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Sample records for bonding hydration ion

  1. Nitriles as directionally tolerant hydrogen bond acceptors: IR-UV ion depletion spectroscopy of benzenepropanenitrile and its hydrate clusters

    Science.gov (United States)

    Robertson, Patrick A.; Lobo, Isabella A.; Wilson, David J. D.; Robertson, Evan G.

    2016-09-01

    Benzenepropanenitrile (BPN) and its hydrate clusters are studied by R2PI and IR-UV ion-depletion spectroscopy in the CH/OH stretch regions, aided by theoretical calculations. A single water molecule binds to the terminal nitrile 'lone-pair' of the anti-BPN host, but there is also evidence for a side-type structure with OH donating to the nitrile π-electrons. In the gauche-BPN cluster, water is located at an intermediate angle that facilitates O⋯HC(ortho) interaction. A wide range of attachment angles is possible, as the intrinsic preference for linear hydrogen bonding is mediated by additional CH⋯O interactions that depend on molecular geometry near the nitrile group.

  2. Hydration of highly charged ions.

    Science.gov (United States)

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

    2011-08-01

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

  3. Differential stability of 2'F-ANA*RNA and ANA*RNA hybrid duplexes: roles of structure, pseudohydrogen bonding, hydration, ion uptake and flexibility.

    Science.gov (United States)

    Watts, Jonathan K; Martín-Pintado, Nerea; Gómez-Pinto, Irene; Schwartzentruber, Jeremy; Portella, Guillem; Orozco, Modesto; González, Carlos; Damha, Masad J

    2010-04-01

    Hybrids of RNA with arabinonucleic acids 2'F-ANA and ANA have very similar structures but strikingly different thermal stabilities. We now present a thorough study combining NMR and other biophysical methods together with state-of-the-art theoretical calculations on a fully modified 10-mer hybrid duplex. Comparison between the solution structure of 2'F-ANA*RNA and ANA*RNA hybrids indicates that the increased binding affinity of 2'F-ANA is related to several subtle differences, most importantly a favorable pseudohydrogen bond (2'F-purine H8) which contrasts with unfavorable 2'-OH-nucleobase steric interactions in the case of ANA. While both 2'F-ANA and ANA strands maintained conformations in the southern/eastern sugar pucker range, the 2'F-ANA strand's structure was more compatible with the A-like structure of a hybrid duplex. No dramatic differences are found in terms of relative hydration for the two hybrids, but the ANA*RNA duplex showed lower uptake of counterions than its 2'F-ANA*RNA counterpart. Finally, while the two hybrid duplexes are of similar rigidities, 2'F-ANA single strands may be more suitably preorganized for duplex formation. Thus the dramatically increased stability of 2'F-ANA*RNA and ANA*RNA duplexes is caused by differences in at least four areas, of which structure and pseudohydrogen bonding are the most important.

  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. Molecular mechanisms of decomposition of hydrated Na+Cl- ion pairs under planar nanopore conditions

    Science.gov (United States)

    Shevkunov, S. V.

    2017-02-01

    The decomposition of Na+Cl- ion pairs under the conditions of a nanoscopic planar pore with structureless walls in a material contact with water vapor at 298 K is simulated by Monte Carlo method. The transition from the state of a contact ion pair (CIP) to the state of solvent-separated ion pair (SSIP) is shown to occur as a result of an increase in the vapor pressure over a pore after exceeding the threshold number of molecules in a hydrate shell. It is found that the planar form of a molecular cluster under the conditions of a narrow pore does not level an abrupt structural transition and the formation of hydrogen bonds in the hydrate shell starts after three molecules are added. The hydrogen bond length under pore conditions is found to be resistant to variations in the hydrate shell size and coincides with that in water under normal conditions.

  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. Adsorption of hydrated hydroxide and hydronium ions on Ag(1 1 1). A quantum mechanical investigation

    Science.gov (United States)

    Patrito, E. M.; Paredes-Olivera, P.

    2003-03-01

    In this paper we have studied comparatively the adsorption of hydroxide and hydronium ions, extending our previous study on hydronium adsorption [J. Phys. Chem. B. 105 (2001) 7227] and emphasizing the adsorption of hydroxide. The calculations were performed on the 111 surface of silver using ab initio quantum mechanical methods (Hartree-Fock+Moller-Plesset second order perturbation theory). The adsorption was investigated for the bare and the hydrated ions (up to three water molecules). Binding energies, equilibrium structures and charge transfer processes were investigated. While the successive hydration of hydronium detaches the ion from the surface, the hydrated hydroxide anion remains specifically adsorbed. Charge transfer processes between the adsorbates and the surface were studied using electron density difference plots and effective charges obtained from Mulliken populations and from surface-dipole moment curves. The energetics of the surface reactions leading to the formation of the hydrated hydronium and hydroxide ions from the bare adsorbed ions and water molecules was also investigated. Both reactions are exothermic mainly due to the formation of strong hydrogen bonds. The effect of an external homogeneous electric field perpendicular to the surface on different adsorbate properties was investigated for the bare and hydrated hydroxide ion in order to model the environment of the electrical double layer. The electric field affects the orientation of the water molecules on the surface and the hydroxide surface distance.

  8. Hydrated alizarin complexes: hydrogen bonding and proton transfer.

    Science.gov (United States)

    Huh, Hyun; Cho, Sung Haeng; Heo, Jiyoung; Kim, Nam Joon; Kim, Seong Keun

    2012-07-07

    We investigated the hydrogen bonding structures and proton transfer for the hydration complexes of alizarin (Az) produced in a supersonic jet using fluorescence excitation (FE), dispersed laser induced fluorescence (LIF), visible-visible hole burning (HB), and fluorescence detected infrared (FDIR) spectroscopy. The FDIR spectrum of bare Az with two O-H groups exhibits two vibrational bands at 3092 and 3579 cm(-1), which, respectively, correspond to the stretching vibration of O1-H1 that forms a strong intramolecular hydrogen bond with the C9=O9 carbonyl group and the stretching vibration of O2-H2 that is weakly hydrogen-bonded to O1-H1. For the 1:1 hydration complex Az(H(2)O)(1), we identified three conformers. In the most stable conformer, the water molecule forms hydrogen bonds with the O1-H1 and O2-H2 groups of Az as a proton donor and proton acceptor, respectively. In the other conformers, the water binds to the C10=O10 group in two nearly isoenergetic configurations. In contrast to the sharp vibronic peaks in the FE spectra of Az and Az(H(2)O)(1), only broad, structureless absorption was observed for Az(H(2)O)(n) (n≥ 2), indicating a facile decay process, possibly due to proton transfer in the electronic excited state. The FDIR spectrum with the wavelength of the probe laser fixed at the broad band exhibited a broad vibrational band near the O2-H2 stretching vibration frequency of the most stable conformer of Az(H(2)O)(1). With the help of theoretical calculations, we suggest that the broad vibrational band may represent the occurrence of proton transfer by tunnelling in the electronic ground state of Az(H(2)O)(n) (n≥ 2) upon excitation of the O2-H2 vibration.

  9. Hofmeister effects: interplay of hydration, nonelectrostatic potentials, and ion size.

    Science.gov (United States)

    Parsons, Drew F; Boström, Mathias; Lo Nostro, Pierandrea; Ninham, Barry W

    2011-07-21

    The classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloids, and corresponding theories of electrolytes, are unable to explain ion specific forces between colloidal particles quantitatively. The same is true generally, for surfactant aggregates, lipids, proteins, for zeta and membrane potentials and in adsorption phenomena. Even with fitting parameters the theory is not predictive. The classical theories of interactions begin with continuum solvent electrostatic (double layer) forces. Extensions to include surface hydration are taken care of with concepts like inner and outer Helmholtz planes, and "dressed" ion sizes. The opposing quantum mechanical attractive forces (variously termed van der Waals, Hamaker, Lifshitz, dispersion, nonelectrostatic forces) are treated separately from electrostatic forces. The ansatz that separates electrostatic and quantum forces can be shown to be thermodynamically inconsistent. Hofmeister or specific ion effects usually show up above ≈10(-2) molar salt. Parameters to accommodate these in terms of hydration and ion size had to be invoked, specific to each case. Ionic dispersion forces, between ions and solvent, for ion-ion and ion-surface interactions are not explicit in classical theories that use "effective" potentials. It can be shown that the missing ionic quantum fluctuation forces have a large role to play in specific ion effects, and in hydration. In a consistent predictive theory they have to be included at the same level as the nonlinear electrostatic forces that form the skeletal framework of standard theory. This poses a challenge. The challenges go further than academic theory and have implications for the interpretation and meaning of concepts like pH, buffers and membrane potentials, and for their experimental interpretation. In this article we overview recent quantitative developments in our evolving understanding of the theoretical origins of specific ion, or Hofmeister effects. These are demonstrated

  10. Unfolding of Hydrated Alkyl Diammonium Cations Revealed by Cryogenic Ion Mobility-Mass Spectrometry.

    Science.gov (United States)

    Servage, Kelly A; Fort, Kyle L; Silveira, Joshua A; Shi, Liuqing; Clemmer, David E; Russell, David H

    2015-07-22

    Hydration of the ammonium ion plays a key role in determining the biomolecular structure as well as local structure of water in aqueous environments. Experimental data obtained by cryogenic ion mobility-mass spectrometry (cryo-IM-MS) show that dehydration of alkyl diammonium cations induces a distinct unfolding transition at a critical number of water molecules, n = 21 to 23, n = 24 to 26, and n = 27 to 29, for 1,7-diaminoheptane, 1,8-diaminooctane, and 1,10-diaminodecane, respectively. Results are also presented that reveal compelling evidence for unique structural transitions of hydrated ammonium ions associated with the development of the hydrogen-bond network around individual charged groups. The ability to track the evolution of structure upon stepwise dehydration provides direct insight into the intricate interplay between solvent-molecule interactions that are responsible for defining conformations. Such insights are potentially valuable in understanding how ammonium ion solvation influences conformation(s) of larger biomolecules.

  11. Coordination variation of hydrated Cu2+/Br1- ions traversing the interfacial water in mesopores

    Science.gov (United States)

    Wang, Q.; Huang, X. F.; Li, C. X.; Pan, L. Q.; Wu, Z. H.; Hu, T. D.; Jiang, Z.; Huang, Y. Y.; Cao, Z. X.; Sun, G.; Lu, K. Q.

    2012-06-01

    Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm) by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ˜35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

  12. Coordination variation of hydrated Cu2+/Br1− ions traversing the interfacial water in mesopores

    Directory of Open Access Journals (Sweden)

    Q. Wang

    2012-06-01

    Full Text Available Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ∼35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

  13. 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…

  14. A hydrated ion model of [UO2] 2 + in water: Structure, dynamics, and spectroscopy from classical molecular dynamics

    Science.gov (United States)

    Pérez-Conesa, Sergio; Torrico, Francisco; Martínez, José M.; Pappalardo, Rafael R.; Sánchez Marcos, Enrique

    2016-12-01

    A new ab initio interaction potential based on the hydrated ion concept has been developed to obtain the structure, energetics, and dynamics of the hydration of uranyl in aqueous solution. It is the first force field that explicitly parameterizes the interaction of the uranyl hydrate with bulk water molecules to accurately define the second-shell behavior. The [UO2(H2O)5 ] 2 + presents a first hydration shell U-O average distance of 2.46 Å and a second hydration shell peak at 4.61 Å corresponding to 22 molecules using a coordination number definition based on a multisite solute cavity. The second shell solvent molecules have longer mean residence times than those corresponding to the divalent monatomic cations. The axial regions are relatively de-populated, lacking direct hydrogen bonding to apical oxygens. Angle-solved radial distribution functions as well as the spatial distribution functions show a strong anisotropy in the ion hydration. The [UO2(H2O)5 ] 2 + solvent structure may be regarded as a combination of a conventional second hydration shell in the equatorial and bridge regions, and a clathrate-like low density region in the axial region. Translational diffusion coefficient, hydration enthalpy, power spectra of the main vibrational modes, and the EXAFS spectrum simulated from molecular dynamics trajectories agree fairly well with the experiment.

  15. 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.

  16. 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.

  17. Properties of Hydrated Alkali Metals Aimed at the Ion Channel Selectivity

    Institute of Scientific and Technical Information of China (English)

    AN Hai-Long; LIU Yu-Zhi; ZHANG Su-Hua; ZHAN Yong; ZHANG Hai-Lin

    2008-01-01

    The hydration structure properties of different alkali metal ions with eight water molecules and potassium ions with different numbers of water molecules are studied using the mixed density functional theory, B3LYP, with 6-311G basis set. The hydration structures are obtained from structure optimization and the optimum numbers of water molecules in the innermost hydration shell for the alkali metal ions are found. Some useful information about the ion channel selectivity is presented.

  18. 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...

  19. 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.

  20. 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.

  1. 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)

    WU RongLiang; JI Qing; KONG Bin; YANG XiaoZhen

    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 func-tions 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 concentra-tion 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 con-tacts 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%.

  2. 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%.

  3. A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates.

    Science.gov (United States)

    Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K; Alavi, Saman; Yasuoka, Kenji

    2015-05-21

    Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C5H11OH can be enclosed into the 5(12)6(4) cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates. The simulations clearly showed the formation of guest-host hydrogen bonds and the incorporation of the O-H group of 3-methyl-1-butanol guest molecules into the framework of the sII 5(12)6(4) cages, with the remaining hydrophobic part of the amyl-alcohol molecule well accommodated into the cages. The calculated vibrational spectra of alcohol O-H bonds showed large frequency shifts due to the strong guest-host hydrogen bonding. The 2-methyl-2-butanol guests form strong hydrogen bonds with the cage water molecules in the sH clathrate, but are not incorporated into the water framework. By comparing the structures of the alcohols in the hydrate phases, the effect of the location of O-H groups in the butyl chain of the guest molecules on the crystalline structure of the clathrate hydrates is indicated.

  4. Negative ion photoelectron spectroscopy of the copper-aspartic acid anion and its hydrated complexes

    Science.gov (United States)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.; Martínez, Ana; Salpin, Jean-Yves; Schermann, Jean-Pierre

    2010-08-01

    Negative ions of copper-aspartic acid Cu(Asp)- and its hydrated complexes have been produced in the gas phase and studied by anion photoelectron spectroscopy. The vertical detachment energies (VDE) of Cu(Asp)- and Cu(Asp)-(H2O)1,2 were determined to be 1.6, 1.95, and 2.20 eV, respectively. The spectral profiles of Cu(Asp)-(H2O)1 and Cu(Asp)-(H2O)2 closely resembled that of Cu(Asp)-, indicating that hydration had not changed the structure of Cu(Asp)- significantly. The successive shifts to higher electron binding energies by the spectra of the hydrated species provided measures of their stepwise solvation energies. Density functional calculations were performed on anionic Cu(Asp)- and on its corresponding neutral. The agreement between the calculated and measured VDE values implied that the structure of the Cu(Asp)- complex originated with a zwitterionic form of aspartic acid in which a copper atom had inserted into the N-H bond.

  5. 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, ...

  6. Hydration Repulsion between Carbohydrate Surfaces Mediated by Temperature and Specific Ions

    Science.gov (United States)

    Chen, Hsieh; Cox, Jason R.; Ow, Hooisweng; Shi, Rena; Panagiotopoulos, Athanassios Z.

    2016-06-01

    Stabilizing colloids or nanoparticles in solution involves a fine balance between surface charges, steric repulsion of coating molecules, and hydration forces against van der Waals attractions. At high temperature and electrolyte concentrations, the colloidal stability of suspensions usually decreases rapidly. Here, we report a new experimental and simulation discovery that the polysaccharide (dextran) coated nanoparticles show ion-specific colloidal stability at high temperature, where we observed enhanced colloidal stability of nanoparticles in CaCl2 solution but rapid nanoparticle-nanoparticle aggregation in MgCl2 solution. The microscopic mechanism was unveiled in atomistic simulations. The presence of surface bound Ca2+ ions increases the carbohydrate hydration and induces strongly polarized repulsive water structures beyond at least three hydration shells which is farther-reaching than previously assumed. We believe leveraging the binding of strongly hydrated ions to macromolecular surfaces represents a new paradigm in achieving absolute hydration and colloidal stability for a variety of materials, particularly under extreme conditions.

  7. Temporal evolution of helix hydration in a light-gated ion channel correlates with ion conductance.

    Science.gov (United States)

    Lórenz-Fonfría, Víctor A; Bamann, Christian; Resler, Tom; Schlesinger, Ramona; Bamberg, Ernst; Heberle, Joachim

    2015-10-27

    The discovery of channelrhodopsins introduced a new class of light-gated ion channels, which when genetically encoded in host cells resulted in the development of optogenetics. Channelrhodopsin-2 from Chlamydomonas reinhardtii, CrChR2, is the most widely used optogenetic tool in neuroscience. To explore the connection between the gating mechanism and the influx and efflux of water molecules in CrChR2, we have integrated light-induced time-resolved infrared spectroscopy and electrophysiology. Cross-correlation analysis revealed that ion conductance tallies with peptide backbone amide I vibrational changes at 1,665(-) and 1,648(+) cm(-1). These two bands report on the hydration of transmembrane α-helices as concluded from vibrational coupling experiments. Lifetime distribution analysis shows that water influx proceeded in two temporally separated steps with time constants of 10 μs (30%) and 200 μs (70%), the latter phase concurrent with the start of ion conductance. Water efflux and the cessation of the ion conductance are synchronized as well, with a time constant of 10 ms. The temporal correlation between ion conductance and hydration of helices holds for fast (E123T) and slow (D156E) variants of CrChR2, strengthening its functional significance.

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

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2008-01-01

    . 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 anion DBS...

  9. Influence of hydration on ion-biomolecule interactions: M(+)(indole)(H2O)(n) (M = Na, K; n = 3-6).

    Science.gov (United States)

    Ke, Haochen; Lisy, James M

    2015-10-14

    The indole functional group can be found in many biologically relevant molecules, such as neurotransmitters, pineal hormones and medicines. Indole has been used as a tractable model to study the hydration structures of biomolecules as well as the interplay of non-covalent interactions within ion-biomolecule-water complexes, which largely determine their structure and dynamics. With three potential binding sites: above the six- or five-member ring, and the N-H group, the competition between π and hydrogen bond interactions involves multiple locations. Electrostatic interactions from monovalent cations are in direct competition with hydrogen bonding interactions, as structural configurations involving both direct cation-indole interactions and cation-water-indole bridging interactions were observed. The different charge densities of Na(+) and K(+) give rise to different structural conformers at the same level of hydration. Infrared spectra with parallel hybrid functional-based calculations and Gibbs free energy calculations revealed rich structural insights into the Na(+)/K(+)(indole)(H2O)3-6 cluster ion complexes. Isotopic (H/D) analyses were applied to decouple the spectral features originating from the OH and NH stretches. Results showed no evidence of direct interaction between water and the NH group of indole (via a σ-hydrogen bond) at current levels of hydration with the incorporation of cations. Hydrogen bonding to a π-system, however, was ubiquitous at hydration levels between two and five.

  10. 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.

  11. 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.

  12. Alteration of gas phase ion polarizabilities upon hydration in high dielectric liquids.

    Science.gov (United States)

    Buyukdagli, Sahin; Ala-Nissila, T

    2013-07-28

    We investigate the modification of gas phase ion polarizabilities upon solvation in polar solvents and ionic liquids. To this aim, we develop a classical electrostatic theory of charged liquids composed of solvent molecules modeled as finite size dipoles, and embedding polarizable ions that consist of Drude oscillators. In qualitative agreement with ab initio calculations of polar solvents and ionic liquids, the hydration energy of a polarizable ion in both types of dielectric liquid is shown to favor the expansion of its electronic cloud. Namely, the ion carrying no dipole moment in the gas phase acquires a dipole moment in the liquid environment, but its electron cloud also reaches an enhanced rigidity. We find that the overall effect is an increase of the gas phase polarizability upon hydration. In the specific case of ionic liquids, it is shown that this hydration process is driven by a collective solvation mechanism where the dipole moment of a polarizable ion induced by its interaction with surrounding ions self-consistently adds to the polarization of the liquid, thereby amplifying the dielectric permittivity of the medium in a substantial way. We propose this self-consistent hydration as the underlying mechanism behind the high dielectric permittivities of ionic liquids composed of small charges with negligible gas phase dipole moment. Hydration being a correlation effect, the emerging picture indicates that electrostatic correlations cannot be neglected in polarizable liquids.

  13. 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

    , 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...... of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules can then be calculated as a difference. The values determined this way may be called membrane hydration numbers. The results yield the following membrane hydration numbers: Li+: 5.3-5.5; Na+ 4...... membrane....

  14. Hydration and hydrogen bonding of carbonyls in dimyristoyl-phosphatidylcholine bilayer.

    Science.gov (United States)

    Volkov, Victor V; Nuti, Francesca; Takaoka, Yuji; Chelli, Riccardo; Papini, Anna Maria; Righini, Roberto

    2006-07-26

    We combine two-color ultrafast infrared spectroscopy and molecular dynamics simulation to investigate the hydration of carbonyl moieties in a dimyristoyl-phosphatidylcholine bilayer. Excitation with femtosecond infrared pulses of the OD stretching mode of heavy water produces a time dependent change of the absorption band of the phospholipid carbonyl groups. This intermolecular vibrational coupling affects the entire C=O band, thus suggesting that the optical inhomogeneity of the infrared response of carbonyl in phospholipid membranes cannot be attributed to the variance in hydration. Both the experimental and the theoretical results demonstrate that sn-1 carbonyl has a higher propensity to form hydrogen bonds with water in comparison to sn-2. The time-resolved experiment allows following the evolution of the system from a nonequilibrium localization of energy in the OD stretching mode to a thermally equilibrated condition and provides the characteristic time constants of the process. The approach opens a new opportunity for investigation of intermolecular structural relations in complex systems, like membranes, polymers, proteins, and glasses.

  15. Alteration of gas phase ion polarizabilities upon hydration in high dielectric liquids

    OpenAIRE

    2013-01-01

    We investigate the modification of gas phase ion polarizabilities upon solvation in polar solvents and ionic liquids. To this aim, we develop a classical electrostatic theory of charged liquids composed of solvent molecules modeled as finite size dipoles, and embedding polarizable ions that consist of Drude oscillators. In qualitative agreement with ab-initio calculations of polar solvents and ionic liquids, the hydration energy of a polarizable ion in both type of dielectric liquid is shown ...

  16. Hydration and hydrogen bond network of water around hydrophobic surface investigated by terahertz spectroscopy.

    Science.gov (United States)

    Shiraga, K; Suzuki, T; Kondo, N; Ogawa, Y

    2014-12-21

    Water conformation around hydrophobic side chains of four amino acids (glycine, L-alanine, L-aminobutyric acid, and L-norvaline) was investigated via changes in complex dielectric constant in the terahertz (THz) region. Each of these amino acids has the same hydrophilic backbone, with successive additions of hydrophobic straight methylene groups (-CH2-) to the side chain. Changes in the degree of hydration (number of dynamically retarded water molecules relative to bulk water) and the structural conformation of the water hydrogen bond (HB) network related to the number of methylene groups were quantitatively measured. Since dielectric responses in the THz region represent water relaxations and water HB vibrations at a sub-picosecond and picosecond timescale, these measurements characterized the water relaxations and HB vibrations perturbed by the methylene apolar groups. We found each successive straight -CH2- group on the side chain restrained approximately two hydrophobic hydration water molecules. Additionally, the number of non-hydrogen-bonded (NHB) water molecules increased slightly around these hydrophobic side chains. The latter result seems to contradict the iceberg model proposed by Frank and Evans, where water molecules are said to be more ordered around apolar surfaces. Furthermore, we compared the water-hydrophilic interactions of the hydrophilic amino acid backbone with those with the water-hydrophobic interactions around the side chains. As the hydrophobicity of the side chain increased, the ordering of the surrounding water HB network was altered from that surrounding the hydrophilic amino acid backbone, thereby diminishing the fraction of NHB water and ordering the surrounding tetrahedral water HB network.

  17. 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.

  18. 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...

  19. Asymmetric hydration structure around calcium ion restricted in micropores fabricated in activated carbons

    Science.gov (United States)

    Ohkubo, Takahiro; Kusudo, Tomoko; Kuroda, Yasushige

    2016-11-01

    The adsorbed phase and hydration structure of an aqueous solution of Ca(NO3)2 restricted in micropores fabricated in activated carbons (ACs) having different average pore widths (0.63 and 1.1 nm) were investigated with the analysis of adsorption isotherms and x-ray absorption fine structure (XAFS) spectra on Ca K-edge. The adsorbed density of Ca2+ per unit micropore volume in the narrower pore was higher than in the wider pore, while the adsorbed amount per unit mass of carbon with the narrower pore was half of the amount of ACs with the larger pore. On the other hand, variations in the bands assigned to double-electron (KM I) and 1s  →  3d excitations in XAFS spectra demonstrate the formation of a distorted hydration cluster around Ca2+ in the micropore, although the structural parameters of hydrated Ca2+ in the micropores were almost consistent with the bulk aqueous solution, as revealed by the analysis of extended XAFS (EXAFS) spectra. In contrast to the hydration structure of monovalent ions such as Rb+, which generally presents a dehydrated structure in smaller than 1 nm micropores in ACs, the present study clearly explains that the non-spherically-symmetric structure of hydrated Ca2+ restricted in carbon micropores whose sizes are around 1 nm is experimentally revealed where any dehydration phenomena from the first hydration shell around Ca2+ could not be observed.

  20. 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

  1. Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds.

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Mó, Otilia; Yáñez, Manuel; Del Bene, Janet E

    2015-01-21

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the structures, binding energies, and bonding characteristics of binary complexes HFBe:FCl, R2Be:FCl, and FCl:N-base, and of ternary complexes HFBe:FCl:N-base and R2Be:FCl:N-base for R = H, F, Cl; N-base = NH3, NHCH2, NCH. Dramatic synergistic cooperative effects have been found between the Be···F beryllium bonds and the Cl···N halogen bonds in ternary complexes. The Cl···N traditional halogen bonds and the Be···F beryllium bonds in binary complexes become significantly stronger in ternary complexes, while the F-Cl bond weakens. Charge-transfer from F to the empty p(σ) orbital of Be leads to a bending of the XYBe molecule and a change in the hybridization of Be, which in the limit becomes sp(2). As a function of the intrinsic basicity of the nitrogen base and the intrinsic acidity of the Be derivative, the halogen-bond type evolves from traditional to chlorine-shared to ion-pair bonds. The mechanism by which an ion-pair complex is formed is similar to that involved in the dissociative proton attachment process. EOM-CCSD spin-spin coupling constants (1X)J(Cl-N) across the halogen bond in these complexes also provide evidence of the same evolution of the halogen-bond type.

  2. Hydrogen bond network in the hydration layer of the water confined in nanotubes increasing the dielectric constant parallel along the nanotube axis

    Science.gov (United States)

    Qi, Wenpeng; Zhao, Hongwei

    2015-09-01

    The water confined in nanotubes has been extensively studied, because of the potential usages in drug delivery and desalination. The radial distribution of the dielectric constant parallel along the nanotube axis was obtained by molecular dynamics simulations in a carbon nanotube and a nanotube with a very small van der Waals potential. The confined water was divided into two parts, the middle part water and the hydration water. In both cases, the hydrogen bond orientation of the middle water is isotropic, while the hydrogen bonds in hydration layers are apt to parallel along the nanotube axis. Therefore, the hydration water has higher dipole correlations increasing the dielectric constant along the nanotube axis.

  3. 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.

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

    Directory of Open Access Journals (Sweden)

    Ruth Schwaiger

    2016-02-01

    Full Text Available 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 −7 mbar, we observed on these cubic particles the attack of residual physisorbed water molecules from the indium substrate. As a result, thin magnesium hydroxide layers spontaneously grew, giving rise to characteristic volume expansion effects, which depended on the size of the particles. Rounding of the originally sharp cube edges leads to a significant loss of the morphological 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(OH2 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.

  5. Hydrogen-bond vibrational and energetic dynamical properties in sI and sII clathrate hydrates and in ice Ih: Molecular dynamics insights.

    Science.gov (United States)

    Chakraborty, Somendra Nath; English, Niall J

    2015-10-21

    Equilibrium molecular dynamics (MD) simulations have been performed on cubic (sI and sII) polymorphs of methane hydrate, and hexagonal ice (ice Ih), to study the dynamical properties of hydrogen-bond vibrations and hydrogen-bond self-energy. It was found that hydrogen-bond energies are greatest in magnitude in sI hydrates, followed by sII, and their energies are least in magnitude in ice Ih. This is consistent with recent MD-based findings on thermal conductivities for these various materials [N. J. English and J. S. Tse, Phys. Rev. Lett. 103, 015901 (2009)], in which the lower thermal conductivity of sI methane hydrate was rationalised in terms of more strained hydrogen-bond arrangements. Further, modes for vibration and energy-transfer via hydrogen bonds in sI hydrate were found to occur at higher frequencies vis-à-vis ice Ih and sII hydrate in both the water-librational and OH⋯H regions because of the more strained nature of hydrogen bonds therein.

  6. Advances in obsidian hydration dating by secondary ion mass spectrometry: World examples

    Energy Technology Data Exchange (ETDEWEB)

    Liritzis, I. [University of the Aegean, Dept. of Mediterranean Studies, Laboratory of Archaeometry, 1 Demokratias Ave., Rhodes 85100 (Greece)], E-mail: liritzis@rhodes.aegean.gr; Laskaris, N. [University of the Aegean, Dept. of Mediterranean Studies, Laboratory of Archaeometry, 1 Demokratias Ave., Rhodes 85100 (Greece)

    2009-01-15

    Since 1960 the potential of obsidian as a chronometer in archaeology has been subjected to several drawbacks and studies. While economical, simple and fast, obsidian hydration dating today is generally unreliable. A novel approach towards obsidian hydration dating, named SIMS-SS, has recently been initiated based on modelling the hydrogen profile acquired by secondary ion mass spectrometry (SIMS), following Fick's diffusion law, and the rationale of surface saturation (SS) with water molecules. The new nuclear method is presented with significant refinement regarding numerical calculation of age parameters, the suitability criteria of the sampling area and the spectral shape of the concentration dependant H{sup +} profile. A reappraisal is applied to thirteen obsidian specimens from all over the world ranging some 100's to 30,000 years old. The results reinforce the precision and reliability of the SIMS-SS method, enhancing its wide applicability.

  7. 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…

  8. 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

  9. Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

    Science.gov (United States)

    Ahmed, Mohammed; Singh, Ajay K; Mondal, Jahur A; Sarkar, Sisir K

    2013-08-22

    Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water.

  10. On the hydrates of codeine phosphate: the remarkable influence of hydrogen bonding on the crystal size.

    Science.gov (United States)

    Runčevski, Tomče; Petruševski, Gjorgji; Makreski, Petre; Ugarkovic, Sonja; Dinnebier, Robert E

    2014-07-07

    Codeine phosphate forms three hydrates and two anhydrates. The sesquihydrate and hemihydrate, which differ by one water molecule, are stable at room temperature. The influence of this molecule on the internal crystal structure and how it translates into the external crystal shape are reported.

  11. Metal ion hydrocarbon bidentate bonding in alkyl acetates, methyl alkanoates, alcohols and 1-alkenes: a comparative study.

    Science.gov (United States)

    Burgers, Peter C; Holmes, John L; Terlouwc, Johan K

    2016-01-01

    The relative affinity of the monovalent metal ions Li(+), Na(+), Cu(+) and Ag(+) towards a series of aliphatic alkyl acetates and some selected 1-alkenes (P) was examined using the kinetic method. A detailed analysis of the dissociation characteristics of a series of mixed metal-bound dimer ions of the type P1-M(+)-P2 and the evaluated proton affinities (PAs) of the monomers shows that the affinity of the cation towards long-chain alkyl acetates and alkenes (having a chain length ≤ C4) is markedly enhanced. In line with recent studies of nitriles, alcohols and methyl alkanoates, this is attributed to a bidentate interaction of the metal ion with the functional group or double bond and the aliphatic chain. In particular, the longer chain alkyl acetates, methyl alkanoates and alcohols show a remarkably similar behaviour with respect to silver ion hydrocarbon bonding. The Ag(+) adducts of the alkyl acetates dissociate by loss of CH3COOH. This reaction becomes more pronounced at longer chain lengths, which points to metal ion bidentate formation in [Ag(+)···1-alkene] product ions having a long hydrocarbon chain. In the same vein, the heterodimers [1- hexene···Ag(+)···1-heptene] and [1- heptene···Ag(+)···1-octene] dissociate primarily into [Ag(+)···1-heptene] and [Ag(+)···1-octene] ions, respectively. Hydrocarbon bidentate formation in [Ag(+)···1-octene] also reveals itself by the reluctance of this ion to react with water in an ion trap, as opposed to [Ag(+)···1-hexene] which readily undergoes hydration.

  12. 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.

  13. Neutrons describe ectoine effects on water H-bonding and hydration around a soluble protein and a cell membrane

    Science.gov (United States)

    Zaccai, Giuseppe; Bagyan, Irina; Combet, Jérôme; Cuello, Gabriel J.; Demé, Bruno; Fichou, Yann; Gallat, François-Xavier; Galvan Josa, Victor M.; von Gronau, Susanne; Haertlein, Michael; Martel, Anne; Moulin, Martine; Neumann, Markus; Weik, Martin; Oesterhelt, Dieter

    2016-08-01

    Understanding adaptation to extreme environments remains a challenge of high biotechnological potential for fundamental molecular biology. The cytosol of many microorganisms, isolated from saline environments, reversibly accumulates molar concentrations of the osmolyte ectoine to counterbalance fluctuating external salt concentrations. Although they have been studied extensively by thermodynamic and spectroscopic methods, direct experimental structural data have, so far, been lacking on ectoine-water-protein interactions. In this paper, in vivo deuterium labeling, small angle neutron scattering, neutron membrane diffraction and inelastic scattering are combined with neutron liquids diffraction to characterize the extreme ectoine-containing solvent and its effects on purple membrane of H. salinarum and E. coli maltose binding protein. The data reveal that ectoine is excluded from the hydration layer at the membrane surface and does not affect membrane molecular dynamics, and prove a previous hypothesis that ectoine is excluded from a monolayer of dense hydration water around the soluble protein. Neutron liquids diffraction to atomic resolution shows how ectoine enhances the remarkable properties of H-bonds in water—properties that are essential for the proper organization, stabilization and dynamics of biological structures.

  14. Adsorption behavior of some metal ions on hydrated amorphous titanium dioxide surface

    Directory of Open Access Journals (Sweden)

    Panit Sherdshoopongse

    2005-09-01

    Full Text Available Titanium dioxide was prepared from titanium tetrachloride and diluted ammonia solution at low temperature. The product obtained was characterized by XRD, EDXRF, TGA, DSC, and FT-IR techniques. It was found that the product was in the form of hydrated amorphous titanium dioxide, TiO2·1.6H2O (ha- TiO2. Ha-TiO2 exhibits high BET surface area at 449 m2/g. Adsorptions of metal ions onto the ha-TiO2 surface were investigated in the batch equilibrium experiments, using Mn(II, Fe(III, Cu(II, and Pb(II solutions. The concentrations of metal ions were determined by atomic absorption spectrometer. The adsorption isotherms of all metal ions were studied at pH 7. The adsorption of Mn(II, Cu(II, and Pb(II ions on ha-TiO2 conformed to the Langmuir isotherm while that of Fe(III fit equally well to both Langmuir and Freundlich isotherms.

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

    OpenAIRE

    Adams, S.; R.P. Rao

    2010-01-01

    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...

  16. Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings

    Science.gov (United States)

    Liu, Jian; Shi, Guosheng; Fang, Haiping

    2017-02-01

    Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

  17. 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.

  18. A Study of Secondary Ion Triple Bond Analogues.

    Science.gov (United States)

    1980-08-20

    into the formation of cluster ions have measured secondary energy spectra (35-42] and the effects of surface adsorbed gases on secondary yields [43,44...GeCI’ Cl:Ge 0.13 GaTe Te:GaP 0.1 SnAs a Sn:GaAs 0.08 SiBr+ Br:Si < 0.02 Sicl+ CI:Si < 0.01 SiSb- Sb:Si c GeAs As :Ge d Gap Ge: GaP e InSe - Se:InPh f... GaSe Se:GaAs f GeBr Br:Ge f GeSb Sb :Ge f SiAS Si: GaAs 9 a Not a triple bond analogue b ’to Ge detected, (signal < "cps) c Large SiSb- signal, implant

  19. Hydrogen bond fluctuations of the hydration shell of the bromide anion

    NARCIS (Netherlands)

    Timmer, R.L.A.; Bakker, H.J.

    2009-01-01

    We study the hydrogen bond dynamics of solutions of LiBr and NaBr in isotopically diluted water (2% HDO:D2O) with femtosecond spectral hole-burning spectroscopy. We study the frequency fluctuations of the O-H stretch vibrations of the HDO molecules and observe spectral dynamics with time constants o

  20. THE HYDRATION OF AN ION-LEACHABLE GLASS USED IN GLASS-IONOMER CEMENTS

    Directory of Open Access Journals (Sweden)

    Jacek Klos

    2016-07-01

    Full Text Available A study is reported in which the interaction between a typical ionomer glass and water was evaluation in order to evaluate the importance of hydration in the setting of glass-ionomer cements. Glass G338 was mixed with water and the slurries were allowed to harden in metal moulds to create cylindrical specimens 6 mm high x 4 mm diameter. Samples of these specimens were found to disintegrate when placed in water. Following hardening at 37 °C for 1 hour in the moulds, one series of specimens was stored at 95% RH for 23 h, 1 week and 4 weeks, and the other stored for the same lengths of time, but sealed in the moulds. Raman spectra were recorded for glass G338 and glass-water blends stored for 24 hours and 4 weeks. The cylindrical specimens were found to have a degree of structural integrity, but proved to be extremely weak in compression (all specimens of whatever age up to 4 weeks having strengths of less that 1 MPa. Specimens lost mass on storage at 95% RH. Raman spectra showed no additional bands due to glass-water interactions compared with the dry glass itself, and changes in intensity were difficult to interpret, due to Fermi resonance in the regions of interest. It is concluded that binding in these specimens is due to hydrogen bonding between layers of water adsorbed onto glass powder surfaces.

  1. Theoretical study of the bonding of the first- and second-row transition-metal positive ions to acetylene

    Science.gov (United States)

    Sodupe, M.; Bauschlicher, Charles W., Jr.

    1991-01-01

    The bonding of transition-metal ions to acetylene is studied by using a theoretical treatment that includes electron correlation. The ions on the left side of the first and second transition rows insert into the pi bond to form a three-membered ring. On the right side of the row the bonding is electrostatic. The trends in bonding are discussed.

  2. 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.

  3. 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

    2016-10-01

    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.

  4. The investigation of structure and IR spectra for hydrated potassium ion clusters K+(H2O)n=1-16 by density functional theory*

    Science.gov (United States)

    Zhu, Fayan; Zhou, Hongxia; Zhou, Yongquan; Miao, Juntao; Fang, Chunhui; Fang, Yan; Sun, Pengchao; Ge, Haiwen; Liu, Hongyan

    2016-11-01

    The hydration of K+(H2O)n has been widely studied and believe to be important for understanding solvent properties in biological and chemical systems. However, understanding the structure and the spectrum information K+(H2O)n with changing n is limited. Here, we investigated the clusters K+(H2O)n=1-16 and further studied the IR spectrums of the most stable clusters with density functional theory. The configuration, bond length, vibration frequency were given out. It shows that K+(H2O)8(H2O)n, a distorted square antiprism in inner layer, is the main configuration with hydration distance rK - OI 0.296 nm when the hydration number n is bigger than 8. The saturated hydration number is 8 in the first hydration layer and the water molecules of the second hydration sphere have little effect on the inner ones when n> 8. A detailed classification about the hydrated water molecules was made according to the role of acceptor or donor hydrogen bonding in clusters. The vibration frequency of the different kinds of water molecules were also detailly identified. The results are valuable for further determination of the K+(H2O)n clusters in aqueous solutions. Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2016-60529-7

  5. Pulsed laser positive ion desorption from a model hydrated inorganic crystal (CaHPO 4·2H 2O) at 248 nm

    Science.gov (United States)

    Dawes, M. L.; Langford, S. C.; Dickinson, J. T.

    1998-05-01

    We examine the laser-induced positive ion emission of a typical, wide band gap, hydrated inorganic single crystal, CaHPO 4·2H 2O (brushite), at 248 nm (KrF excimer) in vacuum. As-grown brushite is quite resistant to laser damage and yields little ion emission at fluences below 1 J/cm 2. In the presence of surface damage by abrasion or heating-induced transformations, intense laser-induced ion emission appears at lower fluences. The ion energy and fluence dependence are consistent with a defect mediated, multiple photon emission mechanism. In particular, the transport of hydrated Ca + to the surface, followed by adsorption at anion defects (and removal of water by evaporation), can provide an ideal environment for ion emission. The implications with regard to the UV laser ablation of hydrated environmental and biological minerals are discussed.

  6. On the bonding and the electric field gradient of the uranyl ion

    NARCIS (Netherlands)

    de Jong, WA; Visscher, L; Nieuwpoort, WC

    1999-01-01

    Molecular properties of the uranyl ion ([UO2](2+)) are studied using both a non-relativistic and a relativistic method. Inclusion of relativity leads to a bond length expansion and makes the electric field gradient (EFG) at the uranium nucleus strongly dependent on the U-O bond distance, The non-rel

  7. Bonding Analysis on the Crystallization of Magnesium Carbonate Hydrates%基于水合碳酸镁结晶过程的化学键分析

    Institute of Scientific and Technical Information of China (English)

    闫小星; 李云飞; 薛冬峰; 晏成林; 王雷

    2007-01-01

    基于晶体学结构,将化学键理论定量地应用到水合碳酸镁Mg5(CO3)4(OH)2·4H2O和MgOgO3·3H2O的结晶行为研究中,以此指导和控制实际晶体的生长行为.根据所选晶面的化学键数目和强度,可以计算出该晶面的垂直生长速率,从而方便地预测出Mg5(CO3)4(OH)2·4H2O和MMgO3·3H2O晶体的理想形貌.Mg5(CO3)4(OH)2·4H2O晶体表现出六方片状的结晶习性,MgCO3·3H2O则具有六方柱的理想形貌.在实验中,六方片状的Mg5(CO3)4(OH)2-114心O和MgO3·3H2O六方柱可以通过简单的液相反应获得,证明我们的理论计算与实验结果完全相符.目前研究结果表明,单晶生长可以通过热力学意义上调整组成原子或离子的成键方式获得本质上的改进,这一过程为我们从动力学角度优化实验策略提供了更广阔的空间.%The chemical bonding theory is used to investigate the fundamental crystallization behaviours of magnesium carbonate hydrate crystals Mg5(CO3)4OH)2·4H2O and MgCO3·3H2O in terms of crystallographic structure, with the aim to guide and control the practical crystal growth. The ideal morphology of Mg5(CO3)4(OH)2·4H2O and MgCO3·3H2O crystals has readily been predicted, by calculating the vertical growth rate of selected planes in terms of the bond number and bond strength. Theoretically,Mg5 (CO3)4(OH)2·4H2O crystal exhibits hexagonal plate-shaped characteristics, while MgCO3·3H2O crystal possesses a hexagonal prism morphology. Experimentally, the hexagonal Mg5(CO3)4(OH)2·4H2O micro-platelets and MgCO3 ·3H2O micro-prisms with reproducible shape can be obtained by a simple liquid phase reaction. Theoretical results are in a good agreement with our experimental observations. Single crystal growth can be improved by tuning the bonding modification of constituent atoms or ions, such a process can leave us a great space to kinetically maximize our experimental strategies.

