WorldWideScience

Sample records for bonding hydration ion

  1. Unexpected Hydration of a Triple Bond During DNA Synthesis

    DEFF Research Database (Denmark)

    Fatthalla, Maha I.; Pedersen, Erik B.

    2016-01-01

    acidic conditions, polarizes the triple bond in the intercalator and this makes hydration of the triple bond possible during the DNA synthesis and an oligonucleotide with 1-(indol-3-yl)-2-(pyren-1-yl)ethanone as the intercalator is formed. Insertion of the unhydrated and hydrated linker systems gave...

  2. Multicavity SCRF calculation of ion hydration energies

    International Nuclear Information System (INIS)

    Diercksen, B.H.F.; Karelson, M.; Tamm, T.

    1994-01-01

    The hydration energies of the proton, hydroxyl ion, and several inorganic ions were calculated using the multicavity self-consistent reaction field (MCa SCRF) method developed for the quantum-mechanical modeling of rotationally or flexible systems in dielectric media. The ionic complexes H 3 O + (H2O) 4 , OH - (H2O) 4 , NH + 4 (H2O) 4 , and Hal - (H2O) 4 , where Hal = F, Cl, or Br, have been studied. Each complex was divided between five spheres, corresponding to the central ion and four water molecules in their first coordination sphere, respectively. Each cavity was surrounded by a polarizable medium with the dielectric permittivity of water at room temperature (80). The ionic hydration energies of ions were divided into specific and nonspecific parts. After accounting for the cavity-formation energy using scaled particle theory, good agreement between the total calculated and experimental hydration energies was obtained for all ions studied

  3. 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...

  4. Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

    Science.gov (United States)

    Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

    2017-12-01

    Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

  5. Hydration numbers of trivalent lanthanide and actinide ions

    International Nuclear Information System (INIS)

    David, F.; Fourest, B.; Duplessis, J.

    1987-01-01

    Investigations on the structure of actinide aquo ions and determination of hydration numbers have to be studied, essentially, through radiochemical methods. They measured the transport numbers, diffusion coefficient D by the open end capillary method and ionic mobility u by electrophoresis. Both methods show a discontinuity in the transport number corresponding to the crystallographic radius of Eu 3+ or Bk 3+ ion. They deduced the volume of the actinide aquo ions, and the coordination number in the primary sphere. From calculations of the electrostriction phenomenon in the vicinity of central ion, they obtained effective volume of the water molecules and the dynamic hydration number corresponding to the second hydration sphere

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  7. On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

    Science.gov (United States)

    Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

    2014-10-28

    The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) water water in the hydration shell of anions.

  8. 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.

  9. 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…

  10. Spectroscopic study of trivalent rare earth ions in calcium nitrate hydrate melt

    International Nuclear Information System (INIS)

    Fujii, Toshiyuki; Asano, Hideki; Kimura, Takaumi; Yamamoto, Takeshi; Uehara, Akihiro; Yamana, Hajimu

    2006-01-01

    Influence of the water content to chemical status of trivalent rare earth ions in calcium nitrate hydrate melt was studied by spectroscopic techniques. Fluorescence spectrometry for Eu(III) in Ca(NO 3 ) 2 .RH 2 O and electronic absorption spectrometry for Nd(III) in Ca(NO 3 ) 2 .RH 2 O were performed for analyzing the changing coordination symmetries through the changes in their hypersensitive transitions. Raman spectroscopic study and EXAFS study were performed for Y(NO 3 ) 3 solutions and Y(III) in Ca(NO 3 ) 2 .RH 2 O for analyzing the oxygen bonding to Y(III). Luminescence lifetime study of Eu(III) and Dy(III) in Ca(NO 3 ) 2 .RH 2 O was performed for evaluating the hydration number changes. Results of these spectroscopic studies indicated that, with the decrease of water content (R), the hydration number decreases while the interaction between trivalent rare earth ion and nitrate ion increases. It was also revealed that the symmetry of the coordination sphere gets distorted gradually by this interaction

  11. 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.

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

    International Nuclear Information System (INIS)

    Plumridge, T.H.

    2001-01-01

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

  13. 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.

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

    Science.gov (United States)

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

    2017-10-13

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

  15. Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

    International Nuclear Information System (INIS)

    Bilewicz, A.; Narbutt, J.; Dybczynski, R.

    1992-01-01

    The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(II), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10 -3 *mol*dm -3 . Cations of zinc, manganese and mercury which form much weaker ammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions. (author) 10 refs.; 4 figs.; 1 tab

  16. A structural study of nepheline hydrate I, an inorganic ion exchanger

    International Nuclear Information System (INIS)

    Hansen, S.

    1985-01-01

    The crystal structures of nepheline hydrates I, Na 3 Al 3 Si 3 O 12 x 2H 2 O, and three compounds produced by ion exchange with aqueous KCl, RbCl and CsCl at 80 degrees C, have been studied using X-ray diffraction methods. This synthetic silicate has a tetrahedral framework with a two-dimensional pore system consisting of perpendicular 8-ring and 6-ring channels. The long-range ordering of Si and Al into adjacent tetrahedra is well developed. Some aspects of the topology, geometry and bonding of the tetrahedral frame are discussed. Related framework types are derived by unit cell twinning of the idealized cristobalite structure. A limit in the ion exchange is observed when about 1/3 of the Na + ions have been replaced. This behaviour is explained by the restricted volume of two Na sites situated in the 6-ring channel. The readily exchangeable ions and water molecules in the 8-ring channels an arrangement which gradually changes when the size of the alkali metal-ion increases. Most K + -exchanged crystals have a unit cell which is determined by the translational symmetry of the framework, while the original Na form has a two-fold superstructure and the Rb + -exchanged form has a five-fold superstructure. Caesium-ion-exchanged crystals have incommensurate structures. The occurrence of superstructures is related to long-range ordering of the species in the 8-ring channels. (author)

  17. Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

    Science.gov (United States)

    Srivastava, Abhinav; Debnath, Ananya

    2018-03-01

    Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t-3/2. The asymptotic t-3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations

  18. Fragmentation of pure and hydrated clusters of 5Br-uracil by low energy carbon ions: observation of hydrated fragments

    Czech Academy of Sciences Publication Activity Database

    Castrovilli, M. C.; Markush, P.; Bolognesi, P.; Rousseau, P.; Maclot, S.; Cartoni, A.; Delaunay, R.; Domaracka, A.; Kočišek, Jaroslav; Huber, B. A.; Avaldi, L.

    2017-01-01

    Roč. 19, č. 30 (2017), s. 19807-19814 ISSN 1463-9076 Institutional support: RVO:61388955 Keywords : fragmentation * nano-hydrated 5BrU clusters * low energy carbon ions Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.123, year: 2016

  19. Cleaning of diffusion bonding surface by argon ion bombardment treatment

    International Nuclear Information System (INIS)

    Wang, Airu; Ohashi, Osamu; Yamaguchi, Norio; Aoki, Masanori; Higashi, Yasuo; Hitomi, Nobuteru

    2003-01-01

    The specimens of oxygen-free high conductivity copper, SUS304L stainless steel and pure iron were treated by argon ion bombardment and then were bonded by diffusion bonding method. The effects of argon ion bombardment treatment on faying surface morphology, tensile strength of bonding joints and inclusions at the fracture surface were investigated. The results showed that argon ion bombardment treatment was effective to remove the oxide film and contamination at the faying surface and improve the quality of joints. The tensile strength of the bonded joints was improved, and minimum bonding temperature to make the metallic bonding at the interface was lowered by argon ion bombardment treatment. At the joints with argon ion bombardment treatment, ductile fractured surface was seen and the amount of inclusions was obviously decreased

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

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2008-01-01

    of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...... direct calculation of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules is calculated as a difference. The results yield the following primary hydration numbers: Li+: 5.5-5.6; Na+: 4.0-4.1; K+: 2.0-2.5; Rb+: 0.6-1.2; Cs+: ~0. The most important...

