward, T. M.; Tironi, I. G.

    1998-09-01

    The increasing demand for accurate equations of state of fluids under extreme conditions and the need for a detailed microscopic picture of aqueous fluids in some areas of geochemistry (e.g., mineral dissolution/precipitation kinetics) potentially make molecular dynamics (MD) simulations a powerful tool for theoretical geochemistry. We present MD simulations of infinitely dilute and 1 molal aqueous NaCl solutions that have been carried out in order to study the systematics of hydration and ion association over a wide range of conditions from ambient to supercritical and compare them to the available experimental data. In the dilute case, the hydration number of the Na + ion remains essentially constant around 5.5 from ambient to supercritical temperatures when the density is kept constant at 1 g cm -3 but decreases to below 5 along the liquid-vapor curve. In both cases, the average ion-first shell water distance decreases by about 0.03 Å from ambient to near critical temperatures. The Cl - ion shows a slight expansion of the first hydration shell by about 0.02 Å from ambient to near critical temperatures. The geometric definition of the first hydration shell becomes ambiguous due to a shift of the position of the first minimum of the Cl-O radial distribution function. In the case of the 1 molal solution, the contraction of the Na + first hydration shell is similar to that in the dilute case whereas the hydration number decreases drastically from 4.9 to 2.8 due to strong ion association. The released waters are replaced on a near 1:1 basis by chloride ions. Polynuclear clusters as predicted by Oelkers and Helgeson (1993b) are observed in the high temperature systems. The hydration shell of the Cl --ion shows significant deviation from the behavior in dilute systems, that is, at near vapor saturated conditions, the expansion of the hydration shell is significantly larger (0.12 Å from ambient to near critical temperatures). Due to a very large shift of the first

  12. Theoretical study of the hydrated Gd3+ ion: Structure, dynamics, and charge transfer

    OpenAIRE

    Clavaguéra, C.; Calvo, Florent; Dognon, J.-P.

    2006-01-01

    The dynamical processes taking place in the first coordination shells of the gadolinium (III) ion are important for improving the contrast agent efficiency in magnetic-resonance imaging. An extensive study of the gadolinium (III) ion solvated by a water cluster is reported, based on molecular dynamics simulations. The AMOEBA force field [P. Y. Ren and J. W. Ponder, J. Phys. Chem. B 107, 5933 (2003)] that includes many-body polarization effects is used to describe the interactions among water ...

  13. Chemical Bonding States of TiC Films before and after Hydrogen Ion Irradiation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    TiC films deposited by rf magnetron sputtering followed by Ar+ ion bombardment were irradiated with a hydrogen ion beam. X-ray photoelectron spectroscopy (XPS) was used for characterization of the chemical bonding states of C and Ti elements of the TiC films before and after hydrogen ion irradiation, in order to understand the effect of hydrogen ion irradiation on the films and to study the mechanism of hydrogen resistance of TiC films. Conclusions can be drawn that ion bombardment at moderate energy can cause preferential physical sputtering of carbon atoms from the surface of low atomic number (Z) material. This means that ion beam bombardment leads to the formation of a non-stoichiometric composition of TiC on the surface.TiC films prepared by ion beam mixing have the more excellent characteristic of hydrogen resistance. One important cause, in addition to TiC itself, is that there are many vacant sites in TiC created by ion beam mixing.These defects can easily trap hydrogen and effectively enhance the effect of hydrogen resistance.

  14. Hydrogen Bonding between Metal-Ion Complexes and Noncoordinated Water: Electrostatic Potentials and Interaction Energies.

    Science.gov (United States)

    Andrić, Jelena M; Misini-Ignjatović, Majda Z; Murray, Jane S; Politzer, Peter; Zarić, Snežana D

    2016-07-01

    The hydrogen bonding of noncoordinated water molecules to each other and to water molecules that are coordinated to metal-ion complexes has been investigated by means of a search of the Cambridge Structural Database (CSD) and through quantum chemical calculations. Tetrahedral and octahedral complexes that were both charged and neutral were studied. A general conclusion is that hydrogen bonds between noncoordinated water and coordinated water are much stronger than those between noncoordinated waters, whereas hydrogen bonds of water molecule in tetrahedral complexes are stronger than in octahedral complexes. We examined the possibility of correlating the computed interaction energies with the most positive electrostatic potentials on the interacting hydrogen atoms prior to interaction and obtained very good correlation. This study illustrates the fact that electrostatic potentials computed for ground-state molecules, prior to interaction, can provide considerable insight into the interactions. PMID:26989883

  15. Tuning the intermolecular proton bond in the H5O2+ `Zundel ion' scaffold

    DEFF Research Database (Denmark)

    Olesen, S. G.; Guasco, T. L.; Roscioli, J. R.; Johnson, M. A.

    The Zundel ion, H2O center dot H+center dot H2O, provides a versatile scaffold with which to explore the quantum structure of the intermolecular proton bond (IPB). This information is encoded in the vibrational frequencies adopted by the shared proton, nu(sp), which are observed to follow a remar...... context of the extreme sensitivity of IPBs to their solvation environments. (C) 2011 Elsevier B.V. All rights reserved....

  16. Theoretical study of the hydrated Gd3+ ion: Structure, dynamics, and charge transfer

    Science.gov (United States)

    Clavaguéra, Carine; Calvo, Florent; Dognon, Jean-Pierre

    2006-02-01

    The dynamical processes taking place in the first coordination shells of the gadolinium (III) ion are important for improving the contrast agent efficiency in magnetic-resonance imaging. An extensive study of the gadolinium (III) ion solvated by a water cluster is reported, based on molecular dynamics simulations. The AMOEBA force field [P. Y. Ren and J. W. Ponder, J. Phys. Chem. B 107, 5933 (2003)] that includes many-body polarization effects is used to describe the interactions among water molecules, and is extended here to treat the interactions between them and the gadolinium ion. In this purpose accurate ab initio calculations have been performed on Gd3+-H2O for extracting the relevant parameters. Structural data of the first two coordination shells and some dynamical properties such as the water exchange rate between the first and second coordination shells are compared to available experimental results. We also investigate the charge transfer processes between the ion and its solvent, using a fluctuating charges model fitted to reproduce electronic structure calculations on [Gd(H2O)n]3+ complexes, with n ranging from 1 to 8. Charge transfer is seen to be significant (about one electron) and correlated with the instantaneous coordination of the ion.

  17. Quantitative assessment of the multiplicity of carbon-halogen bonds: carbenium and halonium ions with F, Cl, Br, and I.

    Science.gov (United States)

    Kalescky, Robert; Zou, Wenli; Kraka, Elfi; Cremer, Dieter

    2014-03-13

    CX (X = F, Cl, Br, I) and CE bonding (E = O, S, Se, Te) was investigated for a test set of 168 molecules using the local CX and CE stretching force constants k(a) calculated at the M06-2X/cc-pVTZ level of theory. The stretching force constants were used to derive a relative bond strength order (RBSO) parameter n. As alternative bond strength descriptors, bond dissociation energies (BDE) were calculated at the G3 level or at the two-component NESC (normalized elimination of the small component)/CCSD(T) level of theory for molecules with X = Br, I or E = Se, Te. RBSO values reveal that both bond lengths and BDE values are less useful when a quantification of the bond strength is needed. CX double bonds can be realized for Br- or I-substituted carbenium ions where as suitable reference the double bond of the corresponding formaldehyde homologue is used. A triple bond cannot be realized in this way as the diatomic CX(+) ions with a limited π-donor capacity for X are just double-bonded. The stability of halonium ions increases with the atomic number of X, which is reflected by a strengthening of the fractional (electron-deficient) CX bonds. An additional stability increase of up to 25 kcal/mol (X = I) is obtained when the X(+) ion can form a bridged halonium ion with ethene such that a more efficient 2-electron-3-center bonding situation is created. PMID:24555526

  18. Fabrication of ion-sliced lithium niobate slabs using helium ion implantation and Cu-Sn bonding

    Energy Technology Data Exchange (ETDEWEB)

    Xiang, Bing-Xi [School of Physics, Shandong University, Jinan (China); Guan, Jing; Wang, Lei [School of Physics, Shandong University, Jinan (China); Key Laboratory of Particle Physics and Particle Irradiation, Ministry of Education, Jinan (China); Jiao, Yang [College of Physics and Electronics, Shandong Normal University, Jinan, Shandong (China)

    2014-10-15

    The fabrication of LiNbO{sub 3} waveguide slabs with sub-micron thickness is presented using He ion-induced splitting and the Cu-Sn bonding technique. The exfoliation time of implanted LiNbO{sub 3} was investigated as a function of annealing temperatures to reveal the activation energies during the splitting process. Defect-free waveguide films with large areas of several cm{sup 2} are consistently produced by using the inter-diffusion bonding of Cu-Sn interface. The fabricated film was investigated by using the Rutherford backscattering/channeling method and dark mode spectroscopy. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Specific Ions Modulate Diffusion Dynamics of Hydration Water on Lipid Membrane Surfaces

    OpenAIRE

    Song, Jinsuk; Franck, John; Pincus, Philip; Kim, Mahn Won; Han, Songi

    2014-01-01

    Effects of specific ions on the local translational diffusion of water near large hydrophilic lipid vesicle surfaces were measured by Overhauser dynamic nuclear polarization (ODNP). ODNP relies on an unpaired electron spin-containing probe located at molecular or surface sites to report on the dynamics of water protons within ∼10 Å from the spin probe, which give rise to spectral densities for electron–proton cross-relaxation processes in the 10 GHz regime. This pushes nuclear magnetic resona...

  20. Structure of hydrated complexes formed by metal ions of groups I-III of the Periodic table in aqueous electrolyte solutions under ambient conditions

    International Nuclear Information System (INIS)

    Published and authors' experimental data on the structure of aqueous electrolyte solutions under standard conditions were generalized to ascertain the dependences of the solution structural parameters on chemical nature of dissolved compounds of alkali, alkaline-earth metals, cadmium, scandium, yttrium, lanthanum and indium. Hydrate complexes of metal ions formed in aqueous solutions were systematized, depending on cation size, charge and structure of their external electronic shell

  1. Surfactants at Single-Walled Carbon Nanotube-Water Interface: Physics of Surfactants, Counter-Ions, and Hydration Shell

    Science.gov (United States)

    Khare, Ketan S.; Phelan, Frederick R., Jr.

    Specialized applications of single-walled carbon nanotubes (SWCNTs) require an efficient and reliable method to sort these materials into monodisperse fractions with respect to their defining metrics (chirality, length, etc.) while retaining their physical and chemical integrity. A popular method to achieve this goal is to use surfactants that individually disperse SWCNTs in water and then to separate the resulting colloidal mixture into fractions that are enriched in monodisperse SWCNTs. Recently, experiments at NIST have shown that subtle point mutations of chemical groups in bile salt surfactants have a large impact on the hydrodynamic properties of SWCNT-surfactant complexes during ultracentrifugation. These results provide strong motivation for understanding the rich physics underlying the assembly of surfactants around SWCNTs, the structure and dynamics of counter ions around the resulting complex, and propagation of these effects into the first hydration shell. Here, all-atom molecular dynamics simulations are used to investigate the thermodynamics of SWCNT-bile salt surfactant complexes in water with an emphasis on the buoyant characteristics of the SWCNT-surfactant complexes. Simulation results will be presented along with a comparison with experimental data. Official contribution of the National Institute of Standards and Technology; not subject to copyright in the United States.

  2. Synthesis and characterization of the hydrated niobium V oxide for application as ion exchanger

    International Nuclear Information System (INIS)

    Hydrous oxides were considered a candidate material for applications as ion-exchangers, since they show a low solubility and excellent regeneration capacity. This work presents a new process to obtain Nb2 O5. n H2 O and discusses the main results from the powder characterization. The powder characteristics were determined by chemical, BET, ATD and ATG analyses, infrared spectroscopy, X-ray diffraction, mercury porosimetry and SEM observations. The powder showed uniform sized and porous agglomerates and crystalline structure at low temperatures. At the end these characteristics are compared with of the conventional niobium V oxide obtained from alkaline fusion process. (author)

  3. Surface Modification and Direct Bonding of Different Materials Irradiated H2O Ion

    Science.gov (United States)

    Nishimoto, Kazufumi; Ishizawa, Naoya; Ueda, Hiroyasu; Noda, Daiji; Hattori, Tadashi

    Reliable joining technologies are essential for fabrication of microstructures such as micro-machines, and particularly technologies that are capable of jointing different types of materials. However, these technologies cannot be used for materials that have different rates of thermal expansion or in cases where the adhesives have an effect on the properties of the component materials. Our research focused on developing a direct jointing technology which employs hydrogen bonding. In this technology, OH radicals are absorbed into the surface of the material to be bonded by modifying its surface properties by ion irradiation. We studied the modification of the surface properties of two resins, (SU-8 and PMMA) by H2O ion irradiation and Ar cleaning. It was confirmed that the presence of H2O ions on the surface of these resins improved their hydrophilic properties and also the peel strengths of Cu membrane s deposited onto both resins. Based on the results of these studies, a series of experiments were conducted in which two different materials, (copper plus one or other of the resins) were joined directly and the results were evaluated. Each of the resins could be joined to copper by heating to a temperature of 100°C and pressurizing to 10 MPa. This jointing technology will now be applied to the fabrication of the tilt sensors that we are currently developing.

  4. Ion diffusion at the bonding interface of undoped YAG/Yb:YAG composite ceramics

    Science.gov (United States)

    Fujioka, Kana; Sugiyama, Akira; Fujimoto, Yasushi; Kawanaka, Junji; Miyanaga, Noriaki

    2015-08-01

    Cation diffusion across a boundary between ytterbium (Yb)-doped and undoped yttrium aluminum garnet (YAG) ceramics was examined by electron microprobe analysis (EPMA). Polished Yb:YAG and undoped YAG ceramics were bonded by surface treatment with argon fast atom beam, and then heat-treated at 1400 or 1600 °C for 50 h or at 1400 °C for 10 h under vacuum. We obtained EPMA mapping images of the bonded samples that clearly showed the bulk and grain-boundary diffusion of Y and Yb ions. The number density profiles showed that the total diffusion distances of Yb and Y ions were almost equal and approximately 2 and 15 μm at 1400 and 1600 °C, respectively, and the dependence of diffusion distance on heating time was weak. The diffusion curves were well modeled by Harrison type B kinetics including bulk and grain-boundary diffusion. In addition, it was found that Si ions added to the samples as a sintering aid might be segregated at the grain boundary by heat treatment, and diffused only along grain boundaries.

  5. Effects of metal ions and disulfide bonds on the activity of phosphodiesterase from Trimeresurus stejnegeri venom.

    Science.gov (United States)

    Peng, Lili; Xu, Xiaolong; Guo, Mingchun; Yan, Xincheng; Wang, Shasha; Gao, Shang; Zhu, Shanshan

    2013-06-01

    Obviously different from the other known phosphodiesterases, the phosphodiesterase from Trimeresurus stejnegeri venom (TS-PDE) consists of two different chains linked with disulfide bonds and contains both endogenous Cu(2+) and Zn(2+). Cu(2+) and Zn(2+) are important for its phosphodiesterase activity. In this study, the effects of metal ions and small-molecule reductants on its structure and activity have been investigated by polyacrylamide gel electrophoresis, high performance liquid chromatography, fluorescence and electron paramagnetic resonance spectroscopy. The results show that TS-PDE has one class of Zn(2+) binding site and two classes of Cu(2+) binding site, including the high affinity activator sites and the low affinity sites. Cu(2+) ions function as a switch for its phosphodiesterase activity. The catalytic activity of TS-PDE does not have an absolute requirement for Cu(2+) and Zn(2+). Mg(2+), Mn(2+), Ni(2+), Co(2+) and Ca(2+) are all effective for its phosphodiesterase activity. TS-PDE has seven disulfide bonds and ten free cysteine residues. l-Ascorbate inhibits the phosphodiesterase activity of TS-PDE through reduction of the Cu(2+), while dithiothreitol, glutathione and tris(2-carboxyethyl)phosphine inhibit the phosphodiesterase activity of TS-PDE by reducing both the Cu(2+) and disulfide bonds. The catalytic activity of TS-PDE relies on its disulfide bonds and bimetallic cluster. In addition, biologically-relevant reductants, glutathione and l-ascorbate, have been found to be endogenous inhibitors to the phosphodiesterase activity of TS-PDE. PMID:23775423

  6. Pentagonal dodecahedron methane hydrate cage and methanol system—An ab initio study

    Indian Academy of Sciences (India)

    Snehanshu Pal; T K Kundu

    2013-03-01

    Density functional theory based studies have been performed to elucidate the role of methanol as an methane hydrate inhibitor. A methane hydrate pentagonal dodecahedron cage’s geometry optimization, natural bond orbital (NBO) analysis, Mullikan charge determination, electrostatic potential evaluation and vibrational frequency calculation with and without the presence of methanol using WB97XD/6-31++G(d,p) have been carried out. Calculated geometrical parameters and interaction energies indicate that methanol destabilizes pentagonal dodecahedron methane hydrate cage (1CH4@512) with and without the presence of sodium ion. NBO analysis and red shift of vibrational frequency reveal that hydrogen bond formation between methanol and water molecules of 1CH4@512 cage is favourable subsequently after breaking its original hydrogen bonded network.

  7. DFT Study of the effects of counter ions on bonding, molecular and spectral properties of pentaflourophenyl xenonium diflouride cation

    Indian Academy of Sciences (India)

    Hossein Tavakol; Neda Khedri

    2015-09-01

    The structures and properties of pentaflourophenyl xenonium diflouride cation (PFF) have been studied in their salts with 12 different counter ions using DFT calculations. The results demonstrated the huge effect of counter ion on all properties. The hybridization values, obtained from the NBO calculations, showed that xenon mostly used pure p orbital in their bonds, especially in Xe-F bond. Calculated binding energies (Hb) and (Gb) indicated that the best anions for PFF are OH-, F-, BH-4 and OAc-. Moreover, the variations of HOMO and LUMO energies and the reactivity parameters have been investigated for all structures. The results of QTAIM calculations confirmed the covalent nature of Xe-C bond and the electrostatic nature of other xenon bonds. Finally, IR frequencies, NMR chemical shifts and NMR coupling constants were calculated to examine the effect of counter ion on the spectral properties of studied structures.

  8. Time- and Space-Resolved SAXS Experiments Inform on Phase Transition Kinetics in Hydrated, Liquid-Crystalline Films of Polyion-Surfactant Ion "Complex Salts".

    Science.gov (United States)

    Li, Joaquim; Gustavsson, Charlotte; Piculell, Lennart

    2016-05-24

    Detailed time- and space-resolved SAXS experiments show the variation with hydration of liquid crystalline structures in ethanol-cast 5-80 μm thick films of polyion-surfactant ion "complex salts" (CS). The CS were dodecyl- (C12) or hexadecyl- (C16) trimethylammonium surfactants with polyacrylate (DP 25 or 6000) counter-polyions. The experiments were carried out on vertical films in humid air above a movable water bath, so that gradients of hydration were generated, which could rapidly be altered. Scans over different positions along a film, kept fixed relative to the bath, showed that the surfactant aggregates of the various liquid-crystalline CS structures grow in cross-sectional area with decreasing hydration. This behavior is attributed to the low water content. Studies of films undergoing rapid dehydration, made possible by the original experimental setup, gave strong evidence that some of the investigated systems remain kinetically trapped for minutes in a nonequilibrium Pm3n micellar cubic phase before switching to the equilibrium P6mm 2D hexagonal phase. Both the length of the polyion and the length of the surfactant hydrocarbon "tail" affect the kinetics of the phase transition. The slowness of the cubic-to-hexagonal structural transition is attributed to the fact that it requires major rearrangements of the polyions and surfactant ions relative to each other. By contrast, other structure changes, such as between the hexagonal and rectangular phases, were observed to occur much more rapidly. PMID:27153140

  9. Prediction and analysis of the structure of hydrated Mn2+, V2+, Ti3 and Cr3 ions by means of the MD simulation methods

    International Nuclear Information System (INIS)

    Classical Molecular dynamics (MD) and hybrid Quantum/Molecular Mechanics-Molecular Dynamics (QM/MM-MD) simulations have been performed to investigate structural properties of Mn(II), V(II), Cr(III) and Ti(III) cations in aqueous solution. The first hydration sphere in QM/MM-MD simulations is treated quantum mechanically, while the rest of the system is described by classical analytical two- and three-body potentials. The results obtained for the first hydration shell from this method are in agreement with experimental data, showing 100 % of 6 fold coordination around the ion in all cases. The results prove that non/additive contributions are mandatory for an accurate description of ion hydration. Within the QM/MM method, the inclusion of a perturbation field describing the remaining system was shown to be an accurate tool for evaluating the first shell structure, and thus to be a good alternative for systems, where the construction of a three-body correction function is difficult or too time-consuming. (author)

  10. Chloral Hydrate

    Science.gov (United States)

    Chloral hydrate, a sedative, is used in the short-term treatment of insomnia (to help you fall asleep and ... Chloral hydrate comes as a capsule and liquid to take by mouth and as a suppository to insert rectally. ...

  11. Hydration of the trivalent lanthanide ion 152Eu (III) in aqueous solutions at 298 K and similarity with the trivalent transplutonium element ion 241Am (III)

    International Nuclear Information System (INIS)

    Ionic self-diffusion coefficients data for 152Eu (III) and 241Am (III) are reported for concentrations of a supporting electrolyte of Gd(NO3)3-HNO3 or Nd(ClO4)3-HClO4 aqueous solutions up to 1.14 mol.L-1 at 2 C. The open-end capillary method (O.E.C.M.) is used for the determination of the ionic self-diffusion coefficients at pH = 2.50 labelled with tracers 152Eu (III) and 241Am (III). The fitting in polynomial forms of the experimental self-diffusion coefficients versus the square root of the ionic strength : - permits a comparison between the limiting diffusion coefficient value against the square root of the ionic strength and the limiting coefficients at infinite dilute solutions taken from conductimetric measurements in the literature using the Nernst-Einstein expression. - shows that the variation of D versus the square root of supporting electrolyte concentration is not linear in dilute solution. The divergence to the Onsager limiting law starts from 10-3 M and we aim to extend the validity range up to 0.2 M or more, by proposition of semi-empirical model with one adjustable parameter b. A study of Walden's law behaviour at variable concentrations can provide an interesting discussion for an eventual expression if the parameter b. The similarity in the ionic transport process (4f and 5f elements) leads us to conclude as a further consequence, it may be argued that of 152Eu (III) and 241Am (III) ions have the same hydration as a tripositive ion (with a comparable ionic radius) in the absence of hydrolysis, association and complexing (by choice of an acidic medium at pH 2.50)

  12. Effect of hydrogen bonding and complexation with metal ions on the fluorescence of luotonin A.

    Science.gov (United States)

    Miskolczy, Zsombor; Biczók, László

    2013-05-01

    Fluorescence characteristics of a biologically active natural alkaloid, luotonin A (LuA), were studied by steady-state and time-resolved spectroscopic methods. The rate constant of the radiationless deactivation from the singlet-excited state diminished by more than one order of magnitude when the solvent polarity was changed from toluene to water. Dual emission was found in polyfluorinated alcohols of large hydrogen bond donating ability due to photoinitiated proton displacement along the hydrogen bond. In CH2Cl2, LuA produced both 1 : 1 and 1 : 2 hydrogen-bonded complexes with hexafluoro-2-propanol (HFIP) in the ground state. Photoexcitation of the 1 : 2 complex led to protonated LuA, whose fluorescence appeared at a long wavelength. LuA served as a bidentate ligand forming 1 : 1 complexes with metal ions in acetonitrile. The stability of the complexes diminished in the series of Cd(2+) > Zn(2+) > Ag(+), and upon competitive binding of water to the metal cations. The effect of chelate formation on the fluorescent properties was revealed. PMID:23487318

  13. Marked influence of the nature of the chemical bond on CP-violating signature in molecular ions HBr+ and HI+

    International Nuclear Information System (INIS)

    Heavy polar molecules offer a great sensitivity to the electron electric dipole moment (EDM). To guide emerging searches for EDMs with molecular ions, we estimate the EDM-induced energy corrections for hydrogen halide ions HBr+ and HI+ in their respective ground X 2Π3/2 states. We find that the energy corrections due to EDM for the two ions differ by an unexpectedly large factor of 15. We demonstrate that a major part of this enhancement is due to a dissimilarity in the nature of the chemical bond for the two ions: the bond that is nearly of ionic character in HBr+ exhibits predominantly a covalent nature in HI+. We conclude that because of this enhancement the HI+ ion may be a potentially competitive candidate for the EDM search

  14. Ion beam effects on the hydrogenated bonds of amorphous silicon carbide

    International Nuclear Information System (INIS)

    Ion irradiation of amorphous hydrogenated silicon carbide films introduces additional disorder into the films and leads to chemical modifications. These effects were monitored using Infrared, UV-visible optical and Raman spectroscopies. Samples were prepared by plasma enhanced chemical vapour deposition (PECVD), then irradiated with 300 keV Ar+ to fluences ranging from 5x1013 to 1x1015 cm-2. The hydrogen concentration was determined by elastic recoil detection analysis using 2.0 MeV He+ beam. After ion irradiation, the absorption coefficient in the UV-visible energy range was observed to increase by an order of magnitude, while the optical energy gap decreases from 3.2 eV to 2.0 eV. These changes are due to the formation of carbon clusters, as evidenced by the carbon yield in Raman measurements. Infrared spectra indicate that this excess of carbon atoms results from the breaking of CHn bonds in the as-grown film and by a concomitant decrease in the hydrogen concentration. In addition, defects created by ion bombardment change the oscillator strength of the Si-H vibrational modes

  15. Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin, E-mail: gaoyq@pku.edu.cn [Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering and Biodynamic Optical Imaging Center, Peking University, Beijing 100871 (China)

    2015-12-14

    In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics.

  16. Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

    International Nuclear Information System (INIS)

    In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics

  17. Collecting high-order interactions in an effective pairwise intermolecular potential using the hydrated ion concept: The hydration of Cf{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Galbis, Elsa; Pappalardo, Rafael R.; Marcos, Enrique Sánchez, E-mail: sanchez@us.es [Departmento de Química Física, Universidad de Sevilla, 41012 Seville (Spain); Hernández-Cobos, Jorge [Instituto de Ciencias Físicas, UNAM, Apartado Postal 48-3, 62251 Cuernavaca (Mexico)

    2014-06-07

    This work proposes a new methodology to build interaction potentials between a highly charged metal cation and water molecules. These potentials, which can be used in classical computer simulations, have been fitted to reproduce quantum mechanical interaction energies (MP2 and BP86) for a wide range of [M(H{sub 2}O){sub n}]{sup m+}(H{sub 2}O){sub ℓ} clusters (n going from 6 to 10 and ℓ from 0 to 18). A flexible and polarizable water shell model (Mobile Charge Density of Harmonic Oscillator) has been coupled to the cation-water potential. The simultaneous consideration of poly-hydrated clusters and the polarizability of the interacting particles allows the inclusion of the most important many-body effects in the new polarizable potential. Applications have been centered on the californium, Cf(III) the heaviest actinoid experimentally studied in solution. Two different strategies to select a set of about 2000 structures which are used for the potential building were checked. Monte Carlo simulations of Cf(III)+500 H{sub 2}O for three of the intermolecular potentials predict an aquaion structure with coordination number close to 8 and average R{sub Cf−−O} in the range 2.43–2.48 Å, whereas the fourth one is closer to 9 with R{sub Cf−−O} = 2.54 Å. Simulated EXAFS spectra derived from the structural Monte Carlo distribution compares fairly well with the available experimental spectrum for the simulations bearing 8 water molecules. An angular distribution similar to that of a square antiprism is found for the octa-coordination.

  18. Versatile micropipette technology based on deep reactive ion etching and anodic bonding for biological applications

    International Nuclear Information System (INIS)

    A novel, versatile and robust technology to manufacture transparent micropipettes, suitable for biological applications, is presented here. Up to three deep reactive ion etchings have been included in the manufacturing process, providing highly controlled geometry of reservoirs, connection cavities and inlet ports. Etching processes have been used for the definition of chip and reservoir and for nozzle release. Additionally, special design considerations have been developed to facilitate micro-to-macro fluidic connections. Implementation of anodic bonding to seal a glass substrate to the fluidic structure etched on Si, allowed observation of the flow inside the reservoir. Flow tests have been conducted by filling channels with different fluids. Flow was observed under an optical microscope, both during capillary filling and also during pumping. Dispensing has been demonstrated by functionalizing the surface of an AFM cantilever. Mechanical tests performed by piercing live mouse cells with FIB-sharpened micropipettes suggest the design is sturdy for biological piercing applications

  19. Correlation between the paramagnetic resonance parameters and the chemical bond: transition metals ions and muonium

    International Nuclear Information System (INIS)

    In the scope of the study on the paramagnetic resonance spectra of a point defect in a crystal, a method for evaluating the spin Hamiltonian coefficients is proposed. The approach is based on the study of correlation functions. Simple equations between the crystal chemical bonds and the spectroscopic discrimination factors are obtained. The investigation carried out on cations and anions showed the importance of the local analysis. Moreover, it allowed the muonium analysis to be extended to the transition metal ions. The experimental device consists in an electron paramagnetic resonance (EPR) spectrometer computer-aided unit, enabling the EPR automatic display by means of a computer-aided design system. The experimental results of the BaF2 characterization and the study of Mn+2 in CuBr and CuI are reported

  20. Mechanical properties considerations for use of epoxy insulators and bonded joints in neutral beam ion sources

    International Nuclear Information System (INIS)

    In the Doublet III (D-III) neutral beam injectors, cast, rigid-epoxy insulators are joined to the AISI 304 stainless steel corona rings with semi-rigid epoxy adhesive. Selected mechanical properties of these materials were measured between 110C and 650C, well below the material temperature limits, to identify the trends and to confirm adequate mechanical strength for the insulators. Significant creep deformation was measured at 220C. Empirical relationships were developed to predict long term strain over a range of stress and temperature of design interest. Delayed failure was observed in bonded specimens at stress levels well below the ultimate strength. In order to protect the D-III neutral beam ion source epoxy from elevated temperature effects, a chill was installed in the cooling water circuit. Outgassing measurements of the insulator epoxy were made and found to be low and primarily H2O

  1. The anti-supercooling effect of surface-modified nano-scaled SiO2 in hydrated salts phase transition system

    International Nuclear Information System (INIS)

    Phase change characteristics of hydrate salt were analyzed for a system consisting of three types of SiO2 nano-particles doped phase change materials (PCMs). By using the three nano-particles of Aerosol SiO2, RNS-A SiO2 and Liquid phase SiO2, the surface effect of the interaction between nano-particles and hydrate salts was investigated. The time-temperature curves and Differential Scanning Calorimeter (DSC) testing results showed that Aerosol SiO2 had the most effective and stable performance as the nucleators for hydrate salts. The analysis of FT-IR showed that there were strong characteristic hydroxyl bonds on the surface of Aerosol SiO2. And the designed hydroxyl controllable silica gel system could prove the effect of hydroxyl bonds on suppressing supercooling of hydrate salts. It was concluded that supercooling of hydrate salts could be easily suppressed by the nano-additives with high specific surface area and strong polar hydroxyls in the surface. The ion-exchange attraction between hydroxyls and hydrate salts might mainly result in the supersaturation of hydrate salts in the interface of nano-particles. And then the supercooling of hydrate salts could be suppressed. The theoretical analysing model based on interionic attraction is a novel approach for investigating the nucleation of hydrate salts. And this result might provide a potential low-cost approach for the applications of nano-additives in building energy storage and coolant.

  2. A Valence Bond Model for Aqueous Cu(II) and Zn(II) Ions in the AMOEBA Polarizable Force Field

    OpenAIRE

    Xiang, Jin Yu; Ponder, Jay W.

    2012-01-01

    A general molecular mechanics (MM) model for treating aqueous Cu2+ and Zn2+ ions was developed based on valence bond (VB) theory and incorporated into the AMOEBA polarizable force field. Parameters were obtained by fitting molecular mechanics energies to that computed by ab initio methods for gas phase tetra- and hexa-aqua metal complexes. Molecular dynamics (MD) simulations using the proposed AMOEBA-VB model were performed for each transition metal ion in aqueous solution and solvent coordin...

  3. Ion-induced secondary electron emission, optical and hydration resistant behavior of MgO, Mg–Mo–O and Mg–Ce–O thin films

    International Nuclear Information System (INIS)

    Optical transmittance, hydration resistance and secondary electron emission characteristics of e-beam evaporated pure and Mo- or Ce-containing MgO thin films have been investigated. While the increased grain size and pyramidal columnar morphology following incorporation of molybdenum and cerium in MgO are responsible for the excellent discharge characteristics, emergence of neutral {100} and {110} MgO surfaces preferentially give rise to high optical transmittance (∼ 92–100%) and stability against hydration. Further, addition of Mo (or Ce) in MgO causes significant increase in defect density which, in turn, enhances the photoluminescence (PL) emission from 5-, 4- and 3-coordination sites. The changes lead to lowering of the breakdown voltage and hence improvement in the secondary electron emission (SEE) efficiency. These facts have been supported by ion-induced SEE yield (γ) deduced from the a.c. breakdown voltage observed, taking neon as a discharge gas, and determined semi-empirically as well with Hagstrum's theory based on Auger neutralization process using (i) band offset parameters and surface band gap data derived from X-ray photoelectron spectroscopy signal and (ii) information of defect energy levels obtained from photoluminescence (PL) measurements. The experimental values of neon ion-induced SEE yield (γ) are found to be 0.35, 0.42 and 0.39 for MgO, Mg–Mo–O (x = 0.035) and Mg–Ce–O (x = 0.01) thin films, respectively. - Highlights: • Higher hydration resistance • Increased photoluminescence emission • Higher secondary electron emission

  4. Statistical Examination of the a and a + 1 Fragment Ions from 193 nm Ultraviolet Photodissociation Reveals Local Hydrogen Bonding Interactions

    Science.gov (United States)

    Morrison, Lindsay J.; Rosenberg, Jake A.; Singleton, Jonathan P.; Brodbelt, Jennifer S.

    2016-05-01

    Dissociation of proteins and peptides by 193 nm ultraviolet photodissociation (UVPD) has gained momentum in proteomic studies because of the diversity of backbone fragments that are produced and subsequent unrivaled sequence coverage obtained by the approach. The pathways that form the basis for the production of particular ion types are not completely understood. In this study, a statistical approach is used to probe hydrogen atom elimination from a + 1 radical ions, and different extents of elimination are found to vary as a function of the identity of the C-terminal residue of the a product ions and the presence or absence of hydrogen bonds to the cleaved residue.

  5. Ions colliding with clusters of fullerenes—Decay pathways and covalent bond formations

    International Nuclear Information System (INIS)

    We report experimental results for the ionization and fragmentation of weakly bound van der Waals clusters of n C60 molecules following collisions with Ar2+, He2+, and Xe20+ at laboratory kinetic energies of 13 keV, 22.5 keV, and 300 keV, respectively. Intact singly charged C60 monomers are the dominant reaction products in all three cases and this is accounted for by means of Monte Carlo calculations of energy transfer processes and a simple Arrhenius-type [C60]n+→C60++(n−1)C60 evaporation model. Excitation energies in the range of only ∼0.7 eV per C60 molecule in a [C60]13+ cluster are sufficient for complete evaporation and such low energies correspond to ion trajectories far outside the clusters. Still we observe singly and even doubly charged intact cluster ions which stem from even more distant collisions. For penetrating collisions the clusters become multiply charged and some of the individual molecules may be promptly fragmented in direct knock-out processes leading to efficient formations of new covalent systems. For Ar2+ and He2+ collisions, we observe very efficient C119+ and C118+ formation and molecular dynamics simulations suggest that they are covalent dumb-bell systems due to bonding between C59+ or C58+ and C60 during cluster fragmentation. In the Ar2+ case, it is possible to form even smaller C120−2m+ molecules (m= 2–7), while no molecular fusion reactions are observed for the present Xe20+ collisions

  6. Ions colliding with clusters of fullerenes-Decay pathways and covalent bond formations

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, F.; Zettergren, H.; Chen, T.; Gatchell, M.; Alexander, J. D.; Stockett, M. H.; Schmidt, H. T.; Cederquist, H. [Department of Physics, Stockholm University, S-106 91 Stockholm (Sweden); Rousseau, P.; Chesnel, J. Y.; Capron, M.; Poully, J. C.; Mery, A.; Maclot, S.; Adoui, L. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Universite de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen cedex 05 (France); Universite de Caen Basse-Normandie, Esplanade de la Paix, F-14032 Caen (France); Wang, Y.; Martin, F. [Departamento de Quimica, Modulo 13, Universidad Autonoma de Madrid, 28049 Madrid (Spain); Instituto Madrileno de Estudios Avanzados en Nanociencia (IMDEA-Nano), Cantoblanco, 28049 Madrid (Spain); Rangama, J.; Domaracka, A.; Vizcaino, V. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Universite de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen cedex 05 (France); and others

    2013-07-21

    We report experimental results for the ionization and fragmentation of weakly bound van der Waals clusters of n C{sub 60} molecules following collisions with Ar{sup 2+}, He{sup 2+}, and Xe{sup 20+} at laboratory kinetic energies of 13 keV, 22.5 keV, and 300 keV, respectively. Intact singly charged C{sub 60} monomers are the dominant reaction products in all three cases and this is accounted for by means of Monte Carlo calculations of energy transfer processes and a simple Arrhenius-type [C{sub 60}]{sub n}{sup +}{yields}C{sub 60}{sup +}+(n-1)C{sub 60} evaporation model. Excitation energies in the range of only {approx}0.7 eV per C{sub 60} molecule in a [C{sub 60}]{sub 13}{sup +} cluster are sufficient for complete evaporation and such low energies correspond to ion trajectories far outside the clusters. Still we observe singly and even doubly charged intact cluster ions which stem from even more distant collisions. For penetrating collisions the clusters become multiply charged and some of the individual molecules may be promptly fragmented in direct knock-out processes leading to efficient formations of new covalent systems. For Ar{sup 2+} and He{sup 2+} collisions, we observe very efficient C{sub 119}{sup +} and C{sub 118}{sup +} formation and molecular dynamics simulations suggest that they are covalent dumb-bell systems due to bonding between C{sub 59}{sup +} or C{sub 58}{sup +} and C{sub 60} during cluster fragmentation. In the Ar{sup 2+} case, it is possible to form even smaller C{sub 120-2m}{sup +} molecules (m= 2-7), while no molecular fusion reactions are observed for the present Xe{sup 20+} collisions.

  7. Distribution of calcium ions at the interface between resin bonding materials and tooth dentin. Use of commercially available adhesive systems.

    Science.gov (United States)

    Hanaizumi, Y; Maeda, T; Takano, Y

    1998-01-01

    It has been proposed that calcium ions play a key role in chemical (chelate) binding between the adhesive resin and dentin surface. However, no data is available concerning how calcium ions are distributed at the binding sites. The aim of this study is to demonstrate calcium ions at the resin-dentin interface by means of X-ray microanalysis and calcium ion-sensitive histochemical staining. The dentin surface in human teeth was ground by use of 240 grit silicon carbide abrasive paper under running water and treated with the dentin-primer and adhesive resin in Clearfil Liner Bond System or IMPERVA Bond System according to the manufacturer's instructions. After removing dentin matrix and isolating adhesive resin by the KOH-digestion method, one half of the samples were processed for scanning electron microscopy. The rest were embedded in Epon 812 and processed either for glyoxal bis (2-hydroxyanil) (GBHA) staining or transmission electron microscopy combined with X-ray microanalysis. Transmission electron microscopy revealed Ca-phosphate deposits at the bottom of the resin-impregnated layer. The adhesive resin above the resin-impregnated layer was amorphous and showed no precipitates of Ca-phosphate. GBHA displayed intense calcium reactions throughout the resin-impregnated layer and also moderate ones in the 10 microns (Clearfil Liner Bond System) or 30 microns (IMPERVA Bonding System) thick boundary zone of the adhesive resin as well as in the resin tags. These data are the first to offer a distinct localization of calcium ions within the adhesive resin at the dentin-resin interface. PMID:9800373

  8. The effect of working pressure on the chemical bond structure and hydrophobic properties of PET surface treated by N ion beams bombardment

    International Nuclear Information System (INIS)

    Polyethylene terephthalate (PET) surface was bombarded by N ion beams at room temperature. Varying the working pressure of the ion beams, PET surfaces with different composition and properties were obtained. Characterization by X-ray photoelectron spectrometry showed that only on film surface, ester bonds, especially C-O bonds, were broken and N element chemical bonded with C. The influence depth was less than 5 nm because of the lower ion energy (about 103 eV). Contact angle results revealed that with increasing the working pressure of ion beams, the contact angle of PET surface to pure water increased from 51 deg. to 130 deg.. With these results, one conclusion could be deduced that the hydrophilic and hydrophobic properties of PET surface could be influenced by N atom chemical bond with C, which in turn is controlled by the working pressure of N ion beams.

  9. Hydrogen bond-assisted aggregation-induced emission and application in the detection of the Zn(ii) ion.

    Science.gov (United States)

    Wang, Dan; Li, Shu-Mu; Li, Yu-Fei; Zheng, Xiang-Jun; Jin, Lin-Pei

    2016-05-28

    The compounds of 3-aminopyridine-2-carboxylic acid with K(+) (1) and Zn(2+) (2) were found to be AIE-active. The AIE behaviours could be attributed to the restriction of intramolecular rotation (RIR) and vibration (RIV) via hydrogen bonds, resulting in rigidity enhancement of the molecules. An AIE-based fluorescence turn on chemosensor for the Zn(ii) ion has been developed in aqueous media with high selectivity and sensitivity. PMID:27126357

  10. Gas Hydrates

    International Nuclear Information System (INIS)

    Gas hydrates are solid, similar to the ice and made up of rigid cages of water molecules, that they contain gas molecules, mainly methane, they can be formed and to remain stable to discharges pressures and relatively low temperatures, since present enough quantity of hydrocarbons is. The presence of the Gas Hydrates has been detected in high latitudes under the permafrost (Siberia and Alaska) and under the deep marine in silts of continental margins and elevations of the sea bottom (coast out California, Bearing Sea, Beaufort sea, coast out Newfoundland, Baltimore Canyon, Mexico Gulf and Colombian basin among other) its presence has also been postulated in intracratonics basins like in the Black and Caspio Sea. Gas hydrates have been known from 1810, but only in 1934 the first publication appeared (Hammer Schmidt) in connection with the gas piper line for the hydrates formation. The geologic occurrence is known from 1960 with the discovery for the Russian of Messoyakha Field (Siberia) and in 1972 for Arch-Exxon in the well Eilleen State 2 in Alaska. The quantity of gas present in the gas hydrates postulated in the world is considered that 18 x 1015 m3 could reach (6.5 x 105 American Quintillion cubic feet) the above-mentioned means that there would be more carbon in the gas hydrates than the acquaintance twice or estimated in the reservations of fossil fuels of the world and that this energy source could replace the world necessities until the X XI century. In Colombia two areas have been postulated with gas hydrates: Colombian basin in the Caribbean Sea and the Panama Basin

  11. Comment on ``Measurements of the hydration numbers for halide ions by the mass spectrometric method of field evaporation of ions out of solution'' [Chem. Phys. Lett. 242 (1995) 390

    Science.gov (United States)

    Symons, Martyn C. R.

    2000-08-01

    It has been suggested by Dunsyuryun, Karpov and Morozov that two different terms should be used to describe the solvation of halide ions in aqueous solutions. The term co-ordination number gives the primary `solvation number' (ca. 6), whilst the term hydration number gives the number of water molecules that stay co-ordinated to the anions as they move through the liquid (ca. 2). Here it is suggested that since these two terms are widely used to mean the same thing, it is better not to change one of them. It is also suggested that the number of water molecules that move with ions is variable and ill defined and that it is not appropriate to specify a precise number for this.