  8. Influence des ions sur le pouvoir hydratant de l'ure e: e tude sur peau de porc ex vivo.

    Science.gov (United States)

    Dupuis, L; Manfait, M; Serpier, H; Capon, F; Kalis, B

    1997-02-01

    This study deals with the influence of ions (NaCl and MgSO4) in a W/O emulsion containing 10% urea. Moisturization kinetics are assessed by corneometry on pig skin ex vivo. The formula's influence on urea penetration is measured by infrared spectrometry with an ATR device and the stripping method. Corneometry and spectroscopy were chosen to record simultaneously the hydratation levels and urea localization into superficial cell layers. Urea crystallization after evaporation of emulsions and aqueous solutions is described. Results show that urea does not hydrate nor penetrate when applied to the skin through an aqueous gel. In a W/O emulsion, sodium chloride increases the ability of urea to moisturize without improving penetration. In vitro urea crystallization is disturbed by sodium chloride or magnesium sulphate for solutions and emulsions. This stabilization by ions is correlated with good moisturization values. The stabilization of urea in the solute state provided by ions increases its water epidermal binding capacity without enhancing penetration.

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

    Science.gov (United States)

    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.

  10. Semiconductor thin film transfer by wafer bonding and advanced ion implantation layer splitting technologies

    Science.gov (United States)

    Lee, Tien-Hsi

    Wafer bonding is an attractive technology for modern semiconductor and microelectronic industry due to its variability in allowing combination of materials. Initially, the bonding of wafers of the same material, such as silicon-silicon wafer bonding has been major interest. In the meantime, research interest has shifted to the bonding of dissimilar materials such as silicon to quartz or to sapphire. Thermal stress coming from the different expansion coefficients usually is a barrier to the success of dissimilar material bonding. Thermal stress may cause debonding, sliding, cracking, thermal misfit dislocations, or film wrinkle to impair the quality of the transferred layer. This dissertation presents several effective approaches to solve the thermal stress problem. These approaches concern bonding processes (low vacuum bonding and storage), thinning (advanced ion implantation layer splitting), and annealing processes (accumulative effect of blister generation) and are combined to design the best heat-treatment cycle. For this propose the concept of hot bonding is used in order to effectively minimize the thermal mismatch of dissimilar material bonding during the bonding and thinning procedures. During the initial bonding and bond strengthening phase, the difference in the temperature between bonding and annealing processes should be decreased as much as possible to avoid excessive thermal stresses. This concept can be realized either by increasing the bonding temperature or by decreasing the annealing temperature. A thinning technique has to employed that can thin the device wafer before debonding occurs due to the thermal stress generated either from the cooling-down process in the first case or by the annealing process itself in the late case. The ion implantation layer splitting method, also known as the Smart-cutsp°ler process, developed by Bruel at LEIT in France is a practical thinning technique which satisfies the above requirement. In the study, an

  11. Magnetic Interactions in the Copper Complex (L-Aspartato)(1,10-phenanthroline)copper(II) Hydrate. An Exchange-Coupled Extended System with Two Dissimilar Copper Ions.

    Science.gov (United States)

    Brondino, Carlos D.; Calvo, Rafael; Atria, Ana María; Spodine, Evgenia; Nascimento, Otaciro R.; Peña, Octavio

    1997-07-02

    We report EPR measurements in single-crystal samples at the microwave frequencies 9.8 and 34.3 GHz and magnetic susceptibility measurements in polycrystalline samples for the ternary complex of copper with aspartic acid and phenanthroline, (L-aspartato)(1,10-phenanthroline)copper(II) hydrate. The crystal lattice of this compound is composed of two dissimilar copper ions identified as Cu(A) and Cu(B), which are in two types of copper chains called A and B, respectively, running parallel to the b crystal axis. The copper ions in the A chains are connected by the aspartic acid molecule, and those in the B chains by a chemical path that involves a carboxylate bridge and a hydrogen bond. Both chains are held together by a complex network of hydrogen bonds and by hydrophobic interactions between aromatic amines. Magnetic susceptibility data indicate a Curie-Weiss behavior in the studied temperature range (2-300 K). The EPR spectra at 9.8 GHz display a single exchange collapsed resonance for any magnetic field orientation, in the so-called strong exchange regime. Those at 34.3 GHz are within the so-called weak exchange regime and display two resonances which belong to each type of copper ion chain. The decoupling of the spectra at 34.3 GHz using a theory based on Anderson's model for the case of two weakly exchange coupled spins S = (1)/(2) allows one to obtain the angular variation of the squares of the g-factor and the peak-to-peak line width of each resonance. This model also allows one to evaluate the exchange parameter |J(AB)/k| = 2.7(6) mK associated with the chemical path connecting dissimilar copper ions. The line width data obtained for each component of the spectra at 34.3 GHz are analyzed in terms of a model based on Kubo and Tomita's theory, to obtain the exchange parameters |J(A)/k| = 0.77(2) K and |J(B)/k| = 1.44(2) K associated with the chemical paths connecting the similar copper ions of types A and B, respectively.

  12. Normal mode gating motions of a ligand-gated ion channel persist in a fully hydrated lipid bilayer model.

    Science.gov (United States)

    Bertaccini, Edward J; Trudell, James R; Lindahl, Erik

    2010-08-18

    We have previously used molecular modeling and normal-mode analyses combined with experimental data to visualize a plausible model of a transmembrane ligand-gated ion channel. We also postulated how the gating motion of the channel may be affected by the presence of various ligands, especially anesthetics. As is typical for normal-mode analyses, those studies were performed in vacuo to reduce the computational complexity of the problem. While such calculations constitute an efficient way to model the large scale structural flexibility of transmembrane proteins, they can be criticized for neglecting the effects of an explicit phospholipid bilayer or hydrated environment. Here, we show the successful calculation of normal-mode motions for our model of a glycine α-1 receptor, now suspended in a fully hydrated lipid bilayer. Despite the almost uniform atomic density, the introduction of water and lipid does not grossly distort the overall gating motion. Normal-mode analysis revealed that even a fully immersed glycine α-1 receptor continues to demonstrate an iris-like channel gating motion as a low-frequency, high-amplitude natural harmonic vibration consistent with channel gating. Furthermore, the introduction of periodic boundary conditions allows the examination of simultaneous harmonic vibrations of lipid in synchrony with the protein gating motions that are compatible with reasonable lipid bilayer perturbations. While these perturbations tend to influence the overall protein motion, this work provides continued support for the iris-like motion model that characterizes gating within the family of ligand-gated ion channels.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    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...

  14. 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..

  15. SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .3. EFFECT OF SULFOLANE ON THE EQUILIBRIUM CONVERSION

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1992-01-01

    The liquid-phase hydration of cyclohexene, a pseudo-first-order reversible reaction catalyzed by a strong acid ion-exchange resin, was investigated in solvent mixtures of water and sulfolane. Macroporous Amberlite XE 307 was used because of its superior catalytic activity. Chemical equilibrium conve

  16. Some theoretical considerations concerning ion hydration in the case of ion transfer between water and 1,2-dichloroethane

    CERN Document Server

    Sánchez, C; Baruzzi, A M; Leiva, E P M

    1997-01-01

    Some aspects of direct ion transfer across the water/1,2-dichloroethane are analyzed using a very simple model based on thermodynamic considerations. It was concluded that ion solvation by water molecules may occur in some particular cases in the organic phase, delivering an important contribution to the Gibbs free energy of ion transfer between the aqueous and the organic phase. In general terms, this particular type of transfer should be favored in the case of highly charged small ions at interfaces with a relatively low surface tension and a large difference between the reciprocal of the corresponding dielectric constants.

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

    Science.gov (United States)

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

  18. Ferrimagnetic Properties of Bond Dilution Mixed Blume-Capel Model with Random Single-Ion Anisotropy

    Institute of Scientific and Technical Information of China (English)

    LIU Lei; YAN Shi-Lei

    2005-01-01

    We study the ferrimagnetic properties of spin 1/2 and spin-1 systems by means of the effective field theory.The system is considered in the framework of bond dilution mixed Blume-Capel model (BCM) with random single-ion anisotropy. The investigation of phase diagrams and magnetization curves indicates the existence of induced magnetic ordering and single or multi-compensation points. Special emphasis is placed on the influence of bond dilution and random single-ion anisotropy on normal or induced magnetic ordering states and single or multi-compensation points.Normal magnetic ordering states take on new phase diagrams with increasing randomness (bond and anisotropy), while anisotropy induced magnetic ordering states are always occurrence no matter whether concentration of anisotropy is large or small. Existence and disappearance of compensation points rely strongly on bond dilution and random single-ion anisotropy.Some results have not been revealed in Previous papers and predicted by Néel theory of ferrimagnetism.

  19. 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.

  20. Bond energies and structures of ammonia-sulfuric acid positive cluster ions.

    Science.gov (United States)

    Froyd, Karl D; Lovejoy, Edward R

    2012-06-21

    New particle formation in the atmosphere is initiated by nucleation of gas-phase species. The small molecular clusters that act as seeds for new particles are stabilized by the incorporation of an ion. Ion-induced nucleation of molecular cluster ions containing sulfuric acid generates new particles in the background troposphere. The addition of a proton-accepting species to sulfuric acid cluster ions can further stabilize them and may promote nucleation under a wider range of conditions. To understand and accurately predict atmospheric nucleation, the stabilities of each molecular cluster within a chemical family must be known. We present the first comprehensive measurements of the ammonia-sulfuric acid positive ion cluster system NH(4)(+)(NH(3))(n)(H(2)SO(4))(s). Enthalpies and entropies of individual growth steps within this system were measured using either an ion flow reactor-mass spectrometer system under equilibrium conditions or by thermal decomposition of clusters in an ion trap mass spectrometer. Low level ab initio structural calculations provided inputs to a master equation model to determine bond energies from thermal decomposition measurements. Optimized ab initio structures for clusters up through n = 3, s = 3 are reported. Upon addition of ammonia and sulfuric acid pairs, internal proton transfer generates multiple NH(4)(+) and HSO(4)(-) ions within the clusters. These multiple-ion structures are up to 50 kcal mol(-1) more stable than corresponding isomers that retain neutral NH(3) and H(2)SO(4) species. The lowest energy n = s clusters are composed entirely of ions. The addition of acid-base pairs to the core NH(4)(+) ion generates nanocrystals that begin to resemble the ammonium bisulfate bulk crystal starting with the smallest n = s cluster, NH(4)(+)(NH(3))(1)(H(2)SO(4))(1). In the absence of water, this cluster ion system nucleates spontaneously for conditions that encompass most of the free troposphere.

  1. Assessing the accuracy of approximate treatments of ion hydration based on primitive quasichemical theory

    Science.gov (United States)

    Roux, Benoît; Yu, Haibo

    2010-06-01

    Quasichemical theory (QCT) provides a framework that can be used to partition the influence of the solvent surrounding an ion into near and distant contributions. Within QCT, the solvation properties of the ion are expressed as a sum of configurational integrals comprising only the ion and a small number of solvent molecules. QCT adopts a particularly simple form if it is assumed that the clusters undergo only small thermal fluctuations around a well-defined energy minimum and are affected exclusively in a mean-field sense by the surrounding bulk solvent. The fluctuations can then be integrated out via a simple vibrational analysis, leading to a closed-form expression for the solvation free energy of the ion. This constitutes the primitive form of quasichemical theory (pQCT), which is an approximate mathematical formulation aimed at reproducing the results from the full many-body configurational averages of statistical mechanics. While the results from pQCT from previous applications are reasonable, the accuracy of the approach has not been fully characterized and its range of validity remains unclear. Here, a direct test of pQCT for a set of ion models is carried out by comparing with the results of free energy simulations with explicit solvent. The influence of the distant surrounding bulk on the cluster comprising the ion and the nearest solvent molecule is treated both with a continuum dielectric approximation and with free energy perturbation molecular dynamics simulations with explicit solvent. The analysis shows that pQCT can provide an accurate framework in the case of a small cation such as Li+. However, the approximation encounters increasing difficulties when applied to larger cations such as Na+, and particularly for K+. This suggests that results from pQCT should be interpreted with caution when comparing ions of different sizes.

  2. Origins of hydration lubrication.

    Science.gov (United States)

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

    2015-01-14

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

  3. 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.

  4. Hydration and hydrolysis of thorium(IV) in aqueous solution and the structures of two crystalline thorium(IV) hydrates.

    Science.gov (United States)

    Torapava, Natallia; Persson, Ingmar; Eriksson, Lars; Lundberg, Daniel

    2009-12-21

    Solid octaaqua(kappa(2)O-perchlorato)thorium(IV) perchlorate hydrate, [Th(H(2)O)(8)(ClO(4))](ClO(4))(3).H(2)O, 1, and aquaoxonium hexaaquatris(kappaO-trifluoromethanesulfonato)thorium(IV) trisaquahexakis(kappaO-trifluoromethanesulfonato)thorinate(IV), H(5)O(2)[Th(H(2)O)(6)(OSO(2)CF(3))(3)][Th(H(2)O)(3)(OSO(2)CF(3))(6)], 2, were crystallized from concentrated perchloric and trifluoromethanesulfonic acid solutions, respectively. 1 adopts a severely distorted tricapped trigonal prismatic configuration with an additional oxygen from the perchlorate ion at a longer distance. 2 consists of individual hexaaquatris(kappaO-trifluoromethanesulfonato)thorium(IV) and trisaquahexakis(kappaO-trifluoromethanesulfonato)thorinate(IV) ions and an aquaoxonium ion bridging these two ions through hydrogen bonding. The hydrated thorium(IV) ion is nine-coordinated in aqueous solution as determined by extended X-ray absorption fine structure (EXAFS) and large angle X-ray scattering (LAXS). The LAXS studies also showed a second hydration sphere of about 18 water molecules, and traces of a 3rd hydration sphere. Structural studies in aqueous solution of the hydrolysis products of thorium(IV) have identified three different types of hydrolysis species: a mu(2)O-hydroxo dimer, [Th(2)(OH)(2)(H(2)O)(12)](6+), a mu(2)O-hydroxo tetramer, [Th(4)(OH)(8)(H(2)O)(16)](8+), and a mu(3)O-oxo hexamer, [Th(6)O(8)(H(2)O)(n)](8+). Detailed structures of these three hydrolysis species are given. A compilation of reported solid state structures of actinoid(IV) compounds with oxygen donor ligands show a strong correlation between the An-O bond distance and the coordination number. The earlier reported U-O bond distance in the hydrated uranium(IV) ion in aqueous solution, confirmed in this study, is related to nine-coordination. The hydrated tri- and tetravalent actinoid ions in aqueous solution all seem to be nine-coordinated. The trivalent ions show a significant difference in bond distance to prismatic and

  5. Micro-bond contact model and its parameters for the deep-sea methane hydrate bearing soils%深海能源土微观力学胶结模型及参数研究

    Institute of Scientific and Technical Information of China (English)

    蒋明镜; 肖俞; 朱方园

    2012-01-01

    天然气水合物主要以胶结物形式存在深海能源土颗粒之间,对能源土强度影响显著,因此研究水合物胶结接触力学特性对能源土力学性质研究有重要作用,而其中的关键是水合物胶结模型及胶结参数的确定。首先,引入并讨论了一种微观胶结接触模型及其对于能源土胶结接触力学特性的适用性;其次,通过文献资料系统分析,获取不同温度、压力及水合物密度条件下天然气水合物的强度与弹性模量表达式;最后,进一步研究了水合物微观胶结模型中的胶结参数,该类水合物微观胶结参数取决于能源土中水合物埋藏深度(赋存环境压力)、温度、水合物密度,这些宏观参量容易确定。%Methane hydrate (MH), which has significant influences on the strength of methane hydrate bearing soils, exits mainly in the form of cement materials between soil particles. Hence, the study of bond mechanical behavior of MH between soil particles is significant to the research of methane hydrate bearing soils, of which the keypoint is the determination of the micro-contact model and corresponding bond parameters of MH. First, a micro-bond contact model is introduced to reflect the contact properties of the soil particles. Second, the strengths and elastic modulus of MH (such as the tensile strength, compressive strength, shear strength and torsion strength) are obtained through the literatures about methane hydrate triaxial tests. Finally, micro bond parameters needed by the contact model are obtained. The results show that the micro bond parameters of gas hydrate are determined by the saturation and strength parameters of gas hydrate, which can be obtained through the temperature, density of hydrate and its burial depth which are easy to be determined.

  6. Quenching of the excited state of hydrated Europium(III) ions by electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, K.

    1993-08-01

    This thesis explores the oxidation-reduction chemistry of the excited state of Eu(III) ions, *Eu{sub aq}{sup 3+}, in aqueous solutions. Evidence is presented for the quenching of *Eu{sup 3+} by reductive electron transfer. It is concluded that *Eu{sup 3+} is not a strong energy transfer reagent. The reactivity of *Eu{sub aq}{sup 3+} is compared with that of *UO{sub 2}{sup 2+}.

  7. The elimination of corrosiveness of hydrated ethanol by using ion exchange resin; Eliminador da corrosividade do alcool etilico hidratado combustivel pelo tratamento com resinas de troca ionica

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Aurelio N. de; Tanaka, Deniol K. [Instituto de Pesquisas Tecnologicas (IPT), Sao Paulo, SP (Brazil)

    1986-12-31

    Based on ion exchange principles and the chemical analysis of regularly produced hydrated alcohol and considering corrosion problems found when this alcohol is used as fuel, the use of ion exchange resins is proposed to purify hydrated alcohol and hence eliminate corrosiveness. This alternative takes advantage of high efficiency with significantly low cost compared to other alternatives or to surface treatments required as function of the aggressive characteristics of fuel. Available preliminary results shows a modification in the aggressive characteristics of alcohol fuel as well as the possibility to obtain adequate physico-chemical properties of final product and the ability to standardize products from different sources or regions. Additional research work and follow up from vehicles testings with treated alcohol were done and they confirm presented results. 12 figs., 6 tabs.

  8. Near-Quantitative Agreement of Model-Free DFT-MD Predictions with XAFS Observations of the Hydration Structure of Highly Charged Transition-Metal Ions.

    Science.gov (United States)

    Fulton, John L; Bylaska, Eric J; Bogatko, Stuart; Balasubramanian, Mahalingam; Cauët, Emilie; Schenter, Gregory K; Weare, John H

    2012-09-20

    First-principles dynamics simulations (DFT, PBE96, and PBE0) and electron scattering calculations (FEFF9) provide near-quantitative agreement with new and existing XAFS measurements for a series of transition-metal ions interacting with their hydration shells via complex mechanisms (high spin, covalency, charge transfer, etc.). This analysis does not require either the development of empirical interparticle interaction potentials or structural models of hydration. However, it provides consistent parameter-free analysis and improved agreement with the higher-R scattering region (first- and second-shell structure, symmetry, dynamic disorder, and multiple scattering) for this comprehensive series of ions. DFT+GGA MD methods provide a high level of agreement. However, improvements are observed when exact exchange is included. Higher accuracy in the pseudopotential description of the atomic potential, including core polarization and reducing core radii, was necessary for very detailed agreement. The first-principles nature of this approach supports its application to more complex systems.

  9. An Ion Exchange Study of Possible Hydridized 5f Bonding in theActinides

    Energy Technology Data Exchange (ETDEWEB)

    Diamond, R.M.; Street, Jr., K.; Seaborg, G.T.

    1951-08-28

    A study has been made of the elution behavior of curium(III), americium(III), plutonium(III), actinium(III), plutonium(IV), neptunium(IV), uraniuM(IV), thorium(IV), neptunium(V), plutonium (VI), uranium (VI), lanthanum(III), cerium(III), europium(III), ytterbium(III), ytterium(III), strontium(II), barium(II), radium(II), cesium(I) with 3.2 M, 6.2 M, 9.3 M, and 12.2 M HCl solutions from Dowex-50 cation exchange resin columns. These elutions show that in high concentrations of hydrochloric acid the actinides form complex ions with chloride ion to a much greater extent than the lanthanides. The strengths of the tripositive actinide complex ions apparently go in the order plutonium > americium> curium, although their ionic radii also decrease in this same order. To explain these results, a partial covalent character may be ascribed to the bonding in the transuranium complex ions. It is shown that a reasonable structure for such covalent bonding involves hybridization of the 5f orbitals in the actinide elements.

  10. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    Science.gov (United States)

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.

  11. 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.

  12. Energy decomposition analysis of cation-π, metal ion-lone pair, hydrogen bonded, charge-assisted hydrogen bonded, and π-π interactions.

    Science.gov (United States)

    Sharma, Bhaskar; Srivastava, Hemant Kumar; Gayatri, Gaddamanugu; Sastry, Garikapati Narahari

    2015-03-30

    This study probes the nature of noncovalent interactions, such as cation-π, metal ion-lone pair (M-LP), hydrogen bonding (HB), charge-assisted hydrogen bonding (CAHB), and π-π interactions, using energy decomposition schemes-density functional theory (DFT)-symmetry-adapted perturbation theory and reduced variational space. Among cation-π complexes, the polarization and electrostatic components are the major contributors to the interaction energy (IE) for metal ion-π complexes, while for onium ion-π complexes (NH4+, PH4+, OH3+, and SH3+) the dispersion component is prominent. For M-LP complexes, the electrostatic component contributes more to the IE except the dicationic metal ion complexes with H2 S and PH3 where the polarization component dominates. Although electrostatic component dominates for the HB and CAHB complexes, dispersion is predominant in π-π complexes.

  13. Chemically bonded phosphorus/graphene hybrid as a high performance anode for sodium-ion batteries.

    Science.gov (United States)

    Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Hu, Shi; Yi, Ran; Tang, Duihai; Walter, Timothy; Regula, Michael; Choi, Daiwon; Li, Xiaolin; Manivannan, Ayyakkannu; Wang, Donghai

    2014-11-12

    Room temperature sodium-ion batteries are of great interest for high-energy-density energy storage systems because of low-cost and natural abundance of sodium. Here, we report a novel phosphorus/graphene nanosheet hybrid as a high performance anode for sodium-ion batteries through facile ball milling of red phosphorus and graphene stacks. The graphene stacks are mechanically exfoliated to nanosheets that chemically bond with the surfaces of phosphorus particles. This chemical bonding can facilitate robust and intimate contact between phosphorus and graphene nanosheets, and the graphene at the particle surfaces can help maintain electrical contact and stabilize the solid electrolyte interphase upon the large volume change of phosphorus during cycling. As a result, the phosphorus/graphene nanosheet hybrid nanostructured anode delivers a high reversible capacity of 2077 mAh/g with excellent cycling stability (1700 mAh/g after 60 cycles) and high Coulombic efficiency (>98%). This simple synthesis approach and unique nanostructure can potentially be applied to other phosphorus-based alloy anode materials for sodium-ion batteries.

  14. Hydration and ion pair formation in common aqueous La(III) salt solutions--a Raman scattering and DFT study.

    Science.gov (United States)

    Rudolph, Wolfram W; Irmer, Gert

    2015-01-01

    Raman spectra of aqueous lanthanum perchlorate, triflate (trifluorosulfonate), chloride and nitrate solutions were measured over a broad concentration (0.121-3.050 mol L(-1)) range at room temperature (23 °C). A very weak mode at 343 cm(-1) with a full width at half height at 49 cm(-1) in the isotropic spectrum suggests that the nona-aqua La(III) ion is thermodynamically stable in dilute perchlorate solutions (∼0.2 mol L(-1)) while in concentrated perchlorate solutions outer-sphere ion pairs and contact ion pairs are formed. The La(3+) nona-hydrate was also detected in a 1.2 mol L(-1) La(CF3SO3)3(aq). In lanthanum chloride solutions chloro-complex formation was detected over the measured concentration range from 0.5-3.050 mol L(-1). The chloro-complexes in LaCl3(aq) are fairly weak and disappear with dilution. At a concentration complexes disappeared. In LaCl3 solutions, with additional HCl, a series of chloro-complexes of the type [La(OH2)(9-n)Cln](+3-n) (n = 1-3) were formed. The La(NO3)3(aq) spectra were compared with a spectrum of a 0.409 mol L(-1) NaNO3(aq) and it was concluded that in La(NO3)3(aq) over the concentration range from 0.121-1.844 mol L(-1), nitrato-complexes, [La(OH2)(9-n)(NO3)n](+3-n) (n = 1, 2) were formed. These nitrato-complexes are quite weak and disappear with dilution La(OH2)9](3+) with the polarizable dielectric continuum are in good agreement with data from recent structural experimental measurements and high quality simulations. The DFT frequency of the La-O stretching mode at 328.2 cm(-1), is only slightly smaller than the experimental one.

  15. Comparison of ion sites and diffusion paths in glasses obtained by molecular dynamics simulations and bond valence analysis

    OpenAIRE

    Muller, Christian; Zienicke, Egbert; Adams, Stefan; Habasaki, Junko; Maass, Philipp

    2006-01-01

    Based on molecular dynamics simulations of a lithium metasilicate glass we study the potential of bond valence sum calculations to identify sites and diffusion pathways of mobile Li ions in a glassy silicate network. We find that the bond valence method is not well suitable to locate the sites, but allows one to estimate the number of sites. Spatial regions of the glass determined as accessible for the Li ions by the bond valence method can capture up to 90% of the diffusion path. These regio...

  16. 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.

  17. 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.

  18. Proton-driven amide bond-cleavage pathways of gas-phase peptide ions lacking mobile protons.

    Science.gov (United States)

    Bythell, Benjamin J; Suhai, Sándor; Somogyi, Arpád; Paizs, Béla

    2009-10-07

    The mobile proton model (Dongre, A. R., Jones, J. L., Somogyi, A. and Wysocki, V. H. J. Am. Chem. Soc. 1996, 118 , 8365-8374) of peptide fragmentation states that the ionizing protons play a critical role in the gas-phase fragmentation of protonated peptides upon collision-induced dissociation (CID). The model distinguishes two classes of peptide ions, those with or without easily mobilizable protons. For the former class mild excitation leads to proton transfer reactions which populate amide nitrogen protonation sites. This enables facile amide bond cleavage and thus the formation of b and y sequence ions. In contrast, the latter class of peptide ions contains strongly basic functionalities which sequester the ionizing protons, thereby often hindering formation of sequence ions. Here we describe the proton-driven amide bond cleavages necessary to produce b and y ions from peptide ions lacking easily mobilizable protons. We show that this important class of peptide ions fragments by different means from those with easily mobilizable protons. We present three new amide bond cleavage mechanisms which involve salt-bridge, anhydride, and imine enol intermediates, respectively. All three new mechanisms are less energetically demanding than the classical oxazolone b(n)-y(m) pathway. These mechanisms offer an explanation for the formation of b and y ions from peptide ions with sequestered ionizing protons which are routinely fragmented in large-scale proteomics experiments.

  19. Dielectric spectroscopy investigation of ion-containing and intermolecular hydrogen-bonded polymer systems

    Science.gov (United States)

    Atorngitjawat, Pornpen

    Ion-containing and intermolecular hydrogen-bonded polymers are used widely in a variety of industrial and commercial applications, from food packaging to battery electrolytes to pharmaceuticals. Yet the dynamics of these polymers, which are both complex and important to the application, are poorly understood. This thesis provides the first systematic study of the dynamics of several ion-containing and intermolecular hydrogen-bonded polymers by broadband dielectric relaxation spectroscopy. The systems under consideration include sulfonated polystyrene (SPS) in acid (SPS-H) and neutralized forms, and mixtures of poly(2-vinylpyridine) (P2VPy) with lithium perchlorate (LiClO4) and low molecular weight phenolic molecules. Dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, small-angle X-ray scattering and wide-angle X-ray diffraction were employed in a complementary role. Multiple relaxations were generally observed at high temperatures. For SPS ionomers, the segmental process, Maxwell-Wagner-Sillars interfacial polarization, and electrode polarization were detected. Three relaxations were also found in spectra of SPS-H, attributed to the segmental process, hydrogen bond association/dissociation, and electrode polarization. Three dielectric relaxations above the segmental process were observed for P2VPy-LiClO4 mixtures: ion-mode relaxation, slow hindered segmental relaxation and electrode polarization. However, only electrode polarization was observed above the segmental relaxation for all P2VPy--small phenolic molecule mixtures, except P2VPy + 10 mol% 2,3,3,4,4,5-hexahydroxybenzophenone. This mixture exhibited an additional relaxation due to Maxwell-Wagner-Sillars interfacial polarization, arising from the existence of phase-separated complexes within the P2VPy matrix. Sub-Tg local relaxations were suppressed by ionic intermolecular interactions for SPS ionomers and P2VPy-LiClO4 mixtures. Intermolecular hydrogen

  20. 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.

  1. Amide bond cleavage initiated by coordination with transition metal ions and tuned by an auxiliary ligand.

    Science.gov (United States)

    Yang, Yongpo; Lu, Chunxin; Wang, Hailong; Liu, Xiaoming

    2016-06-21

    The reaction of ligand , N,N-bis(pyridin-2-ylmethyl)acetamide, with five transition metal salts, FeCl3·6H2O, CuCl2·2H2O, Cu(ClO4)2·6H2O, ZnCl2 and K2PtCl4/KI, produced five metal complexes, [(μ-O)(FeClL')(FeCl3)] (), [CuLCl2] (), [CuBPA(ClO4)(CHCN)] ClO4 (), [ZnLCl2] () and [PtLI2] (), where = 1-(2,4,5-tri(pyridin-2-yl)-3-(pyridin-2-ylmethyl)imidazolidin-1-yl)ethanone which formed in situ, and BPA = bis(pyridin-2-ylmethyl)amine. The ligand and complexes were characterized by a variety of spectroscopic techniques including X-ray single crystal diffraction where applicable. Depending on the metal ion and auxiliary ligand of the complex, the acetyl group of the ligand could be either intact or cleaved. When ferric chloride hexahydrate was used, the deacetylation proceeded even further and a novel heterocyclic compound () was formed in situ. A possible mechanism was proposed for the formation of the heterocyclic compound found in complex . Our results indicate that to cleave effectively an amide bond, it is essential for a metal centre to bind to the amide bond and the metal centre is of sufficient Lewis acidity.

  2. ATR-FTIR study of water in Nafion membrane combined with proton conductivity measurements during hydration/dehydration cycle.

    Science.gov (United States)

    Kunimatsu, Keiji; Bae, Byungchan; Miyatake, Kenji; Uchida, Hiroyuki; Watanabe, Masahiro

    2011-04-21

    We have conducted combined time-resolved attenuated total reflection Fourier transform infrared (ATR-FTIR) and proton conductivity measurements of Nafion NRE211 membrane during hydration/dehydration cycles at room temperature. Conductivity change was interpreted in terms of different states of water in the membrane based on its δ(HOH) vibrational spectra. It was found that hydration of a dry membrane leads first to complete dissociation of the sulfonic acid groups to liberate hydrated protons, which are isolated from each other and have δ(HOH) vibrational frequency around 1740 cm(-1). The initial hydration is not accompanied by a significant increase of the proton conductivity. Further hydration gives rise to a rapid increase of the conductivity in proportion to intensity of a new δ(HOH) band around 1630 cm(-1). This was interpreted in terms of formation of channels of weakly hydrogen-bonded water to combine the isolated hydrophilic domains containing hydrated protons and hydrated sulfonate ions produced during the initial stage of hydration. Upon dehydration, proton conductivity drops first very rapidly due to loss of the weakly hydrogen bonded water from the channels to leave hydrophilic domains isolated in the membrane. Dehydration of the protons proceeds very slowly after significant loss of the proton conductivity.

  3. 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.

  4. Halogen-bonding for visual chloride ion sensing: a case study using supramolecular poly(aryl ether) dendritic organogel systems.

    Science.gov (United States)

    Liu, Zhi-Xiong; Sun, Yihua; Feng, Yu; Chen, Hui; He, Yan-Mei; Fan, Qing-Hua

    2016-02-07

    A convenient and straightforward method for the visual recognition of chloride ion has been established through a chloride-responsive dendritic organogel. The specificity was largely attributed to the higher binding affinity of the dendritic gelator for chloride compared with other anions through halogen bonding interactions.

  5. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    , not all of them are white like snow. Some hydrates from the deep Gulf of Mexico are richly colored in shades of yellow, orange, or even red. The ice-like masses are beautiful, and contrast with the dull gray of deep sea muds. Hydrates from the Blake... volcanoes and associated gas hydrates: Marine Geology, v. 167, p. 29-42. Milkov, A.V. and R. Sassen, 2001a, Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope: Marine Geology, v. 179, pp. 71-83. Milkov, A.V., Sassen, R...

  6. Hydration energies of deprotonated amino acids from gas phase equilibria measurements.

    Science.gov (United States)

    Wincel, Henryk

    2008-08-01

    Singly hydrated clusters of deprotonated amino acids were studied using an electrospray high-pressure mass spectrometer equipped with a pulsed ion-beam reaction chamber. Thermochemical data, DeltaH(o), DeltaS(o), and DeltaG(o), for the hydration reaction [AA - H](-) + H(2)O = [AA - H](-).(H(2)O) were obtained from gas-phase equilibria determinations for AA = Gly, Ala, Val, Pro, Phe, Lys, Met, Trp, Gln, Arg, and Asp. The hydration free-energy changes are found to depend significantly on the side-chain substituents. The water binding energy in [AA - H](-).(H(2)O) increases with the gas-phase acidity of AA. The anionic hydrogen bond strengths in [AA - H](-).(H(2)O) are compared with those of the cationic bonds in the corresponding AAH(+).(H(2)O) systems.

  7. Uv Photodissociation Spectroscopy of Temperature Controlled Hydrated Phenol Cluster Cation

    Science.gov (United States)

    Kurusu, Itaru; Yagi, Reona; Kasahara, Yasutoshi; Ishikawa, Haruki

    2016-06-01

    Owing to various developments of spectroscopic techniques, microscopic hydration structures of various clusters in the gas phase have been determined so far. The next step for further understanding of the microscopic hydration is to reveal the temperature effect, such as a fluctuation of the hydration structure. Thus, we have been carrying out photodissociation spectroscopy on the hydrated phenol cation clusters, [PhOH(H_2O)_n]^+, trapped in our temperature-variable ion trap. After the last symposium, we succeeded in improving our experimental condition and recorded the UV photodissociation spectra of [PhOH(H_2O)_5]^+ at the trap temperatures of 20, 50, and 100 K. We identified three groups of bands by their temperature dependence in the spectra. Based on the results of the DFT calculations, we estimated the temperature dependence of the relative populations among the isomers. As a results, the isomers were grouped into three groups having different motifs of the hydrogen-bond structures. Comparing the experimental with the theoretical results, we assigned the relation between the band carriers and the hydrogen-bond structure motifs. Details of the discussion will be presented in the paper. H. Ishikawa, T. Nakano, T. Eguchi, T. Shibukawa, K. Fuke, Chem. Phys. Lett. 514, 234 (2011) R. Yagi, Y. Kasahara, H. Ishikawa, WH12, the 70th International Symposium on Molecular Spectroscopy (2015)

  8. Graphene-bonded and -encapsulated si nanoparticles for lithium ion battery anodes.

    Science.gov (United States)

    Wen, Yang; Zhu, Yujie; Langrock, Alex; Manivannan, Ayyakkannu; Ehrman, Sheryl H; Wang, Chunsheng

    2013-08-26

    Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high-capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one-step aerosol spraying of surface-modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50-100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene-encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open-ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g⁻¹ (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g⁻¹ at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene-encapsulated Si anodes combined with the scalable and one-step aerosol synthesis technique makes this material very promising for lithium ion batteries.

  9. 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.

  10. Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

    Science.gov (United States)

    Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

    2015-12-09

    Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-15

    Chemical imaging of single cells is important in capturing biological dynamics. Single cell correlative imaging is realized between structured illumination microscopy (SIM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) using System for Analysis at the Liquid Vacuum Interface (SALVI), a multimodal microreactor. SIM characterized cells and guided subsequent ToF-SIMS analysis. Dynamic ToF-SIMS provided time- and space-resolved cell molecular mapping. Lipid fragments were identified in the hydrated cell membrane. Principal component analysis was used to elucidate chemical component differences among mouse lung cells that uptake zinc oxide nanoparticles. Our results provided submicron chemical spatial mapping for investigations of cell dynamics at the molecular level.

  12. Effects of single bond-ion and single bond-diradical form on the stretching vibration of Cdbnd N bridging bond in 4,4‧-disubstituted benzylidene anilines

    Science.gov (United States)

    Cao, Chao-Tun; Bi, Yakun; Cao, Chenzhong

    2016-06-01

    Fifty-seven samples of model compounds, 4,4‧-disubstituted benzylidene anilines, p-X-ArCH = NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νCdbnd N of the Cdbnd N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νCdbnd N, that is there are mainly three modes in the stretching vibration of Cdbnd N bond: (I) polar double bond form Cdbnd N, (II) single bond-ion form C+-N- and (III) single bond-diradical form Crad -Nrad . The contributions of the forms (I) and (II) to the change of νCdbnd N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II).

  13. An intravenous clarithromycin lipid emulsion with a high drug loading, H-bonding and a hydrogen-bonded ion pair complex exhibiting excellent antibacterial activity

    Directory of Open Access Journals (Sweden)

    Haoyu Gong

    2016-10-01

    Full Text Available The aim of this study was to develop an intravenous clarithromycin lipid emulsion (CLE with good stability and excellent antibacterial activity. The CLE was prepared by the thin-film dispersed homogenization method. The interaction between clarithromycin (CLA and cholesteryl hemisuccinate (CHEMS was confirmed by DSC, FT-IR and 1H NMR analysis. The interfacial drug loading, thermal sterilization, freeze–thaw stability, and in vitro and in vivo antibacterial activity were investigated systematically. DSC, FT-IR and 1H NMR spectra showed that CHEMS (CLA: CHEMS, M ratio 1:2 could interact with CLA through H-bonding and a hydrogen-bonded ion pair. The CHEMS was found necessary to maintain the stability of CLE. Ultracentrifugation showed that almost 88% CLA could be loaded into the interfacial layer. The optimized CLE formulation could withstand autoclaving at 121 °C for 10 min and remain stable after three freeze–thaw cycles. The in vitro susceptibility test revealed that the CLA–CHEMS ion-pair and CLE have similar activity to the parent drug against many different bacterial strains. The in vivo antibacterial activity showed that the ED50 of intravenous CLE was markedly lower than that of CLA solution administrated orally. CLE exhibited pronounced antibacterial activity and might be a candidate for a new nanocarrier for CLA with potential advantages over the current commercial formulation.

  14. Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions.

    Science.gov (United States)

    Chen, Jianzhong; Green, Kari B; Nichols, Kelly K

    2015-08-01

    A series of different types of wax esters (represented by RCOOR') were systematically studied by using electrospray ionization (ESI) collision-induced dissociation tandem mass spectrometry (MS/MS) along with pseudo MS(3) (in-source dissociation combined with MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer. The tandem mass spectra patterns resulting from dissociation of ammonium/proton adducts of these wax esters were influenced by the wax ester type and the collision energy applied. The product ions [RCOOH2](+), [RCO](+) and [RCO-H2O](+) that have been reported previously were detected; however, different primary product ions were demonstrated for the three wax ester types including: (1) [RCOOH2](+) for saturated wax esters, (2) [RCOOH2](+), [RCO](+) and [RCO-H2O](+) for unsaturated wax esters containing only one double bond in the fatty acid moiety or with one additional double bond in the fatty alcohol moiety, and (3) [RCOOH2](+) and [RCO](+) for unsaturated wax esters containing a double bond in the fatty alcohol moiety alone. Other fragments included [R'](+) and several series of product ions for all types of wax esters. Interestingly, unusual product ions were detected, such as neutral molecule (including water, methanol and ammonia) adducts of [RCOOH2](+) ions for all types of wax esters and [R'-2H](+) ions for unsaturated fatty acyl-containing wax esters. The patterns of tandem mass spectra for different types of wax esters will inform future identification and quantification approaches of wax esters in biological samples as supported by a preliminary study of quantification of isomeric wax esters in human meibomian gland secretions.

  15. 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

    2016-03-01

    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.

  16. Hydrogen bond breaking in aqueous solutions near the critical point

    Science.gov (United States)

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2001-01-01

    The nature of water-anion bonding is examined using X-ray absorption fine structure spectroscopy on a 1mZnBr2/6m NaBr aqueous solution, to near critical conditions. Analyses show that upon heating the solution from 25??C to 500??C, a 63% reduction of waters occurs in the solvation shell of ZnBr42-, which is the predominant complex at all pressure-temperature conditions investigated. A similar reduction in the hydration shell of waters in the Br- aqua ion was found. Our results indicate that the water-anion and water-water bond breaking mechanisms occurring at high temperatures are essentially the same. This is consistent with the hydration waters being weakly hydrogen bonded to halide anions in electrolyte solutions. ?? 2001 Elsevier Science B.V.

  17. Dielectric saturation of the ion hydration shell and interaction between two double helices of DNA in mono- and multivalent electrolyte solutions: foundations of the epsilon-modified Poisson-Boltzmann theory.