  1. 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.

  2. 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...... may depend on the details of ion hydration. Although the solvation of alkali metal ions in aqueous solution has been discussed for many years, there is still no clear consensus. Part of the discrepancy is simply that different methods measure over different time scales, and therefore do...... not necessarily define the same hydration shell. This work presents a systematic study of one special variant of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS-). The technique...

  3. Heavy ion beam measurement of the hydration of cementitious materials

    International Nuclear Information System (INIS)

    Livingston, R.A.; Schweitzer, J.S.; Spillane, T.; Zickefoose, J.; Rolfs, C.; Becker, H.-W.; Kubsky, S.; Castellote, M.; Viedma, P.G. de; Cheung, J.

    2008-01-01

    Full text: The setting and development of strength of Portland cement concrete depends upon the reaction of water with various phases in the Portland cement including dicalcium silicate (C 2 S), tricalcium silicate (C 3 S) and tricalcium aluminate (C 3 A). The early age hydration reaction and setting time are determined by surface layers on the cement grains that form a region that is only a few 100 nm thick. This has been difficult to observe with conventional methods. Ion beam techniques have been used to investigate these layers in detail at the Tandem Accelerator facility of the University of the Ruhr in Bochum, Germany. The primary method has been Nuclear Resonance Reaction Analysis (NRRA) involving the 1 H( 15 N,αγ) 12 C reaction to measure the hydrogen depth profile. This technique has an H detection sensitivity of about 10 ppm and an H-depth resolution of a few nm at the surface.. Freshly cleaved mica is used as a calibration standard for conversion of gamma-ray counts to H concentration. The beam energy to depth conversion factor is obtained by numerical simulation using the Monte Carlo code TRIM. NRRA with the 1 H( 19 F, αγ) 16 O reaction has also been used to measure the hydrogen depth profile. Some samples were implanted with a 131 Xe layer in order to measure the depth profile of other significant elements such as calcium with Rutherford Backscattering (RBS), and also to measure the erosion of the surface layers

  4. Hydration structures of U(III) and U(IV) ions from ab initio molecular dynamics simulations

    International Nuclear Information System (INIS)

    Leung, Kevin; Nenoff, Tina M.

    2012-01-01

    We apply DFT+U-based ab initio molecular dynamics simulations to study the hydration structures of U(III) and U(IV) ions, pertinent to redox reactions associated with uranium salts in aqueous media. U(III) is predicted to be coordinated to 8 water molecules, while U(IV) has a hydration number between 7 and 8. At least one of the innershell water molecules of the hydrated U(IV) complex becomes spontaneously deprotonated. As a result, the U(IV)–O pair correlation function exhibits a satellite peak at 2.15 Å associated with the shorter U(IV)–(OH − ) bond. This feature is not accounted for in analysis of extended x-ray absorption fine structure and x-ray adsorption near edge structure measurements, which yield higher estimates of U(IV) hydration numbers. This suggests that it may be useful to include the effect of possible hydrolysis in future interpretation of experiments, especially when the experimental pH is close to the reported hydrolysis equilibrium constant value.

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

    International Nuclear Information System (INIS)

    Poole, T.S.; Wakeley, L.D.; Young, C.L.

    1994-03-01

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

  6. Effects of ion concentration on the hydrogen bonded structure of ...

    Indian Academy of Sciences (India)

    WINTEC

    Effects of ion concentration on the hydrogen bonded structure of water in the vicinity of ions in aqueous NaCl solutions. A NAG. 1. , D CHAKRABORTY and A CHANDRA*. Department of Chemistry, Indian Institute of Technology, Kanpur 208 016. 1. Present address: Department of Chemistry and Chemical Engineering,.

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

    International Nuclear Information System (INIS)

    Kanno, H.

    1998-01-01

    Full text: It is now well established that the inner-sphere hydration number of aqua-rare earth ions changes from nine to eight in the middle of the rare earth series. This hydration number change greatly affects the complex formation of rare earth ions as we observe irregular variations in most series behaviours of the complex formation constant (K) in aqueous solution systems when K being plotted against 1/r or r (r is ionic radius of rare earth ion). Furthermore, it shows very anomalous concentration dependence in the sense that nona-aqua Ln 3+ ion increases in number with increase in salt concentration in aqueous rare earth salt solution (salt chloride, perchlorate). In this report, a theoretical derivation of the formation constant (K) for the inner-sphere complex formation of rare earth ions with a monodentate ligand was made by taking account of both the hydration number change in the middle of the series and its anomalous salt concentration dependence. The series behaviour of the formation constant against 1/r (or r) is successfully explained with using the empirical finding that K varies almost linearly with 1/r (or r) in the region where only one hydration number dominates. This success is also taken as evidence that the anomalous salt concentration dependence of the hydration number change is caused by the outer-sphere complex formation of rare earth ions with the condition that nona-aqua rare earth ions form outer-sphere complexes more easily than octa-aqua ions

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

    International Nuclear Information System (INIS)

    Pommeret, S.; Renault, J.P.; Le Caer, S.; Vigneron, G.; Palmer, J.; Lima, M.; Righini, R.

    2006-01-01

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

  9. Hydration effect on ion exchange resin irradiated by swift heavy ions and gamma rays

    Science.gov (United States)

    Boughattas, I.; Labed, V.; Gerenton, A.; Ngono-Ravache, Y.; Dannoux-Papin, A.

    2018-06-01

    Gamma radiolysis of ion exchange resins (IER) is widely studied since the sixties, as a function of different parameters (resin type, dose, atmosphere, water content …). However, to our knowledge, there are very few data concerning hydrogen emission from anionic and cationic resins irradiated at high Linear Energy Transfers (LET). In the present work, we focus on the influence of hydration on hydrogen emission, in anionic and cationic resins irradiated under inert atmosphere using Swift Heavy Ions (SHI) and gamma irradiations. The radiation chemical yield of molecular hydrogen is nonlinear with water content for both resins. The molecular hydrogen production depends first on the water form in IER (free or linked) and second on the solubility of degradation products. Three steps have been observed: at lower water content where G(H2) is stable, at 50%, G(H2) increases due to reactions between water radiolytic species and the resin functional groups and at high water content, G(H2) decreases probably due to its accumulation in water and its consumption by hydroxyl radicals in the supernatant.