  12. In Situ Binding Sb Nanospheres on Graphene via Oxygen Bonds as Superior Anode for Ultrafast Sodium-Ion Batteries.

    Science.gov (United States)

    Wan, Fang; Guo, Jin-Zhi; Zhang, Xiao-Hua; Zhang, Jing-Ping; Sun, Hai-Zhu; Yan, Qingyu; Han, Dong-Xue; Niu, Li; Wu, Xing-Long

    2016-03-30

    Graphene incorporation should be one effective strategy to develop advanced electrode materials for a sodium-ion battery (SIB). Herein, the micro/nanostructural Sb/graphene composite (Sb-O-G) is successfully prepared with the uniform Sb nanospheres (∼100 nm) bound on the graphene via oxygen bonds. It is revealed that the in-situ-constructed oxygen bonds play a significant role on enhancing Na-storage properties, especially the ultrafast charge/discharge capability. The oxygen-bond-enhanced Sb-O-G composite can deliver a high capacity of 220 mAh/g at an ultrahigh current density of 12 A/g, which is obviously superior to the similar Sb/G composite (130 mAh/g at 10 A/g) just without Sb-O-C bonds. It also exhibits the highest Na-storage capacity compared to Sb/G and pure Sb nanoparticles as well as the best cycling performance. More importantly, this Sb-O-G anode achieves ultrafast (120 C) energy storage in SIB full cells, which have already been shown to power a 26-bulb array and calculator. All of these superior performances originate from the structural stability of Sb-O-C bonds during Na uptake/release, which has been verified by ex situ X-ray photoelectron spectroscopies and infrared spectroscopies. PMID:26960386

  13. Retention of alkali ions by hydrated low-pH cements: Mechanism and Na+/K+ selectivity

    International Nuclear Information System (INIS)

    Low-pH cements, also referred to as low-alkalinity cements, can be designed by replacing significant amounts of Portland cement by pozzolanic materials. Their pore solution is characterized by a pH near 11, and an alkali concentration much lower than that of Portland cement. This work investigates the retention of sodium and potassium by a hydrated low-pH cement comprising 60% Portland cement and 40% silica fume. It is shown that sorption of potassium is higher than that of sodium and mainly results from counterion charge balancing of the C-S-H negative surface charge. To explain the greater retention of potassium compared to sodium, it is postulated that potassium, unlike sodium, may enter the interlayer of C-S-H to compensate the negative charges in the interlayer, in addition to the external surfaces. This assumption is supported by structural characterization of C-S-H using X-ray diffraction

  14. Investigation of the potential of silica-bonded macrocyclic ligands for separation of metal ions from nuclear waste

    International Nuclear Information System (INIS)

    This report describes the testing of some novel separations materials known as SuperLig trademark materials for their ability to separate efficiently and selectively certain metal ions from a synthetic, nonradioactive nuclear waste solution. The materials, developed and patented by IBC Advanced Technologies, are highly selective macrocyclic ligands that have been covalently bonded to silica gel. The SuperLig trademark materials that were tested are: (1) SuperLig trademark 601 for barium (Ba2+) and strontium (Sr2+) separation, (2) SuperLig trademark 602 for cesium (Cs+) and rubidium (Rb+) separation, (3) SuperLig trademark 27 for palladium (Pd2+) separation, and (4) SuperLig trademark II for silver (Ag+) and ruthenium (Ru3+) separation. Our observations show that the technology for separating metal ions using silica-bonded macrocycles is essentially sound and workable to varying degrees of success that mainly depend on the affinity of the macrocycle for the metal ion of interest. It is expected that ligands will be discovered or synthesized that are amenable to separating metal ions of interest using this technology. Certainly more development, testing, and evaluation is warranted. 3 figs., 11 tabs

  15. A theoretical study on 2‧-deoxyguanosine and its mono-hydration: Intermolecular hydrogen bonding weakening induces the fluorescence strengthening

    Science.gov (United States)

    Liu, Yufang; Yang, Yonggang; Jiang, Kai; Shi, Deheng; Sun, Jinfeng

    2012-03-01

    The time-dependent density functional theory (TDDFT) method has been applied to investigate the excited states of 2'-deoxyguanosine (2'-dG) and its monohydrated complex (2'-dG-W1). The intramolecular hydrogen bonding N3⋯H2-O2 of the keto conformer is weakened in the S1 state, while that of the enol conformers is strengthened. The two intermolecular hydrogen bondings of 2'-dG-W1 are weakened in the S1 state, while N3⋯H2-O2 gets more strengthened. Moreover, the fluorescence of 2'-dG-W1 is shifted to higher frequencies compared with that of monomer 2'-deoxyguanosine. Therefore, it is concluded that the weakening of intermolecular hydrogen bonding in the S1 state induces fluorescence strengthening of 2'-deoxyguanosine.

  16. Calcium Aluminate Cement Hydration Model

    Directory of Open Access Journals (Sweden)

    Matusinović, T.

    2011-01-01

    Full Text Available Calcium aluminate cement (AC is a very versatile special cement used for specific applications. As the hydration of AC is highly temperature dependent, yielding structurally different hydration products that continuously alter material properties, a good knowledge of thermal properties at early stages of hydration is essential. The kinetics of AC hydration is a complex process and the use of single mechanisms models cannot describe the rate of hydration during the whole stage.This paper examines the influence of temperature (ϑ=5–20 °C and water-to-cement mass ratio (mH /mAC = 0.4; 0.5 and 1.0 on hydration of commercial iron-rich AC ISTRA 40 (producer: Istra Cement, Pula, Croatia, which is a part of CALUCEM group, Figs 1–3. The flow rate of heat generation of cement pastes as a result of the hydration reactions was measured with differential microcalorimeter. Chemically bonded water in the hydrated cement samples was determined by thermo-gravimetry.Far less heat is liberated when cement and water come in contact for the first time, Fig. 1, than in the case for portland cement (PC. Higher water-to-cement ratio increases the heat evolved at later ages (Fig. 3 due to higher quantity of water available for hydration. A significant effect of the water-to-cement ratio on the hydration rate and hydration degree showed the importance of water as being the limiting reactant that slows down the reaction early. A simplified stoichiometric model of early age AC hydration (eq. (8 based on reaction schemes of principal minerals, nominally CA, C12A7 and C4AF (Table 1, was employed. Hydration kinetics after the induction period (ϑ < 20 °C had been successfully described (Fig. 4 and Table 2 by a proposed model (eq. (23 which simultaneously comprised three main mechanisms: nucleation and growth, interaction at phase boundary, and mass transfer. In the proposed kinetic model the nucleation and growth is proportional to the amount of reacted minerals (eq

  17. Efficient Covalent Bond Formation in Gas-Phase Peptide-Peptide Ion Complexes with the Photoleucine Stapler

    Science.gov (United States)

    Shaffer, Christopher J.; Andrikopoulos, Prokopis C.; Řezáč, Jan; Rulíšek, Lubomír; Tureček, František

    2016-04-01

    Noncovalent complexes of hydrophobic peptides GLLLG and GLLLK with photoleucine (L*) tagged peptides G(L* n L m )K (n = 1,3, m = 2,0) were generated as singly charged ions in the gas phase and probed by photodissociation at 355 nm. Carbene intermediates produced by photodissociative loss of N2 from the L* diazirine rings underwent insertion into X-H bonds of the target peptide moiety, forming covalent adducts with yields reaching 30%. Gas-phase sequencing of the covalent adducts revealed preferred bond formation at the C-terminal residue of the target peptide. Site-selective carbene insertion was achieved by placing the L* residue in different positions along the photopeptide chain, and the residues in the target peptide undergoing carbene insertion were identified by gas-phase ion sequencing that was aided by specific 13C labeling. Density functional theory calculations indicated that noncovalent binding to GL*L*L*K resulted in substantial changes of the (GLLLK + H)+ ground state conformation. The peptide moieties in [GL*L*LK + GLLLK + H]+ ion complexes were held together by hydrogen bonds, whereas dispersion interactions of the nonpolar groups were only secondary in ground-state 0 K structures. Born-Oppenheimer molecular dynamics for 100 ps trajectories of several different conformers at the 310 K laboratory temperature showed that noncovalent complexes developed multiple, residue-specific contacts between the diazirine carbons and GLLLK residues. The calculations pointed to the substantial fluidity of the nonpolar side chains in the complexes. Diazirine photochemistry in combination with Born-Oppenheimer molecular dynamics is a promising tool for investigations of peptide-peptide ion interactions in the gas phase.

  18. Gas Hydrates

    International Nuclear Information System (INIS)

    The hydrates of gas are solid, similar to the ice, made up of rigid cages of molecules of water that they contain molecules of gas, mainly methane. They can be formed and to remain stable to discharges pressures and relatively low temperatures, since present enough quantity of hydrocarbons. The quantity of present gas in the hydrates of gas postulated in the world is considered that could reach 18 x 10 15 m3 (6.5 x 10 5 TCF - American trillion cubic feet). The above mentioned means that there would be more carbon in the hydrates of gas than the acquaintance twice or estimated in the reservations of fossil fuels of the world. And that this energy source could replace the world necessities until the X XI Century. In Colombia two areas have been postulated with hydrates of Gas: the Colombian basin in the Caribbean Sea and the Panama Basin in the Pacific Ocean, with dear reservations of gas that overcome 120 and 300 TCF respectively. These quantities are very favorably compared with the conventional Colombian reservations of gas of only 11 TCF

  19. Geomechanical Modeling of Gas Hydrate Bearing Sediments

    Science.gov (United States)

    Sanchez, M. J.; Gai, X., Sr.

    2015-12-01

    This contribution focuses on an advance geomechanical model for methane hydrate-bearing soils based on concepts of elasto-plasticity for strain hardening/softening soils and incorporates bonding and damage effects. The core of the proposed model includes: a hierarchical single surface critical state framework, sub-loading concepts for modeling the plastic strains generally observed inside the yield surface and a hydrate enhancement factor to account for the cementing effects provided by the presence of hydrates in sediments. The proposed framework has been validated against recently published experiments involving both, synthetic and natural hydrate soils, as well as different sediments types (i.e., different hydrate saturations, and different hydrates morphologies) and confinement conditions. The performance of the model in these different case studies was very satisfactory.

  20. Hydration thermodynamics of pyrochlore structured oxides from TG and first principles calculations.

    Science.gov (United States)

    Bjørheim, Tor S; Besikiotis, Vasileios; Haugsrud, Reidar

    2012-11-21

    In this contribution we investigate trends in the defect chemistry and hydration thermodynamics of rare-earth pyrochlore structured oxides, RE(2)X(2)O(7) (RE = La-Lu and X = Ti, Sn, Zr and Ce). First principles density functional theory (DFT) calculations have been performed to elucidate trends in the general defect chemistry and hydration enthalpy for the above-mentioned series. Further, to justify the use of such theoretical methods, the hydration properties of selected compositions were studied by means of thermogravimetric measurements. Both DFT calculations and TG measurements indicate that the hydration enthalpy becomes less exothermic with decreasing radii of RE ions within the RE(2)X(2)O(7) series (X = Ti, Sn, Zr and Ce), while it is less dependent on the X site ion. The observed hydration trends are discussed in connection with trends in the stability of both protons and oxygen vacancies and changes in the electronic density of states and bonding environment through the series. Finally, the findings are discussed with respect to existing correlations for other binary and ternary oxides. PMID:23001186

  1. Kinetics and mechanism of elementary act of electron transfer in alcohol radicals oxidation by hydrated trivalent iron ions

    International Nuclear Information System (INIS)

    The method of competing reactions has been employed to measure the velocity constants of one-electron oxidation of oxyalkyl radicals by Fe(3) ions upon γ-radiolysis of aqueous methanol, ethanol and isopropanol in the presence of Fe(3) ions and tetranitromethane. It is shown that if such factors as non-adiabaticity, reorganization of intermolecular degrees of freedom, core tunnelling effects and spin effects are taken into account, the quantum theory of outerspheric electron transfer in polar media provides for quantitative agreement of the measured velocity constants with experimental results

  2. Cryogenic Ion Mobility-Mass Spectrometry: Tracking Ion Structure from Solution to the Gas Phase.

    Science.gov (United States)

    Servage, Kelly A; Silveira, Joshua A; Fort, Kyle L; Russell, David H

    2016-07-19

    Electrospray ionization (ESI) combined with ion mobility-mass spectrometry (IM-MS) is adding new dimensions, that is, structure and dynamics, to the field of biological mass spectrometry. There is increasing evidence that gas-phase ions produced by ESI can closely resemble their solution-phase structures, but correlating these structures can be complicated owing to the number of competing effects contributing to structural preferences, including both inter- and intramolecular interactions. Ions encounter unique hydration environments during the transition from solution to the gas phase that will likely affect their structure(s), but many of these structural changes will go undetected because ESI-IM-MS analysis is typically performed on solvent-free ions. Cryogenic ion mobility-mass spectrometry (cryo-IM-MS) takes advantage of the freeze-drying capabilities of ESI and a cryogenically cooled IM drift cell (80 K) to preserve extensively solvated ions of the type [M + xH](x+)(H2O)n, where n can vary from zero to several hundred. This affords an experimental approach for tracking the structural evolution of hydrated biomolecules en route to forming solvent-free gas-phase ions. The studies highlighted in this Account illustrate the varying extent to which dehydration can alter ion structure and the overall impact of cryo-IM-MS on structural studies of hydrated biomolecules. Studies of small ions, including protonated water clusters and alkyl diammonium cations, reveal structural transitions associated with the development of the H-bond network of water molecules surrounding the charge carrier(s). For peptide ions, results show that water networks are highly dependent on the charge-carrying species within the cluster. Specifically, hydrated peptide ions containing lysine display specific hydration behavior around the ammonium ion, that is, magic number clusters with enhanced stability, whereas peptides containing arginine do not display specific hydration around the

  3. The application of Guided Ion Beam Tandem Mass Spectrometer; Bond dissociation energies of bare and ligated copper group cluster anions

    International Nuclear Information System (INIS)

    Threshold energies, fragmentation patterns, and integral cross sections for the reactions of collision induced dissociations of bare and ligated copper group cluster anions are determined using a Guided Ion Beam Tandem Mass Spectrometer (GIB-MS). The bond breaking patterns for the copper cluster anions show dramatic even/odd tendencies, e.g., all copper group anions generate as the predominant reaction product, Carbon monoxide is weakly bound to copper group cluster anions. Cohesive energies of the bare copper and silver cluster anions are determined and exhibit a good correspondence with estimate cohesive energies by the model of Miedema.

  4. Study of the action of phosphate ions contained in the mixing water on the hydration of a Portland cement; Etude de l'action des phosphates presents dans l'eau de gachage sur l'hydratation d'un ciment Portland

    Energy Technology Data Exchange (ETDEWEB)

    Benard, Ph

    2005-12-15

    Cementation is considered as the most attractive solution for the conditioning of low and intermediate radioactive wastes. The species contained in these wastes can strongly influence the reactivity of the cement pastes, it is in particular the case of the ortho-phosphate ions which are found in the evaporation concentrates. The aim of our work was to determine the influence of these ions on the hydration and the rheological properties of the cement pastes at early age as well as the mechanical and physical properties on the hardened material. (author)

  5. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    borehole samples and by its characteristic responses in seismic- reflection profiles and oil-well electric logs. Beneath the ocean, gas hydrate exists where water depths exceed 500 meters (depending on sea bottom temperature), and it can occur within a... layer of sediment as much as hundreds of meters thick directly beneath the sea floor; the base of the layer is limited by geothermal gradient (increasing temperature). At high latitudes, it exists in association with permafrost. Need for study...

  6. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates.

    Science.gov (United States)

    Miskowiec, Andrew; Kirkegaard, Marie C; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W; Trowbridge, Lee; Rondinone, Adam; Anderson, Brian

    2015-12-10

    We report a novel production method for uranium oxyfluoride [(UO2)7F14(H2O)7]·4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl fluoride, UO2F2, through the gas phase at ambient temperatures followed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7]·4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous structure), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielastic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform restricted motion on a length scale commensurate with the O-H bond (r = 0.92 Å). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps(-1)) than their hydrogen-bonded partners (Dr = 28.7 ps(-1)). PMID:26575434

  7. 人工神经网络应用于金属离子水化能的研究%Study on the Hydration Energy of Metal Ions by Using Artificial Neural Network

    Institute of Scientific and Technical Information of China (English)

    杨兴华; 印春生; 蔡文生; 李伟; 潘忠孝

    2000-01-01

      采用函数连接型神经网络(FLN),以金属离子的电荷、半径、价电子结构、电负性及空价轨道数NE为输入参数,与51种已知金属离子水化能数据进行了定量关联,并用所建立的非线性FLN模型对32种金属离子的未知水化能作出了预报。%  Functional-link net (FLN), a single-layer neural network without the hidden neurons, is employed to estimate and predict the hydration energy of metallic ions, by using a set of atomic structural parameters, such as electric charges (Z), ionic radii (r), electron numbers in the valence layer (f, d, s), principal quantum numbers in the outer-shell (n), electronegativity (XP), and the number of s, p, d empty orbits in valence shell of the metallic ions(NE). The results obtained show a good relationship between the calculated and experimental hydration energy data with a fitting correlation coefficient 0.9995. Hydration energy data of 32 metallic ions lake of experimental data are predicted effectively with the trained FLN.

  8. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    Energy Technology Data Exchange (ETDEWEB)

    Soniat, Marielle; Rick, Steven W., E-mail: srick@uno.edu [Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148 (United States); Kumar, Revati [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70808 (United States)

    2015-07-28

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  9. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    International Nuclear Information System (INIS)

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface

  10. Analysis of molecular species of triacylglycerols from vegetable oils containing fatty acids with non-methylene-interrupted double bonds, by HPLC in the silver-ion mode

    Energy Technology Data Exchange (ETDEWEB)

    Joh, Y.; Kim, S. [Dong A Univ., Pusan (Korea, Republic of)

    1998-10-20

    The possibilities for application of silver ion HPLC to analysis of the triacylglycerols containing conjugate trienoic acids and {Delta}{sup 5}-polymethylene-interrupted acids and proportions of triacylglycerol fractions obtained by silver-ion HPLC from the seed oil of Momordica charantia double bonds were examined, respectively. The triacylglycerols of seed oils containing conjugate trienoic acids such as {alpha}-eleostearic acid (C{sub 18:3 9c,11t,13t}) and punicic acid (C{sub 18:3} {sub 9c,11t,13c}) were resolved by silver-ion HPLC. Fractions were fractionated on the basis of the number and configuration of double bonds in the species, and the elution profile is quite different from that of the species comprising exclusively saturated and unsaturated fatty acids with methylene-interrupted double bonds ; for instance, the species (DT(c2)) composed of one dienoic acid and two conjugate trienoic acids eluted much earlier than the species (D{sub 2}T{sub c}) composed of two dienoic acids and one conjugate trienoic acid, in spite of having larger number of double bonds. This means that the interaction of conjugate double bonds with silver ions is weaker than that of methylene-interrupted double bonds, presumably because of the delocalization of {pi}-electrons in conjugate double bonds. In this instance, the strength of interaction of a conjugate trienoic double bond system with silver ions seemed to be between that of methylene-interrupted dienoic and monoenoic double bond systems. Triacylglycerols of the seeds of Ginkgo biloba have been resolved by HPLC in the silver-ion mode according to the number and position of double bonds. In this instance, the strength of interaction between the {pi}-electrons of double bonds in the fatty acyl residues and silver ions is in the order; C{sub 18:3{omega}3}>C(20:3){Delta}{sup 5,11,14}C{sub 18:3}{Delta}{sup 5,9,12}>= C{sub 18:2{omega}6}>C{sub 18:2}{Delta}{sup 5,9}>C{sub 18:1{omega}9}>C{sub 18:1ome= ga7}. 49 refs., 2 figs., 2 tabs.

  11. Ion solvation and hydrogen bonding in Eu 3+-doped mono-urethanesil hybrids carrying pendant short polyether chains

    Science.gov (United States)

    Gonçalves, M. C.; de Zea Bermudez, V.; Ostrovskii, D.; Carlos, L. D.

    2002-06-01

    Sol-gel derived Eu 3+-doped materials based on a poly(oxyethylene)/siloxane hybrid host incorporating two coordinating functionalities (polymer ether- and cross-link carbonyl-type oxygen atoms) have been investigated by mid-infrared and Raman spectroscopies with the goal of elucidating the cation/polymer and cation/cross-link interactions and hydrogen bonding. The organic/inorganic matrix of these ormosils is composed of a siliceous backbone bonded through urethane groups to methyl end-capped polyether chains with approximately seven oxyethylene repeat units. This framework, called mono-urethanesil, has been doped with europium triflate, Eu(CF 3SO 3) 3. Xerogels with salt composition n (where n is the molar ratio of OCH 2CH 2 moieties per Eu 3+ ion) ranging from ∞ to 5 have been analyzed. The results obtained indicate that in the mono-urethanesils with n≥60 the Eu 3+ ions coordinate solely to the urethane carbonyl oxygen atoms. The first evidences of the complexation of the polyether chains to the cations have been found at a salt concentration that corresponds to n=40, that is considerably lower than the saturation level the carbonyl groups has attained (in theory at n=7). At a higher salt content (n<40), both types of cation coordination are apparent.

  12. Clinoenstatite coatings have high bonding strength, bioactive ion release, and osteoimmunomodulatory effects that enhance in vivo osseointegration.

    Science.gov (United States)

    Wu, Chengtie; Chen, Zetao; Wu, Qianju; Yi, Deliang; Friis, Thor; Zheng, Xuebin; Chang, Jiang; Jiang, Xinquan; Xiao, Yin

    2015-12-01

    A number of coating materials have been developed over past two decades seeking to improve the osseointegration of orthopedic metal implants. Despite the many candidate materials trialed, their low rate of translation into clinical applications suggests there is room for improving the current strategies for their development. We therefore propose that the ideal coating material(s) should possess the following three properties: (i) high bonding strength, (ii) release of functional ions, and (iii) favourable osteoimmunomodulatory effects. To test this proposal, we developed clinoenstatite (CLT, MgSiO3), which as a coating material has high bonding strength, cytocompability and immunomodulatory effects that are favourable for in vivo osteogenesis. The bonding strength of CLT coatings was 50.1 ± 3.2 MPa, more than twice that of hydroxyapatite (HA) coatings, at 23.5 ± 3.5 MPa. CLT coatings released Mg and Si ions, and compared to HA coatings, induced an immunomodulation more conducive for osseointegration, demonstrated by downregurelation of pro-inflammatory cytokines, enhancement of osteogenesis, and inhibition of osteoclastogenesis. In vivo studies demonstrated that CLT coatings improved osseointegration with host bone, as shown by the enhanced biomechanical strength and increased de novo bone formation, when compared with HA coatings. These results support the notion that coating materials with the proposed properties can induce an in vivo environment better suited for osseointegration. These properties could, therefore, be fundamental when developing high-performance coating materials. PMID:26318815

  13. Polyethylene oxide hydration in grafted layers

    Science.gov (United States)

    Dormidontova, Elena; Wang, Zilu

    Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

  14. On the electrolytic generation of hydrated electron

    International Nuclear Information System (INIS)

    Investigations on the electrolytic generation of hydrated electron in oxygenated as well as oxygen-free solutions at different pH were undertaken. Since sup(-e)aq is known to react rapidly with O2 yielding the transient O2- ion, the latter was looked for through its interaction with phosphite ions resulting in their oxidation near the cathode. It appears from the results that in electrolytic processes, the primary electron (esup(-)sub(cathode)) probably reacts directly with reactive solutes like oxygen, bypassing the hydration step. Data obtained in oxygen-free solutions, however, support the possible formation of hydrated electron at least in alkaline solutions. (author)

  15. Natural Gas Hydrates

    OpenAIRE

    Ersland, Geir

    2010-01-01

    The experimental set-up with the MRI monitoring apparatus was capable of forming large quantities of methane hydrates in sandstone pores and monitor hydrate growth patterns for various initial conditions. Spontaneous conversion of methane hydrate to carbon dioxide hydrate occurred when methane hydrate, in porous media, was exposed to liquid carbon dioxide. The MRI images did not detect any significant increase in signal in the hydrate saturated cores that would indicate the presence of free w...

  16. A valence bond model for aqueous Cu(II) and Zn(II) ions in the AMOEBA polarizable force field.

    Science.gov (United States)

    Xiang, Jin Yu; Ponder, Jay W

    2013-04-01

    A general molecular mechanics (MM) model for treating aqueous Cu(2+) and Zn(2+) ions was developed based on valence bond (VB) theory and incorporated into the atomic multipole optimized energetics for biomolecular applications (AMOEBA) polarizable force field. Parameters were obtained by fitting MM energies to that computed by ab initio methods for gas-phase tetra- and hexa-aqua metal complexes. Molecular dynamics (MD) simulations using the proposed AMOEBA-VB model were performed for each transition metal ion in aqueous solution, and solvent coordination was evaluated. Results show that the AMOEBA-VB model generates the correct square-planar geometry for gas-phase tetra-aqua Cu(2+) complex and improves the accuracy of MM model energetics for a number of ligation geometries when compared to quantum mechanical (QM) computations. On the other hand, both AMOEBA and AMOEBA-VB generate results for Zn(2+)-water complexes in good agreement with QM calculations. Analyses of the MD trajectories revealed a six-coordination first solvation shell for both Cu(2+) and Zn(2+) ions in aqueous solution, with ligation geometries falling in the range reported by previous studies. PMID:23212979

  17. Selective C–H bond activation of alkanes by gas-phase metal ions

    Czech Academy of Sciences Publication Activity Database

    Roithová, J.; Schröder, Detlef

    2010-01-01

    Roč. 110, č. 2 (2010), s. 1170-1211. ISSN 0009-2665 R&D Projects: GA AV ČR KJB400550704; GA ČR GA203/08/1487 Grant ostatní: European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : alkanes * C-H bond activation * density functional theory * mass spectrometry * matrix isolation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 33.033, year: 2010

  18. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    Science.gov (United States)

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cvačka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa. PMID:25701424

  19. Desalination utilizing clathrate hydrates (LDRD final report).

    Energy Technology Data Exchange (ETDEWEB)

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy (Sandia National Laboratories, Albuquerque, NM); Greathouse, Jeffery A. (Sandia National Laboratories, Albuquerque, NM); Majzoub, Eric H. (University of Missouri, Columbia, MO)

    2008-01-01

    show that R141b hydrate is stable at temperatures up to 265K, while the isomer hydrate is only stable up to 150K. Despite hydrogen bonding between guest and host, R141b molecules rotated freely within the water cage. The Raman spectrum of R141b in both the pure and hydrate phases was also compared with vibrational analysis from both computational methods. In particular, the frequency of the C-Cl stretch mode (585 cm{sup -1}) undergoes a shift to higher frequency in the hydrate phase. Raman spectra also indicate that this peak undergoes splitting and intensity variation as the temperature is decreased from 4 C to -4 C.

  20. Instantaneous, parameter-free methods to define a solute’s hydration shell

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Anupam [Heidelberg Institute for Theoretical Studies, Schloss-Wolfsbrunnenweg 35, 69118 Heidelberg (Germany); Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076 (India); Higham, Jonathan [Manchester Institute of Biotechnology, The University of Manchester, 131 Princess Street, Manchester M1 7DN (United Kingdom); School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Henchman, Richard H. [Heidelberg Institute for Theoretical Studies, Schloss-Wolfsbrunnenweg 35, 69118 Heidelberg (Germany); Manchester Institute of Biotechnology, The University of Manchester, 131 Princess Street, Manchester M1 7DN (United Kingdom); School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom)

    2015-12-21

    A range of methods are presented to calculate a solute’s hydration shell from computer simulations of dilute solutions of monatomic ions and noble gas atoms. The methods are designed to be parameter-free and instantaneous so as to make them more general, accurate, and consequently applicable to disordered systems. One method is a modified nearest-neighbor method, another considers solute-water Lennard-Jones overlap followed by hydrogen-bond rearrangement, while three methods compare various combinations of water-solute and water-water forces. The methods are tested on a series of monatomic ions and solutes and compared with the values from cutoffs in the radial distribution function, the nearest-neighbor distribution functions, and the strongest-acceptor hydrogen bond definition for anions. The Lennard-Jones overlap method and one of the force-comparison methods are found to give a hydration shell for cations which is in reasonable agreement with that using a cutoff in the radial distribution function. Further modifications would be required, though, to make them capture the neighboring water molecules of noble-gas solutes if these weakly interacting molecules are considered to constitute the hydration shell.

  1. Synthetic ion transporters that work with anion-π interactions, halogen bonds, and anion-macrodipole interactions.

    Science.gov (United States)

    Vargas Jentzsch, Andreas; Hennig, Andreas; Mareda, Jiri; Matile, Stefan

    2013-12-17

    The transport of ions and molecules across lipid bilayer membranes connects cells and cellular compartments with their environment. This biological process is central to a host of functions including signal transduction in neurons and the olfactory and gustatory sensing systems, the translocation of biosynthetic intermediates and products, and the uptake of nutrients, drugs, and probes. Biological transport systems are highly regulated and selectively respond to a broad range of physical and chemical stimulation. A large percentage of today's drugs and many antimicrobial or antifungal agents take advantage of these systems. Other biological transport systems are highly toxic, such as the anthrax toxin or melittin from bee venom. For more than three decades, organic and supramolecular chemists have been interested in developing new transport systems. Over time, curiosity about the basic design has evolved toward developing of responsive systems with applications in materials sciences and medicine. Our early contributions to this field focused on the introduction of new structural motifs with emphasis on rigid-rod scaffolds, artificial β-barrels, or π-stacks. Using these scaffolds, we have constructed selective systems that respond to voltage, pH, ligands, inhibitors, or light (multifunctional photosystems). We have described sensing applications that cover the three primary principles of sensor development: immunosensors that use aptamers, biosensors (an "artificial" tongue), and differential sensors (an "artificial" nose). In this Account, we focus on our recent interest in applying synthetic transport systems as analytical tools to identify the functional relevance of less common noncovalent interactions, anion-π interactions, halogen bonds, and anion-macrodipole interactions. Anion-π interactions, the poorly explored counterpart of cation-π interactions, occur in aromatic systems with a positive quadrupole moment, such as TNT or hexafluorobenzene. To observe

  2. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO{sub 2} hydrate equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Sabil, Khalik M., E-mail: khalik_msabil@petronas.com.m [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Universiti Teknologi PETRONAS, Chemical Engineering Programme, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Roman, Vicente R.; Witkamp, Geert-Jan [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Peters, Cor J., E-mail: C.J.Peters@tudelft.n [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Petroleum Institute, Chemical Engineering Program, Bu Hasa Building, Room 2207A, P.O. Box 2533, Abu Dhabi (United Arab Emirates)

    2010-03-15

    the strength of ionic-hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water network are the major factors that contribute to hydrate inhibition by electrolytes.

  3. Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

    International Nuclear Information System (INIS)

    The separation of minor actinides from high-level waste (HLW) remains a difficult problem. A wide series of compounds based on two cobalt bis(dicarbollide) ions [(1,2-C2B9H10)(1',2'-C2B9H11)-3,3'-Co(III)]- (COSAN) covalently bonded to a diglycolyl amide platform via diethyleneglycol connectors was prepared by reaction of the diglycolic acid dichloride with various ammonium derivatives of the ion COSAN with the aim to develop new class of extractants for trivalent radionuclides from acidic waste solutions. The extractants of general formulation [{(N,N-(8-CH2-CH2O)2-1,2-C2B9H10) (1',2'-C2B9H11)-3,3'-Co (N,N'-R)NCOCH2}2-O]Na2 differed in substitution on the amidic nitrogen (by e.g. butyl-, hexyl-, octyl-, t-octyl-, dodecyl-, benzyl-groups). Compounds were characterized by combination of 11B, 1H and 13C NMR spectroscopy, ESI-MS, HPLC, and TLC RF. The purity of all species was better than 98%. Most of the compounds proved to be very efficient extraction agents and enabled effective extraction of europium(III) and americium(III) from nitric acid solutions. The recovery of the trivalent radionuclides from the loaded organic phase was possible by using ammonium citrate or even better by using solution of ammonium citrate and ammonium DTPA (diethylenetriamine pentaacetate). (orig.)

  4. Phase diagram and magnetization structures of spin-3/2 bond-alternating Ising chains with single-ion anisotropy

    Science.gov (United States)

    Liu, Guang-Hua; Dou, Jun-Ya; Tian, Guang-Shan

    2016-02-01

    By the infinite time-evolving block decimation (iTEBD) algorithm, the magnetization process of the spin-3/2 bond-alternating Ising chain with single-ion anisotropy (D) is investigated. Magnetization plateaus including detailed magnetization structures of three different cases are uncovered, and three rich ground-state phase diagrams are explicitly determined. Especially, for the uniform antiferromagnetic case, a phase transition line at D=J, which divides the Mz=0 (Mz =1/2) plateau into two phases, are detected by the magnetization structure and the ground-state energy, and a updated phase diagram is proposed. Such a transition line was not recognized by the average magnetization previously. A same transition line (D=J) is also detected in the phase diagram of the antiferromagnetic-ferromagnetic alternating case. Magnetization plateaus are found to be easily induced for the classical Ising systems without quantum fluctuations, and the single-ion anisotropy plays a key role in the formation of Mz = 1/2 and 1 plateaus in the present model.

  5. Hydrate bearing clayey sediments: Formation and gas production concepts

    KAUST Repository

    Jang, Jaewon

    2016-06-20

    Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

  6. Collision-induced dissociation of fatty acid [M - 2H + Na]- ions: charge-directed fragmentation and assignment of double bond position.

    Science.gov (United States)

    Thomas, Michael C; Altvater, Jens; Gallagher, Thomas J; Nette, Geoffrey W

    2014-11-01

    The collision-induced dissociation (CID) of cationic fatty acid-metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid-sodium ion complexes, referred to as [M - 2H + Na] (-) ions. In the current manuscript, the CID behavior of these [M - 2H + Na] (-) ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the α-carbon in the formation of fatty acid [M - H + NaF](-) ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M - 2H + Na](-) ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon-carbon double bonds. In addition, CID of [M - 2H + Na](-) ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ∆(9,12,15)18:3, ∆(6,9,12)18:3, and ∆(5,8,11)18:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the α-carbon. PMID:25142324

  7. Physical properties of gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kliner, J.T.R.; Grozic, J.L.H. [Calgary Univ., AB (Canada)

    2003-07-01

    Gas hydrates are naturally occurring, solid crystalline compounds (clathrates) that encapsulate gas molecules inside the lattices of hydrogen bonded water molecules within a specific temperature-pressure stability zone. Estimates of the total quantity of available methane gas in natural occurring hydrates are based on twice the energy content of known conventional fossil fuels reservoirs. Accurate and reliable in-situ quantification techniques are essential in determining the economic viability of this potential energy yield, which is dependent upon several factors such as sensitivity of the temperature-pressure stability zone, sediment type, porosity, permeability, concentration/abundance of free gas, spatial distribution in pore spaces, specific cage occupancy, and the influence of inhibitors. Various techniques like acoustic P and S waves, time domain reflectometry, and electrical resistance have been used to analyze the quantity and spatial distribution of the gas hydrate samples. These techniques were reviewed and the results obtained in the course of gas hydrate research were presented. 34 refs., 8 figs.

  8. Investigation of the Ionic Hydration in Aqueous Salt Solutions by Soft X-ray Emission Spectroscopy.

    Science.gov (United States)

    Jeyachandran, Y L; Meyer, F; Benkert, A; Bär, M; Blum, M; Yang, W; Reinert, F; Heske, C; Weinhardt, L; Zharnikov, M

    2016-08-11

    Understanding the molecular structure of the hydration shells and their impact on the hydrogen bond (HB) network of water in aqueous salt solutions is a fundamentally important and technically relevant question. In the present work, such hydration effects were studied for a series of representative salt solutions (NaCl, KCl, CaCl2, MgCl2, and KBr) by soft X-ray emission spectroscopy (XES) and resonant inelastic soft X-ray scattering (RIXS). The oxygen K-edge XES spectra could be described with three components, attributed to initial state HB configurations in pure water, water molecules that have undergone an ultrafast dissociation initiated by the X-ray excitation, and water molecules in contact with salt ions. The behavior of the individual components, as well as the spectral shape of the latter component, has been analyzed in detail. In view of the role of ions in such effects as protein denaturation (i.e., the Hofmeister series), we discuss the ion-specific nature of the hydration shells and find that the results point to a predominant role of anions as compared to cations. Furthermore, we observe a concentration-dependent suppression of ultrafast dissociation in all salt solutions, associated with a significant distortion of intact HB configurations of water molecules facilitating such a dissociation. PMID:27442708

  9. Dynamics of hydrated starch saccharides

    International Nuclear Information System (INIS)

    We report here elastic neutron scattering data on glucose and on two of its polymeric forms: amylose and amylopectin. We have covered the hydration range from the dry state to about 0.6 g water/g dry saccharide. The data indicate, in all the analysed systems, the presence of a dynamic glass-like transition similar to that observed in hydrated proteins. The fact that this feature is observed also in a relatively small molecule like glucose confirms the hypothesis already put forward by other authors, that this transition in biomolecular species is essentially triggered and driven by the interaction of the macromolecule with the network of fluctuating H-bond of the solvent

  10. Dynamics of hydrated starch saccharides

    Science.gov (United States)

    Di Bari, M.; Deriu, A.; Albanese, G.; Cavatorta, F.

    2003-08-01

    We report here elastic neutron scattering data on glucose and on two of its polymeric forms: amylose and amylopectin. We have covered the hydration range from the dry state to about 0.6 g water/g dry saccharide. The data indicate, in all the analysed systems, the presence of a dynamic glass-like transition similar to that observed in hydrated proteins. The fact that this feature is observed also in a relatively small molecule like glucose confirms the hypothesis already put forward by other authors, that this transition in biomolecular species is essentially triggered and driven by the interaction of the macromolecule with the network of fluctuating H-bond of the solvent.

  11. Tetrahydrofuran Clathrate Hydrate Formation

    OpenAIRE

    Conrad, Heiko; Lehmkuhler, Felix; Sternemann, Christian; Sakko, Arto; Paschek, Dietmar; Simonelli, Laura; Huotari, Simo; Feroughi, Omid; Tolan, Metin; HÀmÀlÀinen, Keijo

    2009-01-01

    We report on the formation of tetrahydrofuran clathrate hydrate studied by x-ray Raman scattering measurements at the oxygen K edge. A comparison of x-ray Raman spectra measured from water-tetrahydrofuran mixtures and tetrahydrofuran hydrate at different temperatures supports stochastic hydrate formation models rather than models assuming hydrate precursors. This is confirmed by molecular dynamics simulations and density functional theory calculations of x-ray Raman spectra. In addition, chan...

  12. HYDRATION AND ENZYME ACTIVITY

    OpenAIRE

    Poole, P.

    1984-01-01

    Hydration induced conformation and dynamic changes are followed using a variety of experimental techniques applied to hen egg white lysozyme. These changes are completed just before the onset of enzyme activity, which occurs before all polar groups are hydrated, and before monolayer coverage is attained. We suggest that these hydration induced changes are necessary for the return of enzyme activity.

  13. High temperature stability, interface bonding, and mechanical behavior in (beta)-NiAl and Ni3Al matrix composites with reinforcements modified by ion beam enhanced deposition

    Science.gov (United States)

    Grummon, D. S.

    1993-01-01

    Diffusion-bonded NiAl-Al2O3 and Ni3Al-Al2O3 couples were thermally fatigued at 900 C for 1500 and 3500 cycles. The fiber-matrix interface weakened after 3500 cycles for the Saphikon fibers, while the Altex, PRD-166, and FP fibers showed little, if any, degradation. Diffusion bonding of fibers to Nb matrix is being studied. Coating the fibers slightly increases the tensile strength and has a rule-of-mixtures effect on elastic modulus. Push-out tests on Sumitomo and FP fibers in Ni aluminide matrices were repeated. Al2O3 was evaporated directly from pure oxide rod onto acoustically levitated Si carbide particles, using a down-firing, rod-fed electron beam hearth; superior coatings were subsequently produced using concurrent irradiation with 200-eV argon ion-assist beam. The assist beam produced adherent films with reduced tensile stresses. In diffusion bonding in B-doped Ni3Al matrices subjected to compressive bonding at 40 MPa at 1100 C for 1 hr, the diffusion barriers failed to prevent catastrophic particle-matrix reaction, probably because of inadequate film quality. AlN coatings are currently being experimented with, produced by both reactive evaporation and by N(+)-ion enhanced deposition. A 3-kW rod-fed electron-beam-heated evaporation source has been brought into operation.

  14. Gas hydrate and humans

    Science.gov (United States)

    Kvenvolden, K.A.

    2000-01-01

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

  15. Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

    Science.gov (United States)

    Sepehr, Fatemeh; Paddison, Stephen J

    2015-06-01

    Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane. PMID:25954916

  16. Exploitation of subsea gas hydrate reservoirs

    Science.gov (United States)

    Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge

    2016-04-01

    Natural gas hydrates are considered to be a potential energy resource in the future. They occur in permafrost areas as well as in subsea sediments and are stable at high pressure and low temperature conditions. According to estimations the amount of carbon bonded in natural gas hydrates worldwide is two times larger than in all known conventional fossil fuels. Besides technical challenges that have to be overcome climate and safety issues have to be considered before a commercial exploitation of such unconventional reservoirs. The potential of producing natural gas from subsea gas hydrate deposits by various means (e.g. depressurization and/or injection of carbon dioxide) is numerically studied in the frame of the German research project »SUGAR«. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into a numerical model. The physics of the process leads to strong non-linear couplings between hydraulic fluid flow, hydrate dissociation and formation, hydraulic properties of the sediment, partial pressures and seawater solution of components and the thermal budget of the system described by the heat equation. This paper is intended to provide an overview of the recent development regarding the production of natural gas from subsea gas hydrate reservoirs. It aims at giving a broad insight into natural gas hydrates and covering relevant aspects of the exploitation process. It is focused on the thermodynamic principles and technological approaches for the exploitation. The effects occurring during natural gas production within hydrate filled sediment layers are identified and discussed by means of numerical simulation results. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is described and compared for different strategies. The simulations are complemented by calculations for different safety relevant problems.

  17. Covalent Bond Formation of Uranium Ions in a LiCl-KCl Eutectic Melt at 450 .deg. C: Spectroscopic Evidence from Their UV-VIS Spectra

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Young Hwan; Bae, Sang Eun; Oh, Seung Yong; Kim, Jong Yun; Song, Kyu Seok; Yeon, Jei Won [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2012-05-15

    Molten salt based electrochemical processes, so called pyroprocessing, have been proposed as a new option for the advanced spent nuclear fuel cycle. One of the important steps in the pyroprocessing of the spent nuclear fuel is the electrorefining of uranium in molten LiCl based media. The knowledge on the electronic states of uranium ions in molten salt media is essential for understanding their optical, electrochemical properties. Electronic absorption spectra may provide detailed information on the chemical state of the ions. Several studies have been reported for the past decades on the electronic absorption spectra of uranium ion species in high temperature molten salt media. However, no attempts have been made to interpret the spectra with respect to the electronic state and chemical bonding point of view. Here, report the results of insitu measurement and interpretation of the electronic spectra of the U(III) and U(IV) ion species in a LiCl- KCl eutectic melt at in terms of chemical bonding

  18. Methane Hydrate Field Program

    Energy Technology Data Exchange (ETDEWEB)

    None

    2013-12-31

    This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report. • Historical Methane Hydrate Project Review Report • Methane Hydrate Workshop Report • Topical Report: Marine Methane Hydrate Field Research Plan • Final Scientific/Technical Report

  19. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  20. Hard three-dimensional sp2 carbon-bonded phase formed by ion beam irradiation of fullerene, a-C and polymeric a-C:H films

    International Nuclear Information System (INIS)

    The formation of new carbon amorphous phase through the ion irradiation of fullerene, a-C and polymeric a-C:H films is presented. The carbon films were subjected to N irradiation at 400 keV in the fluence range from 1013 to 3 x 1016 N cm-2. Modifications in the carbon structure, as function of the irradiation fluence, were investigated using the Rutherford backscattering spectrometry, nuclear reaction analysis, Fourier transform infrared, Raman spectroscopy, UV-VIS-NearIR spectrophotometry and nanoindentation techniques. After high fluence, the three carbon samples were transformed into very similar hard (∼14 GPa) and non-hydrogenated amorphous carbon layers with very low optical gaps (∼0.2 eV) and an unusual sp2 rich-bonded atomic network. The mechanical properties of the irradiated films correlated with the bonding topologies of this new sp2 carbon phase are analyzed in terms of the constraint-counting model. The results show that the unusual rigidity was achieved by the distortion of the sp2 carbon bond angles, giving origin to a constrained three-dimensional sp2 carbon bonded network

  1. Structure of neat and hydrated liquid nicotine and laser resonant desorption of clusters from nicotine-water solutions

    Science.gov (United States)

    Mihesan, Claudia; Ziskind, Michael; Focsa, Cristian; Seydou, Mahamadou; Lecomte, Frédéric; Schermann, Jean Pierre

    2008-11-01

    The microscopic structures of neat liquid nicotine and nicotine-water mixtures are examined through infrared spectroscopy and laser resonant desorption mass-spectroscopy. The infrared spectra of the solutions are analyzed using DFT calculations of homogenous and mixed hydrogen-bonded clusters. Neat nicotine and hydrated nicotine cluster are experimentally observed through IR laser resonant desorption of a nicotine/water ice mixture followed by laser ionization mass-spectrometry. A sizable fraction of those cluster ions is the result of laser ionization of small neutral clusters already present in the sample.

  2. Sticky dissociative electron transfer to polychloroacetamides. In-cage ion-dipole interaction control through the dipole moment and intramolecular hydrogen bond.