    Science.gov (United States)

    Gavryushov, Sergei

    2007-05-17

    Potentials of mean force between single Na+, Ca2+, and Mg2+ cations and a highly charged spherical macroion in SPC/E water have been determined using molecular dynamics simulations. Results are compared to the electrostatic energy calculations for the primitive polarization model (PPM) of hydrated cations describing the ion hydration shell as a dielectric sphere of low permittivity (Gavryushov, S.; Linse, P. J. Phys. Chem. B 2003, 107, 7135). Parameters of the ion dielectric sphere and radius of the macroion/water dielectric boundary were extracted by means of this comparison to approximate the short-range repulsion of ions near the interface. To explore the counterion distributions around a simplified model of DNA, the obtained PPM parameters for Na+ and Ca2+ have been substituted into the modified Poisson-Boltzmann (MPB) equations derived for the PPM and named the epsilon-MPB (epsilon-MPB) theory. epsilon-MPB results for DNA suggest that such polarization effects are important in the case of 2:1 electrolyte and highly charged macromolecules. The three-dimensional implementation of the epsilon-MPB theory was also applied to calculation of the energies of interaction between two parallel macromolecules of DNA in solutions of NaCl and CaCl2. Being compared to results of MPB calculations without the ion polarization effects, it suggests that the ion hydration shell polarization and inhomogeneous solvent permittivity might be essential factors in the experimentally known hydration forces acting between charged macromolecules and bilayers at separations of less than 20 A between their surfaces.

  18. Ion-Pair Halogen Bonds in 2-Halo-Functionalized Imidazolium Chloride Receptors: Substituent and Solvent Effects.

    Science.gov (United States)

    Nunes, Rafael; Costa, Paulo J

    2017-01-03

    The interaction of 2-halo-functionalized imidazolium derivatives (n-X(+) ; X=Cl, Br, I) with a chloride anion through ion-pair halogen bonds (n-X⋅Cl) was studied by means of DFT and ab initio calculations. A method benchmark was performed on 2-bromo-1H-imidazol-3-ium in association with chloride (1-Br⋅Cl); MP2 yielded the best results when compared with CCSD(T) calculations. The interaction energies (ΔE) in the gas phase are high and, although the electrostatic interaction is strong owing to the ion-pair nature of the system, large X⋅⋅⋅Cl(-) Wiberg bond orders and contributions from charge transfer (nCl- →σ*C-X) are obtained. These values drop considerably in chloroform and water; this shows that solvent plays a role in modulating the interaction and that gas-phase calculations are particularly unrealistic for experimental applications. The introduction of electron-withdrawing groups in the 4,5-positions of the imidazolium (e.g., -NO2 , -F) increases the halogen-bond strength in both the gas phase and solvent, including water. The effect of the substituents on the 1,3-positions (N-H groups) also depends on the solvent. The variation of ΔE can be predicted through a two-parameter linear regression that optimizes the weights of charge-transfer and electrostatic interactions, which are different in vacuum and in solvent (chloroform and water). These results could be used in the rational design of efficient chloride receptors based on halogen bonds that work in solution, in particular, in an aqueous environment.

  19. Influence of a Neighboring Charged Group on Hydrophobic Hydration Shell Structure.

    Science.gov (United States)

    Davis, Joel G; Zukowski, Samual R; Rankin, Blake M; Ben-Amotz, Dor

    2015-07-23

    Raman multivariate curve resolution (Raman-MCR), as well as quantum and classical calculations, are used to probe water structural changes in the hydration shells of carboxylic acids and tetraalkyl ammonium ions with various aliphatic chain lengths. The results reveal that water molecules in the hydration shell around the hydrophobic chains undergo a temperature and chain length dependent structural transformation resembling that previously observed in aqueous solutions of n-alcohols. Deprotonation of the carboxylic acid headgroup (at pH ∼ 7) is found to suppress the onset of the hydration-shell structural transformation around the nearest aliphatic methylene group. Tetraalkyl ammonium cations are found to more strongly suppress the water structural transformation, perhaps reflecting the greater intramolecular charge delocalization and suppression of dangling OH defects in water's tetrahedral H-bond network. The observed coupling between ionic and hydrophobic groups, as well as the associated charge asymmetry, may influence the hydrophobicity of proteins and other materials.

  20. Localization of Fatty Acyl and Double Bond Positions in Phosphatidylcholines Using a Dual Stage CID Fragmentation Coupled with Ion Mobility Mass Spectrometry

    NARCIS (Netherlands)

    Castro-Perez, J.; Roddy, T.P.; Nibbering, N.M.M.; Shah, V.; McLaren, D.G.; Previs, S.; Attygalle, A.B.; Herath, K.; Chen, Z.; Wang, S.P.; Mitnaul, L.; Hubbard, B.K.; Vreeken, R.J.; Johns, D.G.; Hankemeier, Th.

    2011-01-01

    (+) was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium

  1. 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)

  2. 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.

  3. Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs complexes with 4-aminophenylarsonic acid

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2017-02-01

    Full Text Available The structures of the alkali metal (K, Rb and Cs complex salts with 4-aminophenylarsonic acid (p-arsanilic acid manifest an isotypic series with the general formula [M2(C6H7AsNO32(H2O3], with M = K {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO32(H2O3], (I}, Rb {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO32(H2O3], (II}, and Cs {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO32(H2O3], (III}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water molecule, with the two hydrogen p-arsanilate ligands and the second water molecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I to eight-coordinate in both (II and (III, with overall M—O bond-length ranges of 2.694 (5–3.009 (7 (K, 2.818 (4–3.246 (4 (Rb and 2.961 (9–3.400 (10 Å (Cs. The additional three bonds in (II and (III are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100 are generated through a number of bridging bonds involving the water molecules (including hydrogen-bonding interactions, as well as through the arsanilate O atoms. These layers are linked across [100] through amine N—H...O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.

  4. Production of an ion-exchange membrane-catalytic electrode bonded material for electrolytic cells

    Science.gov (United States)

    Takenaka, H.; Torikai, E.

    1986-01-01

    A good bond is achieved by placing a metal salt in solution on one side of a membrane and a reducing agent on the other side so that the reducing agent penetrates the membrane and reduces the metal. Thus, a solution containing Pt, Rh, etc., is placed on one side of the membrane and a reducing agent such as NaBH, is placed on the other side. The bonded metal layer obtained is superior in catalytic activity and is suitable as an electrode in a cell such as for solid polymer electrolyte water electrolysis.

  5. 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.

  6. Ion channel stability and hydrogen bonding. Molecular modelling of channels formed by synthetic alamethicin analogues.

    Science.gov (United States)

    Breed, J; Kerr, I D; Molle, G; Duclohier, H; Sansom, M S

    1997-12-04

    Several analogues of the channel-forming peptaibol alamethicin have been demonstrated to exhibit faster switching between channel substates than does unmodified alamethicin. Molecular modelling studies are used to explore the possible molecular basis of these differences. Models of channels formed by alamethicin analogues were generated by restrained molecular dynamics in vacuo and refined by short molecular dynamics simulations with water molecules within and at either mouth of the channel. A decrease in backbone solvation was found to correlate with a decrease in open channel stability between alamethicin and an analogue in which all alpha-amino-isobutyric acid residues of alamethicin were replaced by leucine. A decrease in the extent of hydrogen-bonding at residue 7 correlates with lower open channel stabilities of analogues in which the glutamine at position 7 was replaced by smaller polar sidechains. These two observations indicate the importance of alamethicin/water H-bonds in stabilizing the open channel.

  7. Improved methods for Feynman path integral calculations of vibrational-rotational free energies and application to isotopic fractionation of hydrated chloride ions.

    Science.gov (United States)

    Mielke, Steven L; Truhlar, Donald G

    2009-04-23

    We present two enhancements to our methods for calculating vibrational-rotational free energies by Feynman path integrals, namely, a sequential sectioning scheme for efficiently generating random free-particle paths and a stratified sampling scheme that uses the energy of the path centroids. These improved methods are used with three interaction potentials to calculate equilibrium constants for the fractionation behavior of Cl(-) hydration in the presence of a gas-phase mixture of H(2)O, D(2)O, and HDO. Ion cyclotron resonance experiments indicate that the equilibrium constant, K(eq), for the reaction Cl(H(2)O)(-) + D(2)O right harpoon over left harpoon Cl(D(2)O)(-) + H(2)O is 0.76, whereas the three theoretical predictions are 0.946, 0.979, and 1.20. Similarly, the experimental K(eq) for the Cl(H(2)O)(-) + HDO right harpoon over left harpoon Cl(HDO)(-) + H(2)O reaction is 0.64 as compared to theoretical values of 0.972, 0.998, and 1.10. Although Cl(H(2)O)(-) has a large degree of anharmonicity, K(eq) values calculated with the harmonic oscillator rigid rotator (HORR) approximation agree with the accurate treatment to within better than 2% in all cases. Results of a variety of electronic structure calculations, including coupled cluster and multireference configuration interaction calculations, with either the HORR approximation or with anharmonicity estimated via second-order vibrational perturbation theory, all agree well with the equilibrium constants obtained from the analytical surfaces.

  8. Conductivity Changes Of Conducting Polymers With Electro-statically Bonded Counter-ions For Organic Memories

    Science.gov (United States)

    Sim, R.; Chan, M. Y.; ASW, Wong; Lee, P. S.

    2011-12-01

    In this work, polyaniline: polystyrene sulfonated (PANI: PSS) spin-coated on ITO glass topped by gold electrodes results in a highly conductive junction which can be open circuited by application of a high current density. The conduction mechanism changes from an ohmic contact to a non-ohmic contact after electrical bias application, and is believed to be due to phase segregation of the electro-statically bonded PANI and PSS at the polymer interface. We believe this phase segregation behavior is applicable for organic resistive memory function.

  9. Modeling the Nanophase Structural Dynamics of Phenylated Sulfonated Poly Ether Ether Ketone Ketone (Ph-SPEEKK) Membranes as a Function of Hydration

    Energy Technology Data Exchange (ETDEWEB)

    Lins, Roberto D.; Devanathan, Ramaswami; Dupuis, Michel

    2011-03-03

    Solvated phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) membranes in the presence of hydronium ions were modeled by classical molecular dynamics simulations. The characterization of the nanophase structure and dynamics of such membranes was carried out as a function of the water content lambda, where lambda is the number of water molecules per sulfonate group, for lambda values of 3.5, 6, 11, 25, and 40. Analysis of pair correlation functions supports the experimental observation of membrane swelling upon hydration as well the increase in water and hydronium ion diffusion with increasing lambda. While the average number of hydrogen bonds between hydronium ions and sulfonate groups is dramatically affected by the hydration level, the average lifetime of the hydrogen bonds remains essentially constant. The membrane is found to be relatively rigid and its overall flexibility shows little dependence on water content. Compared to Nafion, water and ion diffusion coefficients are considerably smaller at lower hydration levels and room temperature. However, at higher lambda values of 25 and 40 these coefficients are comparable to those in Nafion at a lambda value of 16. This study also shows that water diffusion in Ph-SPEEKK membranes at low hydration levels can be significantly improved by raising the temperature with important implications for proton conductivity.

  10. 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).

  11. Effect of lead ion on the hydration of compound phosphate based magnesium phosphate cement%铅离子对复合磷酸盐磷酸镁水泥水化硬化特性的影响∗

    Institute of Scientific and Technical Information of China (English)

    石军兵; 赖振宇; 卢忠远; 黄陈程; 廖其龙

    2015-01-01

    In this paper,the effect of lead ion on the hydration of compound phosphate based magnesium phos-phate cement and its leaching properties was studied.The results show that the compressive strength of com-pound phosphate based magnesium phosphate cement decrease with the increase of lead ion content.High con-tent of lead ion has no significant effect on the setting time of magnesium phosphate cement.During the hydra-tion of compound phosphate based magnesium phosphate cement,lead ion has no significant effect on the pH of the system,but the hydration exothermic peak is delayed by lead ion adding.The lead ion also reduced the amount of hydration heat and affected the degree of crystallization of the main hydration products.In the late hydration reaction of composite magnesium phosphate cement,when the content of lead nitrate is 10% or more the obvious Pb2 P2 O7 diffraction peak can be found.The leaching toxicity of lead ion is 43μg/L and it is lower than the national standard.%研究了铅离子对复合磷酸盐磷酸镁水泥水化硬化特性的影响及其在复合磷酸盐磷酸镁水泥中的稳定性。实验结果表明,复合磷酸盐磷酸镁水泥抗压强度随着铅离子掺量的增加而降低,其中硝酸铅掺量达到10%时,复合磷酸盐磷酸镁水泥的各个龄期的抗压强度发生明显下降。铅离子对复合磷酸盐磷酸镁水泥凝结时间没有明显影响。在复合磷酸盐磷酸镁水泥水化过程中,铅离子对水泥体系的 pH 值影响不大,但能够造成水泥水化放热峰出现的时间延迟,水化放热的总量减少并影响主要水化产物的结晶程度。在复合磷酸盐磷酸镁水泥水化反应后期,当硝酸铅掺量达到10%以上时,在水化产物中出现了较为明显的 Pb2 P2 O7的衍射峰。复合磷酸盐磷酸镁水泥固化铅离子的浸出毒性试验结果(43μg/L)远低于国家标准要求(5 mg/L)。

  12. Critical Properties of the Bond-Diluted Mixed Transverse Ising Spin System with Single-Ion Anisotropy

    Institute of Scientific and Technical Information of China (English)

    YAN ShiLei; DENG LingLing; YANG ChuanZhang

    2001-01-01

    The critical properties of the bond-diluted mixed spin-1/2 and spin-1 transverse Ising system with singleion anisotropy are investigated by means of the effective field theory with correlations. Particular emphasis is given to the square lattice for which phase diagrams are obtained. If transverse field varies in the certain ranges we find that the tricritical point is obtained for the value of the bond concentration in a restricted region. We also observe that the reentrant phase transition may occur in the present system if single-ion anisotropy parameter is not large and if transverse field is small. On the other hand, for certain values of the system parameters, new induced magnetic ordering can be obtained. We find a number of interesting phenomena that are not predicted by previous literatures. The influence of the transverse field on the behaviours of the reentrant phase transition and induced magnetic ordering is discussed. A detailed description of the phase transition is presented.``

  13. Role of hydrogen bonding in ligand interaction with the N-methyl-D-aspartate receptor ion channel

    Energy Technology Data Exchange (ETDEWEB)

    Leeson, P.D.; Carling, R.W.; James, K.; Smith, J.D.; Moore, K.W.; Wong, E.H.; Baker, R. (Merck Sharp Laboratory, Harlow, Essex (England))

    1990-05-01

    Displacement of (3H)MK-801 (dizocilpine, 1) binding to rat brain membranes has been used to evaluate the affinities of novel dibenzocycloalkenimines related to 1 for the ion channel binding site (also known as the phencyclidine or PCP receptor) on the N-methyl-D-aspartate (NMDA) subtype of excitory amino acid receptor. In common with many other agents having actions in the central nervous system, these compounds contain a hydrophobic aromatic moiety and a basic nitrogen atom. The conformational rigidity of these ligands provides a unique opportunity to evaluate the importance of specific geometrical properties that influence active-site recognition, in particular the role of the nitrogen atom in hydrogen-bonding interactions. The relative affinities (IC50s) of hydrocarbon-substituted analogues of 1 and ring homologated cyclooctenimines illustrate the importance of size-limited hydrophobic binding of both aryl rings and of the quaternary C-5 methyl group. Analysis of the binding of a series of the 10 available structurally rigid dibenzoazabicyclo(x.y.z)alkanes, by using molecular modeling techniques, uncovered a highly significant correlation between affinity and a proposed ligand-active site hydrogen bonding vector (r = 0.950, p less than 0.001). These results are used to generate a pharmacophore of the MK-801 recognition site/PCP receptor, which accounts for the binding of all of the known ligands.

  14. Localization of fatty acyl and double bond positions in phosphatidylcholines using a dual stage CID fragmentation coupled with ion mobility mass spectrometry.

    Science.gov (United States)

    Castro-Perez, Jose; Roddy, Thomas P; Nibbering, Nico M M; Shah, Vinit; McLaren, David G; Previs, Stephen; Attygalle, Athula B; Herath, Kithsiri; Chen, Zhu; Wang, Sheng-Ping; Mitnaul, Lyndon; Hubbard, Brian K; Vreeken, Rob J; Johns, Douglas G; Hankemeier, Thomas

    2011-09-01

    A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M + Li](+) was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C(15)H(31)CO(+), m/z 239) or 18:1 (9Z) (C(17)H(33)CO(+), m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H(2)C-HC = CH-CH = CH(2)). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of (13)C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.

  15. Facile Synthesis of Layer Structured GeP3/C with Stable Chemical Bonding for Enhanced Lithium-Ion Storage

    Science.gov (United States)

    Qi, Wen; Zhao, Haihua; Wu, Ying; Zeng, Hong; Tao, Tao; Chen, Chao; Kuang, Chunjiang; Zhou, Shaoxiong; Huang, Yunhui

    2017-01-01

    Recently, metal phosphides have been investigated as potential anode materials because of higher specific capacity compared with those of carbonaceous materials. However, the rapid capacity fade upon cycling leads to poor durability and short cycle life, which cannot meet the need of lithium-ion batteries with high energy density. Herein, we report a layer-structured GeP3/C nanocomposite anode material with high performance prepared by a facial and large-scale ball milling method via in-situ mechanical reaction. The P-O-C bonds are formed in the composite, leading to close contact between GeP3 and carbon. As a result, the GeP3/C anode displays excellent lithium storage performance with a high reversible capacity up to 1109 mA h g−1 after 130 cycles at a current density of 0.1 A g−1. Even at high current densities of 2 and 5 A g−1, the reversible capacities are still as high as 590 and 425 mA h g−1, respectively. This suggests that the GeP3/C composite is promising to achieve high-energy lithium-ion batteries and the mechanical milling is an efficient method to fabricate such composite electrode materials especially for large-scale application. PMID:28240247

  16. Poly(ethylene oxide)-bonded stationary phase for separation of inorganic anions in capillary ion chromatography.

    Science.gov (United States)

    Linda, Roza; Lim, Lee Wah; Takeuchi, Toyohide

    2013-06-14

    A tosylated-poly(ethylene oxide) (PEO) reagent was reacted with primary amino groups of an aminopropylsilica packing material (TSKgel NH2-60) in acetonitrile to form PEO-bonded stationary phase. The reaction was a single and simple step reaction. The prepared stationary phase was able to separate inorganic anions. The retention behavior of six common inorganic anions on the prepared stationary phase was examined under various eluent conditions in order to clarify its separation/retention mechanism. The elution order of the tested anions was iodate, bromate, bromide, nitrate, iodide, and thiocyanate, which was similar as observed in common ion chromatography. The retention of inorganic anions could be manipulated by ion exchange interaction which is expected that the eluent cation is coordinated among the PEO chains and it works as the anion-exchange site. Cations and anions of the eluent therefore affected the retention of sample anions. We demonstrated that the retention of the analyte anions decreased with increasing eluent concentration. The repeatability of retention time for the six anions was satisfactory on this column with relative standard deviation values from 1.1 to 4.3% when 10mM sodium chloride was used as the eluent. Compared with the unmodified TSKgel NH2-60, the prepared stationary phase retained inorganic anions more strongly and the selectivity was also improved. The present stationary phase was applied for the determination of inorganic anions contained in various water samples.

  17. 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.

  18. 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.

  19. Erratum : Critical Properties of Spin-1 Antiferromagnetic Heisenberg Chains with Bond Alternation and Uniaxial Single-Ion-Type Anisotropy (vol 69, pg 237, 2000)

    OpenAIRE

    飛田, 和男

    2008-01-01

    Original Paper :Critical Properties of Spin-1 Antiferromagnetic Heisenberg Chains with Bond Alternation and Uniaxial Single-Ion-Type AnisotropyWei Chen, Kazuo Hida and Bryan Clifford Sanctuary Journal of the Physical Society of Japan 69 (2000) pp.237-241

  20. Clathrate hydrates in nature.

    Science.gov (United States)

    Hester, Keith C; Brewer, Peter G

    2009-01-01

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

  1. 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.

  2. Ion mobility mass spectrometry as a potential tool to assign disulfide bonds arrangements in peptides with multiple disulfide bridges.

    Science.gov (United States)

    Echterbille, Julien; Quinton, Loïc; Gilles, Nicolas; De Pauw, Edwin

    2013-05-07

    Disulfide bridges play a major role in defining the structural properties of peptides and proteins. However, the determination of the cysteine pairing is still challenging. Peptide sequences are usually achieved using tandem mass spectrometry (MS/MS) spectra of the totally reduced unfolded species, but the cysteine pairing information is lost. On the other hand, MS/MS experiments performed on native folded species show complex spectra composed of nonclassical ions. MS/MS alone does not allow either the cysteine pairing or the full sequence of an unknown peptide to be determined. The major goal of this work is to set up a strategy for the full structural characterization of peptides including disulfide bridges annotation in the sequence. This strategy was developed by combining ion mobility spectrometry (IMS) and collision-induced dissociation (CID). It is assumed that the opening of one S-S bridge in a peptide leads to a structural evolution which results in a modification of IMS drift time. In the presence of multiple S-S bridges, the shift in arrival time will depend on which disulfide(s) has (have) been reduced and on the shape adopted by the generated species. Due to specific fragmentations observed for each species, CID experiments performed after the mobility separation could provide not only information on peptide sequence but also on the localization of the disulfide bridges. To achieve this goal, synthetic peptides containing two disulfides were studied. The openings of the bridges were carried out following different experimental conditions such as reduction, reduction/alkylation, or oxidation. Due to disulfide scrambling highlighted with the reduction approaches, oxidation of S-S bonds into cysteic acids appeared to be the best strategy. Cysteine connectivity was then unambiguously determined for the two peptides, without any disulfide scrambling interference.

  3. Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

    2016-12-29

    The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometry of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.

  4. The solid phase extraction of some metal ions using palladium nanoparticles attached to silica gel chemically bonded by silica-bonded N-propylmorpholine as new sorbent prior to their determination by flame atomic absorption spectroscopy.

    Science.gov (United States)

    Ghaedi, M; Rezakhani, M; Khodadoust, S; Niknam, K; Soylak, M

    2012-01-01

    In this research at first palladium nanoparticle attached to a new chemically bonded silica gel has been synthesized and has been characterized with different techniques such as X-ray diffraction (XRD), fourier transform infrared (FT-IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Then, this new sorbent (chemically modified silica gel with N-propylmorpholine (PNP-SBNPM)) was efficiently used for preconcentration of some metal ions in various food samples. The influence of effective variables including mass of sorbent, flow rate, pH of sample solutions and condition of eluent such as volume, type and concentration on the recoveries of understudy metal ions were investigated. Following the optimization of variables, the interfering effects of some foreign ions on the preconcentration and determination of the investigated metal ions described. At optimum values of variables, all investigated metal ions were efficiently recovered with efficiency more than 95%, relative standard deviation (RSD) between 2.4 and 2.8, and detection limit in the range of 1.4-2.7 ng mL⁻¹. The present method is simple and rapidly applicable for the determination of the understudied metal ions (ng mL⁻¹) in different natural food samples.

  5. The Solid Phase Extraction of Some Metal Ions Using Palladium Nanoparticles Attached to Silica Gel Chemically Bonded by Silica-Bonded N-Propylmorpholine as New Sorbent prior to Their Determination by Flame Atomic Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    M. Ghaedi

    2012-01-01

    Full Text Available In this research at first palladium nanoparticle attached to a new chemically bonded silica gel has been synthesized and has been characterized with different techniques such as X-ray diffraction (XRD, fourier transform infrared (FT-IR, transmission electron microscopy (TEM, and scanning electron microscopy (SEM. Then, this new sorbent (chemically modified silica gel with N-propylmorpholine (PNP-SBNPM was efficiently used for preconcentration of some metal ions in various food samples. The influence of effective variables including mass of sorbent, flow rate, pH of sample solutions and condition of eluent such as volume, type and concentration on the recoveries of understudy metal ions were investigated. Following the optimization of variables, the interfering effects of some foreign ions on the preconcentration and determination of the investigated metal ions described. At optimum values of variables, all investigated metal ions were efficiently recovered with efficiency more than 95%, relative standard deviation (RSD between 2.4 and 2.8, and detection limit in the range of 1.4–2.7 ng mL−1. The present method is simple and rapidly applicable for the determination of the understudied metal ions (ng mL−1 in different natural food samples.

  6. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stamm, A.; Schwing, K.; Gerhards, M., E-mail: gerhards@chemie.uni-kl.de [TU Kaiserslautern, Fachbereich Chemie and Research Center Optimas, Erwin-Schroedinger-Straße 52, D-67663 Kaiserslautern (Germany)

    2014-11-21

    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S{sub 0}) and cationic (D{sub 0}) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC){sub 2} as well as its mono- and dihydrate (7H4MC){sub 2}(H{sub 2}O){sub 1-2} are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction.

  7. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy.

    Science.gov (United States)

    Stamm, A; Schwing, K; Gerhards, M

    2014-11-21

    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S0) and cationic (D0) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC)2 as well as its mono- and dihydrate (7H4MC)2(H2O)1-2 are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction.

  8. Hydration of protein–RNA recognition sites

    Science.gov (United States)

    Barik, Amita; Bahadur, Ranjit Prasad

    2014-01-01

    We investigate the role of water molecules in 89 protein–RNA complexes taken from the Protein Data Bank. Those with tRNA and single-stranded RNA are less hydrated than with duplex or ribosomal proteins. Protein–RNA interfaces are hydrated less than protein–DNA interfaces, but more than protein–protein interfaces. Majority of the waters at protein–RNA interfaces makes multiple H-bonds; however, a fraction do not make any. Those making H-bonds have preferences for the polar groups of RNA than its partner protein. The spatial distribution of waters makes interfaces with ribosomal proteins and single-stranded RNA relatively ‘dry’ than interfaces with tRNA and duplex RNA. In contrast to protein–DNA interfaces, mainly due to the presence of the 2′OH, the ribose in protein–RNA interfaces is hydrated more than the phosphate or the bases. The minor groove in protein–RNA interfaces is hydrated more than the major groove, while in protein–DNA interfaces it is reverse. The strands make the highest number of water-mediated H-bonds per unit interface area followed by the helices and the non-regular structures. The preserved waters at protein–RNA interfaces make higher number of H-bonds than the other waters. Preserved waters contribute toward the affinity in protein–RNA recognition and should be carefully treated while engineering protein–RNA interfaces. PMID:25114050

  9. Ion association in natural brines

    Science.gov (United States)

    Truesdell, A.H.; Jones, B.F.

    1969-01-01

    Natural brines, both surface and subsurface, are highly associated aqueous solutions. Ion complexes in brines may be ion pairs in which the cation remains fully hydrated and the bond between the ions is essentially electrostatic, or coordination complexes in which one or more of the hydration water molecules are replaced by covalent bonds to the anion. Except for Cl-, the major simple ions in natural brines form ion pairs; trace and minor metals in brines form mainly coordination complexes. Limitations of the Debye-Hu??ckel relations for activity coefficients and lack of data on definition and stability of all associated species in concentrated solutions tend to produce underestimates of the degree of ion association, except where the brines contain a very high proportion of Cl-. Data and calculations on closed basin brines of highly varied composition have been coupled with electrode measurements of single-ion activities in an attempt to quantify the degree of ion association. Such data emphasize the role of magnesium complexes. Trace metal contents of closed basin brines are related to complexes formed with major anions. Alkaline sulfo- or chlorocarbonate brines (western Great Basin) carry significant trace metal contents apparently as hydroxides or hydroxy polyions. Neutral high chloride brines (Bonneville Basin) are generally deficient in trace metals. With a knowledge of the thermodynamic properties of a natural water, many possible reactions with other phases (solids, gases, other liquids) may be predicted. A knowledge of these reactions is particularly important in the study of natural brines which may be saturated with many solid phases (silicates, carbonates, sulfates, etc.), which may have a high pH and bring about dissolution of other phases (silica, amphoteric hydroxides, CO2, etc.), and which because of their high density may form relatively stable interfaces with dilute waters. ?? 1969.

  10. Crystal structure of N,N,N',N',N'',N''-hexa-methyl-guanidinium cyanate 1.5-hydrate.

    Science.gov (United States)

    Tiritiris, Ioannis; Kantlehner, Willi

    2015-12-01

    The title hydrated salt, C7H18N3 (+)·OCN(-).1.5H2O, was synthesized starting from N,N,N',N',N'',N''-hexa-methyl-guanidinium chloride by a twofold anion-exchange reaction. The asymmetric unit contains two cations, two cyanate anions and three water mol-ecules. One cation shows orientational disorder and two sets of N-atom positions were found related by a 60° rotation, with an occupancy ratio of 0.852 (6):0.148 (6). The C-N bond lengths in both guanidin-ium ions range from 1.329 (2) to 1.358 (10) Å, indicating double-bond character, pointing towards charge delocalization within the NCN planes. Strong O-H⋯N hydrogen bonds between the crystal water mol-ecules and the cyanate ions and strong O-H⋯O hydrogen bonds between the water mol-ecules are present, resulting in a two-dimensional hydrogen bonded network running parallel to the (001) plane. The hexa-methyl-guanidinium ions are packed in between the layers built up by water mol-ecules and cyanate ions.

  11. Geometric isotope effects on small chloride ion water clusters with path integral molecular dynamics simulations

    Science.gov (United States)

    Wang, Qi; Suzuki, Kimichi; Nagashima, Umpei; Tachikawa, Masanori; Yan, Shiwei

    2013-11-01

    The geometric isotope effects on the structures of hydrated chloride ionic hydrogen bonded clusters are explored by carrying out path integral molecular dynamics simulations. First, an outer shell coordinate is selected to display the rearrangement of single and multi hydration shell cluster structures. Next, to show the competition of intramolecular and intermolecular nuclear quantum effects, the intramolecular OH∗ stretching and intermolecular ion-water wagging motions are studied for single and multi shell structures, respectively. The results indicate that the intermolecular nuclear quantum effects stabilize the ionic hydrogen bonds in single shell structures, while they are destabilized through the competition with intramolecular nuclear quantum effects in multi shell structures. In addition, the correlations between ion-water stretching motion and other cluster vibrational coordinates are discussed. The results indicate that the intermolecular nuclear quantum effects on the cluster structures are strongly related to the cooperation of the water-water hydrogen bond interactions.

  12. Structural and dynamical aspects of the unsymmetric hydration of Sb(III): an ab initio quantum mechanical charge field molecular dynamics simulation.

    Science.gov (United States)

    Lim, Len Herald V; Bhattacharjee, Anirban; Asam, S Sikander; Hofer, Thomas S; Randolf, Bernhard R; Rode, Bernd M

    2010-03-01

    An ab initio quantum mechanical charge field molecular dynamics (QMCF MD) simulation was performed to investigate the behavior of the Sb(3+) ion in aqueous solution. The simulation reveals a significant influence of the residual valence shell electron density on the solvation structure and dynamics of Sb(3+). A strong hemidirectional behavior of the ligand binding pattern is observed for the first hydration shell extending up to the second hydration layer. The apparent domain partitioned structural behavior was probed by solvent reorientational kinetics and three-body distribution functions. The three-dimensional hydration space was conveniently segmented such that domains having different properties were properly resolved. The approach afforded a fair isolation of localized solvent structural and dynamical motifs that Sb(3+) seems to induce to a remarkable degree. Most intriguing is the apparent impact of the lone pair electrons on the second hydration shell, which offers insight into the mechanistic aspects of hydrogen bonding networks in water. Such electronic effects observed in the hydration of Sb(3+) can only be studied by applying a suitable quantum mechanical treatment including first and second hydration shell as provided by the QMCF ansatz.

  13. Antibacterial polyetheretherketone implants immobilized with silver ions based on chelate-bonding ability of inositol phosphate: processing, material characterization, cytotoxicity, and antibacterial properties.

    Science.gov (United States)

    Kakinuma, H; Ishii, K; Ishihama, H; Honda, M; Toyama, Y; Matsumoto, M; Aizawa, M

    2015-01-01

    We developed a novel antibacterial implant by forming a hydroxyapatite (HAp) film on polyetheretherketone (PEEK) substrate, and then immobilizing silver ions (Ag(+) ) on the HAp film based on the chelate-bonding ability of inositol phosphate (IP6). First, the PEEK surface was modified by immersion into concentrated sulfuric acid for 10 min. HAp film was formed on the acid-treated PEEK via the soft-solution process using simulated body fluid (SBF), urea, and urease. After HAp coating, specimens were immersed into IP6 solution, and followed by immersion into silver nitrite solution at concentrations of 0, 0.5, 1, 5 or 10 mM. Ag(+) ions were immobilized on the resulting HAp film due to the chelate-bonding ability of IP6. On cell-culture tests under indirect conditions by Transwell, MC3T3-E1 cells on the specimens derived from the 0.5 and 1 mM Ag(+) solutions showed high relative growth when compared with controls. Furthermore, on evaluation of antibacterial activity in halo test, elution of Ag(+) ions from Ag(+) -immobilized HAp film inhibited bacterial growth. Therefore, the above-mentioned results demonstrated that specimens had both biocompatibility and strong antibacterial activity. The present coating therefore provides bone bonding ability to the implant surface and prevents the formation of biofilms in the early postoperative period.

  14. 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.

  15. Interrelationships among biological activity, disulfide bonds, secondary structure, and metal ion binding for a chemically synthesized 34-amino-acid peptide derived from alpha-fetoprotein.

    Science.gov (United States)

    MacColl, R; Eisele, L E; Stack, R F; Hauer, C; Vakharia, D D; Benno, A; Kelly, W C; Mizejewski, G J

    2001-10-01

    A 34-amino-acid peptide has been chemically synthesized based on a sequence from human alpha-fetoprotein. The purified peptide is active in anti-growth assays when freshly prepared in pH 7.4 buffer at 0.20 g/l, but this peptide slowly becomes inactive. This functional change is proven by mass spectrometry to be triggered by the formation of an intrapeptide disulfide bond between the two cysteine residues on the peptide. Interpeptide cross-linking does not occur. The active and inactive forms of the peptide have almost identical secondary structures as shown by circular dichroism (CD). Zinc ions bind to the active peptide and completely prevents formation of the inactive form. Cobalt(II) ions also bind to the peptide, and the UV-Vis absorption spectrum of the cobalt-peptide complex shows that: (1) a near-UV sulfur-to-metal-ion charge-transfer band had a molar extinction coefficient consistent with two thiolate bonds to Co(II); (2) the lowest-energy visible d-d transition maximum at 659 nm, also, demonstrated that the two cysteine residues are ligands for the metal ion; (3) the d-d molar extinction coefficient showed that the metal ion-ligand complex was in a distorted tetrahedral symmetry. The peptide has two cysteines, and it is speculated that the other two metal ion ligands might be the two histidines. The Zn(II)- and Co(II)-peptide complexes had similar peptide conformations as indicated by their ultraviolet CD spectra, which differed very slightly from that of the free peptide. Surprisingly, the cobalt ions acted in the reverse of the zinc ions in that, instead of stabilizing anti-growth form of the peptide, they catalyzed its loss. Metal ion control of peptide function is a saliently interesting concept. Calcium ions, in the conditions studied, apparently do not bind to the peptide. Trifluoroethanol and temperature (60 degrees C) affected the secondary structure of the peptide, and the peptide was found capable of assuming various conformations in solution

  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. Unconventional hydrogen bonding to organic ions in the gas phase: stepwise association of hydrogen cyanide with the pyridine and pyrimidine radical cations and protonated pyridine.

    Science.gov (United States)

    Hamid, Ahmed M; El-Shall, M Samy; Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G

    2014-08-07

    Equilibrium thermochemical measurements using the ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes for the stepwise association of HCN molecules with the pyridine and pyrimidine radical cations forming the C5H5N(+·)(HCN)n and C4H4N2 (+·)(HCN)n clusters, respectively, with n = 1-4. For comparison, the binding of 1-4 HCN molecules to the protonated pyridine C5H5NH(+)(HCN)n has also been investigated. The binding energies of HCN to the pyridine and pyrimidine radical cations are nearly equal (11.4 and 12.0 kcal/mol, respectively) but weaker than the HCN binding to the protonated pyridine (14.0 kcal/mol). The pyridine and pyrimidine radical cations form unconventional carbon-based ionic hydrogen bonds with HCN (CH(δ+)⋯NCH). Protonated pyridine forms a stronger ionic hydrogen bond with HCN (NH(+)⋯NCH) which can be extended to a linear chain with the clustering of additional HCN molecules (NH(+)⋯NCH··NCH⋯NCH) leading to a rapid decrease in the bond strength as the length of the chain increases. The lowest energy structures of the pyridine and pyrimidine radical cation clusters containing 3-4 HCN molecules show a strong tendency for the internal solvation of the radical cation by the HCN molecules where bifurcated structures involving multiple hydrogen bonding sites with the ring hydrogen atoms are formed. The unconventional H-bonds (CH(δ+)⋯NCH) formed between the pyridine or the pyrimidine radical cations and HCN molecules (11-12 kcal/mol) are stronger than the similar (CH(δ+)⋯NCH) bonds formed between the benzene radical cation and HCN molecules (9 kcal/mol) indicating that the CH(δ+) centers in the pyridine and pyrimidine radical cations have more effective charges than in the benzene radical cation.

  18. Proton-bound cluster ions in ion mobility spectrometry.

    Science.gov (United States)

    Ewing, R G; Eiceman, G A; Stone, J A

    1999-10-28

    Gaseous oxygen and nitrogen bases, both singly and as binary mixtures, have been introduced into ion mobility spectrometers to study the appearance of protonated molecules, and proton-bound dimers and trimers. At ambient temperature it was possible to simultaneously observe, following the introduction of molecule A, comparable intensities of peaks ascribable to the reactant ion (H2O)nH+, the protonated molecule AH+ and AH+ H2O, and the symmetrical proton bound dimer A2H+. Mass spectral identification confirmed the identifications and also showed that the majority of the protonated molecules were hydrated and that the proton-bound dimers were hydrated to a much lesser extent. No significant peaks ascribable to proton-bound trimers were obtained no matter how high the sample concentration. Binary mixtures containing molecules A and B, in some cases gave not only the peaks unique to the individual compounds but also peaks due to asymmetrical proton bound dimers AHB+. Such ions were always present in the spectra of mixtures of oxygen bases but were not observed for several mixtures of oxygen and nitrogen bases. The dimers, which were not observable, notable for their low hydrogen bond strengths, must have decomposed in their passage from the ion source to the detector, i.e. in a time less than approximately 5 ms. When the temperature was lowered to -20 degrees C, trimers, both homogeneous and mixed, were observed with mixtures of alcohols. The importance of hydrogen bond energy, and hence operating temperature, in determining the degree of solvation of the ions that will be observed in an ion mobility spectrometer is stressed. The possibility is discussed that a displacement reaction involving ambient water plays a role in the dissociation.

  19. Origin and character of gaseous hydrocarbons in the hydrate and non-hydrate charged sediments on the Norway - Svalbard margins

    Energy Technology Data Exchange (ETDEWEB)

    Vaular, Espen Nesheim

    2011-05-15

    Gas incubated in clathrate water-structures, stabilizes the hydrogen bonded substance termed gas hydrate. In the marine environment vast amount of carbon is stored as gas hydrates within the temperature and pressure zone these ice-like structures are stable. Natural gas hydrate mapping and characterization is important basic research that brings about critical knowledge concerning various topics. Natural gas hydrates is a vital part of the carbon cycle, it is a potential energy resource (and thereby a potential climate agent) and it is a potential geo-hazard. One of the goals the GANS initiative aimed at exploring, was the hydrate bearing sediment of the Norway -Svalbard margins, to investigate the character and expansion of natural gas hydrates. Part of the investigation was to define how the gas in the hydrated sediment was produced and where it came from. As a result this thesis addresses the matter of light hydrocarbon characterization and origin in two Norwegian hydrate deposits. On cruises to Vestnesa on the Svalbard margin and to Nyegga in the mid-Norwegian margin, samples of hydrate charged and non-hydrate charged sediments were obtained and analyzed. Through compositional and isotopic analyses the origin of the hydrate bound gas in the fluid escape feature G11 at Nyegga was determined. The hydrate incubated methane is microbial produced as well as parts of the hydrate bound ethane. The compositional analysis in both the Nyegga area and at the Vestnesa Ridge points at thermogenic contributions in the sediment interstitials and pore water. The two hydrate bearing margins show large differences in hydrocarbon content and microbial activity in the pockmarks investigated. The gravity cores from the penetrated pockmark at Vestnesa showed low hydrocarbon content and thus suggest ceased or periodic venting. The fluid flow escape features at Nyegga show large variety of flux rates based on ROV monitoring and headspace analysis of the sediment and pore water. The

  20. Proton transfer in hydrogen-bonded network of phenol molecules: intracluster formation of water.

    Science.gov (United States)

    Lengyel, Jozef; Gorejová, Radka; Herman, Zdeněk; Fárník, Michal

    2013-11-07

    Electron ionization and time-of-flight mass spectrometry was used to investigate the phenol clusters (PhOH)n of different size from single molecule to large clusters: in coexpansion with He, the dimers n = 2 are mostly generated; in Ar, large species of n ≥ 10 also occur. Besides [(PhOH)n](+•) cluster ion series, hydrated phenol cluster ions [(PhOH)n·xH2O](+•) with up to x = 3 water molecules and dehydrated phenol clusters [(PhOH)n-H2O](+•) were observed. The hydrated phenol series exhibits minima and maxima that are interpreted as evidence for proton transfer between the hydrogen bonded cluster ions of cyclic structures. The proton transfer leads to a water generation within the clusters, and subsequent elimination of the diphenyl ether molecule(s) from the cluster yields the hydrated phenol cluster ions. Alternatively, a water molecule release yields a series of dehydrated phenols, among which the diphenyl ether ion [PhOPh](+•) (n = 2) constitutes the maximum.