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

    International Nuclear Information System (INIS)

    Ohkubo, Takahiro; Kusudo, Tomoko; Kuroda, Yasushige

    2016-01-01

    The adsorbed phase and hydration structure of an aqueous solution of Ca(NO 3 ) 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 Ca 2+ 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 Ca 2+ in the micropore, although the structural parameters of hydrated Ca 2+ 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 Ca 2+ restricted in carbon micropores whose sizes are around 1 nm is experimentally revealed where any dehydration phenomena from the first hydration shell around Ca 2+ could not be observed. (paper)

  11. Halocarbons as hydrogen bond acceptors: a spectroscopic study of haloethylbenzenes (PhCH2CH2X, X = F, Cl, Br) and their hydrate clusters.

    Science.gov (United States)

    Robertson, Patrick A; Villani, Luigi; Dissanayake, Uresha L M; Duncan, Luke F; Abbott, Belinda M; Wilson, David J D; Robertson, Evan G

    2018-03-28

    The electronic spectra of 2-bromoethylbenzene and its chloro and fluoro analogues have been recorded by resonant two-photon ionisation (R2PI) spectroscopy. Anti and gauche conformers have been assigned by rotational band contour analysis and IR-UV ion depletion spectroscopy in the CH region. Hydrate clusters of the anti conformers have also been observed, allowing the role of halocarbons as hydrogen bond acceptors to be examined in this context. The donor OH stretch of water bound to chlorine is red-shifted by 36 cm -1 , or 39 cm -1 in the case of bromine. Although classed as weak H-bond acceptors, halocarbons are favourable acceptor sites compared to π systems. Fluorine stands out as the weakest H-bond acceptor amongst the halogens. Chlorine and bromine are also weak H-bond acceptors, but allow for more geometric lability, facilitating complimentary secondary interactions within the host molecule. Ab initio and DFT quantum chemical calculations, both harmonic and anharmonic, aid the structural assignments and analysis.

  12. The Structure and Transport of Water and Hydrated Ions Within Hydrophobic, Nanoscale Channels

    International Nuclear Information System (INIS)

    Holt, J.K.; Herberg, J.L.; Wu, Y.; Schwegler, E.; Mehta, A.

    2009-01-01

    The purpose of this project includes an experimental and modeling investigation into water and hydrated ion structure and transport at nanomaterials interfaces. This is a topic relevant to understanding the function of many biological systems such as aquaporins that efficiently shuttle water and ion channels that permit selective transport of specific ions across cell membranes. Carbon nanotubes (CNT) are model nanoscale, hydrophobic channels that can be functionalized, making them artificial analogs for these biological channels. This project investigates the microscopic properties of water such as water density distributions and dynamics within CNTs using Nuclear Magnetic Resonance (NMR) and the structure of hydrated ions at CNT interfaces via X-ray Absorption Spectroscopy (XAS). Another component of this work is molecular simulation, which can predict experimental measurables such as the proton relaxation times, chemical shifts, and can compute the electronic structure of CNTs. Some of the fundamental questions this work is addressing are: (1) what is the length scale below which nanoscale effects such as molecular ordering become important, (2) is there a relationship between molecular ordering and transport?, and (3) how do ions interact with CNT interfaces? These are questions of interest to the scientific community, but they also impact the future generation of sensors, filters, and other devices that operate on the nanometer length scale. To enable some of the proposed applications of CNTs as ion filtration media and electrolytic supercapacitors, a detailed knowledge of water and ion structure at CNT interfaces is critical.

  13. Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities.

    Science.gov (United States)

    Orozco, Carlos A; Chun, Byong W; Geng, Guoqing; Emwas, Abdul H; Monteiro, Paulo J M

    2017-04-11

    Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29 Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

  14. Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities

    KAUST Repository

    Orozco, Carlos A.; Chun, Byong W.; Geng, Guoqing; Emwas, Abdul-Hamid M.; Monteiro, Paulo J. M.

    2017-01-01

    Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

  15. Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities

    KAUST Repository

    Orozco, Carlos A.

    2017-03-24

    Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

  16. Relative Free Energies for Hydration of Monovalent Ions from QM and QM/MM Simulations.

    Science.gov (United States)

    Lev, Bogdan; Roux, Benoît; Noskov, Sergei Yu

    2013-09-10

    Methods directly evaluating the hydration structure and thermodynamics of physiologically relevant cations (Na(+), K(+), Cl(-), etc.) have wide ranging applications in the fields of inorganic, physical, and biological chemistry. All-atom simulations based on accurate potential energy surfaces appear to offer a viable option for assessing the chemistry of ion solvation. Although MD and free energy simulations of ion solvation with classical force fields have proven their usefulness, a number of challenges still remain. One of them is the difficulty of force field benchmarking and validation against structural and thermodynamic data obtained for a condensed phase. Hybrid quantum mechanical/molecular mechanical (QM/MM) models combined with sampling algorithms have the potential to provide an accurate solvation model and to incorporate the effects from the surrounding, which is often missing in gas-phase ab initio computations. Herein, we report the results from QM/MM free energy simulations of Na(+)/K(+) and Cl(-)/Br(-) hydration where we simultaneously characterized the relative thermodynamics of ion solvation and changes in the solvation structure. The Flexible Inner Region Ensemble Separator (FIRES) method was used to impose a spatial separation between QM region and the outer sphere of solvent molecules treated with the CHARMM27 force field. FEP calculations based on QM/MM simulations utilizing the CHARMM/deMon2k interface were performed with different basis set combinations for K(+)/Na(+) and Cl(-)/Br(-) perturbations to establish the dependence of the computed free energies on the basis set level. The dependence of the computed relative free energies on the size of the QM and MM regions is discussed. The current methodology offers an accurate description of structural and thermodynamic aspects of the hydration of alkali and halide ions in neat solvents and can be used to obtain thermodynamic data on ion solvation in condensed phase along with underlying

  17. Discrete element analysis of the mechanical properties of deep-sea methane hydrate-bearing soils considering interparticle bond thickness

    Science.gov (United States)

    Jiang, Mingjing; He, Jie; Wang, Jianfeng; Zhou, Yaping; Zhu, Fangyuan

    2017-12-01

    Due to increasing global energy demands, research is being conducted on the mechanical properties of methane hydrate-bearing soils (MHBSs), from which methane hydrate (MH) will be explored. This paper presents a numerical approach to study the mechanical properties of MHBSs. The relationship between the level of MH saturation and the interparticle bond thickness is first obtained by analyzing the scanning electron microscope images of MHBS samples, in which is the bridge connecting the micromechanical behavior captured by the DEM with the macroscopic properties of MHBSs. A simplified thermal-hydromechanical (THM) bond model that considers the different bond thicknesses is then proposed to describe the contact behavior between the soil particles and those incorporated into the discrete element method (DEM). Finally, a series of biaxial compression tests are carried out with different MH saturations under different effective confining pressures to analyze the mechanical properties of deep-sea MHBSs. The results of the DEM numerical simulation are also compared with the findings from triaxial compression tests. The results show that the macromechanical properties of deep-sea MHBSs can be qualitatively captured by the proposed DEM. The shear strength, cohesion, and volumetric contraction of deep-sea MHBSs increase with increasing MH saturation, although its influence on the internal friction angle is obscure. The shear strength and volumetric contraction increase with increasing effective confining pressure. The peak shear strength and the dilation of MHBSs increase as the critical bond thickness increases, while the residual deviator stress largely remains the same at a larger axial strain. With increasing the axial strain, the percentage of broken bonds increases, along with the expansion of the shear band.

  18. 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.