    Science.gov (United States)

    Costentin, Cyrille; Louault, Cyril; Robert, Marc; Teillout, Anne-Lucie

    2005-03-31

    The reductive cleavage of chloro- and polychloroacetamides in N,N-dimethylformamide gives new insights into the nature of the in-cage ion radical cluster formed upon dissociative electron transfer. Within the family of compounds investigated, the electrochemical reduction leads to the successive expulsion of chloride ions. At each stage the electron transfer is concerted with the breaking of the C-Cl bond and acts as the rate-determining step. The reduction further leads to the formation of the corresponding carbanion with the injection of a second electron, which is in turn protonated by a weak acid added to the solution. From the joint use of cyclic voltammetric data, the sticky dissociative electron-transfer model and quantum ab initio calculations, the interaction energies within the cluster fragments (*R, Cl-) resulting from the first electron transfer to the parent RCl molecule are obtained. It is shown that the stability of these adducts, which should be viewed as an essentially electrostatic radical-ion pair, is mainly controlled by the intensity of the dipole moment of the remaining radical part and may eventually be strengthened by the formation of an intramolecular hydrogen bond, as is the case with 2-chloroacetamide. PMID:16833619

  3. Guided ion-beam studies of the reactions of Con+ (n=2-20) with O2: Cobalt cluster-oxide and -dioxide bond energies

    International Nuclear Information System (INIS)

    The kinetic-energy dependence for the reactions of Con+ (n=2-20) with O2 is measured as a function of kinetic energy over a range of 0 to 10 eV in a guided ion-beam tandem mass spectrometer. A variety of Com+, ComO+, and ComO2+ (m≤n) product ions is observed, with the dioxide cluster ions dominating the products for all larger clusters. Reaction efficiencies of Con+ cations with O2 are near unity for all but the dimer. Bond dissociation energies for both cobalt cluster oxides and dioxides are derived from threshold analysis of the energy dependence of the endothermic reactions using several different methods. These values show little dependence on cluster size for clusters larger than three atoms. The trends in this thermochemistry and the stabilities of oxygenated cobalt clusters are discussed. The bond energies of Con+-O for larger clusters are found to be very close to the value for desorption of atomic oxygen from bulk-phase cobalt. Rate constants for O2 chemisorption on the cationic clusters are compared with results from previous work on cationic, anionic, and neutral cobalt clusters

  4. Ultrafast phosphate hydration dynamics in bulk H{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Costard, Rene, E-mail: costard@mbi-berlin.de; Tyborski, Tobias; Fingerhut, Benjamin P., E-mail: fingerhut@mbi-berlin.de; Elsaesser, Thomas [Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie, D-12489 Berlin (Germany)

    2015-06-07

    Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H{sub 2}PO{sub 4}{sup −} ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric (ν{sub S}(PO{sub 2}{sup −})) and asymmetric (ν{sub AS}(PO{sub 2}{sup −})) PO{sub 2}{sup −} stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH){sub 2}) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the ν{sub S}(PO{sub 2}{sup −}) and ν{sub AS}(PO{sub 2}{sup −}) transition frequencies with larger frequency excursions for ν{sub AS}(PO{sub 2}{sup −}). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO{sub 2}{sup −}) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H{sub 2}PO{sub 4}{sup −}/H{sub 2}O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.

  5. Molecular Dynamics Study of Twister Ribozyme: Role of Mg(2+) Ions and the Hydrogen-Bonding Network in the Active Site.

    Science.gov (United States)

    Ucisik, Melek N; Bevilacqua, Philip C; Hammes-Schiffer, Sharon

    2016-07-12

    The recently discovered twister ribozyme is thought to utilize general acid-base catalysis in its self-cleavage mechanism, but the roles of nucleobases and metal ions in the mechanism are unclear. Herein, molecular dynamics simulations of the env22 twister ribozyme are performed to elucidate the structural and equilibrium dynamical properties, as well as to examine the role of Mg(2+) ions and possible candidates for the general base and acid in the self-cleavage mechanism. The active site region and the ends of the pseudoknots were found to be less mobile than other regions of the ribozyme, most likely providing structural stability and possibly facilitating catalysis. A purported catalytic Mg(2+) ion and the closest neighboring Mg(2+) ion remained chelated and relatively immobile throughout the microsecond trajectories, although removal of these Mg(2+) ions did not lead to any significant changes in the structure or equilibrium motions of the ribozyme on the microsecond time scale. In addition, a third metal ion, a Na(+) ion remained close to A1(O5'), the leaving group atom, during the majority of the microsecond trajectories, suggesting that it might stabilize the negative charge on A1(O5') during self-cleavage. The locations of these cations and their interactions with key nucleotides in the active site suggest that they may be catalytically relevant. The P1 stem is partially melted at its top and bottom in the crystal structure and further unwinds in the trajectories. The simulations also revealed an interconnected network comprised of hydrogen-bonding and π-stacking interactions that create a relatively rigid network around the self-cleavage site. The nucleotides involved in this network are among the highly conserved nucleotides in twister ribozymes, suggesting that this interaction network may be important to structure and function. PMID:27295275

  6. A novel technique using DNA denaturation to detect multiply induced single-strand breaks in a hydrated plasmid DNA molecule by X-ray and 4He2+ ion irradiation

    International Nuclear Information System (INIS)

    To detect multiple single-strand breaks (SSBs) produced in plasmid DNA molecules by direct energy deposition from radiation tracks, we have developed a novel technique using DNA denaturation by which irradiated DNA is analysed as single-strand DNA (SS-DNA). The multiple SSBs that arise in both strands of DNA, but do not induce a double-strand break, are quantified as loss of SS-DNA using agarose gel electrophoresis. We have applied this method to X-ray and 4He2+ ion-irradiated samples of fully hydrated pUC18 plasmid DNA. The fractions of both SS-DNA and closed circular DNA (CC-DNA) exponentially decrease with the increasing dose of X rays and 4He2+ ions. The efficiency of the loss of SS-DNA was half that of CC-DNA for both types of irradiation, indicating that one of two strands in DNA is not broken when one SSB is produced in CC-DNA by irradiation. Contrary to our initial expectation, these results indicate that SSBs are not multiply induced even by high linear energy transfer radiation distributed in both strands. (authors)

  7. Atomistic modelling of the hydration of CaSO 4

    Science.gov (United States)

    Adam, Craig D.

    2003-08-01

    Atomistic modelling techniques, using empirical potentials, have been used to simulate a range of structures formed by the hydration of γ-CaSO 4 and described as CaSO 4· nH 2O (0commercial importance and has been subjected to much experimental study. These simulation studies demonstrate significant water-matrix interactions that influence the crystallography of the hydrated phase. The existence of two types of hydration site has been predicted, including one within the Ca 2+coordination sphere. Close correlation between water molecule bonding energy, Ca 2+-O w bond length and unit-cell volume have been established. This shows that as the number of water molecules within the unit cell increases, the bonding energy increases and the unit cell contracts. However around n=0.5, this process reaches a turning point with the incorporation of further waters resulting in reduced binding energy and an expanding unit cell.

  8. Multi-species Ionic Diffusion in Concrete with Account to Interaction Between Ions in the Pore Solution and the Cement Hydrates

    DEFF Research Database (Denmark)

    Johannesson, Björn

    2007-01-01

    electron probe micro analysis (EPMA) data. A close agreement of the simulated results to measured data is found for the specific studied example. The model includes the ionic species Cl-, Na+, OH-, Ca2+, K+ and SO42- and solid phases with variable composition. From the EPMA measurements the total...... results concerning the multi-species action during chloride penetration. In the model the chemical interaction between ions in solids and in pore solution is assumed governed by simple ion exchange processes only. The drawback using this approach is that the chemical part is lacking important physical...

  9. Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica.

    Science.gov (United States)

    Vieira, Eduardo G; Soares, Isaac V; Dias Filho, Newton L; da Silva, Niléia C; Garcia, Edemir F; Bastos, Andréa C; Perujo, Sérgio D; Ferreira, Tamires T; Rosa, André H; Fraceto, Leonardo F

    2013-02-01

    A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and (13)C and (29)Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmol g(-1)) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. PMID:23116858

  10. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.

    2014-07-01

    The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

  11. Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate.

    Science.gov (United States)

    Bouchet, Aude; Schütz, Markus; Dopfer, Otto

    2016-01-18

    Hydration has a drastic impact on the structure and function of flexible biomolecules, such as aromatic ethylamino neurotransmitters. The structure of monohydrated protonated phenylethylamine (H(+) PEA-H2 O) is investigated by infrared photodissociation (IRPD) spectroscopy of cold cluster ions by using rare-gas (Rg=Ne and Ar) tagging and dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level. Monohydration of this prototypical neurotransmitter gives an insight into the first step of the formation of its solvation shell, especially regarding the competition between intra- and intermolecular interactions. The spectra of Rg-tagged H(+) PEA-H2 O reveal the presence of a stable insertion structure in which the water molecule is located between the positively charged ammonium group and the phenyl ring of H(+) PEA, acting both as a hydrogen bond acceptor (NH(+) ⋅⋅⋅O) and donor (OH⋅⋅⋅π). Two other nearly equivalent isomers, in which water is externally H bonded to one of the free NH groups, are also identified. The balance between insertion and external hydration strongly depends on temperature. PMID:26584245

  12. Ion-Induced Dipole Interactions and Fragmentation Times : C$\\alpha$ -C$\\beta$ Chromophore Bond Dissociation Channel

    CERN Document Server

    Soorkia, Satchin; Kumar, Sunil; Pérot-Taillandier, Marie; Lucas, Bruno; Jouvet, Christophe; Barat, Michel; Fayeton, Jacqueline A

    2015-01-01

    The fragmentation times corresponding to the loss of the chromophore (C$\\alpha$-- C$\\beta$ bond dissociation channel) after photoexcitation at 263 nm have been investigated for several small peptides containing tryptophan or tyrosine. For tryptophan-containing peptides, the aromatic chromophore is lost as an ionic fragment (m/z 130), and the fragmentation time increases with the mass of the neutral fragment. In contrast, for tyrosine-containing peptides the aromatic chromophore is always lost as a neutral fragment (mass = 107 amu) and the fragmentation time is found to be fast (\\textless{}20 ns). These different behaviors are explained by the role of the postfragmentation interaction in the complex formed after the C$\\alpha$--C$\\beta$ bond cleavage.

  13. Withdrawing Nutrition, Hydration

    Science.gov (United States)

    Module eleven of the EPEC-O Self-Study Original Version discusses the general aspects of withholding or withdrawing of life-sustaining therapies, and presents a specific application to artificial nutrition and hydration.

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

    Science.gov (United States)

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

    2012-01-01

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

  15. Hydration of Portland cement with additions of calcium sulfoaluminates

    Energy Technology Data Exchange (ETDEWEB)

    Le Saout, Gwenn, E-mail: gwenn.le-saout@mines-ales.fr [Empa, Swiss Federal Laboratories for Materials Science and Technology, Concrete and Construction Chemistry Laboratory, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); Lothenbach, Barbara [Empa, Swiss Federal Laboratories for Materials Science and Technology, Concrete and Construction Chemistry Laboratory, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); Hori, Akihiro [DENKA Chemicals GmbH, Wehrhahn-Center, Cantadorstr. 3, D-40211 Duesseldorf (Germany); Higuchi, Takayuki [Denki Kagaku Kogyo Kabushiki Kaisha (DENKA), Omi, Itoigawa, Niigata, 949-0393 (Japan); Winnefeld, Frank [Empa, Swiss Federal Laboratories for Materials Science and Technology, Concrete and Construction Chemistry Laboratory, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland)

    2013-01-15

    The effect of mineral additions based on calcium aluminates on the hydration mechanism of ordinary Portland cement (OPC) was investigated using isothermal calorimetry, thermal analysis, X-ray diffraction, scanning electron microscopy, solid state nuclear magnetic resonance and pore solution analysis. Results show that the addition of a calcium sulfoaluminate cement (CSA) to the OPC does not affect the hydration mechanism of alite but controls the aluminate dissolution. In the second blend investigated, a rapid setting cement, the amorphous calcium aluminate reacts very fast to ettringite. The release of aluminum ions strongly retards the hydration of alite but the C-S-H has a similar composition as in OPC with no additional Al to Si substitution. As in CSA-OPC, the aluminate hydration is controlled by the availability of sulfates. The coupling of thermodynamic modeling with the kinetic equations predicts the amount of hydrates and pore solution compositions as a function of time and validates the model in these systems.

  16. Hydration of Portland cement with additions of calcium sulfoaluminates

    International Nuclear Information System (INIS)

    The effect of mineral additions based on calcium aluminates on the hydration mechanism of ordinary Portland cement (OPC) was investigated using isothermal calorimetry, thermal analysis, X-ray diffraction, scanning electron microscopy, solid state nuclear magnetic resonance and pore solution analysis. Results show that the addition of a calcium sulfoaluminate cement (CSA) to the OPC does not affect the hydration mechanism of alite but controls the aluminate dissolution. In the second blend investigated, a rapid setting cement, the amorphous calcium aluminate reacts very fast to ettringite. The release of aluminum ions strongly retards the hydration of alite but the C–S–H has a similar composition as in OPC with no additional Al to Si substitution. As in CSA–OPC, the aluminate hydration is controlled by the availability of sulfates. The coupling of thermodynamic modeling with the kinetic equations predicts the amount of hydrates and pore solution compositions as a function of time and validates the model in these systems.

  17. Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation

    Science.gov (United States)

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Lee, Bo Ram; Park, Da-Hye; Han, Kunwoo; Lee, Kun-Hong

    2013-08-01

    As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media.

  18. Experimental characterization and modelling of acoustic velocity and electrical resistance in hydrate bearing sediments

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Y.; Zhang, W.; Liu, Y.; Ren, S. [China Univ. of Petroleum, Dongying (China). Inst. of Petroleum Engineering

    2008-07-01

    In the development of gas hydrate resources, characterization of natural gas hydrate bearing sediments is important. Solid hydrates fill the voids of the matrix formed by sand grains and change their cementation condition, which have a significant impact on the resistance and sound velocity of the sand matrix. Acoustic velocity and electrical resistivity are important methods in well-logging of conventional oil/gas reservoirs. They can also be effectively utilized in the characterization of gas hydrate-bearing sediments. Solid hydrates fill the voids between sand grains and change the cementation condition of the sand matrix, which can enhance the propagation of sounds, increasing the sound velocity. Since electric ions are excluded in hydrate, hydrate formation can change the distribution and mobility of electrolytes in sub sea sediments, which will affect the resistance of the sand matrix. This paper presented a study that involved experiments that measured the acoustic P-wave velocity and electrical properties of sandpacks with methane hydrate formed under simulated subsea sediment conditions. The paper discussed the key findings of the experiments in order to correlate the resistivity and acoustic P-wave velocity with hydrate saturation in porous media. The effects of hydrate on the resistivity and ultrasonic velocity of hydrate bearing sand matrix were revealed and modeled. It was concluded that the resistivity of the sandpack bearing with hydrate slightly decreased when hydrate saturation was low, probably because of the hydrate's ion exclusion effect. An increased resistivity with higher hydrate saturation could be explained by a blockage mechanism of hydrates formed in the pores. 11 refs., 1 tab., 8 figs.

  19. Covalent bonding and J–J mixing effects on the EPR parameters of Er3 + ions in GaN crystal

    Science.gov (United States)

    Rui-Peng, Chai; Long, Li; Liang, Liang; Qing, Pang

    2016-07-01

    The EPR parameters of trivalent Er3+ ions doped in hexagonal GaN crystal have been studied by diagonalizing the 364×364 complete energy matrices. The results indicate that the resonance ground states may be derived from the Kramers doublet Γ6. The EPR g-factors may be ascribed to the stronger covalent bonding and nephelauxetic effects compared with other rare-earth doped complexes, as a result of the mismatch of ionic radii of the impurity Er3+ ion and the replaced Ga3+ ion apart from the intrinsic covalency of host GaN. Furthermore, the J–J mixing effects on the EPR parameters from the high-lying manifolds have been evaluated. It is found that the dominant J–J mixing contribution is from the manifold 2K15/2, which accounts for about 2.5%. The next important J–J contribution arises from the crystal–field mixture between the ground state 4I15/2 and the first excited state 4I13/2, and is usually less than 0.2%. The contributions from the rest states may be ignored. Project supported by the Foundation of Education Department of Shaanxi Province, China (Grant No. 16JK1461).

  20. Physicochemical and structural studies of clathrate hydrates of tetrabutylammonium polyacrylates.

    Science.gov (United States)

    Terekhova, Irina S; Manakov, Andrey Yu; Komarov, Vladislav Yu; Villevald, Galina V; Burdin, Alexander A; Karpova, Tamara D; Aladko, Eugeny Ya

    2013-03-01

    In this work, physicochemical and structural studies have been carried out for semiclathrate hydrates of linear (un-cross-linked) and cross-linked tetrabutylammonium polyacrylates with different degrees of cross-linking of the polymeric guest molecules (n = 0.5, 1, 2, 3%) and different degrees of substitution of proton ions of carboxylic groups in poly(acrylic acid) for TBA cations (x = 1, 0.8, 0.6). The changes in the hydrates' stability and composition depending on the outlined parameters were examined in the course of phase diagram studies of the binary systems water-tetrabutylammonium polyacrylates using differential thermal analysis method and calorimetric measurements of fusion enthalpies of the hydrates. Phase diagram studies of the binary system water-linear tetrabutylammonium polyacrylate revealed the formation of four hydrates. Based on the data of chemical analysis of hydrate crystals the compositions of all hydrates have been determined. Single-crystal X-ray diffraction studies revealed a tetragonal structure, space group 4/m, and unit cell parameters are close for different hydrates and lie in the ranges a = 23.4289-23.4713 Å and c = 12.3280-12.3651 Å (150 K). The structure can be related to tetragonal structure I typical for the clathrate hydrates of tetraalkylammonium salts with monomeric anions. Powder X-ray diffraction analyses confirmed the identity of the above crystal structure to that of the hydrates with cross-linked tetrabutylammonium polyacrylates. The behavior of TBA polyacrylate hydrates under the pressure of methane was studied and quantitative assessment of the gas content in the hydrates was made using volumetric analysis method. PMID:23383955

  1. Cation Hydration Constants by Proton NMR: A Physical Chemistry Experiment.

    Science.gov (United States)

    Smith, Robert L.; And Others

    1988-01-01

    Studies the polarization effect on water by cations and anions. Describes an experiment to illustrate the polarization effect of sodium, lithium, calcium, and strontium ions on the water molecule in the hydration spheres of the ions. Analysis is performed by proton NMR. (MVL)

  2. Room temperature synthesis of hydrated nickel(III) oxide and study of its effect on Cr(VI) ions removal and bacterial culture

    Science.gov (United States)

    Dey, Sayan; Bhattacharjee, Swarupananda; Bose, Raj Shekhar; Ghosh, Chandan Kr.

    2015-06-01

    Cr(VI) ion is a toxic inorganic affluent that causes carcinogenic effects on the human body. Another problem that requires immediate attention is the fouling of water borne metal surface by micro-organisms. The present study aims to suggest the synthesis of Ni2O3·H2O nanoparticles and to investigate its heavy metal adsorption capacity and bacteriotoxicity in order to address the current global problems. Stable Ni2O3·H2O nanoparticles having various particle sizes were synthesized using active halogenation of nickel(II) precursor at different temperatures. Phase purity was investigated by X-ray diffraction technique. Due to high surface area, surface heterogeneity and surface polarity, they show excellent adsorption affinity (up to 73.9 % removal capacity) of heavy metal ions like Cr(VI). Adsorption isotherms (Freundlich and Langmuir) are plotted for them. Kinetics of the adsorption process reveals it to be pseudo-first-order kinetic in nature. They are also found to be fairly toxic to bacterial subcultures. Maximum value of the minimum inhibitory concentration and minimum bactericidal concentration were found to be ~0.54 and 0.58 mg/l for particles synthesized at 70 °C. It was observed that Cr(VI) adsorption highly depends on the surface heterogeneity, while the bactericidal effect depends on the size of the nanoparticles so-prepared. Hence, the prepared particles could be used as a potential material for Cr(VI) ion removal and as an antifouling agent.

  3. Phase equilibrium condition of marine carbon dioxide hydrate

    International Nuclear Information System (INIS)

    Highlights: ► CO2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl− ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

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

    OpenAIRE

    Chang, Seok-Woo

    2012-01-01

    Mineral trioxide aggregate (MTA) was developed in early 1990s and has been successfully used for root perforation repair, root end filling, and one-visit apexification. MTA is composed mainly of tricalcium silicate and dicalcium silicate. When MTA is hydrated, calcium silicate hydrate (CSH) and calcium hydroxide is formed. Formed calcium hydroxide interacts with the phosphate ion in body fluid and form amorphous calcium phosphate (ACP) which finally transforms into calcium deficient hydroxyap...

  5. A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl2 hydrates and MgCl2 hydrates for seasonal heat storage.

    Science.gov (United States)

    Pathak, Amar Deep; Nedea, Silvia; Zondag, Herbert; Rindt, Camilo; Smeulders, David

    2016-04-21

    Salt hydrates store solar energy in chemical form via a reversible dehydration-hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The mixture of CaCl2 and MgCl2 hydrates has been shown experimentally to have exceptional cycle stability and improved kinetics. However, the optimal operating conditions for the mixture are unknown. To understand the appropriate balance between dehydration and hydrolysis kinetics in the mixtures, it is essential to gain in-depth insight into the mixture components. We present a GGA-DFT level study to investigate the various gaseous structures of CaCl2 hydrates and to understand the relative stability of their conformers. The hydration strength and relative stability of conformers are dominated by electrostatic interactions. A wide network of intramolecular homonuclear and heteronuclear hydrogen bonds is observed in CaCl2 hydrates. Equilibrium product concentrations are obtained during dehydration and hydrolysis reactions under various temperature and pressure conditions. The trend of the dehydration curve with temperature in CaCl2 hydrates is similar to the experiments. Comparing these results to those of MgCl2 hydrates, we find that CaCl2 hydrates are more resistant towards hydrolysis in the temperature range of 273-800 K. Specifically, the present study reveals that the onset temperatures of HCl formation, a crucial design parameter for MgCl2 hydrates, are lower than for CaCl2 hydrates except for the mono-hydrate. PMID:27004734

  6. Chemical imaging of molecular changes in a hydrated single cell by dynamic secondary ion mass spectrometry and super-resolution microscopy.

    Science.gov (United States)

    Hua, Xin; Szymanski, Craig; Wang, Zhaoying; Zhou, Yufan; Ma, Xiang; Yu, Jiachao; Evans, James; Orr, Galya; Liu, Songqin; Zhu, Zihua; Yu, Xiao-Ying

    2016-05-16

    Chemical imaging of single cells at the molecular level is important in capturing biological dynamics. Single cell correlative imaging is realized between super-resolution microscopy, namely, structured illumination microscopy (SIM), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) using a multimodal microreactor (i.e., System for Analysis at the Liquid Vacuum Interface, SALVI). SIM characterized cells and guided subsequent ToF-SIMS analysis. Lipid fragments were identified in the cell membrane via dynamic ToF-SIMS depth profiling. Positive SIMS spectra show intracellular potassium and sodium ion transport due to exposure to nanoparticles. Spectral principal component analysis elucidates differences in chemical composition among healthy alveolar epithelial mouse lung C10 cells, cells that uptake zinc oxide nanoparticles, and various wet and dry control samples. The observation of Zn(+) gives the first direct evidence of ZnO NP uptake and dissolution by the cell membrane. Our results provide submicron chemical mapping for investigating cell dynamics at the molecular level. PMID:27053104

  7. Gas-phase reaction of CeVO5(+) cluster ions with C2H4: the reactivity of cluster bonded peroxides.

    Science.gov (United States)

    Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

    2015-02-21

    Cerium-vanadium oxide cluster cations CeVO5(+) were generated by laser ablation, mass-selected using a quadrupole mass filter, thermalized through collisions with helium atoms, and then reacted with ethene molecules in a linear ion trap reactor. The cluster reactions have been characterized by time-of-flight mass spectrometry and density functional theory calculations. The CeVO5(+) cluster has a closed-shell electronic structure and contains a peroxide (O2(2-)) unit. The cluster bonded O2(2-) species is reactive enough to oxidize a C2H4 molecule to generate C2H4O2 that can be an acetic acid molecule. Atomic oxygen radicals (O(-)˙), superoxide radicals (O2(-)˙), and peroxides are the three common reactive oxygen species. The reactivity of cluster bonded O(-)˙ and O2(-)˙ radicals has been widely studied while the O2(2-) species were generally thought to be much less reactive or inert toward small molecules under thermal collision conditions. This work is among the first to report the reactivity of the peroxide unit on transition metal oxide clusters with hydrocarbon molecules, to the best of our knowledge. PMID:25573178

  8. Substitutional NaCl hydration in ice

    Science.gov (United States)

    Feibelman, Peter J.

    2007-06-01

    Na+ and Cl- can replace water molecules in ice Ih with minimal lattice strain and without disrupting the crystal’s H-bond network. First-principles calculations show that substitutional solvation is endothermic by as little as 0.49eV per ion pair. Interstitial ion solvation is less favorable by >1.5eV .

  9. The hydrogen bond network structure within the hydration shell around simple osmolytes: Urea, tetramethylurea, and trimethylamine-N-oxide, investigated using both a fixed charge and a polarizable water model

    Science.gov (United States)

    Kuffel, Anna; Zielkiewicz, Jan

    2010-07-01

    Despite numerous experimental and computer simulation studies, a controversy still exists regarding the effect of osmolytes on the structure of surrounding water. There is a question, to what extent some of the contradictory results may arise from differences in potential models used to simulate the system or parameters employed to describe physical properties of the mixture and interpretation of the results. Bearing this in mind, we determine two main aims of this work as follows: description of the water-water hydrogen bond network structure within the solvation layer around solute molecules (urea, trimethylamine-N-oxide, and tetramethylurea), and also comparison of rigid simple point charges (SPC) and polarizable (POL3) models of water. The following quantities have been examined: radial distribution functions of water molecules around the investigated solutes, both local and overall characteristics of the hydrogen bond network structure (using recently elaborated method), along with estimation of the mean energy of a single hydrogen bond, and also the probability distributions which describe the orientation of a single water particle plane relatively to the center of mass of the solute molecule. As an independent method for the evaluation of the degree of changes in local structural ordering, a harmonic approximation has been adopted to estimate the absolute entropy of water. It was found that within the solvation shell of the investigated solutes, the structure of hydrogen bond network changes only slightly comparing to bulk water. Therefore, we conclude that the investigated osmolyte molecules do not disturb significantly the structure of surrounding water. This conclusion was also confirmed by calculations of the absolute entropy of water using a harmonic approximation. In the immediate vicinity of the solutes, we observe that the water-water hydrogen bonds are slightly more stable; they are slightly less distorted and a little shorter than in bulk water

  10. PART II. HYDRATED CEMENTS

    Directory of Open Access Journals (Sweden)

    Milan Drabik

    2014-09-01

    Full Text Available Essential focus of the study has been to acquire thermoanalytical events, incl. enthalpies of decompositions - ΔH, of technological materials based on two types of Portland cements. The values of thermoanalytical events and also ΔH of probes of technological compositions, if related with the data of a choice of minerals of calcium-silicate-sulfate-aluminate hydrates, served as a valued input for the assessment of phases present and phase changes due to the topical hydraulic processes. The results indicate mainly the effects of "standard humidity" or "wet storage" of the entire hydration/hydraulic treatment, but also the presence of cement residues alongside calcium-silicate-sulfate-aluminate hydrates (during the tested period of treatment. "A diluting" effect of unhydrated cement residues upon the values of decomposition enthalpies in the studied multiphase system is postulated and discussed

  11. Protein hydration and dynamics

    International Nuclear Information System (INIS)

    Inelastic neutron scattering can measure the protein thermal fluctuations under the physiological aqueous environment, especially it is powerful to observe the low-energy protein dynamics in THz region, which are revealed theoretically to be coupled with solvations. Neutron enables the selective observation of protein and hydration water by deuteration. The complementary analysis with molecular dynamics simulation is also effective for the study of protein hydration. Some examples of the application toward the understanding of molecular basis of protein functions will be introduced. (author)

  12. Formation of porous gas hydrates

    CERN Document Server

    Salamatin, Andrey N

    2015-01-01

    Gas hydrates grown at gas-ice interfaces are examined by electron microscopy and found to have a submicron porous texture. Permeability of the intervening hydrate layers provides the connection between the two counterparts (gas and water molecules) of the clathration reaction and makes further hydrate formation possible. The study is focused on phenomenological description of principal stages and rate-limiting processes that control the kinetics of the porous gas hydrate crystal growth from ice powders. Although the detailed physical mechanisms involved in the porous hydrate formation still are not fully understood, the initial stage of hydrate film spreading over the ice surface should be distinguished from the subsequent stage which is presumably limited by the clathration reaction at the ice-hydrate interface and develops after the ice grain coating is finished. The model reveals a time dependence of the reaction degree essentially different from that when the rate-limiting step of the hydrate formation at...

  13. Measurement of CO2 diffusivity in synthetic and saline aquifer solutions at reservoir conditions: the role of ion interactions

    Science.gov (United States)

    Jafari Raad, Seyed Mostafa; Azin, Reza; Osfouri, Shahriar

    2015-11-01

    Storage and disposal of CO2 as the main component of greenhouse gases in saline aquifers require careful measurement of diffusivity for predicting rate of transfer and cumulative amount of trapped gas. Little information is available on diffusion of CO2 in highly concentrated saline aquifers at reservoir conditions. In this study, diffusivity of CO2 was measured into different solutions, including saline aquifer taken from oil field, distilled water and synthetic solutions prepared from four most common ions, Mg2+, Ca2+, K+, Na+. The roles of salvation effect and hydration phenomenon were studied on diffusivity of dissolved CO2. Synthetic solutions were prepared at concentration ranges of 83-200 g/l. Experimental measurements were reported at temperature and pressure ranges of 30-40 °C and 5,880-6,265 kPa, respectively. Results show that both type and concentration of ion affect CO2 diffusivity. Diffusion coefficient was found dependent on effective radius of hydrated ions. Also, CO2 diffusivity increase by increasing strength of bonds between ion and neighbor water molecules. Also, presence of ions in water solution creates hydration competition between solution metal ions and aqua ions from diffusive gas. The Mg2+ cation, which has strongest hydration competition among other ions, has an increasing effect on gas diffusivity into saline aquifer. However, increasing ion concentration in solution decreases diffusivity of CO2 due to growth in fraction of contact ion pairs. Results of this study provide unique measures of CO2 diffusion coefficient in saline aquifer at high pressure and temperature conditions and conceptual information about effect of each common saline formation ion on gas diffusivity.

  14. Theoretical study of methanol as inhibitor and cyclopentane as stabilizer of dodecahedron methane hydrate cage

    Science.gov (United States)

    Pal, Snehanshu; Kundu, T. K.

    2015-02-01

    Density Functional Theory (DFT) based simulations have been performed to explain the role of methanol as an inhibitor and the role of cyclopentane as a promoter for methane hydrate. Interaction energy, Mullikan charges and electrostatic potential parameters for combined system of methanol and dodecahedron methane hydrate as well as cyclopentane and dodecahedron (512) methane hydrate cage are calculated using B3LYP functional (with and without dispersion function) and 6-31G(d) basis set. Methane hydrate formation inhibition by methanol and methane hydrate stabilization by cyclopentane is critically analyzed based on electrostatic potential and Mullikan charge. It is observed that hydrogen bond between water molecules of clathrate 512 cages become stronger in presence of cyclopentane and weaker in presence of methanol. It is also found that methanol breaks some hydrogen bonds of water molecules.

  15. Aluminum Sulfate 18 Hydrate

    Science.gov (United States)

    Young, Jay A.

    2004-01-01

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

  16. Wet hydrate dissolution plant

    Directory of Open Access Journals (Sweden)

    Stanković Mirjana S.

    2003-01-01

    Full Text Available The IGPC Engineering Department designed basic projects for a wet hydrate dissolution plant, using technology developed in the IGPC laboratories. Several projects were completed: technological, machine, electrical, automation. On the basis of these projects, a production plant with capacity of 50,000 t/y was manufactured, at "Zeolite Mira", Mira (VE, Italy, in 1997, for increasing detergent zeolite production from 50,000 to 100,000 t/y. Several goals were realized by designing a wet hydrate dissolution plant. Main goal was increasing the detergent zeolite production capacity. The technological cycle of NaOH was closed, and no effluents emitted, and there is no pollution. Wet hydrate dissolution is now fully continuous, which is important for maintaining zeolite production quality, as well as for simplifying production. The wet hydrate production process is fully automatized, and the product has uniform quality. The production process can be controlled manually, which is necessary during start-up, and repairs. By installing additional process equipment (centrifugal pumps and dissolving reactors technological bottlenecks were overcome, and by adjusting NaOH tanks and dissolving reactors, the capacities of the process equipment was fully utilized.

  17. Engineering the bonding scheme in C-S-H: The iono-covalent framework

    International Nuclear Information System (INIS)

    On the basis of recent molecular simulation and experimental studies, we discuss two possible strategies for tuning the mechanical properties of cementitious materials by modifying the bonding scheme in the hydrates at molecular level. We focus the discussion on the calcium silicate hydrates (C-S-H). A first strategy would be based on the strengthening of the network of cohesion forces acting between the individual C-S-H lamellae or between their crystallites. Atomic scale simulations by ab initio, molecular dynamics and energy minimization techniques show that the iono-covalent forces between individual C-S-H layers or C-S-H layer stacks, separated by strongly localized calcium ions and water molecules, are orders of magnitude larger than the ionic correlation forces acting between C-S-H surfaces separated by nm- or multi-nm-thick layers of mobile water molecules and ions. The elastic properties derived from this iono-covalent bonding scheme are in good agreement with experimental values obtained by ultrasonic or statistical ('grid') nanoindentation techniques. The concept picture for C-S-H which follows is that of a crystalline semi-continuum, with dense domains ('crystallites' or 'particles') iono-covalently bonded to each other, possibly entangled also, and embedded as long as the mesoscale porosity is water-saturated in a relatively weak attractive stress field due to fluctuating electrostatic forces. Depending on the size, the aspect ratio, and the turbostratic order of the crystallites, and also the composition of the interstitial solution, the relative importance of each contribution could be modified. This provides the basis for a better control of properties such as early age or long term strength development for instance. In this respect, the microstructure-properties relationships in clay minerals provide interesting leads, pointing to the importance of bonding continuity rather than bond strength. A second strategy to tune the mechanical properties of

  18. Mechanical behavior of a composite interface: Calcium-silicate-hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Palkovic, Steven D.; Moeini, Sina; Büyüköztürk, Oral, E-mail: obuyuk@mit.edu [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Yip, Sidney [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-07-21

    The generalized stacking fault (GSF) is a conceptual procedure historically used to assess shear behavior of defect-free crystalline structures through molecular dynamics or density functional theory simulations. We apply the GSF technique to the spatially and chemically complex quasi-layered structure of calcium-silicate-hydrates (C-S-H), the fundamental nanoscale binder within cementitious materials. A failure plane is enforced to calculate the shear traction-displacement response along a composite interface containing highly confined water molecules, hydroxyl groups, and calcium ions. GSF simulations are compared with affine (homogeneous) shear simulations, which allow strain to localize naturally in response to the local atomic environment. Comparison of strength and deformation behavior for the two loading methods shows the composite interface controls bulk shear deformation. Both models indicate the maximum shear strength of C-S-H exhibits a normal-stress dependency typical of cohesive-frictional materials. These findings suggest the applicability of GSF techniques to inhomogeneous structures and bonding environments, including other layered systems such as biological materials containing organic and inorganic interfaces.

  19. Mechanical behavior of a composite interface: Calcium-silicate-hydrates

    International Nuclear Information System (INIS)

    The generalized stacking fault (GSF) is a conceptual procedure historically used to assess shear behavior of defect-free crystalline structures through molecular dynamics or density functional theory simulations. We apply the GSF technique to the spatially and chemically complex quasi-layered structure of calcium-silicate-hydrates (C-S-H), the fundamental nanoscale binder within cementitious materials. A failure plane is enforced to calculate the shear traction-displacement response along a composite interface containing highly confined water molecules, hydroxyl groups, and calcium ions. GSF simulations are compared with affine (homogeneous) shear simulations, which allow strain to localize naturally in response to the local atomic environment. Comparison of strength and deformation behavior for the two loading methods shows the composite interface controls bulk shear deformation. Both models indicate the maximum shear strength of C-S-H exhibits a normal-stress dependency typical of cohesive-frictional materials. These findings suggest the applicability of GSF techniques to inhomogeneous structures and bonding environments, including other layered systems such as biological materials containing organic and inorganic interfaces

  20. The influence of H-bonding on the 'ambidentate' coordination behaviour of the thiocyanate ion to Cd(II): a combined experimental and theoretical study.

    Science.gov (United States)

    Hazari, Alokesh; Das, Lakshmi Kanta; Bauzá, Antonio; Frontera, Antonio; Ghosh, Ashutosh

    2014-06-01

    Two new trinuclear hetero-metallic copper(II)-cadmium(II) complexes [(CuL)2Cd(NCS)2] (1) and [(CuL(R))2Cd(SCN)2] (2) have been synthesized using [CuL] and [CuL(R)] as "metalloligands" (where H2L = N,N'-bis(salicylidene)-1,4-butanediamine and H2L(R) = N,N'-bis(2-hydroxybenzyl)-1,4-butanediamine) respectively. Both the complexes were characterized by elemental analysis, various spectroscopic methods and single crystal XRD. Complex 1 is an angular trinuclear species, in which two terminal four-coordinate square planar "metalloligands" [CuL] are coordinated to a central Cd(II) through double phenoxido bridges along with two mutually cis nitrogen atoms of terminal thiocyanate ions. In complex 2, which is linear, in addition to the double phenoxido bridge, two SCN(-) coordinate to the trans positions of the central octahedral Cd(II) via S atoms. Theoretical calculations on the energetic difference between the two possible coordination modes of the thiocyanate anion to the Cd atom reveal that N-coordination is preferred over S-coordination in agreement with the much greater abundance of the reported N-bonded structures. In 2, there is a strong N-H···NCS-Cd H-bonding interaction, the binding energy of which is computed to be approximately -9.3 kcal mol(-1), which is sufficient to compensate the 9.0 kcal mol(-1) of energetic cost due to the unusual Cd-SCN coordination mode. PMID:24715108

  1. Classification of proton configurations of gas hydrate frameworks

    International Nuclear Information System (INIS)

    All molecular configurations differing in the position of hydrogen atoms (protons) in hydrogen bonds and satisfying periodic boundary conditions have been calculated for the unit cells of CS-I, HS-III, and TS-IV gas hydrate frameworks. The configurations obtained are ranged according to the number of stronger trans-configurations of hydrogen-bound molecular pairs and according to the type of spatial symmetry. The configuration symmetry was analyzed taking into account the additional antisymmetry operation, which is related to the change in the direction of all hydrogen bonds. The strong dependence of the framework properties on the specific position of protons in H bonds is established.

  2. Mechanical and electromagnetic properties of northern Gulf of Mexico sediments with and without THF hydrates

    Science.gov (United States)

    Lee, J.Y.; Santamarina, J.C.; Ruppel, C.

    2008-01-01

    Using an oedometer cell instrumented to measure the evolution of electromagnetic properties, small strain stiffness, and temperature, we conducted consolidation tests on sediments recovered during drilling in the northern Gulf of Mexico at the Atwater Valley and Keathley Canyon sites as part of the 2005 Chevron Joint Industry Project on Methane Hydrates. The tested specimens include both unremolded specimens (as recovered from the original core liner) and remolded sediments both without gas hydrate and with pore fluid exchanged to attain 100% synthetic (tetrahydrofuran) hydrate saturation at any stage of loading. Test results demonstrate the extent to which the electromagnetic and mechanical properties of hydrate-bearing marine sediments are governed by the vertical effective stress, stress history, porosity, hydrate saturation, fabric, ionic concentration of the pore fluid, and temperature. We also show how permittivity and electrical conductivity data can be used to estimate the evolution of hydrate volume fraction during formation. The gradual evolution of geophysical properties during hydrate formation probably reflects the slow increase in ionic concentration in the pore fluid due to ion exclusion in closed systems and the gradual decrease in average pore size in which the hydrate forms. During hydrate formation, the increase in S-wave velocity is delayed with respect to the decrease in permittivity, consistent with hydrate formation on mineral surfaces and subsequent crystal growth toward the pore space. No significant decementation/debonding occurred in 100% THF hydrate-saturated sediments during unloading, hence the probability of sampling hydrate-bearing sediments without disturbing the original sediment fabric is greatest for samples in which the gas hydrate is primarily responsible for maintaining the sediment fabric and for which the time between core retrieval and restoration of in situ effective stress in the laboratory is minimized. In evaluating the

  3. Pectin as an Extraordinary Natural Kinetic Hydrate Inhibitor

    Science.gov (United States)

    Xu, Shurui; Fan, Shuanshi; Fang, Songtian; Lang, Xuemei; Wang, Yanhong; Chen, Jun

    2016-03-01

    Pectin as a novel natural kinetic hydrate inhibitor, expected to be eco-friendly and sufficiently biodegradable, was studied in this paper. The novel crystal growth inhibition (CGI) and standard induction time methods were used to evaluate its effect as hydrate inhibitor. It could successfully inhibit methane hydrate formation at subcooling temperature up to 12.5 °C and dramatically slowed the hydrate crystal growth. The dosage of pectin decreased by 66% and effective time extended 10 times than typical kinetic inhibitor. Besides, its maximum growth rate was no more than 2.0%/h, which was far less than 5.5%/h of growth rate for PVCap at the same dosage. The most prominent feature was that it totally inhibited methane hydrate crystal rapid growth when hydrate crystalline occurred. Moreover, in terms of typical natural inhibitors, the inhibition activity of pectin increased 10.0-fold in induction time and 2.5-fold in subcooling temperature. The extraordinary inhibition activity is closely related to its hydrogen bonding interaction with water molecules and the hydrophilic structure. Finally, the biodegradability and economical efficiency of pectin were also taken into consideration. The results showed the biodegradability improved 75.0% and the cost reduced by more than 73.3% compared to typical commercial kinetic inhibitors.

  4. A Molecular Dynamic Simulation of Hydrated Proton Transfer in Perfluorosulfonate Ionomer Membranes (Nafion 117

    Directory of Open Access Journals (Sweden)

    Hong Sun

    2015-01-01

    Full Text Available A molecular dynamic model based on Lennard-Jones Potential, the interaction force between two particles, molecular diffusion, and radial distribution function (RDF is presented. The diffusion of the hydrated ion, triggered by both Grotthuss and vehicle mechanisms, is used to study the proton transfer in Nafion 117. The hydrated ion transfer mechanisms and the effects of the temperature, the water content in the membrane, and the electric field on the diffusion of the hydrated ion are analyzed. The molecular dynamic simulation results are in good agreement with those reported in the literature. The modeling results show that when the water content in Nafion 117 is low, H3O+ is the main transfer ion among the different hydrated ions. However, at higher water content, the hydrated ion in the form of H+(H2O2 is the main transfer ion. It is also found that the negatively charged sulfonic acid group as the fortified point facilitates the proton transfer in Nafion 117 better than the free water molecule. The diffusion of the hydrated ion can be improved by increasing the cell temperature, the water content in Nafion, and the electric field intensity.

  5. Hydration of calcium sulfoaluminate cements - Experimental findings and thermodynamic modelling

    International Nuclear Information System (INIS)

    Calcium sulfoaluminate cements (CSA) are a promising low-CO2 alternative to ordinary Portland cements and are as well of interest concerning their use as binder for waste encapsulation. In this study, the hydration of two CSA cements has been investigated experimentally and by thermodynamic modelling between 1 h and 28 days at w/c ratios of 0.72 and 0.80, respectively. The main hydration product of CSA is ettringite, which precipitates together with amorphous Al(OH)3 until the calcium sulfate is consumed after around 1-2 days of hydration. Afterwards, monosulfate is formed. In the presence of belite, straetlingite occurs as an additional hydration product. The pore solution analysis reveals that straetlingite can bind a part of the potassium ions, which are released by the clinker minerals. The microstructure of both cements is quite dense even after 16 h of hydration, with not much pore space available at a sample age of 28 days. The pore solution of both cements is dominated during the first hours of hydration by potassium, sodium, calcium, aluminium and sulfate; the pH is around 10-11. When the calcium sulfate is depleted, the sulfate concentration drops by a factor of 10. This increases pH to around 12.5-12.8. Based on the experimental data, a thermodynamic hydration model for CSA cements based on cement composition, hydration kinetics of clinker phases and calculations of thermodynamic equilibria by geochemical speciation has been established. The modelled phase development with ongoing hydration agrees well with the experimental findings.

  6. Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

    Science.gov (United States)

    Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

    2009-01-01

    We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

  7. Role of composition, bond covalency, and short-range order in the disordering of stannate pyrochlores by swift heavy ion irradiation

    Science.gov (United States)

    Tracy, Cameron L.; Shamblin, Jacob; Park, Sulgiye; Zhang, Fuxiang; Trautmann, Christina; Lang, Maik; Ewing, Rodney C.

    2016-08-01

    A2S n2O7 (A =Nd ,Sm,Gd,Er,Yb,and Y) materials with the pyrochlore structure were irradiated with 2.2 GeV Au ions to systematically investigate disordering of this system in response to dense electronic excitation. Structural modifications were characterized, over multiple length scales, by transmission electron microscopy, x-ray diffraction, and Raman spectroscopy. Transformations to amorphous and disordered phases were observed, with disordering dominating the structural response of materials with small A -site cation ionic radii. Both the disordered and amorphous phases were found to possess weberite-type local ordering, differing only in that the disordered phase exhibits a long-range, modulated arrangement of weberite-type structural units into an average defect-fluorite structure, while the amorphous phase remains fully aperiodic. Comparison with the behavior of titanate and zirconate pyrochlores showed minimal influence of the high covalency of the Sn-O bond on this phase behavior. An analytical model of damage accumulation was developed to account for simultaneous amorphization and recrystallization of the disordered phase during irradiation.