  1. Microstructural investigation of Si-ion-irradiated single crystal 3C-SiC and SA-Tyrannohex SiC fiber-bonded composite at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Chun-Yu [Institute of Nuclear Engineering and Science, National Tsing-Hua University, Hsinchu 30013, Taiwan (China); Tsai, Shuo-Cheng [Department of Engineering and System Science, National Tsing-Hua University, Hsinchu 30013, Taiwan (China); Lin, Hua-Tay [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Chen, Fu-Rong [Department of Engineering and System Science, National Tsing-Hua University, Hsinchu 30013, Taiwan (China); Kai, Ji-Jung, E-mail: ceer0001@gmail.com [Institute of Nuclear Engineering and Science, National Tsing-Hua University, Hsinchu 30013, Taiwan (China); Department of Engineering and System Science, National Tsing-Hua University, Hsinchu 30013, Taiwan (China)

    2013-11-15

    Silicon carbides (SiCs) are considered as one of the promising candidates for structural and core materials used in fusion reactor and high temperature gas-cooled reactor (HTGR) due to its high thermal stability, and good resistance to irradiation and chemical attack. Single crystal 3C-SiC with less intrinsic defects was used to precisely characterize the radiation-induced defects in 3C-SiC. In addition, there are limited discussions related to radiation effect of SA-Tyrannohex fiber-bonded composite at high temperatures. Therefore, in this study, single crystal 3C-SiC thin film and SA-Tyrannohex SiC fiber-bonded composite were irradiated at 1000–1350 °C with 7 MeV Si{sup 3+} ion to simulate the neutron irradiation in reactors. The microstructure of the irradiated SiC was examined by using high resolution transmission electron microscope (HRTEM). In irradiated single crystal 3C-SiC, high resolution images showed that the planar defects were extrinsic stacking faulted loop with changing atomic sequences and intrinsic stacking faulted loop, i.e. vacancy loop. In addition, dislocation loops, voids, and edge dislocations in SA-Tyrannohex SiC fiber-bonded composite after irradiation were investigated. Besides, larger voids (with diameter 10–40 nm) formed in alumina with preferred orientation after irradiation perhaps resulting in degradation of strength of the SA-Tyrannohex SiC fiber-bonded composite.

  2. Charge transfer and polarization for chloride ions bound in ClC transport proteins: natural bond orbital and energy decomposition analyses.

    Science.gov (United States)

    Church, Jonathan; Pezeshki, Soroosh; Davis, Christal; Lin, Hai

    2013-12-19

    ClC transport proteins show a distinct "broken-helix" architecture, in which certain α-helices are oriented with their N-terminal ends pointed toward the binding sites where the chloride ions are held extensively by the backbone amide nitrogen atoms from the helices. To understand the effectiveness of such binding structures, we carried out natural bond orbital analysis and energy decomposition analysis employing truncated active-site model systems for the bound chloride ions along the translocation pore of the EcClC proteins. Our results indicated that the chloride ions are stabilized in such a binding environment by electrostatic, polarization, and charge-transfer interactions with the backbone and a few side chains. Up to ~25% of the formal charges of the chloride ions were found smeared out to the surroundings primarily via charge transfer from the chloride's lone pair n(Cl) orbitals to the protein's antibonding σ*(N-H) or σ*(O-H) orbitals; those σ* orbitals are localized at the polar N-H and O-H bonds in the chloride's first solvation shells formed by the backbone amide groups and the side chains of residues Ser107, Arg147, Glu148, and Tyr445. Polarizations by the chloride ions were dominated by the redistribution of charge densities among the π orbitals and lone pair orbitals of the protein atoms, in particular the atoms of the backbone peptide links and of the side chains of Arg147, Glu148, and Tyr445. The substantial amounts of electron density involved in charge transfer and in polarization were consistent with the large energetic contributions by the two processes revealed by the energy decomposition analysis. The significant polarization and charge-transfer effects may have impacts on the mechanisms and dynamics of the chloride transport by the ClC proteins.

  3. Hydration of Acetylene: A 125th Anniversary

    Science.gov (United States)

    Ponomarev, Dmitry A.; Shevchenko, Sergey M.

    2007-01-01

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

  4. Characterizing Ni(II) hydration in aqueous solution using DFT and EXAFS.

    Science.gov (United States)

    Liu, H Y; Fang, C H; Fang, Y; Zhou, Y Q; Ge, H W; Zhu, F Y; Sun, P C; Miao, J T

    2016-01-01

    In the present work, a detailed investigation of Ni(II) hydration in water solutions was carried out using density functional theory (DFT) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The hydrated characteristics of [Ni(H2O)n](2+) clusters, such as energy parameters, atomic charge distributions, and bond parameters, were explored using DFT with Becke's three-parameter exchange potential and the Lee-Yang-Parr correlation functional (B3LYP). DFT calculations indicated that the preferred structure of the first hydration shell of Ni(II) generally has a coordination number of six and is almost unaffected by the water molecules in the outer solvation shell, whereas the structure of the second solvation shell varies as the hydration proceeds. EXAFS measurements are reported for aqueous NiSO4 and Ni(NO3)2 solutions and the Ni(NO3)2·6H2O crystal. Analysis of the EXAFS spectra of these three systems using a multiparameter fitting procedure showed that, in each case, the first coordination shell consists of six water molecules with a Ni-O coordination distance of 2.04 Å, and that there is no Ni-S or Ni-N coordination in the first shell. There was no evidence of outer-shell SO4(2-) or NO3(-) ions substituting inner-sphere water molecules in NiSO4 and Ni(NO3)2. The characteristics of Ni(II) hydration obtained from DFT calculations agreed well with those obtained experimentally using EXAFS.

  5. Molecular dynamics simulations of triflic acid and triflate ion/water mixtures: a proton conducting electrolytic component in fuel cells.

    Science.gov (United States)

    Sunda, Anurag Prakash; Venkatnathan, Arun

    2011-11-30

    Triflic acid is a functional group of perflourosulfonated polymer electrolyte membranes where the sulfonate group is responsible for proton conduction. However, even at extremely low hydration, triflic acid exists as a triflate ion. In this work, we have developed a force-field for triflic acid and triflate ion by deriving force-field parameters using ab initio calculations and incorporated these parameters with the Optimized Potentials for Liquid Simulations - All Atom (OPLS-AA) force-field. We have employed classical molecular dynamics (MD) simulations with the developed force field to characterize structural and dynamical properties of triflic acid (270-450 K) and triflate ion/water mixtures (300 K). The radial distribution functions (RDFs) show the hydrophobic nature of CF(3) group and presence of strong hydrogen bonding in triflic acid and temperature has an insignificant effect. Results from our MD simulations show that the diffusion of triflic acid increases with temperature. The RDFs from triflate ion/water mixtures shows that increasing hydration causes water molecules to orient around the SO(3)(-) group of triflate ions, solvate the hydronium ions, and other water molecules. The diffusion of triflate ions, hydronium ion, and water molecules shows an increase with hydration. At λ = 1, the diffusion of triflate ion is 30 times lower than the diffusion of triflic acid due to the formation of stable triflate ion-hydronium ion complex. With increasing hydration, water molecules break the stability of triflate ion-hydronium ion complex leading to enhanced diffusion. The RDFs and diffusion coefficients of triflate ions, hydronium ions and water molecules resemble qualitatively the previous findings using per-fluorosulfonated membranes.

  6. Characterization of the primary hydration shell of the hydroxide ion with H2 tagging vibrational spectroscopy of the OH- ṡ (H2O)n=2,3 and OD- ṡ (D2O)n=2,3 clusters

    Science.gov (United States)

    Gorlova, Olga; DePalma, Joseph W.; Wolke, Conrad T.; Brathwaite, Antonio; Odbadrakh, Tuguldur T.; Jordan, Kenneth D.; McCoy, Anne B.; Johnson, Mark A.

    2016-10-01

    We report the isotope-dependent vibrational predissociation spectra of the H2-tagged OH- ṡ (H2O)n=2,3 clusters, from which we determine the strongly coordination-dependent energies of the fundamentals due to the OH groups bound to the ion and the intramolecular bending modes of the water molecules. The HOH bending fundamental is completely missing in the delocalized OH- ṡ (H2O) binary complex but is recovered upon adding the second water molecule, thereby establishing that the dihydrate behaves as a hydroxide ion solvated by two essentially intact water molecules. The energies of the observed OH stretches are in good agreement with the values predicted by Takahashi and co-workers [Phys. Chem. Chem. Phys. 17, 25505 (2015); 15, 114 (2013)] with a theoretical model that treats the strong anharmonicities at play in this system with explicit coupling between the bound OH groups and the O-O stretching modes on an extended potential energy surface. We highlight a surprising similarity between the spectral signatures of OH- ṡ (H2O)3 and the excess proton analogue, H3O+ ṡ (H2O)3, both of which correspond to completed hydration shells around the proton defect. We discuss the origin of the extreme solvatochromicity displayed by both OH- and H+ in the context of the anomalously large "proton polarizabilities" of the H5O2+ and H3O2- binary complexes.

  7. 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.

  8. Folding of RNA tertiary structure: Linkages between backbone phosphates, ions, and water.

    Science.gov (United States)

    Draper, David E

    2013-12-01

    The functional forms of many RNAs have compact architectures. The placement of phosphates within such structures must be influenced not only by the strong electrostatic repulsion between phosphates, but also by networks of interactions between phosphates, water, and mobile ions. This review first explores what has been learned of the basic thermodynamic constraints on these arrangements from studies of hydration and ions in simple DNA molecules, and then gives an overview of what is known about ion and water interactions with RNA structures. A brief survey of RNA crystal structures identifies several interesting architectures in which closely spaced phosphates share hydration shells or phosphates are buried in environments that provide intramolecular hydrogen bonds or site-bound cations. Formation of these structures must require strong coupling between the uptake of ions and release of water.

  9. Hydration Assessment of Athletes

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ KEY POINTS · Although there is no scientific consensus for 1 ) howbest to assess the hydration status of athletes, 2)what criteria to use as acceptable outcome measurements, or 3) the best time to apply practical assessment methods, there are methods that can be used toprovide athletes with useful feedback about their hydration status

  10. Silica chemically bonded N-propyl kriptofix 21 and 22 with immobilized palladium nanoparticles for solid phase extraction and preconcentration of some metal ions.

    Science.gov (United States)

    Ghaedi, Mehrorang; Niknam, Khodabakhsh; Zamani, Saeed; Larki, Habib Abasi; Roosta, Mostafa; Soylak, Mustafa

    2013-08-01

    Silica gel chemically bonded N-propyl kriptofix 21 (SBNPK 21) and N-propyl kriptofix 22 (SBNPK 22) and subsequently immobilized with palladium nanoparticles (PNP-SBNPK 21 and PNP-SBNPK 22) to produce two new complexing lipophilic materials. Then these novel sorbents were applied for the enrichment of some metal ions and their subsequent determination by flame atomic absorption spectroscopy (FAAS). The influences of the variables including pH, amount of solid phase, sample flow rate, eluent conditions and sample volume on the metal ion recoveries were investigated. The detection limit of proposed method was in the interval 2.1-2.3 and 1.7-2.8 ng mL(-1) for PNP-SBNPK 21 and PNP-SBNPK 22 respectively, while the preconcentration factor was 80 for two sorbents. The relative standard deviations of recoveries were between 1.23-1.31 and 1.28-1.49 for PNP-SBNPK 21 and PNP-SBNPK 22 respectively. The method has high sorption-preconcentration efficiency even in the presence of various interfering ions. Due to the reasonable selectivity of proposed method, the relative standard deviation of recoveries of all understudied metal ions in some complicated matrices was less than 3.0%.

  11. Unexpected linear ion trap collision-induced dissociation and Fourier transform ion cyclotron resonance infrared multi-photon dissociation fragmentation of a hydrated C-glycoside of 5-fluorouridine formed by the action of the pseudouridine synthases RluA and TruB.

    Science.gov (United States)

    Miracco, Edward J; Bogdanov, Bogdan; Mueller, Eugene G

    2011-09-30

    As part of the investigation of the pseudouridine synthases, 5-fluorouridine in RNA was employed as a mechanistic probe. The hydrated, rearranged product of 5-fluorouridine was isolated as part of a dinucleotide and found to undergo unusual fragmentation during mass spectrometry, with the facile loss of HNCO from the product pyrimidine ring favored over phosphodiester bond rupture. Although the loss of HNCO from uridine and pseudouridine is well established, the pericyclic process leading to their fragmentation cannot operate with the saturated pyrimidine ring in the product of 5-fluorouridine. Based on the MS(n) results and calculations reported here, a new mechanism relying on the peculiar disposition of the functional groups of the product pyrimidine ring is proposed to account for the unusually facile fragmentation.

  12. Modeling DNA hydration: comparison of calculated and experimental hydration properties of nuclic acid bases.

    Science.gov (United States)

    Poltev, V I; Malenkov, G G; Gonzalez, E J; Teplukhin, A V; Rein, R; Shibata, M; Miller, J H

    1996-02-01

    Hydration properties of individual nucleic acid bases were calculated and compared with the available experimental data. Three sets of classical potential functions (PF) used in simulations of nucleic acid hydration were juxtaposed: (i) the PF developed by Poltev and Malenkov (PM), (ii) the PF of Weiner and Kollman (WK), which together with Jorgensen's TIP3P water model are widely used in the AMBER program, and (iii) OPLS (optimized potentials for liquid simulations) developed by Jorgensen (J). The global minima of interaction energy of single water molecules with all the natural nucleic acid bases correspond to the formation of two water-base hydrogen bonds (water bridging of two hydrophilic atoms of the base). The energy values of these minima calculated via PM potentials are in somewhat better conformity with mass-spectrometric data than the values calculated via WK PF. OPLS gave much weaker water-base interactions for all compounds considered, thus these PF were not used in further computations. Monte Carlo simulations of the hydration of 9-methyladenine, 1-methyluracil and 1-methylthymine were performed in systems with 400 water molecules and periodic boundary conditions. Results of simulations with PM potentials give better agreement with experimental data on hydration energies than WK PF. Computations with PM PF of the hydration energy of keto and enol tautomers of 9-methylguanine can account for the shift in the tautomeric equilibrium of guanine in aqueous media to a dominance of the keto form in spite of nearly equal intrinsic stability of keto and enol tautomers. The results of guanine hydration computations are discussed in relation to mechanisms of base mispairing errors in nucleic acid biosynthesis. The data presented in this paper along with previous results on simulation of hydration shell structures in DNA duplex grooves provide ample evidence for the advantages of PM PF in studies of nucleic-acid hydration.

  13. Silica chemically bonded N-propyl kriptofix 21 and 22 with immobilized palladium nanoparticles for solid phase extraction and preconcentration of some metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Ghaedi, Mehrorang, E-mail: m_ghaedi@mail.yu.ac.ir [Chemistry Department, Yasouj University, Yasouj, 75914-353 (Iran, Islamic Republic of); Niknam, Khodabakhsh, E-mail: niknam@pgu.ac.ir [Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr, 75169 (Iran, Islamic Republic of); Zamani, Saeed; Abasi Larki, Habib [Chemistry Department, Islamic Azad University, Omidiyeh Branch, Omidiyeh (Iran, Islamic Republic of); Roosta, Mostafa [Chemistry Department, Yasouj University, Yasouj, 75914-353 (Iran, Islamic Republic of); Soylak, Mustafa [Chemistry Department, University of Erciyes, 38039 Kayseri (Turkey)

    2013-08-01

    Silica gel chemically bonded N-propyl kriptofix 21 (SBNPK 21) and N-propyl kriptofix 22 (SBNPK 22) and subsequently immobilized with palladium nanoparticles (PNP-SBNPK 21 and PNP-SBNPK 22) to produce two new complexing lipophilic materials. Then these novel sorbents were applied for the enrichment of some metal ions and their subsequent determination by flame atomic absorption spectroscopy (FAAS). The influences of the variables including pH, amount of solid phase, sample flow rate, eluent conditions and sample volume on the metal ion recoveries were investigated. The detection limit of proposed method was in the interval 2.1–2.3 and 1.7–2.8 ng mL{sup −1} for PNP-SBNPK 21 and PNP-SBNPK 22 respectively, while the preconcentration factor was 80 for two sorbents. The relative standard deviations of recoveries were between 1.23–1.31 and 1.28–1.49 for PNP-SBNPK 21 and PNP-SBNPK 22 respectively. The method has high sorption-preconcentration efficiency even in the presence of various interfering ions. Due to the reasonable selectivity of proposed method, the relative standard deviation of recoveries of all understudied metal ions in some complicated matrices was less than 3.0%. Highlights: • Highly selective sorbents for solid phase extraction were synthesized. • The method has been successfully applied for the determination of trace metals ions. • Excellent properties of the sorbent have been illustrated in detail.

  14. FTIR Study of New Chemical Bond Formation in N-doped Carbon under Swift Pb ion Irradiation

    Institute of Scientific and Technical Information of China (English)

    ZhaoZhiming; SongYin; WangZhiguang; JinYunfan; A.Benyagoub; M.Toulemonde

    2003-01-01

    Since Liu and Cohen predicted that the bulk modulus of carbon nitride films with the structure of β-C3N4 are comparable or even surpass those of diamond, intensive experimental efforts have been done to synthesize this new material. Various kinds of synthesized methods have been applied to fabricate carbon nitride films, whereas samples with sufficient amounts of crystallized C3N4 structure or with mechanical properties comparable to the predicted values have not been reported. From the basic of ion-solid interaction, Wang, et al. have proposed a novel method, "low energy ion implantation + swift heavy ion irradiation", for synthesizing compound in atom mixed materials. This method has been used in the present work.

  15. 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.

  16. Experimental investigation of the EPR parameters and molecular orbital bonding coefficients for VO{sup 2+} ion in NaH{sub 2}PO{sub 4}·2H{sub 2}O single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Kalfaoğlu, Emel [Ondokuz Mayıs University, Faculty of Sciences, Department of Physics, 55139 Kurupelit-Samsun (Turkey); Karabulut, Bünyamin, E-mail: bbulut@omu.edu.tr [Ondokuz Mayıs University, Faculty of Engineering, Department of Computer Engineering, 55139 Kurupelit-Samsun (Turkey)

    2016-09-15

    Electron paramagnetic resonance (EPR) spectra of VO{sup 2+} ions in NaH{sub 2}PO{sub 4}·2H{sub 2}O single crystal have been studied. The spin-Hamiltonian parameters and molecular orbital bonding coefficients were calculated. The angular variation of the EPR spectra shows two different VO{sup 2+} complexes. These are located in different chemical environment and each environment contains four magnetically inequivalent VO{sup 2+} sites. The crystal field around VO{sup 2+} ion is approximately axially symmetric since a strong V=O bond distorts the crystal lattice. Spin Hamiltonian parameters and molecular orbital bonding coefficients were calculated from the EPR data and the nature of bonding in the complex was discussed together.

  17. Experimental investigation of the EPR parameters and molecular orbital bonding coefficients for VO2+ ion in NaH2PO4·2H2O single crystals

    Science.gov (United States)

    Kalfaoğlu, Emel; Karabulut, Bünyamin

    2016-09-01

    Electron paramagnetic resonance (EPR) spectra of VO2+ ions in NaH2PO4·2H2O single crystal have been studied. The spin-Hamiltonian parameters and molecular orbital bonding coefficients were calculated. The angular variation of the EPR spectra shows two different VO2+ complexes. These are located in different chemical environment and each environment contains four magnetically inequivalent VO2+ sites. The crystal field around VO2+ ion is approximately axially symmetric since a strong V=O bond distorts the crystal lattice. Spin Hamiltonian parameters and molecular orbital bonding coefficients were calculated from the EPR data and the nature of bonding in the complex was discussed together.

  18. Metal ion-promoted cleavage of nucleoside diphosphosugars: a model for reactions of phosphodiester bonds in carbohydrates.

    Science.gov (United States)

    Dano, Meisa; Elmeranta, Marjukka; Hodgson, David R W; Jaakkola, Juho; Korhonen, Heidi; Mikkola, Satu

    2015-12-01

    Cleavage of five different nucleoside diphosphosugars has been studied in the presence of Cu(2+) and Zn(2+) complexes. The results show that metal ion catalysts promote the cleavage via intramolecular transesterification whenever a neighbouring HO group can adopt a cis-orientation with respect to the phosphate. The HO group attacks the phosphate and two monophosphate products are formed. If such a nucleophile is not available, Cu(2+) complexes are able to promote a nucleophilic attack of an external nucleophile, e.g. a water molecule or metal ion coordinated HO ligand, on phosphate. With the Zn(2+) complex, this was not observed.

  19. Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding

    Science.gov (United States)

    Wittmaack, Klaus

    2013-03-01

    implantation can be evaluated as a function of Cs coverage. The summarised results imply that secondary ions are commonly not formed by charge transfer between an escaping atom and the electronic system of the sample but are already emitted as ions. The probability of ion formation appears to be controlled by the local ionic character of the alkali-target atom bonds, i.e., by the difference in electronegativity between the involved elements as well as by the electron affinity and the ionisation potential of the departing atom. This idea is supported by the finding that Si- yields exhibit the same very strong dependence on Cs coverage as Si+ and O- yields on the oxygen fraction in oxygen loaded Si. Most challenging to theoreticians is the finding that the ionisation probability is independent of the emission velocity of sputtered ions. This phenomenon cannot be rationalised along established routes of thinking. Different concepts need to be explored. An old, somewhat exotic idea takes account of the heavy perturbation created for a very short period of time at the site of ion emission (dynamic randomisation). Molecular dynamics simulations are desirable to clarify the issue. Ultimately it may be possible to describe all phenomena of enhanced or suppressed secondary ion formation, produced either by surface loading with alkali atoms or by enforced surface oxidation, on the basis of a single universal model. There is plenty of room for exciting new studies.

  20. XPS of fast-frozen hematite colloids in NaCl aqueous solutions: I. Evidence for the formation of multiple layers of hydrated sodium and chloride ions induced by the {001} basal plane

    Energy Technology Data Exchange (ETDEWEB)

    Shchukarev, Andrei; Boily, Jean F.; Felmy, Andrew R.

    2007-12-13

    The influence of the {001} basal plane of hematite on the composition of fast-frozen centrifuged wet pastes of hematite prepared at pH 4 and 9 and at ionic strengths of 0, 10 and 100 mM NaCl was investigated by x-ray photoelectron spectroscopy. Two hematite preparations consisted of micrometer-sized platelets with 42% (HEM-1) and 95% (HEM-8) of the surface terminated by the {001} basal plane. A third preparation of spherical shape with no recognizable crystal plane (HEM-control) was used as a control to these experiments. All hematite samples responded to changes in pH and ionic strength, showing that acid/base reactions of surface hydroxyl groups control the composition of the paste. The HEM-1 and HEM-8 sample exhibited divergent properties at the highest ionic strength (100 mM) with energy loss features in the Na 1s and Cl 2p spectra and an important water content. As the spectra were typical of hydrated Na+ and Cl- ions and that the surface concentrations were unusually large, the HEM-1 and HEM-8 samples are proposed to induce the formation of a three-dimensional distribution of these ions in the paste. The sodium, chloride and water content was also correlated to the fraction of the {001} basal plane present in the sample and provided evidence for an approximate stochiometric Na:Cl:H2O ratio of 1:1:2. The {001} basal plane of hematite is consequently proposeD to be the cause of this feature.

  1. Bond breaking, electron pushing, and proton pulling: active and passive roles in the interaction between aqueous ions and water as manifested in the O 1s Auger decay.

    Science.gov (United States)

    Pokapanich, W; Ottosson, N; Svensson, S; Ohrwall, G; Winter, B; Björneholm, O

    2012-01-12

    A core-ionized H(2)O molecule in liquid water primarily relaxes through normal Auger decay, leading to a two-hole final state in which both valence holes are localized on the same water molecule. Electronic coupling to the environment, however, allows for alternative decays resembling Intermolecular Coulombic Decay (ICD), producing final states with one of the holes delocalized on a neighboring water molecule. Here we present an experimental study of such minority processes, which adds to our understanding of dynamic interactions of electronically excited H(2)O molecules with their local surrounding in liquid water and aqueous solution. We show that the solvation of metal-halide salts considerably influences these minority decay channels from the water O 1s(-1) state. By breaking water-water bonds, both the metal cations and halide anions are found to reduce the decay into water-water delocalized states, thus having a ″passive″ effect on the Auger spectrum. The halide anions also play an ″active″ role by opening a new ICD-like decay pathway into water-halide delocalized states. The importance of this contribution increases from F(-) to I(-), which we suggest to be caused by a directional polarization of the halide anion toward the core-ionized H(2)O(+) cation in the intermediate state of the Auger process. This increases the electronic overlap between the two centers and makes delocalized decays more probable. We furthermore show that F(-), the smallest and most strongly hydrated of the halides, plays an additional role as proton puller during the core-hole lifetime, resulting in proton dynamics on the low femtosecond time scale. Our results represent a step forward toward a better understanding of how aqueous solutions, when exposed to soft X-rays, channel excess energy. This has implications for several aspects of physical and radiation chemistry, as well as biology.

  2. 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.

  3. 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.

  4. Hydration behaviour of polyhydroxylated fullerenes

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez-Zavala, J G [Departamento de Ciencias Exactas y Tecnologicas, Centro Universitario de Los Lagos, Universidad de Guadalajara, Enrique Diaz de Leon S/N, 47460 Jalisco (Mexico); Barajas-Barraza, R E [Departamento de Matematicas y Fisica, Instituto Tecnologico y de Estudios Superiores de Occidente, Periferico Sur, Manuel Gomez MorIn No 8585, 45604 Jalisco (Mexico); Padilla-Osuna, I; Guirado-Lopez, R A, E-mail: jgrz@culagos.udg.mx, E-mail: ebarajas@iteso.mx, E-mail: ismael@ifisica.uaslp.mx, E-mail: guirado@ifisica.uaslp.mx [Instituto de Fisica ' Manuel Sandoval Vallarta' , Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, 78000 San Luis Potosi (Mexico)

    2011-10-28

    We have performed semi-empirical as well as density functional theory calculations in order to analyse the hydration properties of both bare C{sub 60} and highly hydroxylated C{sub 60}(OH){sub 26} fullerenes. In all of our calculations, a total of 42 and 98 water molecules are always surrounding our here-considered carbon nanostructures. We found different wetting properties as a function of the chemical composition and structure of the OH-molecular over-layer covering the fullerene surface. In the case of bare C{sub 60}, water adsorption reveals that the H{sub 2}O species are not uniformly arranged around the carbon network but rather forms water droplets of different sizes, clearly revealing the hydrophobic nature of the C{sub 60} structure. In contrast, in the polyhydroxylated C{sub 60}(OH){sub 26} fullerenes, the degree of wetting is strongly influenced by the precise location of the hydroxyl groups. We found that different adsorbed configurations for the OH-molecular coating can lead to the formation of partially hydrated or completely covered C{sub 60}(OH){sub 26} compounds, a result that could be used to synthesize fullerene materials with different degrees of wettability. By comparing the relative stability of our hydroxylated structures in both bare and hydrated conditions we obtain that the energy ordering of the C{sub 60}(OH){sub 26} isomers can change in the presence of water. The radial distribution function of our hydrated fullerenes reveals that water near these kinds of surfaces is densely packed. In fact, by counting the number of H{sub 2}O molecules which are adsorbed, by means of hydrogen bonds, to the surface of our more stable C{sub 60}(OH){sub 26} isomer, we found that it varies in the range of 5-10, in good agreement with experiments. Finally, by comparing the calculated optical absorption spectra of various C{sub 60}(OH){sub 26} structures in the presence and absence of water molecules, we note that only slight variations in the position and

  5. Wet hydrate dissolution plant

    OpenAIRE

    Stanković Mirjana S.; Kovačević Branimir T.; Pezo Lato L.

    2003-01-01

    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 ...

  6. 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)

  7. 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

    The penetration and leaching of ionic species in concrete are studied by using a model based on the Nernst-Planck equations. A finite element procedure is used to solve the coupled non-linear governing equations. A numerical example is performed in which the results are compared to measured...... 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...... relevance in terms of standard solubility thermodynamics. On the other hand the presented model is capable of accurately simulate the well documented peak behavior of the chloride profiles and the measured high content of calcium ions in pore solution under conditions when also chlorides is present...

  8. Influence des ions lithium et borate sur l'hydratation de ciments sulfo-alumineux : application au conditionnement de résines échangeuses d'ions boratées

    OpenAIRE

    2015-01-01

    In pressurized water reactors, a solution of boric acid, the pH of which is controlled by the addition of lithium hydroxide, is injected in the primary circuit. Boron acts as a neutron moderator and helps controlling the fission reactions. The primary coolant is purified by flowing through columns of ion exchange resins. These resins are periodically renewed and constitute a low-level radioactive waste. In addition to radionuclides, they mainly contain borate and lithium ions. They are curren...

  9. An Effective Hamiltonian Molecular Orbital-Valence Bond (MOVB) Approach for Chemical Reactions Applied to the Nucleophilic Substitution Reaction of Hydrosulfide Ion and Chloromethane.

    Science.gov (United States)

    Song, Lingchun; Mo, Yirong; Gao, Jiali

    2009-01-01

    An effective Hamiltonian mixed molecular orbital and valence bond (EH-MOVB) method is described to obtain an accurate potential energy surface for chemical reactions. Building upon previous results on the construction of diabatic and adiabatic potential surfaces using ab initio MOVB theory, we introduce a diabatic-coupling scaling factor to uniformly scale the ab initio off-diagonal matrix element H(12) such that the computed energy of reaction from the EH-MOVB method is in agreement with the target value. The scaling factor is very close to unity, resulting in minimal alteration of the potential energy surface of the original MOVB model. Furthermore, the relative energy between the reactant and product diabatic states in the EH-MOVB method can be improved to match the experimental energy of reaction. A key ingredient in the EH-MOVB theory is that the off-diagonal matrix elements are functions of all degrees of freedom of the system and the overlap matrix is explicitly evaluated. The EH-MOVB method has been applied to the nucleophilic substitution reaction between hydrosulfide and chloromethane to illustrate the methodology and the results were matched to reproduce the results from ab initio valence bond self-consistent valence bond (VBSCF) calculations. The diabatic coupling (the off-diagonal matrix element in the generalized secular equation) has small variations along the minimum energy reaction path in the EH-MOVB model, whereas it shows a maximum value at the transition state and has nearly zero values in the regions of the ion-dipole complexes from VBSCF calculations. The difference in the diabatic coupling stabilization is attributed to the large overlap integral in the computationally efficient MOVB method.

  10. Theoretical and computational studies of hydrophobic and hydrophilic hydration: Towards a molecular description of the hydration of proteins

    Science.gov (United States)

    Garde, Shekhar

    The unique balance of forces underlying biological processes-such as protein folding, aggregation, molecular recognition, and the formation of biological membranes-owes its origin in large part to the surrounding aqueous medium. A quantitative description of fundamental noncovalent interactions, in particular hydrophobic and electrostatic interactions at molecular- scale separations, requires an accurate description of water structure. Thus, the primary goals of our research are to understand the role of water in mediating interactions between molecules and to incorporate this understanding into molecular theories for calculating water-mediated interactions. We have developed a molecular model of hydrophobic interactions that uses methods of information theory to relate hydrophobic effects to the density fluctuations in liquid water. This model provides a quantitative description of small-molecule hydration thermodynamics, as well as insights into the entropies of unfolding globular proteins. For larger molecular solutes, we relate the inhomogeneous water structure in their vicinity to their hydration thermodynamics. We find that the water structure in the vicinity of nonpolar solutes is only locally sensitive to the molecular details of the solute. Water structures predicted using this observation are used to study the association of two neopentane molecules and the conformational equilibria of n-pentane molecule. We have also studied the hydration of a model molecular ionic solute, a tetramethylammonium ion, over a wide range of charge states of the solute. We find that, although the charge dependence of the ion hydration free energy is quadratic, negative ions are more favorably hydrated compared to positive ions. Moreover, this asymmetry of hydration can be reconciled by considering the differences in water organization surrounding positive and negative ions. We have also developed methods for predicting water structure surrounding molecular ions and relating

  11. 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.

  12. SEPARATION OF CHOLESTEROL ESTERS BY SILVER ION CHROMATOGRAPHY USING HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY OR SOLID-PHASE EXTRACTION COLUMNS PACKED WITH A BONDED SULFONIC-ACID PHASE

    NARCIS (Netherlands)

    HOVING, EB; MUSKIET, FAJ; CHRISTIE, WW

    1991-01-01

    Two methods for the separation of cholesterol esters, based on the number of double bonds in their fatty acid moieties, are presented. Silver ion chromatography, usually performed on thin-layer chromatographic plates, was made suitable for high-performance liquid chromatography (HPLC) and solid-phas

  13. 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

  14. Surface characteristics of nanocrystalline apatites: effect of mg surface enrichment on morphology, surface hydration species, and cationic environments.

    Science.gov (United States)

    Bertinetti, Luca; Drouet, Christophe; Combes, Christele; Rey, Christian; Tampieri, Anna; Coluccia, Salvatore; Martra, Gianmario

    2009-05-19

    The incorporation of foreign ions, such as Mg2+, exhibiting a biological activity for bone regeneration is presently considered as a promising route for increasing the bioactivity of bone-engineering scaffolds. In this work, the morphology, structure, and surface hydration of biomimetic nanocrystalline apatites were investigated before and after surface exchange with such Mg2+ ions, by combining chemical alterations (ion exchange, H2O-D2O exchanges) and physical examinations (Fourier transform infrared spectroscopy (FTIR) and high-resolution transmission electron microscopy (HRTEM)). HRTEM data suggested that the Mg2+/Ca2+ exchange process did not affect the morphology and surface topology of the apatite nanocrystals significantly, while a new phase, likely a hydrated calcium and/or magnesium phosphate, was formed in small amount for high Mg concentrations. Near-infrared (NIR) and medium-infrared (MIR) spectroscopies indicated that the samples enriched with Mg2+ were found to retain more water at their surface than the Mg-free sample, both at the level of H2O coordinated to cations and adsorbed in the form of multilayers. Additionally, the H-bonding network in defective subsurface layers was also noticeably modified, indicating that the Mg2+/Ca2+ exchange involved was not limited to the surface. This work is intended to widen the present knowledge on Mg-enriched calcium phosphate-based bioactive materials intended for bone repair applications.

  15. 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...

  16. [Hydration in clinical practice].

    Science.gov (United States)

    Maristany, Cleofé Pérez-Portabella; Segurola Gurruchaga, Hegoi

    2011-01-01

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

  17. Efeito do íon comum na reação de hidratação do MgO Common-ion effect on the MgO hydration reaction

    Directory of Open Access Journals (Sweden)

    L. F. Amaral

    2008-03-01

    equilibrium shifting, known as common-ion effect, on the MgO hydration was evaluated adding several additives (MgCl2, MgSO4, CaCl2 e KOH. Among them, the CaCl2 delayed the reaction, whereas KOH showed opposite behavior. MgCl2 and MgSO4 presented similar results and both effects (reaction delay and speed up, depending of their concentration in suspensions. The possible explanation for these behaviors are discussed in this paper. The results were evaluated considering the kinetics and the thermodynamics of the reaction, and the mechanical damages caused in the materials.

  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 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

  20. 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.

  1. 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.

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

    Science.gov (United States)

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

    2016-09-14

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

  3. Overview: Nucleation of clathrate hydrates

    Science.gov (United States)

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

    2016-12-01

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

  4. A study on gas hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byoung Jae; Jung, Tae Jin; Sunwoo, Don [Korea Institute of Geology Mining and Materials, Taejon (Korea, Republic of)

    1996-12-01

    Sufficient documents were reviewed to understand solid components of water and gaseous hydrocarbon known as gas hydrates, which represent an important potential energy resource of the future. The review provides us with valuable information on crystal structures, kinetics, origin and distribution of gas hydrates. In addition, the review increased our knowledge of exploration and development methods of gas hydrates. Large amounts of methane, the principal component of natural gas, in the form of solid gas hydrate are found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Natural gas hydrates are stable in some environments where the hydrostatic pressure exerted by overlying water column is sufficient for hydrate formation and stability. The required high pressures generally restrict gas hydrate to sediments beneath water of approximately 400 m. Higher sediment temperatures at greater subbottom depths destabilize gas hydrates. Based on the pressure- temperature condition, the outer continental margin of East Sea where water depth is deep enough to form gas hydrate is considered to have high potential of gas hydrate accumulations. (author). 56 refs., tabs., figs.

  5. Selective and reactive hydration of nitriles to amides in water using silver nanoparticles stabilized by organic ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kawai, Koji [Hokkaido University, Division of Materials Science and Engineering, Faculty of Engineering (Japan); Kawakami, Hayato [Miyoshi Oil & Fat Co., Ltd. (Japan); Narushima, Takashi; Yonezawa, Tetsu, E-mail: tetsu@eng.hokudai.ac.jp [Hokkaido University, Division of Materials Science and Engineering, Faculty of Engineering (Japan)

    2015-02-15

    Water-dispersible silver nanoparticles stabilized by silver–carbon covalent bonds were prepared. They exhibited high catalytic activities for the selective hydration of nitriles to amides in water. The activation of a nitrile group by the functional groups of the substrates and the hydrophobic layer on the nanoparticles influenced the catalyzed reaction were confirmed. Alkyl nitriles could also be selectively hydrated.

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

    Science.gov (United States)

    Wincel, Henryk

    2012-09-01

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

  7. The influence of SO2 and NO2 impurities on CO2 gas hydrate formation and stability.

    Science.gov (United States)

    Beeskow-Strauch, Bettina; Schicks, Judith M; Spangenberg, Erik; Erzinger, Jörg

    2011-04-11

    The sequestration of industrially emitted CO(2) in gas hydrate reservoirs has been recently discussed as an option to reduce atmospheric greenhouse gas. This CO(2) contains, despite much effort to clean it, traces of impurities such as SO(2) and NO(2) . Here, we present results of a pilot study on CO(2) hydrates contaminated with 1% SO(2) or 1% NO(2) and show the impact on hydrate formation and stability. Microscopic observations show similar hydrate formation rates, but an increase in hydrate stability in the presence of SO(2). Laser Raman spectroscopy indicates a strong enrichment of SO(2) in the liquid and hydrate phase and its incorporation in both large and small cages of the hydrate lattice. NO(2) is not verifiable by laser Raman spectroscopy, only the presence of nitrate ions could be confirmed. Differential scanning calorimetry analyses show that hydrate stability and dissociation enthalpy of mixed CO(2)-SO(2) hydrates increase, but that only negligible changes arise in the presence of NO(2) impurities. X-ray diffraction data reveal the formation of sI hydrate in all experiments. The conversion rates of ice+gas to hydrate increase in the presence of SO(2), but decrease in the presence of NO(2). After hydrate dissociation, SO(2) and NO(2) dissolved in water and form strong acids.

  8. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  9. Hydration and physical performance.

    Science.gov (United States)

    Murray, Bob

    2007-10-01

    There is a rich scientific literature regarding hydration status and physical function that began in the late 1800s, although the relationship was likely apparent centuries before that. A decrease in body water from normal levels (often referred to as dehydration or hypohydration) provokes changes in cardiovascular, thermoregulatory, metabolic, and central nervous function that become increasingly greater as dehydration worsens. Similarly, performance impairment often reported with modest dehydration (e.g., -2% body mass) is also exacerbated by greater fluid loss. Dehydration during physical activity in the heat provokes greater performance decrements than similar activity in cooler conditions, a difference thought to be due, at least in part, to greater cardiovascular and thermoregulatory strain associated with heat exposure. There is little doubt that performance during prolonged, continuous exercise in the heat is impaired by levels of dehydration >or= -2% body mass, and there is some evidence that lower levels of dehydration can also impair performance even during relatively short-duration, intermittent exercise. Although additional research is needed to more fully understand low-level dehydration's effects on physical performance, one can generalize that when performance is at stake, it is better to be well-hydrated than dehydrated. This generalization holds true in the occupational, military, and sports settings.

  10. Thermodynamic Properties of Hydrogen + Tetra-n-Butyl Ammonium Bromide Semi-Clathrate Hydrate

    Directory of Open Access Journals (Sweden)

    Shunsuke Hashimoto

    2010-01-01

    Full Text Available Thermodynamic stability and hydrogen occupancy on the hydrogen + tetra-n-butyl ammonium bromide semi-clathrate hydrate were investigated by means of Raman spectroscopic and phase equilibrium measurements under the three-phase equilibrium condition. The structure of mixed gas hydrates changes from tetragonal to another structure around 95 MPa and 292 K depending on surrounding hydrogen fugacity. The occupied amount of hydrogen in the semi-clathrate hydrate increases significantly associated with the structural transition. Tetra-n-butyl ammonium bromide semi-clathrate hydrates can absorb hydrogen molecules by a pressure-swing without destroying the hydrogen bonds of hydrate cages at 15 MPa or over.

  11. Effects of water on mortar-brick bond

    NARCIS (Netherlands)

    Groot, C.J.W.P.

    1995-01-01

    The quality of bond in masonry is, to a large extent, a function of the (i) the hydration conditions and (ii) the mortar composition of the mortar-brick interface. For insight into the effects of these parameters on bond performance it is essential to dispose of quantitative information about water

  12. Observation of ice sheet formation on methane and ethane gas hydrates using a scanning confocal microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nagao, J.; Shimomura, N.; Ebinuma, T.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira, Sapporo (Japan). Methane Hydrate Research Lab.

    2008-07-01

    Interest in gas hydrates has increased in recent years due to the discovery of large deposits under the ocean floor and in permafrost regions. Natural gas hydrates, including methane, is expected to become a new energy source and a medium for energy storage and transportation. Gas hydrates consist of an open network of water molecules that are hydrogen-bonded in a similar manner to ice. Gas molecules are interstitially engaged under high pressures and low temperatures. Although the dissociation temperature of methane hydrate under atmospheric pressure is about 193 K, studies have shown that methane hydrate can be stored at atmospheric pressure and 267 K for 2 years. Because of this phenomenon, known as self-preservation, transportation and storage of methane hydrate can occur at temperature conditions milder than those for liquefied methane gas at atmospheric pressure. This study examined the surface changes of methane and ethane hydrates during dissociation using an optical microscope and confocal scanning microscope (CSM). This paper reported on the results when the atmospheric gas pressure was decreased. Ice sheets formed on the surfaces of methane and ethane gas hydrates due to depressurizing dissociation of methane and ethane hydrates when the methane and ethane gas pressures were decreased at designated temperatures. The dissociation of methane gas hydrate below below 237 K resulted in the generation of small ice particles on the hydrate surface. A transparent ice sheet formed on the hydrate surface above 242 K. The thickness of the ice sheet on the methane hydrate surface showed the maximum of ca. 30 {mu}m at 253 K. In the case of ethane hydrates, ice particles and ice sheets formed below 262 and 267 respectively. Since the ice particles and ice sheets were formed by water molecules generated during the gas hydrate dissociation, the mechanism of ice sheet formation depends on the dissociation rate of hydrate, ice particle sintering rate, and water molecule

  13. 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.

  14. 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)

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

    Science.gov (United States)

    Djikaev, Y S; Ruckenstein, E

    2013-11-14

    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.