  19. Sensitivity of hydrogen bonds of DNA and RNA to hydration, as gauged by 1JNH measurements in ethanol-water mixtures

    International Nuclear Information System (INIS)

    Manalo, Marlon N.; Kong Xiangming; LiWang, Andy

    2007-01-01

    Hydrogen-bond lengths of nucleic acids are (1) longer in DNA than in RNA, and (2) sequence dependent. The physicochemical basis for these variations in hydrogen-bond lengths is unknown, however. Here, the notion that hydration plays a significant role in nucleic acid hydrogen-bond lengths is tested. Watson-Crick N1...N3 hydrogen-bond lengths of several DNA and RNA duplexes are gauged using imino 1 J NH measurements, and ethanol is used as a cosolvent to lower water activity. We find that 1 J NH values of DNA and RNA become less negative with added ethanol, which suggests that mild dehydration reduces hydrogen-bond lengths even as the overall thermal stabilities of these duplexes decrease. The 1 J NH of DNA are increased in 8 mol% ethanol to those of RNA in water, which suggests that the greater hydration of DNA plays a significant role in its longer hydrogen bonds. The data also suggest that ethanol-induced dehydration is greater for the more hydrated G:C base pairs and thereby results in greater hydrogen-bond shortening than for the less hydrated A:T/U base pairs of DNA and RNA

  20. The role of calcium ions and lignosulphonate plasticiser in the hydration of cement

    International Nuclear Information System (INIS)

    Grierson, L.H.; Knight, J.C.; Maharaj, R.

    2005-01-01

    Experiments involving equilibrium dialysis, conductivity, X-ray diffraction analysis (XRD), differential thermal analysis (DTA) and isothermal titration calorimetry (ITC) have been carried out to investigate the role of calcium ions and polymeric plasticisers in cement/admixture hydration. Results from a study of lignosulphonic acid, sodium salt, acetate as a plasticiser shows that a plasticiser has dual role; one mainly as a kinetic inhibitor (poison) in cement hydration mechanism and the other as a dispersant. Evidence of a weak Ca 2+ binding to lignosulphonate sulphonic moieties was found at low ionic strengths of 0.1 M using ITC. No evidence of formal Ca 2+ binding to lignosulphonate sulphonic acid moieties was found using equilibrium dialysis at higher ionic strength of 1 M (ionic strengths of 0.4 M are typically found in Portland cement pore solution), as is often suggested in cement/admixture literature

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

    Science.gov (United States)

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

    2015-03-04

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

  2. Production of Hydrated Metal Ions by Fast Ion or Atom Beam Sputtering. Collision-Induced Dissociation and Successive Hydration Energies of Gaseous Cu+ with 1-4 Water Molecules

    NARCIS (Netherlands)

    Magnera, Thomas F.; David, Donald E.; Stulik, Dusan; Orth, Robert G.; Jonkman, Harry T.; Michl, Josef

    1989-01-01

    Low-temperature sputtering of frozen aqueous solutions of metal salts, of hydrated crystalline transition-metal salts, of frosted metal surfaces, and of frosted metal salts with kiloelectronvolt energy rare gas atoms or ions produces copious amounts of cluster ions, among which M+(H2O)n and/or

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

    Energy Technology Data Exchange (ETDEWEB)

    Sessa, Francesco; D’Angelo, Paola, E-mail: p.dangelo@uniroma1.it [Dipartimento di Chimica, Università di Roma “La Sapienza,” P. le A. Moro 5, 00185 Roma (Italy); Spezia, Riccardo [CNRS, UMR 8587, Laboratoire Analyse et Modelisation Pour la Biologie et l’Environnement, Université d’Evry Val d’Essonne, Blvd. F. Mitterrand, 91025 Evry Cedex (France)

    2016-05-28

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

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

    International Nuclear Information System (INIS)

    Pommeret, S.; Renault, J.P.; Caeer, S.Le; Vigneron, G.; Vuilleumier, R.; Bratos, S.; Leicknam, J.Cl.

    2006-01-01

    In the present contribution a review of the recent work on the H bond dynamics, in absence of any reactant and a new theory that unambiguously establishes a new link between spectroscopic observation and geometric properties is presented, along with results on the radiation chemistry of nanoporous media and its influence on the H bond network of an interface

  5. Comparison of Freezing and Hydrate Formation Methods in Removing Chloride and Bromide Ions from Brine

    Directory of Open Access Journals (Sweden)

    Marzieh Fattahi

    2018-01-01

    Full Text Available The growing population and enhanced industrial activities coupled with limitations on freshwater availability have led to efforts to desalinate salt water from the seas. Membrane and thermal technologies are the two commonly used for this purpose. In this study, the direct freezing and hydrate formation techniques were used for salt water desalination. Materials and Methods: Distilled water, sodium chloride, and sodium bromide were used as raw materials in the experiments. The experimental setup included a stationary reactor with two coaxial cylinders, in which ice crystals were deposited outside the cool inner cylinder to increase the salt concentration in the residual brine. An electrical conductivity instrument was used to measure sal removal. Results: Salt removal was shown to decrease with increasing salt concentration in the direct freeze method. A different trend was, however, observed in the hydrate formation method; salt removal was negligible at low concentrations in this method but increased at high concentrations before a constant value was reached. Overall, the hydrate formation recorded a higher salt removal efficiency than the other method. To investigate the effect of anion size on salt removal efficiency, experiments were carried out using NaCl and NaBr, which have the same cation but different anion sizes. Result showed that removal efficiency increased with increasing anion size. Conclusion: It was found that increasing ion radius leads to the lower likelihood of ion presence in the crystal lattice, thereby reducing salt removal efficiency. On the other hand, low concentrations of salt serve as site for the generation of cores, which naturally serve as removal accelerators.

  6. Explicit hydration of ammonium ion by correlated methods employing molecular tailoring approach

    Science.gov (United States)

    Singh, Gurmeet; Verma, Rahul; Wagle, Swapnil; Gadre, Shridhar R.

    2017-11-01

    Explicit hydration studies of ions require accurate estimation of interaction energies. This work explores the explicit hydration of the ammonium ion (NH4+) employing Møller-Plesset second order (MP2) perturbation theory, an accurate yet relatively less expensive correlated method. Several initial geometries of NH4+(H2O)n (n = 4 to 13) clusters are subjected to MP2 level geometry optimisation with correlation consistent aug-cc-pVDZ (aVDZ) basis set. For large clusters (viz. n > 8), molecular tailoring approach (MTA) is used for single point energy evaluation at MP2/aVTZ level for the estimation of MP2 level binding energies (BEs) at complete basis set (CBS) limit. The minimal nature of the clusters upto n ≤ 8 is confirmed by performing vibrational frequency calculations at MP2/aVDZ level of theory, whereas for larger clusters (9 ≤ n ≤ 13) such calculations are effected via grafted MTA (GMTA) method. The zero point energy (ZPE) corrections are done for all the isomers lying within 1 kcal/mol of the lowest energy one. The resulting frequencies in N-H region (2900-3500 cm-1) and in O-H stretching region (3300-3900 cm-1) are in found to be in excellent agreement with the available experimental findings for 4 ≤ n ≤ 13. Furthermore, GMTA is also applied for calculating the BEs of these clusters at coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory with aVDZ basis set. This work thus represents an art of the possible on contemporary multi-core computers for studying explicit molecular hydration at correlated level theories.