  8. CB-TE2A(+)·Cl(-)·3H2O: a short intermolecular hydrogen bond between zwitterionic bicyclo[6.6.2]tetraamine macrocycles.

    Science.gov (United States)

    Jurek, Paul; Reibenspies, Joseph H; Kiefer, Garry E

    2016-02-01

    1,4,8,11-Tetraazabicyclo[6.6.2]hexadecane-4,11-diacetic acid (CB-TE2A) is of much interest in nuclear medicine for its ability to form copper complexes that are kinetically inert, which is beneficial in vivo to minimize the loss of radioactive copper. The structural chemistry of the hydrated HCl salt of CB-TE2A, namely 11-carboxymethyl-1,8-tetraaza-4,11-diazoniabicyclo[6.6.2]hexadecane-4-acetate chloride trihydrate, C16H31N4O4(+)·Cl(-)·3H2O, is described. The compound crystallized as a positively charged zwitterion with a chloride counter-ion. Two of the amine groups in the macrocyclic ring are protonated. Formally, a single negative charge is shared between two of the carboxylic acid groups, while one chloride ion balances the charge. Two intramolecular hydrogen bonds are observed between adjacent pairs of N atoms of the macrocycle. Two intramolecular hydrogen bonds are also observed between the protonated amine groups and the pendant carboxylate groups. A short intermolecular hydrogen bond is observed between two partially negatively charged O atoms on adjacent macrocycles. The result is a one-dimensional polymeric zigzag chain that propagates parallel to the crystallographic a direction. A second intermolecular interaction is a hydrogen-bonding network in the crystallographic b direction. The carbonyl group of one macrocycle is connected through the three water molecules of hydration to the carbonyl group of another macrocycle. PMID:26846499

  9. The hydration structure of DNA and proteins

    International Nuclear Information System (INIS)

    Water-soluble proteins are surrounded by water molecules, and the water molecules mediate the biological processes: i.e. the protein folding, the enzymatic reaction, the molecular recognition via hydrogen bonds, electrostatic interactions and van der Waals interactions. It is essential to know the structural information such as orientation and dynamical behavior of water molecules including hydrogen atoms in order to characterize these interactions. The neutron analysis can determine the positions of the hydrogen atoms at the medium resolution in the protein crystallography (dmin∼2.0 A). Recently we have constructed the high-resolution neutron diffractometer (BIX) dedicated for the biological macromolecules. By using this diffractometer, the high resolution (1.5 or 1.6A) neutron structure analyses of sperm whale myoglobin, a wild-type rubredoxin from Pyrococcus furiosus, and the rubredoxin mutant have been successfully carried out and their hydration structure including hydrogen atoms have been observed. Hydrogen atoms in the water molecule can be clearly identified in two boomerang-shaped water molecules and the forming of the hydrogen bonds between the two water molecules can be recognized well. It has been concluded that hydration structure observed by the high resolution neutron protein crystallography provides where a water molecule locates, and how it binds to the neighbor atoms, and how it behaves. (M.Suetake)

  10. Modeling Hydrates and the Gas Hydrate Markup Language

    OpenAIRE

    Wang, Weihua; Moridis, George; Wang, Runqiang; Xiao, Yun; Li, Jianhui

    2007-01-01

    Natural gas hydrates, as an important potential fuels, flow assurance hazards, and possible factors initiating the submarine geo-hazard and global climate change, have attracted the interest of scientists all over the world. After two centuries of hydrate research, a great amount of scientific data on gas hydrates has been accumulated. Therefore the means to manage, share, and exchange these data have become an urgent task. At present, metadata (Markup Language) is recognized as one of the mo...

  11. Molecular simulations of CO2 and mixed CH4-CO2 hydrates intercalated on smectites.

    Science.gov (United States)

    Martos-Villa, Rubén; Sainz-Díaz, C. Ignacio; Mata Campo, M. Pilar

    2013-04-01

    Natural gas hydrates (NGH) are crystalline compounds consisting of methane molecules encaged in cavities of a hydrogen-bonded network of water molecules. Gas hydrates have a general formula X?nH2O, where X is the guest molecule within a water cage, and n is the hydration number per guest molecule. The crystal structure sI consists of 46 water molecules per unit cell, forming two dodecahedron (small 512) and six tetradecahedron (large 51262) cages and is formed when small guest molecules such as methane or carbon dioxide are trapped. Considerable amounts of methane hydrates can be found in permafrost regions and sediments of the ocean floor in outer continental margin regions where medium pressures, low temperatures and high methane gas concentration in water can be reached. Gas hydrates are important because hydrate decomposition would cause the methane release into atmosphere causing great impact on Earth's climate. On the other hand, these NGH are seen as a potential major energy resource. The recent increase in anthropogenic CO2 gas released to the atmosphere and its contribution to global warming, makes necessary to investigate new ways of CO2 storage. The possibility of replacing natural gas by CO2 from NGH has been investigated. There are thermodynamic evidences that support the replacement in hydrate at appropriate conditions. The comparison of their hydrate phase equilibrium conditions suggests the occurrence of a transition zone between both hydrate equilibrium curves where CO2 hydrates can exist while CH4 hydrates dissociate into methane gas and water. Any further investigation of the mixed CH4-CO2 gas hydrate properties could lead to major breakthroughs in the fields of unconventional resource production and carbon sequestration. Clay minerals are major constituents of ocean sediments, the study of interactions between these minerals with hydrates on the seafloor can be useful to determine variations on hydrate stability field, and to know the properties

  12. Rapid gas hydrate formation process

    Science.gov (United States)

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

    2013-01-15

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

  13. Femtosecond study of the effects of ions on the reorientation dynamics of water

    CERN Document Server

    van der Post, Sietse T; Bakker, Huib J

    2013-01-01

    We study the effects of ions on the reorientation dynamics of liquid water with polarization-resolved femtosecond mid-infared spectroscopy. We probe the anisotropy of the excitation of the O-D stretch vibration of HDO molecules in solutions of NaCl, NaI and tetra-alkylammonium bromide salts in 8 percent HDO:H2O. We find that the reorientation O-D groups of HDO molecules hydrating the Cl- and I- anions occurs on two different time scales with time constants of 2pm0.3 ps and 9pm2 ps. The fast component is due to a wobbling motion of the O-D group that keeps the hydrogen bond with the halogenic anion intact. For solutions of tetra-alkylammonium bromide salts we observe a very strong slowing down of the reorientation of water that is associated with the hydration of the hydrophobic alkyl groups of the tetra-alkylammonium ions.

  14. Gas hydrate cool storage system

    Science.gov (United States)

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

    1984-09-12

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

  15. Hydrate Monitoring using Capacitive Sensors

    OpenAIRE

    Bayati, Zahra

    2013-01-01

    Gas hydrates are of particular interest in petroleum industry since their formation during oil-production can be a major risk factor. Gas hydrates can block pipelines, interrupt production, and in worst case even cause bursting flow lines. There are a few strategies available to monitor the hydrocarbon flow in pipelines in order to give an early warning system against hydrate formation. A potential technique is to monitor changes in the dielectric properties of the flow, and relate these to h...

  16. Hydration of lysozyme as observed by infrared spectrometry.

    Science.gov (United States)

    Liltorp, K; Maréchal, Y

    2005-11-01

    Infrared spectra of a film of lysozyme 3 mum thick, immersed in an atmosphere displaying a relative humidity, or hygrometry, which spans the whole range from 0 to 1 at room temperature, are recorded. The evolution of the spectra with this relative humidity is quantitatively analyzed on the basis of a newly proposed method. It allows the precise measurement of the quantity of water that remains embedded inside the dried sample at each stage of hydration, and the definition, in terms of chemical reactions of the three hydration mechanisms that correspond to the three hydration spectra on which all experimental spectra can be decomposed. With respect to preceding similar studies, some refinements are introduced that allow improvement of the interpretation, but that also raise some new questions, which mainly concern the structure of the hydrogen-bond network around the carbonyl peptide groups. PMID:15986502

  17. Uranyl p-toluenesulfonate and its crystal hydrates, synthesis, and dehydration-hydration processes

    International Nuclear Information System (INIS)

    While uranyl benzenesulfonate (UBS) crystallizes from aqueous solutions as monohydrate, uranyl p-toluenesulfonate (UPTS) crystallizes as pentahydrate, UPTS solubility in water is 2.57 mol.kg-1, which is about one-half the solubility of UBS (4.85 mol.kg-1). We synthesized the lowest hydrates of UPTS and the anhydrous salt and studied the hydration of anhydrous UPTS in air at various water vapour pressures. Thermogravimetry and gravimetry in air under standard conditions revealed that the hydrate shell of UPTS.5H2O possess a layer structure. After thorough grinding and storage of the product in air for 3-4 days we obtained stable UPTS.3H20. In conditions of slow crystallization from aqueous solutions, crystals of UO2(CH3C6H4S03)2.5H20 were obtained. Their size was 5 mm x 3 mm, the crystal had regular faces. The coordination of sulfonate ions to uranyl (apparently bidentate) in UPTS and its hydrates is similar to that in UBS

  18. Gas hydrates of Lake Baikal

    OpenAIRE

    Khlystov, O.; De Batist, M.; Shoji, H; Nishio, S.; L. Naudts; J. Poort

    2011-01-01

    This paper reviews some of the results of recent gas-hydrate studies in Lake Baikal, the only fresh-water lake in the world containing gas hydrates in its sedimentary infill. We give a historical overview of the different investigations and discoveries and highlight some recent breakthroughs in our understanding of the Baikal hydrate system. The importance of mapping mud volcanoes and gas seeps is stressed, as these are currently the only locations where gas hydrates at or very close to the f...

  19. Hydration Energies of Protonated and Sodiated Thiouracils

    Science.gov (United States)

    Wincel, Henryk

    2014-12-01

    Hydration reactions of protonated and sodiated thiouracils (2-thiouracil, 6-methyl-2-thiouracil, and 4-thiouracil) generated by electrospray ionization have been studied in a gas phase at 10 mbar using a pulsed ion-beam high-pressure mass spectrometer. The thermochemical data, ΔH o n, ΔS o n, and ΔG o n, for the hydrated systems were obtained by equilibrium measurements. The water binding energies of protonated thiouracils, [2SU]H+ and [6Me2SU]H+, were found to be of the order of 51 kJ/mol for the first, and 46 kJ/mol for the second water molecule. For [4SU]H+, these values are 3-4 kJ/mol lower. For sodiated complexes, these energies are similar for all studied systems, and varied between 62 and 68 kJ/mol for the first and between 48 and 51 kJ/mol for the second water molecule. The structural aspects of the precursors for hydrated complexes are discussed in conjunction with available literature data.

  20. On the Bonding Properties of Trivalent Actinide and Lanthanide Ions: U(III)-Cl, Np(III)-Cl and Ce(III)-Cl Bonding in a LiCl-KCl Eutectic Melt at 450 .deg. C: Spectroscopic Evidences from Their ∫-d and ∫-∫ Electronic Transitions

    International Nuclear Information System (INIS)

    While studying the chemical behavior of actinide ions in the chloride based molten salt, we recognized the importance of the 5∫-5d transitions of the actinide ions in interpreting the bonding properties of the An-Cl complexes. We aimed to explain the nature of chemical bonding in the U(III)-Cl and Np(III)-Cl and Ce(III)-Cl focusing on interpretation of their electronic absorption spectra. Measurement units interfaced with a glove box.furnace system were designed and set up for spectro and electrochemical measurements simultaneously in high temperature molten salt media. The experimental details of the spectro-electrochemical measurement are described in our recent paper

  1. On the Bonding Properties of Trivalent Actinide and Lanthanide Ions: U(III)-Cl, Np(III)-Cl and Ce(III)-Cl Bonding in a LiCl-KCl Eutectic Melt at 450 .deg. C: Spectroscopic Evidences from Their ∫-d and ∫-∫ Electronic Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Young-Hwan; Bae, Sang-Eun; Kim, Jong-Yun; Park, Tae-Hong [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    While studying the chemical behavior of actinide ions in the chloride based molten salt, we recognized the importance of the 5∫-5d transitions of the actinide ions in interpreting the bonding properties of the An-Cl complexes. We aimed to explain the nature of chemical bonding in the U(III)-Cl and Np(III)-Cl and Ce(III)-Cl focusing on interpretation of their electronic absorption spectra. Measurement units interfaced with a glove box.furnace system were designed and set up for spectro and electrochemical measurements simultaneously in high temperature molten salt media. The experimental details of the spectro-electrochemical measurement are described in our recent paper.

  2. Phase equilibrium of methane hydrate in silica sand containing chloride salt solution

    International Nuclear Information System (INIS)

    Highlights: • Methane hydrate equilibria in silica sand-ionic solution are obtained. • Hydrate equilibria in fine sand-solution shift more than single sand or solution. • Electrostatic and capillary forces affect hydrate equilibria in fine sand-solution. • Hydrate equilibria in coarse sand-solution agree with those in single solution. • Hydrate equilibria in coarse sand-solution are mainly affected by ions. - Abstract: Hydrate equilibrium is the most important foundation for other hydrate issues, especially for marine environment condition. In this work, the silica sand containing NaCl/MgCl2/CaCl2 aqueous solution were used to simulate marine sediment for investigating methane hydrate equilibrium using isochoric multi-step heating dissociation method. All measurements were performed in a temperature and pressure range of (279.5 to 289.7) K and (8.32 to 17.52) MPa, respectively. The results suggest that the equilibrium of methane hydrate in fine-grained silica sand containing chloride salt solution shifts more greatly to the left relative to that in single silica sand or solution. This is because water molecules reduce more chances to combine with gas molecules that is caused by the capillary force and the electrostatic attractions from the surface and electrolyte ions. However, hydrate equilibrium in coarse-grained silica sand containing chloride salt solution is in rough agreement with that in ionic solution of the corresponding concentration that indicates that hydrate equilibrium is mainly influenced by ions while the impact of solid particles is negligible

  3. X-ray and Neutron Diffraction in the Study of Organic Crystalline Hydrates

    Directory of Open Access Journals (Sweden)

    Katharina Fucke

    2010-07-01

    Full Text Available A review. Diffraction methods are a powerful tool to investigate the crystal structure of organic compounds in general and their hydrates in particular. The laboratory standard technique of single crystal X-ray diffraction gives information about the molecular conformation, packing and hydrogen bonding in the crystal structure, while powder X-ray diffraction on bulk material can trace hydration/dehydration processes and phase transitions under non-ambient conditions. Neutron diffraction is a valuable complementary technique to X-ray diffraction and gives highly accurate hydrogen atom positions due to the interaction of the radiation with the atomic nuclei. Although not yet often applied to organic hydrates, neutron single crystal and neutron powder diffraction give precise structural data on hydrogen bonding networks which will help explain why hydrates form in the first place.

  4. Quasichemical and structural analysis of polarizable anion hydration

    Science.gov (United States)

    Rogers, David M.; Beck, Thomas L.

    2010-01-01

    Quasichemical theory is utilized to analyze the relative roles of solute polarization and size in determining the structure and thermodynamics of bulk anion hydration for the Hofmeister series Cl-, Br-, and I-. Excellent agreement with experiment is obtained for whole salt hydration free energies using the polarizable AMOEBA force field. The total hydration free energies display a stronger dependence on ion size than on polarizability. The quasichemical approach exactly partitions the solvation free energy into inner-shell, outer-shell packing, and outer-shell long-ranged contributions by means of a hard-sphere condition. The inner-shell contribution becomes slightly more favorable with increasing ion polarizability, indicating electrostriction of the nearby waters. Small conditioning radii, even well inside the first maximum of the ion-water(oxygen) radial distribution function, result in Gaussian behavior for the long-ranged contribution that dominates the ion hydration free energy. This in turn allows for a mean-field treatment of the long-ranged contribution, leading to a natural division into first-order electrostatic, induction, and van der Waals terms. The induction piece exhibits the strongest ion polarizability dependence, while the larger-magnitude first-order electrostatic piece yields an opposing but weaker polarizability dependence. The van der Waals piece is small and positive, and it displays a small ion specificity. The sum of the inner-shell, packing, and long-ranged van der Waals contributions exhibits little variation along the anion series for the chosen conditioning radii, targeting electrostatic effects (influenced by ion size) as the largest determinant of specificity. In addition, a structural analysis is performed to examine the solvation anisotropy around the anions. As opposed to the hydration free energies, the solvation anisotropy depends more on ion polarizability than on ion size: increased polarizability leads to increased anisotropy

  5. Quasichemical and structural analysis of polarizable anion hydration.

    Science.gov (United States)

    Rogers, David M; Beck, Thomas L

    2010-01-01

    Quasichemical theory is utilized to analyze the relative roles of solute polarization and size in determining the structure and thermodynamics of bulk anion hydration for the Hofmeister series Cl(-), Br(-), and I(-). Excellent agreement with experiment is obtained for whole salt hydration free energies using the polarizable AMOEBA force field. The total hydration free energies display a stronger dependence on ion size than on polarizability. The quasichemical approach exactly partitions the solvation free energy into inner-shell, outer-shell packing, and outer-shell long-ranged contributions by means of a hard-sphere condition. The inner-shell contribution becomes slightly more favorable with increasing ion polarizability, indicating electrostriction of the nearby waters. Small conditioning radii, even well inside the first maximum of the ion-water(oxygen) radial distribution function, result in Gaussian behavior for the long-ranged contribution that dominates the ion hydration free energy. This in turn allows for a mean-field treatment of the long-ranged contribution, leading to a natural division into first-order electrostatic, induction, and van der Waals terms. The induction piece exhibits the strongest ion polarizability dependence, while the larger-magnitude first-order electrostatic piece yields an opposing but weaker polarizability dependence. The van der Waals piece is small and positive, and it displays a small ion specificity. The sum of the inner-shell, packing, and long-ranged van der Waals contributions exhibits little variation along the anion series for the chosen conditioning radii, targeting electrostatic effects (influenced by ion size) as the largest determinant of specificity. In addition, a structural analysis is performed to examine the solvation anisotropy around the anions. As opposed to the hydration free energies, the solvation anisotropy depends more on ion polarizability than on ion size: increased polarizability leads to increased

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

    International Nuclear Information System (INIS)

    CO2 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 CO2 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 CO2 (CO2 + CH4/N2/H2) 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 CO2, CH4, and N2. 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 to conclude about

  7. Ductile flow of methane hydrate

    Science.gov (United States)

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

    2003-01-01

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

  8. Some thermodynamical aspects of protein hydration water

    International Nuclear Information System (INIS)

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

  9. Some thermodynamical aspects of protein hydration water

    Energy Technology Data Exchange (ETDEWEB)

    Mallamace, Francesco, E-mail: francesco.mallamace@unime.it [Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy); Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States); Corsaro, Carmelo [Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy); CNR-IPCF, Viale F. Stagno D’Alcontres 37, I-98158 Messina (Italy); Mallamace, Domenico [Dipartimento SASTAS, Università di Messina, I-98166 Messina (Italy); Vasi, Sebastiano [Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy); Vasi, Cirino [CNR-IPCF, Viale F. Stagno D’Alcontres 37, I-98158 Messina (Italy); Stanley, H. Eugene [Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States); Chen, Sow-Hsin [Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-06-07

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

  10. Storage of molecular hydrogen into leaky clathrate hydrate cages

    International Nuclear Information System (INIS)

    Full text: Efficient storage of hydrogen into compact media is an essential challenge to establish a hydrogen economy. A nanostructured compound made of water and gas molecules, which is called as clathrate hydrate, is one reasonable choice for this important task. Its structure consists of three-dimensional network of hydrogen-bonded water molecules (host cages) and small nonpolar molecules (guests) encaged within this network. The clathrate hydrate medium is chemically durable, environmentally benign, and also free from the necessity of expensive rare metals. Large amount of molecular hydrogen up to 3.8 wt.% was successfully stored into the structure II hydrogen clathrate hydrate (Fd3m space group, lattice constant ∼ 1.7 nm), while it is only synthesized at low temperature and/or high pressure conditions which are not suitable for industrial applications. Required pressure to put significant amount of hydrogen into the hydrate structure is much reducible by blending in additional guest species acting as a hydrate promoter. The promoter molecules added to the system occupy some of the cages to stabilize the hydrate structure at lower pressures, so that the hydrogen storage capacity is partly reduced instead. In addition to the problem of storage capacity, kinetic aspect of hydrogen clathrate hydrate synthesis is also essential for the expected application. Its conventional production scheme was by freezing promoter's solution contacting with pressurized hydrogen gas; it then takes long time for crystal growth. We have established an alternative scheme enabling much faster synthesis (Okuchi et al., Appl. Phys. Lett., 91, 171903, 2007). We found that when hydrogen-free clathrate hydrate powders including a promoter (tetrahydrofuran) was contacted with pressurized hydrogen gas, hydrogen was quickly absorbed into the hydrate medium. We observed the absorption kinetics by nuclear magnetic resonance spectroscopy as a function of hydrogen pressure and temperature. In

  11. Temperature effect on the small-to-large crossover lengthscale of hydrophobic hydration

    International Nuclear Information System (INIS)

    The thermodynamics of hydration is expected to change gradually from entropic for small solutes to enthalpic for large ones. The small-to-large crossover lengthscale of hydrophobic hydration depends on the thermodynamic conditions of the solvent such as temperature, pressure, presence of additives, etc. We attempt to shed some light on the temperature dependence of the crossover lengthscale by using a probabilistic approach to water hydrogen bonding that allows one to obtain an analytic expression for the number of bonds per water molecule as a function of both its distance to a solute and solute radius. Incorporating that approach into the density functional theory, one can examine the solute size effects on its hydration over the entire small-to-large lengthscale range at a series of different temperatures. Knowing the dependence of the hydration free energy on the temperature and solute size, one can also obtain its enthalpic and entropic contributions as functions of both temperature and solute size. These functions can provide some interesting insight into the temperature dependence of the crossover lengthscale of hydrophobic hydration. The model was applied to the hydration of spherical particles of various radii in water in the temperature range from T = 293.15 K to T = 333.15 K. The model predictions for the temperature dependence of the hydration free energy of small hydrophobes are consistent with the experimental and simulational data on the hydration of simple molecular solutes. Three alternative definitions for the small-to-large crossover length-scale of hydrophobic hydration are proposed, and their temperature dependence is obtained. Depending on the definition and temperature, the small-to-large crossover in the hydration mechanism is predicted to occur for hydrophobes of radii from one to several nanometers. Independent of its definition, the crossover length-scale is predicted to decrease with increasing temperature

  12. Flow assurance intervention, hydrates remediation

    Energy Technology Data Exchange (ETDEWEB)

    Mancini, Christopher S. [Oceaneering International Inc., Houston, TX (United States)

    2012-07-01

    This paper addresses the issues of removing hydrates in sub sea flow lines and associated equipment with an Remotely Operated Vehicle (ROV) of opportunity and a multi-service-vessel (MSV). The paper is split into three topics: the equipment used with the ROV, assessing the interface points and handling fluids produced from drawing down the pressure. Each section is explained thoroughly and backed up with real world experience. The equipment section details information from actual jobs performed and why the particular components were utilized. The system is generally contained in an ROV mounted skid. Pumps are utilized to draw down the pressure inside the hydrated section of equipment, removing one of the three necessary components for hydrates formation. Once the section is pumped down, several options exist for handling the fluids pumped out of the system: pumping to surface, re-injection into the well, or injection into an operating flow line. This method of hydrates remediation is both economical and timely. Hydrate blockages form in low temperatures and high pressures. Reducing the pressure or increasing the temperature so the conditions lie to the right of the hydrate dissociation curve will slowly decompose the blockage. Depressurization and the use of MEG or methanol will give favorable conditions to remove the hydrate plug. Oceaneering has the capabilities to remove hydrates using the FRS in conjunction with an installation vessel to dispose of the gas and fluid removed from the flow line. Hydrate remediation techniques should be implemented into the initial design to reduce costs later. The cost of stopped production combined with the day rate for equipment needed for hydrate removal outweighs the costs if no technique is utilized. (author)

  13. Structure-Property of Metal Organic Frameworks Calcium Terephthalates Anodes for Lithium-ion Batteries

    International Nuclear Information System (INIS)

    Graphical Abstract: Effects of hydration water in calcium terephthalates anodes on the structure, operational voltage and electrochemical performance are systematically studied. Display Omitted -- Highlights: •Metal organic frameworks CaC8H4O4·3H2O and CaC8H4O4 are applied as anodes for lithium ion batteries. •Appearance of hydration water leads different crystallography structures and electrochemical performance. •Anhydrous CaC8H4O4 has a spacious ordered layer structure, a higher Ca-O chemical bonding interaction and a higher transparent lithium ion diffusion coefficient, delivering a higher capacity, better cycling performance and rate performance than CaC8H4O4·3H2O. -- Abstract: Metal organic frameworks have attracted considerable interest as electrode materials for lithium ion batteries. In this paper, the metal organic frameworks hydrated calcium terephthalate (CaC8H4O4·3H2O) and anhydrous calcium terephthalate (CaC8H4O4) as anodes for lithium ion batteries are comparatively studied. Crystallography and local chemical bond analysis are combined to interpret the structure-property of calcium terephthalates. Results show that the anhydrous CaC8H4O4 has a spacious ordered layer structure and a higher Ca-O chemical bonding interaction, delivering a higher capacity, better cycling performance and rate performance than CaC8H4O4·3H2O

  14. Crystal chemistry and structure refinement of five hydrated calcium borates

    Science.gov (United States)

    Clark, J.R.; Appleman, D.E.; Christ, C.L.

    1964-01-01

    The crystal structures of the five known members of the series Ca2B6O11??xH2O (x = 1, 5, 5, 7, 9, and 13) have been refined by full-matrix least-squares techniques, yielding bond distances and angles with standard errors of less than 0??01 A?? and 0??5??, respectively. The results illustrate the crystal chemical principles that govern the structures of hydrated borate compounds. The importance of hydrogen bonding in the ferroelectric transition of colemanite is confirmed by more accurate proton assignments. ?? 1964.

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2016-03-01

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

  17. Investigation on Gas Storage in Methane Hydrate

    Institute of Scientific and Technical Information of China (English)

    Zhigao Sun; Rongsheng Ma; Shuanshi Fan; Kaihua Guo; Ruzhu Wang

    2004-01-01

    The effect of additives (anionic surfactant sodium dodecyl sulfate (SDS), nonionic surfactant alkyl polysaccharide glycoside (APG), and liquid hydrocarbon cyclopentane (CP)) on hydrate induction time and formation rate, and storage capacity was studied in this work. Micelle surfactant solutions were found to reduce hydrate induction time, increase methane hydrate formation rate and improve methane storage capacity in hydrates. In the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation were reduced. The critical micelle concentrations of SDS and APG water solutions were found to be 300× 10-6 and 500× 10-6 for methane hydrate formation system respectively. The effect of anionic surfactant (SDS) on methane storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduced hydrate induction time and improved hydrate formation rate, but could not improve methane storage in hydrates.

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

    International Nuclear Information System (INIS)

    Crystalline (monomeric) soybean and (tetrameric) sweet potato β-amylase were shown to catalyze the cis hydration of maltal (α-D-glucopyranosyl-2-deoxy-D-arabino-hex-1-enitol) to form β-2-deoxymaltose. As reported earlier with the sweet potato enzyme, maltal hydration in D2O by soybean β-amylase was found to exhibit an unusually large solvent deuterium kinetic isotope effect (VH/VD=6.5), a reaction rate linearly dependent on the mole fraction of deuterium, and 2-deoxy-[2(a)-2H]maltose as product. These results indicate (for each β-amylase) that protonation is the rate-limiting step in a reaction involving a nearly symmetric one-proton transition state and that maltal is specifically protonated from above the double bond. That maltal undergoes cis hydration provides evidence in support of a general-acid-catalyzed, carbonium ion mediated reaction. Of fundamental significance is that β-amylase protonates maltal from a direction opposite that assumed for protonating strach, yet creates products of the same anomeric configuration from both. Such stereochemical dichotomy argues for the overriding role of protein structures is dictating the steric outcome of reactions catalyzed by a glycosylase, by limiting the approach and orientation of water or other acceptors to the reaction center

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

    OpenAIRE

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

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measuremen...

  20. Structural characteristics of hydrated protons in the conductive channels: effects of confinement and fluorination studied by molecular dynamics simulation.

    Science.gov (United States)

    Zhang, Ning; Song, Yuechun; Ruan, Xuehua; Yan, Xiaoming; Liu, Zhao; Shen, Zhuanglin; Wu, Xuemei; He, Gaohong

    2016-09-21

    The relationship between the proton conductive channel and the hydrated proton structure is of significant importance for understanding the deformed hydrogen bonding network of the confined protons which matches the nanochannel. In general, the structure of hydrated protons in the nanochannel of the proton exchange membrane is affected by several factors. To investigate the independent effect of each factor, it is necessary to eliminate the interference of other factors. In this paper, a one-dimensional carbon nanotube decorated with fluorine was built to investigate the independent effects of nanoscale confinement and fluorination on the structural properties of hydrated protons in the nanochannel using classical molecular dynamics simulation. In order to characterize the structure of hydrated protons confined in the channel, the hydrogen bonding interaction between water and the hydrated protons has been studied according to suitable hydrogen bond criteria. The hydrogen bond criteria were proposed based on the radial distribution function, angle distribution and pair-potential energy distribution. It was found that fluorination leads to an ordered hydrogen bonding structure of the hydrated protons near the channel surface, and confinement weakens the formation of the bifurcated hydrogen bonds in the radial direction. Besides, fluorination lowers the free energy barrier of hydronium along the nanochannel, but slightly increases the barrier for water. This leads to disintegration of the sequential hydrogen bond network in the fluorinated CNTs with small size. In the fluorinated CNTs with large diameter, the lower degree of confinement produces a spiral-like sequential hydrogen bond network with few bifurcated hydrogen bonds in the central region. This structure might promote unidirectional proton transfer along the channel without random movement. This study provides the cooperative effect of confinement dimension and fluorination on the structure and hydrogen

  1. Calculation of Vibrational Spectra of p-Ethylbenzenesulfonic Acid Hydrates

    Science.gov (United States)

    Zelenkovskii, V. M.; Bezyazychnaya, T. V.; Soldatov, V. S.

    2013-09-01

    Quantum-chemical calculations of vibrational spectra of the sulfonated ion-exchanger model p-ethylbenzenesulfonic acid hydrated by 1-10 water molecules and its dimer were calculated by the non-empirical SCF MO LCAO method with the 6-31G(d) basis set. The calculated results were compared with experimental IR and Raman spectra of sulfonated ion exchangers. The infl uence of hydration on the vibrational frequencies of functional groups in the ion exchangers was analyzed. It was shown that the sulfonic acid was completely dissociated if three and more water molecules per functional group were present. Bands near 1130 cm-1 were due to S-O-H bending vibrations in the absence of water molecules and C-S-O-H3O combination vibrations with 3-6 water molecules per sulfonic acid.

  2. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Directory of Open Access Journals (Sweden)

    Sposito Garrison

    2002-09-01

    Full Text Available Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

  3. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    International Nuclear Information System (INIS)

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH2-CH2O)2-1,2-C2B9H10)(1',2'-C2B9H11)-3,3'-Co]- (CMPO = Ph2P(O)-CH2C(O)NR, R = C4H9 (3b), -C12H25 (4b), -CH2-C6H5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11B NMR, 1H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  4. Structure of the ordered hydration of amino acids in proteins: analysis of crystal structures

    Energy Technology Data Exchange (ETDEWEB)

    Biedermannová, Lada, E-mail: lada.biedermannova@ibt.cas.cz; Schneider, Bohdan [Institute of Biotechnology CAS, Videnska 1083, 142 20 Prague (Czech Republic)

    2015-10-27

    The hydration of protein crystal structures was studied at the level of individual amino acids. The dependence of the number of water molecules and their preferred spatial localization on various parameters, such as solvent accessibility, secondary structure and side-chain conformation, was determined. Crystallography provides unique information about the arrangement of water molecules near protein surfaces. Using a nonredundant set of 2818 protein crystal structures with a resolution of better than 1.8 Å, the extent and structure of the hydration shell of all 20 standard amino-acid residues were analyzed as function of the residue conformation, secondary structure and solvent accessibility. The results show how hydration depends on the amino-acid conformation and the environment in which it occurs. After conformational clustering of individual residues, the density distribution of water molecules was compiled and the preferred hydration sites were determined as maxima in the pseudo-electron-density representation of water distributions. Many hydration sites interact with both main-chain and side-chain amino-acid atoms, and several occurrences of hydration sites with less canonical contacts, such as carbon–donor hydrogen bonds, OH–π interactions and off-plane interactions with aromatic heteroatoms, are also reported. Information about the location and relative importance of the empirically determined preferred hydration sites in proteins has applications in improving the current methods of hydration-site prediction in molecular replacement, ab initio protein structure prediction and the set-up of molecular-dynamics simulations.

  5. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo

    2010-11-25

    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  6. A computational study of bond-breaking process of Cu-Si bond during ion sputtering of a Cu/Si(1 1 1) surface, based on molecular orbital theory

    International Nuclear Information System (INIS)

    A theoretical approach based on molecular orbital theory has been provided. By applying this theory to a bond-breaking process, the ionization probability of Cu adsobates sputtered from a ''5x5''-Cu/Si(1 1 1) surface has been studied. Three important aspects have been confirmed: (1) importance of a long range electrostatic potential such as the image potential, (2) importance of the coulomb repulsive potential between the Cu 4s spin-up and spin-down electron, and finally (3) acceleration and deceleration effects depending on charge state, which is a result of the interplay of the molecular bonding interaction and the long range electrostatic interaction. The measurements of ionization probability will provide us more information of the adiabatic potential curves of the reactants from the surfaces

  7. On Graphene Hydrate

    OpenAIRE

    Wang, Wei L.; Kaxiras, Efthimios

    2010-01-01

    Using first-principles calculations, we show that the formation of carbohydrate directly from carbon and water is energetically favored when graphene membrane is subjected to aqueous environment with difference in chemical potential across the two sides. The resultant carbohydrate is two-dimensional, where the hydrogen atoms are exclusively attached on one side of graphene while the hydroxyl groups on the other side form a herringbone reconstruction that optimizes hydrogen bonding. We show th...

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

    Science.gov (United States)

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

    2015-10-01

    The reaction of sulfur hexafluoride with gas-phase hydrated electrons (H2O)n(-), n ≈ 60-130, is investigated at temperatures T = 140-300 K by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. SF6 reacts with a temperature-independent rate of 3.0 ± 1.0 × 10(-10) cm(3) s(-1) via exclusive formation of the hydrated F(-) anion and the SF5(•) radical, which evaporates from the cluster. Nanocalorimetry yields a reaction enthalpy of ΔHR,298K = 234 ± 24 kJ mol(-1). Combined with literature thermochemical data from bulk aqueous solution, these result in an F5S-F bond dissociation enthalpy of ΔH298K = 455 ± 24 kJ mol(-1), in excellent agreement with all high-level quantum chemical calculations in the literature. A combination with gas-phase literature thermochemistry also yields an experimental value for the electron affinity of SF5(•), EA(SF5(•)) = 4.27 ± 0.25 eV. PMID:26356833

  9. Hydration in soccer: a review

    OpenAIRE

    Monteiro Cristiano Ralo; Guerra Isabela; Barros Turíbio Leite de

    2003-01-01

    Hydration should be considered before, during and after the exercise. This review intends to approach the main points of hydration process in soccer. The replacement of fluids during exercise is proportional to some factors, such as: exercise intensity; climatic conditions; the athlete's acclimatization; the athlete's physical conditioning; physiologic individual characteristics and the player's biomechanics. Performance is improved when players ingest not only water but also carbohydrate. Th...

  10. Preparation and characterization of titanium dioxide nanotube array supported hydrated ruthenium oxide catalysts

    Science.gov (United States)

    Giang, Thi Phuong Ly; Tran, Thi Nhu Mai; Le, Xuan Tuan

    2012-03-01

    This work aimed at preparing and characterizing TiO2 nanotube supported hydrated ruthenium oxide catalysts. First of all, we succeeded in preparing TiO2 nanotube arrays by electrochemical anodization of titanium metal at 20 V for 8 h in a 1M H3PO4+0.5 wt% HF solution as evidenced from scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) results. The hydrated ruthenium oxide was then deposited onto TiO2 nanotubes by consecutive exchange of protons by Ru3+ ions, followed by formation of hydrated oxide during the alkali treatment. Further XPS measurements showed that the modified samples contain not only hydrated ruthenium oxide but also hydrated ruthenium species Ru(III)-OH.

  11. Hydration water and microstructure in calcium silicate and aluminate hydrates

    International Nuclear Information System (INIS)

    Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C3S, C2S) and aluminates (C3A, C4AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm-1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide angle x

  12. Ionic conduction in different hydrated V2O5 film

    Science.gov (United States)

    Saatci, A. Evrim; Gökdemir, F. Pınar; Menda, U. Deneb; Kavak, Pelin; Özdemir, Orhan; Kutlu, Kubilay

    2012-09-01

    Because of the layered structure of vanadium pentoxide films (V2O5), approved by XRD measurement, sensitized from different hydrated V2O5.nH2O sols, demonstrated anisotropic conductivities in current voltage (I-V) measurement. Conductivity values, originated from electronic and ionic conductions, differed provided that measurements were performed in a direction parallel to the ribbons rather than perpendicular to them. The overall electrical conductivity of V2O5nH2O sols mainly depended on the hydration state n and the amount of reduced V4+ ions in which n was determined around 4-6 [1] from the basal distance (17.6 Å) through XRD measurement while V4+ ions were determined through FTIR analysis. Electronic conduction prevailed in dehydrated V2O50.5H2O sols whereas non-stoichiometric vanadium pentoxide was a mixed-valence compound and its electronic properties arised from electron hopping between V4+ and V5+ ions so-called "small polaron model". Indeed, reduction/oxidation peaks in lithium (Li+) intercalation by cyclic voltammograms (CV) indicated the V4+ and V5+ ions in V2O5 sols. Temperature dependent I-V analysis showed Arheniuss type activation energy, EA, and located in between 0.3-0.5 eV; proposing ionic conduction rather than electronic conduction, specifically proton diffusion in V2O5 film. Indeed, hydration state greater than 0.5 predicted ionic conduction [1].

  13. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  14. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  15. Molecular dynamics simulations of carbon dioxide hydrate growth in electrolyte solutions of NaCl and MgCl2

    Science.gov (United States)

    Yi, Lizhi; Liang, Deqing; Zhou, Xuebing; Li, Dongliang; Wang, Jianwei

    2014-12-01

    Molecular dynamics simulations are performed to study the growth of carbon dioxide (CO2) hydrate in electrolyte solutions of NaCl and MgCl2. The kinetic behaviour of the hydrate growth is examined in terms of cage content, density profile, and mobility of ions and water molecules, and how these properties are influenced by added NaCl and MgCl2. Our simulation results show that both NaCl and MgCl2 inhibit the CO2 hydrate growth. With a same mole concentration or ion density, MgCl2 exhibits stronger inhibition on the growth of CO2 hydrate than NaCl does. The growth rate of the CO2 hydrate in NaCl and MgCl2 solutions decreases slightly with increasing pressure. During the simulations, the Na+, Mg2+, and Cl- ions are mostly excluded by the growing interface front. We find that these ions decrease the mobility of their surrounding water molecules, and thus reduce the opportunity for these water molecules to form cage-like clusters toward hydrate formation. We also note that during the growth processes, several 51263 cages appear at the hydrate/solution interface, although they are finally transformed to tetrakaidecahedral (51262) cages. Structural defects consisting of one water molecule trapped in a cage with its hydrogen atoms being attracted by two Cl- ions have also been observed.

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

    International Nuclear Information System (INIS)

    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 CH3F and a large polar molecule induces defects on the clathrate hydrate framework that allow intercage guest dynamics. 13C NMR chemical shifts of a CH3F/CH4/TBME sH hydrate and a temperature analysis of the 2H NMR powder lineshapes of a CD3F/THF sII and CD3F/TBME sH hydrate, displayed evidence that the populations of CH4 and CH3F in the D and D′ cages were in a state of rapid exchange. A hydrogen bonding analysis using molecular dynamics simulations on the TBME/CH3F and TBME/CH4 sH hydrates showed that the presence of CH3F enhances the hydrogen bonding probability of the TBME molecule with the water molecules of the cavity. Similar results were obtained for THF/CH3F and THF/CH4 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 CH3F molecules between adjacent small cages

  17. ESR of vanadyl ions in Mg(H2O)6H2EDTA single crystals

    Science.gov (United States)

    Narayana, M.

    1980-04-01

    An ESR study of single crystals of Mg(H2O)6H2EDTA doped with very small concentrations of vanadyl ions showed the spectra and spin-Hamiltonian parameters to be totally different from those obtained in an earlier study with higher concentrations of VO2+. The results obtained in the present study are comparable with the data of VO(H2O)52+ in other hydrated salts like alums, etc. In low concentrations, VO2+ takes up two preferred orientations along Mg-Ow1 and Mg-Ow2 in the host octahedron. The hyperfine splitting is slightly less than that in other hydrated salts, most probably due to the strong hydrogen bonding involving the metal-water octahedra in Mg(H2O)6H2EDTA.

  18. Computer simulation of the hydration of a chloride anion in a nanopore with hydrophilic walls

    Science.gov (United States)

    Shevkunov, S. V.

    2016-05-01

    The hydration of a single-charged chloride anion Cl- in a model plane nanopore with structureless hydrophilic walls in water vapor at room temperature is simulated using the Monte Carlo method. It is established that the adsorption of a fraction of associate molecules Cl-(H2O)N on the walls enhances its thermodynamic stability and simulates the hydration of the ion at low vapor pressures. It is shown that a second stability crisis forms on the curve of the hydration work function in the mode of weak wall hydrophilicity.

  19. Guided ion beam studies of the reactions of Nin+ (n=2-18) with O2: Nickel cluster oxide and dioxide bond energies

    International Nuclear Information System (INIS)

    The kinetic energy dependences of the reactions of Nin+ (n=2-18) with O2 are studied in a guided ion beam tandem mass spectrometer. A variety of NimO2+, NimO+, and Nim+ product ions, where m≤n, are observed, with the dioxide cluster ions dominating the products for all larger reactant cluster ions. Reaction efficiencies are near unity for all but the smallest clusters. The energy dependences of the product cross sections are analyzed in several different ways to determine thermochemistry for both the first and second oxygen atom binding to nickel cluster ions. These values show little dependence on cluster size for clusters larger than three atoms. The trends in this thermochemistry are discussed and compared to bulk phase oxidation values

  20. ARE MODELS OF ANION HYDRATION OVERBOUND ? THE SOLVATION OF THE ELECTRON AND CHLORIDE ANION COMPARED

    OpenAIRE

    Sprik, M.

    1991-01-01

    By means of a fully polarizable model for the chloride ion-water interaction we show that the modelling of anion solvation suffers from a similar inconsistency as the current electron-solvent potentials. Either the bulk hydration enthalpies are correct with the first hydration shell overbound, or the potential is adapted to describe the local environment of the solute at the expense of a major loss of solvation enthalpy. It is argued that boundary effects in the simulation are at least partly...

  1. Hydrogen bond dynamics and vibrational spectral diffusion in aqueous solution of acetone: A first principles molecular dynamics study

    Indian Academy of Sciences (India)

    Bhabani S Mallik; Amalendu Chandra

    2012-01-01

    We present an ab initio molecular dynamics study of vibrational spectral diffusion and hydrogen bond dynamics in aqueous solution of acetone at room temperature. It is found that the frequencies of OD bonds in the acetone hydration shell have a higher stretch frequency than those in the bulk water. Also, on average, the frequencies of hydration shell OD modes are found to increase with increase in the acetone-water hydrogen bond distance. The vibrational spectral diffusion of the hydration shell water molecules reveals three time scales: A short-time relaxation (∼80 fs) corresponding to the dynamics of intact acetone-water hydrogen bonds, a slower relaxation (∼1.3 ps) corresponding to the lifetime of acetone-water hydrogen bonds and another longer time constant (∼12 ps) corresponding to the escape dynamics of water from the solute hydration shell. The present first principles results are compared with those of available experiments and classical simulations.

  2. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.;

    1999-01-01

    Vapour phase hydration of purl cement clinker minerals at reduced relative humidities is described. This is relevant to modern high performance concrete that may self-desiccate during hydration and is also relevant to the quality of the cement during storage. Both the oretical considerations and...... experimental data are presented showing that C(3)A can hydrate at lower humidities than either C3S or C2S. It is suggested that the initiation of hydration during exposure to water vapour is nucleation controlled. When C(3)A hydrates at low humidity, the characteristic hydration product is C(3)AH(6...