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

    Science.gov (United States)

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

    2016-08-01

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

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

    Directory of Open Access Journals (Sweden)

    Thomas M. Vlasic

    2016-08-01

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

  18. Single crystal electron paramagnetic resonance spectra of Cu(II) ions in Cu(tyrosine)(2): a study of weak exchange interactions mediated by resonance assisted hydrogen bonds (RAHB).

    Science.gov (United States)

    Paredes-García, Verónica; Santana, Ricardo C; Madrid, Rosa; Baldo, Bianca; Vega, Andrés; Spodine, Evgenia

    2012-09-01

    EPR measurements have been performed on single crystals of [Cu(L-tyrosine)(2)](∞) at 33.8 GHz and at room temperature. The EPR spectra display partially resolved EPR lines for most orientations of the magnetic field in the ab plane, and only one resonance for orientations close to the crystal axes, while only a single line is observed along any direction in the ca and cb crystal planes. This behavior is a result of the selective collapse of the resonances corresponding to the four copper sites in the unit cell produced by the exchange interactions between the copper ions. The magnitudes of the exchange interactions between the copper ions were evaluated from the angular variation of the line width and the collapse of the EPR lines. The value |J(AD)/k(B)|=0.8 K between neighboring copper atoms at 4.942 Å is assigned to a syn-anti equatorial-apical carboxylate bridge with a total bond length of 6.822 Å, while the small value |J(AB)/k(B)|=0.004 K is assigned to a long bridge of 11 atoms with a total bond length of 19.186 Å, that includes one resonance assisted hydrogen bond (RAHB). This finding is discussed in terms of values obtained for similar paths in other model compounds and in proteins.

  19. 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.

  20. 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.

  1. Dependence of the osmotic coefficients and average ionic activity coefficients on hydrophobic hydration in solutions

    Science.gov (United States)

    Sergievskii, V. V.; Rudakov, A. M.

    2016-08-01

    The model that considers the nonideality of aqueous solutions of electrolytes with allowance for independent contributions of hydration of ions of various types and electrostatic interactions was substantiated using the cluster ion model. The empirical parameters in the model equations were found to be the hydrophilic and hydrophobic hydration numbers of ions in the standard state and the dispersion of their distribution over the stoichiometric coefficients. A mathematically adequate description of the concentration dependences of the osmotic coefficients and average ion activity coefficients of electrolytes was given for several systems. The difference in the rate of the decrease in the hydrophilic and hydrophobic hydration numbers of ions leads to extremum concentration dependences of the osmotic coefficients, which were determined by other authors from isopiestic data for many electrolytes and did not find explanation.

  2. 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

  3. Exchange interaction between TCNQ and transition metal ion mediated by hydrogen bonds in [Mn(phen)3](TCNQ)2·H2O and [Co(phen)3](TCNQ)2·H2O

    Science.gov (United States)

    Šoltésová, D.; Vasylets, G.; Čižmár, E.; Botko, M.; Cheranovskii, V.; Starodub, V.; Feher, A.

    2016-12-01

    The magnetic properties, specific heat and EPR spectra of anion-radical salts [Mn(phen)3](TCNQ)2·H2O and [Co(phen)3](TCNQ)2·H2O, in which TCNQ molecules and transition metal ions are not connected by covalent bonds and magnetic interactions are mediated via hydrogen bonds, were investigated. Measurements of the magnetic response were performed down to 1.8 K in magnetic fields up to 7 T. The heat capacity of investigated compounds was measured in temperature range from 0.38 K to 35 K in magnetic fields up to 9 T for [Mn(phen)3](TCNQ)2·H2O and up to 3 T for [Co(phen)3](TCNQ)2·H2O. The EPR spectra of studied samples were investigated for both samples in the temperature range from 2 K to 300 K. Theoretical model of weakly-coupled magnetic units composed of four TCNQ anion radicals and of two transition metal ions was proposed for interpretation of obtained data. The energy of exchange interactions between TCNQ molecules and transition metal ion is important for the description of low-temperature behavior of studied anion-radical salts and was estimated to be in the range of 1.3-1.5 K.

  4. Catalysis of gas hydrates by biosurfactants in seawater-saturated sand/clay

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, R. E.; Kothapalli, C.; Lee, M.S. [Mississippi State University, Swalm School of Chemical Engineering, MS (United States); Woolsey, J. R. [University of Mississippi, Centre of Marine Resources and Environmental Technology, MS (United States)

    2003-10-01

    Large gas hydrate mounds have been photographed in the seabed of the Gulf of Mexico and elsewhere. According to industry experts, the carbon trapped within gas hydrates is two or three times greater than all known crude oil, natural gas and coal reserves in the world. Gas hydrates, which are ice-like solids formed from the hydrogen bonding of water as water temperature is lowered under pressure to entrap a suitable molecular-size gas in cavities of the developing crystal structure, are found below the ocean floor to depths exhibiting temperature and pressure combinations within the appropriate limits. The experiments described in this study attempt to ascertain whether biosurfactant byproducts of microbial activity in seabeds could catalyze gas hydrate formation. Samples of five possible biosurfactants classifications were used in the experiments. Results showed that biosurfactants enhanced hydrate formation rate between 96 per cent and 288 percent, and reduced hydrate induction time 20 per cent to 71 per cent relative to the control. The critical micellar concentration of rhamnolipid/seawater solution was found to be 13 ppm at hydrate-forming conditions. On the basis of these results it was concluded that minimal microbial activity in sea floor sands could achieve the threshold concentration of biosurfactant that would greatly promote hydrate formation. 28 refs., 2 tabs., 4 figs.

  5. 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.

  6. 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.

  7. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  8. Hydrates fighting tools; Des outils de lutte contre les hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    2003-04-01

    Shell Exploration and Production company (SEPCo) is the operator of the 'Popeye' deep offshore field in the Gulf of Mexico. Thanks to the introduction of a low dosing hydrates inhibitor (LDHI) elaborated by Shell Global Solutions, the company has added a 7.5 Gpc extra volume of gas to its recoverable reserves. This new technology avoids the plugging of pipes by hydrates formation. (J.S.)

  9. Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

    Science.gov (United States)

    Uddin, M; Coombe, D

    2014-03-20

    Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to

  10. 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.

  11. Mechanism of gypsum hydration

    Directory of Open Access Journals (Sweden)

    Pacheco, G.

    1991-06-01

    Full Text Available There is an hypothesis that the mechanism o f gypsum hydration and dehydration is performed through two simultaneous phenomena. In this study we try to clear up this phenomenon using chlorides as accelerators or a mixture of ethanol-methanol as retarders to carry out the gypsum setting. Natural Mexican gypsum samples and a hemihydrate prepared in the laboratory are used. The following analytical techniques are used: MO, DRX, DTA, TG and DTG. In agreement with the obtained results, it can be concluded: that colloid formation depends on the action of accelerators or retarders and the crystals are a consequence of the quantity of hemihydrate formed.

    En el mecanismo de hidratación y deshidratación del yeso existe la hipótesis de que éste se efectúa por dos fenómenos simultáneos. Este estudio intenta esclarecer estos fenómenos, empleando: cloruros como aceleradores o mezcla etanol-metanol como retardadores para efectuar el fraguado del yeso. Se emplean muestras de yeso de origen natural mexicano y hemihydrate preparado en laboratorio; se utilizan técnicas analíticas: MO, DRX, DTA, TG y DTG. De acuerdo a los resultados obtenidos se puede deducir: que la formación del coloide depende de la acción de los agentes aceleradores o retardadores y que los cristales son consecuencia de la cantidad de hemihidrato formado.

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

    Science.gov (United States)

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

    2015-11-01

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

  13. Thermodynamic studies of ionic hydration and interactions for amino acid ionic liquids in aqueous solutions at 298.15 K.

    Science.gov (United States)

    Dagade, Dilip H; Madkar, Kavita R; Shinde, Sandeep P; Barge, Seema S

    2013-01-31

    Amino acid ionic liquids are a special class of ionic liquids due to their unique acid-base behavior, biological significance, and applications in different fields such as templates in synthetic chemistry, stabilizers for biological macromolecules, etc. The physicochemical properties of these ionic liquids can easily be altered by making the different combinations of amino acids as anion along with possible cation modification which makes amino acid ionic liquids more suitable to understand the different kinds of molecular and ionic interactions with sufficient depth so that they can provide fruitful information for a molecular level understanding of more complicated biological processes. In this context, volumetric and osmotic coefficient measurements for aqueous solutions containing 1-ethyl-3-methylimidazolium ([Emim]) based amino acid ionic liquids of glycine, alanine, valine, leucine, and isoleucine are reported at 298.15 K. From experimental osmotic coefficient data, mean molal activity coefficients of ionic liquids were estimated and analyzed using the Debye-Hückel and Pitzer models. The hydration numbers of ionic liquids in aqueous solutions were obtained using activity data. Pitzer ion interaction parameters are estimated and compared with other electrolytes reported in the literature. The nonelectrolyte contribution to the aqueous solutions containing ionic liquids was studied by calculating the osmotic second virial coefficient through an application of the McMillan-Mayer theory of solution. It has been found that the second osmotic virial coefficient which includes volume effects correlates linearly with the Pitzer ion interaction parameter estimated independently from osmotic data as well as the hydrophobicity of ionic liquids. The enthalpy-entropy compensation effect, explained using the Starikov-Nordén model of enthalpy-entropy compensation, and partial molar entropy analysis for aqueous [Emim][Gly] solutions are made by using experimental Gibb

  14. Experimental study on geochemical characteristic of methane hydrate formed in porous media

    Institute of Scientific and Technical Information of China (English)

    Qiang Chen; Changling Liu; Yuguang Ye

    2009-01-01

    The natural occurrence of methane hydrates in marine sediments has been intensively studied over the past decades, and geochemical charac-teristic of hydrate is one of the most attractive research fields. In this paper, we discussed the geochemical anomaly during hydrate formation in porous media. By doing so, we also investigated the temperature influence on hydrate formation under isobaric condition. It turns out that sub-cooling is an important factor to dominate hydrate formation. Larger subcooling provides more powerful driving force for hydrate formation. During the geochemical anomaly research, six kinds of ions and the total dissolved salt (TDS) were measured before and after the experiment in different porous media. The result is that all kinds of ionic concentration increased after hydrate formation which can be defined as salting out effect mainly affected by gas consumption. But the variation ratio of different ions is not equal. Ca2+ seems to be the most significantly influenced one, and its variation ratio is up to 80%. Finally, we theoretically made a model to calculate the TDS variation, the result is in good accordance with measured one, especially when gas consumption is large.

  15. [NMF and cosmetology of cutaneous hydration].

    Science.gov (United States)

    Marty, J-P

    2002-01-01

    In the stratum corneum, the water binds to the intracellular hygroscopic and hydrosoluble substances called "natural moisturizing factors" or NMF. These "natural moisturizing factors" contained in the corneocytes are formed during epidermal differentiation and may represent up to 10 p. cent of the corneocyte mass. They are principally amino acids, carboxylic pyrrolidone acid, lactic acid, urea, glucose and mineral ions. Keratinization plays an important part in the formation of NMF that exhibit strong osmotic potential attracting the water molecules. The binding of water to NMF is the static aspect of cutaneous hydration. The second, dynamic, aspect is related to the selective permeability of the stratum corneum and to its lipid barrier properties, the permeability of which depends on the integrity and nature of the inter-corneocyte lipids and their lamellar organization between the cells. In these conditions, hydration cosmetics rely on two concepts that can be isolated or associated: the supply of hydrophilic substances to the stratum corneum, capable of attracting and retaining water (moisturizer) or capable of restoring the barrier in order to restore normal water loss or of protecting it against aggression (occlusive).

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

    Science.gov (United States)

    Shevkunov, S. V.

    2016-09-01

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

  17. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals.

    Science.gov (United States)

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo

    2015-09-18

    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

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

    OpenAIRE

    Lixin Kuang; Yibing Yu; Yunzhong Tu; Ling Zhang; Fulong Ning; Guosheng Jiang; Tianle Liu

    2011-01-01

    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% Na 2 CO 3 , 10% polyethylene glycol, 20% NaCl, 4% SMP-2, 1% ...

  19. 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...

  20. Hydration and rotational diffusion of levoglucosan in aqueous solutions

    Science.gov (United States)

    Corezzi, S.; Sassi, P.; Paolantoni, M.; Comez, L.; Morresi, A.; Fioretto, D.

    2014-05-01

    Extended frequency range depolarized light scattering measurements of water-levoglucosan solutions are reported at different concentrations and temperatures to assess the effect of the presence and distribution of hydroxyl groups on the dynamics of hydration water. The anhydro bridge, reducing from five to three the number of hydroxyl groups with respect to glucose, considerably affects the hydration properties of levoglucosan with respect to those of mono and disaccharides. In particular, we find that the average retardation of water dynamics is ≈3-4, that is lower than ≈5-6 previously found in glucose, fructose, trehalose, and sucrose. Conversely, the average number of retarded water molecules around levoglucosan is 24, almost double that found in water-glucose mixtures. These results suggest that the ability of sugar molecules to form H-bonds through hydroxyl groups with surrounding water, while producing a more effective retardation, it drastically reduces the spatial extent of the perturbation on the H-bond network. In addition, the analysis of the concentration dependence of the hydration number reveals the aptitude of levoglucosan to produce large aggregates in solution. The analysis of shear viscosity and rotational diffusion time suggests a very short lifetime for these aggregates, typically faster than ≈20 ps.

  1. Tetrahydrofuran hydrate decomposition characteristics in porous media

    Science.gov (United States)

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

    2016-12-01

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

  2. 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.

  3. 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.

  4. 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:

  5. Progress of Gas Hydrate Studies in China

    Institute of Scientific and Technical Information of China (English)

    樊栓狮; 汪集旸

    2006-01-01

    A brief overview is given on the gas hydrate-related research activities carried out by Chinese researchers in the past 15 years. The content involves: (1) Historical review. Introducing the gas hydrate research history in China; (2) Gas hydrate research groups in China. There are nearly 20 groups engaged in gas hydrate research now; (3) Present studies.Including fundamental studies, status of the exploration of natural gas hydrate resources in the South China Sea region, and development of hydrate-based new techniques; (4) Future development.

  6. 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...

  7. 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.

  8. Cooperative hydrophobic/hydrophilic interactions in the hydration of dimethyl ether.

    Science.gov (United States)

    Utiramerur, S; Paulaitis, M E

    2010-04-21

    Cooperative interactions in the hydration of dimethyl ether (DME) relative to its purely hydrophobic analog, propane, are analyzed by expressing the free energy of hydration in terms of an "inner-shell" contribution from water molecular packing and chemical association, and an "outer-shell" contribution described by the mean binding energy of the solute to the solution and fluctuations in this binding energy. We find that nonadditive, cooperative interactions associated with strong correlations in the binding energy fluctuations of the methyl groups and ether oxygen play a dominant role in the hydration of DME relative to propane. The electrostatic nature of these interactions is revealed in a multi-Gaussian analysis of hydration substates, which shows that the formation of favorable ether oxygen-water hydrogen bonds is correlated with less favorable methyl group-water interactions, and vice versa. We conclude that the group additive distinction between the hydrophobic hydration of the DME methyl groups and hydrophilic hydration of the ether oxygen is lost in the context of these cooperative interactions. Our results also suggest that the binding energy fluctuations of constituent hydrophobic/hydrophilic groups are more sensitive than local water density fluctuations for characterizing the hydration of heterogeneous interfaces.

  9. 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.)

  10. Vibrational and structural relaxation of hydrated protons in Nafion membranes

    Science.gov (United States)

    Liu, Liyuan; Lotze, Stephan; Bakker, Huib J.

    2017-02-01

    We study the vibrational dynamics of the bending mode at 1730 cm-1 of proton hydration structures in Nafion membranes with polarization-resolved infrared (IR) pump-probe spectroscopy. The bending mode relaxes to an intermediate state with a time constant T1 of 170 ± 30 fs. Subsequently, the dissipated energy equilibrates with Teq of 1.5 ± 0.2 ps. The transient absorption signals show a long-living anisotropy, which indicates that for part of the excited proton hydration clusters the vibrational energy dissipation results in a local structural change, e.g. the breaking of a local hydrogen bond. This structural relaxation relaxes with a time constant of 38 ± 4 ps.

  11. Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

    Science.gov (United States)

    Ke, Haochen; van der Linde, Christian; Lisy, James M.

    2014-06-01

    Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

  12. Chelation ion chromatography of alkaline earth and transition metals a using monolithic silica column with bonded N-hydroxyethyliminodiacetic acid functional groups.

    Science.gov (United States)

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Jones, Phil; Paull, Brett

    2013-02-08

    A commercially available porous silica monolithic column (Onyx Monolithic Si, 100 mm×4.6 mm I.D.) was 'in-column' covalently functionalised with 2-hydroxyethyliminodiacetic acid (HEIDA) groups, and applied to the simultaneous and rapid separation of alkaline earth and transition metal ions, using high-performance chelation ion chromatography (HPCIC). With a 0.3mM dipicolinic acid (DPA) containing eluent, the baseline separation of various common transition and heavy metal ions and the four alkaline earth metal ions could be achieved in under 14 min with a flow rate of just 0.8 mL/min. Detection was achieved using spectrophotometric detection at 540 nm after post-column reaction (PCR) with 4-(2-pyridylazo)-resorcinol (PAR). Significant effects from variation of eluent nature, concentration and temperature upon selectivity and retention were demonstrated with the new monolithic silica chelating phase. Under optimised conditions (0.165 M LiNO(3) eluent, pH 2.5), peak efficiencies of 54,000, 60,000 and 64,000 N/m, for Zn(2+), Mn(2+) and Cd(2+), respectively, were recorded, far exceeding that previously reported for IDA based chelation ion exchange columns.

  13. 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.

  14. 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.

  15. Laser Desorption Supersonic Jet Spectroscopy of Hydrated Tyrosine

    Science.gov (United States)

    Oba, Hikari; Shimozono, Yoko; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Carcabal, Pierre

    2013-06-01

    The structure of tyrosine (tyr) consists of amino-acid chain and phenol, and it has roughly two possible binding sites for water, amino-acid site and phenolic OH site. Investigating how water molecule binds to tyr will give fundamental information for hydrations of peptide and protein. Resonance enhanced multi photon ionization (REMPI) spectrum of tyr-water 1:1 cluster has already been reported by de Vries and co-workers, however, no analysis on the hydrated structures has been reported. In the REMPI spectrum, two clusters of bands are observed; one appears at ˜35600 cm^{-1} energy region which is the almost same with 0-0 transitions of tyr monomer, and another is observed at ˜300 cm^{-1} lower than the former. Based on the electronic transition energy of phenylalanine and the hydrated clusters, the former is expected to be derived from a structure that water binds to amino acid site. On the other hand, it is plausibly predicted that the latter originates from a structure that water binds to phenolic OH group, because the electronic transition of mono hydrated phenol is ˜300 cm^{-1} red-shifted from the monomer. We applied IR dip spectroscopy which can measure conformer selective IR spectra to the tyr-(H_{2}O)_{1} clusters by using laser desorption supersonic jet technique to confirm the assignments. Especially in the phenolic OH bound isomer, it was found that the intra molecular hydrogen bond within amino-acid chain, which is far from the water molecule and cannot interact directly with each other, is strengthened by the hydration. A. Abio-Riziq et al., J. Phys. Chem. A, 115, 6077 (2011). Y. Shimozono, et al., Phys. Chem. Chem. Phys., (2013) DOI: 10.1039/c3cp43573c. T. Ebata et al., Phys. Chem. Chem. Phys., 8, 4783 (2006). T. Watanabe et al., J. Chem. Phys., 105, 408 (1996).

  16. A multistate empirical valence bond model for solvation and transport simulations of OH- in aqueous solutions.

    Science.gov (United States)

    Ufimtsev, Ivan S; Kalinichev, Andrey G; Martinez, Todd J; Kirkpatrick, R James

    2009-11-07

    We describe a new multistate empirical valence bond (MS-EVB) model of OH(-) in aqueous solutions. This model is based on the recently proposed "charged ring" parameterization for the intermolecular interaction of hydroxyl ion with water [Ufimtsev, et al., Chem. Phys. Lett., 2007, 442, 128] and is suitable for classical molecular simulations of OH(-) solvation and transport. The model reproduces the hydration structure of OH(-)(aq) in good agreement with experimental data and the results of ab initio molecular dynamics simulations. It also accurately captures the major structural, energetic, and dynamic aspects of the proton transfer processes involving OH(-) (aq). The model predicts an approximately two-fold increase of the OH(-) mobility due to proton exchange reactions.

  17. Great Market Potential of Hydrazine Hydrate

    Institute of Scientific and Technical Information of China (English)

    Shi Yuying

    2007-01-01

    @@ Stable consumption growth worldwide Hydrazine hydrate is an organic chemical raw material with extensive applications. The world's capacity to produce hydrazine hydrate has reached more than 200 thousand t/atoday (based on 100% hydrazine content).

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

    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; Thorell, Alva; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

    2014-11-15

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  19. 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

    2016-06-01

    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.

  20. Molecular Dynamics Modeling of Hydrated Calcium-Silicate-Hydrate (CSH) Cement Molecular Structure

    Science.gov (United States)

    2014-08-30

    properties of key hydrated cement constituent calcium-silicate-hydrate (CSH) at the molecular, nanometer scale level. Due to complexity, still unknown...public release; distribution is unlimited. Molecular Dynamics Modeling of Hydrated Calcium-Silicate- Hydrate (CSH) Cement Molecular Structure The views... Cement Molecular Structure Report Title Multi-scale modeling of complex material systems requires starting from fundamental building blocks to

  1. Hydration and Thermal Expansion in Anatase Nanoparticles.

    Science.gov (United States)

    Zhu, He; Li, Qiang; Ren, Yang; Fan, Longlong; Chen, Jun; Deng, Jinxia; Xing, Xianran

    2016-08-01

    A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

  2. Hydration and Thermal Expansion in Anatase Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, He [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 China; Li, Qiang [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 China; Ren, Yang [Argonne National Laboratory, X-Ray Science Division, Argonne IL 60439 USA; Fan, Longlong [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 China; Chen, Jun [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 China; Deng, Jinxia [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 China; Xing, Xianran [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 China

    2016-06-06

    A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

  3. Terahertz sensing of corneal hydration.

    Science.gov (United States)

    Singh, Rahul S; Tewari, Priyamvada; Bourges, Jean Louis; Hubschman, Jean Pierre; Bennett, David B; Taylor, Zachary D; Lee, H; Brown, Elliott R; Grundfest, Warren S; Culjat, Martin O

    2010-01-01

    An indicator of ocular health is the hydrodyanmics of the cornea. Many corneal disorders deteriorate sight as they upset the normal hydrodynamics of the cornea. The mechanisms include the loss of endothelial pump function of corneal dystophies, swelling and immune response of corneal graft rejection, and inflammation and edema, which accompany trauma, burn, and irritation events. Due to high sensitivity to changes of water content in materials, a reflective terahertz (300 GHz and 3 THz) imaging system could be an ideal tool to measure the hydration level of the cornea. This paper presents the application of THz technology to visualize the hydration content across ex vivo porcine corneas. The corneas, with a thickness variation from 470 - 940 µm, were successfully imaged using a reflective pulsed THz imaging system, with a maximum SNR of 50 dB. To our knowledge, no prior studies have reported on the use of THz in measuring hydration in corneal tissues or other ocular tissues. These preliminary findings indicate that THz can be used to accurately sense hydration levels in the cornea using a pulsed, reflective THz imaging system.

  4. Hydration kinetics of transgenic soybeans

    Directory of Open Access Journals (Sweden)

    Aline Francielle Fracasso

    2015-01-01

    Full Text Available The kinetic and experimental analyses of the hydration process of transgenic soybeans (BRS 225 RR are provided. The importance of the hydration process consists of the grain texture modifications which favor grinding and extraction of soybeans. The soaking isotherms were obtained for four different temperatures. Results showed that temperature affected transgenic soybeans´ hydration rate and time. Moisture content d.b. of the soybeans increased from 0.12 ± 0.01 kg kg-1 to 1.45 ± 0.19 kg kg-1 during 270 min. of process. Two models were used to fit the kinetic curves: an empirical model developed by Peleg (1988 and a phenomenological one, proposed by Omoto et al. (2009. The two models adequately represented the hydration kinetics. Peleg model was applied to the experimental data and the corresponding parameters were obtained and correlated to temperature. The model by Omoto et al. (2009 showed a better statistical fitting. Although Ks was affected by temperature (Ks = 0.38079 exp (-2289.3 T-1, the equilibrium concentration remained practically unchanged.

  5. Contribution of hydration to protein folding thermodynamics. I. The enthalpy of hydration.

    Science.gov (United States)

    Makhatadze, G I; Privalov, P L

    1993-07-20

    The enthalpy of hydration of polar and non-polar groups upon protein unfolding has been estimated for four globular proteins in the temperature range 5 to 125 degrees C, using structural information on the groups in these proteins exposed to water in the native and unfolded states and volume-corrected calorimetric information on the enthalpy and heat capacity of transfer into water of various model compounds. It has been shown that the enthalpy of hydration of polar groups greatly exceeds the enthalpy of hydration of non-polar groups. At low temperatures both these enthalpies are negative and change in opposite direction with increasing temperature. Subtracting the total enthalpy of hydration of polar and non-polar groups from the calorimetrically determined enthalpy of protein unfolding, the total enthalpy of internal interactions maintaining the native protein structure has been determined. Using thermodynamic information on the sublimation of organic crystals, the total enthalpy was divided into two components: one associated with the interactions between the non-polar groups (van der Waals interaction) and the rest associated with the interactions between polar groups (hydrogen bonding). This made it possible to estimate the overall enthalpies of disruption of contacts between the polar groups with their exposure to water and between the non-polar groups with their exposure to water. It appears that these enthalpies have opposite signs in the temperature range considered and change in opposite directions with increasing temperature. The enthalpy of transfer of non-polar groups from the protein interior into water is negative below 25 degrees C and positive above. The enthalpy of transfer of polar groups from the protein interior into water is positive at low temperatures and becomes negative at higher temperatures. Over the considered temperature range, however, the enthalpy of transfer of non-polar groups dominates. This results in a positive enthalpy of

  6. 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.

  7. 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.

  8. Tetrahydrofuran-promoted clathrate hydrate phase equilibria of CO{sub 2} in aqueous electrolyte solutions

    Energy Technology Data Exchange (ETDEWEB)

    Sabil, K.M.; Roman, V.R. [Delft Univ. of Technology, Delft (Netherlands). Physical Chemistry and Molecular Thermodynamics; Witkamp, G.J.; Peters, C.J. [Delft Univ. of Technology, Delft, (Netherlands). Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering

    2008-07-01

    The phase behavior of a system consisting of carbon dioxide (CO{sub 2}) hydrates is of significant importance for many industrial and natural processes. Carbon dioxide and water are part of natural gas streams and they are also found in oil reservoirs during enhanced oil recovery. Formation of hydrate in these cases may cause problems during production and processing. Alternatively, carbon dioxide hydrate formation may be desirable since it can facilitate separation processes, freezing and refrigeration processes and sequestration of CO{sub 2}. The need for phase equilibrium data of systems, particularly electrolyte solutions containing CO{sub 2} are therefore needed. This paper presented a study that attempted to measure the hydrate equilibrium condition for quaternary system consisting of CO{sub 2}, tetrahydrofuran (THF), an electrolyte and water. The purpose of the study was to examine the competing effect of tetrahydrofuran and an electrolyte on the phase behavior of CO{sub 2} hydrates when both were simultaneously present in a system at hydrate forming condition and to compare the effect of different salts inhibition on tetrahydrofuran-promoted CO{sub 2} hydrate. Six different electrolytes were utilized, including sodium chloride, calcium chloride, magnesium chloride, potassium bromide, sodium fluoride and sodium bromide. It was concluded that the inhibiting effect among the cations increased with increasing charge of the cation and its radius. It was also found that the inhibiting effect of the anions decreased with a decrease on their ion radius. 12 refs., 4 figs.

  9. 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.

  10. A theoretical study on effect of hydrogen bond and molecular-ion interaction on Octogen(HMX) trigger bond%氢键和分子-离子相互作用对奥克托今(HMX)引发键影响的理论研究

    Institute of Scientific and Technical Information of China (English)

    李满; 王艳红; 黄红英; 王建龙; 罗军

    2016-01-01

    To obtain the method of reducing the sensitivity of explosives , we investigated the formation of twelve HMX complexes ( six of them are hydrogen -bond complexes and the other six are molecular -ion complexes ) under three levels, the B3LYP/6-311++G(2df,2p), B3LYP/aug-cc-pVTZ and MP2(full)/6-311++G(2df,2p), based on B3LYP and MP2(full) theory.Changes of the length, the strength and nitro charges of the trigger bond N -NO2 have been carried on the detail consideration.Additionally , the essence of structure and energy variation was revealed based on atoms in moleculars ( AIM) theory.The results indicated that the bond length is shortened , the dissociation energy is enlarged , nitro charge is increased , bond is strengthened , and the sensitivity is reduced.Furthermore , a linear relation ( R2 =0.9984 ) between the bond dissociation en-ergy variations (ΔBDEs) and the two interactions was obtained.%为了寻找能够降低炸药感度的方法,借助B3LYP和MP2(full)理论,在B3LYP/6-311++G(2df,2p)、B3LYP/aug-cc-pVTZ和MP2(full)/6-311++G(2df,2p)三种水平下,分别研究了与HMX形成的12种复合物(六种氢键复合物和六种分子-离子复合物),并对引发键N-NO2键长和强度的变化及硝基电荷的变化等进行了详细的考量,最后借助分子中原子( AIM)理论揭示了结构和能量变化的本质.结果表明,在形成复合物后,引发键键长变短,离解能增大,硝基电荷增多,引发键增强,感度降低,同时引发键离解能的变化(ΔBDEs)与这两种相互作用能呈良好的线性关系(R2=0.9984).

  11. Role of Lanthanide-Ligand bonding in the magnetization relaxation of mononuclear single-ion magnets: A case study on Pyrazole and Carbene ligated LnIII(Ln=Tb, Dy, Ho, Er) complexes

    Indian Academy of Sciences (India)

    TULIKA GUPTA; GUNASEKARAN VELMURUGAN; THAYALAN RAJESHKUMAR; GOPALAN RAJARAMAN

    2016-10-01

    Ab initio CASSCF+RASSI-SO+SINGLE_ANISO and DFT based NBO and QTAIM investigations were carried out on a series of trigonal prismatic M(BcMe)₃ (M = Tb(1), Dy(2), Ho(3), Er(4), [BcMe]⁻ = dihydrobis (methylimidazolyl) borate) and M(BpMe)₃ (M = Tb(1a), Dy(2a), Ho(3a), Er(4a) [BpMe]⁻ = dihydrobis (methypyrazolyl) borate) complexes to ascertain the anisotropic variations of these two ligand field environments and the influence of Lanthanide-ligand bonding on the magnetic anisotropy. Among all the complexes studied, only 1 and 2 show large Ucal (computed energy barrier for magnetization reorientation) values of 256.4 and 268.5 cm⁻¹, respectively and this is in accordance with experiment. Experimentally only frequency dependent χ” tails are observed for complex 1a and our calculation predicts a large Ucalof 229.4 cm⁻¹ for this molecule. Besides these, none of the complexes (3, 4, 2a, 3a and 4a) computed to possess large energy barrier and this is affirmed by the experiments. These observed differences in the magnetic properties are correlated to the Ln-Ligand bonding. Our calculations transpire comparatively improved Single-Ion Magnet (SIM) behaviour for carbene analogues due to the more axially compressed trigonal prismatic ligand environment. Furthermore, our detailed Mulliken charge, spin density, NBO and Wiberg bond analysis implied stronger Ln...H–BH agostic interaction for pyrazole analogues. Further, QTAIM analysis reveals the physical nature of coordination, covalent, and fine details of the agostic interactions in all the eight complexes studied. Quite interestingly, for the first time, using the Laplacian density, we are able to quantify the prolate and oblate nature of the electron clouds in lanthanides and this is expected to have a far reaching outcome beyond the examples studied.

  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. Evaluating the mucoadhesive properties of drug delivery systems based on hydrated thiolated alginate.

    Science.gov (United States)

    Davidovich-Pinhas, Maya; Harari, Offer; Bianco-Peled, Havazelet

    2009-05-21

    Mucoadhesive polymers have been proposed as drug delivery carriers due to their ability to adhere to the mucus layer. A relatively new class of mucoadhesive polymers, termed thiomers, was suggested as an improved carrier capable of creating disulfide covalent bond with the mucus. Since the wet physiological environment is likely to cause any delivery system to adsorb water and arrive hydrated to its target, studying the performance of mucoadhesive systems in their hydrated form is of major importance. Model thiomer, alginate-thiol, were synthesized and characterized the product using Nuclear Magnetic Resonance (NMR), Fourier Transform Infra Red spectroscopy (FTIR). The swelling behavior was determined gravimetrically and found to be affected from the thiolation. Interactions between the alginate-thiol and mucin glycoproteins, which are believed to be an outcome of disulfide bonds, were verified using rheology experiments. Adhesion of hydrated tablets with different cross linking densities to porcine's fresh small intestine tissue were characterized using a Lloyd Tensile Machine. It was shown that the thiolation did not improve the adhesion properties of hydrated tablets. It appears that the benefit achieved by adding thiol group to the polymer in dry tablet form was flawed in hydrated form due to formation of inter-molecular disulfide junctions.

  14. What can quantum chemistry tell us about Pa(V) hydration and hydrolysis?

    Energy Technology Data Exchange (ETDEWEB)

    Siboulet, B. [CEA Marcoule, Lab. de Conception des Architectures Moleculaires (DRCP/SCPS), 30 (France); Marsden, C.J. [Universite P. Sabatier, Lab. de Physique Quantique, CNRS-UMR 5626, 31 - Toulouse (France); Vitorge, P. [CEA Saclay, Lab. de Speciation des Radionucleides et Molecules (UMR 8587DPC/SECR), 91 - Gif-sur-Yvette (France)

    2008-12-15

    Published liquid-liquid extraction studies of Pa(V) were interpreted with aqueous mono-, di- and tri cations. B3LYP DFT is applied here to such cations surrounded by two explicit hydration layers: Linear or tetrahedral geometries are found for the Pa(V) aquo ions. PaO{sub 2}{sup +} is similar to the other AnO{sub 2}{sup +} cations, but has strong apical bonds, resulting from the highly negative O{sub yl} charge, which decreases along the An(V) series. This explains the instability of PaO{sub 2}{sup +} in water, and the differences with the heavier An(V). PaO{sub 2}{sup +} di-protonates to give Pa(OH){sub 2}{sup 3+} and can further di-hydrolyze to give T{sub d}-Pa(OH){sub 4}{sup +}, which might very well be the most stable Pa(V) mono cation. PaOOH{sup 2+} is confirmed to be the Pa(V) aqueous di cation invoked in the literature for pH{<=} 1.4 {+-} 0.7. PaO{sup 3+} is confirmed in sulfate solution, with a bond length close to 180 pm. Pa(OH){sub 2}{sup 3+} cannot be excluded in other conditions. The strong influence of the solvent was not fully taken into account in most previous theoretical studies that focused only on bare or partially solvated PaO{sub 2}{sup +}. Toraishi et al. have studied hydrated Pa(V) and our work confirms this study and its qualitative interpretation. The new tetrahedral Pa(OH){sub 4}{sup +} geometry that is shown here to be important opens the field to further quantum chemical studies of Pa(V) and other f-elements. As a test for the two-shell model approach for Pa(V), fluoride coordination to Pa(V) is studied and compared with published EXAFS data: an excellent fit is obtained with the well-established species PaF{sub 7}{sup 2-}, but most other stoichiometries tested are precluded. (authors)

  15. 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.

  16. 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.

  17. 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...... 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 of large...

  18. 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

    2016-08-16

    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.

  19. 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

    2016-08-01

    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.

  20. Electronic structure and bonding in crystalline peroxides

    Science.gov (United States)

    Königstein, Markus; Sokol, Alexei A.; Catlow, C. Richard A.

    1999-08-01

    Hartree-Fock and density-functional PW91 theories as realized in the CRYSTAL95 code have been applied to investigate the structural and electronic properties of Ba, Sr, and Ca peroxide materials with the calcium carbide crystal structure, results for which are compared with those for the corresponding oxides. Special attention is paid to the stabilization of the peroxide molecular ion O2-2 in the ionic environment provided by the lattice, and to chemical bonding effects. In order to describe the covalent bonding within the O2-2 ion and the polarization of the O- ion in the crystal electrostatic field, it is essential to include an account of the effects of electron correlation. The PW91 density functional has allowed us to reproduce the crystallographic parameters within a 3% error. The chemical bonding within the peroxide molecular ion has a complex nature with a balance between the weak covalent bond of σz type and the strong electrostatic repulsion of the closed-shell electron groups occupying O 2s and O 2px and 2py states. Compression of the peroxide ion in the ionic crystals gives rise to an excessive overlap of the O 2s closed shells of the two O- ions of a peroxide molecular ion O2-2, which in turn determines the antibonding character of the interaction and chemical bonding in the O2-2 molecular ion.

  1. Well log characterization of natural gas hydrates

    Science.gov (United States)

    Collett, Timothy S.; Lee, Myung W.

    2011-01-01

    In the last 25 years we have seen significant advancements in the use of downhole well logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From an early start of using wireline electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells drilled in Arctic permafrost environments to today where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. The most established and well known use of downhole log data in gas hydrate research is the use of electrical resistivity and acoustic velocity data (both compressional- and shear-wave data) to make estimates of gas hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. New downhole logging tools designed to make directionally oriented acoustic and propagation resistivity log measurements have provided the data needed to analyze the acoustic and electrical anisotropic properties of both highly inter-bedded and fracture dominated gas hydrate reservoirs. Advancements in nuclear-magnetic-resonance (NMR) logging and wireline formation testing have also allowed for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids (i.e., free-water along with clay and capillary bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas hydrate reservoir properties (i.e., permeabilities) needed to accurately predict gas production rates for various gas hydrate

  2. Thermal conductivity of hydrate-bearing sediments

    Science.gov (United States)

    Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn

    2009-11-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

  3. Thermal conductivity of hydrate-bearing sediments

    Science.gov (United States)

    Cortes, D.D.; Martin, A.I.; Yun, T.S.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    2009-01-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces. Copyright 2009 by the American Geophysical Union.

  4. 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.

  5. Dielectric relaxation spectroscopy shows a sparingly hydrated interface and low counterion mobility in triflate micelles.

    Science.gov (United States)

    Lima, Filipe S; Chaimovich, Hernan; Cuccovia, Iolanda M; Buchner, Richard

    2013-08-13

    The properties of ionic micelles are affected by the nature of the counterion. Specific ion effects can be dramatic, inducing even shape and phase changes in micellar solutions, transitions apparently related to micellar hydration and counterion binding at the micellar interface. Thus, determining the hydration and dynamics of ions in micellar systems capable of undergoing such transitions is a crucial step in understanding shape and phase changes. For cationic micelles, such transitions are common with large organic anions as counterions. Interestingly, however, phase separation also occurs for dodecyltrimethylammonium triflate (DTATf) micelles in the presence of sodium triflate (NaTf). Specific ion effects for micellar solutions of dodecyltrimethylammonium chloride (DTAC), bromide (DTAB), methanesulfonate (DTAMs), and triflate (DTATf) were studied with dielectric relaxation spectroscopy (DRS), a technique capable of monitoring hydration and counterion dynamics of micellar aggregates. In comparison to DTAB, DTAC, and DTAMs, DTATf micelles were found to be considerably less hydrated and showed reduced counterion mobility at the micellar interface. The obtained DTATf and DTAMs data support the reported central role of the anion's -CF3 moiety with respect to the properties of DTATf micelles. The reduced hydration observed for DTATf micelles was rationalized in terms of the higher packing of this surfactant compared to that of other DTA-based systems. The decreased mobility of Tf(-) anions condensed at the DTATf interface strongly suggests the insertion of Tf(-) in the micellar interface, which is apparently driven by the strong hydrophobicity of -CF3.

  6. 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.

  7. 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.

  8. Role of the hydrophobic and hydrophilic sites in the dynamic crossover of the protein-hydration water

    Science.gov (United States)

    Köhler, Mateus Henrique; Barbosa, Rafael C.; da Silva, Leandro B.; Barbosa, Marcia C.

    2017-02-01

    Molecular dynamics simulations were performed to study the water structure and dynamics in the hydration shell of the globular TS-Kappa protein. The results show that for a wide range of temperatures the diffusion coefficient of water near the protein surface is lower than in bulk. A crossover in the diffusion behavior of hydration water is observed at different temperatures for hydrophilic and hydrophobic vicinities. We have found a correlation between the crossover in the hydrophilic case and the protein dynamical transition. An explanation in terms of the competition between water-water water-protein H-bond formation is provided based on H-bond network analysis.

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

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, Igor L.; Udachin, Konstantin A.; Ratcliffe, Christopher I. [National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1A 0R6 (Canada); Alavi, Saman; Ripmeester, John A., E-mail: John.Ripmeester@nrc-cnrc.gc.ca [National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1A 0R6 (Canada); Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia V6T 1Z3 (Canada)

    2015-02-21

    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)-CO{sub 2} and isobutane-CO{sub 2}, that are predicted to enhance or to diminish guest–host hydrogen bonding interactions as compared to those in pure CO{sub 2} hydrate and we have studied guest dynamics in each using {sup 13}C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO{sub 2} sII hydrate using the combined single crystal X-ray diffraction and {sup 13}C NMR powder pattern data and have performed molecular dynamics-simulation of the CO{sub 2} 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 CO{sub 2} hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO{sub 2} molecules in the THF-CO{sub 2} 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 10

  10. Proton hydration in aqueous solution: Fourier transform infrared studies of HDO spectra

    Science.gov (United States)

    Śmiechowski, Maciej; Stangret, Janusz

    2006-11-01

    This paper attempts to elucidate the number and nature of the hydration spheres around the proton in an aqueous solution. This phenomenon was studied in aqueous solutions of selected acids by means of Fourier transform infrared spectroscopy of semiheavy water (HDO), isotopically diluted in H2O. The quantitative version of difference spectrum procedure was applied for the first time to investigate such systems. It allowed removal of bulk water contribution and separation of the spectra of solute-affected HDO. The obtained spectral data were confronted with ab initio calculated structures of small gas-phase and polarizable continuum model (PCM) solvated aqueous clusters, H+(H2O)n, n =2-8, in order to help in establishing the structural and energetic states of the consecutive hydration spheres of the hydrated proton. This was achieved by comparison of the calculated optimal geometries with the interatomic distances derived from HDO band positions. The structure of proton hydration shells outside the first hydration sphere essentially follows the model structure of other hydrated cations, previously revealed by affected HDO spectra. The first hydration sphere complex in diluted aqueous solutions was identified as an asymmetric variant of the regular Zundel cation [The Hydrogen Bond: Recent Developments in Theory and Experiments, edited by P. Schuster, G. Zundel, and C. Sandorfy (North-Holland, Amsterdam, 1976), Vol. II, p. 683], intermediate between the ideal Zundel and Eigen structures [E. Wicke et al., Z. Phys. Chem. Neue Folge 1, 340 (1954)]. Evidence was found for the existence of strong and short hydrogen bonds, with oxygen-oxygen distance derived from the experimental affected spectra equal 2.435Å on average and in the PCM calculations about 2.41-2.44Å. It was also evidenced for the first time that the proton possesses four well-defined hydration spheres, which were characterized in terms of hydrogen bonds' lengths and arrangements. Additionally, an outer

  11. Extraction of metal ions using chemically modified silica gel covalently bonded with 4,4'-diaminodiphenylether and 4,4'-diaminodiphenylsulfone-salicylaldehyde Schiff bases.