  7. Structure of the Hydrated Platinum(II) Ion And the Cis-Diammine-Platinum(II) Complex in Acidic Aqueous Solution: An EXAFS Study

    Energy Technology Data Exchange (ETDEWEB)

    Jalilehvand, F.; Laffin, L.J.

    2009-05-18

    Careful analysis of Pt L{sub 3}-edge extended X-ray absorption fine structure (EXAFS) spectra shows that the hydrated platinum(II) ion in acidic (HClO{sub 4}) aqueous solution binds four water molecules with the Pt-O bond distance 2.01(2) {angstrom} and one (or two) in the axial position at 2.39(2) {angstrom}. The weak axial water coordination is in accordance with the unexpectedly small activation volume previously reported for water exchange in an interchange mechanism with associative character. The hydrated cis-diammineplatinum(II) complex has a similar coordination environment with two ammine and two aqua ligands strongly bound with Pt-O/N bond distances of 2.01(2) {angstrom} and, in addition, one (or two) axial water molecule at 2.37(2) {angstrom}. This result provides a new basis for theoretical computational studies aiming to connect the function of the anticancer drug cis-platin to its ligand exchange reactions, where usually four-coordinated square planar platinum(II) species are considered as the reactant and product. {sup 195}Pt NMR spectroscopy has been used to characterize the Pt(II) complexes.

  8. Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

    Science.gov (United States)

    Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

    2018-05-23

    Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

  9. Anomalous surface behavior of hydrated guanidinium ions due to ion pairing

    Science.gov (United States)

    Ekholm, Victor; Vazdar, Mario; Mason, Philip E.; Bialik, Erik; Walz, Marie-Madeleine; Öhrwall, Gunnar; Werner, Josephina; Rubensson, Jan-Erik; Jungwirth, Pavel; Björneholm, Olle

    2018-04-01

    Surface affinity of aqueous guanidinium chloride (GdmCl) is compared to that of aqueous tetrapropylammonium chloride (TPACl) upon addition of sodium chloride (NaCl) or disodium sulfate (Na2SO4). The experimental results have been acquired using the surface sensitive technique X-ray photoelectron spectroscopy on a liquid jet. Molecular dynamics simulations have been used to produce radial distribution functions and surface density plots. The surface affinities of both TPA+ and Gdm+ increase upon adding NaCl to the solution. With the addition of Na2SO4, the surface affinity of TPA+ increases, while that of Gdm+ decreases. From the results of MD simulations it is seen that Gdm+ and SO4 2 - ions form pairs. This finding can be used to explain the decreased surface affinity of Gdm+ when co-dissolved with SO4 2 - ions. Since SO4 2 - ions avoid the surface due to the double charge and strong water interaction, the Gdm+-SO4 2 - ion pair resides deeper in the solutions' bulk than the Gdm+ ions. Since TPA+ does not form ion pairs with SO4 2 -, the TPA+ ions are instead enriched at the surface.

  10. Selective permeability of uranyl peroxide nanocages to different alkali ions: influences from surface pores and hydration shells

    International Nuclear Information System (INIS)

    Gao, Yunyi; Haso, Fadi; Zhou, Jing; Hu, Lang; Liu, Tianbo; Szymanowski, Jennifer E.S.; Burns, Peter C.

    2015-01-01

    The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion-transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm-sized, fullerene-shaped molecular cluster Li_4_8_+_mK_1_2(OH)_m[UO_2(O_2)(OH)]_6_0_-(H_2O)_n (m∼20 and n∼310) (U_6_0) shows selective permeability to different alkali ions. The subnanometer pores on the water-ligand-rich surface of U_6_0 are able to block Rb"+ and Cs"+ ions from passing through, while allowing Na"+ and K"+ ions, which possess larger hydrated sizes, to enter the interior space of U_6_0. An interestingly high entropy gain during the binding process between U_6_0 and alkali ions suggests that the hydration shells of Na"+/K"+ and U_6_0 are damaged during the interaction. The ion selectivity of U_6_0 is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. 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

    2017-02-24

    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.

  12. SOLVENT EFFECTS IN THE LIQUID-PHASE HYDRATION OF CYCLOHEXENE CATALYZED BY A MACROPOROUS STRONG ACID ION-EXCHANGE RESIN

    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, macroporous Amberlite XE 307, was investigated in solvent mixtures of water and sulfolane. A decrease by a factor of 3 and 6 is observed in the experimentally measured

  13. Picosecond ultrasonics study of the modification of interfacial bonding by ion implantation

    International Nuclear Information System (INIS)

    Tas, G.; Loomis, J.J.; Maris, H.J.; Bailes, A.A. III; Seiberling, L.E.

    1998-01-01

    We report on experiments in which picosecond ultrasonic techniques are used to investigate the modification of interfacial bonding that results from ion implantation. The bonding is studied through measurements of the acoustic reflection coefficient at the interface. This method is nondestructive and can be used to create a map of the variation of the bonding over the area of the interface. copyright 1998 American Institute of Physics

  14. Structure and dynamics of hydrated Fe(II) and Fe(III) ions. Quantum mechanical and molecular mechanical simulations

    International Nuclear Information System (INIS)

    Remsungnen, T.

    2002-11-01

    Classical molecular dynamics (MD) and combined em ab initio quantum mechanical/molecular mechanical molecular dynamics (QM/MM-MD) simulations have been performed to investigate structural, dynamical and energetical properties of Fe(II), and Fe(III) transition metal ions in aqueous solution. In the QM/MM-MD simulations the ion and its first hydration sphere were treated at the Hartree-Fock ab initio quantum mechanical level, while ab initio generated pair plus three-body potentials were employed for the remaining system. For the classical MD simulation the pair plus three-body potential were employed for all ion-water interactions. The coordination number of the first hydration shell is 100 % of 6 in both cases. The number of waters in the second hydration shell obtained from classical simulations are 13.4 and 15.1 for Fe(II) and Fe(III), respectively, while QM/MM-MD gives the values of 12.4 and 13.4 for Fe(II) and Fe(III). The energies of hydration obtained from MD and QM/MM-MD for Fe(II) are 520 and 500 kcal/mol, and for Fe(III) 1160 and 1100 kcal/mol respectively. The mean residence times of water in the second shell obtained from QM/MM-MD are 24 and 48 ps for Fe(II) and Fe(III), respectively. In contrast to the data obtained from classical MD simulation, the QM/MM-MD values are all in good agreement with the experimental data available. These investigations and results clearly indicate that many-body effects are essential for the proper description of all properties of the aqueous solution of both Fe(II) and Fe(III) ions. (author)

  15. Influence of lithium and boron ions on calcium sulfo-aluminate cement hydration: application for the conditioning of boron ion exchange resins

    International Nuclear Information System (INIS)