  3. Distinguishing Bonds.

    Science.gov (United States)

    Rahm, Martin; Hoffmann, Roald

    2016-03-23

    The energy change per electron in a chemical or physical transformation, ΔE/n, may be expressed as Δχ̅ + Δ(VNN + ω)/n, where Δχ̅ is the average electron binding energy, a generalized electronegativity, ΔVNN is the change in nuclear repulsions, and Δω is the change in multielectron interactions in the process considered. The last term can be obtained by the difference from experimental or theoretical estimates of the first terms. Previously obtained consequences of this energy partitioning are extended here to a different analysis of bonding in a great variety of diatomics, including more or less polar ones. Arguments are presented for associating the average change in electron binding energy with covalence, and the change in multielectron interactions with electron transfer, either to, out, or within a molecule. A new descriptor Q, essentially the scaled difference between the Δχ̅ and Δ(VNN + ω)/n terms, when plotted versus the bond energy, separates nicely a wide variety of bonding types, covalent, covalent but more correlated, polar and increasingly ionic, metallogenic, electrostatic, charge-shift bonds, and dispersion interactions. Also, Q itself shows a set of interesting relations with the correlation energy of a bond. PMID:26910496

  4. Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

    Science.gov (United States)

    Tan, Ming-Liang; Miller, Benjamin T.; Te, Jerez; Cendagorta, Joseph R.; Brooks, Bernard R.; Ichiye, Toshiko

    2015-02-01

    The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol VE as a function of ethanol mole fraction XE is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has "brittle" hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water.

  5. Local and bulk hydration of zwitterionic glycine and its analogues through molecular simulations.

    Science.gov (United States)

    White, Andrew; Jiang, Shaoyi

    2011-02-01

    Molecular dynamics simulations were used to characterize the differences in hydration between glycine and two of its zwitterionic analogues: N,N-dimethylglycine and N,N,N-trimethylglycine (glycine betaine). The hydration of dodecane and oligo(ethylene glycol) was studied for reference. Both structuring and dynamics of bulk and bound water were examined using a variety of properties and at multiple concentrations. Metrics, such as radial distribution functions and residence times, were used to characterize hydration. Also, we used more specialized metrics that can discriminate between subtle differences in hydration, such as condensed phase order parameters, Voronoi tessellations, and multidimensional pair-pair correlation functions. Trimethylglycine was found to have a unique hydration shell that extends across the entire molecule and has no specific interactions between solute molecules. Also, we found that dimethylglycine has a similar hydration structure to that of trimethylglycine despite its hydrogen-bond donor. Glycine was found to aggregate and have a more disjoint hydration shell. All three zwitterions were found to structurally affect water within 1.5-2.0 coordination shells. Lastly, trimethylglycine is disperse in solution even at very high concentrations, and water rapidly moves between trimethylglycine amine groups. This work has meaningful implications for protein stability where trimethylglycine is known to prevent protein aggregation and nonfouling interfaces where trimethylglycine prevents nonspecific protein adsorption. PMID:21174438

  6. Raman and DFT Study on N-H+…Cl- Hydrogen Bonding in 1,1,3,3-Tetra-Methylguanidinium Chloride forming an Ion-pair Molecule in the Vapor Phase

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Riisager, Anders; Fehrmann, Rasmus

    gaseous free states without any assumed symmetry. The calculations on the monomeric [TMGH]+ ion and the dimeric ion pair converged to give geometries near the established crystal structure of the [TMGH]Cl salt. This salt is known to contain dimeric ion pairs of the kind [TMGH]ClCl[TMGH](Fig.1......).Experimentally obtained Raman scattering spectra of the compound (as the solid, as solutes in ethanolic and aqueous solutions and as a vapor at 225 ºC) are presented and assigned, by comparing to the ab initio vibrational analyses (calculated IR and Raman band positions and intensities). It is concluded that...... dimeric molecular ion pairs with four N-H+…Cl- hydrogen bonds seem to exist also in the solutions, and probably are responsible for the relatively high solubility of the “salt” in ethanol. The “salt” can be easily sublimed at about 200-230 oC. The Raman spectrum of the vapor at 225 ºC has a characteristic...

  7. Multi-photon ionization and fragmentation of uracil: Neutral excited-state ring opening and hydration effects

    Energy Technology Data Exchange (ETDEWEB)

    Barc, B.; Ryszka, M.; Spurrell, J.; Dampc, M.; Limão-Vieira, P.; Parajuli, R.; Mason, N. J.; Eden, S. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom)

    2013-12-28

    Multi-photon ionization (MPI) of the RNA base uracil has been studied in the wavelength range 220–270 nm, coinciding with excitation to the S{sub 2}(ππ*) state. A fragment ion at m/z = 84 was produced by 2-photon absorption at wavelengths ≤232 nm and assigned to C{sub 3}H{sub 4}N{sub 2}O{sup +} following CO abstraction. This ion has not been observed in alternative dissociative ionization processes (notably electron impact) and its threshold is close to recent calculations of the minimum activation energy for a ring opening conical intersection to a σ(n-π)π* closed shell state. Moreover, the predicted ring opening transition leaves a CO group at one end of the isomer, apparently vulnerable to abstraction. An MPI mass spectrum of uracil-water clusters is presented for the first time and compared with an equivalent dry measurement. Hydration enhances certain fragment ion pathways (particularly C{sub 3}H{sub 3}NO{sup +}) but represses C{sub 3}H{sub 4}N{sub 2}O{sup +} production. This indicates that hydrogen bonding to water stabilizes uracil with respect to neutral excited-state ring opening.

  8. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, K.; Bosáková, Z.; Cvačka, Josef

    2015-01-01

    Roč. 407, č. 17 (2015), s. 5175-5188. ISSN 1618-2642 R&D Projects: GA ČR GAP206/12/0750 Institutional support: RVO:61388963 Keywords : double bond * gas-phase chemistry * lipidomics * olive oil * vernix caseosa Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.436, year: 2014

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

    Science.gov (United States)

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

    2007-02-01

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

  10. Molecular dynamics of poly(N-vinylcaprolactam) hydrate

    CERN Document Server

    Lebedev, V T; Toeroek, G; Cser, L; Kali, G

    2002-01-01

    Poly(N-vinylcaprolactam)-D sub 2 O has been studied by Neutron Spin Echo (NSE) in the temperature range from -60 C to +40 C. Hydration (propor to 7 D sub 2 O molecules per chain unit) transforms the rigid-chain polymer into an elastomer, making the glass-transition temperature drop from T sub G =147 C (dry polymer) to T sub G =-20 C. The hydration shell, created by hydrogen bonds of water molecules with C=O groups, remains stable up to propor to 50 C. The molecular mobility is enhanced by the addition of water, showing a maximum in the window T=-20 to +5 C. The anomalous dynamics was studied in the time domain t=0.003-5 ns (momentum transfer q=0.55 nm sup - sup 1), and demonstrated the hybridisation of transversal modes and reputations of the chains. (orig.)

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

    International Nuclear Information System (INIS)

    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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase

  12. Neutron protein crystallography hydrogen protons and hydration in bio-macromolecules

    CERN Document Server

    Niimura, Nobuo

    2011-01-01

    This text is dedicated to the emerging field of neutron protein crystallography (NPC). It covers all of the practical aspects of NPC and demonstrates how NPC can explore protein features such as hydrogen bonds, protonation and deprotonation of amino acid residues, and hydration structures.

  13. Raman and infrared spectroscopic studies of the structure of water (H2O, HOD, D2O) in stoichiometric crystalline hydrates and in electrolyte solutions

    International Nuclear Information System (INIS)

    The chapter of reviews presents in particular the Badger-Bauer-rule, distance and angle dependence of O-H...Y hydrogen bond and the structure of aqueous electrolyte solutions. A chapter of vibrational spectroscopic investigations of crystalline hydrates - metal perchlorate hydrates follows. Two further chapters just so investigate metal halide hydrates and some sulfate hydrates and related systems. The following chapter describes near infrared spectroscopic investigations of HOD(D2O) and its electrolyte solutions. The concluding chapter contains thermodynamic consequences and some properties of electrolyte solutions from vibrational spectroscopic investigations. (SPI)

  14. Spectroscopic and bond-topological investigation of interstitial volatiles in beryl from Slovakia

    Science.gov (United States)

    Fridrichová, Jana; Bačík, Peter; Bizovská, Valéria; Libowitzky, Eugen; Škoda, Radek; Uher, Pavel; Ozdín, Daniel; Števko, Martin

    2016-03-01

    Nine beryl samples from Western Carpathians, Slovakia, were investigated by infrared and Raman spectroscopy and differential thermal analysis. Two types of water H2O I and H2O II were detected. Infrared spectroscopy proved the presence of water type I and II in the presence of alkali cations with several bands: (1) symmetric stretching vibration—ν1; (2) antisymmetric stretching mode—ν3; (3) bending vibration—ν2. The presence of singly and doubly coordinated type II water (IIs and IId) was confirmed by single-crystal IR spectroscopy. From Raman spectra a band at 3606 cm-1 was assigned to ν1 of water type I and the range of 3597-3600 cm-1 to water type II. The presence of doubly coordinating water indicates a relatively highly hydrated environment with the presence of alkali ions including Na as the dominant cation coordinated by H2O II. CO2 bands were detected only by single-crystal IR spectroscopy. Thermal analysis proved total water loss in the range of 1.4-2.0 wt% and three main dehydration events. Based on the study of bond-topological arrangements two molecules of H2O IId are each bound with two H···O1 bonds and one Na-OW bond with an angular distortion, and by releasing one H2O molecule more stable H2O IIs is produced. The H2O I molecule is bound only by two equivalent hydrogen bonds. The H2O IIs molecule with a Na-OW bond strength of 0.28 vu and two H···O1 bonds of 0.14 vu without any forced angular distortion is the most stable of all.

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

    International Nuclear Information System (INIS)

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na2SO4–H2O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions

  16. Is the Surface of Gas Hydrates Dry?

    OpenAIRE

    Nobuo Maeda

    2015-01-01

    Adhesion (cohesion) and agglomeration properties of gas hydrate particles have been a key to hydrate management in flow assurance in natural gas pipelines. Despite its importance, the relevant data in the area, such as the surface energy and the interfacial energy of gas hydrates with gas and/or water, are scarce; presumably due to the experimental difficulties involved in the measurements. Here we review what is known about the surface energy and the interfacial energy of gas hydrates to dat...

  17. 77 FR 40032 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2012-07-06

    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee.... SUPPLEMENTARY INFORMATION: Purpose of the Committee: The purpose of the Methane Hydrate Advisory Committee is...

  18. 75 FR 9886 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2010-03-04

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... Methane Hydrate Advisory Committee is to provide advice on potential applications of methane hydrate...

  19. Diffusion bonding

    Science.gov (United States)

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  20. Mesoscale texture of cement hydrates.

    Science.gov (United States)

    Ioannidou, Katerina; Krakowiak, Konrad J; Bauchy, Mathieu; Hoover, Christian G; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J-M; Del Gado, Emanuela

    2016-02-23

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium-silicate-hydrates (C-S-H) during cement hydration. Controlling structure and properties of the C-S-H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C-S-H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C-S-H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C-S-H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C-S-H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  1. Physical activity, hydration and health

    Directory of Open Access Journals (Sweden)

    Ascensión Marcos

    2014-06-01

    Full Text Available Since the beginning of mankind, man has sought ways to promote and preserve health as well as to prevent disease. Hydration, physical activity and exercise are key factors for enhancing human health. However, either a little dose of them or an excess can be harmful for health maintenance at any age. Water is an essential nutrient for human body and a major key to survival has been to prevent dehydration. However, there is still a general controversy regarding the necessary amount to drink water or other beverages to properly get an adequate level of hydration. In addition, up to now the tools used to measure hydration are controversial. To this end, there are several important groups of variables to take into account such as water balance, hydration biomarkers and total body water. A combination of methods will be the most preferred tool to find out any risk or situation of dehydration at any age range. On the other hand, physical activity and exercise are being demonstrated to promote health, avoiding or reducing health problems, vascular and inflammatory diseases and helping weight management. Therefore, physical activity is also being used as a pill within a therapy to promote health and reduce risk diseases, but as in the case of drugs, dose, intensity, frequency, duration and precautions have to be evaluated and taken into account in order to get the maximum effectiveness and success of a treatment. On the other hand, sedentariness is the opposite concept to physical activity that has been recently recognized as an important factor of lifestyle involved in the obesogenic environment and consequently in the risk of the non-communicable diseases. In view of the literature consulted and taking into account the expertise of the authors, in this review a Decalogue of global recommendations is included to achieve an adequate hydration and physical activity status to avoid overweight/obesity consequences.

  2. INFLUENCE OF POZZOLANA ON THE HYDRATION OF C4AF RICH CEMENT IN CHLORIDE ENVIRONMENT

    Directory of Open Access Journals (Sweden)

    IRMANTAS BARAUSKAS

    2013-03-01

    Full Text Available This study investigated the influence of natural pozzolana - opoka additive on the hydration of C4AF rich cement and the effects of chloride ions on the hydrates formed. In the samples, 25 % (by weight of the sintered C4AF rich cement and OPC was replaced with pozzolana. The mixtures were hardened for 28 days in water, soaked in a saturated NaCl solution for 3 months at 20°C. It was estimated that under normal conditions, pozzolana additive accelerates the hydration of calcium silicates and initiates the formation of CO32- - AFm in the Brownmillerite rich cement. However, the hydration of Brownmillerite cement with opoka additive is still slower to compare with hydration of Portland cement. Also, opoka decreases total porosity and threshold pore diameter of Brownmillerite cement paste after two days of hydration. After 28 days of hydration threshold pore diameter became smaller even to compare with threshold pore diameter of Portland cement. Opoka additive promotes the formation of Friedel’s salt in Brownmillerite samples treated in saturated NaCl solution, because CO32-–AFm affected by saturated NaCl solution become unstable and takes part in reactions producing Friedel’s salt.

  3. The Hydration and Carbonation of Tricalcium Aluminate (C3A) in the Presence of Heavy Metals

    Institute of Scientific and Technical Information of China (English)

    CHEN Quanyuan; C. D. Hills; M. Tyrer; I. Slipper

    2005-01-01

    The hydration of tricalcium aluminate (C3A) has a significant effect on the effectiveness of cement-based systems. In addition, the carbonation of hydration products of C3A is particularly important in respect of durability performance. The present work investigates the hydration and carbonation reactions of C3A and the changes induced by the presence of the heavy metal ions such as Zn2+, Pb2+, Cu2+ and Cr3+ by X-ray diffractometry (XRD). During hydration of C3A, gehlenite hydrate, hydrogarnet, calcium monoaluminate (C4AHx) and calcium carboaluminate were detected in C3A pastes except the Zn2+doped paste, where hydrogarnet did not form. The examinations revealed that heavy metals coexisted with gehlenite hydrate, calcium monoaluminate (C4AHx) and calcium carboaluminate, inhibiting the formation of hydrogarnet. Hydrating C3A was liable to be carbonated on exposure to air and carbon dioxide, especially in the presence of heavy metals, resulting in the formation of carboaluminate and/or calcium carbonate. The presence of heavy metals in-fluenced the polymorphism of calcium carbonate,ndicating that heavy metals could co-precipitate with calcium to form a carbonate solid solution.

  4. Enzymic excision of ultraviolet-induced cytosine hydrates from left-handed DNA

    International Nuclear Information System (INIS)

    Ultraviolet irradiation of DNA produces a variety of pyrimidine modifications. These include cytosine hydrate (5,6-dihydro-6-hydroxycytosine), released as a free base by E. coli endonuclease III. The enzymic excision of cytosine hydrate by this purified enzyme was investigated by assaying release of labeled photoproduct from DNA into the ethanol-soluble fraction. Ultraviolet-irradiated poly(dG-dC):poly(dG-dC), radio-labeled in cytosines, was used as substrate. Shifts between the right-handed B-conformation and the left-handed Z-conformation were effected by heating the polymer in the presence of either Ni[II] or Co[II]. Conformational states were determined by ultraviolet circular dichroism. Rates of enzymic cytosine hydrate release did not differ between the different substrate conformations, B-DNA and Z-DNA. Irradiation of left-handed poly(dG-dC):poly(dG-dC) resulted in cytosine hydrate formation. Therefore, neither formation nor enzymic excision of ultraviolet-induced cytosine hydrates are substantially affected by the DNA conformational state. Cytosine hydrates are most likely to occur in alternating purine:pyrimidine sequences. Such segments can adopt the Z-conformation as a result of reactions with chemical carcinogens, the presence of metal ions, or negative superhelicity. These results indicate repair of cytosine hydrates to be likely, regardless of the DNA conformational state

  5. Bonding of Co Ions in ZSM-5, Ferrierite, and Mordenite: An X-ray Absorption, UV-Vis and IR Study

    Czech Academy of Sciences Publication Activity Database

    Drozdová, L.; Prins, R.; Dědeček, Jiří; Sobalík, Zdeněk; Wichterlová, Blanka

    2002-01-01

    Roč. 106, č. 9 (2002), s. 2240-2248. ISSN 1089-5647 R&D Projects: GA ČR GA104/00/0640 Institutional research plan: CEZ:AV0Z4040901 Keywords : ZSM-5 * Co(II)ions * Vis spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.611, year: 2002

  6. Sorption selectivity of alkali metal ions in polymer inclusion ion exchange membranes

    International Nuclear Information System (INIS)

    Sorption selectivity of different alkali metal ions in polymer inclusion cation exchange membranes has been studied. The concentration of the metal ions were measured using neutron activation analysis. The results show the selectivity of polymer inclusion membranes for metal ions in the order Na++++. The trend have been explained in terms of the radius of the hydrated metal ion. (author)

  7. Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids.

    Science.gov (United States)

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

    2016-01-01

    Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes. PMID:27526869

  8. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K.

    1995-12-31

    Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

  9. Handbook of gas hydrate properties and occurrence

    Energy Technology Data Exchange (ETDEWEB)

    Kuustraa, V.A.; Hammershaimb, E.C.

    1983-12-01

    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  10. Is the Surface of Gas Hydrates Dry?

    Directory of Open Access Journals (Sweden)

    Nobuo Maeda

    2015-06-01

    Full Text Available Adhesion (cohesion and agglomeration properties of gas hydrate particles have been a key to hydrate management in flow assurance in natural gas pipelines. Despite its importance, the relevant data in the area, such as the surface energy and the interfacial energy of gas hydrates with gas and/or water, are scarce; presumably due to the experimental difficulties involved in the measurements. Here we review what is known about the surface energy and the interfacial energy of gas hydrates to date. In particular, we ask a question as to whether pre-melting can occur on the surface of gas hydrates. Surface thermodynamic analyses show that pre-melting is favoured to occur on the surface of gas hydrates, however, not sufficient data are available to assess its thickness. The effects of the existence of pre-melting layers on the cohesion and friction forces between gas hydrate particles are also discussed.

  11. Separation of water through gas hydrate formation

    DEFF Research Database (Denmark)

    Boch Andersen, Torben; Thomsen, Kaj

    2009-01-01

    Gas hydrate is normally recognized as a troublemaker in the oil and gas industry. However, gas hydrate has some interesting possibilities when used in connection with separation of water. Nordic Sugar has investigated the possibility of using gas hydrates for concentration of sugar juice. The goa...... of large volumes and the needs for high pressure. The process could be interesting for concentration of heat sensitive, high value products......Gas hydrate is normally recognized as a troublemaker in the oil and gas industry. However, gas hydrate has some interesting possibilities when used in connection with separation of water. Nordic Sugar has investigated the possibility of using gas hydrates for concentration of sugar juice. The goal...... of the project was to formulate an alternative separation concept, which can replace the traditional water evaporation process in the sugar production. Work with the separation concept showed that gas hydrates can be used for water separation. The process is not suitable for sugar production because...

  12. DNA hydration studied by neutron fiber diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Fuller, W.; Forsyth, V.T.; Mahendrasingam, A.; Langan, P.; Pigram, W.J. [Keele Univ. (United Kingdom)] [and others

    1994-12-31

    The development of neutron high angle fiber diffraction to investigate the location of water around the deoxyribonucleic acid (DNA) double-helix is described. The power of the technique is illustrated by its application to the D and A conformations of DNA using the single crystal diffractometer, D19, at the Institute Laue-Langevin, Grenoble and the time of flight diffractometer, SXD, at the Rutherford Appleton ISIS Spallation Neutron Source. These studies show the existence of bound water closely associated with the DNA. The patterns of hydration in these two DNA conformations are quite distinct and are compared to those observed in X-ray single crystal studies of two-stranded oligodeoxynucleotides. Information on the location of water around the DNA double-helix from the neutron fiber diffraction studies is combined with that on the location of alkali metal cations from complementary X-ray high angle fiber diffraction studies at the Daresbury Laboratory SRS using synchrotron radiation. These analyses emphasize the importance of viewing DNA, water and ions as a single system with specific interactions between the three components and provide a basis for understanding the effect of changes in the concentration of water and ions in inducing conformations] transitions in the DNA double-helix.

  13. On the free energy of ionic hydration

    CERN Document Server

    Hummer, G; García, A E; Hummer, Gerhard; Pratt, Lawrence R.; Garcia, Angel E.

    1995-01-01

    The hydration free energies of ions exhibit an approximately quadratic dependence on the ionic charge, as predicted by the Born model. We analyze this behavior using second-order perturbation theory. This provides effective methods to calculating free energies from equilibrium computer simulations. The average and the fluctuation of the electrostatic potential at charge sites appear as the first coefficients in a Taylor expansion of the free energy of charging. Combining the data from different charge states allows calculation of free-energy profiles as a function of the ionic charge. The first two Taylor coefficients of the free-energy profiles can be computed accurately from equi- librium simulations; but they are affected by a strong system-size dependence. We apply corrections for these finite-size effects by using Ewald lattice sum- mation and adding the self-interactions consistently. Results are presented for a model ion with methane-like Lennard-Jones parameters in SPC water. We find two very closely ...

  14. Comparative atomic-scale hydration of the ceramide and phosphocholine headgroup in solution and bilayer environments.

    Science.gov (United States)

    Gillams, Richard J; Lorenz, Christian D; McLain, Sylvia E

    2016-06-14

    Previous studies have used neutron diffraction to elucidate the hydration of the ceramide and the phosphatidylcholine headgroup in solution. These solution studies provide bond-length resolution information on the system, but are limited to liquid samples. The work presented here investigates how the hydration of ceramide and phosphatidylcholine headgroups in a solution compares with that found in a lipid bilayer. This work shows that the hydration patterns seen in the solution samples provide valuable insight into the preferential location of hydrating water molecules in the bilayer. There are certain subtle differences in the distribution, which result from a combination of the lipid conformation and the lipid-lipid interactions within the bilayer environment. The lipid-lipid interactions in the bilayer will be dependent on the composition of the bilayer, whereas the restricted exploration of conformational space is likely to be applicable in all membrane environments. The generalized description of hydration gathered from the neutron diffraction studies thus provides good initial estimation for the hydration pattern, but this can be further refined for specific systems. PMID:27306021

  15. DFT-based inhibitor and promoter selection criteria for pentagonal dodecahedron methane hydrate cage

    Indian Academy of Sciences (India)

    Snehanshu Pal; T K Kundu

    2013-09-01

    Density functional theory (DFT)-based simulations have been performed to provide electronic structure property correlation based reasoning for conceptualizing the effect of encapsulated methane molecule on the formation of methane hydrate cages, the role of methanol and ethylene glycol as inhibitor and the role of tetra-hydro-furan (THF) and cyclopentane as promoter of methane hydrate. Geometry optimization of 512 cage, 51262 cage and 51264 cage with and without encapsulated methane and the cluster of 512 cage with ethylene glycol, methanol, cyclopentane have been performed by density functional theory using B97X-D/6-31++G(d,p) method. Methane hydrate formation inhibition by methanol and ethylene glycol as well as methane hydrate stabilization by cyclopentane and tetrahydrofuran are critically analysed based on the interaction energy, free energy change, dipole moment and infrared frequency calculation. Calculation of free energy change for formation of methane hydrate with/without reagents at various temperature and pressure using optimized structure is reported here. It is observed that hydrogen bond between water molecules of clathrate 512 cages become stronger in the presence of cyclopentane and tetrahydrofuran but weaker/broken in the presence of ethylene glycol and methanol. Simulated results correspond well with experimental findings and can be useful for designing new inhibitor and promoter molecules for gas hydrate formation.

  16. Comparative atomic-scale hydration of the ceramide and phosphocholine headgroup in solution and bilayer environments

    Science.gov (United States)

    Gillams, Richard J.; Lorenz, Christian D.; McLain, Sylvia E.

    2016-06-01

    Previous studies have used neutron diffraction to elucidate the hydration of the ceramide and the phosphatidylcholine headgroup in solution. These solution studies provide bond-length resolution information on the system, but are limited to liquid samples. The work presented here investigates how the hydration of ceramide and phosphatidylcholine headgroups in a solution compares with that found in a lipid bilayer. This work shows that the hydration patterns seen in the solution samples provide valuable insight into the preferential location of hydrating water molecules in the bilayer. There are certain subtle differences in the distribution, which result from a combination of the lipid conformation and the lipid-lipid interactions within the bilayer environment. The lipid-lipid interactions in the bilayer will be dependent on the composition of the bilayer, whereas the restricted exploration of conformational space is likely to be applicable in all membrane environments. The generalized description of hydration gathered from the neutron diffraction studies thus provides good initial estimation for the hydration pattern, but this can be further refined for specific systems.

  17. The effect of hydrate saturation on water retention curves in hydrate-bearing sediments

    Science.gov (United States)

    Mahabadi, Nariman; Zheng, Xianglei; Jang, Jaewon

    2016-05-01

    The experimental measurement of water retention curve in hydrate-bearing sediments is critically important to understand the behavior of hydrate dissociation and gas production. In this study, tetrahydrofuran (THF) is selected as hydrate former. The pore habit of THF hydrates is investigated by visual observation in a transparent micromodel. It is confirmed that THF hydrates are not wetting phase on the quartz surface of the micromodel and occupy either an entire pore or part of pore space resulting in change in pore size distribution. And the measurement of water retention curves in THF hydrate-bearing sediments with hydrate saturation ranging from Sh = 0 to Sh = 0.7 is conducted for excess water condition. The experimental results show that the gas entry pressure and the capillary pressure increase with increasing hydrate saturation. Based on the experimental results, fitting parameters for van Genuchten equation are suggested for different hydrate saturation conditions.

  18. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    Science.gov (United States)

    Sultan, N.; Bohrmann, G.; Ruffine, L.; Pape, T.; Riboulot, V.; Colliat, J.-L.; De Prunelé, A.; Dennielou, B.; Garziglia, S.; Himmler, T.; Marsset, T.; Peters, C. A.; Rabiu, A.; Wei, J.

    2014-04-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

  19. Pi Bond Orders and Bond Lengths

    Science.gov (United States)

    Herndon, William C.; Parkanyi, Cyril

    1976-01-01

    Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

  20. Facilitating guest transport in clathrate hydrates by tuning guest-host interactions

    International Nuclear Information System (INIS)

    The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO2 and isobutane-CO2, that are predicted to enhance or to diminish guest–host hydrogen bonding interactions as compared to those in pure CO2 hydrate and we have studied guest dynamics in each using 13C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO2 sII hydrate using the combined single crystal X-ray diffraction and 13C NMR powder pattern data and have performed molecular dynamics-simulation of the CO2 dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO2 hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO2 molecules in the THF-CO2 hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A–host water–guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 106 than a published calculated value

  1. A Hydrate Database: Vital to the Technical Community

    OpenAIRE

    Sloan, D.; Kuznetsov, F; Lal, K; Loewner, R; Makogon, Y; Moridis, G.; Ripmeester, J; Royer, Jean-Jacques; Smith, T.; Tohidi, B; Uchida, T; Wang, J; Wang, W.; Xiao, Y.

    2007-01-01

    Natural gas hydrates may contain more energy than all the combined other fossil fuels, causing hydrates to be a potentially vital aspect of both energy and climate change. This article is an overview of the motivation, history, and future of hydrate data management using a CODATA vehicle to connect international hydrate databases. The basis is an introduction to the Gas Hydrate Markup Language (GHML) to connect various hydrate databases. The accompanying four articles on laboratory hydrate da...

  2. Quasichemical analysis of the cluster-pair approximation for the thermodynamics of proton hydration

    Energy Technology Data Exchange (ETDEWEB)

    Pollard, Travis [Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221 (United States); Beck, Thomas L. [Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221 (United States); Department of Physics, University of Cincinnati, Cincinnati, Ohio 45221 (United States)

    2014-06-14

    A theoretical analysis of the cluster-pair approximation (CPA) is presented based on the quasichemical theory of solutions. The sought single-ion hydration free energy of the proton includes an interfacial potential contribution by definition. It is shown, however, that the CPA involves an extra-thermodynamic assumption that does not guarantee uniform convergence to a bulk free energy value with increasing cluster size. A numerical test of the CPA is performed using the classical polarizable AMOEBA force field and supporting quantum chemical calculations. The enthalpy and free energy differences are computed for the kosmotropic Na{sup +}/F{sup −} ion pair in water clusters of size n = 5, 25, 105. Additional calculations are performed for the chaotropic Rb{sup +}/I{sup −} ion pair. A small shift in the proton hydration free energy and a larger shift in the hydration enthalpy, relative to the CPA values, are predicted based on the n = 105 simulations. The shifts arise from a combination of sequential hydration and interfacial potential effects. The AMOEBA and quantum chemical results suggest an electrochemical surface potential of water in the range −0.4 to −0.5 V. The physical content of single-ion free energies and implications for ion-water force field development are also discussed.

  3. Quasichemical analysis of the cluster-pair approximation for the thermodynamics of proton hydration

    Science.gov (United States)

    Pollard, Travis; Beck, Thomas L.

    2014-06-01

    A theoretical analysis of the cluster-pair approximation (CPA) is presented based on the quasichemical theory of solutions. The sought single-ion hydration free energy of the proton includes an interfacial potential contribution by definition. It is shown, however, that the CPA involves an extra-thermodynamic assumption that does not guarantee uniform convergence to a bulk free energy value with increasing cluster size. A numerical test of the CPA is performed using the classical polarizable AMOEBA force field and supporting quantum chemical calculations. The enthalpy and free energy differences are computed for the kosmotropic Na+/F- ion pair in water clusters of size n = 5, 25, 105. Additional calculations are performed for the chaotropic Rb+/I- ion pair. A small shift in the proton hydration free energy and a larger shift in the hydration enthalpy, relative to the CPA values, are predicted based on the n = 105 simulations. The shifts arise from a combination of sequential hydration and interfacial potential effects. The AMOEBA and quantum chemical results suggest an electrochemical surface potential of water in the range -0.4 to -0.5 V. The physical content of single-ion free energies and implications for ion-water force field development are also discussed.

  4. Quasichemical analysis of the cluster-pair approximation for the thermodynamics of proton hydration

    International Nuclear Information System (INIS)

    A theoretical analysis of the cluster-pair approximation (CPA) is presented based on the quasichemical theory of solutions. The sought single-ion hydration free energy of the proton includes an interfacial potential contribution by definition. It is shown, however, that the CPA involves an extra-thermodynamic assumption that does not guarantee uniform convergence to a bulk free energy value with increasing cluster size. A numerical test of the CPA is performed using the classical polarizable AMOEBA force field and supporting quantum chemical calculations. The enthalpy and free energy differences are computed for the kosmotropic Na+/F− ion pair in water clusters of size n = 5, 25, 105. Additional calculations are performed for the chaotropic Rb+/I− ion pair. A small shift in the proton hydration free energy and a larger shift in the hydration enthalpy, relative to the CPA values, are predicted based on the n = 105 simulations. The shifts arise from a combination of sequential hydration and interfacial potential effects. The AMOEBA and quantum chemical results suggest an electrochemical surface potential of water in the range −0.4 to −0.5 V. The physical content of single-ion free energies and implications for ion-water force field development are also discussed

  5. Dipolar response of hydrated proteins

    CERN Document Server

    Matyushov, Dmitry V

    2011-01-01

    The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins. The effective dielectric constant of the solvated protein, representing the average dipole moment induced at the protein by a uniform external field, shows a remarkable variation among the proteins studied by numerical simulations. It changes from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility of ubiquitin, that is a dia-electric dipolar response and negative dielectrophoresis. It means that a protein carrying an average dipole of ~240 D is expected to repel from the region of a stronger electric field. This outcome is the result of a negative cross-correlation between the protein and water dipoles, compensating for the positive variance of the protein dipole in the overall dipolar susceptibility. This phenomenon can be characterized as overscreening of protein's dipole by the hydration shell. In contrast to the neutral ubiquitin, charged protei...

  6. Uranyl p-toluenesulphonate and its crystal hydrates. Synthesis and dehydration-hydration processes

    International Nuclear Information System (INIS)

    Lowest hydrates of uranyl p-toluenesulphonate (UPTS) and anhydrous salt were synthesised. The dehydration-hydration processes were studied by thermal gravimetric analysis. It has been established that the hydrate shell of UPTS has a layered structure. The IR spectra of UPTS and its hydrates were recorded. It was found that the IR spectra of UPTS crystal hydrates of the same composition, produced in dehydration-hydration, noticeably differ in the range of water vibrations and are the same in the range corresponding to vibrations of sulphonate groups. (author)

  7. Uranyl p-toluenesulphonate and its crystal hydrates. Synthesis and dehydration-hydration processes

    Science.gov (United States)

    Baluev, A. V.; Mityakhina, V. S.; Bogachev, S. V.; Suglobova, I. G.

    2003-01-01

    Lowest hydrates of uranyl p-toluenesulphonate (UPTS) and anhydrous salt were synthesised. The dehydration-hydration processes were studied by thermal gravimetric analysis. It has been established that the hydrate shell of UPTS has a layered structure. The IR spectra of UPTS and its hydrates were recorded. It was found that the IR spectra of UPTS crystal hydrates of the same composition, produced in dehydration-hydration, noticeably differ in the range of water vibrations and are the same in the range corresponding to vibrations of sulphonate groups.

  8. Lattice constants and expansivities of gas hydrates from 10 K up to the stability limit

    Science.gov (United States)

    Hansen, T. C.; Falenty, A.; Kuhs, W. F.

    2016-02-01

    The lattice constants of hydrogenated and deuterated CH4-, CO2-, Xe- (clathrate structure type I) and N2-hydrates (clathrate structure type II) from 10 K up to the stability limit were established in neutron- and synchrotron diffraction experiments and were used to derive the related thermal expansivities. The following results emerge from this analysis: (1) The differences of expansivities of structure type I and II hydrates are fairly small. (2) Despite the larger guest-size of CO2 as compared to methane, CO2-hydrate has the smaller lattice constants at low temperatures, which is ascribed to the larger attractive guest-host interaction of the CO2-water system. (3) The expansivity of CO2-hydrate is larger than for CH4-hydrate which leads to larger lattice constants for the former at temperatures above ˜150 K; this is likely due to the higher motional degrees of freedom of the CO2 guest molecules. (4) The cage occupancies of Xe- and CO2-hydrates affect significantly the lattice constants. (5) Similar to ice Ih, the deuterated compounds have generally slightly larger lattice constants which can be ascribed to the somewhat weaker H-bonding. (6) Compared to ice Ih, the high temperature expansivities are about 50% larger; in contrast to ice Ih and the empty hydrate, there is no negative thermal expansion at low temperature. (7) A comparison of the experimental results with lattice dynamical work, with models based on an Einstein oscillator model, and results from inelastic neutron scattering suggest that the contribution of the guest atoms' vibrational energy to thermal expansion is important, most prominently for CO2- and Xe-hydrates.

  9. Lattice constants and expansivities of gas hydrates from 10 K up to the stability limit

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, T. C. [Institut Laue-Langevin, 71 Avenue des Martyrs, 38000 Grenoble (France); Falenty, A.; Kuhs, W. F. [GZG, Abt. Kristallographie, Universität Göttingen, Goldschmidtstrasse 1, 37077 Göttingen (Germany)

    2016-02-07

    The lattice constants of hydrogenated and deuterated CH{sub 4}-, CO{sub 2}-, Xe- (clathrate structure type I) and N{sub 2}-hydrates (clathrate structure type II) from 10 K up to the stability limit were established in neutron- and synchrotron diffraction experiments and were used to derive the related thermal expansivities. The following results emerge from this analysis: (1) The differences of expansivities of structure type I and II hydrates are fairly small. (2) Despite the larger guest-size of CO{sub 2} as compared to methane, CO{sub 2}-hydrate has the smaller lattice constants at low temperatures, which is ascribed to the larger attractive guest-host interaction of the CO{sub 2}-water system. (3) The expansivity of CO{sub 2}-hydrate is larger than for CH{sub 4}-hydrate which leads to larger lattice constants for the former at temperatures above ∼150 K; this is likely due to the higher motional degrees of freedom of the CO{sub 2} guest molecules. (4) The cage occupancies of Xe- and CO{sub 2}-hydrates affect significantly the lattice constants. (5) Similar to ice Ih, the deuterated compounds have generally slightly larger lattice constants which can be ascribed to the somewhat weaker H-bonding. (6) Compared to ice Ih, the high temperature expansivities are about 50% larger; in contrast to ice Ih and the empty hydrate, there is no negative thermal expansion at low temperature. (7) A comparison of the experimental results with lattice dynamical work, with models based on an Einstein oscillator model, and results from inelastic neutron scattering suggest that the contribution of the guest atoms’ vibrational energy to thermal expansion is important, most prominently for CO{sub 2}- and Xe-hydrates.

  10. Lattice constants and expansivities of gas hydrates from 10 K up to the stability limit

    International Nuclear Information System (INIS)

    The lattice constants of hydrogenated and deuterated CH4-, CO2-, Xe- (clathrate structure type I) and N2-hydrates (clathrate structure type II) from 10 K up to the stability limit were established in neutron- and synchrotron diffraction experiments and were used to derive the related thermal expansivities. The following results emerge from this analysis: (1) The differences of expansivities of structure type I and II hydrates are fairly small. (2) Despite the larger guest-size of CO2 as compared to methane, CO2-hydrate has the smaller lattice constants at low temperatures, which is ascribed to the larger attractive guest-host interaction of the CO2-water system. (3) The expansivity of CO2-hydrate is larger than for CH4-hydrate which leads to larger lattice constants for the former at temperatures above ∼150 K; this is likely due to the higher motional degrees of freedom of the CO2 guest molecules. (4) The cage occupancies of Xe- and CO2-hydrates affect significantly the lattice constants. (5) Similar to ice Ih, the deuterated compounds have generally slightly larger lattice constants which can be ascribed to the somewhat weaker H-bonding. (6) Compared to ice Ih, the high temperature expansivities are about 50% larger; in contrast to ice Ih and the empty hydrate, there is no negative thermal expansion at low temperature. (7) A comparison of the experimental results with lattice dynamical work, with models based on an Einstein oscillator model, and results from inelastic neutron scattering suggest that the contribution of the guest atoms’ vibrational energy to thermal expansion is important, most prominently for CO2- and Xe-hydrates

  11. The Development Path for Hydrate Natural Gas

    Science.gov (United States)

    Johnson, A. H.; Max, M. D.

    2008-12-01

    The question of when gas hydrate will become a commercially viable resource most concerns those nations with the most severe energy deficiencies. With the vast potential attributed to gas hydrate as a new gas play, the interest is understandable. Yet the resource potential of gas hydrate has persistently remained just over the horizon. While technical and economic hurdles have pushed back the timeline for development, considerable progress has been made in the past five years. An important lesson learned is that an analysis of the factors that control the formation of high grade hydrate deposits must be carried out so that both exploration and recovery scenarios can be modeled and engineered. Commercial hydrate development requires high concentrations of hydrate in porous, permeable reservoirs. It is only from such deposits that gas may be recovered in commercial quantities. While it is unrealistic to consider the global potential of gas hydrate to be in the hundreds of thousands of tcfs, there is a strong potential in the hundreds of tcfs or thousands of tcfs. Press releases from several national gas hydrate research programs have reported gas hydrate "discoveries". These are, in fact, hydrate shows that provide proof of the presence of hydrate where it may previously only have been predicted. Except in a few isolated areas, valid resource assessments remain to be accomplished through the identification of suitable hosts for hydrate concentrations such as sandstone reservoirs. A focused exploration effort based on geological and depositional characteristics is needed that addresses hydrate as part of a larger petroleum system. Simply drilling in areas that have identifiable bottom simulating reflectors (BSRs) is unlikely to be a viable exploration tool. It is very likely that with drilling on properly identified targets, commercial development could become a reality in less than a decade.

  12. Gas hydrates: Technology status report

    Energy Technology Data Exchange (ETDEWEB)

    1987-01-01

    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  13. Micelle Structure and Hydrophobic Hydration.

    Science.gov (United States)

    Long, Joshua A; Rankin, Blake M; Ben-Amotz, Dor

    2015-08-26

    Despite the ubiquity and utility of micelles self-assembled from aqueous surfactants, longstanding questions remain regarding their surface structure and interior hydration. Here we combine Raman spectroscopy with multivariate curve resolution (Raman-MCR) to probe the hydrophobic hydration of surfactants with various aliphatic chain lengths, and either anionic (carboxylate) or cationic (trimethylammonium) head groups, both below and above the critical micelle concentration. Our results reveal significant penetration of water into micelle interiors, well beyond the first few carbons adjacent to the headgroup. Moreover, the vibrational C-D frequency shifts of solubilized deuterated n-hexane confirm that it resides in a dry, oil-like environment (while the localization of solubilized benzene is sensitive to headgroup charge). Our findings imply that the hydrophobic core of a micelle is surrounded by a highly corrugated surface containing hydrated non-polar cavities whose depth increases with increasing surfactant chain length, thus bearing a greater resemblance to soluble proteins than previously recognized. PMID:26222042

  14. Effect of hydrogenation, low energy ion irradiation and annealing on hydrogen bonding to polycrystalline diamond surface studied by high resolution electron energy loss spectroscopy

    International Nuclear Information System (INIS)

    The effects of different processes of hydrogenation, thermal treatment and ion irradiation of hydrogenated polycrystalline diamond surface have been investigated by means of high resolution electron energy loss spectroscopy (HR-EELS). Analysis of the different contributions in the CH stretching, overtones and combination modes, as well as changes in relative intensities of the diamond CC and CHx related vibrations allowed us to identify the CHx adsorbed species on the diamond surface following the different treatments. Ex-situ hydrogenation of diamond surface by means of exposure to H-MW plasma results in a fully hydrogenated well-ordered diamond surface and etching of the amorphous phase located on the grain boundaries present on the sample after CVD-deposition. Annealing this surface to 600 C results in some subtle changes in the HR-EELS, probably associated with decomposition of CHx (x=2,3) adsorbed species. Ion irradiation on the surface induces partial desorption of hydrogen from the diamond phase and a large amount of amorphous defects, some of them of sp and the most of them of sp2 character. Annealing to 600-700 C of the irradiated surface leads to hydrogen desorption. In-situ hydrogenation of the irradiated and annealed sample does not restore the diamond structure, and results in hydrogenated amorphous surface, unstable with thermal annealing above 600-700 C. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  15. Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C(.).

    Science.gov (United States)

    Pei, Linsen; Farrar, James M

    2016-08-11

    We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3(+) product. The large rearrangement in geometry as the C4H3(+) products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2(+) species. PMID:27434380

  16. Lanthanoids(III) and actinoids(III) in water: Diffusion coefficients and hydration enthalpies from polarizable molecular dynamics simulations

    International Nuclear Information System (INIS)

    By using polarizable molecular dynamics (MD) simulations of lanthanoid(III) and actinoid(III) ions in water, we obtained ionic diffusion coefficients and hydration enthalpies for both series. These values are in good agreement with experiments. Simulations thus allow us to relate them to microscopic structure. In particular, across the series the diffusion coefficients decrease, reflecting the increase of ion-water interaction. Hydration enthalpies also show that interactions increase from light to heavy ions in agreement with experiment. The apparent contradictory result of the decrease of the diffusion coefficient with decreasing ionic radius is tentatively explained in terms of dielectric friction predominance on Stokes' diffusive regime. (authors)

  17. Fundamentals and applications of gas hydrates.

    Science.gov (United States)

    Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

    2011-01-01

    Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties. PMID:22432618

  18. Development of Alaskan gas hydrate resources

    Energy Technology Data Exchange (ETDEWEB)

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

  19. SEISMIC STUDIES OF MARINE GAS HYDRATES

    Institute of Scientific and Technical Information of China (English)

    SONG Haibin

    2003-01-01

    We give a brief introduction of developments of seismic methods in the studies of marine gas hydrates. Then we give an example of seismic data processing for BSRs in western Nankai accretionary prism, a typical gas hydrate distribution region. Seismic data processing is proved to be important to obtain better images of BSRs distribution. Studies of velocity structure of hydrated sediments are useful for better understanding the distribution of gas hydrates. Using full waveform inversion, we successfully derived high-resolution velocity model of a double BSR in eastern Nankai Trough area. Recent survey and research show that gas hydrates occur in the marine sediments of the South China Sea and East China Sea.But we would like to say seismic researches on gas hydrate in China are very preliminary.

  20. Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics

    Directory of Open Access Journals (Sweden)

    Carles Calero

    2016-04-01

    Full Text Available Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water–water and water–lipid hydrogen bonds (HBs. We calculate the rotational and translational slowdown of the dynamics of water confined in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water–lipids HBs last longer than water–water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water–water HBs become more persistent as the hydration is lowered. We attribute this effect (i to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii to the higher probability of water–lipid HBs as the hydration decreases. Our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.