    Science.gov (United States)

    Dey, R K; Jha, Usha; Singh, A C; Samal, S; Ray, Alok R

    2006-08-01

    Two new chelating materials (Si-DDE-o-HB, and Si-DDS-o-HB) were synthesized by modifying the activated silica gel phase with Schiff bases of 4,4'-diaminodiphenylether (DDE)/4,4'-diaminodiphenylsulfone (DDS) and o-hydroxybenzaldehyde (o-HB). The synthesized materials were characterized by FTIR and BET surface area measurement techniques. The extraction of metal ions such as Zn2+, Mn2+ and Cr3+ by the chelating material Si-DDE-o-HB was found to be higher than that by Si-DDS-o-HB. The order of metal sorption was found to be Zn2+ > Mn2+ > Cr3+. The correlation coefficients for Freundlich and Langmuir adsorption isotherms were compared for the sorption of Zn2+ onto the chelating material. The loading and elution of the metal ion solution was examined at optimum pH 7.5 and 0.5 cm3 min-1 flow rate of the solution using a column technique. The preconcentration factor for the elution of Zn2+ using dilute HNO3 was found to be 66.2 with a breakthrough volume of 15 cm3. The data obtained for the preconcentration of Zn2+ by the column technique suggested that the material Si-DDE-o-HB can find industrial applications.

  12. Tri- and tetra-substituted cyclen based lanthanide(III) ion complexes as ribonuclease mimics: a study into the effect of log Ka, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP).

    Science.gov (United States)

    Fanning, Ann-Marie; Plush, Sally E; Gunnlaugsson, Thorfinnur

    2015-05-28

    A series of tetra-substituted 'pseudo' dipeptide ligands of cyclen (1,4,7,10,-tetraazacyclododecane) and a tri-substituted 3'-pyridine ligand of cyclen, and the corresponding lanthanide(III) complexes were synthesised and characterised as metallo-ribonuclease mimics. All complexes were shown to promote hydrolysis of the phosphodiester bond of 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP, τ1/2 = 5.87 × 10(3) h), a well known RNA mimic. The La(III) and Eu(III) tri-substituted 3'-pyridine lanthanide(III) complexes being the most efficient in promoting such hydrolysis at pH 7.4 and at 37 °C; with τ1/2 = 1.67 h for La(III) and 1.74 h for Eu(III). The series was developed to provide the opportunity to investigate the consequences of altering the lanthanide(III) ion, coordination ability and hydrophobicity of a metallo-cavity on the rate of hydrolysis using the model phosphodiester, HPNP, at 37 °C. To further provide information on the role that the log Ka of the metal bound water plays in phosphodiester hydrolysis the protonation constants and the metal ion stability constants of both a tri and tetra-substituted 3'pyridine complex were determined. Our results highlighted several key features for the design of lanthanide(III) ribonucelase mimics; the presence of two metal bound water molecules are vital for pH dependent rate constants for Eu(III) complexes, optimal pH activity approximating physiological pH (∼7.4) may be achieved if the log Ka values for both MLOH and ML(OH)2 species occur in this region, small changes to hydrophobicity within the metallo cavity influence the rate of hydrolysis greatly and an amide adjacent to the metal ion capable of forming hydrogen bonds with the substrate is required for achieving fast hydrolysis.

  13. Synthesis of hydrated lutetium carbonate

    Energy Technology Data Exchange (ETDEWEB)

    Song Liu [South China Univ. of Technology, Dept. of Applied Chemistry, Guangdong (China); Rong-jun Ma [Changsha Research Institute of Minig and Metallurgy, Hunan (China)

    1997-09-01

    Crystalline lutetium carbonate was synthesized for the corresponding chloride using ammonium bicarbonate as precipitant. The chemical analyses suggest that the synthesized lutetium carbonate is a hydrated basic carbonate or oxycarbonate. The X-ray powder diffraction data are presented. The IR data for the compound show the presence of two different carbonate groups. There is no stable intermediate carbonate in the process of thermal decomposition of the lutetium carbonate. (au) 15 refs.

  14. The influence of water flow (reversal) on bond strength development in young masonry

    NARCIS (Netherlands)

    Groot, C.; Larbi, J.

    1999-01-01

    Water loss from the fresh mortar is believed to be related to mortar-brick bond strength development in masonry. Recent research on mortar-brick bond has shown that, particularly, effects of water flow on the composition and the hydration conditions of the mortar-brick interface have to be taken int

  15. Spectral and structural studies of dimethylphenyl betaine hydrate

    Science.gov (United States)

    Szafran, M.; Ostrowska, K.; Katrusiak, A.; Dega-Szafran, Z.

    2014-07-01

    Hydrates of betaines can be divided into four groups depending on the interactions of their water molecules with the carboxylate group. Dimethylphenyl betaine crystallizes as monohydrate (1), in which water molecules mediate in hydrogen bonds between the carboxylate groups. The water molecules are H-bonded only to one oxygen atom of the dimethylphenyl betaine molecules and link them into a chain via two O(1 W)sbnd H⋯O hydrogen bonds of the lengths 2.779(2) and 2.846(2) Å. The structures of monomer (2) and dimer (4) hydrates in vacuum, and the structure of monomer (3) in an aqueous environment have been optimized by the B3LYP/6-311++G(d,p) approach and the geometrical results have been compared with the X-ray diffraction data of 1. The calculated IR frequencies for the optimized structure have been used for the assignments of FTIR bands, the broad absorption band in the range 3415-3230 cm-1 has been assigned to the O(1w)sbnd H⋯O hydrogen bonds. The correlations between the experimental 1H and 13C NMR chemical shifts (δexp) of 1 in D2O and the magnetic isotropic shielding constants (σcalc) calculated by the GIAO/B3LYP/6-311G++(d,p) approach, using the screening solvation model (COSMO), δexp = a + b σcalc, for optimized molecule 3 in water solution are linear and well reproduce the experimental chemical shifts.

  16. Uncovering the Sensitivity of Amide-II Vibration to Peptide-Ion Interactions.

    Science.gov (United States)

    Zhao, Juan; Wang, Jianping

    2016-09-15

    In this work, linear infrared spectroscopy was used to examine the effect of salt on the amide-II mode in a model β-peptide (N-ethylpropionamide, NEPA) in its deuterated form, to reveal the sensitivity of this mode in reporting peptide-ion interactions. In comparison to the case of NEPA in water, the amide-II spectra mainly showed a red-shifted component in four typical saline solutions (NaCl, CaCl2, MgCl2, and AlCl3) examined in this work. Our results suggest that highly populated hydrated ion complexes under high salt concentration conditions destroy the hydration layer of the model peptide and result in mostly a salting-out state of the peptide. Molecular dynamics simulations suggest that the hydrated cation mainly interacts with the peptide backbone on the amide C═O side, whereas the hydrated anion interacts on the amide N-H side. As the amide-II mode is mainly a combination of the C-N stretching and N-H in-plane-bending vibrations, this mode is advantageous in being responsive to ionic interaction from both the C═O and N-H sides. Such a dual sensitivity should be very useful in probing the breaking and/or formation of the interamide hydrogen bond between the C═O and N-H groups, which is a very important interaction involved in the solvation and stabilization, as well as folding/unfolding of proteins.

  17. Crystallite size distributions of marine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Klapp, S.A.; Bohrmann, G.; Abegg, F. [Bremen Univ., Bremen (Germany). Research Center of Ocean Margins; Hemes, S.; Klein, H.; Kuhs, W.F. [Gottingen Univ., Gottingen (Germany). Dept. of Crystallography

    2008-07-01

    Experimental studies were conducted to determine the crystallite size distributions of natural gas hydrate samples retrieved from the Gulf of Mexico, the Black Sea, and a hydrate ridge located near offshore Oregon. Synchrotron radiation technology was used to provide the high photon fluxes and high penetration depths needed to accurately analyze the bulk sediment samples. A new beam collimation diffraction technique was used to measure gas hydrate crystallite sizes. The analyses showed that gas hydrate crystals were globular in shape. Mean crystallite sizes ranged from 200 to 400 {mu}m for hydrate samples taken from the sea floor. Larger grain sizes in the hydrate ridge samples suggested differences in hydrate formation ages or processes. A comparison with laboratory-produced methane hydrate samples showed half a lognormal curve with a mean value of 40{mu}m. Results of the study showed that a cautious approach must be adopted when transposing crystallite-size sensitive physical data from laboratory-made gas hydrates to natural settings. It was concluded that crystallite size information may also be used to resolve the formation ages of gas hydrates when formation processes and conditions are constrained. 48 refs., 1 tab., 9 figs.

  18. Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate.

    Science.gov (United States)

    Falenty, Andrzej; Hansen, Thomas C; Kuhs, Werner F

    2014-12-11

    Gas hydrates are ice-like solids, in which guest molecules or atoms are trapped inside cages formed within a crystalline host framework (clathrate) of hydrogen-bonded water molecules. They are naturally present in large quantities on the deep ocean floor and as permafrost, can form in and block gas pipelines, and are thought to occur widely on Earth and beyond. A natural point of reference for this large and ubiquitous family of inclusion compounds is the empty hydrate lattice, which is usually regarded as experimentally inaccessible because the guest species stabilize the host framework. However, it has been suggested that sufficiently small guests may be removed to leave behind metastable empty clathrates, and guest-free Si- and Ge-clathrates have indeed been obtained. Here we show that this strategy can also be applied to water-based clathrates: five days of continuous vacuum pumping on small particles of neon hydrate (of structure sII) removes all guests, allowing us to determine the crystal structure, thermal expansivity and limit of metastability of the empty hydrate. It is the seventeenth experimentally established crystalline ice phase, ice XVI according to the current ice nomenclature, has a density of 0.81 grams per cubic centimetre (making it the least dense of all known crystalline water phases) and is expected to be the stable low-temperature phase of water at negative pressures (that is, under tension). We find that the empty hydrate structure exhibits negative thermal expansion below about 55 kelvin, and that it is mechanically more stable and has at low temperatures larger lattice constants than the filled hydrate. These observations attest to the importance of kinetic effects and host-guest interactions in clathrate hydrates, with further characterization of the empty hydrate expected to improve our understanding of the structure, properties and behaviour of these unique materials.

  19. 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.

  20. Simulation of an anion in water: effect of ion polarizability

    Science.gov (United States)

    Karim, Omar A.

    1991-10-01

    A polarizable-polar water model is used to study the structure of wate near a chloride ion. A semi-classical description of ion polarizability is included. Significant changes in the solute-solvent distribution functions are observed. When compared with a simulation without ion polarizability, it is found that the hydration number is further decreased when ion polarizability is present.

  1. Study of Formation Mechanisms of Gas Hydrate

    Science.gov (United States)

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

    2015-04-01

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

  2. 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.

  3. 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.

  4. Phosphate-bonded glass cements for geothermal wells. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Rockett, T.J.

    1979-09-01

    Calcium aluminosilicate glasses were found to react with phosphoric acid in three ways depending upon silica content. Above 55% SiO/sub 2/ they are insoluble while below 50% they dissolve readily. The transition compositions release calcium and aluminum ions and a silica gel phase replaces the glass. Activation energies in the order of 10 kcal/mole are associated with the dissolution. Equilibrium studies in the systems CaO-P/sub 2/O/sub 5/-H/sub 2/O, Al/sub 2/O/sub 3/-P/sub 2/O/sub 5/-H/sub 2/O, and CaO-Al/sub 2/O/sub 3/-P/sub 2/O/sub 5/-H/sub 2/O were made to determine the phases which are stable at 200/sup 0/C in excess water. The CaO system shows hydroxylapatite, monetite and monocalcium orthophosphate are the stable phases. The Al/sub 2/O/sub 3/ system contains augelite, berlinite, and a high phosphate aluminum hydrate. The quaternary system shows the above phase plus a lime alumina hydrogarnet and crandallite. Cement made from a glass frit of the composition 45% SiO/sub 2/: 24% CaO: 24% Al/sub 2/O/sub 3/ has a compressive strength of 500 psi after several days in steam at 200/sup 0/C and 800 psi after months in steam. Bonding of cements to mild steel are discussed.

  5. Terahertz Time Domain Spectroscopy for Structure-II Gas Hydrates

    DEFF Research Database (Denmark)

    Takeya, Kei; Zhang, Caihong; Kawayama, Iwao

    2009-01-01

    For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has a charact...

  6. 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...... prehydration may occur. In the report both theoretical considerations and experimental data are presented. It is suggested that the initiation of hydration during water vapour exposure is nucleation controlled....

  7. 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.

  8. The Hydration Structure of Carbon Monoxide by Ab Initio Methods

    CERN Document Server

    Awoonor-Williams, Ernest

    2016-01-01

    The solvation of carbon monoxide (CO) in liquid water is important for understanding its toxicological effects and biochemical roles. In this paper, we use ab initio molecular dynamics (AIMD) and CCSD(T)-F12 calculations to assess the accuracy of the Straub and Karplus molecular mechanical (MM) model for CO(aq). The CCSD(T)-F12 CO--H2O potential energy surfaces show that the most stable structure corresponds to water donating a hydrogen bond to the C center. The MM-calculated surface it incorrectly predicts that the O atom is a stronger hydrogen bond acceptor than the C atom. The AIMD simulations indicate that CO is solvated like a hydrophobic solute, with very limited hydrogen bonding with water. The MM model tends to overestimate the degree of hydrogen bonding and overestimates the atomic radius of the C atom. The calculated Gibbs energy of hydration is in good agreement with experiment (9.3 kJ/mol calc. vs 10.7 kJ/mol exptl.). The calculated diffusivity of CO(aq) in TIP3P-model water was 5.19 x 10-5 cm2/s ...

  9. Prediction of Refrigerant Gas Hydrates Formation Conditions

    Institute of Scientific and Technical Information of China (English)

    Deqing Liang; Ruzhu Wang; Kaihua Guo; Shuanshi Fan

    2001-01-01

    A fugacity model was developed for prediction of mixed refrigerant gas hydrates formation conditions based on the molecule congregation and solution theories. In this model, g as hydrates were regarded as non-ideal solid solution composed of water groups and guest molecules, and the expressions of fugacity of guest molecules in hydrate phase was proposed accordingly. It has been shown that the developed model can indicate successfully the effect of guest-guest molecule interaction. The results showed that the model can describe better the characteristics of phase equilibrium of mixed refrigerant gas hydrates and predictions are in good agreement with experimental data.

  10. Temperature influence on lanthanoids (III) hydration from molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Duvail, M.; Vitorge, P.; Spezia, R. [Univ Evry Val Essonne, Lab Analyse and Modelisat Biol and Environm, CNRS, UMR 8587, F-91025 Evry (France); Vitorge, P. [CEA Saclay, Nucl Energy Div, Dept Phys Chem, SECR, LSRM, F-91991 Gif Sur Yvette (France)

    2010-07-01

    We studied temperature dependence of lanthanoid (III) cations hydration by molecular dynamics simulations using explicit polarization. The main effect of the temperature (T) is to increase exchange frequencies between the two main stoichiometries and the proportions of the minor species. Activation energies for self-exchange reaction have a minimum in the middle of the series and the CN values of all Ln{sup 3+} ions tends to a limit 8.5 value at high temperature. Linear variations are found through the series for the Gibbs energies of water exchange reactions being at the origin of the coordination number sigmoidal variation across the series. (authors)

  11. 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

    2016-02-01

    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.

  12. Elastic neutron scattering study of water dynamics in ion-exchanged type-A zeolites.

    Science.gov (United States)

    Corsaro, C; Crupi, V; Longo, F; Majolino, D; Venuti, V; Wanderlingh, U

    2005-12-01

    With the aim to investigate, by means of elastic neutron scattering, the effects produced by the cation substitution on the dynamics of water in zeolites, we measured, using a neutron backscattering spectrometer, the temperature dependence of mean-square atomic displacements [u2] derived from window integrated quasielastic spectra of fully and partially hydrated Na-A and Mg50-A zeolites. The results, collected in the 20-273 K temperature range, reveal that, at low temperature, the [u2] shows a harmonic trend independent of hydration and cation substitution, and, at higher temperatures, the onset of a non-Gaussian dynamics of the elastic intensity. This latter takes place at T approximately 200 K and approximately 150 K for fully and partially hydrated samples, respectively. This behavior has been interpreted in terms of reorientational jumps of H atoms described by two-site processes within an asymmetric double-minimum potential. In spite of its simplicity, the model seems to reproduce the rearrangement of the hydrogen bond network of zeolitic water. The fit results indicate a reduced proton mobility by diminishing the water content and by the induced Na+-->Mg2+ ion exchange, in agreement with previous incoherent quasielastic neutron scattering results at higher temperatures.

  13. 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.

  14. 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.

  15. 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…

  16. 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.

  17. 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.

  18. Why continuum electrostatics theories cannot explain biological structure, polyelectrolytes or ionic strength effects in ion-protein interactions.

    Science.gov (United States)

    Collins, Kim D

    2012-06-01

    Continuum electrostatics models for ions in water provide apparent long range electrostatic explanations for the forces on ions. However the electro-chemical free energy of solvation of ions resides largely in the first two water layers, which control the interfacial behavior of the ions and require explicit modeling to capture their distinctive behaviors. The resulting short range forces produce such surprising charge density-dependent behaviors as ion adsorption onto nonpolar surfaces, like charge aggregation of ions, and substantial ion pairing preferences, which arise largely from the affinity of specific ions for individual water molecules. Specific ion effects controlled by the local water affinity of the ion show a diagnostic change of sign between strongly hydrated Na(+) and weakly hydrated K(+) and between strongly hydrated F(-) and weakly hydrated Cl(-), in both cases marking the strength of water-water interactions in bulk solution, a critical benchmark missing from continuum electrostatics models.

  19. 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

  20. Glycine zinc sulfate penta­hydrate: redetermination at 10 K from time-of-flight neutron Laue diffraction

    Science.gov (United States)

    Fortes, A. Dominic; Howard, Christopher M.; Wood, Ian G.; Gutmann, Matthias J.

    2016-01-01

    Single crystals of glycine zinc sulfate penta­hydrate [systematic name: hexa­aqua­zinc tetra­aquadiglycinezinc bis­(sulfate)], [Zn(H2O)6][Zn(C2H5NO2)2(H2O)4](SO4)2, have been grown by isothermal evaporation from aqueous solution at room temperature and characterized by single-crystal neutron diffraction. The unit cell contains two unique ZnO6 octa­hedra on sites of symmetry -1 and two SO4 tetra­hedra with site symmetry 1; the octa­hedra comprise one [tetra­aqua-diglycine zinc]2+ ion (centred on one Zn atom) and one [hexa­aqua­zinc]2+ ion (centred on the other Zn atom); the glycine zwitterion, NH3 +CH2COO−, adopts a monodentate coordination to the first Zn atom. All other atoms sit on general positions of site symmetry 1. Glycine forms centrosymmetric closed cyclic dimers due to N—H⋯O hydrogen bonds between the amine and carboxyl­ate groups of adjacent zwitterions and exhibits torsion angles varying from ideal planarity by no more than 1.2°, the smallest values for any known glycine zwitterion not otherwise constrained by a mirror plane. This work confirms the H-atom locations estimated in three earlier single-crystal X-ray diffraction studies with the addition of independently refined fractional coordinates and Uij parameters, which provide accurate inter­nuclear X—H (X = N, O) bond lengths and consequently a more accurate and precise depiction of the hydrogen-bond framework. PMID:27746937

  1. 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.

  2. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Trueba, Alondra Torres [Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada); Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Separation Technology Group, Den Dolech 2, 5612 AZ Eindhoven (Netherlands); Kroon, Maaike C. [Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Separation Technology Group, Den Dolech 2, 5612 AZ Eindhoven (Netherlands); Peters, Cor J. [Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Separation Technology Group, Den Dolech 2, 5612 AZ Eindhoven (Netherlands); The Petroleum Institute, Chemical Engineering Department, P. O. Box 2533, Abu Dhabi (United Arab Emirates); Moudrakovski, Igor L.; Ratcliffe, Christopher I.; Ripmeester, John A., E-mail: John.Ripmeester@nrc-cnrc.gc.ca [Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada); Alavi, Saman [Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada); Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada)

    2014-06-07

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

  4. 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.

  5. 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.

  6. Influence of nano-sized materials on the formation of CH{sub 4} hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Y.B.; Lee, J.D.; Kim, Y.S.; Lee, M.S. [Korea Inst. of Industrial Technology, Busan (Korea, Republic of). Busan Research Center; Yoon, S.Y. [Pusan National Univ., Busan (Korea, Republic of). School of Materials Science and Engineering

    2008-07-01

    Gas hydrates will play an important role in the development of new technologies for storing and transporting natural gas. The hydrates are crystalline compounds that consist of hydrogen-bonded water molecules formed into cages, and the guest molecules that occupy the cages. In this study, nano-sized titanium dioxide, silver and silica (TiO{sub 2}-Ag-SiO{sub 2}) sols were prepared using a sol-gel process with a reduction agent and investigated using thermographic and differential thermal analysis (TGA-DTA); transmission electron microscopy (TEM); X-ray diffraction (XRD); and Fourier Transform Infrared (FT-IR) spectroscopy. The aim of the study was to determine the influence of the nano-sized particles on methane hydrate formation. Experimental data on the kinetics of hydrate formation were obtained at pressures of 3.50 MPa and at a temperature of 273.7 K. Results of the DTA and GTA analyses showed that the weight of the particles sharply decreased up to 350 degrees C and then decreased more slowly from 350 degrees C to 900 degrees C. Exothermic peaks were reached at 480 degrees C, after which no further phase transformations occurred. XRD patterns showed that at 500 degrees C, the particles were identified as nanocrystalline anatase without silver diffraction peaks. The TEM micrographs showed that the particles possessed a spherical morphology with a narrow size distribution. It was concluded that the particles promoted methane hydrate formation. 9 refs., 6 figs.

  7. 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.

  8. Raman Spectroscopic Studies of Methane Gas Hydrates

    DEFF Research Database (Denmark)

    Hansen, Susanne Brunsgaard; Berg, Rolf W.

    2009-01-01

    A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.......A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory....

  9. Dynamics of a photoexcited hydrated electron

    NARCIS (Netherlands)

    Pshenichnikov, M.S.; Baltuška, A.; Wiersma, D.A.; Kärtner, F.X.

    2004-01-01

    Combining photon-echo and frequency-resolved pump-probe techniques with extremely short laser pulses that consist of only few optical cycles, we investigate the dynamics of the equilibrated hydrated electron. The pure dephasing time of the hydrated electron deduced from the photon-echo measurements

  10. 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...

  11. 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.

  12. Investigations into surfactant/gas hydrate relationship

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Rudy; Zhang, Guochang; Dearman, Jennifer; Woods, Charles [Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS 39762 (United States)

    2007-03-15

    Gas hydrates have unique physical properties portending useful industrial applications of gas storage, gas separation, or water desalination. When gas hydrates were found in the early 1990s to occur naturally and abundantly in seafloors, three other primary interests and concerns emerged: potential new energy source, climate threat from their greenhouse gases, and seafloor instabilities. This paper presents research showing how anionic synthetic surfactants helped develop an industrial gas hydrate storage process for natural gas and how naturally-occurring in-situ anionic biosurfactants influence the formation and placement of gas hydrates in ocean sediments. The catalytic effects, mechanisms, and surface specificities imparted by synthetic surfactants in the gas storage process and imparted by biosurfactants in porous media are discussed. The Bacillus subtilis bacterium that is indigenous to gas hydrate mounds in the Gulf of Mexico was cultured in the laboratory. Its biosurfactant was separated and found to catalyze gas hydrates in porous media. The experiments indicate that seafloor-biosurfactants can be produced rapidly in-situ to achieve threshold concentrations whereby hydrates are promoted. The biosurfactants accumulate and promote hydrate formation on specific mineral surfaces such as sodium montmorillonite. (author)

  13. Structural Investigations of Portland Cement Components, Hydration, and Effects of Admixtures by Solid-State NMR Spectroscopy

    DEFF Research Database (Denmark)

    Skibsted, Jørgen Bengaard; Andersen, Morten D.; Jakobsen, Hans Jørgen

    2006-01-01

    for the C-S-H phase formed during hydration. It will be demonstrated that Al3+ and flouride guest-ions in the anhydrous and hydrated calcium silicates can be studied in detail by 27Al and 19F MAS NMR, thereby providing information on the local structure and the mechanisms for incorporation of these ions...... in the cement phases. The role of flouride ions is of special interest for mineralized Portland cements and it demonstrated that the location of these anions in anhydrous and hydrated Portland cements can be clarified using 19F MAS or 29Si{19F} CP/MAS NMR despite these cements contain only about 0.2 wt...

  14. 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.

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the

  16. Compound Natural Gas Hydrate: A Natural System for Separation of Hydrate-Forming Gases

    Science.gov (United States)

    Max, M. D.; Osegovic, J. P.

    2007-12-01

    Natural processes that separate materials from a mixture may exert a major influence on the development of the atmospheres and surfaces of planets, moons, and other planetary bodies. Natural distillation and gravity separation, amongst others, are well known means of differentiating materials through liquid-gas partitioning. One of the least known attributes of clathrate (gas) hydrates is their potential effect on the evolution of planetary system oceans and atmospheres. Gas hydrates separate gases from mixtures of gases by concentrating preferred hydrate-forming materials (HFM) guests within the water-molecule cage structure of crystalline hydrate. Different HFMs have very different fields of stability. When multiple hydrate formers are present, a preference series based on their selective uptake exists. Compound hydrate, which is formed from two or more species of HFM, extract preferred HFM from a mixture in very different proportions to their relative percentages of the original mixture. These compound hydrates can have different formation and dissociation conditions depending on the evolution of the environment. That is, the phase boundary of the compound hydrate that is required for dissociation lies along a lower pressure - higher temperature course. Compound hydrates respond to variations in temperature, pressure, and HFM composition. On Earth, the primary naturally occurring hydrate of interest to global climate modeling is methane hydrate. Oceanic hydrate on Earth is the largest store of carbon in the biosphere that is immediately reactive to environmental change, and is capable of releasing large amounts of methane into the atmosphere over a short geological time span. Hydrate formation is essentially metastable and is very sensitive to environmental change and to gas flux. Where natural variations in temperature and pressure varies so that hydrate will form and dissociate in some cyclical manner, such as in oceans where sea level is capable of rising and

  17. 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

  18. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-07-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  19. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-06-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  20. 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.

  1. Effect of Ions Doping on Calcining and Hydration Properties of High-strength Low-calcium Portland Clinker%离子掺杂对高强低钙硅酸盐水泥熟料煅烧性能的影响

    Institute of Scientific and Technical Information of China (English)

    周双喜; 陈鹏飞; 喻乐华; 邓文武

    2015-01-01

    With view to the new requirements of energy-saving emission reduction and low-carbon economy, the research and development ( R&D ) of low calcium cement has great significance . This paper probes into firing different content belite cement clinkers and proportioning different raw materials, which finds out that the burnability of clinkers can be improved remarkably by ions adopting and the crystal form can be stabilized by adopting B2O3. Using chemical reagent and industrial raw materials, by chemical analysis, XRD (X-ray diffraction), lithofacies analysis and SEM, effects of ions doping on calcining and hydration properties of high strength low calcium portland clinker are discussed in details. Results show that the most suitable temperature of clinkers sintering is 1 350℃, can be in steady existence by adding stabilizers, and fossil has its best morphology under the condition of complete mineral crystallizing cement when the calcination temperature ranges from 1 400℃ to 1 450℃ with w(C2S) being 45% and w(C3S) 30% of the content.%选择几种不同生料进行配方,烧制不同含量硅酸二钙水泥熟料,在煅烧过程中通过阴离子掺杂来研究对熟料易烧性能的影响,并添加稳定剂B2O3使贝利特保持活性较高的晶型;运用XRD、岩相分析、SEM等测试手段,初步探讨了离子掺杂对高强低钙硅酸盐水泥熟料煅烧和水化性能的影响. 主要结论是,最佳的煅烧温度为1 350℃,稳定剂的加入可以促进熟料中的稳定存在;其次,当煅烧温度在1 400~1 450℃,w(C2S)含量在45%、w(C3S)含量30%时,熟料矿物结晶完整,矿物形貌最好,其早龄期的水化产物量也最多.

  2. 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.

  3. Experimental Study of Natural Gas Storage in Hydrates

    Institute of Scientific and Technical Information of China (English)

    孙志高; 王如竹; 郭开华; 樊栓狮

    2004-01-01

    Hydrate formation rate plays an important role in the making of hydrates for natural gas storage. The effect of sodium dodecyl sulfate (SDS), alkyl polysaccharide glycoside (APG) and cyclopentane (CP) on natural gas hydrate formation rate, induction time and storage capacity was studied. Micellar surfactant solutions were found to increase hydrate formation rate in a quiescent system and improve hydrate formation rate and natural gas storage capacity. The process of hydrate formation includes two stages with surfactant presence. Hydrate forms quickly in the first stage, and then the formation rate is slowed down. Surfactants (SDS or APG) reduce the induction time of hydrate formation. The effect of an anionic surfactant (SDS) on gas storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduces the induction time of hydrate formation, but can not improve the natural gas storage capacity in hydrates.

  4. Observation of water dangling OH bonds around dissolved nonpolar groups.

    Science.gov (United States)

    Perera, P N; Fega, K R; Lawrence, C; Sundstrom, E J; Tomlinson-Phillips, J; Ben-Amotz, Dor

    2009-07-28

    We report the experimental observation of water dangling OH bonds in the hydration shells around dissolved nonpolar (hydrocarbon) groups. The results are obtained by combining vibrational (Raman) spectroscopy and multivariate curve resolution (MCR), to reveal a high-frequency OH stretch peak arising from the hydration shell around nonpolar (hydrocarbon) solute groups. The frequency and width of the observed peak is similar to that of dangling OH bonds previously detected at macroscopic air-water and oil-water interfaces. The area of the observed peak is used to quantify the number of water dangling bonds around hydrocarbon chains of different length. Molecular dynamics simulation of the vibrational spectra of water molecules in the hydration shell around neopentane and benzene reveals high-frequency OH features that closely resemble the experimentally observed dangling OH vibrational bands around neopentyl alcohol and benzyl alcohol. The red-shift of approximately 50 cm(-1) induced by aromatic solutes is similar to that previously observed upon formation of a pi-H bond (in low-temperature benzene-water clusters).

  5. Gas Hydrate Storage of Natural Gas

    Energy Technology Data Exchange (ETDEWEB)

    Rudy Rogers; John Etheridge

    2006-03-31

    Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

  6. Influence of Chloride-Ion Adsorption Agent on Chloride Ions in Concrete and Mortar

    Directory of Open Access Journals (Sweden)

    Gai-Fei Peng

    2014-04-01

    Full Text Available The influence of a chloride-ion adsorption agent (Cl agent in short, composed of zeolite, calcium aluminate hydrate and calcium nitrite, on the ingress of chloride ions into concrete and mortar has been experimentally studied. The permeability of concrete was measured, and the chloride ion content in mortar was tested. The experimental results reveal that the Cl agent could adsorb chloride ions effectively, which had penetrated into concrete and mortar. When the Cl agent was used at a dosage of 6% by mass of cementitious materials in mortar, the resistance to the penetration of chloride ions could be improved greatly, which was more pronounced when a combination of the Cl agent and fly ash or slag was employed. Such an effect is not the result of the low permeability of the mortar, but might be a result of the interaction between the Cl agent and the chloride ions penetrated into the mortar. There are two possible mechanisms for the interaction between the Cl agent and chloride ion ingress. One is the reaction between calcium aluminate hydrate in the Cl agent and chloride ions to form Friedel’s salt, and the other one is that calcium aluminate hydrate reacts with calcium nitrite to form AFm during the early-age hydration of mortar and later the NO2− in AFm is replaced by chloride ions, which then penetrate into the mortar, also forming Friedel’s salt. More research is needed to confirm the mechanisms.

  7. 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.

  8. Hydration Properties of Ground Granulated Blast-Furnace Slag (GGBS Under Different Hydration Environments

    Directory of Open Access Journals (Sweden)

    Shuhua LIU

    2017-02-01

    Full Text Available The hydration properties of various cementitious materials containing Ground Granulated Blast-furnace Slag (GGBS, two alkali-activated slag cements (AAS-1 and AAS-2 in which sodium silicate and sodium hydroxide act as alkaline activators respectively, supersulfated cement (SSC and slag Portland cement(PSC, are compared with ordinary Portland cement (OPC to investigate the effect of activating environment on the hydration properties in this study by determining the compressive strength of the pastes, the hydration heat of binders within 96 hours, and the hydration products at age of 28 days. The results show that C-S-H gels are the main hydrated products for all cementitious systems containing GGBS. Ca(OH2 is the hydration products of OPC and PSC paste. However, ettringite and gypsum crystals instead of Ca(OH2 are detected in SSC paste. Additionally, tobermorite, a crystalline C-S-H, and calcite are hydrated products in AAS-1. Tobermorite, cowlesite and calcite are hydrated products of AAS-2 as well. Based on strength results, AAS-1 paste exhibits the highest compressive strength followed by POC, PSC, SSC in order at all testing ages and AAS-2 give the lowest compressive strength except for the early age at 3 days, which is higher than SSC but still lower than PSC. From hydration heat analysis, alkalinity in the reaction solution is a vital factor influencing the initial hydration rate and the initial hydration rate from higher to lower is AAS-2, AAS-1, OPC, PSC and SSC. Although AAS possesses a faster reaction rate in the initial hours, cumulative hydration heat of AAS is comparably lower than that of OPC, but higher than those of PSC and SSC in turn, which indicates that the hydration heat of clinkers is much higher than that of slag.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14934

  9. 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

  10. 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.

  11. Gas hydrate dissociation structures in submarine slopes

    Energy Technology Data Exchange (ETDEWEB)

    Gidley, I.; Grozic, J.L.H. [Calgary Univ., AB (Canada). Dept. of Civil Engineering

    2008-07-01

    Studies have suggested that gas hydrates may play a role in submarine slope failures. However, the mechanics surrounding such failures are poorly understood. This paper discussed experimental tests conducted on a small-scale physical model of submarine soils with hydrate inclusions. The laboratory tests investigated the effects of slope angle and depth of burial of the hydrate on gas escape structures and slope stability. Laponite was used to model the soils due to its ability to swell and produce a clear, colorless thixotropic gel when dispersed in water. An R-11 refrigerant was used to form hydrate layers and nodules. The aim of the experiment was to investigate the path of the fluid escape structures and the development of a subsequent slip plane caused by the dissociation of the R-11 hydrates. Slope angles of 5, 10, and 15 degrees were examined. Slopes were examined using high-resolution, high-speed imaging techniques. Hydrate placement and slope inclinations were varied in order to obtain stability data. Results of the study showed that slope angle influenced the direction of travel of the escaping gas, and that the depth of burial affected sensitivity to slope angle. Theoretical models developed from the experimental data have accurately mapped deformations and stress states during testing. Further research is being conducted to investigate the influence of the size, shape, and placement of the hydrates. 30 refs., 15 figs.

  12. Prospecting for marine gas hydrate resources

    Science.gov (United States)

    Boswell, Ray; Shipp, Craig; Reichel, Thomas; Shelander, Dianna; Saeki, Tetsuo; Frye, Matthew; Shedd, William; Collett, Timothy S.; McConnell, Daniel R.

    2016-01-01

    As gas hydrate energy assessment matures worldwide, emphasis has evolved away from confirmation of the mere presence of gas hydrate to the more complex issue of prospecting for those specific accumulations that are viable resource targets. Gas hydrate exploration now integrates the unique pressure and temperature preconditions for gas hydrate occurrence with those concepts and practices that are the basis for conventional oil and gas exploration. We have aimed to assimilate the lessons learned to date in global gas hydrate exploration to outline a generalized prospecting approach as follows: (1) use existing well and geophysical data to delineate the gas hydrate stability zone (GHSZ), (2) identify and evaluate potential direct indications of hydrate occurrence through evaluation of interval of elevated acoustic velocity and/or seismic events of prospective amplitude and polarity, (3) mitigate geologic risk via regional seismic and stratigraphic facies analysis as well as seismic mapping of amplitude distribution along prospective horizons, and (4) mitigate further prospect risk through assessment of the evidence of gas presence and migration into the GHSZ. Although a wide range of occurrence types might ultimately become viable energy supply options, this approach, which has been tested in only a small number of locations worldwide, has directed prospect evaluation toward those sand-hosted, high-saturation occurrences that were presently considered to have the greatest future commercial potential.

  13. 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.

  14. 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.

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by Maurer Technology, Noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition. We plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. We also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. We are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. We hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, our goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  16. 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.

  17. Size and stability of liposomes: a possible role of hydration and osmotic forces.

    Science.gov (United States)

    Sabín, J; Prieto, G; Ruso, J M; Hidalgo-Alvarez, R; Sarmiento, F

    2006-08-01

    Dynamic light scattering and electrophoretic mobility measurements have been used to characterize the size, size distribution and zeta potentials (zeta-potentials) of egg yolk phosphatidylcholine (EYPC) liposomes in the presence of monovalent ions ( Na(+) and K(+)). To study the stability of liposomes the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory has been extended by introducing the hydrated radius of the adsorbed ions onto the liposome surfaces. The decrease of liposome size is explained on the basis of the membrane impermeability to some ions which generate osmotic forces, which leads to evacuate water from liposome inside.

  18. Periodic quantum chemical studies on anhydrous and hydrated acid clinoptilolite.

    Science.gov (United States)

    Valdiviés Cruz, Karell; Lam, Anabel; Zicovich-Wilson, Claudio M

    2014-08-07

    Periodic quantum chemistry methods as implemented in the crystal09 code were considered to study acid clinoptilolite (HEU framework type), both anhydrous and hydrated. The most probable location of acid sites and water molecules together with other structural details has been the object of particular attention. Calculations were performed at hybrid and pristine DFT levels of theory with a VDZP quality basis set in order to compare performances. It arises that PBE0 provides the best agreement with experimental data as concerns structural features and the most stable Al distribution in the framework. The role of the water molecule distribution in the stability of the systems, the most probable structure that they induce in the material, and their eventual influence on further chemical modification processes, such as dealumination, are discussed in detail. Results show that, apart from the usually considered interactions of water molecules with the zeolite framework, that is, a H-bond with Brönsted acid sites and coordination with framework Al as Lewis ones, it is necessary to consider cooperation of other weaker effects so as to fully understand the hydration effect in this kind of materials.

  19. 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....

  20. Infrared spectroscopy of weakly bound molecular ions

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, Lisa I-Ching

    1988-11-01

    The infrared spectra of a series of hydrated hydronium cluster ions and of protonated ethane ion are presented. A tandem mass spectrometer is ideally suited to obtaining the spectra of such weakly bound molecular ions. Traditional absorption spectroscopy is not feasible in these situations, so the techniques described in this thesis make use of some consequence of photon absorption with higher sensitivity than simply attenuation of laser power. That consequence is dissociation. By first mass selecting the parent ion under study and then mass selecting the fragment ion formed from dissociation, the near unit detection efficiency of ion counting methods has been used to full advantage.

  1. Proton percolation on hydrated lysozyme powders

    OpenAIRE

    Careri, G; Giansanti, A; Rupley, John A.

    1986-01-01

    The framework of percolation theory is used to analyze the hydration dependence of the capacitance measured for protein samples of pH 3-10, at frequencies from 10 kHz to 4 MHz. For all samples there is a critical value of the hydration at which the capacitance sharply increases with increase in hydration level. The threshold hc = 0.15 g of water per g of protein is independent of pH below pH 9 and shows no solvent deuterium isotope effect. The fractional coverage of the surface at hc is in cl...

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. A study of desalination using CO{sub 2} hydrate technology

    Energy Technology Data Exchange (ETDEWEB)

    Lee, J.D.; Kim, Y.S. [Korea Inst. of Industrial Technology, Busan (Korea, Republic of); Lee, H.J.; Kim, Y.D. [Pusan National Univ., Busan (Korea, Republic of). School of Materials Science and Engineering

    2008-07-01

    Desalination processes use distillation or reverse osmosis methods to produce drinking water from sea water. However, conventional desalination processes are costly. This paper described a gas hydrate desalination process based on a liquid-to-solid phase change coupled with a physical process designed to separate solids from the remaining liquid phase. The kinetics of carbon dioxide (CO{sub 2}) hydrates in an sodium chloride (NaC1) solution were investigated to show the potential application of the CO{sub 2} hydrate formation and decomposition process for seawater desalination. The apparatus consisted of a reactor and supply vessel with temperature and pressure control systems. The decomposition process was conducted after the solution had been drained from the reactor using a squeeze method. The NaC1 ions were trapped in the cavities built by water molecules as well as on the hydrate surface. Results of the study suggested that additional drain processes are needed to increase the desalination efficiency of seawater. Initial CO{sub 2} hydrate formation rates were higher than rates observed in seawater. It was concluded that the method can be used for seawater desalination as well in other purification processes. 7 refs., 2 tabs., 5 figs.

  7. 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

  8. 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...

  9. 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.

  10. 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 pro...