    Dhoury, Melanie

    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 currently encapsulated in an organic matrix before being stored in a near-surface repository. An evolution of the process is considered, involving the replacement of the organic matrix by a mineral one. In this PhD study, the potential of calcium sulfo-aluminate cements (CSAC) to solidify/stabilize borated resins in the presence of lithium is investigated. These binders have the advantage to form hydrates which can incorporate borate ions in their structure, and their hydration is less retarded than that of Portland cement.An analytical approach is adopted, based on a progressive increase in the complexity of the investigated systems. Hydration of ye-elimite-rich CSAC is thus successively investigated in the presence of (i) lithium salts, (ii) lithium hydroxide and sodium borate, and (iii) lithium hydroxide and borated ion exchange resins. The experimental investigation is supplemented by thermodynamic modelling using a database specially developed for the needs of the study. Lithium ions are shown to accelerate CSAC hydration by decreasing the duration of the period of low thermal activity. The postulated mechanism involves the precipitation of lithium-containing aluminum hydroxide. On the contrary, sodium borate retards CSAC hydration by increasing the duration of the period of low thermal activity. Ulexite, a poorly crystallized mineral containing sodium and borates, transiently precipitates at early age. As long as ulexite is present, dissolution of ye-elimite is strongly slowed

  16. The influence of ion hydration on nucleation and growth of LiF crystals in aqueous solution.

    Science.gov (United States)

    Lanaro, G; Patey, G N

    2018-01-14

    Molecular dynamics (MD) simulations are employed to investigate crystal nucleation and growth in oversaturated aqueous LiF solutions. Results obtained for a range of temperatures provide evidence that the rate of crystal growth is determined by a substantial energy barrier (∼49 kJ mol -1 ) related to the loss of water from the ion hydration shells. Employing direct MD simulations, we do not observe spontaneous nucleation of LiF crystals at 300 K, but nucleation is easily observable in NVT simulations at 500 K. This contrasts with the NaCl case, where crystal nucleation is directly observed in similar simulations at 300 K. Based on these observations, together with a detailed analysis of ion clustering in metastable LiF solutions, we argue that the ion dehydration barrier also plays a key role in crystal nucleation. The hydration of the relatively small Li + and F - ions strongly influences the probability of forming large, crystal-like ion clusters, which are a necessary precursor to nucleation. This important factor is not accounted for in classical nucleation theory.

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

    International Nuclear Information System (INIS)

    Liu Lei; Yan Shilei

    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 Neel theory of ferrimagnetism.

  18. Infrared study of the nature of the copper ion--alkyne bond in Y zeolite

    International Nuclear Information System (INIS)

    Pichat, P.

    1975-01-01

    The infrared spectra of acetylene, deuterated acetylene, propyne, and but-2-yne, chemisorbed in Cu, Na--Y zeolites, which have undergone various treatments, were studied. It is concluded that the OH groups interact only with the weakly absorbed molecules, the Cu + ions are not involved, the acetylenic hydrogen atoms do not take part in the bonding, the Cu 2+ ion--alkyne bone results mainly from π donation from the unsaturated hydrocarbon to the metallic ion. (auth)

  19. 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.

  20. Change of chemical bond and wettability of polylacticacid implanted with high-flux carbon ion

    International Nuclear Information System (INIS)

    Zhang Jizhong; Kang Jiachen; Zhang Xiaoji; Zhou Hongyu

    2008-01-01

    Polylacticacid (PLA) was submitted to high-flux carbon ion implantation with energy of 40 keV. It was investigated to the effect of ion fluence (1 x 10 12 -1 x 10 15 ions/cm 2 ) on the properties of the polymer. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), wettability, and roughness were employed to study change of structure and properties of the as-implanted PLA samples. Six carbon bonds, that is, C, C-H, C-O-C, C-O, O-C-O, and >C=O, were observed on surfaces of the as-implanted PLA samples. The intensities of various chemical bonds changed with increasing ion fluence. AFM images displayed that there was irradiation damage and that it was related closely with ion fluence. At fluence as high as 1 x 10 15 ions/cm 2 surface-restructuring phenomenum took place on the surface of the PLA. Wettability was also affected by the variation on the fluence. With increasing ion fluence, the water contact angle of the as-implanted PLA samples changed gradually reaching a maximum of 76.5 deg. with 1 x 10 13 ions/cm 2 . The experimental results revealed that carbon ion fluence strongly affected surface chemical bond, morphology, wettability, and roughness of the PLA samples

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

    International Nuclear Information System (INIS)

    Bankura, Arindam; Chandra, Amalendu

    2012-01-01

    Highlights: ► A theoretical study of hydroxide ion-water clusters is carried for varying cluster size and temperature. ► The structures of OH − (H 2 O) n are found out through quantum chemical calculations for n = 4, 8, 16 and 20. ► The finite temperature behavior of the clusters is studied through ab initio dynamical simulations. ► The spectral features of OH modes (deuterated) and their dependence on hydrogen bonding states of water are discussed. ► The mechanism and kinetics of proton transfer processes in these anionic clusters are also investigated. - Abstract: We have investigated the hydration structure and dynamics of OH − (H 2 O) n clusters (n = 4, 8, 16 and 20) by means of quantum chemical and ab initio molecular dynamics calculations. Quantum chemical calculations reveal that the solvation structure of the hydroxide ion transforms from three and four-coordinated surface states to five-coordinated interior state with increase in cluster size. Several other isomeric structures with energies not very different from the most stable isomer are also found. Ab initio simulations show that the most probable configurations at higher temperatures need not be the lowest energy isomeric structure. The rates of proton transfer in these clusters are found to be slower than that in bulk water. The vibrational spectral calculations reveal distinct features for free OH (deuterated) stretch modes of water in different hydrogen bonding states. Effects of temperature on the structural and dynamical properties are also investigated for the largest cluster considered here.

  2. Antibacterial activity and ion release of bonding agent containing amorphous calcium phosphate nanoparticles.

    Science.gov (United States)

    Chen, Chen; Weir, Michael D; Cheng, Lei; Lin, Nancy J; Lin-Gibson, Sheng; Chow, Laurence C; Zhou, Xuedong; Xu, Hockin H K

    2014-08-01

    Recurrent caries at the margins is a primary reason for restoration failure. The objectives of this study were to develop bonding agent with the double benefits of antibacterial and remineralizing capabilities, to investigate the effects of NACP filler level and solution pH on Ca and P ion release from adhesive, and to examine the antibacterial and dentin bond properties. Nanoparticles of amorphous calcium phosphate (NACP) and a quaternary ammonium monomer (dimethylaminododecyl methacrylate, DMADDM) were synthesized. Scotchbond Multi-Purpose (SBMP) primer and adhesive served as control. DMADDM was incorporated into primer and adhesive at 5% by mass. NACP was incorporated into adhesive at filler mass fractions of 10%, 20%, 30% and 40%. A dental plaque microcosm biofilm model was used to test the antibacterial bonding agents. Calcium (Ca) and phosphate (P) ion releases from the cured adhesive samples were measured vs. filler level and solution pH of 7, 5.5 and 4. Adding 5% DMADDM and 10-40% NACP into bonding agent, and water-aging for 28 days, did not affect dentin bond strength, compared to SBMP control at 1 day (p>0.1). Adding DMADDM into bonding agent substantially decreased the biofilm metabolic activity and lactic acid production. Total microorganisms, total streptococci, and mutans streptococci were greatly reduced for bonding agents containing DMADDM. Increasing NACP filler level from 10% to 40% in adhesive increased the Ca and P ion release by an order of magnitude. Decreasing solution pH from 7 to 4 increased the ion release from adhesive by 6-10 folds. Bonding agents containing antibacterial DMADDM and remineralizer NACP were formulated to have Ca and P ion release, which increased with NACP filler level from 10% to 40% in adhesive. NACP adhesive was "smart" and dramatically increased the ion release at cariogenic pH 4, when these ions would be most-needed to inhibit caries. Therefore, bonding agent containing DMADDM and NACP may be promising to inhibit

  3. Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

    Science.gov (United States)

    Rissanen, Kari; Haukka, Matti

    2015-01-01

    The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

  4. Separation of the lanthanides on high-efficiency bonded phases and conventional ion-exchange resins

    International Nuclear Information System (INIS)

    Elchuk, S.; Cassidy, R.M.