  1. Theoretical Investigation on the Adsorption of Ag+ and Hydrated Ag+ Cations on Clean Si(111)Surface

    Institute of Scientific and Technical Information of China (English)

    SHENG Yong-Li; LI Meng-Hua; WANG Zhi-Guo; LIU Yong-Jun

    2008-01-01

    In this paper,the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111)surface were investigated by using cluster(Gaussian 03)and periodic(DMol3)ab initio calculations.Si(111)surface was described with cluster models(Si14H17 and Si22H21)and a four-silicon layer slab with periodic boundary conditions.The effect of basis set superposition error(BSSE)was taken into account by applying the counterpoise correction.The calculated results indicated that the binding energies between hydrated Ag+ cations and clean Si(111)surface are large,suggesting a strong interaction between hydrated Ag+ cations and the semiconductor surface.With the increase of number,water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Ag+ cation.The Ag+ cation in aqueous solution will safely attach to the clean Si(111)surface.

  2. Methane hydrates as potential energy resource: Part 2 - Methane production processes from gas hydrates

    International Nuclear Information System (INIS)

    Three processes have been proposed for dissociation of methane hydrates: thermal stimulation, depressurization, and inhibitor injection. The obvious production approaches involve depressurization, heating and their combinations. The depressurization method is lowering the pressure inside the well and encouraging the methane hydrate to dissociate. Its objective is to lower the pressure in the free-gas zone immediately beneath the hydrate stability zone, causing the hydrate at the base of the hydrate stability zone to decompose. The thermal stimulation method is applied to the hydrate stability zone to raise its temperature, causing the hydrate to decompose. In this method, a source of heat provided directly in the form of injected steam or hot water or another heated liquid, or indirectly via electric or sonic means. This causes methane hydrate to decompose and generates methane gas. The methane gas mixes with the hot water and returns to the surface, where the gas and hot water are separated. The chemical inhibition method seeks to displace the natural-gas hydrate equilibrium condition beyond the hydrate stability zone's thermo-dynamic conditions through injection of a liquid inhibitor chemical adjacent to the hydrate. In this method, inhibitor such as methanol is injected from surface down to methane hydrate-bearing layers. The thermal stimulation method is quite expensive. The chemical inhibitor injection method is also expensive. The depressurization method may prove useful to apply more than one production.

  3. Which, if any, hydrates will crystallise? Predicting hydrate formation of two dihydroxybenzoic acids†

    OpenAIRE

    Braun, Doris E.; Karamertzanis, Panagiotis G.; Price, Sarah L.

    2011-01-01

    A study of two dihydroxybenzoic acid isomers shows that computational methods can be used to predict hydrate formation, the compound : water ratio and hydrate crystal structures. The calculations also help identify a novel hydrate found in the solid form screening that validates this study.

  4. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    Science.gov (United States)

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  5. Polyethylene Glycol Drilling Fluid for Drilling in Marine Gas Hydrates-Bearing Sediments: An Experimental Study

    Directory of Open Access Journals (Sweden)

    Lixin Kuang

    2011-01-01

    Full Text Available Shale inhibition, low-temperature performance, the ability to prevent calcium and magnesium-ion pollution, and hydrate inhibition of polyethylene glycol drilling fluid were each tested with conventional drilling-fluid test equipment and an experimental gas-hydrate integrated simulation system developed by our laboratory. The results of these tests show that drilling fluid with a formulation of artificial seawater, 3% bentonite, 0.3% Na2CO3, 10% polyethylene glycol, 20% NaCl, 4% SMP-2, 1% LV-PAC, 0.5% NaOH and 1% PVP K-90 performs well in shale swelling and gas hydrate inhibition. It also shows satisfactory rheological properties and lubrication at temperature ranges from −8 °C to 15 °C. The PVP K-90, a kinetic hydrate inhibitor, can effectively inhibit gas hydrate aggregations at a dose of 1 wt%. This finding demonstrates that a drilling fluid with a high addition of NaCl and a low addition of PVP K-90 is suitable for drilling in natural marine gas-hydrate-bearing sediments.

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

    International Nuclear Information System (INIS)

    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)

  7. Hydration modes of an amphiphilic molecule 2: NMR, FTIR and theoretical study of the interactions in the system water-1,2-dimethoxyethane

    International Nuclear Information System (INIS)

    Graphical abstract: Using NMR spectroscopy, PFG measurements, relaxations and NOESY, as well as FTIR spectroscopy and DFT calculations, 1,2-dimethoxyethane is shown to form a hydrate with five water molecules bound by cooperative hydrogen bonds. Highlights: → Binding of water to DME leads to tgt conformation at all water/DME ratios. → Water is bound to DME in a tight envelope containing at least five water molecules. → The hydration envelope is built up by cooperative O-H...O and O...H-C hydrogen bonds. - Abstract: Using 1H and 13C NMR spectra, PFG NMR self-diffusion measurements, 1H and 13C NMR relaxations and 1H NOESY NMR spectra, FTIR spectra and quantum-chemical DFT and MP2 calculations, the interaction of 1,2-dimethoxyethane (DME) with water (W) was re-examined. It was confirmed that, primarily, one W molecule forms two O...H hydrogen bonds with DME in tgt conformation. At medium and higher W contents, however, larger hydrates of DME are formed, predominantly with five W molecules. The compact structure of the hydrate is warranted by O...H hydrogen bonds, some of them perceptibly tighter than those in the primary hydrate, and by non-classical CH3...O hydrogen bonds.

  8. Hydration in soccer: a review

    Directory of Open Access Journals (Sweden)

    Monteiro Cristiano Ralo

    2003-01-01

    Full Text Available Hydration should be considered before, during and after the exercise. This review intends to approach the main points of hydration process in soccer. The replacement of fluids during exercise is proportional to some factors, such as: exercise intensity; climatic conditions; the athlete's acclimatization; the athlete's physical conditioning; physiologic individual characteristics and the player's biomechanics. Performance is improved when players ingest not only water but also carbohydrate. The rates that carbohydrate and water are absorbed by the organism are limited by the rates of gastric emptying and intestinal absorption. The composition of drinks offered to the players should be influenced by the relative importance of the need of supplying carbohydrates or water; it should be remembered that the depletion of carbohydrate can result in fatigue and decrease of performance, but it is not usually a life-threatening condition. The addition of carbohydrate in these drinks increases the concentrations of blood glucose, increases the use of external fuel through the increase of the glucose oxidation in the muscles and it spares muscle glycogen. So, the ingestion of carbohydrate before and during the exercise can delay the emergence of fatigue and increase the players' performance. Several tactics can be used to avoid dehydration, like hyperhydration before exercise and player's acclimatization. The ideal situation to restore the player's fluid losses is between the sessions of exercises. Since soccer is a sport with quite peculiar characteristics related to hydration, the players should be concerned and educated about the importance of fluid ingestion before, during and after the exercise.

  9. Competition between hydrogen and halogen bonding in halogenated 1-methyluracil: Water systems.

    Science.gov (United States)

    Hogan, Simon W L; van Mourik, Tanja

    2016-03-30

    The competition between hydrogen- and halogen-bonding interactions in complexes of 5-halogenated 1-methyluracil (XmU; X = F, Cl, Br, I, or At) with one or two water molecules in the binding region between C5-X and C4O4 is investigated with M06-2X/6-31+G(d). In the singly-hydrated systems, the water molecule forms a hydrogen bond with C4O4 for all halogens, whereas structures with a halogen bond between the water oxygen and C5-X exist only for X = Br, I, and At. Structures with two waters forming a bridge between C4O and C5-X (through hydrogen- and halogen-bonding interactions) exist for all halogens except F. The absence of a halogen-bonded structure in singly-hydrated ClmU is therefore attributed to the competing hydrogen-bonding interaction with C4O4. The halogen-bond angle in the doubly-hydrated structures (150-160°) is far from the expected linearity of halogen bonds, indicating that significantly non-linear halogen bonds may exist in complex environments with competing interactions. © 2016 Wiley Periodicals, Inc. PMID:26773851

  10. Dissecting Hydrophobic Hydration and Association

    OpenAIRE

    Remsing, Richard C.; Weeks, John D.

    2015-01-01

    We use appropriately defined short ranged reference models of liquid water to clarify the different roles local hydrogen bonding, van der Waals attractions, and long ranged electrostatic interactions play in the solvation and association of apolar solutes in water. While local hydrogen bonding in- teractions dominate hydrophobic effects involving small solutes, longer ranged electrostatic and dis- persion interactions are found to be increasingly important in the description of interfacial st...

  11. Protein dynamics: hydration and cavities

    Directory of Open Access Journals (Sweden)

    K. Heremans

    2005-08-01

    Full Text Available The temperature-pressure behavior of proteins seems to be unique among the biological macromolecules. Thermodynamic as well as kinetic data show the typical elliptical stability diagram. This may be extended by assuming that the unfolded state gives rise to volume and enthalpy-driven liquid-liquid transitions. A molecular interpretation follows from the temperature and the pressure dependence of the hydration and cavities. We suggest that positron annihilation spectroscopy can provide additional quantitative evidence for the contributions of cavities to the dynamics of proteins. Only mature amyloid fibrils that form from unfolded proteins are very resistant to pressure treatment.

  12. Formation rate of natural gas hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Mork, Marit

    2002-07-01

    The rate of methane hydrate and natural gas hydrate formation was measured in a 9.5 litre stirred tank reactor of standard design. The experiments were performed to better understand the performance and scale-up of a reactor for continuous production of natural gas hydrates. The hydrate formation rate was measured at steady-state conditions at pressures between 70 and 90 bar and temperatures between 7 and 15 deg C. Between 44 and 56 % of the gas continuously supplied to the reactor was converted to hydrate. The experimental results show that the rate of hydrate formation is strongly influenced by gas injection rate and pressure. The effect of stirring rate is less significant and subcooling has no observable effect on the formation rate. Hydrate crystal concentration and gas composition do not influence the hydrate formation rate. Observations of produced hydrate crystals indicate that the crystals are elongated, about 5 micron in diameter and 10 micron long. Analysis of the results shows that the rate of hydrate formation is dominated by gas-liquid mass transfer. A mass transfer model, the bubble-to-crystal model, was developed for the hydrate formation rate in a continuous stirred tank reactor, given in terms of concentration driving force and an overall mass transfer coefficient. The driving force is the difference between the gas concentration at the gas-liquid interface and at the hydrate crystal surface. These concentrations correspond to the solubility of gas in water at experimental temperature and pressure and the solubility of gas at hydrate equilibrium temperature and experimental pressure, respectively. The overall mass transfer coefficient is expressed in terms of superficial gas velocity and impeller power consumption, parameters commonly used in study of stirred tank reactors. Experiments and modeling show that the stirred tank reactor has a considerable potential for increased production capacity. However, at higher hydrate production rates the

  13. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    International Nuclear Information System (INIS)

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments

  14. Effect of fatty acids on phase behavior of hydrated dipalmitoylphosphatidylcholine bilayer: saturated versus unsaturated fatty acids.

    Science.gov (United States)

    Inoue, T; Yanagihara, S; Misono, Y; Suzuki, M

    2001-02-01

    The effect of some fatty acids on the phase behavior of hydrated dipalmitoylphosphatidylcholine (DPPC) bilayer was investigated with special interest in possible difference between saturated and unsaturated fatty acids. The phase behavior of hydrated DPPC bilayer was followed by a differential scanning calorimetry and a Fourier transform infrared spectroscopy. The addition of palmitic acid (PA) increased the bilayer phase transition temperature with the increase of the PA content in the mixture. In addition, DPPC molecules in gel phase bilayer became more rigid in the presence of PA compared with those in the absence of PA. This effect of PA on the phase behavior of hydrated DPPC bilayer is common to other saturated fatty acids, stearic acid, myristic acid, and also to unsaturated fatty acid with trans double bond, elaidic acid. Contrary to these fatty acids, oleic acid (OA), the unsaturated fatty acid with cis double bond in the acyl chain, exhibited quite different behavior. The effect of OA on the bilayer phase transition temperature was rather small, although a slight decrease in the temperature was appreciable. Furthermore, the IR spectral results demonstrated that the perturbing effect of OA on the gel phase bilayer of DPPC was quite small. These results mean that OA does not disturb the hydrated DPPC bilayer significantly. PMID:11269932

  15. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Science.gov (United States)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V.

    2016-01-01

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  16. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V., E-mail: aneimark@rutgers.edu [Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854-8058 (United States)

    2016-01-07

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  17. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane.

    Science.gov (United States)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V

    2016-01-01

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments. PMID:26747818

  18. Hydrogen speciation in hydrated layers on nuclear waste glass

    International Nuclear Information System (INIS)

    The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 and 165, and PNL 76-68), which were leached at 900C (all glasses) or hydrated in a vapor-saturated atmosphere at 2020C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was found in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 μm layer on SRL-131 glass formed by leaching at 900C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H+ interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups

  19. Synthesis, dehydration and hydration processes of uranyl p-toluenesulfonate and its crystal hydrates

    International Nuclear Information System (INIS)

    Uranyl p-toluenesulfonate was synthesized and studied. This salt crystallizes from aqueous solution as pentahydrate. Its solubility is 2.57 mol/kg at 25 Deg C. Anhydrous salt and lower hydrates were prepared. Hydration of the anhydrous salt in the air at various steam pressures are studied. Thermogravimetric data show that uranyl p-toluenesulfonate pentahydrate has the layered structure of hydration shell. IR spectra of crystal hydrates with the same composition obtained by means of dehydration-hydration procedure are the same in the region of frequencies of sulfonate group and differ in the region of water vibrations

  20. Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Ming-Liang; Te, Jerez; Cendagorta, Joseph R. [Department of Chemistry, Georgetown University, Washington, District of Columbia 20057 (United States); Miller, Benjamin T.; Brooks, Bernard R. [Laboratory of Computational Biology, National Heart, Lung, and Blood Institute, National Institutes of Health, Rockville, Maryland 20892 (United States); Ichiye, Toshiko, E-mail: ti9@georgetown.edu [Department of Chemistry, Georgetown University, Washington, District of Columbia 20057 (United States); Laboratory of Computational Biology, National Heart, Lung, and Blood Institute, National Institutes of Health, Rockville, Maryland 20892 (United States)

    2015-02-14

    The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol V{sub E} as a function of ethanol mole fraction X{sub E} is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water.

  1. Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures.

    Science.gov (United States)

    Tan, Ming-Liang; Miller, Benjamin T; Te, Jerez; Cendagorta, Joseph R; Brooks, Bernard R; Ichiye, Toshiko

    2015-02-14

    The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol VE as a function of ethanol mole fraction XE is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has "brittle" hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water. PMID:25681917

  2. Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

    International Nuclear Information System (INIS)

    The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol VE as a function of ethanol mole fraction XE is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water

  3. Hydration and translocation of an excess proton in water clusters: An ab initio molecular dynamics study

    Indian Academy of Sciences (India)

    Arindam Bankura; Amalendu Chandra

    2005-10-01

    The hydration structure and translocation of an excess proton in hydrogen bonded water clusters of two different sizes are investigated by means of finite temperature quantum simulations. The simulations are performed by employing the method of Car–Parrinello molecular dynamics where the forces on the nuclei are obtained directly from `on the fly' quantum electronic structure calculations. Since no predefined interaction potentials are used in this scheme, it is ideally suited to study proton translocation processes which proceed through breaking and formation of chemical bonds. The coordination number of the hydrated proton and the index of oxygen to which the excess proton is attached are calculated along the simulation trajectories for both the clusters.

  4. CO2 capture by gas hydrate crystallization: Application on the CO2-N2 mixture

    International Nuclear Information System (INIS)

    CO2 capture and sequestration represent a major industrial and scientific challenge of this century. There are different methods of CO2 separation and capture, such as solid adsorption, amines adsorption and cryogenic fractionation. Although these processes are well developed at industrial level, they are energy intensive. Hydrate formation method is a less energy intensive and has an interesting potential to separate carbon dioxide. Gas hydrates are Document crystalline compounds that consist of hydrogen bonded network of water molecules trapping a gas molecule. Gas hydrate formation is favored by high pressure and low temperature. This study was conducted as a part of the SECOHYA ANR Project. The objective is to study the thermodynamic and kinetic conditions of the process to capture CO2 by gas hydrate crystallization. Firstly, we developed an experimental apparatus to carry out experiments to determine the thermodynamic and kinetic formation conditions of CO2-N2 gas hydrate mixture in water as liquid phase. We showed that the operative pressure may be very important and the temperature very low. For the feasibility of the project, we used TBAB (Tetrabutylammonium Bromide) as thermodynamic additive in the liquid phase. The use of TBAB may reduce considerably the operative pressure. In the second part of this study, we presented a thermodynamic model, based on the van der Waals and Platteeuw model. This model allows the estimation of thermodynamic equilibrium conditions. Experimental equilibrium data of CO2-CH4 and CO2-N2 mixtures are presented and compared to theoretical results. (author)

  5. Hydration sites of unpaired RNA bases: a statistical analysis of the PDB structures

    Directory of Open Access Journals (Sweden)

    Carugo Oliviero

    2011-10-01

    Full Text Available Abstract Background Hydration is crucial for RNA structure and function. X-ray crystallography is the most commonly used method to determine RNA structures and hydration and, therefore, statistical surveys are based on crystallographic results, the number of which is quickly increasing. Results A statistical analysis of the water molecule distribution in high-resolution X-ray structures of unpaired RNA nucleotides showed that: different bases have the same penchant to be surrounded by water molecules; clusters of water molecules indicate possible hydration sites, which, in some cases, match those of the major and minor grooves of RNA and DNA double helices; complex hydrogen bond networks characterize the solvation of the nucleotides, resulting in a significant rigidity of the base and its surrounding water molecules. Interestingly, the hydration sites around unpaired RNA bases do not match, in general, the positions that are occupied by the second nucleotide when the base-pair is formed. Conclusions The hydration sites around unpaired RNA bases were found. They do not replicate the atom positions of complementary bases in the Watson-Crick pairs.

  6. Gas hydrate inhibition of drilling fluid additives

    Energy Technology Data Exchange (ETDEWEB)

    Xiaolan, L.; Baojiang, S.; Shaoran, R. [China Univ. of Petroleum, Dongying (China). Inst. of Petroleum Engineering

    2008-07-01

    Gas hydrates that form during offshore well drilling can have adverse impacts on well operational safety. The hydrates typically form in the risers and the annulus between the casing and the drillstring, and can stop the circulation of drilling fluids. In this study, experiments were conducted to measure the effect of drilling fluid additives on hydrate inhibition. Polyalcohols, well-stability control agents, lubricating agents, and polymeric materials were investigated in a stirred tank reactor at temperatures ranging from -10 degree C to 60 degrees C. Pressure, temperature, and torque were used to detect onset points of hydrate formation and dissociation. The inhibitive effect of the additives on hydrate formation was quantified. Phase boundary shifts were measured in terms of temperature difference or sub-cooling gained when chemicals were added to pure water. Results showed that the multiple hydroxyl groups in polyalcohol chemicals significantly inhibited hydrate formation. Polymeric and polyacrylamide materials had only a small impact on hydrate formation, while sulfonated methyl tannins were found to increase hydrate formation. 6 refs., 1 tab., 4 figs.

  7. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede

    1998-01-01

    This report deals with gas phase hydration of pure cement clinker minerals at reduced relative humidities. This is an important subject in relation to modern high performance concrete which may self-desiccate during hydration. In addition the subject has relevance to storage stability where...

  8. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.; Glasser, Fred P.

    1999-01-01

    Vapour phase hydration of purl cement clinker minerals at reduced relative humidities is described. This is relevant to modern high performance concrete that may self-desiccate during hydration and is also relevant to the quality of the cement during storage. Both the oretical considerations and...

  9. 78 FR 37536 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2013-06-21

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  10. 76 FR 59667 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2011-09-27

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... of the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice...

  11. 78 FR 26337 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2013-05-06

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  12. A new geotechnical gas hydrates research laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Grozic, J.L.H. [Calgary Univ., AB (Canada)

    2003-07-01

    Gas hydrates encapsulate natural gas molecules in a very compact form, as ice-like compounds composed of water molecules. Permafrost environments and offshore areas contain vast quantities of gas hydrates within soil and rock. This paper describes the role played by gas hydrates in submarine slope instability, their potential as a sustainable energy source, and their effects on global climate change. A new state-of-the-art laboratory located at the University of Calgary, which was developed to study the geomechanical behaviour of gas hydrate-sediment mixtures, was also presented. A specialized high pressure low temperature triaxial apparatus capable of performing a suite of tests on gas hydrate-sediment mixtures is housed in this laboratory. Extensive renovations were required in order to enable the use of methane gas to simulate natural hydrate formation conditions. The laboratory is specifically designed to examine the properties and behaviour of reconstituted gas hydrate-sediment mixtures and natural gas hydrate core samples. 26 refs., 9 figs.

  13. The effects of mucopolysaccharide polysulphate on hydration and elasticity of human skin.

    Science.gov (United States)

    Wanitphakdeedecha, Rungsima; Eimpunth, Sasima; Manuskiatti, Woraphong

    2011-01-01

    Background. Mucopolysaccharide polysulphate (MPS) has been used in medicine as an anti-inflammatory and antithrombotic agent for over 50 years. Its chemical structure permits considerable hydrogen bonding with adjacent water molecules, which effectively leads to hydration of the surrounding tissue. In addition, it stimulates endogenous hyaluronate synthesis, resulting in an increase in water-binding capacity and viscoelasticity of the skin. Objective. To study the efficacy of 0.1% MPS on hydration and elasticity of human skin. Methods. The first part of this study was a randomized double blind placebo-controlled study which included 60 female volunteers aged 30-45 years with dry skin, defined by Corneometer CM 825. The volunteers were treated with either 0.1% MPS or vehicle control. All subjects were asked to apply 1 g of cream to their face twice daily for a total period of 4 weeks. Skin hydration and elasticity were measured at baseline and week 4 with Corneometer CM 825 and cutometer MPA 580, respectively, at forehead and both cheeks. The second part of this study focused on the efficacy of 0.1% MPS on skin hydration after single application. 20 female volunteers aged 30-45 years with dry skin, defined by Corneometer CM 825, were recruited to the study. All subjects were asked to apply 2 g of 0.1% MPS cream on entirely randomly selected forearm. Skin hydration at the middle of both forearms was measured at baseline, immediately after application, and every 1 hour after application for a period of 10 hours. Results. 57 subjects (28 in vehicle control group, 29 in MPS) completed treatment protocol. The baseline skin hydration of both groups was not significantly different (P = 0.47). Hower, there was a statistically significant difference in skin hydration at 4 weeks between MPS and placebo group (P = 0.01). Skin elasticity was significantly improved at week 4 in both groups (vehicle-control, P < 0.01, and MPS, P < 0.01). However, no significant

  14. The Effects of Mucopolysaccharide Polysulphate on Hydration and Elasticity of Human Skin

    Directory of Open Access Journals (Sweden)

    Rungsima Wanitphakdeedecha

    2011-01-01

    Full Text Available Background. Mucopolysaccharide polysulphate (MPS has been used in medicine as an anti-inflammatory and antithrombotic agent for over 50 years. Its chemical structure permits considerable hydrogen bonding with adjacent water molecules, which effectively leads to hydration of the surrounding tissue. In addition, it stimulates endogenous hyaluronate synthesis, resulting in an increase in water-binding capacity and viscoelasticity of the skin. Objective. To study the efficacy of 0.1% MPS on hydration and elasticity of human skin. Methods. The first part of this study was a randomized double blind placebo-controlled study which included 60 female volunteers aged 30–45 years with dry skin, defined by Corneometer CM 825. The volunteers were treated with either 0.1% MPS or vehicle control. All subjects were asked to apply 1 g of cream to their face twice daily for a total period of 4 weeks. Skin hydration and elasticity were measured at baseline and week 4 with Corneometer CM 825 and cutometer MPA 580, respectively, at forehead and both cheeks. The second part of this study focused on the efficacy of 0.1% MPS on skin hydration after single application. 20 female volunteers aged 30–45 years with dry skin, defined by Corneometer CM 825, were recruited to the study. All subjects were asked to apply 2 g of 0.1% MPS cream on entirely randomly selected forearm. Skin hydration at the middle of both forearms was measured at baseline, immediately after application, and every 1 hour after application for a period of 10 hours. Results. 57 subjects (28 in vehicle control group, 29 in MPS completed treatment protocol. The baseline skin hydration of both groups was not significantly different (P=0.47. Hower, there was a statistically significant difference in skin hydration at 4 weeks between MPS and placebo group (P=0.01. Skin elasticity was significantly improved at week 4 in both groups (vehicle-control, P<0.01, and MPS, P<0.01. However, no

  15. Novel hard, tough HfAlSiN multilayers, defined by alternating Si bond structure, deposited using modulated high-flux, low-energy ion irradiation of the growing film

    International Nuclear Information System (INIS)

    Hf1−x−yAlxSiyN (0 ≤ x ≤ 0.14, 0 ≤ y ≤ 0.12) single layer and multilayer films are grown on Si(001) at 250 °C using ultrahigh vacuum magnetically unbalanced reactive magnetron sputtering from a single Hf0.6Al0.2Si0.2 target in mixed 5%-N2/Ar atmospheres at a total pressure of 20 mTorr (2.67 Pa). The composition and nanostructure of Hf1−x−yAlxSiyN films are controlled by varying the energy Ei of the ions incident at the film growth surface while maintaining the ion-to-metal flux ratio constant at eight. Switching Ei between 10 and 40 eV allows the growth of Hf0.78Al0.10Si0.12N/Hf0.78Al0.14Si0.08N multilayers with similar layer compositions, but in which the Si bonding state changes from predominantly Si–Si/Si–Hf for films grown with Ei = 10 eV, to primarily Si–N with Ei = 40 eV. Multilayer hardness values, which vary inversely with bilayer period Λ, range from 20 GPa with Λ = 20 nm to 27 GPa with Λ = 2 nm, while fracture toughness increases directly with Λ. Multilayers with Λ = 10 nm combine relatively high hardness, H ∼ 24 GPa, with good fracture toughness

  16. Polyelectrolyte conformational transition in aqueous solvent mixture influenced by hydrophobic interactions and hydrogen bonding effects: PAA-water-ethanol.

    Science.gov (United States)

    Sappidi, Praveenkumar; Natarajan, Upendra

    2016-03-01

    Molecular dynamics simulations of poly(acrylic acid) PAA chain in water-ethanol mixture were performed for un-ionized and ionized cases at different degree-of-ionization 0%, 80% and 100% of PAA chain by Na(+) counter-ions and co-solvent (ethanol) concentration in the range 0-90vol% ethanol. Aspects of structure and dynamics were investigated via atom pair correlation functions, number and relaxation of hydrogen bonds, nearest-neighbor coordination numbers, and dihedral angle distribution function for back-bone and side-groups of the chain. With increase in ethanol concentration, chain swelling is observed for un-ionized chain (f=0) and on the contrary chain shrinkage is observed for partially and fully ionized cases (i.e., f=0.8 and 1). For un-ionized PAA, with increase in ethanol fraction ϕeth the number of PAA-ethanol hydrogen bonds increases while PAA-water decreases. Increase in ϕeth leads to PAA chain expansion for un-ionized case and chain shrinkage for ionized case, in agreement with experimental observations on this system. For ionized-PAA case, chain shrinkage is found to be influenced by intermolecular hydrogen bonding with water as well as ethanol. The localization of ethanol molecules near the un-ionized PAA backbone at higher levels of ethanol is facilitated by a displacement of water molecules indicating presence of specific ethanol hydration shell, as confirmed by results of the RDF curves and coordination number calculations. This behavior, controlled by hydrogen bonding provides a significant contribution to such a conformational transition behavior of the polyelectrolyte chain. The interactions between counter-ions and charges on the PAA chain also influence chain collapse. The underlying origins of polyelectrolyte chain collapse in water-alcohol mixtures are brought out for the first time via explicit MD simulations by this study. PMID:26803232

  17. Experimental Setup to Characterize Bentonite Hydration Processes

    International Nuclear Information System (INIS)

    We present an experimental setup to follow-up the hydration process of a bentonite. Clay samples, of 2 cm x 12 cm x 12 cm, were made and introduced in a Hele-Shaw cell with two PMM windows and two steel frames. In hydration experiments, a fluid enters by an orifice in the frame, located both at the top and the bottom of the cell, to perform hydration in both senses. To get a uniform hydration we place a diffuser near the orifice. Volume influxes in hydration cells are registered in time. The evolution of the developed interface was recorded on a videotape. The video cameras was fixed to a holder so that the vertical direction in the monitor was the same as the direction of the larger extension of the cell. (Author) 6 refs

  18. Hydrate plug decomposition: Measurements and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Yousif, M.H.; Dunayevsky, V.A.

    1995-12-31

    Depressurization (venting) is almost the only option available to remove hydrate blockages from subsea natural gas or gas condensate pipelines. This process is normally applied with little or no accurate information about the plug location, size or composition. Hydrate decomposition by depressurization is a heat and mass transfer dependent process. Quantifying this dependency is necessary to perform an optimum plug removal scheme. In this paper, a moving boundary mathematical model is developed to predict the decomposition rate of a hydrate plug under various depressurization scenarios. The model was validated experimentally by measuring the rate of decomposition of hydrate plugs in a 2 inch internal diameter, 38.5 inch long pipe. The motion of the hydrate plug/gas interface is tracked by 16 pairs of infrared light transmitters and receivers diametrically positioned across the pipe.

  19. Raman spectral evidence for hydration forces between collagen triple helices

    OpenAIRE

    Leikin, S; Parsegian, V A; Yang, W.-H.; Walrafen, G. E.

    1997-01-01

    Hydration forces are thought to result from the energetic cost of water rearrangement near macromolecular surfaces. Raman spectra, collected on the same collagen samples on which these forces were measured, reveal a continuous change in water hydrogen-bonding structure as a function of separation between collagen triple helices. The varying spectral parameters track the force-distance curve. The energetic cost of water “restructuring,” estimated from the spectra, is consistent with the measur...

  20. The Effects of Mucopolysaccharide Polysulphate on Hydration and Elasticity of Human Skin

    OpenAIRE

    Rungsima Wanitphakdeedecha; Sasima Eimpunth; Woraphong Manuskiatti

    2011-01-01

    Background. Mucopolysaccharide polysulphate (MPS) has been used in medicine as an anti-inflammatory and antithrombotic agent for over 50 years. Its chemical structure permits considerable hydrogen bonding with adjacent water molecules, which effectively leads to hydration of the surrounding tissue. In addition, it stimulates endogenous hyaluronate synthesis, resulting in an increase in water-binding capacity and viscoelasticity of the skin. Objective. To study the efficacy of 0.1% MPS on hydr...

  1. Mössbauer, XRD, and Complex Thermal Analysis of the Hydration of Cement with Fly Ash

    OpenAIRE

    Vili Lilkov; Ognyan Petrov; Yana Tzvetanova; Plamen Savov; Milen Kadiyski

    2013-01-01

    Hydration of cement with and without fly ash is studied with Mössbauer spectroscopy, XRD, and thermal analysis. Iron in cement is present as Fe3+-ions and occupies two octahedral positions, with close isomer shifts and quadrupole splittings. Iron in fly ash is present as Fe2+ and Fe3+, and the Mössbauer spectra display three doublets—two for Fe3+ in octahedral coordination and one for Fe2+. A third doublet was registered in the hydrating plain cement pastes after the 5th day, due to Fe3+ in t...

  2. Synthesis of pure zeolite P2 from calcium silicate hydrate; tobermorite

    OpenAIRE

    Nasser Y. Mostafa; Rasha A. Garib; Z. K. Heiba; Abd-Elkader, Omar H.; M. M. Al-Majthoub

    2015-01-01

    Calcium silicate hydrate phases offer the possibility to become potential zeolites precursors due to its high silica contents. Pure calcium silicate hydrate phase; tobermorite (Ca5Si6O16(OH)2·4H2O), was prepared by hydrothermal method at 175°C. Tobermorite was sucssefully converted to Zeolite P2 for the first time via refluxing in 3 M NaOH solution and in the presence of Al source. Sodium hydroxide removed calcium ions from the interlayers of calcium silicate phase and form mesoporous zeolite...

  3. Ab initio studies of ionization potentials of hydrated hydroxide and hydronium

    CERN Document Server

    Swartz, Charles W

    2013-01-01

    The ionization potential distributions of hydrated hydroxide and hydronium are computed with many-body approach for electron excitations with configurations generated by {\\it ab initio} molecular dynamics. The experimental features are well reproduced and found to be closely related to the molecular excitations. In the stable configurations, the ionization potential is mainly perturbed by water molecules within the first solvation shell. On the other hand, electron excitation is delocalized on both proton receiving and donating complex during proton transfer, which shifts the excitation energies and broadens the spectra for both hydrated ions.

  4. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated

  5. Overview on Hydrate Coring, Handling and Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Jon Burger; Deepak Gupta; Patrick Jacobs; John Shillinglaw

    2003-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Worldwide, gas hydrate is estimated to hold about 1016 kg of organic carbon in the form of methane (Kvenvolden et al., 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In June 2002, Westport Technology Center was requested by the Department of Energy (DOE) to prepare a ''Best Practices Manual on Gas Hydrate Coring, Handling and Analysis'' under Award No. DE-FC26-02NT41327. The scope of the task was specifically targeted for coring sediments with hydrates in Alaska, the Gulf of Mexico (GOM) and from the present Ocean Drilling Program (ODP) drillship. The specific subjects under this scope were defined in 3 stages as follows: Stage 1: Collect information on coring sediments with hydrates, core handling, core preservation, sample transportation, analysis of the core, and long term preservation. Stage 2: Provide copies of the first draft to a list of experts and stakeholders designated by DOE. Stage 3: Produce a second draft of the manual with benefit of input from external review for delivery. The manual provides an overview of existing information available in the published literature and reports on coring, analysis, preservation and transport of gas hydrates for laboratory analysis as of June 2003. The manual was delivered as draft version 3 to the DOE Project Manager for distribution in July 2003. This Final Report is provided for records purposes.

  6. Positron annihilation and nuclear magnetic resonance study of the phase behavior of water confined in mesopores at different levels of hydration.

    Science.gov (United States)

    Maheshwari, Priya; Dutta, Dhanadeep; Mukherjee, Saurabh; Madhu, Perunthiruthy K; Mote, Kaustubh R; Pujari, Pradeep K

    2016-05-14

    We investigated the molecular origin of the phase behavior of water confined in MCM 41 mesopores at different levels of hydration using positron annihilation spectroscopic and nuclear magnetic resonance techniques. The level of hydration influenced the phase behavior of the nanoconfined water. Two transitions above and below the bulk freezing temperature were observed depending on the level of hydration. At the highest level of hydration, nucleation seemed to predominate over the effect of confinement, leading to the complete freezing of water, whereas disrupted H-bonding dominated at the lowest level of hydration, leading to the disappearance of the transitions. A transition at c. T = 188 K (close to the reported glass transition temperature of interface-affected water) was observed at intermediate hydration level. This study suggests that the H-bonding network within nanoconfined water, which can be tampered by the degree of hydration, is the key factor responsible for the phase behavior of supercooled water. This study on the phase behavior and associated transitions of nanoconfined water has implications for nanofluidics and drug-delivery systems, in addition to understanding the fundamentals of water in confinement. PMID:27105178

  7. Dissecting hydrophobic hydration and association.

    Science.gov (United States)

    Remsing, Richard C; Weeks, John D

    2013-12-12

    We use appropriately defined short-ranged reference models of liquid water to clarify the different roles local hydrogen bonding, van der Waals attractions, and long-ranged electrostatic interactions play in the solvation and association of apolar solutes in water. While local hydrogen bonding interactions dominate hydrophobic effects involving small solutes, longer-ranged electrostatic and dispersion interactions are found to be increasingly important in the description of interfacial structure around large solutes. The hydrogen bond network sets the solute length scale at which a crossover in solvation behavior between these small and large length scale regimes is observed. Unbalanced long-ranged forces acting on interfacial water molecules are also important in hydrophobic association, illustrated here by analysis of the association of model methane and buckminsterfullerene solutes. PMID:23944226

  8. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  9. Bond energies of ThO+ and ThC+: A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O2 and CO

    Science.gov (United States)

    Cox, Richard M.; Citir, Murat; Armentrout, P. B.; Battey, Samuel R.; Peterson, Kirk A.

    2016-05-01

    Kinetic energy dependent reactions of Th+ with O2 and CO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO+ in the reaction of Th+ with O2 is observed to be exothermic and barrierless with a reaction efficiency at low energies of k/kLGS = 1.21 ± 0.24 similar to the efficiency observed in ion cyclotron resonance experiments. Formation of ThO+ and ThC+ in the reaction of Th+ with CO is endothermic in both cases. The kinetic energy dependent cross sections for formation of these product ions were evaluated to determine 0 K bond dissociation energies (BDEs) of D0(Th+-O) = 8.57 ± 0.14 eV and D0(Th+-C) = 4.82 ± 0.29 eV. The present value of D0 (Th+-O) is within experimental uncertainty of previously reported experimental values, whereas this is the first report of D0 (Th+-C). Both BDEs are observed to be larger than those of their transition metal congeners, TiL+, ZrL+, and HfL+ (L = O and C), believed to be a result of lanthanide contraction. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to coupled-cluster singles and doubles with iterative triples and quadruples (CCSDTQ) for ThC, ThC+, ThO, and ThO+, as well as more approximate CCSD with perturbative (triples) [CCSD(T)] calculations where a semi-empirical model was used to estimate spin-orbit energy contributions. Finally, the ThO+ BDE is compared to other actinide (An) oxide cation BDEs and a simple model utilizing An+ promotion energies to the reactive state is used to estimate AnO+ and AnC+ BDEs. For AnO+, this model yields predictions that are typically within experimental uncertainty and performs better than density functional theory calculations presented previously.

  10. 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.

  11. Methane Recovery from Hydrate-bearing Sediments

    Energy Technology Data Exchange (ETDEWEB)

    J. Carlos Santamarina; Costas Tsouris

    2011-04-30

    Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with

  12. Clathrate hydrate tuning for technological purposes

    Science.gov (United States)

    di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco

    2010-05-01

    Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006

  13. 13-(N,N-Dimethylaminomicheliolide 0.08-hydrate

    Directory of Open Access Journals (Sweden)

    Peter A. Crooks

    2013-12-01

    Full Text Available The title compound, C17H27NO3·0.08H2O {sytematic name: (3R,3aS,9R,9aS,9bS-3-[(dimethylaminomethyl]-9-hydroxy-6,9-dimethyl-3,3a,4,5,7,8,9,9a-octahydroazuleno[4,5-b]furan-2(9bH-one 0.08-hydrate}, exhibits intramolecular O—H...O hydrogen bonding to form a ring of graph-set motif S(6. As well as this intramolecular hydrogen bond with the lactone-ring O atom, the hydroxy H atom forms an O—H...O hydrogen bond to the low-occupancy partial water molecule [occupancy = 0.078 (2]. The water molecule is correlated with disorder of the N(CH32 group [major–minor occupancy factors are 0.922 (2:0.078 (2]. The dihedral angle between the mean planes of the trans-fused seven-membered ring and the lactone ring is 4.42 (9°.

  14. Modeling of Cation Binding in Hydrated 2:1 Clay Minerals - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Smith, David E.

    2000-09-14

    Hydrated 2:1 clay minerals are high surface area, layered silicates that play a unique role in determining the fate of radionuclides in the environment. This project consisted of developing and implementing computer simulation methods for molecular characterization of the swelling and ion exchange properties of Hydrated 2:1 clay minerals, and the subsequent analysis and theoretical modeling with a view toward improving contaminant transport modeling as well as soil remediation and radionuclide containment strategies. Project results included the (a) development of simulation methods to treat clays under environmentally relevant conditions of variable water vapor pressure; (b) calculation of clay swelling thermodynamics as a function of interlayer ion size and charge (calculated quantities include immersion energies, free energies, and entropies of swelling); and (c) calculation of ion exchange free energies, including contributions from changing interlayer water contents and layer spacing.

  15. Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

    Science.gov (United States)

    Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

    2013-01-01

    As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

  16. Direct current-induced electrogenerated chemiluminescence of hydrated and chelated Tb(III) at aluminum cathodes

    International Nuclear Information System (INIS)

    Cathodic DC polarization of oxide-covered aluminum produces electrogenerated chemiluminescence from hydrated and chelated Tb(III) ions in aqueous electrolyte solutions. At the moment of cathodic voltage onset, a strong cathodic flash is observed, which is attributed to a tunnel emission of hot electrons into the aqueous electrolyte solution and the successive chemical reactions with the luminophores. However, within a few milliseconds the insulating oxide film is damaged and finally dissolved due to (i) indiffusion of protons or alkali metal ions into the thin oxide film, (ii) subsequent hydrogen evolution at the aluminum/oxide interface and (iii) alkalization of the electrode surface induced by hydrogen evolution reaction. When the alkalization of the electrode surface has proceeded sufficiently, chemiluminescence is generated with increasing intensity. Aluminum metal, short-lived Al(II), Al(I) or atomic hydrogen and its conjugated base form, hydrated electron, can act as highly reducing species in addition to the less energetic heterogeneously transferred electrons from the aluminum electrode. Tb(III) added as a hydrated ion in the solution probably luminesces in the form of Tb(OH)3 or Tb(OH)4- by direct redox reactions of the central ion whereas multidentate aromatic ligand chelated Tb(III) probably luminesces by ligand sensitized chemiluminescence mechanism in which ligand is first excited by one-electron redox reactions, which is followed by intramolecular energy transfer to the central ion which finally emits light

  17. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  18. Calcium and magnesium silicate hydrates

    International Nuclear Information System (INIS)

    Deep geological disposals are planed to discard long-lived intermediate-level and high-level radioactive wastes. Clay-based geological barriers are expected to limit the ingress of groundwater and to reduce the mobility of radioelements. In the interaction zone between the cement and the clay based material alteration can occur. Magnesium silicate hydrates (M-S-H) have been observed due to the reaction of magnesium sulfate containing groundwater with cements or in the interaction zone between low-pH type cement and clays. M-S-H samples synthesized in the laboratory showed that M-S-H has a variable composition within 0.7 ≤ Mg/Si ≤ 1.5. TEM/EDS analyses show an homogeneous gel with no defined structure. IR and 29Si NMR data reveal a higher polymerization degree of the silica network in M-S-H compared to calcium silicate hydrates (C-S-H). The presence of mainly Q3 silicate tetrahedrons in M-S-H indicates a sheet like or a triple-chain silica structure while C-S-H is characterised by single chain-structure. The clear difference in the silica structure and the larger ionic radius of Ca2+ (1.1 Angstrom) compared to Mg2+ (0.8 Angstrom) make the formation of an extended solid solution between M-S-H and C-S-H gel improbable. In fact, the analyses of synthetic samples containing both magnesium and calcium in various ratios indicate the formation of separate M-S-H and C-S-H gels with no or very little uptake of magnesium in CS-H or calcium in M-S-H

  19. Anomalous porosity preservation and preferential accumulation of gas hydrate in the Andaman accretionary wedge, NGHP-01 site 17A

    Energy Technology Data Exchange (ETDEWEB)

    Rose, Kelly K.; Johnson, Joel E.; Torres, Marta E.; Hong, WeiLi; Giosan, Liviu; Solomon, E.; Kastner, Miriam; Cawthern, Thomas; Long, Philip E.; Schaef, Herbert T.

    2014-12-01

    In addition to well established properties that control the presence or absence of the hydrate stability zone, such as pressure, temperature, and salinity, additional parameters appear to influence the concentration of gas hydrate in host sediments. The stratigraphic record at Site 17A in the Andaman Sea, eastern Indian Ocean, illustrates the need to better understand the role pore-scale phenomena play in the distribution and presence of marine gas hydrates in a variety of subsurface settings. In this paper we integrate field-generated datasets with newly acquired sedimentology, physical property, imaging and geochemical data with mineral saturation and ion activity products of key mineral phases such as amorphous silica and calcite, to document the presence and nature of secondary precipitates that contributed to anomalous porosity preservation at Site 17A in the Andaman Sea. This study demonstrates the importance of grain-scale subsurface heterogeneities in controlling the occurrence and distribution of concentrated gas hydrate accumulations in marine sediments, and document the importance that increased permeability and enhanced porosity play in supporting gas concentrations sufficient to support gas hydrate formation. The grain scale relationships between porosity, permeability, and gas hydrate saturation documented at Site 17A likely offer insights into what may control the occurrence and distribution of gas hydrate in other sedimentary settings.

  20. Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

    Energy Technology Data Exchange (ETDEWEB)

    Manohara, G.V. [Department of Chemistry, The Central College Campus, Bangalore University, Bangalore 560 001 (India); Vishnu Kamath, P., E-mail: vishnukamath8@hotmail.com [Department of Chemistry, The Central College Campus, Bangalore University, Bangalore 560 001 (India); Milius, Wolfgang [Department of Inorganic Chemistry I, University of Bayreuth, Bayreuth D-95440 (Germany)

    2012-12-15

    Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueous exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 {mu}m. - Graphical abstract: Schematic of the hydrated, dehydrated and interstratified phases observed during the hydration-dehydration of Ni/Al-CH{sub 3}COO LDH. Highlights: Black-Right-Pointing-Pointer Ni/Al-acetate LDHs were synthesized by HPFS method by hydrolysis of acetamide. Black-Right-Pointing-Pointer Intercalated acetate ion shows reversible hydration with variation in humidity. Black-Right-Pointing-Pointer An ordered interstratified phase was observed during hydration/dehydration cycle. Black-Right-Pointing-Pointer A solution type equilibrium is observed between hydration-dehydration phases. Black-Right-Pointing-Pointer These LDHs undergo facile aqueous exfoliation.