  11. Solid and liquid phase equilibria and solid-hydrate formation in binary mixtures of water with amines

    Institute of Scientific and Technical Information of China (English)

    车冠全; 彭文烈; 黄良恩; 古喜兰; 车飙

    1997-01-01

    Solid and liquid phase diagrams have been constructed for {water+triethylamine,or+N,N-dimethylformamide(DMF) or+N,N-dimethlacetamide (DMA)} Solid-hydrates form with the empirical formulae N(C2H5)3 3H2O,DMF 3H2O,DMF 2H2O,DMA 3H2O and (DMA)2 3H2O.All are congruently melting except the first which melts incongruently.The solid-hydrate formation is attributed to hydrogen bond.The results are compared with the references

  12. 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.

  13. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Donn McGuire; Thomas Williams; Bjorn Paulsson; Alexander Goertz

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a drilling hazard by the oil and gas industry for years. Drilling engineers working in Russia, Canada and the USA have documented numerous problems, including drilling kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates as a potential energy source agree that the resource potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained from physical samples taken from actual hydrate-bearing rocks. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The project team drilled and continuously cored the Hot Ice No. 1 well on Anadarko-leased acreage beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and used for determining physical characteristics of hydrates and surrounding rock. After the well was logged, a 3D vertical seismic profile (VSP) was recorded to calibrate the shallow geologic section with seismic data and to investigate techniques to better resolve lateral subsurface variations of potential hydrate-bearing strata. Paulsson Geophysical Services, Inc. deployed their 80 level 3C clamped borehole seismic receiver array in the wellbore to record samples every 25 ft. Seismic vibrators were successively positioned at 1185 different surface positions in a circular pattern around the wellbore. This technique generated a 3D image of the subsurface. Correlations were

  14. 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.

  15. 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.)

  16. 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.

  17. [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.

  18. XANES Reveals the Flexible Nature of Hydrated Strontium in Aqueous Solution.

    Science.gov (United States)

    D'Angelo, Paola; Migliorati, Valentina; Sessa, Francesco; Mancini, Giordano; Persson, Ingmar

    2016-05-05

    X-ray absorption near-edge structure (XANES) spectroscopy has been used to determine the structure of the hydrated strontium in aqueous solution. The XANES analysis has been carried out using solid [Sr(H2O)8](OH)2 as reference model. Classical and Car-Parrinello molecular dynamics (MD) simulations have been carried out and in the former case two different sets of Lennard-Jones parameters have been used for the Sr(2+) ion. The best performing theoretical approach has been chosen on the basis of the experimental results. XANES spectra have been calculated starting from MD trajectories, without carrying out any minimization of the structural parameters. This procedure allowed us to properly account for thermal and structural fluctuations occurring in the aqueous solution in the analysis of the experimental spectrum. A deconvolution procedure has been applied to the raw absorption data thus increasing the sensitivity of XANES spectroscopy. One of the classical MD simulations has been found to provide a XANES theoretical spectrum in better agreement with the experimental data. An 8-fold hydration complex with a Sr-O distance of 2.60 Å has been found to be compatible with the XANES data, in agreement with previous findings. However, the hydration shells of the strontium ions have been found to have a flexible nature with a fast ligand exchange rate between the first and second hydration shell occurring in the picosecond time scale.

  19. Meranzin hydrate from Muraya paniculata

    Directory of Open Access Journals (Sweden)

    Khalijah Awang

    2010-03-01

    Full Text Available The coumarin ring system in the title compound, C15H18O5 [IUPAC name: 8-(2,3-dihydroxy-3-methylbutyl-7-methoxy-2H-1-benzopyran-2-one], isolated from Muraya paniculata, is planar (r.m.s. deviation 0.017 Å. In the crystal, the two hydroxy groups are involved in O—H...O hydrogen bonding with adjacent molecules, forming a sheet structure.

  20. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2004-11-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is 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 a well (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 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. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained

  1. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is 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 a well (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 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. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained

  2. 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

  3. Temperature dependence of polyhedral cage volumes in clathrate hydrates

    Science.gov (United States)

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

    2003-01-01

    The polyhedral cage volumes of structure I (sI) (carbon dioxide, methane, trimethylene oxide) and structure II (sII) (methane-ethane, propane, tetrahydrofuran, trimethylene oxide) hydrates are computed from atomic positions determined from neutron powder-diffraction data. The ideal structural formulas for sI and sII are, respectively, S2L6 ?? 46H2O and S16L???8 ?? 136H2O, where S denotes a polyhedral cage with 20 vertices, L a 24-cage, and L??? a 28-cage. The space-filling polyhedral cages are defined by the oxygen atoms of the hydrogen-bonded network of water molecules. Collectively, the mean cage volume ratio is 1.91 : 1.43 : 1 for the 28-cage : 24-cage : 20-cage, which correspond to equivalent sphere radii of 4.18, 3.79, and 3.37 A??, respectively. At 100 K, mean polyhedral volumes are 303.8, 227.8, and 158.8 A??3 for the 28-cage, 24-cage, and 20-cage, respectively. In general, the 20-cage volume for a sII is larger than that of a sI, although trimethylene oxide is an exception. The temperature dependence of the cage volumes reveals differences between apparently similar cages with similar occupants. In the case of trimethylene oxide hydrate, which forms both sI and sII, the 20-cages common to both structures contract quite differently. From 220 K, the sII 20-cage exhibits a smooth monotonic reduction in size, whereas the sI 20-cage initially expands upon cooling to 160 K, then contracts more rapidly to 10 K, and overall the sI 20-cage is larger than the sII 20-cage. The volumes of the large cages in both structures contract monotonically with decreasing temperature. These differences reflect reoriented motion of the trimethyelene oxide molecule in the 24-cage of sI, consistent with previous spectroscopic and calorimetric studies. For the 20-cages in methane hydrate (sI) and a mixed methane-ethane hydrate (sII), both containing methane as the guest molecule, the temperature dependence of the 20-cage volume in sII is much less than that in sI, but sII is overall

  4. 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...

  5. Preservation of methane hydrate at 1 atm

    Science.gov (United States)

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

    2001-01-01

    A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

  6. Experimental Dissociation of Methane Hydrates Through Depressurization

    Science.gov (United States)

    Borgfeldt, T.; Flemings, P. B.; Meyer, D.; You, K.

    2015-12-01

    We dissociated methane hydrates by stepwise depressurization. The initial hydrates were formed by injecting gas into a cylindrical sample of brine-saturated, coarse-grained sand at hydrate-stable conditions with the intention of reaching three-phase equilibrium. The sample was initially at 1°C with a pore pressure of 1775 psi and a salinity of 7 wt. % NaBr. The depressurization setup consisted of one pump filled with tap water attached to the confining fluid port and a second pump attached to the inlet port where the methane was injected. Depressurization was conducted over sixteen hours at a constant temperature of 1°C. The pore pressure was stepwise reduced from 1775 psi to atmospheric pressure by pulling known volumes of gas from the sample. After each extraction, we recorded the instantaneous and equilibrium pore pressure. 0.503 moles of methane were removed from the sample. The pore pressure decreased smoothly and nonlinearly with the cumulative gas withdrawn from the sample. We interpret that hydrate began to dissociate immediately with depressurization, and it continued to dissociate when the pressure decreased below the three-phase pressure for 1°C and 0 wt. % salinity. Two breaks in slope in the pressure vs. mass extracted data are bounded by smooth, nonlinear curves with differing slopes on either side. We attribute the breaks to dissociation of three zones of hydrate concentration. We created a box model to simulate the experimental behavior. For a 10% initial gas saturation (estimated from the hydrate formation experiment and based on mass conservation), an initial hydrate saturation of 55% is required to match the total methane extracted from the sample. Future experiments will be conducted over a longer timespan while monitoring hydrate dissociation with CT imaging throughout the process.

  7. 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.

  8. Surfactant effects on SF6 hydrate formation.

    Science.gov (United States)

    Lee, Bo Ram; Lee, Ju Dong; Lee, Hyun Ju; Ryu, Young Bok; Lee, Man Sig; Kim, Young Seok; Englezos, Peter; Kim, Myung Hyun; Kim, Yang Do

    2009-03-01

    Sulfur hexafluoride (SF(6)) has been widely used in a variety of industrial processes, but it is one of the most potent greenhouse gases. For this reason, it is necessary to separate or collect it from waste gas streams. One separation method is through hydrate crystal formation. In this study, SF(6) hydrate was formed in aqueous surfactant solutions of 0.00, 0.01, 0.05, 0.15 and 0.20 wt% to investigate the effects of surfactants on the hydrate formation rates. Three surfactants, Tween 20 (Tween), sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), were tested in a semi-batch stirred vessel at the constant temperature and pressures of 276.2 K and 0.78 MPa, respectively. All surfactants showed kinetic promoter behavior for SF(6) hydrate formation. It was also found that SF(6) hydrate formation proceeded in two stages with the second stage being the most rapid. In situ Raman spectroscopy analysis revealed that the increased gas consumption rate with the addition of surfactant was possibly due to the increased gas filling rate in the hydrate cavity.

  9. Two-dimensional protonic percolation on lightly hydrated purple membrane.

    Science.gov (United States)

    Rupley, J A; Siemankowski, L; Careri, G; Bruni, F

    1988-12-01

    The capacitance and dielectric loss factor were measured for a sample of purple membrane of Halobacterium halobium as a function of hydration level (0.017 to >0.2 g of water/g of membrane) and frequency (10 kHz to 10 MHz). The capacitance and the derived conductivity show explosive growth above a threshold hydration level, h(c) approximately 0.0456. The conductivity shows a deuterium isotope effect, H/(2)H = 1.38, in close agreement with expectation for a protonic process. The level h(c) is frequency independent and shows no deuterium isotope effect. These properties are analogous to those found for lysozyme in a related study. Protonic conduction for the purple membrane can be considered, as for lysozyme, within the framework of a percolation model. The critical exponent, t, which describes the conductivity of a percolative system near the threshold, has the value 1.23. This number is in close agreement with expectation from theory for a two-dimensional percolative process. The dielectric properties of the purple membrane are more complex than those of lysozyme, seen in the value of h(c) and in the frequency and hydration dependence of the loss factor. There appear to be preferred regions of proton conduction. The percolation model is based upon stochastic behavior of a system partially populated with conducting elements. This model suggests that ion transport in membranes and its control can be based on pathways formed of randomly connected conducting elements and that a fixed geometry (a proton wire) is not the only possible basis for a mechanism of conduction.

  10. Theoretical Study of Hydrated Cd~(2+) Interactions with Guanine

    Institute of Scientific and Technical Information of China (English)

    王敏; 洒荣建; 吴克琛; 李巧红; 韦永勤

    2012-01-01

    Theoretical study was performed to investigate how the hydration of cadmium ca-tion influences the structure and properties of guanine.The aqueous environment was simulated by both explicit solvent(1-5 water molecules) model and implicit solvent model.For complexes in which Cd2+ attached to the N(7) and O(6) sites of guanine,energy analysis together with the Natural Bonding Orbital(NBO) analysis were performed to elucidate the bonding characteristics in detail.The most stable structures are penta-coordinate complexes without aqua ligand located at the guanine site.Higher number of water ligands corresponds to higher stabilization energies.Average bonding energies of G-Cd increase with the number of water molecules.Bonding energies of water ligands depend on its position in the complexes.The charge distribution of guanine changed with increasing the number of water ligands,which may also influence the base-pairing pattern of guanine.There is positive charge transfer from guanine to aqua ligand as the number of the hydration waters increases.IEFPCM optimization has results comparable to the [CdG(H2O)5]2+ structure 5a.

  11. 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.

  12. STATE OF WATER SORBED ON ION EXCHANGERS

    Institute of Scientific and Technical Information of China (English)

    VenkataramaniB

    1994-01-01

    Water sorption isotherms available in the literatures of Na+-from of Dowex 50W×4 and×8,BioRex-70,Amberlyst-15,Nafion-117,hydrous titanium oxide,crystalline zirconium phosphate and zinc hexacyanoferrate(Ⅱ),have been analysed by the D′Arcy and Watt equation.Hydration of Na+ in the ion exchangers is the predominant interaction of sorbed water.The correlation between the hydration numbers and those obtained for electrolyte solution is found in this paper.Qualitative implications of the state of sorbed water in the ion exchangers on its various characteristic quantities like selectivity,are briefly discussed.

  13. 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, P.; Kofod, Pauli; Song, Y.

    2003-01-01

    In the title compound, [Co(C6H15N3)(C7H15N2S)]S2O6·H2O, the Co-C bond distance is 1.9930 (13) Å, 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 produce...

  14. Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media.

    Science.gov (United States)

    Baldwin, Bernard A; Stevens, Jim; Howard, James J; Graue, Arne; Kvamme, Bjorn; Aspenes, Erick; Ersland, Geir; Husebø, Jarle; Zornes, David R

    2009-06-01

    Magnetic resonance imaging was used to monitor and quantify methane hydrate formation and exchange in porous media. Conversion of methane hydrate to carbon dioxide hydrate, when exposed to liquid carbon dioxide at 8.27 MPa and approximately 4 degrees C, was experimentally demonstrated with MRI data and verified by mass balance calculations of consumed volumes of gases and liquids. No detectable dissociation of the hydrate was measured during the exchange process.

  15. Kinetic studies of gas hydrate formation with low-dosage hydrate inhibitors

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Pipeline blockage by gas hydrates is a serious problem in the petroleum industry.Low-dosage inhibitors have been developed for its cost-effective and environmentally acceptable characteristics.In a 1.072-L reactor with methane,ethane and propane gas mixture under the pressure of about 8.5 MPa at 4 °C,hydrate formation was investigated with low-dosage hydrate inhibitors PVP and GHI1,the change of the compressibility factor and gas composition in the gas phase was analyzed,the gas contents in hydrates were compared with PVP and GHI1 added,and the inhibition mechanism of GHI1 was discussed.The results show that PVP and GHI1 could effectively inhibit the growth of gas hydrates but not nucleation.Under the experimental condition with PVP added,methane and ethane occupied the small cavities of the hydrate crystal unit and the ability of ethane entering into hydrate cavities was weaker than that of methane.GHI1 could effectively inhibit molecules which could more readily form hydrates.The ether and hydroxy group of diethylene glycol monobutyl ether have the responsibility for stronger inhibition ability of GHI1 than PVP.

  16. 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

  17. 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.

  18. T dependence of vibrational dynamics of water in ion-exchanged zeolites A: a detailed Fourier transform infrared attenuated total reflection study.

    Science.gov (United States)

    Crupi, Vincenza; Longo, Francesca; Majolino, Domenico; Venuti, Valentina

    2005-10-15

    In order to explore the influence of cation substitution on the vibrational dynamics of water molecules in zeolites, the evolution of structural properties of the O-H stretching band of water in fully hydrated Na-A and Mg-exchanged A zeolites has been studied, for different percentages of induced ion exchange, by Fourier transform infrared attenuated total reflection spectroscopy as a function of temperature. The differences revealed in the O-H stretching band shapes have been accounted by fitting the spectra as a sum of four components, corresponding to water molecules exhibiting different types of hydrogen bonding. The dependencies of the relative intensities, peak wave numbers, and bandwidths of the resolved components on temperature and Mg2+ content have been discussed. Evidence of the "structure-maker" role played by a zeolitic surface on physisorbed water, systematically enhanced by increasing the percentage of induced ion exchange, is given in the whole explored temperature range.

  19. Verification of simple hydration/dehydration methods to characterize multiple water compartments on tendon type 1 collagen.

    Science.gov (United States)

    Cameron, Ivan L; Short, Nicholas J; Fullerton, Gary D

    2007-06-01

    A molecular model of collagen hydration is used to validate centrifugal dehydration force (CDF) and re-hydration isotherm (RHI) methods to measure and characterize hydration compartments on bovine tendon. The CDF method assesses fluid flow rate from flexor and extensor tendons expressed in (g-water/g-dry mass-minute) and hydration capacity of compartments in (g-water/g-dry mass). Measured water compartment capacities agree with the molecular model of collagen hydration [Fullerton GD, Rahal A. Collagen structure: the molecular source of tendon magic angle effect. J Mag Reson Imag 2007;25:345-361; Fullerton GD, Amurao MR. Evidence that collagen and tendon have monolayer water coverage in the native state. Cell Biol Int 2006;30(1):56-65]. Native tendon hydration has monolayer coverage on collagen h(m)=1.6 g/g which divides into primary hydration on polar surfaces h(pp)=0.8 g/g and secondary hydration h(s)=0.8 g/g bridging over hydrophobic surfaces. Primary hydration is hydrogen bonded to collagen polar side chains h(psc)=0.54 g/g with small free energy or to the protein main chain hydration h(pmc)=0.26 g/g with greater free energy of binding. The CDF method replaces the more time consuming water proton NMR spin-lattice dehydration (NMR titration) method, confirms the presence of three non-bulk water compartments on collagen (h(pmc)=0.26 g/g, h(pp)=0.8 g/g and h(m)=1.6 g/g). This CDF method provides the most reproducible experimental measure of total tissue non-bulk water (TNBW). The re-hydration isotherm method, on the other hand, provides the most accurate measure of the Ramachandran water-bridge capacity h(Ra)=0.0656 g/g. The only equipment needed are: microfilterfuge tubes, a microcentrifuge capable of 14,000 x g or 4MPa, a vacuum drying oven, an accurate balance and curve fitting ability. The newly validated methods should be useful for characterizing multiple water compartments in biological and non-biological materials by allowing direct measurement of water

  20. Composite inorganic membranes containing nanoparticles of hydrated zirconium dioxide for electrodialytic separation

    OpenAIRE

    Dzyazko, Yuliya S; Volfkovich, Yurii M; Sosenkin, Valentin E; Nikolskaya, Nadejda F; Gomza, Yurii P

    2014-01-01

    The aim of the work was to elucidate the nature of charge-selective properties of macroporous composite inorganic membranes modified with nanoparticles of hydrated zirconium dioxide. The membranes have been investigated using methods of standard contact porosimetry, potentiometry, electron microscopy and small-angle X-ray scattering. The ion exchanger has been found to deposit inside pores of ceramics. Differential curves of pore volume distribution have been resolved using Lorentz functions;...

  1. Thermodynamic functions of hydration of hydrocarbons at 298.15 K and 0.1 MPa

    Science.gov (United States)

    Plyasunov, Andrey V.; Shock, Everett L.

    2000-02-01

    An extensive compilation of experimental data yielding the infinite dilution partial molar Gibbs energy of hydration Δ hGO, enthalpy of hydration Δ hHO, heat capacity of hydration Δ hCpO, and volume V2O, at the reference temperature and pressure, 298.15 K and 0.1 MPa, is presented for hydrocarbons (excluding polyaromatic compounds) and monohydric alcohols. These results are used in a least-squares procedure to determine the numerical values of the corresponding properties of the selected functional groups. The simple first order group contribution method, which in general ignores nearest-neighbors and steric hindrance effects, was chosen to represent the compiled data. Following the precedent established by Cabani et al. (1981), the following groups are considered: CH 3, CH 2, CH, C for saturated hydrocarbons; c-CH 2, c-CH, c-C for cyclic saturated hydrocarbons; CH ar, C ar for aromatic hydrocarbons (containing the benzene ring); C=C, C≡C for double and triple bonds in linear hydrocarbons, respectively; c-C=C for the double bond in cyclic hydrocarbons; H for a hydrogen atom attached to the double bond (both in linear and cyclic hydrocarbons) or triple bond; and OH for the hydroxyl functional group. In addition it was found necessary to include the "pseudo"-group I(C-C) to account for the specific interactions of the neighboring hydrocarbon groups attached to the benzene or cyclic ring (in the latter case only for cis-isomers). Results of this study, the numerical values of the group contributions, will allow in most cases reasonably accurate estimations of Δ hGO, Δ hHO, Δ hCpO, and V2O at 298.15 K, 0.1 MPa for many hydrocarbons involved in geochemical and environmental processes.

  2. Experimental characterization of production behavior accompanying the hydrate reformation in methane hydrate bearing sediments

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, T.; Kang, J.M.; Nguyen, H.T. [Seoul National Univ., Seoul (Korea, Republic of); Park, C. [Kangwon National Univ., (Korea, Republic of); Lee, J. [Korea Inst., of Geoscience and Mineral Resources (Korea, Republic of)

    2010-07-01

    This study investigated the production behaviour associated with gas hydrate reformation in methane hydrate-bearing sediment by hot-brine injection. A range of different temperature and brine injection rates were used to analyze the pressure and temperature distribution, the gas production behaviour and the movement of the dissociation front. The study showed that hydrate reformation reduces the production rate considerably at an early time. However, gas production increases during the dissociation, near the outlet because the dissociated methane around the inlet is consumed in reforming the hydrate and increases the hydrate saturation around the outlet. Higher temperature also increases the gas production rate and the speed of the dissociation front. 12 refs., 2 tabs., 4 figs.

  3. Threshold collision-induced dissociation of Sr(2+)(H(2)O)(x) complexes (x=1-6): An experimental and theoretical investigation of the complete inner shell hydration energies of Sr(2+).

    Science.gov (United States)

    Carl, D R; Chatterjee, B K; Armentrout, P B

    2010-01-28

    The sequential bond energies of Sr(2+)(H(2)O)(x) complexes, where x=1-6, are determined by threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer equipped with an electrospray ionization source. The electrospray source produces an initial distribution of Sr(2+)(H(2)O)(x) complexes, where x=6-9. Smaller Sr(2+)(H(2)O)(x) complexes, where x=1-5, are accessed using a recently developed in-source fragmentation technique that takes place in the high pressure region of a rf-only hexapole ion guide. This work constitutes the first experimental study for the complete inner shell of any multiply charged ion. The kinetic energy dependent cross sections are determined over a wide energy range to monitor all possible dissociation products and are modeled to obtain 0 and 298 K binding energies for loss of a single water molecule. These binding energies decrease monotonically for the Sr(2+)(H(2)O) complex to Sr(2+)(H(2)O)(6). Our experimental results agree well with previous literature results obtained by equilibrium and kinetic studies for x=5 and 6. Because there has been limited theory for the hydration of Sr(2+), we also present an in-depth theoretical study on the energetics of the Sr(2+)(H(2)O)(x) systems by employing several levels of theory with multiple effective core potentials for Sr and different basis sets for the water molecules.

  4. Modification of waste carpet with hydrated ferric oxide for recycling as an adsorbent material to recover phosphate from wastewater

    OpenAIRE

    Collinson, Simon R.; Duplá García, Oscar

    2013-01-01

    The surface of waste wool rich carpet was modified to enable recycling as an adsorbent material to remove pollutants from water and to avoid bulky carpets contributing to landfill. The proteins of the wool fibres in waste carpets adsorbed either copper(II) nitrate or iron(II) ions to form nanoparticles of Hydrated Ferric Oxide (HFO). The copper(II) ions reversibly bound to the wool carpet. The strongest binding of the nanoparticles of HFO occurred after first oxidizing the surface epicuticle ...

  5. Authigenic gypsum found in gas hydrate-associated sediments from Hydrate Ridge, the eastern North Pacific

    Institute of Scientific and Technical Information of China (English)

    WANG; Jiasheng; Erwin; Suess; Dirk; Rickert

    2004-01-01

    Characteristic gypsum micro-sphere and granular mass were discovered by binocular microscope in the gas hydrate-associated sediments at cores SO143-221 and SO143/TVG40-2A respectively on Hydrate Ridge of Cascadia margin, the eastern North Pacific. XRD patterns and EPA analyses show both micro-sphere and granular mass of the crystals have the typical peaks and the typical main chemical compositions of gypsum, although their weight percents are slightly less than the others in the non-gas hydrate-associated marine regions. SEM pictures show that the gypsum crystals have clear crystal boundaries, planes, edges and cleavages of gypsum in form either of single crystal or of twin crystals. In view of the fact that there are meanwhile gas hydrate-associated authigenic carbonates and SO42(-rich pore water in the same sediment cores, it could be inferred reasonably that the gypsums formed also authigenically in the gas hydrate-associated environment too, most probably at the interface between the downward advecting sulfate-rich seawater and the below gas hydrate, which spilled calcium during its formation on Hydrate Ridge. The two distinct forms of crystal intergrowth, which are the granular mass of series single gypsum crystals at core SO143/TVG40-2A and the microsphere of gypsum crystals accompanied with detrital components at core SO143-221 respectively, indicate that they precipitated most likely in different interstitial water dynamic environments. So, the distinct authigenic gypsums found in gas hydrate-associated sediments on Hydrate Ridge could also be believed as one of the parameters which could be used to indicate the presence of gas hydrate in an unknown marine sediment cores.

  6. Stabilities and partitioning of arenonium ions in aqueous media.

    Science.gov (United States)

    Lawlor, D A; More O'Ferrall, R A; Rao, S N

    2008-12-31

    The phenathrenonium ion is formed as a reactive intermediate in the solvolysis of 9-dichloroacetoxy-9,10-dihydrophenanthrene in aqueous acetonitrile and undergoes competing reactions with water acting as a base and nucleophile. Measurements of product ratios in the presence of azide ion as a trap and 'clock' yield rate constants kp = 3.7 x 10(10) and kH2O = 1.5 x 10(8) s(-1), respectively. Combining these with rate constants for the reverse reactions (protonation of phenanthrene and acid-catalyzed aromatization of its water adduct) gives equilibrium constants pKa = -20.9 and pK(R) = -11.6. For a series of arenonium and benzylic cations, correlation of log kp with pKa, taking account of the limit to kp set by the relaxation of water (10(11) s(-1)), leads to extrapolation of kp = 9.0 x 10(10) s(-1) and pKa = -24.5 for the benzenonium ion and kp = 6.5 x 10(10) s(-1) and pKa = -22.5 for the 1-naphthalenonium ion. Combining these pKa's with estimates of equilibrium constants pKH2O for the hydration of benzene and naphthalene, and the relationship pKR = pKa + pKH2O based on Hess's law, gives pKR = -2.3 and -8.0 respectively, and highlights the inherent stability of the benzenonium ion. A correlation exists between the partitioning ratio, kp/kH2O, for carbocations reacting in water and KH2O the equilibrium constant between the respective reaction products, i.e., log(kp/kH2O) = 0.46pKH2O - 3.7. It implies that kp exceeds kH2O only when KH2O > 10(8). This is consistent with the proton transfer (a) possessing a lower intrinsic reactivity than reaction of the carbocation with water as a nucleophile and (b) being rate-determining in the hydration of alkenes (and dehydration of alcohols) except when the double bond of the alkene is unusually stabilized, as in the case of aromatic molecules.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Molecular structures of N-ethylpiperidine betaine hydrate and its 1:1 complex with squaric acid

    Science.gov (United States)

    Dega-Szafran, Z.; Dutkiewicz, G.; Kosturkiewicz, Z.; Szafran, M.

    2013-12-01

    N-ethylpiperidine betaine, (N-carboxymethyl-N-ethylpiperidinium inner salt, EtPB) crystallizes as a hydrate. EtPB and water molecules are bonded by intermolecular OH⋯O hydrogen bonds of 2.817(1) and 2.863(1) Å, into a centrosymmetric dimer, in which only one carboxylate oxygen atom is involved in H-bonds formation. In the complex of EtPB with squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione, H2SQ) both carboxylate oxygen atoms are engaged in the hydrogen bonds which links molecules through two short, non-symmetric OH⋯O hydrogen bonds of 2.489(1) and 2.500(1) Å. The preferences of the conformation of the EtPB unit in the hydrogen bond formation have been studied by X-ray diffraction, FTIR and NMR spectroscopy and the results are supported by DFT calculations. EtPB, in hydrate and in the complex, has a chair conformation with the CH3CH2 group in the axial position and the CH2COO substituent in the equatorial position.

  12. Interfacial phenomena in gas hydrate systems.

    Science.gov (United States)

    Aman, Zachary M; Koh, Carolyn A

    2016-03-21

    Gas hydrates are crystalline inclusion compounds, where molecular cages of water trap lighter species under specific thermodynamic conditions. Hydrates play an essential role in global energy systems, as both a hinderance when formed in traditional fuel production and a substantial resource when formed by nature. In both traditional and unconventional fuel production, hydrates share interfaces with a tremendous diversity of materials, including hydrocarbons, aqueous solutions, and inorganic solids. This article presents a state-of-the-art understanding of hydrate interfacial thermodynamics and growth kinetics, and the physiochemical controls that may be exerted on both. Specific attention is paid to the molecular structure and interactions of water, guest molecules, and hetero-molecules (e.g., surfactants) near the interface. Gas hydrate nucleation and growth mechanics are also presented, based on studies using a combination of molecular modeling, vibrational spectroscopy, and X-ray and neutron diffraction. The fundamental physical and chemical knowledge and methods presented in this review may be of value in probing parallel systems of crystal growth in solid inclusion compounds, crystal growth modifiers, emulsion stabilization, and reactive particle flow in solid slurries.

  13. Fourier transform IR spectroscopic study of hydration-induced structure changes in the solid state of omega-gliadins.

    Science.gov (United States)

    Wellner, N; Belton, P S; Tatham, A S

    1996-11-01

    The hydration of omega-gliadins and party deamidated and esterified omega-gliadins has been studied by Fourier transform IR spectroscopy. The secondary structure of the fully hydrated proteins was a mixture of beta-turns and extended chains, with a small amount of intermolecular beta-sheets. The absorption of the glutamine side chain amide groups contributed considerably to the amide I band with two well-defined peaks at 1658 and 1610 cm-1. the amide I band of the dry native sample could not be resolved into single component bands. There the backbone structure seemed to be distorted by extensive hydrogen bonding involving glutamine side chains. With increasing water content, these hydrogen bonds were broken successively by water molecules, resulting in an increase in extended, hydrated structures, which gave rise to the formation of intermolecular beta-sheet structures. Above 35% (w/w) water the beta-sheet content fell sharply and was replaced by extensively hydrated extended structures. An amide I band similar to dissolved poly-L-proline proved that parts of the polymer were in a solution-like state. The replacement of many glutamine side chains in the esterified protein produced more resolved secondary structures even in the dry sample. The beta-sheet content of the dry sample was higher than in the native omega-gliadins, but hydration generally caused very similar changes. At all hydration levels the spectra indicated a more ordered structure than in the native sample. Overall, the modification caused changes that go beyond the simple presence or absence of glutamine bands.

  14. 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

  15. Interface nanochemistry effects on stainless steel diffusion bonding

    Science.gov (United States)

    Cox, M. J.; Carpenter, R. W.; Kim, M. J.

    2002-02-01

    The diffusion-bonding behavior of single-phase austenitic stainless steel depends strongly on the chemistry of the surfaces to be bounded. We found that very smooth (0.5 nm root-mean-square (RMS) roughness), mechanically polished and lapped substrates would bond completely in ultrahigh vacuum (UHV) in 1 hour at 1000 °C under 3.5 MPa uniaxial pressure, if the native oxide on the substrates was removed by ion-beam cleaning, as shown by in-situ Auger analysis. No voids were observed in these bonded interfaces by transmission electron microscopy (TEM), and the strength was equal to that of the unbounded bare material. No bond formed between the substrates if in-situ ion cleaning was not used. The rougher cleaned substrates partially bonded, indicating that roughness, as well as native oxides, reduced the bonding kinetics.

  16. Crystal structure and encapsulation dynamics of ice II-structured neon hydrate.

    Science.gov (United States)

    Yu, Xiaohui; Zhu, Jinlong; Du, Shiyu; Xu, Hongwu; Vogel, Sven C; Han, Jiantao; Germann, Timothy C; Zhang, Jianzhong; Jin, Changqing; Francisco, Joseph S; Zhao, Yusheng

    2014-07-22

    Neon hydrate was synthesized and studied by in situ neutron diffraction at 480 MPa and temperatures ranging from 260 to 70 K. For the first time to our knowledge, we demonstrate that neon atoms can be enclathrated in water molecules to form ice II-structured hydrates. The guest Ne atoms occupy the centers of D2O channels and have substantial freedom of movement owing to the lack of direct bonding between guest molecules and host lattices. Molecular dynamics simulation confirms that the resolved structure where Ne dissolved in ice II is thermodynamically stable at 480 MPa and 260 K. The density distributions indicate that the vibration of Ne atoms is mainly in planes perpendicular to D2O channels, whereas their distributions along the channels are further constrained by interactions between adjacent Ne atoms.

  17. Molecular dynamics simulations of trehalose as a 'dynamic reducer' for solvent water molecules in the hydration shell.

    Science.gov (United States)

    Choi, Youngjin; Cho, Kum Won; Jeong, Karpjoo; Jung, Seunho

    2006-06-12

    Systematic computational work for a series of 13 disaccharides was performed to provide an atomic-level insight of unique biochemical role of the alpha,alpha-(1-->1)-linked glucopyranoside dimer over the other glycosidically linked sugars. Superior osmotic and cryoprotective abilities of trehalose were explained on the basis of conformational and hydration characteristics of the trehalose molecule. Analyses of the hydration number and radial distribution function of solvent water molecules showed that there was very little hydration adjacent to the glycosidic oxygen of trehalose and that the dynamic conformation of trehalose was less flexible than any of the other sugars due to this anisotropic hydration. The remarkable conformational rigidity that allowed trehalose to act as a sugar template was required for stable interactions with hydrogen-bonded water molecules. Trehalose made an average of 2.8 long-lived hydrogen bonds per each MD step, which was much larger than the average of 2.1 for the other sugars. The stable hydrogen-bond network is derived from the formation of long-lived water bridges at the expense of decreasing the dynamics of the water molecules. Evidence for this dynamic reduction of water by trehalose was also established based on each of the lowest translational diffusion coefficients and the lowest intermolecular coulombic energy of the water molecules around trehalose. Overall results indicate that trehalose functions as a 'dynamic reducer' for solvent water molecules based on its anisotropic hydration and conformational rigidity, suggesting that macroscopic solvent properties could be modulated by changes in the type of glycosidic linkages in sugar molecules.

  18. Bonding with Your Baby

    Science.gov (United States)

    ... in infant massage in your area. Breastfeeding and bottle-feeding are both natural times for bonding. Infants respond ... activities include: participating together in labor and delivery feeding ( breast or bottle ); sometimes dad forms a special bond with baby ...

  19. Methane hydrates in nature - Current knowledge and challenges

    Science.gov (United States)

    Collett, Timothy S.

    2014-01-01

    Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

  20. Hydration entropy change from the hard sphere model.

    Science.gov (United States)

    Graziano, Giuseppe; Lee, Byungkook

    2002-12-10

    The gas to liquid transfer entropy change for a pure non-polar liquid can be calculated quite accurately using a hard sphere model that obeys the Carnahan-Starling equation of state. The same procedure fails to produce a reasonable value for hydrogen bonding liquids such as water, methanol and ethanol. However, the size of the molecules increases when the hydrogen bonds are turned off to produce the hard sphere system and the volume packing density rises. We show here that the hard sphere system that has this increased packing density reproduces the experimental transfer entropy values rather well. The gas to water transfer entropy values for small non-polar hydrocarbons is also not reproduced by a hard sphere model, whether one uses the normal (2.8 A diameter) or the increased (3.2 A) size for water. At least part of the reason that the hard sphere model with 2.8 A size water produces too small entropy change is that the size of water is too small for a system without hydrogen bonds. The reason that the 3.2 A model also produces too small entropy values is that this is an overly crowded system and that the free volume introduced in the system by the addition of a solute molecule produces too much of a relief to this crowding. A hard sphere model, in which the free volume increase is limited by requiring that the average surface-to-surface distance between the solute and water molecules is the same as that between the increased-size water molecules, does approximately reproduce the experimental hydration entropy values.

  1. Apparatus investigates geological aspects of gas hydrates

    Science.gov (United States)

    Booth, J.S.; Winters, W.J.; Dillon, William P.

    1999-01-01

    The US Geological Survey has developed a laboratory research system which allows the study of the creation and dissociation of gas hydrates under deepwater conditions and with different sediment types and pore fluids. The system called GHASTLI (gas hydrate and sediment test laboratory instrument) comprises a pressure chamber which holds a sediment specimen, and which can simulate water depths to 2,500m and different sediment overburden. Seawater and gas flow through a sediment specimen can be precisely controlled and monitored. It can simulate a wide range of geology and processes and help to improve understanding of gas hydrate processes and aid prediction of geohazards, their control and potential use as an energy source. This article describes GHASTLI and how it is able to simulate natural conditions, focusing on fluid volume, acoustic velocity-compressional and shear wave, electric resistance, temperature, pore pressure, shear strength, and permeability.

  2. Hydrogen-bonded sheets in benzylmethylammonium hydrogen maleate.

    Science.gov (United States)

    Santacruz, Lynay; Abonia, Rodrigo; Cobo, Justo; Low, John N; Glidewell, Christopher

    2007-10-01

    In the title compound, C(8)H(12)N(+).C(4)H(3)O(4)(-), there is a short and almost linear but asymmetric O-H...O hydrogen bond in the anion. The ions are linked into C(2)(2)(6) chains by two short and nearly linear N-H...O hydrogen bonds and the chains are further weakly linked into sheets by a single C-H...O hydrogen bond.

  3. 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.

  4. Acrylic mechanical bond tests

    Energy Technology Data Exchange (ETDEWEB)

    Wouters, J.M.; Doe, P.J.

    1991-02-01

    The tensile strength of bonded acrylic is tested as a function of bond joint thickness. 0.125 in. thick bond joints were found to posses the maximum strength while the acceptable range of joints varied from 0.063 in. to almost 0.25 in. Such joints are used in the Sudbury Neutrino Observatory.

  5. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  6. 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

  7. Cell hydration as a biomarker for estimation of biological effects of nonionizing radiation on cells and organisms.

    Science.gov (United States)

    Ayrapetyan, Sinerik; De, Jaysankar

    2014-01-01

    "Changes in cell hydration" have been hypothesized as an input signal for intracellular metabolic cascade responsible for biological effects of nonionizing radiation (NIR). To test this hypothesis a comparative study on the impacts of different temperature and NIR (infrasound frequency mechanical vibration (MV), static magnetic field (SMF), extremely low frequency electromagnetic field (ELF EMF), and microwave (MW)) pretreated water on the hydration of barley seeds in its dormant and germination periods was performed. In dormant state temperature sensitivity (Q 10) of seed hydration in distilled water (DW) was less than 2, and it was nonsensitive to NIR treated DW, whereas during the germination period (48-72 hours) seeds hydration exhibited temperature sensitivity Q 10 > 2 and higher sensitivity to NIR treated DW. Obtained data allow us to suggest that the metabolic driving of intracellular water dynamics accompanied by hydrogen bonding and breaking is more sensitive to NIR-induced water structure changes in seed bathing aqua medium than the simple thermodynamic processes such as osmotic gradient driven water absorption by seeds in dormant state. Therefore, cell hydration is suggested to be a universal and extrasensitive biomarker for detection of biological effects of NIR on cells and organisms.

  8. Simulation of subsea gas hydrate exploitation

    Science.gov (United States)

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

    2014-05-01

    The recovery of methane from gas hydrate layers that have been detected in several subsea sediments and permafrost regions around the world is a promising perspective to overcome future shortages in natural gas supply. Being aware that conventional natural gas resources are limited, research is going on to develop technologies for the production of natural gas from such new sources. Thus various research programs have started since the early 1990s in Japan, USA, Canada, India, and Germany to investigate hydrate deposits and develop required technologies. In recent years, intensive research has focussed on the capture and storage of CO2 from combustion processes to reduce climate impact. While different natural or man-made reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid CO2, the storage of CO2 as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in the form of hydrates. Regarding technological implementation many problems have to be overcome. Especially mixing, heat and mass transfer in the reservoir are limiting factors causing very long process times. Within the scope of the German research project »SUGAR« different technological approaches for the optimized exploitation of gas hydrate deposits are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical processes are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs. Simulations based on geological field data have been carried out. The studies focus on the potential of gas production from turbidites and their fitness for CO2 storage. The effects occurring during gas production and CO2 storage within

  9. Component analysis of the protein hydration entropy

    Science.gov (United States)

    Chong, Song-Ho; Ham, Sihyun

    2012-05-01

    We report the development of an atomic decomposition method of the protein solvation entropy in water, which allows us to understand global change in the solvation entropy in terms of local changes in protein conformation as well as in hydration structure. This method can be implemented via a combined approach based on molecular dynamics simulation and integral-equation theory of liquids. An illustrative application is made to 42-residue amyloid-beta protein in water. We demonstrate how this method enables one to elucidate the molecular origin for the hydration entropy change upon conformational transitions of protein.

  10. 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.

  11. 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.

  12. 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.

  13. Temperature-dependent dielectric properties of slightly hydrated horn keratin.

    Science.gov (United States)

    Rizvi, Tasneem Zahra; Khan, Muhammad Abdullah

    2008-04-01

    With an aim to reveal the mechanism of protein-water interaction in a predominantly two phase model protein system this study investigates the frequency and temperature dependence of dielectric constant epsilon' and loss factor epsilon'' in cow horn keratin in the frequency range 30 Hz to 3 MHz and temperature range 30-200 degrees C at two levels of hydration. These two levels of hydration were achieved by exposing the sample to air at 50% relative humidity (RH) at ambient temperature and by evacuating the sample for 72 h at 105 degrees C. A low frequency dispersion (LFD) and an intermediate frequency alpha-dispersion were the two main dielectric responses observed in the air-dried sample. The LFD and the high frequency arm of the alpha-dispersion followed the same fractional power law of frequency. Within the framework of percolation cluster model these dispersions, respectively have been attributed to percolation of protons between and within the clusters of hydrogen-bonded water molecules bound to polar or ionizable protein components. The alpha-dispersion peak, which results from intra-cluster charge percolation conformed to Cole-Cole modified Debye equation. Temperature dependence of the dielectric constant in the air-dried sample exhibited peaks at 120 and 155 degrees C which have been identified as temperatures of onset of release of water bound to polar protein components in the amorphous and crystalline regions, respectively. An overall rise in the permittivity was observed above 175 degrees C, which has been identified as the onset of chain melting in the crystalline region of the protein.

  14. Gas hydrate of Lake Baikal: Discovery and varieties

    Science.gov (United States)

    Khlystov, Oleg; De Batist, Marc; Shoji, Hitoshi; Hachikubo, Akihiro; Nishio, Shinya; Naudts, Lieven; Poort, Jeffrey; Khabuev, Andrey; Belousov, Oleg; Manakov, Andrey; Kalmychkov, Gennаdy

    2013-01-01

    This paper summarizes 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 provide a historical overview of the different investigations and discoveries and highlight some recent breakthroughs in our understanding of the Baikal hydrate system. So far, 21 sites of gas hydrate occurrence have been discovered. Gas hydrates are of structures I and II, which are of thermogenic, microbial, and mixed origin. At the 15 sites, gas hydrates were found in mud volcanoes, and the rest six - near gas discharges. Additionally, depending on type of discharge and gas hydrate structure, they were visually different. Investigations using MIR submersibles allowed finding of gas hydrates at the bottom surface of Lake Baikal at the three sites.