    1979-01-01

    High-performance liquid chromatographic separations (< 20 min) of the lanthanides are illustrated for both 5- and 10-μm bonded-phase strong-acid ion exchangers. The performance of these bonded phase packings is compared with that obtained with a 13-μm styrene-divinylbenzene resin. The eluted metal ions are detected with a variable-wavelength detector after a post-column complexation reaction. The requirements and characteristics of post-column reaction for sensitive metal ion detection after separation on high-performance columns are discussed and the linearity, reproducibility, and sensitivity of the system used in the work are illustrated. The potential of on-column preconcentration for the ultratrace (pg/mL) determination of metal ions is also discussed and illustrated. 7 figures, 2 tables

  5. Aggregation control of quantum dots through ion-mediated hydrogen bonding shielding.

    Science.gov (United States)

    Liu, Jianbo; Yang, Xiaohai; Wang, Kemin; He, Xiaoxiao; Wang, Qing; Huang, Jin; Liu, Yan

    2012-06-26

    Nanoparticle stabilization against detrimental aggregation is a critical parameter that needs to be well controlled. Herein, we present a facile and rapid ion-mediated dispersing technique that leads to hydrophilic aggregate-free quantum dots (QDs). Because of the shielding of the hydrogen bonds between cysteamine-capped QDs, the presence of F(-) ions disassembled the aggregates of QDs and afforded their high colloidal stability. The F(-) ions also greatly eliminated the nonspecific adsorption of the QDs on glass slides and cells. Unlike the conventional colloidal stabilized method that requires the use of any organic ligand and/or polymer for the passivation of the nanoparticle surface, the proposed approach adopts the small size and large diffusion coefficient of inorganic ions as dispersant, which offers the disaggregation a fast reaction dynamics and negligible influence on their intrinsic surface functional properties. Therefore, the ion-mediated dispersing strategy showed great potential in chemosensing and biomedical applications.

  6. Influence of Ba2+ and Sr2+ ions on the hydration process of portland cement and blended cements

    Directory of Open Access Journals (Sweden)

    Živanović, B. M.

    1987-12-01

    Full Text Available This study concerns the influence of the concentration of Sr2+ and Ba2+ ions in mortar batch waters upon the hydration process of various Portland and additive cements. An increase in the mechanical resistence of said cements is observed, after 28 days, when the concentration of Ba2+ and Sr2+ ions in the mortar batch waters increases. This suggests a possible microstructural explanation of said phenomenon.En el presente trabajo se estudia la influencia de la concentración de los iones Sr2+ y Ba2+ en las aguas de amasado sobre el proceso de hidratación de varios cementos portland y de adición. Se comprueba un incremento de las resistencias mecánicas de dichos cementos, a los 28 días, cuando aumenta la concentración de los iones Ba2+ y Sr2+ en las aguas de amasado, lo cual sugiere una posible explicación microestructural a dicho fenómeno.

  7. Bond length contraction in Au nanocrystals formed by ion implantation into thin SiO2

    International Nuclear Information System (INIS)

    Kluth, P.; Johannessen, B.; Giraud, V.; Cheung, A.; Glover, C.J.; Azevedo, G. de M; Foran, G.J.; Ridgway, M.C.

    2004-01-01

    Au nanocrystals (NCs) fabricated by ion implantation into thin SiO 2 and annealing were investigated by means of extended x-ray absorption fine structure (EXAFS) spectroscopy and transmission electron microscopy. A bond length contraction was observed and can be explained by surface tension effects in a simple liquid-drop model. Such results are consistent with previous reports on nonembedded NCs implying a negligible influence of the SiO 2 matrix. Cumulant analysis of the EXAFS data suggests surface reconstruction or relaxation involving a further shortened bond length. A deviation from the octahedral closed shell structure is apparent for NCs of size 25 A

  8. 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

    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

  9. SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .2. EFFECT OF SULFOLANE ON THE REACTION-KINETICS

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    The kinetics of the' hydration of cyclohexene, catalyzed by a strong acid ion-exchange resin, have been studied in a packed bed reactor at temperatures between 353 and 413 K and a pressure of 20 bar. The kinetic rate constants were measured as a function of temperature and solvent composition (0-90

  10. Hydration of urea and alkylated urea derivatives

    Science.gov (United States)

    Kaatze, Udo

    2018-01-01

    Compressibility data and broadband dielectric spectra of aqueous solutions of urea and some of its alkylated derivatives have been evaluated to yield their numbers Nh of hydration water molecules per molecule of solute. Nh values in a broad range of solute concentrations are discussed and are compared to hydration numbers of other relevant molecules and organic ions. Consistent with previous results, it is found that urea differs from other solutes in its unusually small hydration number, corresponding to just one third of the estimated number of nearest neighbor molecules. This remarkable hydration behavior is explained by the large density φH of hydrogen bonding abilities offered by the urea molecule. In terms of currently discussed models of reorientational motions and allied dynamics in water and related associating liquids, the large density φH causes a relaxation time close to that of undisturbed water with most parts of water encircling the solute. Therefore only a small part of disturbed ("hydration") water is left around each urea molecule. Adding alkyl groups to the basic molecule leads to Nh values which, within the series of n-alkylurea derivatives, progressively increase with the number of methyl groups per solute. With n-butylurea, Nh from dielectric spectra, in conformity with many other organic solutes, slightly exceeds the number of nearest neighbors. Compared to such Nh values, hydration numbers from compressibility data are substantially smaller, disclosing incorrect assumptions in the formula commonly used to interpret the experimental compressibilities. Similar to other series of organic solutes, effects of isomerization have been found with alkylated urea derivatives, indicating that factors other than the predominating density φH of hydrogen bond abilities contribute also to the hydration properties.

  11. 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.

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

    International Nuclear Information System (INIS)

    Lee, Wonhee; Lim, Dongwook; Lee, Huen

    2013-01-01

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

  13. Effect of aluminate ions on the heat of hydration of cementitious waste forms

    International Nuclear Information System (INIS)

    Lokken, R.O.

    1993-11-01

    During the hydration and setting of high-salt content liquid waste grouts, considerable heat is generated by exothermic reactions within the grout. These reactions include hydration reactions of cementitious solids and reactions between waste constituents and the solids. Adiabatic temperature rises exceeding 80 degrees C have been estimated for grouts prepared with a dry blend of 47 wt % fly ash, 47 wt % blast furnace slag, and 6 wt % type I/II Portland cement (1) Performance criteria for grout disposal specify that the temperature of the grout waste form must not exceed 90 degrees C (2) To counter the increase in temperature, inert solids were added to the ''47/47/6'' dry blend to reduce the amount of heat-generating solids, thereby decreasing the temperature rise. Based on preliminary results from adiabatic calorimetry, a dry blend consisting of 40 wt % limestone flour, 28 wt % class F fly ash, 28 wt % ground blast furnace slag, and 4 wt % type I/II Portland cement was selected for further testing

  14. 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...