  1. Detection and Production of Methane Hydrate

    Energy Technology Data Exchange (ETDEWEB)

    George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

    2011-12-31

    This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand

  2. Electrical properties of methane hydrate + sediment mixtures

    Science.gov (United States)

    Du Frane, Wyatt L.; Stern, Laura A.; Weitemeyer, Karen A.; Constable, Steven; Roberts, Jeffery J.

    2011-01-01

    As part of our DOE-funded proposal to characterize gas hydrate in the Gulf of Mexico using marine electromagnetic methods, a collaboration between SIO, LLNL, and USGS with the goal of measuring the electrical properties of lab-created methane (CH4) hydrate and sediment mixtures was formed. We examined samples with known characteristics to better relate electrical properties measured in the field to specific gas hydrate concentration and distribution patterns. Here we discuss first-ever electrical conductivity (σ) measurements on unmixed CH4 hydrate (Du Frane et al., 2011): 6 x 10-5 S/m at 5 °C, which is ~5 orders of magnitude lower than seawater. This difference allows electromagnetic (EM) techniques to distinguish highly resistive gas hydrate deposits from conductive water saturated sediments in EM field surveys. More recently, we performed measurements on CH4 hydrate mixed with sediment and we also discuss those initial findings here. Our results on samples free of liquid water are important for predicting conductivity of sediments with pores highly saturated with gas hydrate, and are an essential starting point for comprehensive mixing models.

  3. Gas Hydrates Research Programs: An International Review

    Energy Technology Data Exchange (ETDEWEB)

    Jorge Gabitto; Maria Barrufet

    2009-12-09

    Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

  4. The influence of hydrazine hydrate on the photoconductivity of PbS thin film

    Energy Technology Data Exchange (ETDEWEB)

    Ghamsari, M. Sasani [Solid State Laser Division, Laser Research Center, 11365-8486 Tehran (Iran, Islamic Republic of)]. E-mail: msasani@aeoi.org.ir; Araghi, M.K. [Solid State Laser Division, Laser Research Center, 11365-8486 Tehran (Iran, Islamic Republic of); Farahani, S.J. [Solid State Laser Division, Laser Research Center, 11365-8486 Tehran (Iran, Islamic Republic of)

    2006-08-25

    High quality poly crystalline nanostructured PbS thin film has been deposited on a glass substrate by chemical deposition technique. The hydrazine hydrate as a reducing agent for lead ion has been used for preparation of the film. After deposition, the film has been annealed, and then the influence of hydrazine hydrate on the dark resistivity and photosensitivity of film have been investigated. It was found that in the presence of hydrazine hydrate in chemical deposition bath, the resistance of the prepared film increases to mega ohm. The measured room temperature detectivity of the film is 4 x 10{sup 9} W{sup -1} Hz{sup 1/2} cm at the wavelength of 2.4 {mu}m. The experimental results have shown that the PbS film, which has been prepared according to this procedure, can be applied as an infrared detector in the range of 1.0-3.0 {mu}m.

  5. First-principles stability study of clathrate hydrates under pressure

    Science.gov (United States)

    Thonhauser, Timo; Li, Qi; Kolb, Brian

    2010-03-01

    We present a first-principles DFT study of the structural stability of clathrate hydrates under pressure. These materials form under high pressure and low temperature and consist of polyhedral water cages that form an ice-like framework of hydrogen bonds. Clathrate hydrates can be filled with guest molecules such as methane or molecular hydrogen, in which case these materials and their stability are of interest for energy-storage solutions. Since the interactions between the water molecules themselves---but also between the water molecules and the guest molecules---is at least partly determined by van der Waals forces, we utilize the recently developed self-consistent van der Waals density functional vdW-DF (T. Thonhauser, V.R. Cooper, S. Li, A. Puzder, P. Hyldgaard, and D.C. Langreth, Phys. Rev. B 76, 125112 (2007)). For our simulations we consider the empty host lattice, as well as the host lattice filled with methane and molecular hydrogen, for pressures up to 1 GPa. Our results show that the system undergoes phase transitions from structure I to structure II and finally to structure H, in good agreement with experiment.

  6. Methane hydrate stability and anthropogenic climate change

    Directory of Open Access Journals (Sweden)

    D. Archer

    2007-04-01

    Full Text Available Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO2.

    Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic.

    The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

  7. Methane hydrate stability and anthropogenic climate change

    Directory of Open Access Journals (Sweden)

    D. Archer

    2007-07-01

    Full Text Available Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO2.

    Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic.

    The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release as much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

  8. Dynamics of hydration water in protein

    International Nuclear Information System (INIS)

    Incoherent quasi-elastic neutron scattering studies of in vivo deuterated C-phycocyanin, at different levels of hydration, have been made. We show that the mobility at high temperature, (∝300 K) of the water molecules near the protein surface can be described by relatively simple models. At full hydration the high temperature data can be interpreted using a model where each water molecule is diffusing in a confined space of 3 A in radius. At low hydration, and 298 K, the diffusional behaviour is typical of jump diffusion with a residence time 10 times larger than the one in bulk water at the same temperature. (orig.)

  9. Capture and sequestration of CO2 in the interlayer space of hydrated calcium Montmorillonite clay under various geological burial depth

    Science.gov (United States)

    Yang, W.; Zaoui, A.

    2016-05-01

    We perform, at nanoscale level, the structure and dynamics of carbon dioxide molecules in hydrated Ca-montmorillonite clays. The swelling behaviour of hydrated Wyoming-type Montmorillonite including CO2 molecules and counterions is presented and analysed. In addition, the atom density profile, diffusion behaviours and radial distribution functions of CO2, interlayer water molecules and Calcium ions have been investigated at different geological burial depth of 0 km, 3 km and 6 km, which correspond to various temperature and pressure of simulation conditions. Furthermore, the influence of different hydration state on the dynamical behaviours of carbon dioxide is also explained. The calculated self-diffusion coefficient shows that the carbon dioxide species diffuse more freely with the increase of depth and water content. We also found that the presence of interlayer CO2 inhibits the diffusion of all the mobile species. These results mainly show that the hydrated clay system is an appropriate space capable of absorbing CO2 molecules.

  10. Mechanical and transport properties of NafionRTM for PEM fuel cells; temperature and hydration effects

    Science.gov (United States)

    Majsztrik, Paul William

    This work investigates the mechanical and water transport properties of Nafion, a fully fluorinated ion conducting polymer used as a membrane material in proton exchange membrane fuel cells (PEMFCs). Both of these properties are extremely important to the short and long term operation of fuel cells. Nafion is a viscoelastic material, responding to stress in a time-dependant manner. The result is that Nafion flows under stress and responds dynamically to changes in hydration and stress. Stresses applied to the membrane of a PEM fuel cell, both from clamping as well as strain from changing levels of hydration, cause Nafion to flow. This results in thinning in spots and sometimes leads to the development of pinholes or contact problems between membrane and electrode. Temperature and water content strongly affect Nafion's viscoelastic response, of direct importance for operating PEM fuel cells. The viscoelastic response of Nafion was measured over a range of temperature and hydration using viscoelastic creep. A specially designed creep apparatus with environmental controls was used. It was found that the effects of temperature and hydration on Nafion's viscoelastic response are very complicated. Around room temperature, water acts to plasticize Nafion; elastic modulus and resistance to creep decrease with increasing hydration. As temperature increases, water has the opposite effect on mechanical response; hydration acts to stabilize the material. Mechanical property values are reported over a range of temperature and hydration germane to the operation of PEMFCs. Additionally, the data is used to infer molecular level interactions and the effects of temperature and hydration on microstructure. Hydration of Nafion and other PEMFC materials is required for the high proton conductivity needed for fuel cell operation. Uptake of water by Nafion results in volumetric swelling. Water transport through Nafion was directly measured by permeation. Both liquid and vapor phase

  11. The crystal structure of ianthinite, a mixed-valence uranium oxide hydrate

    International Nuclear Information System (INIS)

    Ianthinite, [U4+2(UO2)4O6(OH)4(H2O)4](H2O)5, is the only known uranyl oxide hydrate mineral that contains U4+, and it has been proposed that ianthinite may be an important Pu4+-bearing phase during the oxidative dissolution of spent nuclear fuel. The crystal structure of ianthinite, orthorhombic, a 7.178(2), b 11.473(2), c 30.39(1) angstrom, V 2502.7 angstrom 3, Z = 4, space group P21cn, has been solved by direct methods and refined by least-squares methods to an R index of 9.7% and a wR index of 12.6% using 888 unique observed [|F| ≥ 5σ |F|] reflections. The structure contains both U6+ and U4+. The U6+ cations are present as roughly linear uranyl ions (Ur) that are in turn coordinated by five O2- and OH-located at the equatorial positions of pentagonal bipyramids. The U4+ cations are coordinated by O2-, OH-and H2O in a distorted octahedral arrangement. The Urφ5 and U4+φ6(φ: O2-, OH-, H2O) polyhedra link by sharing edges to form two symmetrically distinct sheets at z ∼ 0.0 and z ∼0.25 that are parallel to (001). There are five symmetrically distinct H2O groups between the sheets of Uφn polyhedra, and the sheets of Uφn polyhedra are linked together only by hydrogen bonding to the intersheet H2O groups. The crystal-chemical requirements of U4+ and Pu4+ are very similar, indicating that extensive Pu4+ ↔ U4+ substitution can occur within the structure of ianthinite

  12. On Bond Portfolio Management

    OpenAIRE

    Vladislav Kargin

    2002-01-01

    This paper describes a new method of bond portfolio optimization based on stochastic string models of correlation structure in bond returns. The paper shows how to approximate correlation function of bond returns, compute the optimal portfolio allocation using Wiener-Hopf factorization, and check whether a collection of bonds presents arbitrage opportunities.

  13. Hydration dynamics of protein molecules in aqueous solution: Unity among diversity

    Indian Academy of Sciences (India)

    Biman Jana; Subrata Pal; Biman Bagchi

    2012-01-01

    Dielectric dispersion and NMRD experiments have revealed that a significant fraction of water molecules in the hydration shell of various proteins do not exhibit any slowing down of dynamics. This is usually attributed to the presence of the hydrophobic residues (HBR) on the surface, although HBRs alone cannot account for the large amplitude of the fast component. Solvation dynamics experiments and also computer simulation studies, on the other hand, repeatedly observed the presence of a non-negligible slow component. Here we show, by considering three well-known proteins (lysozyme, myoglobin and adelynate kinase), that the fast component arises partly from the response of those water molecules that are hydrogen bonded with the backbone oxygen (BBO) atoms. These are structurally and energetically less stable than those with the side chain oxygen (SCO) atoms. In addition, the electrostatic interaction energy distribution (EIED) of individual water molecules (hydrogen bonded to SCO) with side chain oxygen atoms shows a surprising two peak character with the lower energy peak almost coincident with the energy distribution of water hydrogen bonded to backbone oxygen atoms (BBO). This two peak contribution appears to be quite general as we find it for lysozyme, myoglobin and adenylate kinase (ADK). The sharp peak of EIED at small energy (at less than 2 kBT) for the BBO atoms, together with the first peak of EIED of SCO and the HBRs on the protein surface, explain why a large fraction (∼ 80%) of water in the protein hydration layer remains almost as mobile as bulk water. Significant slowness arises only from the hydrogen bonds that populate the second peak of EIED at larger energy (at about 4 kBT). Thus, if we consider hydrogen bond interaction alone, only 15-20% of water molecules in the protein hydration layer can exhibit slow dynamics, resulting in an average relaxation time of about 5-10 ps. The latter estimate assumes a time constant of 20-100 ps for the slow

  14. Glass powder blended cement hydration modelling

    Science.gov (United States)

    Saeed, Huda

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

  15. Effect of Some Admixtures on the Hydration of Silica Fume and Hydrated Lime

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The effects of sodium salt of naphthalene formaldehyde sulfonic acid and stearic acid on the hydration of silica fume and Ca(0H)2 have been investigated. The hydration was carried out at 60℃ and W/S ratio of 4 for various time intervals namely, 1, 3, 7 and 28 days and in the presence of 0.2% and 5% superplasticizer and stearic acid. The results of the hydration kinetics show that both admixtures accelerate the hydration reaction of silica fume and calcium hydroxide during the first 7 days. Whereas, after 28 days hydration there is no significant effect. Generally, most of free calcium hydroxide seems to be consumed after 28 days. In addition, the phase composition as well as the microstructure of the formed hydrates was examined by using X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) respectively.

  16. Submarine slope failures in the Beaufort Sea; Influence of gas hydrate decomposition

    Science.gov (United States)

    Grozic, J. L.; Dallimore, S.

    2012-12-01

    The continental shelf of the Beaufort Sea is composed of complex of marine and non-marine sequences of clay, silt, and sand. In many areas of the shelf these sediments contain occurrences of ice-bonded permafrost and associated pressure and temperature conditions that are conducive to the occurrence of methane gas hydrates. This complex environment is undergoing dramatic warming, where changes in sea level, ocean bottom temperatures, and geothermal regimes are inducing permafrost thawing and gas hydrate decomposition. Decomposition is inferred to be occurring at the base and top of the gas hydrate stability zone, which will cause sediment weakening and the generation of excess water and free gas. In such settings, the overlying permafrost cap may act as a permeability barrier, which could result in significant excess pore pressures and reduction in sediment stability. The shelf to slope transition is thought to be an area of extensive regional instability with acoustic records indicating there is upwards of 500 km of slumps and glides extending over the entire Beaufort margin. Some of these slide regions are coincident with up-dip limit of the permafrost gas hydrate stability zone. In this paper, a two dimensional model of the Beaufort shelf was constructed to examine the influence of gas hydrate decomposition on slope stability. The model relies on available data on the Beaufort sediments generated from offshore hydrocarbon exploration in the 1980s and 90s, as well as knowledge available from multidisciplinary marine research programs conducted in the outer shelf area. The slope stability model investigates the influence of marine transgression and ocean bottom warming by coupling soil deformation with hydrate dissociation during undrained conditions. By combining mechanical and thermal loading of the sediment, a more accurate indication of slope stability was obtained. The stability analysis results indicate a relatively low factor of safety for the Beaufort

  17. Multicenter bonds, bond valence and bond charge apportion

    International Nuclear Information System (INIS)

    In the same way that the valence of an atom issues from the definition of bond index, we shoe here that the three-center bond index lends itself to the definition of a bond valence. Within the charge of a bond, we show that its self-charge (i.e., the amount of electron kept by the atoms involved in the bond) is parted in a such a way that the more electronegative atom tends to allot more electronic charge than the other atom. We give examples of these quantities and discuss the results for different kinds of chemical systems. We also show some results for four-center indices and report six-center indices for hexagonal rings. (author). 54 refs., 4 figs., 8 tabs

  18. The Co-III-C bond in (1-thia-4,7-diazacyclodecyl-kappa N-3(4),N-7,C-10)(1,4,7-triazacyclononane-kappa N-3(1),N-4,N-7)-cobalt(III) dithionate hydrate

    DEFF Research Database (Denmark)

    Harris, Pernille; Kofod, P.; Song, Y.S.;

    2003-01-01

    In the title compound, [Co(C6H15N3)(C7H15N2S)]S2O6.H2O, the Co-C bond distance is 1.9930 (13) Angstrom, which is shorter than for related compounds with the linear 1,6-diamino-3-thiahexan-4-ide anion in place of the macrocyclic 1-thia-4,7-diazacyclodecan-8-ide anion. The coordinated carbanion...

  19. Electric current characteristic of anodic bonding

    International Nuclear Information System (INIS)

    In this paper, a novel current–time model of anodic bonding is proposed and verified experimentally in order to investigate underlying mechanisms of anodic bonding and to achieve real-time monitoring of bonding procedure. The proposed model provides a thorough explanation for the electric current characteristic of anodic bonding. More significantly, it explains two issues which other models cannot explain. One is the sharp rise in current when a voltage is initially applied during anodic bonding. The other is the unexpected large width of depletion layers. In addition, enlargement of the intimately contacted area during anodic bonding can be obtained from the proposed model, which can be utilized to monitor the bonding process. To verify the proposed model, Borofloat33 glass and silicon wafers were adopted in bonding experiments in SUSS SB6 with five different bonding conditions (350 °C 1200 V; 370 °C 1200 V; 380 °C 1200 V; 380 °C 1000 V; and 380 °C 1400 V). The results indicate that the observed current data highly coincide with the proposed current-time model. For widths of depletion layers, depth profiling using secondary ion mass spectrometry demonstrates that the calculated values by the model are basically consistent with the experimental values as well. (paper)

  20. Experimental Investigation of Effect on Hydrate Formation in Spray Reactor

    Directory of Open Access Journals (Sweden)

    Jianzhong Zhao

    2015-01-01

    Full Text Available The effects of reaction condition on hydrate formation were conducted in spray reactor. The temperature, pressure, and gas volume of reaction on hydrate formation were measured in pure water and SDS solutions at different temperature and pressure with a high-pressure experimental rig for hydrate formation. The experimental data and result reveal that additives could improve the hydrate formation rate and gas storage capacity. Temperature and pressure can restrict the hydrate formation. Lower temperature and higher pressure can promote hydrate formation, but they can increase production cost. So these factors should be considered synthetically. The investigation will promote the advance of gas storage technology in hydrates.

  1. Equilibrium PT curve of methane hydrates in the presence of AlCl3

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Using an experimental transparent sapphire high-pressure cell, three-phase (methane hydrate + AlCl3 solution + methane) equilibrium conditions of methane hydrates in the aqueous solution containing AlCl3 have been investigated under conditions of temperature from 272.15 to 278.15 K and pressure from 4.040 to 8.382 MPa. It could be clearly verified that AlCl3 is of stronger inhibitive effect than that observed for other electrolytes, such as KCl, CaCl2, at the same mole fraction. The induction time of the methane hydrate formation becomes longer when the water activity decreases with the increase of ion charge numbers. Methane hydrates tend to crystallize more easily with higher concentration (AlCl3 concentration of 18%) than lower one (AlCl3 concentration of 10%) in the same electriclyte solution. An empirical exponential equation is presented to calculate the equilibrium temperature and pressure of methane hydrate stable occurrence, and to correlate the measured data for aqueous AlCl3 solution. The results show that there was infinitely small discrepancy between the theoretical computed values and the data oberserved in actual experiments.

  2. Hydrated calcareous oil-shale ash as potential filter media for phosphorus removal in constructed wetlands.

    Science.gov (United States)

    Kaasik, Ago; Vohla, Christina; Mõtlep, Riho; Mander, Ulo; Kirsimäe, Kalle

    2008-02-01

    The P-retention in hydrated calcareous ash sediment from oil-shale burning thermal power plants in Estonia was studied. Batch experiments indicate good (up to 65 mg P g(-1)) P-binding capacity of the hydrated oil-shale ash sediment, with a removal effectiveness of 67-85%. The high phosphorus sorption potential of hydrated oil-shale ash is considered to be due to the high content of reactive Ca-minerals, of which ettringite Ca6Al2(SO4)3(OH)12.26H2O and portlandite Ca(OH)2 are the most important. The equilibrium dissolution of ettringite provides free calcium ions that act as stable nuclei for phosphate precipitation. The precipitation mechanism of phosphorus removal in hydrated ash plateau sediment is suggested by Ca-phosphate formation in batch experiments at different P-loadings. Treatment with a P-containing solution causes partial-to-complete dissolution of ettringite and portlandite, and precipitation of Ca-carbonate and Ca-phosphate phases, which was confirmed by X-ray diffraction (XRD) and scanning electron microscope (SEM)-EDS studies. Thus, the hydrated oil-shale ash sediment can be considered as a potential filtration material for P removal in constructed wetlands for wastewater treatment. PMID:17959214

  3. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    OpenAIRE

    Sultan, Nabil; Bohrmann, G.; Ruffine, Livio; Pape, T.; Riboulot, Vincent; Colliat, J. -l.; De Prunele, Alexis; Dennielou, Bernard; Garziglia, Sebastien; Himmler, Tobias; Marsset, Tania; Peters, C. A.; Rabiu, A.; J. Wei

    2014-01-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indi...

  4. Atomic diffusion properties in wire bonding

    Institute of Scientific and Technical Information of China (English)

    LI Jun-hui; WANG Fu-liang; HAN Lei; DUAN Ji-an; ZHONG Jue

    2006-01-01

    The lift-off characteristics at the interface of thermosonic bond were observed by using scanning electron microscope (JSM-6360LV). The vertical section of bonding point was produced by punching, grinding and ion-sputter thinning, and was tested by using transmission electron microscope (F30). The results show that the atomic diffusion at the bonded interface appears. The thickness of Au/Al interface characterized by atomic diffusion is about 500 nm under ultrasonic and thermal energy. The fracture morphology of lift-off interface is dimples. The tensile fracture appears by pull-test not in bonded interface but in basis material, and the bonded strength at interface is enhanced by diffused atom from the other side.

  5. Novel hard, tough HfAlSiN multilayers, defined by alternating Si bond structure, deposited using modulated high-flux, low-energy ion irradiation of the growing film

    Energy Technology Data Exchange (ETDEWEB)

    Fager, Hanna, E-mail: hanfa@ifm.liu.se; Greczynski, Grzegorz; Jensen, Jens; Lu, Jun; Hultman, Lars [Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping (Sweden); Howe, Brandon M. [Air Force Research Laboratory, Materials and Manufacturing Directorate, Wright-Patterson AFB, Ohio 45433 (United States); Mei, A. B. [Frederick Seitz Materials Research Laboratory and Materials Science Department, University of Illinois, 104 South Goodwin, Urbana, Illinois 61801 (United States); Greene, J. E.; Petrov, Ivan [Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping (Sweden); Frederick Seitz Materials Research Laboratory and Materials Science Department, University of Illinois, 104 South Goodwin, Urbana, Illinois 61801 (United States)

    2015-09-15

    Hf{sub 1−x−y}Al{sub x}Si{sub y}N (0 ≤ x ≤ 0.14, 0 ≤ y ≤ 0.12) single layer and multilayer films are grown on Si(001) at 250 °C using ultrahigh vacuum magnetically unbalanced reactive magnetron sputtering from a single Hf{sub 0.6}Al{sub 0.2}Si{sub 0.2} target in mixed 5%-N{sub 2}/Ar atmospheres at a total pressure of 20 mTorr (2.67 Pa). The composition and nanostructure of Hf{sub 1−x−y}Al{sub x}Si{sub y}N films are controlled by varying the energy E{sub i} of the ions incident at the film growth surface while maintaining the ion-to-metal flux ratio constant at eight. Switching E{sub i} between 10 and 40 eV allows the growth of Hf{sub 0.78}Al{sub 0.10}Si{sub 0.12}N/Hf{sub 0.78}Al{sub 0.14}Si{sub 0.08}N multilayers with similar layer compositions, but in which the Si bonding state changes from predominantly Si–Si/Si–Hf for films grown with E{sub i} = 10 eV, to primarily Si–N with E{sub i} = 40 eV. Multilayer hardness values, which vary inversely with bilayer period Λ, range from 20 GPa with Λ = 20 nm to 27 GPa with Λ = 2 nm, while fracture toughness increases directly with Λ. Multilayers with Λ = 10 nm combine relatively high hardness, H ∼ 24 GPa, with good fracture toughness.

  6. Hydrate Control for Gas Storage Operations

    Energy Technology Data Exchange (ETDEWEB)

    Jeffrey Savidge

    2008-10-31

    The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

  7. Neutron cross section of methane hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Kiyanagi, Y.; Date, S.; Horikawa, T.; Takamine, J.; Iwasa, H.; Kamiyama, T. [Graduate School of Eng., Hokkaido Univ., Sapporo (Japan); Uchida, T.; Ebinuma, T.; Narrita, H. [National Inst. of Advanced Industrial Science, Tsukisamu, Sapporo (Japan); Bennington, S.M. [ISIS Dept., Rutherford Appleton, Chilton, Didcot, Oxon (United Kingdom)

    2004-03-01

    To estimate the neutronic characteristics of methane hydrate and also to synthesize cross section data for simulation we need neutron scattering data ranging wide energy and momentum region. We performed inelastic neutron scattering experiments to get information about the neutron cross section on methane hydrate. It was found that at high momentum transfer region rotational mode as well as vibration mode showed recoil like behavior. On the other hand, at low momentum region, as well known, free rotation like energy levels were observed. The energy level of ice in methane hydrate was very similar to normal ice. The results suggest that the rough expression of the cross section of the methane hydrate is presented by linear combination of the methane and ice. (orig.)

  8. Towards Commercial Gas Production from Hydrate Deposits

    Directory of Open Access Journals (Sweden)

    Richard Dawe

    2011-01-01

    Full Text Available Over the last decade global natural gas consumption has steadily increased since many industrialized countries are substituting natural gas for coal to generate electricity. There is also significant industrialization and economic growth of the heavily populated Asian countries of India and China. The general consensus is that there are vast quantities of natural gas trapped in hydrate deposits in geological systems, and this has resulted in the emerging importance of hydrates as a potential energy resource and an accompanying proliferation of recent studies on the technical and economic feasibility of gas production from hydrates. There are then the associated environmental concerns. This study reviews the state of knowledge with respect to natural gas hydrates and outlines remaining challenges and knowledge gaps.

  9. ConocoPhillips Gas Hydrate Production Test

    Energy Technology Data Exchange (ETDEWEB)

    Schoderbek, David; Farrell, Helen; Howard, James; Raterman, Kevin; Silpngarmlert, Suntichai; Martin, Kenneth; Smith, Bruce; Klein, Perry

    2013-06-30

    Work began on the ConocoPhillips Gas Hydrates Production Test (DOE award number DE-NT0006553) on October 1, 2008. This final report summarizes the entire project from January 1, 2011 to June 30, 2013.

  10. Vibrational dynamics of hydration water in amylose

    CERN Document Server

    Cavatorta, F; Albanese, G; Angelini, N

    2002-01-01

    We present a study of the dynamical properties of hydration water associated with amylose helices, based on low-temperature vibrational spectra collected using the TOSCA inelastic spectrometer at ISIS. The structural constraints of the polysaccharidic chains favour the formation of a high-density structure for water, which has been suggested by Imberty and Perez on the basis of conformational analysis. According to this model, hydration water can only enter the pores formed by six adjacent helices and completely fills the pores at a hydration level of about 0.27-g water/g dry amylose. Our measurements show that the dynamical behaviour of hydration water is similar to that observed in high-density amorphous ice. (orig.)

  11. Hydration states of AFm cement phases

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

    2015-07-15

    The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

  12. Coupled multiphysics modeling of gas hydrate bearing sediments

    OpenAIRE

    Sanchez, Marcelo; Gai, Xuerui; Santamarina, J. Carlos

    2014-01-01

    Gas hydrates are crystalline clathrate compounds made of water and a low molecular gas like methane (Sloan 1998). Gas hydrates are generally present in oil-producing areas and in permafrost regions. Methane hydrate deposits can lead to large-scale submarine slope failures, blowouts, platform foundation failures, and -borehole instability. Gas hydrates constitute also an attractive source of energy as they are estimated to contain very large reserves of methane. Hydrate formation, dissociation...

  13. Experimental Investigation of Effect on Hydrate Formation in Spray Reactor

    OpenAIRE

    Jianzhong Zhao; Yaqin Tian; Yangsheng Zhao; Wenping Cheng

    2015-01-01

    The effects of reaction condition on hydrate formation were conducted in spray reactor. The temperature, pressure, and gas volume of reaction on hydrate formation were measured in pure water and SDS solutions at different temperature and pressure with a high-pressure experimental rig for hydrate formation. The experimental data and result reveal that additives could improve the hydrate formation rate and gas storage capacity. Temperature and pressure can restrict the hydrate formation. Lower ...

  14. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Steve Runyon; Mike Globe; Kent Newsham; Robert Kleinberg; Doug Griffin

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling

  16. Ionic supramolecular bonds preserve mechanical properties and enable synergetic performance at high humidity in water-borne, self-assembled nacre-mimetics

    Science.gov (United States)

    Das, Paramita; Walther, Andreas

    2013-09-01

    Although tremendous effort has been focused on enhancing the mechanical properties of nacre-mimetic materials, conservation of high stiffness and strength against hydration-induced decay of mechanical properties at high humidity remains a fundamental challenge in such water-borne high-performance materials. Herein, we demonstrate that ionic supramolecular bonds, introduced by infiltration of divalent Cu2+ ions, allow efficient stabilization of the mechanical properties of self-assembled water-borne nacre-mimetics based on sustainable sodium carboxymethylcellulose (Na+CMC) and natural sodium montmorillonite nanoclay (Na+MTM) against high humidity (95% RH). The mechanical properties in the highly hydrated state (Young's modulus up to 13.5 GPa and tensile strength up to 125 MPa) are in fact comparable to a range of non-crosslinked nacre-mimetic materials in the dry state. Moreover, the Cu2+-treated nacre-inspired materials display synergetic mechanical properties as found in a simultaneous improvement of stiffness, strength and toughness, as compared to the pristine material. Significant inelastic deformation takes place considering the highly reinforced state. This contrasts the typical behaviour of tight, covalent crosslinks and is suggested to originate from a sacrificial, dynamic breakage and rebinding of transient supramolecular ionic bonds. Considering easy access to a large range of ionic interactions and alteration of counter-ion charge via external stimuli, we foresee responsive and adaptive mechanical properties in highly reinforced and stiff bio-inspired bulk nanocomposites and in other bio-inspired materials, e.g. nanocellulose papers and peptide-based materials.Although tremendous effort has been focused on enhancing the mechanical properties of nacre-mimetic materials, conservation of high stiffness and strength against hydration-induced decay of mechanical properties at high humidity remains a fundamental challenge in such water-borne high

  17. Influence of polysaccharides on cement hydration

    OpenAIRE

    Peschard, Arnaud; Govin, Alexandre; Fredon, Emmanuel; Grosseau, Philippe; Fantozzi, Gilles

    2004-01-01

    This paper is about the influence of polysaccharides on cement hydration. Three polysaccharides were studied: a cellulose ether (CE), a starch ether (SE) and a dextrin (YD). In a concentrated media as well as in a dilute media, admixture CE only revealed a slight effect on cement hydration. Portlandite and ettringite formation and gypsum consumption were slowed down by SE adjunction. Admixture YD induced an acceleration of ettringite formation as well as gypsum consumption whereas portiandite...

  18. Hydration of polyethylene glycol-grafted liposomes.

    OpenAIRE

    Tirosh, O; Barenholz, Y; Katzhendler, J; Priev, A

    1998-01-01

    This study aimed to characterize the effect of polyethylene glycol of 2000 molecular weight (PEG2000) attached to a dialkylphosphatidic acid (dihexadecylphosphatidyl (DHP)-PEG2000) on the hydration and thermodynamic stability of lipid assemblies. Differential scanning calorimetry, densitometry, and ultrasound velocity and absorption measurements were used for thermodynamic and hydrational characterization. Using a differential scanning calorimetry technique we showed that each molecule of PEG...

  19. Emergence of a Stern Layer from the Incorporation of Hydration Interactions into the Gouy-Chapman Model of the Electrical Double Layer.

    Science.gov (United States)

    Brown, Matthew A; Bossa, Guilherme Volpe; May, Sylvio

    2015-10-27

    In one of the most commonly used phenomenological descriptions of the electrical double layer, a charged solid surface and a diffuse region of mobile ions are separated from each other by a thin charge-depleted Stern layer. The Stern layer acts as a capacitor that improves the classical Gouy-Chapman model by increasing the magnitude of the surface potential and limiting the maximal counterion concentration. We show that very similar Stern-like properties of the diffuse double layer emerge naturally from adding a nonelectrostatic hydration repulsion to the electrostatic Coulomb potential. The interplay of electrostatic attraction and hydration repulsion of the counterions and the surface leads to the formation of a diffuse counterion layer that remains well separated from the surface. In addition, hydration repulsions between the ions limit and control the maximal ion concentration and widen the width of the diffuse double layer. Our mean-field model, which we express in terms of electrostatic and hydration potentials, is physically consistent and conceptually similar to the classical Gouy-Chapman model. It allows the incorporation of ion specificity, accounts for hydration properties of charged surfaces, and predicts Stern layer properties, which we analyze in terms of the effective size of the hydrated counterions. PMID:26474036

  20. Mechanism Study of Carbon Dioxide Capture from Ambient Air by Hydration Energy Variation

    Science.gov (United States)

    Shi, X.; Lackner, K. S.

    2014-12-01

    Hydration of neutral and ionic species on solid interfaces plays an important role in a wide range of natural and engineered processes within energy systems as well as biological and environmental systems. Various chemical reactions are significantly enhanced, both in the rate and the extent of the reaction, because of water molecules present or absent at the interface. A novel technology for carbon dioxide capture, driven by the free energy difference between more or less hydrated states of an anionic exchange resin is studied for a new approach to absorb CO2 from ambient air. For these materials the affinity to CO2 is dramatically lowered as the availability of water is increased. This makes it possible to absorb CO2 from air in a dry environment and release it at two orders of magnitude larger partial pressures in a wet environment. While the absorption process and the thermodynamic properties of air capture via ion exchange resins have been demonstrated, the underlying physical mechanisms remain to be understood. In order to rationally design better sorbent materials, the present work elucidates through molecular dynamics and quantum mechanical modeling the energy changes in the carbonate, bicarbonate and hydroxide ions that are induced by hydration, and how these changes affect sorbent properties. A methodology is developed to determine the free energy change during carbonate ion hydrolysis changes with different numbers of water molecules present. This makes it possible to calculate the equilibrium in the reaction CO3--•nH2O ↔ HCO3- • m1H2O + OH- • m2H2O + (n - 1 - m1 - m2)H2O Molecular dynamics models are used to calculate free energies of hydration for the CO32- ion, the HCO3- ion, and the OH- ion as function of the amount of water that is present. A quantum mechanical model is employed to study the equilibrium of the reaction Na2CO3 + H2O ↔ NaHCO3 + NaOHin a vacuum and at room temperature. The computational analysis of the free energy of

  1. Effects of thermodynamic inhibitors on the dissociation of methane hydrate: a molecular dynamics study.

    Science.gov (United States)

    Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

    2015-12-28

    We investigate the effects of methanol and NaCl, which are known as thermodynamic hydrate inhibitors, on the dissociation kinetics of methane hydrate in aqueous solutions by using molecular dynamics simulations. It is shown that the dissociation rate is not constant but changes with time. The dissociation rate in the initial stage is increased by methanol whereas it is decreased by NaCl. This difference arises from the opposite effects of the two thermodynamic inhibitors on the hydration free energy of methane. The dissociation rate of methane hydrate is increased by the formation of methane bubbles in the aqueous phase because the bubbles absorb surrounding methane molecules. It is found that both methanol and NaCl facilitate the bubble formation. However, their mechanisms are completely different from each other. The presence of ions enhances the hydrophobic interactions between methane molecules. In addition, the ions in the solution cause a highly non-uniform distribution of dissolved methane molecules. These two effects result in the easy formation of bubbles in the NaCl solution. In contrast, methanol assists the bubble formation because of its amphiphilic character. PMID:26587576

  2. A revised set of values of single-bond radii derived from the observed interatomic distances in metals by correction for bond number and resonance energy

    OpenAIRE

    Pauling, Linus; Kamb, Barclay

    1986-01-01

    An earlier discussion [Pauling, L. (1947) J. Am. Chem. Soc. 69, 542] of observed bond lengths in elemental metals with correction for bond number and resonance energy led to a set of single-bond metallic radii with values usually somewhat less than the corresponding values obtained from molecules and complex ions. A theory of resonating covalent bonds has now been developed that permits calculation of the number of resonance structures per atom and of the effective resonance energy per bond. ...

  3. Electrical properties of polycrystalline methane hydrate

    Science.gov (United States)

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

    2011-01-01

    Electromagnetic (EM) remote-sensing techniques are demonstrated to be sensitive to gas hydrate concentration and distribution and complement other resource assessment techniques, particularly seismic methods. To fully utilize EM results requires knowledge of the electrical properties of individual phases and mixing relations, yet little is known about the electrical properties of gas hydrates. We developed a pressure cell to synthesize gas hydrate while simultaneously measuring in situ frequency-dependent electrical conductivity (σ). Synthesis of methane (CH4) hydrate was verified by thermal monitoring and by post run cryogenic scanning electron microscope imaging. Impedance spectra (20 Hz to 2 MHz) were collected before and after synthesis of polycrystalline CH4 hydrate from polycrystalline ice and used to calculate σ. We determined the σ of CH4 hydrate to be 5 × 10−5 S/m at 0°C with activation energy (Ea) of 30.6 kJ/mol (−15 to 15°C). After dissociation back into ice, σ measurements of samples increased by a factor of ~4 and Ea increased by ~50%, similar to the starting ice samples.

  4. [Preoperative oral hydration for pregnant women].

    Science.gov (United States)

    Okutomi, Toshiyuki; Kato, Rie

    2011-07-01

    Preoperative oral hydration is an important component of "enhanced recovery after surgery" strategies. This was originally developed for patients undergoing colon surgery. The Obstetric Anesthesia Practice Guideline issued by American Society of Anesthesiologists states that intake of minimum amount of clear fluid 2 hours prior to surgery may be safe. However, anesthesiologists have to consider physiological changes that parturients undergo during pregnancy, such as increased risk of aspiration and impaired glucose tolerance. We also have to consider the potential effect of glucose loading on neonates. Mothers are more likely to develop ketosis by glucose loading. It also stimulates insulin release in the fetus, which can result in neonatal hypoglycemia. In addition, sodium overloading may deteriorate intra-vascular dehydration and cause lung edema to mothers. On the other hand, oral hydration can alleviate a sense of thirst and increase maternal satisfaction. Our data showed that maternal urinal ketone body at delivery tended to decrease with oral hydration during labor. Moreover, some articles suggest that oral hydration may improve utero-placental perfusion. Therefore, we have to balance risks and benefits of oral hydration in parturients. Further investigations are needed among this specific subgroup of patients in order to establish the safe application of preoperative oral hydration. PMID:21800658

  5. Radiometric determination of ion mobility

    International Nuclear Information System (INIS)

    With the aid of radionuclides it is possible to measure the migration rate of ions in an electric field and to determine their mobility. The radiometric method enables studies in aqueous and non-aqueous electrolytes. The influence of the electrolyte on the migration rate is shown for the silver cation Ag+. A microsynthesis of perbromate labelled with 82Br is described. The mobility of BrO4- is compared with the mobilities of BrO3- and of Br- in various electrolytes. A phenomenological consideration of hydration numbers of halogen ions indicates a correlation between ion mass and ion mobility. (author)

  6. Phase Transition of Methane Gas Hydrate and Response of Marine Gas Hydrate Systems to Environmental Changes

    Science.gov (United States)

    Xu, W.

    2003-12-01

    Gas hydrates, which contain mostly methane as the gas component in marine sediment, are stable under relatively high pressure and low temperature conditions such as those found along continental margins and permafrost regions. Its stability is mostly controlled by in-situ pressure, temperature and salinity of pore fluid. Environmentally introduced changes in pressure and temperature can affect the stability of gas hydrate in marine sediment. While certain changes may enhance the process of gas hydrate formation, we are much more interested in the resultant dissociation processes, which may contribute to sub-marine slope instability, seafloor sediment failure, formation of mud volcanoes and pock marks, potential vulnerability of engineering structures, and the risk to drilling and production. We have been developing models to quantify phase transition processes of marine gas hydrates and to investigate the response of marine gas hydrate systems to environmental changes. Methane gas hydrate system is considered as a three-component (water, methane, salt) four-phase (liquid, gas, hydrate, halite) system. Pressure, temperature and salinity of pore fluid constrain the stability of gas hydrate and affect phase transition processes via their effects on methane solubility and fluid density and enthalpy. Compared to the great quantity of studies on its stability in the literature, in-depth research on phase transition of gas hydrate is surprisingly much less. A method, which employs pressure, enthalpy, salinity and methane content as independent variables, is developed to calculate phase transition processes of the three-component four-phase system. Temperature, an intensive thermodynamic parameter, is found not sufficient in describing phase transition of gas hydrate. The extensive thermodynamic parameter enthalpy, on the other hand, is found to be sufficient both in calculation of the phase transition processes and in modeling marine gas hydrate systems. Processes

  7. Hydrogen-bonding patterns in bis[2,4,6-triazaniumylcyclohexane-1,3,5-tris(olate)-κ(3)O,O',O'']germanium(IV) tetrachloride hexahydrate.

    Science.gov (United States)

    Neis, Christian; Morgenstern, Bernd; Hegetschweiler, Kaspar

    2016-01-01

    A first preliminary report on the crystal structure of a hydrated salt formulated as [Ge(taci)2]Cl4·13H2O (taci is 1,3,5-triamino-1,3,5-trideoxy-cis-inositol) appeared more than 20 years ago [Ghisletta (1994). PhD thesis, ETH Zürich. Switzerland]. At that time it was not possible to discriminate unambiguously between the positions of some of the chloride ions and water O atoms, and disorder was thus postulated. In a new determination, a conclusive scheme of hydrogen bonding proves to be a particularly appealing aspect of the structure. Single crystals of the title compound, C12H30GeN6O6(4+)·4Cl(-)·6H2O or [Ge(taci)2]2Cl8·12H2O, were grown from an aqueous solution by slow evaporation of the solvent. The two [Ge(taci)2](4+) cations exhibit a double-adamantane-type structure with exclusive O-atom coordination and approximate D3d symmetry. The taci ligands adopt a zwitterionic form with deprotonated hydroxy groups and protonated amino groups. Both cations are hydrogen bonded to six water molecules. The structure of the hydration shell of the two cations is, however, slightly different. The {[Ge(taci)2]·6H2O}(4+) aggregates are interlinked in all three dimensions by further hydrogen bonds of the types N-H...Cl...H-N, N-H...O(H)2...H-N, (Ge)O...H-O(H)...H-N, N-H...O(H)-H...Cl...H-N, (Ge)O...H-O-H...Cl...H-N, N-H...O(H)-H...Cl...H-(H)O...H-N, (Ge)O...H-O-H...Cl...H-(H)O...H-N and Ge(O)...H-O-H...Cl...H-O-H...O(Ge). PMID:26742824

  8. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting

    2015-01-01

    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

  9. Hydrate pingoes at Nyegga: some characteristic features

    Science.gov (United States)

    Hovland, M.

    2009-04-01

    Hydrate pingoes were observed on the seafloor during two different remotely operated vehicle (ROV)-dives, conducted by Statoil at complex-pockmark G11, at Nyegga, off Mid-Norway. Confirmation that these structures actually represent hydrate ice-cored sediment mounds (pingoes), was done by other investigators (Ivanov et al., 2006). Because it is expected that hydrate pingoes represent relatively dynamic seafloor topographic structures and that their shape and size most probably will change over relatively short time, it is important to know how to recognise them visually. Hovland and Svensen (2006) highlighted five different characteristic aspects that define hydrate pingoes on the sea floor: 1) They are dome- or disc-shaped features, which may attain any size from ~0.5 m in height and upwards. Inside pockmark G11, they were up to 1 m high. 2) They are circular or oval in plan view and may attain lateral sizes on the seafloor ranging upwards from ~0.5 m. Inside G11 they had lengths of several metres and widths of up to 4 m. 3) They have dense communities of organisms growing on their surfaces. At G11, they were overgrown with small pogonophoran tube-worms. 4) They have patches of white or grey bacterial mats growing on their surface, indicating advection (seepage) of reduced pore-waters. 5) They have small pits and patches of fluidized sediments on their surface, indicating pit corrosion of the sub-surface gas hydrate. Because gas hydrates often form in high-porosity, near-surface sediments, where water is readily available, it is thought that they will build up at locations where gases are actively migrating upwards from depth. However, gas hydrates are not stable in the presence of ambient seawater, as seawater is deficient in guest molecule gases (normally methane). Therefore, they tend to build up below surface above conduits for gas flow from depth. But, the near-surface hydrate ice-lenses will continually be corroded by seawater circulating into the sediments

  10. Separation of rare earths from transition metals by liquid–liquid extraction from a molten salt hydrate to an ionic liquid phase

    OpenAIRE

    Rout, Alok; Binnemans, Koen

    2014-01-01

    The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mi...

  11. Effects of polar solvents on the fracture resistance of dentin: Role of water hydration

    Energy Technology Data Exchange (ETDEWEB)

    Ritchie, R O; Nalla, R K; Balooch, M; Ager III, J W; Kruzic, J J; Kinney, J H

    2004-12-10

    Although healthy dentin is invariably hydrated in vivo, from a perspective of examining the mechanisms of fracture in dentin, it is interesting to consider the role of water hydration. Furthermore, it is feasible that exposure to certain polar solvents, e.g., those found in clinical adhesives, can induce dehydration. In the present study, in vitro deformation and fracture experiments, the latter involving a resistance-curve (R-curve) approach (i.e., toughness evolution with crack extension), were conducted in order to assess changes in the constitutive and fracture behavior induced by three common solvents - acetone, ethanol and methanol. In addition, nanoindentation-based experiments to evaluate the deformation behavior at the level of individual collagen fibers and ultraviolet Raman spectroscopy to evaluate changes in bonding were performed. The results indicate a reversible effect of chemical dehydration, with increased fracture resistance, strength, and stiffness associated with lower hydrogen bonding ability of the solvent. These results are analyzed both in terms of intrinsic and extrinsic toughening phenomena to further understand the micromechanisms of fracture in dentin and the specific role of water hydration.