  15. Unraveling the Sc(3+) Hydration Geometry: The Strange Case of the Far-Coordinated Water Molecule.

    Science.gov (United States)

    Migliorati, Valentina; D'Angelo, Paola

    2016-07-05

    The hydration structure and dynamics of Sc(3+) in aqueous solution have been investigated using a combined approach based on quantum mechanical (QM) calculations, molecular dynamics (MD) simulations, and extended X-ray absorption fine structure (EXAFS) spectroscopy. An effective Sc-water two-body potential has been generated from QM calculations and then used in the MD simulation of Sc(3+) in water, and the reliability of the entire procedure has been assessed by comparing the theoretical structural results with the EXAFS experimental data. The outstanding outcome of this work is that the Sc(3+) ion forms a well-defined capped square antiprism (SAP) complex in aqueous solution, where the eight water molecules closest to the ion are located at the vertexes of a SAP polyhedron, while the ninth water molecule occupying the capping position is unusually found at a very long distance from the ion. This far-coordinated water molecule possesses a degree of structure comparable with the other first shell molecules surrounding the ion at much shorter distances, and its presence gave us the unique opportunity to easily identify the geometry of the Sc(3+) coordination polyhedron. Despite very strong ion-water interactions, the Sc(3+) hydration shell is very labile, as the far-coordinated ligand allows first shell water molecules to easily exchange their positions both inside the solvation shell and with the rest of the solvent molecules.

  16. In situ molecular imaging of hydrated biofilm in a microfluidic reactor by ToF-SIMS

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Xin; Yu, Xiao-Ying; Wang, Zhaoying; Yang, Li; Liu, Bingwen; Zhu, Zihua; Tucker, Abigail E.; Chrisler, William B.; Hill, Eric A.; Thevuthasan, Suntharampillai; Lin, Yuehe; Liu, Songqin; Marshall, Matthew J.

    2014-02-26

    The first results of using a novel single channel microfluidic reactor to enable Shewanella biofilm growth and in situ characterization using time-of-flight secondary ion mass spectrometry (ToF-SIMS) in the hydrated environment are presented. The new microfluidic interface allows direct probing of the liquid surface using ToF-SIMS, a vacuum surface technique. The detection window is an aperture of 2 m in diameter on a thin silicon nitride (SiN) membrane and it allows direct detection of the liquid surface. Surface tension of the liquid flowing inside the microchannel holds the liquid within the aperture. ToF-SIMS depth profiling was used to drill through the SiN membrane and the biofilm grown on the substrate. In situ 2D imaging of the biofilm in hydrated state was acquired, providing spatial distribution of the chemical compounds in the biofilm system. This data was compared with a medium filled microfluidic reactor devoid of biofilm and dried biofilm samples deposited on clean silicon wafers. Principle Component Analysis (PCA) was used to investigate these observations. Our results show that imaging biofilms in the hydrated environment using ToF-SIMS is possible using the unique microfluidic reactor. Moreover, characteristic biofilm fatty acids fragments were observed in the hydrated biofilm grown in the microfluidic channel, illustrating the advantage of imaging biofilm in its native environment.

  17. The mechanism of the dehydration of alcohols and the hydration of alkenes in acid solution

    Science.gov (United States)

    Vinnik, M. I.; Obraztsov, P. A.

    1990-01-01

    Kinetic data for the hydration of unsaturated compounds, the dehydration of alcohols, and the isotope exchange of the oxygen atom in alcohols and aqueous solutions of strong acids are analysed to establish the detailed mechanisms of these reactions. The catalytic action of the acid is caused not only by its ability to protonate the reactant but also by the possibility of the formation of reactive complexes of the reactant with the acid hydrates or the molecules of the undissociated acids. Equations are presented whereby the influence of the ionising capacity of the medium on the effective rate constants for the reactions indicated can be taken into account quantitatively. The question of the involvement of carbonium ions as reactive intermediates in reactions involving the dehydration of alcohols, the hydration of unsaturated compounds, and the isotope exchange of the oxygen atom in alcohols is examined. Complexes of the reactant with a solvated proton, the acid molecules, and the acid hydrates are the intermediates in these reactions. The relative contributions of the complexes to the effective rate constant depend on the acid concentration in the aqueous solution. The bibliography includes 65 references

  18. Protection of MOS capacitors during anodic bonding

    Science.gov (United States)

    Schjølberg-Henriksen, K.; Plaza, J. A.; Rafí, J. M.; Esteve, J.; Campabadal, F.; Santander, J.; Jensen, G. U.; Hanneborg, A.

    2002-07-01

    We have investigated the electrical damage by anodic bonding on CMOS-quality gate oxide and methods to prevent this damage. n-type and p-type MOS capacitors were characterized by quasi-static and high-frequency CV-curves before and after anodic bonding. Capacitors that were bonded to a Pyrex wafer with 10 μm deep cavities enclosing the capacitors exhibited increased leakage current and interface trap density after bonding. Two different methods were successful in protecting the capacitors from such damage. Our first approach was to increase the cavity depth from 10 μm to 50 μm, thus reducing the electric field across the gate oxide during bonding from approximately 2 × 105 V cm-1 to 4 × 104 V cm-1. The second protection method was to coat the inside of a 10 μm deep Pyrex glass cavity with aluminium, forming a Faraday cage that removed the electric field across the cavity during anodic bonding. Both methods resulted in capacitors with decreased interface trap density and unchanged leakage current after bonding. No change in effective oxide charge or mobile ion contamination was observed on any of the capacitors in the study.

  19. The influence of hydrogen bonding on partition coefficients

    Science.gov (United States)

    Borges, Nádia Melo; Kenny, Peter W.; Montanari, Carlos A.; Prokopczyk, Igor M.; Ribeiro, Jean F. R.; Rocha, Josmar R.; Sartori, Geraldo Rodrigues

    2017-02-01

    This Perspective explores how consideration of hydrogen bonding can be used to both predict and better understand partition coefficients. It is shown how polarity of both compounds and substructures can be estimated from measured alkane/water partition coefficients. When polarity is defined in this manner, hydrogen bond donors are typically less polar than hydrogen bond acceptors. Analysis of alkane/water partition coefficients in conjunction with molecular electrostatic potential calculations suggests that aromatic chloro substituents may be less lipophilic than is generally believed and that some of the effect of chloro-substitution stems from making the aromatic π-cloud less available to hydrogen bond donors. Relationships between polarity and calculated hydrogen bond basicity are derived for aromatic nitrogen and carbonyl oxygen. Aligned hydrogen bond acceptors appear to present special challenges for prediction of alkane/water partition coefficients and this may reflect `frustration' of solvation resulting from overlapping hydration spheres. It is also shown how calculated hydrogen bond basicity can be used to model the effect of aromatic aza-substitution on octanol/water partition coefficients.

  20. The influence of hydrogen bonding on partition coefficients

    Science.gov (United States)

    Borges, Nádia Melo; Kenny, Peter W.; Montanari, Carlos A.; Prokopczyk, Igor M.; Ribeiro, Jean F. R.; Rocha, Josmar R.; Sartori, Geraldo Rodrigues

    2017-01-01

    This Perspective explores how consideration of hydrogen bonding can be used to both predict and better understand partition coefficients. It is shown how polarity of both compounds and substructures can be estimated from measured alkane/water partition coefficients. When polarity is defined in this manner, hydrogen bond donors are typically less polar than hydrogen bond acceptors. Analysis of alkane/water partition coefficients in conjunction with molecular electrostatic potential calculations suggests that aromatic chloro substituents may be less lipophilic than is generally believed and that some of the effect of chloro-substitution stems from making the aromatic π-cloud less available to hydrogen bond donors. Relationships between polarity and calculated hydrogen bond basicity are derived for aromatic nitrogen and carbonyl oxygen. Aligned hydrogen bond acceptors appear to present special challenges for prediction of alkane/water partition coefficients and this may reflect `frustration' of solvation resulting from overlapping hydration spheres. It is also shown how calculated hydrogen bond basicity can be used to model the effect of aromatic aza-substitution on octanol/water partition coefficients.

  1. Foam drilling in natural gas hydrate

    Directory of Open Access Journals (Sweden)

    Wei Na

    2015-01-01

    Full Text Available The key problem of foam drilling in natural gas hydrate is prediction of characteristic parameters of bottom hole. The simulation shows that when the well depth increases, the foam mass number reduces and the pressure increases. At the same depth, pressure in drill string is always higher than annulus. The research findings provide theoretical basis for safety control.

  2. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, W.; Brouwers, H.J.H.

    2010-01-01

    The alkali-binding capacity of C–S–H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C–S–H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data

  3. Binding Hydrated Anions with Hydrophobic Pockets.

    Science.gov (United States)

    Sokkalingam, Punidha; Shraberg, Joshua; Rick, Steven W; Gibb, Bruce C

    2016-01-13

    Using a combination of isothermal titration calorimetry and quantum and molecular dynamics calculations, we demonstrate that relatively soft anions have an affinity for hydrophobic concavity. The results are consistent with the anions remaining partially hydrated upon binding, and suggest a novel strategy for anion recognition.

  4. Obsidian Hydration Dating in the Undergraduate Curriculum.

    Science.gov (United States)

    Manche, Emanuel P.; Lakatos, Stephen

    1986-01-01

    Provides an overview of obsidian hydration dating for the instructor by presenting: (1) principles of the method; (2) procedures; (3) applications; and (4) limitations. The theory of the method and one or more laboratory exercises can be easily introduced into the undergraduate geology curriculum. (JN)

  5. Acoustic Determination of Methane Hydrate Disssociation Pressures

    Science.gov (United States)

    2011-07-01

    centered- cubic orientation which forms naturally in deep oceans from biogenic gases. It is worth not- ing that this molecular geometry can trap great...until January 2010. At that time, the hydrates were packed in a dewar with liquid nitrogen and shipped from the storage fa- cility at the Naval Research

  6. [Terminal phase hydration, pain and delirium

    DEFF Research Database (Denmark)

    Heick, A.

    2009-01-01

    Hydration of the terminal patient may relieve confusion and complaints of "dry mouth". But it may worsen oedema of the brain, lungs, and extremities, worsen terminal rattling and cause a need for frequent changing of diapers. The decision of whether and how to treat a dying patient with fluids...

  7. A positron annihilation study of hydrated DNA

    DEFF Research Database (Denmark)

    Warman, J. M.; Eldrup, Morten Mostgaard

    1986-01-01

    Positron annihilation measurements are reported for hydrated DNA as a function of water content and as a function of temperature (20 to -180.degree. C) for samples containing 10 and 50% wt of water. The ortho-positronium mean lifetime and its intensity show distinct variations with the degree...

  8. Hydration dynamics near a model protein surface

    Energy Technology Data Exchange (ETDEWEB)

    Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

    2003-09-01

    The evolution of water dynamics from dilute to very high concentration solutions of a prototypical hydrophobic amino acid with its polar backbone, N-acetyl-leucine-methylamide (NALMA), is studied by quasi-elastic neutron scattering and molecular dynamics simulation for both the completely deuterated and completely hydrogenated leucine monomer. We observe several unexpected features in the dynamics of these biological solutions under ambient conditions. The NALMA dynamics shows evidence of de Gennes narrowing, an indication of coherent long timescale structural relaxation dynamics. The translational water dynamics are analyzed in a first approximation with a jump diffusion model. At the highest solute concentrations, the hydration water dynamics is significantly suppressed and characterized by a long residential time and a slow diffusion coefficient. The analysis of the more dilute concentration solutions takes into account the results of the 2.0M solution as a model of the first hydration shell. Subtracting the first hydration layer based on the 2.0M spectra, the translational diffusion dynamics is still suppressed, although the rotational relaxation time and residential time are converged to bulk-water values. Molecular dynamics analysis shows spatially heterogeneous dynamics at high concentration that becomes homogeneous at more dilute concentrations. We discuss the hydration dynamics results of this model protein system in the context of glassy systems, protein function, and protein-protein interfaces.

  9. JOINING MECHANISM OF FIELD-ASSISTED BONDING OF ELECTROLYTE GLASS TO METALS

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Investigations of technological characteristics and bonding mechanism of field-assisted bonding are done, which are for bonding of electrolytes (Pyrex glass) to monocrystal silicon and aluminum. The features of microstructure and the distribution of the diffused elements in the bonding interface area are studied by means of SEM, EDX and XRD, and the influence of the technological factors on the bonding process is also studied. The model of"metal-oxides-glass"of bonding structure and ions diffusion and bonding in the condition of electrical field-assisted are indicated.

  10. Anaerobic oxidation of methane above gas hydrates at Hydrate Ridge, NE Pacific Ocean

    DEFF Research Database (Denmark)

    Treude, T.; Boetius, A.; Knittel, K.;

    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...... bacteria, generates high concentrations of hydrogen sulfide in the surface sediments. The production of sulfide supports chemosynthetic communities that gain energy from sulfide oxidation. Depending on fluid flow, the surface communities are dominated either by the filamentous sulfur bacteria Beggiatoa...

  11. Molecular simulation study of temperature effect on ionic hydration in carbon nanotubes.

    Science.gov (United States)

    Shao, Qing; Huang, Liangliang; Zhou, Jian; Lu, Linghong; Zhang, Luzheng; Lu, Xiaohua; Jiang, Shaoyi; Gubbins, Keith E; Shen, Wenfeng

    2008-04-14

    Molecular dynamics simulations have been performed to investigate the hydration of Li(+), Na(+), K(+), F(-), and Cl(-) inside the carbon nanotubes at temperatures ranging from 298 to 683 K. The structural characteristics of the coordination shells of ions are studied, including the ion-oxygen radial distribution functions, the coordination numbers, and the orientation distributions of the water molecules. Simulation results show that the first coordination shells of the five ions still exist in the nanoscale confinement. Nevertheless, the first coordination shell structures of cations change more significantly than those of anions because of the preferential orientation of the water molecules induced by the carbon nanotube. The first coordination shells of cations are considerably less ordered in the nanotube than in the bulk solution, whereas the change of the first coordination shell structures of the anions is minor. Furthermore, the confinement induces the anomalous behavior of the coordination shells of the ions with temperature. The first coordination shell of K(+) are found to be more ordered as the temperature increases only in the carbon nanotube with the effective diameter of 1.0 nm, implying the enhancement of the ionic hydration with temperature. This is contrary to that in the bulk solution. The coordination shells of the other four ions do not have such behavior in the carbon nanotube with the effective diameter ranging from 0.73 to 1.00 nm. The easier distortion of the coordination shell of K(+) and the match of the shell size and the nanotube size may play roles in this phenomenon. The exchange of water molecules in the first coordination shells of the ions with the solution and the ion diffusion along the axial direction of the nanotube are also investigated. The mobility of the ions and the stability of the coordination shells are greatly affected by the temperature in the nanotube as in the bulk solutions. These results help to understand the

  12. Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

    Science.gov (United States)

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

    2005-01-01

    The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

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

    Directory of Open Access Journals (Sweden)

    Beatrice Castellani

    2014-09-01

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

  14. MORPHOLOGY OF METHANE HYDRATE HOST SEDIMENTS.

    Energy Technology Data Exchange (ETDEWEB)

    JONES,K.W.; FENG,H.; TOMOV,S.; WINTER,W.J.; EATON,M.; MAHAJAN,D.

    2004-12-01

    Results from simulated experiments in several laboratories show that host sediments influence hydrate formation in accord with known heterogeneity of host sediments at sites of gas hydrate occurrence (1). For example, in Mackenzie Delta, NWT Canada (Mallik 2L-38 well), coarser-grained units (pore-filling model) are found whereas in the Gulf of Mexico, the found hydrate samples do not appear to be lithologically controlled. We have initiated a systematic study of sediments, initially focusing on samples from various depths at a specific site, to establish a correlation with hydrate occurrence (or variations thereof) to establish differences in their microstructure, porosity, and other associated properties. The synchrotron computed microtomography (CMT) set-up at the X-27A tomography beam line at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory was used as a tool to study sediments from Blake Ridge at three sub bottom depths of 0.2, 50, and 667 meters. Results from the tomographic analysis of the deepest sample (667 m) are presented here to illustrate how tomography can be used to obtain new insights into the structures of methane hydrate host sediments. The investigation shows the internal grain/pore space resolution in the microstructure and a 3-D visualization of the connecting pathways obtained following data segmentation into pore space and grains within the sediment sample. The analysis gives the sample porosity, specific surface area, mean particle size, and tortuosity, as well. An earlier report on the experimental program has been given by Mahajan et al. (2).

  15. China's Research on Non-conventional Energy Resources- Gas Hydrate

    Institute of Scientific and Technical Information of China (English)

    Pu Ming; Ma Jianguo

    2002-01-01

    @@ Methane exists in ice-like formations called gas hydrate. Hydrate traps methane molecules inside a cage of frozen water. The magnitude of this previously unknown global storehouse of methane is truly staggering and has raised serious inquiry into the possibility of using methane hydrate as a substitute source of energy for oil and conventional natural gas. According to the estimation by PGC, gas hydrate deposits amount to 7.6 × 1018m3 and contain more than twice as much organic carbon as all the world's coal, oil and non-hydrate natural gas combined.

  16. Particle beam technology for control of atomic-bonding state in materials

    Energy Technology Data Exchange (ETDEWEB)

    Ishikawa, Junzo [Kyoto Univ. (Japan). Faculty of Engineering

    1997-03-01

    The atomic-bonding state in materials can be controlled through `kinetic bonding` process by energetic particle beams which have a sufficient atomic kinetic energy. In order to clarify the `kinetic bonding` process the negative-ion beam deposition is considered as an ideal method because the negative ion has no additional active energies. Sputter type heavy negative-ion sources can be used for this purpose. Carbon films prepared by carbon negative-ion beam deposition have a strong dependency of the film properties on ion beam kinetic energy and have a quite high thermal conductivity which is comparable to that of the IIb diamond at a kinetic energy of 50-100 eV/atom. It suggests that new or metastable materials could be formed through the `kinetic bonding` process. Negative-ion beams can also be used for ion implantation, in which charging problems are perfectly reduced. (author)

  17. Ionic hydrates, M(p)X(q).nH(2)O: lattice energy and standard enthalpy of formation estimation.

    Science.gov (United States)

    Jenkins, H Donald Brooke; Glasser, Leslie

    2002-08-26

    This paper is one of a series (see: Inorg. Chem. 1999, 38, 3609; J. Am. Chem. Soc. 2000, 122, 632; Inorg. Chem. 2002, 41, 2364) exploring simple approaches for the estimation of lattice energies of ionic materials, avoiding elaborate computation. Knowledge of lattice energy can lead, via thermochemical cycles, to the evaluation of the underlying thermodynamics involving the preparation and subsequent reactions of inorganic materials. A simple and easy to use equation for the estimation of the lattice energy of hydrate salts, U(POT)(M(p)X(q).nH(2)O) (and therefore for solvated salts, M(p)X(q).nS, in general), using either the density or volume of the hydrate, or of another hydrate, or of the parent anhydrous salt or the volumes of the individual ions, is derived from first principles. The equation effectively determines the hydrate lattice energy, U(POT)(M(p)X(q).nH(2)O), from a knowledge of the (estimated) lattice energy, U(POT)(M(p)X(q)), of the parent salt by the addition of ntheta(U) where theta(U)(H(2)O)/kJ mol(-1) = 54.3 and n is the number of water molecules. The average volume of the water molecule of hydration, V(m)(H(2)O)/nm(3) = 0.0245, has been determined from data on a large series of hydrates by plotting hydrate/parent salt volume differences against n. The enthalpy of incorporation of a gaseous water molecule into the structure of an ionic hydrate, [Delta(f)H degrees (M(p)X(q).nH(2)O,s) - Delta(f)H degrees (M(p)X(q),s) - nDelta(f)H degrees (H(2)O,g)], is shown to be a constant, -56.8 kJ (mol of H(2)O)(-1). The physical implications with regard to incorporation of the water into various types of solid-state structures are considered. Examples are given of the use of the derived hydrate lattice energy equation. Standard enthalpies of formation of a number of hydrates are thereby predicted.

  18. Indian National Gas Hydrate Program Expedition 01 report

    Science.gov (United States)

    Collett, Timothy S.; Riedel, M.; Boswell, R.; Presley, J.; Kumar, P.; Sathe, A.; Sethi, A.; Lall, M.; ,

    2015-01-01

    Gas hydrate is a naturally occurring “ice-like” combination of natural gas and water that has the potential to serve as an immense resource of natural gas from the world’s oceans and polar regions. However, gas-hydrate recovery is both a scientific and a technical challenge and much remains to be learned about the geologic, engineering, and economic factors controlling the ultimate energy resource potential of gas hydrate. The amount of natural gas contained in the world’s gas-hydrate accumulations is enormous, but these estimates are speculative and range over three orders of magnitude from about 2,800 to 8,000,000 trillion cubic meters of gas. By comparison, conventional natural gas accumulations (reserves and undiscovered, technically recoverable resources) for the world are estimated at approximately 440 trillion cubic meters. Gas recovery from gas hydrate is hindered because the gas is in a solid form and because gas hydrate commonly occurs in remote Arctic and deep marine environments. Proposed methods of gas recovery from gas hydrate generally deal with disassociating or “melting” in situ gas hydrate by heating the reservoir beyond the temperature of gas-hydrate formation, or decreasing the reservoir pressure below hydrate equilibrium. The pace of energy-related gas hydrate assessment projects has accelerated over the past several years.

  19. Water retention curve for hydrate-bearing sediments

    Science.gov (United States)

    Dai, Sheng; Santamarina, J. Carlos

    2013-11-01

    water retention curve plays a central role in numerical algorithms that model hydrate dissociation in sediments. The determination of the water retention curve for hydrate-bearing sediments faces experimental difficulties, and most studies assume constant water retention curves regardless of hydrate saturation. This study employs network model simulation to investigate the water retention curve for hydrate-bearing sediments. Results show that (1) hydrate in pores shifts the curve to higher capillary pressures and the air entry pressure increases as a power function of hydrate saturation; (2) the air entry pressure is lower in sediments with patchy rather than distributed hydrate, with higher pore size variation and pore connectivity or with lower specimen slenderness along the flow direction; and (3) smaller specimens render higher variance in computed water retention curves, especially at high water saturation Sw > 0.7. Results are relevant to other sediment pore processes such as bioclogging and mineral precipitation.

  20. Towards a green hydrate inhibitor: imaging antifreeze proteins on clathrates.

    Directory of Open Access Journals (Sweden)

    Raimond Gordienko

    Full Text Available The formation of hydrate plugs in oil and gas pipelines is a serious industrial problem and recently there has been an increased interest in the use of alternative hydrate inhibitors as substitutes for thermodynamic inhibitors like methanol. We show here that antifreeze proteins (AFPs possess the ability to modify structure II (sII tetrahydrofuran (THF hydrate crystal morphologies by adhering to the hydrate surface and inhibiting growth in a similar fashion to the kinetic inhibitor poly-N-vinylpyrrolidone (PVP. The effects of AFPs on the formation and growth rate of high-pressure sII gas mix hydrate demonstrated that AFPs are superior hydrate inhibitors compared to PVP. These results indicate that AFPs may be suitable for the study of new inhibitor systems and represent an important step towards the development of biologically-based hydrate inhibitors.

  1. A Wearable Hydration Sensor with Conformal Nanowire Electrodes.

    Science.gov (United States)

    Yao, Shanshan; Myers, Amanda; Malhotra, Abhishek; Lin, Feiyan; Bozkurt, Alper; Muth, John F; Zhu, Yong

    2017-01-27

    A wearable skin hydration sensor in the form of a capacitor is demonstrated based on skin impedance measurement. The capacitor consists of two interdigitated or parallel electrodes that are made of silver nanowires (AgNWs) in a polydimethylsiloxane (PDMS) matrix. The flexible and stretchable nature of the AgNW/PDMS electrode allows conformal contact to the skin. The hydration sensor is insensitive to the external humidity change and is calibrated against a commercial skin hydration system on an artificial skin over a wide hydration range. The hydration sensor is packaged into a flexible wristband, together with a network analyzer chip, a button cell battery, and an ultralow power microprocessor with Bluetooth. In addition, a chest patch consisting of a strain sensor, three electrocardiography electrodes, and a skin hydration sensor is developed for multimodal sensing. The wearable wristband and chest patch may be used for low-cost, wireless, and continuous monitoring of skin hydration and other health parameters.

  2. Comparative Assessment of Advanced Gay Hydrate Production Methods

    Energy Technology Data Exchange (ETDEWEB)

    M. D. White; B. P. McGrail; S. K. Wurstner

    2009-06-30

    Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to pore clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.

  3. Multiple internal reflectance infrared spectra of variably hydrated hemoglobin and myoglobin films: effects of globin hydration on ligand conformer dynamics and reactivity at the heme.

    Science.gov (United States)

    Brown, W E; Sutcliffe, J W; Pulsinelli, P D

    1983-06-07

    Multiple internal reflectance infrared (IR) spectra are reported for variably hydrated films (1.2-0.1 g of H2O/g of protein) of the carbon monoxy and oxy forms of human Hb and sperm whale Mb. The spectra show that even the limited removal of liquid and icelike hydration constraints at the globin surface is sufficient to cause a dramatic, but completely reversible, shift toward a normally minute population of sterically unhindered, linear-perpendicular, Fe-CO conformer modes (nu CO = 1968-1967 cm-1), and the destabilization of distally hindered, tilted (or bent), Fe-CO modes (nu CO = 1951, 1944-1933 cm-1). Corroborative evidence from IR band broadening trends [delta delta nu 1/2 (1968, 1967 cm-1) approximately 2-4 cm-1], corresponding changes in the visible, and H-D exchange kinetics confirm that the shift toward 1968-1967 cm-1 results in a more open distal heme pocket configuration and that it is also accompanied by a buildup of deoxy-like steric hindrance proximal to the heme. Denaturation effects are eliminated as a potential cause of the shifts, as are specific protein-protein, ion-protein, intersubunit, and MIR crystal-film surface interactions. The hydration effect exhibits globin-dependent and ligand-dependent differences, which highlight the intrinsic importance of distal steric effects within the heme pocket and their dynamic coupling with exterior solvent constraints. CO-photodissociation and O2-exchange experiments conducted on rapidly interconverting (coupled and fully hydrated) and noninterconverting (uncoupled and partially hydrated) Fe-CO conformers also suggest that the open linear-perpendicular mode corresponds to a more tightly bound form of CO than the axially distorted Fe-CO species; similar differences are not evident in Fe-O2, which already prefers a bent end-on geometry within the heme pocket. Control IR spectra aimed at monitoring the progressive effects of various denaturants on HbCO further indicate that this same open mode serves as a

  4. Removal of methyl orange from aqueous solutions through adsorption by calcium aluminate hydrates.

    Science.gov (United States)

    Zhang, Ping; Wang, Tianqi; Qian, Guangren; Wu, Daishe; Frost, Ray L

    2014-07-15

    Methyl orange (MO) is a kind of anionic dye and widely used in industry. In this study, tricalcium aluminate hydrates (Ca-Al-LDHs) are used as an adsorbent to remove methyl orange (MO) from aqueous solutions. The resulting products were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), thermal analysis (TG-DTA) and scanning electron microscope (SEM). The XRD results indicated that the MO molecules were successfully intercalated into the tricalcium aluminate hydrates, with the basal spacing of Ca-Al-LDH expanding to 2.48 nm. The MIR spectrum for CaAl-MO-LDH shows obvious bands assigned to the N=N, N=H stretching vibrations and S=O, SO3(-) group respectively, which are considered as marks to assess MO(-) ion intercalation into the interlayers of LDH. The overall morphology of CaAl-MO-LDH displayed a "honey-comb" like structure, with the adjacent layers expanded.

  5. The observation of scintillation in a hydrated inorganic compound: CeCl3 6H2O

    Energy Technology Data Exchange (ETDEWEB)

    Boatner, Lynn A [ORNL; Neal, John S [ORNL; Ramey, Joanne Oxendine [ORNL; Chakoumakos, Bryan C [ORNL; Custelcean, Radu [ORNL

    2013-01-01

    We have recently reported the discovery of a new family of rare-earth metal-organic single-crystal scintillators based on Ce3+ as the activator ion. Starting with the CeCl3(CH3OH)4 prototype, this family of scintillators has recently been extended to include complex metal-organic adducts produced by reacting CeCl3 with heavier organics (e.g., isomers of propanol and butanol). Some of these new rare-earth metal-organic materials incorporated waters of hydration in their structures, and the observation of scintillation in these hydrated compounds was an original finding for any solid scintillator. In the present work, we now report what is apparently the initial observation of gamma-ray-excited scintillation in an inorganic hydrated material, namely single-crystal monoclinic CeCl3 6H2O. This observation shows that the mechanisms of the various scintillation energy-transfer processes are not blocked by the presence of waters of hydration in an inorganic material and that the observation of scintillation in other hydrated inorganic compounds is not precluded.

  6. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  7. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  8. Hydration index--a better parameter for explaining small molecule hydration in inhibition of ice recrystallization.

    Science.gov (United States)

    Tam, Roger Y; Ferreira, Sandra S; Czechura, Pawel; Chaytor, Jennifer L; Ben, Robert N

    2008-12-24

    Several simple mono- and disaccharides have been assessed for their ability to inhibit ice recrystallization. Two carbohydrates were found to be effective recrystallization inhibitors. D-galactose (1) was the best monosaccharide and D-melibiose (5) was the most active disaccharide. The ability of each carbohydrate to inhibit ice growth was correlated to its respective hydration number reported in the literature. A hydration number reflects the number of tightly bound water molecules to the carbohydrate and is a function of carbohydrate stereochemistry. It was discovered that using the absolute hydration number of a carbohydrate does not allow one to accurately predict its ability to inhibit ice recrystallization. Consequently, we have defined a hydration index in which the hydration number is divided by the molar volume of the carbohydrate. This new parameter not only takes into account the number of water molecules tightly bound to a carbohydrate but also the size or volume of a particular solute and ultimately the concentration of hydrated water molecules. The hydration index of both mono- and disaccharides correlates well with experimentally measured RI activity. C-Linked derivatives of the monosaccharides appear to have RI activity comparable to that of their O-linked saccharides but a more thorough investigation is required. The relationship between carbohydrate concentration and RI activity was shown to be noncolligative and a 0.022 M solution of D-galactose (1) and C-linked galactose derivative (10) inhibited recrystallization as well as a 3% DMSO solution. The carbohydrates examined in this study did not possess any thermal hysteresis activity (selective depression of freezing point relative to melting point) or dynamic ice shaping. As such, we propose that they are inhibiting recrystallization at the interface between bulk water and the quasi liquid layer (a semiordered interface between ice and bulk water) by disrupting the preordering of water.

  9. Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

    Science.gov (United States)

    Collett, Timothy S.; Boswell, Ray; Cochran, J.R.; Kumar, Pushpendra; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna

    2014-01-01

    The Indian National Gas Hydrate Program Expedition 01 (NGHP-01) is designed to study the occurrence of gas hydrate along the passive continental margin of the Indian Peninsula and in the Andaman convergent margin, with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. The NGHP-01 expedition established the presence of gas hydrates in the Krishna-Godavari and Mahanadi Basins, and the Andaman Sea. The expedition discovered in the Krishna-Godavari Basin one of the thickest gas hydrate accumulations ever documented, in the Andaman Sea one of the thickest and deepest gas hydrate stability zones in the world, and established the existence of a fully developed gas hydrate petroleum system in all three basins.

  10. Hydration of an apolar solute in a two-dimensional waterlike lattice fluid.

    Science.gov (United States)

    Buzano, C; De Stefanis, E; Pretti, M

    2005-05-01

    In a previous work, we investigated a two-dimensional lattice-fluid model, displaying some waterlike thermodynamic anomalies. The model, defined on a triangular lattice, is now extended to aqueous solutions with apolar species. Water molecules are of the "Mercedes Benz" type, i.e., they possess a D3 (equilateral triangle) symmetry, with three equivalent bonding arms. Bond formation depends both on orientation and local density. The insertion of inert molecules displays typical signatures of hydrophobic hydration: large positive transfer free energy, large negative transfer entropy (at low temperature), strong temperature dependence of the transfer enthalpy and entropy, i.e., large (positive) transfer heat capacity. Model properties are derived by a generalized first order approximation on a triangle cluster.

  11. A quantum chemistry study of natural gas hydrates.

    Science.gov (United States)

    Atilhan, Mert; Pala, Nezih; Aparicio, Santiago

    2014-04-01

    The structure and properties of natural gas hydrates containing hydrocarbons, CO₂, and N₂ molecules were studied by using computational quantum chemistry methods via the density functional theory approach. All host cages involved in I, II, and H types structures where filled with hydrocarbons up to pentanes, CO₂ and N₂ molecules, depending on their size, and the structures of these host-guest systems optimized. Structural properties, vibrational spectra, and density of states were analyzed together with results from atoms-in-a-molecule and natural bond orbitals methods. The inclusion of dispersion terms in the used functional plays a vital role for obtaining reliable information, and thus, B97D functional was shown to be useful for these systems. Results showed remarkable interaction energies, not strongly affected by the type of host cage, with molecules tending to be placed at the center of the cavities when host cages and guest molecules cavities are of similar size, but with molecules approaching hexagonal faces for larger cages. Vibrational properties show remarkable features in certain regions, with shiftings rising from host-guest interactions, and useful patterns in the terahertz region rising from water surface vibrations strongly coupled with guest molecules. Likewise, calculations on crystal systems for the I and H types were carried out using a pseudopotential approach combined with Grimme's method to take account of dispersion.

  12. Separation and Structure of Chiral S-Malic Acid Hydrate

    Institute of Scientific and Technical Information of China (English)

    NIE,Jing-Jing(聂晶晶); XU,Duan-Jun(徐端钧); WU,Jing-Yun(吴景云); CHIANG,Michael Y.(蒋燕南)

    2002-01-01

    Crystals of the chiral malic acid hydrate ( C4H6O5@H2O ) were unexpectedly obtained from an ethanol ethanol/water solution containing racemic D,L-malic acid and L-asparagine. The crystal belongs to orthorhombic space group P21 21 21 with cell dimensions of a=0.5576(1), b=0.9818(2), c=1.1793(2) nm, V=0.9455(2) nm3, Z=4, μ(Mo Kα) =0.152 mm-1, F(000) =320, Dc= 1.565 g@cm-3, R =0.051, wR =0.136 for 657 observed reflections [I>2σ(I)]. The significant difference in bond distances for carboxyl groups suggests that the crystal consist of malate anion and protonized crystalline water. This is a report for direct separation of racemic mixture, i.e., without the formation of a molecular complex of raceme with a chiral separating reagent.

  13. X-ray absorption spectroscopy of strontium(II) coordination. I. Static and thermal disorder in crystalline, hydrated, and precipitated solids and in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    O' Day, P.A.; Newville, M.; Neuhoff, P.S.; Sahai, N.; Carroll, S.A.

    2000-02-15

    Detailed analyses of crystalline, hydrated, and precipitated strontium compounds and an aqueous strontium solution by synchrotron extended X-ray adsorption fine structure (EXAFS) were used to quantify local thermal and static disorder and the characterize strontium coordination in a variety of oxygen-ligated bonding environments. Comparison of strontium structural coordination determined in this and previous studies suggest that previous EXAFS determinations of hydrated strontium may have underestimated first-shell interatomic distances and coordination numbers because minor contributions to the EXAFS phase-shift and amplitude functions were not accounted for, either theoretically or empirically.

  14. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  15. Experimental techniques for cement hydration studies

    Directory of Open Access Journals (Sweden)

    Andreas Luttge

    2011-10-01

    Full Text Available Cement hydration kinetics is a complex problem of dissolution, nucleation and growth that is still not well understood, particularly in a quantitative way. While cement systems are unique in certain aspects they are also comparable to natural mineral systems. Therefore, geochemistry and particularly the study of mineral dissolution and growth may be able to provide insight and methods that can be utilized in cement hydration research. Here, we review mainly what is not known or what is currently used and applied in a problematic way. Examples are the typical Avrami approach, the application of Transition State Theory (TST to overall reaction kinetics and the problem of reactive surface area. Finally, we suggest an integrated approach that combines vertical scanning interferometry (VSI with other sophisticated analytical techniques such as atomic force microscopy (AFM and theoretical model calculations based on a stochastic treatment.

  16. Advances in understanding hydration of Portland cement

    Energy Technology Data Exchange (ETDEWEB)

    Scrivener, Karen L., E-mail: Karen.scrivener@epfl.ch [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, 1015 (Switzerland); Juilland, Patrick [Sika Technology AG, Zürich (Switzerland); Monteiro, Paulo J.M. [Department of Civil and Environmental Engineering, University of California at Berkeley (United States)

    2015-12-15

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

  17. 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......) to the aqueous phase was found to reduce the gas dissolution rate slightly. However the induction times were prolonged quite substantially upon addition of PVP.The induction time data were correlated using a newly developed induction time model based on crystallization theory also capable of taking into account...... 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...

  18. Methane hydrates and contemporary climate change

    Science.gov (United States)

    Ruppel, Carolyn D.

    2011-01-01

    As the evidence for warming climate became better established in the latter part of the 20th century (IPCC 2001), some scientists raised the alarm that large quantities of methane (CH4) might be liberated by widespread destabilization of climate-sensitive gas hydrate deposits trapped in marine and permafrost-associated sediments (Bohannon 2008, Krey et al. 2009, Mascarelli 2009). Even if only a fraction of the liberated CH4 were to reach the atmosphere, the potency of CH4 as a greenhouse gas (GHG) and the persistence of its oxidative product (CO2) heightened concerns that gas hydrate dissociation could represent a slow tipping point (Archer et al. 2009) for Earth's contemporary period of climate change.

  19. A statistical mechanical description of biomolecular hydration

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-02-01

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

  20. Effects of complexing compounds on sorption of metal ions to cement

    Energy Technology Data Exchange (ETDEWEB)

    Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

    2005-12-15

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  1. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  2. The samurai bond market

    OpenAIRE

    1997-01-01

    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  3. Methane storage in dry water gas hydrates.

    Science.gov (United States)

    Wang, Weixing; Bray, Christopher L; Adams, Dave J; Cooper, Andrew I

    2008-09-03

    Dry water stores 175 v(STP)/v methane at 2.7 MPa and 273.2 K in a hydrate form which is close to the Department of Energy volumetric target for methane storage. Dry water is a silica-stabilized free-flowing powder (95% wt water), and fast methane uptakes were observed (90% saturation uptake in 160 min with no mixing) as a result of the relatively large surface-to-volume ratio of this material.

  4. A Proposed Unified Theory of Hydrated Asteroids

    Science.gov (United States)

    Rivkin, Andrew S.

    2016-10-01

    The last decade has seen tremendous growth in the study of hydrated and hydroxylated minerals (hereafter simply called "hydrated minerals") on asteroids. Several workers have used absorptions in the 3-µm region and a correlated absorption near 0.7 µm to determine not only the presence or absence of these minerals but gain insight into the compositions of asteroid surfaces. Spectra of hundreds of asteroids have been measured and published or presented at meetings, and we are in a position to use these newer datasets to globally assess the patterns and relationships we see, as previously done by Jones et al. (1990) and Takir et al. (2012). There are several points to be addressed by any such assessment. Several different band shapes are seen in the 3-µm region, only one of which is seen in the hydrated meteorites in our collections. However, each of the main 3-µm band shapes is represented among parent bodies of collisional families. There seems to be little correlation in general between asteroid spectral class and 3-µm band shape, save for the Ch meteorites which are overwhelmingly likely to share the same band shape as the CM meteorites. Ceres has an unusual but not unique band shape, which has thus far only been found on the largest asteroids. I will present an outline scenario for the formation and evolution of hydrated asteroids, where aqueous alteration serves to lithify some objects while other objects remain unlithified and still others differentiate and suffer collisional modification. While some details will no doubt be altered to account for better or new information, this scenario is offered as a starting point for discussion.

  5. Bioimpedance in medicine: Measuring hydration influence

    Science.gov (United States)

    Hlubik, J.; Hlubik, P.; Lhotska, L.

    2010-04-01

    The aim of the paper is to present results of our ongoing research focused on the influence of body hydration on the body impedance measurements and also on the influence of the frequency used for the measurement. The question is why to measure human body composition and if these values have beneficial results. First goal of the work deals with a question of measuring human body composition. The performed measurements showed certain influence which must be verified by repeated experiments.

  6. Hydration process in Portland cement blended with activated coal gangue

    Institute of Scientific and Technical Information of China (English)

    Xian-ping LIU; Pei-ming WANG; Min-ju DING

    2011-01-01

    This paper deals with the hydration of a blend of Portland cement and activated coal gangue in order to determine the relationship between the degree of hydration and compressive strength development.The hydration process was investigated by various means:isothermal calorimetry,thermal analysis,non-cvaporable water measurement,and X-ray diffraction analysis.The results show that the activated coal gangue is a pozzolanic material that contributes to the hydration of the cement blend.The pozzolanic reaction occurs over a period of between 7 and 90 d,consuming portlandite and forming both crystal hydrates and ill-crystallized calcium silicate hydrates.These hydrates are similar to those found in pure Portland cement.The results show that if activated coal gangue is substituted for cement at up to 30% (w/w),it does not significantly affect the final compressive strength of the blend.A long-term compressive strength improvement can in fact be achieved by using activated coal gangue as a supplementary cementing material.The relationship between compressive strength and degree of hydration for both pure Portland cement and blended cement can be described with the same equation.However,the parameters are different since blended cement produces fewer calcium silicate hydrates than pure Portland cement at the same degree of hydration.

  7. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara

    2012-05-01

    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

  8. Gas Hydrate Growth Kinetics: A Parametric Study

    Directory of Open Access Journals (Sweden)

    Remi-Erempagamo Tariyemienyo Meindinyo

    2016-12-01

    Full Text Available Gas hydrate growth kinetics was studied at a pressure of 90 bars to investigate the effect of temperature, initial water content, stirring rate, and reactor size in stirred semi-batch autoclave reactors. The mixing energy during hydrate growth was estimated by logging the power consumed. The theoretical model by Garcia-Ochoa and Gomez for estimation of the mass transfer parameters in stirred tanks has been used to evaluate the dispersion parameters of the system. The mean bubble size, impeller power input per unit volume, and impeller Reynold’s number/tip velocity were used for analyzing observed trends from the gas hydrate growth data. The growth behavior was analyzed based on the gas consumptio