  12. Distinguishing between hydrated, partially hydrated or unhydrated clinker in hardened concrete using microscopy

    NARCIS (Netherlands)

    Valcke, S.L.A.; Rooij, M.R. de; Visser, J.H.M.; Nijland, T.G.

    2010-01-01

    Hydration of clinker particles is since long a topic of interest in both designing and optimizing cement composition and its quantity used in concrete. The interest for carefully observing and also quantifying the type or stage of clinker hydration in hardened cement paste is twofold. Firstly, the c

  13. Anaerobic oxidation of methane above gas hydrates at Hydrate Ridge, NE Pacific Ocean

    DEFF Research Database (Denmark)

    Treude, T.; Boetius, A.; Knittel, K.; Wallmann, K.; Jørgensen, BB

    2003-01-01

    At Hydrate Ridge (HR), Cascadia convergent margin, surface sediments contain massive gas hydrates formed from methane that ascends together with fluids along faults from deeper reservoirs. Anaerobic oxidation of methane (AOM), mediated by a microbial consortium of archaea and sulfate-reducing bac...

  14. Hydrate-phobic surfaces: fundamental studies in clathrate hydrate adhesion reduction.

    Science.gov (United States)

    Smith, J David; Meuler, Adam J; Bralower, Harrison L; Venkatesan, Rama; Subramanian, Sivakumar; Cohen, Robert E; McKinley, Gareth H; Varanasi, Kripa K

    2012-05-01

    Clathrate hydrate formation and subsequent plugging of deep-sea oil and gas pipelines represent a significant bottleneck for deep-sea oil and gas operations. Current methods for hydrate mitigation are expensive and energy intensive, comprising chemical, thermal, or flow management techniques. In this paper, we present an alternate approach of using functionalized coatings to reduce hydrate adhesion to surfaces, ideally to a low enough level that hydrodynamic shear stresses can detach deposits and prevent plug formation. Systematic and quantitative studies of hydrate adhesion on smooth substrates with varying solid surface energies reveal a linear trend between hydrate adhesion strength and the practical work of adhesion (γ(total)[1 + cos θ(rec)]) of a suitable probe liquid, that is, one with similar surface energy properties to those of the hydrate. A reduction in hydrate adhesion strength by more than a factor of four when compared to bare steel is achieved on surfaces characterized by low Lewis acid, Lewis base, and van der Waals contributions to surface free energy such that the practical work of adhesion is minimized. These fundamental studies provide a framework for the development of hydrate-phobic surfaces, and could lead to passive enhancement of flow assurance and prevention of blockages in deep-sea oil and gas operations. PMID:22441203

  15. Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes.

    Science.gov (United States)

    Rayne, Sierra; Forest, Kaya

    2016-06-01

    The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds. PMID:26980678

  16. Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator

    International Nuclear Information System (INIS)

    The combination forms of the hydrate dissociation methods in different well systems are divided into 6 main patterns. Dissociation processes of methane hydrate in porous media using the inverted five-spot water flooding method (Pattern 4) are investigated by the experimental observation and numerical simulation. In situ methane hydrate is synthesized in the Cubic Hydrate Simulator (CHS), a 5.832-L cubic reactor. A center vertical well is used as the hot water injection well, while the four vertical wells at the corner are the gas and water production wells. The gas production begins simultaneously with the hot water injection, while after approximately 20 min of compression, the water begins to be produced. One of the common characteristics of the inverted five-spot water flooding method is that both the gas and water production rates decrease with the reduction of the hydrate dissociation rate. The evaluation of the energy efficiency ratio might indicate the inverted five-spot water flooding as a promising gas producing method from the hydrate reservoir. - Highlights: • A three-dimensional 5.8-L cubic pressure vessel is developed. • Gas production of hydrate using inverted five-spot flooding method is studied. • Water/gas production rate and energy efficiency ratio are evaluated. • Temperature distributions of numerical simulation and experiment agree well. • Hydrate dissociation process is a moving boundary problem in this study

  17. Controls on Gas Hydrate Formation and Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  18. Properties of equilibrium carbon dioxide hydrate in porous medium

    Science.gov (United States)

    Voronov, V. P.; Gorodetskii, E. E.; Podnek, V. E.; Grigoriev, B. A.

    2016-09-01

    Specific heat capacity, dissociation heat and hydration number of carbon dioxide hydrate in porous medium are determined by adiabatic calorimetry method. The measurements were carried out in the temperature range 250-290 K and in pressure range 1-5 MPa. The measured specific heat of the hydrate is approximately 2.7 J/(g K), which is significantly larger than the specific heat of methane hydrate. In particular, at heating, larger value of the specific heat of carbon dioxide hydrate is a result of gas emission from the hydrate. The hydration number at the hydrate-gas coexistence changes from 6.2 to 6.9. The dissociation heat of carbon dioxide hydrate varies from the 55 kJ/mol near the upper quadruple point to the 57 kJ/mol near the lower quadruple point.

  19. Influence of pozzolana on C4AF hydratio n and the effects of chloride and sulfate io ns on the hydrates formed

    Directory of Open Access Journals (Sweden)

    RIMVYDAS KAMINSKAS

    2011-09-01

    Full Text Available This study investigated the influence of natural pozzolana additive on the hydration of C4AF (aluminoferrite and the effects of chloride and sulfate ions on the hydrates formed. In the samples, 25% (by weight of the C4AF was replaced with pozzolana. The mixture was then hardened for 28 days in water, soaked in a saturated NaCl solution for 3 months, and then soaked in a 5% Na2SO4 solution for 3 months at 20°C. It is estimated that under normal conditions, pozzolana additive accelerates the formation of CO32-–AFm (monocarboaluminate and gibbsite, however, impede the formation of cubic aluminum hydrates. Also, part of the amorphous SiO2 penetrates into the structure of hydrates of C4AF and initiates the formation of hydrated alumino-silicate (gismondine. Monocarboaluminate affected by NaCl becomes unstable and takes part in reactions producing Ca2Al(OH6Cl·2H2O (hydrocalumite-M. After samples were transferred from a saturated NaCl solution to a 5% Na2SO4 solution, hydrocalumite-M was the source of aluminates for the formation of ettringite. In samples with pozzolana additive, the hydrated alumino-silicate and gibbsite compounds that were formed remained stable in an environment containing chloride and sulfate ions and retarded the corrosion reaction of C4AF hydrates.

  20. Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations.

    Science.gov (United States)

    Chien, Winnie; Anbalagan, Victor; Zandler, Melvin; Van Stipdonk, Michael; Hanna, Dorothy; Gresham, Garold; Groenewold, Gary

    2004-06-01

    The intrinsic hydration of three monopositive uranyl-anion complexes (UO(2)A)(+) (where A = acetate, nitrate, or hydroxide) was investigated using ion-trap mass spectrometry (IT-MS). The relative rates for the formation of the monohydrates [(UO(2)A)(H(2)O)](+), with respect to the anion, followed the trend: Acetate > or = nitrate > hydroxide. This finding was rationalized in terms of the donation of electron density by the strongly basic OH(-) to the uranyl metal center, thereby reducing the Lewis acidity of U and its propensity to react with incoming nucleophiles, viz., H(2)O. An alternative explanation is that the more complex acetate and nitrate anions provide increased degrees of freedom that could accommodate excess energy from the hydration reaction. The monohydrates also reacted with water, forming dihydrates and then trihydrates. The rates for formation of the nitrate and acetate dihydrates [(UO(2)A)(H(2)O)(2)](+) were very similar to the rates for formation of the monohydrates; the presence of the first H(2)O ligand had no influence on the addition of the second. In contrast, formation of the [(UO(2)OH)(H(2)O)(2)](+) was nearly three times faster than the formation of the monohydrate. PMID:15144967

  1. Thermodynamic modeling for clathrate hydrates of ozone

    International Nuclear Information System (INIS)

    Highlights: • We present a phase-equilibrium model for ozone-containing clathrate hydrates. • We determine intermolecular potential parameters for O3. • There is good agreement between the developed model and the experimental data. • The results show the capability of O3 as a guest substance for clathrate hydrates. • We perform parametric studies for O3 storage capacity with various thermodynamic conditions. -- Abstract: We report a theoretical study to predict the phase-equilibrium properties of ozone-containing clathrate hydrates based on the statistical thermodynamics model developed by van der Waals and Platteeuw. The Patel–Teja–Valderrama equation of state is employed for an accurate estimation of the properties of gas phase ozone. We determined the three parameters of the Kihara intermolecular potential for ozone as a = 6.815 · 10−2 nm, σ = 2.9909 · 10−1 nm, and ε · kB−1 = 184.00 K. An infinite set of ε–σ parameters for ozone were determined, reproducing the experimental phase equilibrium pressure–temperature data of the (O3 + O2 + CO2) clathrate hydrate. A unique parameter pair was chosen based on the experimental ozone storage capacity data for the (O3 + O2 + CCl4) hydrate that we reported previously. The prediction with the developed model showed good agreement with the experimental phase equilibrium data within ±2% of the average deviation of the pressure. The Kihara parameters of ozone showed slightly better suitability for the structure-I hydrate than CO2, which was used as a help guest. Our model suggests the possibility of increasing the ozone storage capacity of clathrate hydrates (∼7% on a mass basis) from the previously reported experimental capacity (∼1%)

  2. Hydration effects on gypsum dissolution revealed by in situ nanoscale atomic force microscopy observations

    Science.gov (United States)

    Burgos-Cara, A.; Putnis, C. V.; Rodriguez-Navarro, C.; Ruiz-Agudo, E.

    2016-04-01

    Recent work has suggested that the rates of mineral dissolution in aqueous solutions are dependent on the kinetics of dehydration of the ions building the crystal. Dehydration kinetics will be ultimately determined by the competition between ion-water and water-water interactions, which can be significantly modified by the presence of background ions in solution. At low ionic strength, the effect of electrolytes on ion-water (electrostatic) interactions will dominate (Kowacz et al., 2007). By performing macroscopic and in situ, microscopic (atomic force microscopy) dissolution experiments, the effect of background electrolytes on the dissolution kinetics of gypsum (CaSO4·2H2O) {0 1 0} cleavage surfaces is tested at constant, low ionic strength (IS = 0.05) and undersaturation (saturation index, SI = -0.045). Dissolution rates are systematically lower in the presence of 1:1 background electrolytes than in an electrolyte-free solution, regardless of the nature of the electrolyte tested. We hypothesize that stabilization of the hydration shell of calcium by the presence of background ions can explain this result, based on the observed correlations in dissolution rates with the ionic surface tension increment of the background ion in solution. Stabilization of the cation hydration shell should favor dissolution. However, in the case of strongly hydrated ions such as Ca2+, this has a direct entropic effect that reduces the overall ΔG of the system, so that dissolution is energetically less favorable. Overall, these results provide new evidence that supports cation dehydration being the rate-controlling step for gypsum dissolution, as proposed for other minerals such as barite, dolomite and calcite.

  3. Ion chamber based neutron detectors

    Science.gov (United States)

    Derzon, Mark S; Galambos, Paul C; Renzi, Ronald F

    2014-12-16

    A neutron detector with monolithically integrated readout circuitry, including: a bonded semiconductor die; an ion chamber formed in the bonded semiconductor die; a first electrode and a second electrode formed in the ion chamber; a neutron absorbing material filling the ion chamber; and the readout circuitry which is electrically coupled to the first and second electrodes. The bonded semiconductor die includes an etched semiconductor substrate bonded to an active semiconductor substrate. The readout circuitry is formed in a portion of the active semiconductor substrate. The ion chamber has a substantially planar first surface on which the first electrode is formed and a substantially planar second surface, parallel to the first surface, on which the second electrode is formed. The distance between the first electrode and the second electrode may be equal to or less than the 50% attenuation length for neutrons in the neutron absorbing material filling the ion chamber.

  4. High-Altitude Hydration System

    Science.gov (United States)

    Parazynski, Scott E.; Orndoff, Evelyne; Bue, Grant C.; Schaefbauer, Mark E.; Urban, Kase

    2010-01-01

    Three methods are being developed for keeping water from freezing during high-altitude climbs so that mountaineers can remain hydrated. Three strategies have been developed. At the time of this reporting two needed to be tested in the field and one was conceptual. The first method is Passive Thermal Control Using Aerogels. This involves mounting the fluid reservoir of the climber s canteen to an inner layer of clothing for better heat retention. For the field test, bottles were mounted to the inner fleece layer of clothing, and then aerogel insulation was placed on the outside of the bottle, and circumferentially around the drink straw. When climbers need to drink, they can pull up the insulated straw from underneath the down suit, take a sip, and then put it back into the relative warmth of the suit. For the field test, a data logger assessed the temperatures of the water reservoir, as well as near the tip of the drink straw. The second method is Passive Thermal Control with Copper-Shielded Drink Straw and Aerogels, also mounted to inner layers of clothing for better heat retention. Braided wire emanates from the inside of the fleece jacket layer, and continues up and around the drink straw in order to use body heat to keep the system-critical drink straw warm enough to keep water in the liquid state. For the field test, a data logger will be used to compare this with the above concept. The third, and still conceptual, method is Active Thermal Control with Microcontroller. If the above methods do not work, microcontrollers and tape heaters have been identified that could keep the drink straw warm even under extremely cold conditions. Power requirements are not yet determined because the thermal environment inside the down suit relative to the external environment has not been established. A data logger will be used to track both the external and internal temperatures of the suit on a summit day.

  5. Bonding silicones with epoxies

    Energy Technology Data Exchange (ETDEWEB)

    Tira, J.S.

    1980-01-01

    It is shown that silicones, both room temperature vulcanizing (RTV) and millable rubber (press cured) can be successfully bonded to other materials using plasma treatment and epoxy adhesives. The plasma treatment using dry air atmosphere increases the surface energy of the silicone and thus provides a lower water contact angle. This phenomenon allows the epoxy adhesive to wet the silicone surface and ultimately bond. Bond strengths are sufficiently high to result in failures in the silicone materials rather than the adhesive bond.

  6. Australia's Bond Home Bias

    OpenAIRE

    Mishra, Anil V; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  7. 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.

  8. Coordination number of uranium in crystal hydrates and hydratoetherates of uranyl halogen acetates

    International Nuclear Information System (INIS)

    The coordination number (CN) of uranyl in some crystal hydrates and crystal solvates of uranyl halogenacetates is discussed. When there is no steric hindrance from the carboxylate ion, the probability of a maximum CN of 6 increases with decrease of the electron-donating capacity of the anion, which can be associated with giometric factors and redistribution of electron density in the inner coordination sphere of uranyl

  9. Coordination number of uranium in crystal hydrates and hydratoetherates of uranyl halogen acetates

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.; Suglobova, I.G.

    The coordination number (CN) of uranyl in some crystal hydrates and crystal solvates of uranyl halogenacetates is discussed. When there is no steric hindrance from the carboxylate ion, the probability of a maximum CN of 6 increases with decrease of the electron-donating capacity of the anion, which can be associated with giometric factors and redistribution of electron density in the inner coordination sphere of uranyl.

  10. Triplex hydration: nanosecond molecular dynamics simulation of the solvated triplex formed by mixed sequences

    OpenAIRE

    Ojha, Rajendra P.; Tiwari, Rakesh K.

    2003-01-01

    A theoretical model for the hydration pattern and motion of ions around the triple helical DNA with mixed sequences d(GACTGGTGAC)d(GTCACCAGTC)*d(GACTGGTGAC) in solution, during MD simulation, using the particle mesh Ewald sum method, is elaborated here. The AMBER 5.0 force field has been used during the simulation in solvent. The simulation studies support a dynamically stable atmosphere around the DNA triplex in solution over the entire length of the trajectory. The results have been compare...

  11. Temperature effects on prevalent structures of hydrated Fe+ complexes: Infrared spectroscopy and DFT calculations of Fe+(H2O)n (n = 3–8)

    International Nuclear Information System (INIS)

    Hydrated Fe+ ions are produced in a laser-vaporization cluster source of a triple quadrupole mass spectrometer. The Fe+(H2O)n (n = 3–8) complexes are mass-selected and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region. Density functional theory (DFT) calculations are also carried out for analyzing the experimental IR spectra and for evaluating thermodynamic quantities of low-lying isomers. Solvation through H-bonding instead of direct coordination to Fe+ is observed already at n = 3, indicating the completion of the first hydration shell with two H2O molecules. Size dependent variations in the spectra for n = 5–7 provide evidence for the second-shell completion at n = 6, where a linearly coordinated Fe+(H2O)2 subunit is solvated with four H2O molecules. Overall spectral features for n = 3–8 agree well with those predicted for 2-coordinated structures. DFT calculations predict that such 2-coordinated structures are lowest in energy for smaller n. However, 4-coordinated isomers are predicted to be more stable for n = 7 and 8; the energy ordering is in conflict with the IR spectroscopic observation. Examination of free energy as a function of temperature suggests that the ordering of the isomers at warmer temperatures can be different from the ordering near 0 K. For n = 7 and 8, the 4-coordinated isomers should be observed at low temperatures because they are lowest in enthalpy. Meanwhile, outer-shell waters in the 2-coordinated structures are bound less rigidly; their contribution to entropy is rather large. The 2-coordinated structures become abundant at warmer temperatures, owing to the entropy effect

  12. Malaysia : Bond Market Development

    OpenAIRE

    International Monetary Fund; World Bank

    2013-01-01

    This paper pertains to the bond market development in Malaysia, and provides an overview of the market scenario in the country. Malaysia has been successful in developing the capital markets, particularly bond markets, in the recent past. Now, it faces the challenge of how to improve broader access and efficiency of the bond market. A high degree of investor concentration, dominated by gov...

  13. Complex admixtures of clathrate hydrates in a water desalination method

    Science.gov (United States)

    Simmons, Blake A.; Bradshaw, Robert W.; Dedrick, Daniel E.; Anderson, David W.

    2009-07-14

    Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

  14. Development of hydrate risk quantification in oil and gas production

    Science.gov (United States)

    Chaudhari, Piyush N.

    Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Richard Sigal; Kent Newsham; Thomas Williams; Barry Freifeld; Timothy Kneafsey; Carl Sondergeld; Shandra Rai; Jonathan Kwan; Stephen Kirby; Robert Kleinberg; Doug Griffin

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. The work scope drilled and cored a well The Hot Ice No. 1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report. The Hot Ice No. 1 well was drilled from the surface to a measured depth of 2300 ft. There was almost 100% core recovery from the bottom of surface casing at 107 ft to total depth. Based on the best estimate of the bottom of the methane hydrate stability zone (which used new data obtained from Hot Ice No. 1 and new analysis of data from adjacent wells), core was recovered over its complete range. Approximately 580 ft of porous, mostly frozen, sandstone and 155 of conglomerate were recovered in the Ugnu Formation and approximately 215 ft of porous sandstone were recovered in the West Sak Formation. There were gas shows in the bottom

  16. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  17. Gas hydrates: past and future geohazard?

    Science.gov (United States)

    Maslin, Mark; Owen, Matthew; Betts, Richard; Day, Simon; Dunkley Jones, Tom; Ridgwell, Andrew

    2010-05-28

    Gas hydrates are ice-like deposits containing a mixture of water and gas; the most common gas is methane. Gas hydrates are stable under high pressures and relatively low temperatures and are found underneath the oceans and in permafrost regions. Estimates range from 500 to 10,000 giga tonnes of carbon (best current estimate 1600-2000 GtC) stored in ocean sediments and 400 GtC in Arctic permafrost. Gas hydrates may pose a serious geohazard in the near future owing to the adverse effects of global warming on the stability of gas hydrate deposits both in ocean sediments and in permafrost. It is still unknown whether future ocean warming could lead to significant methane release, as thermal penetration of marine sediments to the clathrate-gas interface could be slow enough to allow a new equilibrium to occur without any gas escaping. Even if methane gas does escape, it is still unclear how much of this could be oxidized in the overlying ocean. Models of the global inventory of hydrates and trapped methane bubbles suggest that a global 3( degrees )C warming could release between 35 and 940 GtC, which could add up to an additional 0.5( degrees )C to global warming. The destabilization of gas hydrate reserves in permafrost areas is more certain as climate models predict that high-latitude regions will be disproportionately affected by global warming with temperature increases of over 12( degrees )C predicted for much of North America and Northern Asia. Our current estimates of gas hydrate storage in the Arctic region are, however, extremely poor and non-existent for Antarctica. The shrinking of both the Greenland and Antarctic ice sheets in response to regional warming may also lead to destabilization of gas hydrates. As ice sheets shrink, the weight removed allows the coastal region and adjacent continental slope to rise through isostacy. This removal of hydrostatic pressure could destabilize gas hydrates, leading to massive slope failure, and may increase the risk of

  18. Biophysical Model of Ion Transport across Human Respiratory Epithelia Allows Quantification of Ion Permeabilities

    OpenAIRE

    Garcia, Guilherme J.M.; Boucher, Richard C.; Elston, Timothy C.

    2013-01-01

    Lung health and normal mucus clearance depend on adequate hydration of airway surfaces. Because transepithelial osmotic gradients drive water flows, sufficient hydration of the airway surface liquid depends on a balance between ion secretion and absorption by respiratory epithelia. In vitro experiments using cultures of primary human nasal epithelia and human bronchial epithelia have established many of the biophysical processes involved in airway surface liquid homeostasis. Most experimental...

  19. Donnan membrane equilibrium is not directly applicable to distributions of ions and water in gels or cells

    OpenAIRE

    Wiggins, Philippa M.; van Ryn, René T.; Ormrod, Dale G. C.

    1991-01-01

    Equilibration of ions and water with a charged gel does not follow the simple equations of the classical Gibbs-Donnan membrane equilibrium. Partition of ions between the gel and the external solution show specific effects, which require that activity coefficients are different in the two compartments. Highly hydrated ions, such as Na+ and H+ are accumulated into the gel water, whereas less highly hydrated ions, such as K+ and NH4+ accumulate in the external water. This selectivity is the obve...

  20. Kinetics of the reactions of hydrated electrons with metal complexes

    International Nuclear Information System (INIS)

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni2+, Co2+ and Cu2+. Rates of the reactions of the complexes with e-(aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e-(aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  1. Hydrate-based heavy metal separation from aqueous solution

    Science.gov (United States)

    Song, Yongchen; Dong, Hongsheng; Yang, Lei; Yang, Mingjun; Li, Yanghui; Ling, Zheng; Zhao, Jiafei

    2016-01-01

    A novel hydrate-based method is proposed for separating heavy metal ions from aqueous solution. We report the first batch of experiments and removal characteristics in this paper, the effectiveness and feasibility of which are verified by Raman spectroscopy analysis and cross-experiment. 88.01–90.82% of removal efficiencies for Cr3+, Cu2+, Ni2+, and Zn2+ were obtained. Further study showed that higher R141b–effluent volume ratio contributed to higher enrichment factor and yield of dissociated water, while lower R141b–effluent volume ratio resulted in higher removal efficiency. This study provides insights into low-energy, intensive treatment of wastewater. PMID:26887357

  2. Discrete element modeling of calcium-silicate-hydrate

    International Nuclear Information System (INIS)

    The discrete element method (DEM) was used to model calcium-silicate-hydrate (C-S-H) at the nanoscale. The C-S-H nanoparticles were modeled as spherical particles with diameters of approximately 5 nm. Interparticle forces included traditional mechanical contact forces, van der Waals forces and ionic correlation forces due to negatively charged C-S-H nanoparticles and ion species in the nanopores. Previous work by the authors demonstrated the DEM method was feasible in studying the properties of the C-S-H nanostructures. In this work, the simulations were performed to look into the effects of nanoparticle packing, nanoparticle morphology, interparticle forces and nanoparticle properties on the deformation mechanisms and mechanical properties of the C-S-H matrix. This work will provide insights into possible ways to improve the properties of the C-S-H matrix. (paper)

  3. Stability evaluation of hydrate-bearing sediments during thermally-driven hydrate dissociation

    Science.gov (United States)

    Kwon, T.; Cho, G.; Santamarina, J.; Kim, H.; Lee, J.

    2009-12-01

    Hydrate-bearing sediments may destabilize spontaneously as part of geological processes, unavoidably during petroleum drilling/production operations, or intentionally as part of gas extraction from the hydrate itself. In all cases, high pore fluid pressure generation is anticipated during hydrate dissociation. This study examined how thermal changes destabilize gas hydrate-bearing sediments. First, an analytical formulation was derived for predicting fluid pressure evolution in hydrate-bearing sediments subjected to thermal stimulation without mass transfer. The formulation captures the self-preservation behavior, calculates the hydrate and free gas quantities during dissociation, considering effective stress-controlled sediment compressibility and gas solubility in aqueous phase. Pore fluid pressure generation is proportional to the initial hydrate fraction and the sediment bulk stiffness; is inversely proportional to the initial gas fraction and gas solubility; and is limited by changes in effective stress that cause the failure of the sediment. Second, the analytical formulation for hydrate dissociation was incorporated as a user-defined function into a verified finite difference code (FLAC2D). The underlying physical processes of hydrate-bearing sediments, including hydrate dissociation, self-preservation, pore pressure evolution, gas dissolution, and sediment volume expansion, were coupled with the thermal conduction, pore fluid flow, and mechanical response of sediments. We conducted the simulations for a duration of 20 years, assuming a constant-temperature wellbore transferred heat to the surrounding hydrate-bearing sediments, resulting in dissociation of methane hydrate in the well vicinity. The model predicted dissociation-induced excess pore fluid pressures which resulted in a large volume expansion and plastic deformation of the sediments. Furthermore, when the critical stress was reached, localized shear failure of the sediment around the borehole was

  4. Formation mechanism of authigenic gypsum in marine methane hydrate settings: Evidence from the northern South China Sea

    Science.gov (United States)

    Lin, Qi; Wang, Jiasheng; Algeo, Thomas J.; Su, Pibo; Hu, Gaowei

    2016-09-01

    During the last decade, gypsum has been discovered widely in marine methane hydrate-bearing sediments. However, whether this gypsum is an in-situ authigenic precipitate remains controversial. The GMGS2 expedition carried out in 2013 by the Guangzhou Marine Geological Survey (GMGS) in the northern South China Sea provided an excellent opportunity for investigating the formation of authigenic minerals and, in particular, the relationship between gypsum and methane hydrate. In this contribution, we analyzed the morphology and sulfur isotope composition of gypsum and authigenic pyrite as well as the carbon and oxygen isotopic compositions of authigenic carbonate in a drillcore from Site GMGS2-08. These methane-derived carbonates have characteristic carbon and oxygen isotopic compositions (δ13C: -57.9‰ to -27.3‰ VPDB; δ18O: +1.0‰ to +3.8‰ VPDB) related to upward seepage of methane following dissociation of underlying methane hydrates since the Late Pleistocene. Our data suggest that gypsum in the sulfate-methane transition zone (SMTZ) of this core precipitated as in-situ authigenic mineral. Based on its sulfur isotopic composition, the gypsum sulfur is a mixture of sulfate derived from seawater and from partial oxidation of authigenic pyrite. Porewater Ca2+ ions for authigenic gypsum were likely generated from carbonate dissolution through acidification produced by oxidation of authigenic pyrite and ion exclusion during methane hydrate formation. This study thus links the formation mechanism of authigenic gypsum with the oxidation of authigenic pyrite and evolution of underlying methane hydrates. These findings suggest that authigenic gypsum may be a useful proxy for recognition of SMTZs and methane hydrate zones in modern and ancient marine methane hydrate geo-systems.

  5. Quantifying hydrate solidification front advancing using method of characteristics

    Science.gov (United States)

    You, Kehua; DiCarlo, David; Flemings, Peter B.

    2015-10-01

    We develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation from gas injection into brine-saturated sediments within the hydrate stability zone. Our solution includes fully coupled multiphase and multicomponent flow and the associated advective transport in a homogeneous system. Our solution shows that hydrate saturation is controlled by the initial thermodynamic state of the system and changed by the gas fractional flow. Hydrate saturation in gas-rich systems can be estimated by 1-cl0/cle when Darcy flow dominates, where cl0 is the initial mass fraction of salt in brine, and cle is the mass fraction of salt in brine at three-phase (gas, liquid, and hydrate) equilibrium. Hydrate saturation is constant, gas saturation and gas flux decrease, and liquid saturation and liquid flux increase with the distance from the gas inlet to the hydrate solidification front. The total gas and liquid flux is constant from the gas inlet to the hydrate solidification front and decreases abruptly at the hydrate solidification front due to gas inclusion into the hydrate phase. The advancing velocity of the hydrate solidification front decreases with hydrate saturation at a fixed gas inflow rate. This analytical solution illuminates how hydrate is formed by gas injection (methane, CO2, ethane, propane) at both the laboratory and field scales.

  6. Simple model of hydrophobic hydration.

    Science.gov (United States)

    Lukšič, Miha; Urbic, Tomaz; Hribar-Lee, Barbara; Dill, Ken A

    2012-05-31

    Water is an unusual liquid in its solvation properties. Here, we model the process of transferring a nonpolar solute into water. Our goal was to capture the physical balance between water's hydrogen bonding and van der Waals interactions in a model that is simple enough to be nearly analytical and not heavily computational. We develop a 2-dimensional Mercedes-Benz-like model of water with which we compute the free energy, enthalpy, entropy, and the heat capacity of transfer as a function of temperature, pressure, and solute size. As validation, we find that this model gives the same trends as Monte Carlo simulations of the underlying 2D model and gives qualitative agreement with experiments. The advantages of this model are that it gives simple insights and that computational time is negligible. It may provide a useful starting point for developing more efficient and more realistic 3D models of aqueous solvation. PMID:22564051

  7. In Situ ATR FTIR Spectroscopic Study of the Formation and Hydration of a Fucoidan/Chitosan Polyelectrolyte Multilayer.

    Science.gov (United States)

    Ho, Tracey T M; Bremmell, Kristen E; Krasowska, Marta; MacWilliams, Stephanie V; Richard, Céline J E; Stringer, Damien N; Beattie, David A

    2015-10-20

    The formation of fucoidan/chitosan-based polyelectrolyte multilayers (PEMs) has been studied with in situ Fourier transform infrared (FTIR) spectroscopy. Attenuated total reflectance (ATR) FTIR spectroscopy has been used to follow the sequential build-up of the multilayer, with peaks characteristic of each polymer being seen to increase in intensity with each respective adsorption stage. In addition, spectral processing has allowed for the extraction of spectra from individual adsorbed layers, which have been used to provide unambiguous determination of the adsorbed mass of the PEM at each stage of formation. The PEM was seen to undergo a transition in growth regimes during build-up: from supra-linear to linear. In addition, the wettability of the PEM has been probed at each stage of the build-up, using the captive bubble contact angle technique. The contact angles were uniformly low, but showed variation in value depending on the nature of the outer polymer layer, and this variation correlated with the overall percentage hydration of the PEM (determined from FTIR and quartz crystal microbalance data). The nature of the hydration water within the polyelectrolyte multilayer has also been studied with FTIR spectroscopy, specifically in situ synchrotron ATR FTIR microscopy of the multilayer confined between two solid surfaces. The acquired spectra have enabled the hydrogen bonding environment of the PEM hydration water to be determined. The PEM hydration water is seen to have an environment in which it is subject to fewer hydrogen bonding interactions than in bulk electrolyte solution. PMID:26421938

  8. [Ion specificity during ion exchange equilibrium in natural clinoptilolite].

    Science.gov (United States)

    He, Yun-Hua; Li, Hang; Liu, Xin-Min; Xiong, Hai-Ling

    2015-03-01

    Zeolites have been widely applied in soil improvement and environment protection. The study on ion specificity during ion exchange equilibrium is of important significance for better use of zeolites. The maximum adsorption capacities of alkali ions during ion exchange equilibrium in the clinoptilolite showed obvious specificity. For alkali metal ions with equivalent valence, the differences in adsorption capacity increased with the decrease of ionic concentration. These results cannot be well explained by the classical theories including coulomb force, ionic size, hydration, dispersion force, classic induction force and surface complexation. We found that the coupling of polarization effects resulted from the quantum fluctuation of diverse alkali metal ions and electric field near the zeolite surface should be the primary reason for specific ion effect during ion exchange in zeolite. The result of this coupling effect was that the difference in the ion dipole moment increased with the increase of surface potential, which further expanded the difference in the adsorption ability between zeolite surface and ions, resulting in different ion exchange adsorption ability at the solid/liquid interface. Due to the high surface charge density of zeolite, ionic size also played an important role in the distribution of ions in the double diffuse layer, which led to an interesting result that distinct differences in exchange adsorption ability of various alkali metal ions were only detected at high surface potential (the absolute value was greater than 0.2 V), which was different from the ion exchange equilibrium result on the surface with low charge density. PMID:25929073

  9. Aggregation of Calcium Silicate Hydrate Nanoplatelets.

    Science.gov (United States)

    Delhorme, Maxime; Labbez, Christophe; Turesson, Martin; Lesniewska, Eric; Woodward, Cliff E; Jönsson, Bo

    2016-03-01

    We study the aggregation of calcium silicate hydrate nanoplatelets on a surface by means of Monte Carlo and molecular dynamics simulations at thermodynamic equilibrium. Calcium silicate hydrate (C-S-H) is the main component formed in cement and is responsible for the strength of the material. The hydrate is formed in early cement paste and grows to form platelets on the nanoscale, which aggregate either on dissolving cement particles or on auxiliary particles. The general result is that the experimentally observed variations in these dynamic processes generically called growth can be rationalized from interaction free energies, that is, from pure thermodynamic arguments. We further show that the surface charge density of the particles determines the aggregate structures formed by C-S-H and thus their growth modes. PMID:26859614

  10. Relaxation mechanism of the hydrated electron.

    Science.gov (United States)

    Elkins, Madeline H; Williams, Holly L; Shreve, Alexander T; Neumark, Daniel M

    2013-12-20

    The relaxation dynamics of the photoexcited hydrated electron have been subject to conflicting interpretations. Here, we report time-resolved photoelectron spectra of hydrated electrons in a liquid microjet with the aim of clarifying ambiguities from previous experiments. A sequence of three ultrashort laser pulses (~100 femtosecond duration) successively created hydrated electrons by charge-transfer-to-solvent excitation of dissolved anions, electronically excited these electrons via the s→p transition, and then ejected them into vacuum. Two distinct transient signals were observed. One was assigned to the initially excited p-state with a lifetime of ~75 femtoseconds, and the other, with a lifetime of ~400 femtoseconds, was attributed to s-state electrons just after internal conversion in a nonequilibrated solvent environment. These assignments support the nonadiabatic relaxation model. PMID:24357314

  11. Propane hydrate nucleation: Experimental investigation and correlation

    DEFF Research Database (Denmark)

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas

    2008-01-01

    In this work the nucleation kinetics of propane gas hydrate has been investigated experimentally using a stirred batch reactor. The experiments have been performed isothermally recording the pressure as a function of time. Experiments were conducted at different stirring rates, but in the same...... supersaturation region. The experiments showed that the gas dissolution rate rather than the induction time of propane hydrate is influenced by a change in agitation. This was especially valid at high stirring rates when the water surface was severely disturbed.Addition of polyvinylpyrrolidone (PVP...... the presence of additives. In most cases reasonable agreement between the data and the model could be obtained. The results revealed that especially the effective surface energy between propane hydrate and water is likely to change when the stirring rate varies from very high to low. The prolongation...

  12. Hydration shells exchange charge with their protein

    DEFF Research Database (Denmark)

    Abitan, Haim; Lindgård, Per-Anker; Nielsen, Bjørn Gilbert;

    2010-01-01

    Investigation of the interaction between a protein and its hydration shells is an experimental and theoretical challenge. Here, we used ultrasonic pressure waves in aqueous solutions of a protein to explore the conformational states of the protein and its interaction with its hydration shells....... In our experiments, the amplitude of an ultrasonic pressure wave is gradually increased (0–20 atm) while we simultaneously measure the Raman spectra from the hydrated protein (β-lactoglobulin and lysozyme). We detected two types of spectral changes: first, up to 70% increase in the intensity...... of the fluorescence background of the Raman spectrum with a typical relaxation time of 30–45 min. Second, we detect changes in the vibrational Raman spectra. To clarify these results we conducted similar experiments with aqueous solutions of amino acids and ethanol. These experiments led us to conclude that, without...

  13. Simulation of Methane Recovery from Gas Hydrates Combined with Storing Carbon Dioxide as Hydrates

    Directory of Open Access Journals (Sweden)

    Georg Janicki

    2011-01-01

    Full Text Available In the medium term, gas hydrate reservoirs in the subsea sediment are intended as deposits for carbon dioxide (CO2 from fossil fuel consumption. This idea is supported by the thermodynamics of CO2 and methane (CH4 hydrates and the fact that CO2 hydrates are more stable than CH4 hydrates in a certain P-T range. The potential of producing methane by depressurization and/or by injecting CO2 is numerically studied in the frame of the SUGAR project. Simulations are performed with the commercial code STARS from CMG and the newly developed code HyReS (hydrate reservoir simulator especially designed for hydrate processing in the subsea sediment. HyReS is a nonisothermal multiphase Darcy flow model combined with thermodynamics and rate kinetics suitable for gas hydrate calculations. Two scenarios are considered: the depressurization of an area 1,000 m in diameter and a one/two-well scenario with CO2 injection. Realistic rates for injection and production are estimated, and limitations of these processes are discussed.

  14. Ground movements associated with gas hydrate production

    International Nuclear Information System (INIS)

    This report deals with a study directed towards a modeling effort on production related ground movements and subsidence resulting from hydrate dissociation. The goal of this research study was to evaluate whether there could be subsidence related problems that could be an impediment to hydrate production. During the production of gas from a hydrate reservoir, it is expected that porous reservoir matrix becomes more compressible which may cause reservoir compression (compaction) under the influence of overburden weight. The overburden deformations can propagate its influence upwards causing subsidence near the surface where production equipment will be located. In the present study, the reservoir compaction is modeled by using the conventional ''stress equilibrium'' approach. In this approach, the overburden strata move under the influence of body force (i.e. self weight) in response to the ''cavity'' generated by reservoir depletion. The present study is expected to provide a ''lower bound'' solution to the subsidence caused by hydrate reservoir depletion. The reservoir compaction anticipated during hydrate production was modeled by using the finite element method, which is a powerful computer modeling technique. The ground movements at the reservoir roof (i.e. reservoir compression) cause additional stresses and disturbance in the overburden strata. In this study, the reservoir compaction was modeled by using the conventional ''stress equilibrium'' approach. In this approach, the overburden strata move under the influence of body force (i.e. self weight) in response to the ''cavity'' generated by reservoir depletion. The resulting stresses and ground movements were computed by using the finite element method. Based on the parameters used in this investigation, the maximum ground subsidence could vary anywhere from 0.50 to 6.50 inches depending on the overburden depth and the size of the depleted hydrate reservoir

  15. Pulse radiolysis study on electrons trapped in semiclathrates and non-clathrate hydrates

    International Nuclear Information System (INIS)

    Trapping of electrons in specific water molecule vacancies, observed previously in crystalline aqueous clathrates, has also been found in semiclathrates (e.g., tetramethylammonium hydroxide pentahydrate), in clathrates showing hydrogen bonds between host and guest molecules (e.g., piperazine clathrate), and also in inorganic hydrates (e.g., sodium carbonate decahydrate). The lifetime of the electron is sometimes longer than in the case of true clathrates; e.g., t/sub 1/2/ = 3.5 ms (first-order decay in piperazine clathrate). The existence of comparatively long-lived electrons at room temperature may be considered a general phenomenon. The condition for its occurrence is the presence of OH- or F- anion, which can substitute for H2O in the aqueous part of the compound and when displaced leaves an electron trap. In other ionic and nonionic compounds, the condition for the trapping of long-lived electrons is protonation of the principal compound, thereby leaving the solution or melt alkaline during the crystallization of the hydrate. Interpretation in terms of preexistent traps invokes the crystal imperfections chemistry, which in the case of hydrates has not yet been noticed. It has been assumed that electrons occupy the vacancies temporarily revealing their presence. In some clathrates and other hydrates, the long-lived electron traps do not occur; instead, the electron shows a similar spectrum (620 nm maximum), decaying by 2-3 orders of magnitude faster than in long-lived traps. It is assumed that this is a case of electron digging its own hole, although an alternative explanation may be through trapping in other kinds of crystal imperfections in the aqueous moiety of the hydrate

  16. Water anomalous thermodynamics, attraction, repulsion, and hydrophobic hydration

    Science.gov (United States)

    Cerdeiriña, Claudio A.; Debenedetti, Pablo G.

    2016-04-01

    A model composed of van der Waals-like and hydrogen bonding contributions that simulates the low-temperature anomalous thermodynamics of pure water while exhibiting a second, liquid-liquid critical point [P. H. Poole et al., Phys. Rev. Lett. 73, 1632 (1994)] is extended to dilute solutions of nonionic species. Critical lines emanating from such second critical point are calculated. While one infers that the smallness of the water molecule may be a relevant factor for those critical lines to move towards experimentally accessible regions, attention is mainly focused on the picture our model draws for the hydration thermodynamics of purely hydrophobic and amphiphilic non-electrolyte solutes. We first focus on differentiating solvation at constant volume from the corresponding isobaric process. Both processes provide the same viewpoint for the low solubility of hydrophobic solutes: it originates from the combination of weak solute-solvent attractive interactions and the specific excluded-volume effects associated with the small molecular size of water. However, a sharp distinction is found when exploring the temperature dependence of hydration phenomena since, in contrast to the situation for the constant-V process, the properties of pure water play a crucial role at isobaric conditions. Specifically, the solubility minimum as well as enthalpy and entropy convergence phenomena, exclusively ascribed to isobaric solvation, are closely related to water's density maximum. Furthermore, the behavior of the partial molecular volume and the partial molecular isobaric heat capacity highlights the interplay between water anomalies, attraction, and repulsion. The overall picture presented here is supported by experimental observations, simulations, and previous theoretical results.

  17. GLASS TRANSITION OF HYDRATED WHEAT GLIADIN POWDERS

    Institute of Scientific and Technical Information of China (English)

    Shao-min Sun; Li Zhao; Yi-hu Song; Qiang Zheng

    2011-01-01

    Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorption ranged from 2.30 db% to 18.21 db%. Glass transition temperature (Tg) of dry wheat gliadin was estimated according to the GordonTaylor equation. Structural heterogeneity at high degrees of hydration was revealed in dielectric temperature and frequency spectra. The activation energies (Ea) of the two relaxations were calculated from Arrhenius equation.

  18. Experimental Study of Gas Hydrate Dynamics

    Science.gov (United States)

    Fandino, O.; Ruffine, L.

    2011-12-01

    Important quantities of methane and other gases are trapped below the seafloor and in the permafrost by an ice-like solid, called gas hydrates or clathrate hydrates. The latter is formed when water is mixing with different gases at high pressures and low temperatures. Due to a their possible use as a source of energy [1] or the problematic related to flow assurance failure in pipelines [2] the understanding of their processes of formation/destabilisation of these structures becomes a goal for many laboratories research as well as industries. In this work we present an experimental study on the stochastic behaviour of hydrate formation from a bulk phase. The method used here for the experiments was to repeat several time the same hydrate formation procedure and to notice the different from one experiment to another. A variable-volume type high-pressure apparatus with two sapphire windows was used. This device, already presented by Ruffine et al.[3], allows us to perform both kinetics and phase equilibrium measurements. Three initial pressure conditions were considered here, 5.0 MPa, 7.5 MPa and 10.0 MPa. Hydrates have been formed, then allowed to dissociate by stepwise heating. The memory effect has also been investigated after complete dissociation. It turned out that, although the thermodynamics conditions of formation and/or destabilization were reproducible. An attempt to determine the influence of pressure on the nucleation induction time will be discussed. References 1. Sum, A. K.; Koh, C. A.; Sloan, E. D., Clathrate Hydrates: From Laboratory Science to Engineering Practice. Industrial & Engineering Chemistry Research 2009, 48, 7457-7465. 2. Sloan, E. D., A changing hydrate paradigm-from apprehension to avoidance to risk management. Fluid Phase Equilibria 2005, 228, 67-74. 3. Ruffine, L.; Donval, J. P.; Charlou, J. L.; Cremière, A.; Zehnder, B. H., Experimental study of gas hydrate formation and destabilisation using a novel high-pressure apparatus. Marine

  19. Dehydration of plutonium or neptunium trichloride hydrate

    Science.gov (United States)

    Foropoulos, Jr., Jerry; Avens, Larry R.; Trujillo, Eddie A.

    1992-01-01

    A process of preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride is provided.

  20. Nanostructure of Calcium Silicate Hydrates in Cements

    KAUST Repository

    Skinner, L. B.

    2010-05-11

    Calcium silicate hydrate (CSH) is the major volume phase in the matrix of Portland cement concrete. Total x-ray scattering measurements with synchrotron x rays on synthetic CSH(I) shows nanocrystalline ordering with a particle diameter of 3.5(5) nm, similar to a size-broadened 1.1 nm tobermorite crystal structure. The CSH component in hydrated tricalcium silicate is found to be similar to CSH(I). Only a slight bend and additional disorder within the CaO sheets is required to explain its nanocrystalline structure. © 2010 The American Physical Society.