  15. Effects of the spaces available for cations in strongly acidic cation-exchange resins on the exchange equilibria by quaternary ammonium ions and on the hydration states of metal ions.

    Science.gov (United States)

    Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio

    2011-10-01

    The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

  16. Sorption rate of uranyl ions by hyphan cellulose exchangers and by hydrated titanium dioxide

    International Nuclear Information System (INIS)

    Ambe, F.; Burba, P.; Lieser, K.H.

    1979-01-01

    Sorption of uranyl ions by the cellulose exchanger Hyphan proceeds rather fast. Two steps are observed with half-times of the order of 10 s and 2 min. The majority of the uranyl ions is bound in 1 min. Sorption of uranyl ions by titanium dioxide is a very slow process. For particle sizes between 0,1 and 0,5 mm the half-time is about 3 h and equilibrium is attained in about 1 day. The effect of stirring suspensions of inorganic sorbents like titanium dioxide in solution is investigated in detail. Sorption of uranyl ions by titanium dioxide and change in pH in solution are measured simultaneously as a function of time. (orig.) [de

  17. Influence of Ba2+ and Sr2+ ions on the hydration process of portland cement and blended cements

    OpenAIRE

    Živanović, B. M.; Petrašinović, Lj.; Milovanović, T.; Karanović, Lj.; Krstanović, I.

    1987-01-01

    This study concerns the influence of the concentration of Sr2+ and Ba2+ ions in mortar batch waters upon the hydration process of various Portland and additive cements. An increase in the mechanical resistence of said cements is observed, after 28 days, when the concentration of Ba2+ and Sr2+ ions in the mortar batch waters increases. This suggests a possible microstructural explanation of said phenomenon.En el presente trabajo se estudia la influencia de la concentración de los iones Sr2+ y...

  18. Intercalation compounds of vanadium pentoxide hydrated with metalporphyrins and lanthanide ions

    International Nuclear Information System (INIS)

    Oliveira, Herenilton Paulino

    1994-01-01

    The lamellar structure of the vanadium pentoxide matrix allows the intercalation of organic molecules, ions and conductor polymers. It is important to emphasize that the vanadium oxide matrix is an intrinsic semiconductor and presents electrochromic properties. In the beginning of this work the method of synthesis and the electrochemical and electrochromic properties were extensively explored. The effect of alkaline metal and lanthanide ions on the structure of vanadium oxide matrix was studied by X-ray and infrared spectroscopy. Moreover, the influence of those ions in the electrochemical, spectro electrochemical and magnetic properties were studied. Finally, some intercalation compounds containing porphyrins were prepared and characterized by elemental analysis, X-ray diffraction, and electronic, vibrational, Moessbauer and X-ray fluorescence spectroscopy. The electrochemical and spectro electrochemical properties were investigated. And the performance of an iron porphyrin based intercalation compound as catalyst for molecular oxygen reduction was evaluated using the rotating ring-disc electrode technique. (author)

  19. Ion exchange centres of sorption of alkaline and alkaline-earth cations on hydrated titanium and tin dioxides

    International Nuclear Information System (INIS)

    Denisova, T.A.; Perekhozheva, T.N.; Sharigin, L.M.; Pletnev, R.N.

    1986-01-01

    The nature of exchange centres of one- and two-charged cations on hydrated titanium and tin dioxides by means of paramagnetic resonance method is studied. The sorption of cations of Na + , Cs + , Ca 2+ was carried out at 25 and 90 deg C at ph=5.0-10.4 on samples of hydrated titanium dioxide and hydrated tin dioxide, obtained by sol gel method and calcined at 150 deg C and 300 deg C accordingly.

  20. Hydration effects on the photoionization energy of 2‧-deoxyguanosine 5‧-phosphate and activation barriers for guanine methylation by carcinogenic methane diazonium ions

    Science.gov (United States)

    Eichler, Daniel R.; Hamann, Haley A.; Harte, Katherine A.; Papadantonakis, George A.

    2017-07-01

    Results from DFT calculations indicate that states originating from gas-phase ionization of the phosphate and the base are degenerate in syn-5‧-dGMP- and that bulk hydration lowers the base-localized ionization energy by diazonium ions are lower at the N7 than at the O6 sites and they are influenced by local ionization energy and steric interference.

  1. Electrical, structural, and bonding changes induced in silicon by H, Ar, and Kr ion-beam etching

    International Nuclear Information System (INIS)

    Singh, R.; Fonash, S.J.; Ashok, S.; Caplan, P.; Shappirio, J.; Hage-Ali, M.; Ponpon, J.

    1983-01-01

    A study to elucidate the role of processing-induced changes in Si, subjected to ion-beam etching has been made. It is shown that these changes can be related to the primary ion beam used in ion-beam etching. Using ESR, trivalently bonded Si has been shown to be present. Fe and Cr have been found to be the main contaminants. An annealing study revealed that the damage can be annealed out at relatively high temperatures

  2. Reactivity of two hydrate forms of europium(3) ethylenediaminetetraacetate in the processes of central ion substitution

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.

    1985-01-01

    Kinetics of central ion substitution in the system EuA - -Cu 2+ , where A 4- -ethylenediaminetetraacetate (pH 6.0, t=25-55 deg C), has been studied spectrophotometrically. It is shown, that the form EuA(H 2 O) 3 - is more reactive as compared with EuA(H 2 O) 2 - . It is found, that equilibrium constant of the process EuA(H 2 O) 3 - reversible EuA(H 2 O) 2 - (1) equals 1 at t=36.2 deg C. The values ΔH and ΔS of the process (1), constituting 13.0+-3.2 kJ/mol and 41.8+-5.5 J/molxdeg respectively, are calculated

  3. Reaction of hydrazine hydrate with oxalic acid: synthesis and crystal structure of dihydrazinium oxalate

    OpenAIRE

    Selvakumar, Rajendran; Premkumar, Thathan; Manivannan, Vadivelu; Saravanan, Kaliannan; Govindarajan, Subbiah

    2014-01-01

    The reaction of oxalic acid with hydrazine hydrate (in appropriate mole ratio) forms the dihydrazinium oxalate under specific experimental condition. The title compound is a molecular salt containing two discrete hydrazinium cations and an oxalate anion. The oxalate anion is perfectly planar and there is a crystallographic centre of symmetry in the middle of the C-C bond. The C-O bond distances are almost equal indicating the presence of resonance in the oxalate ion. The crystal packing is st...

  4. Dispersion- and Exchange-Corrected Density Functional Theory for Sodium Ion Hydration.

    Science.gov (United States)

    Soniat, Marielle; Rogers, David M; Rempe, Susan B

    2015-07-14

    A challenge in density functional theory is developing functionals that simultaneously describe intermolecular electron correlation and electron delocalization. Recent exchange-correlation functionals address those two issues by adding corrections important at long ranges: an atom-centered pairwise dispersion term to account for correlation and a modified long-range component of the electron exchange term to correct for delocalization. Here we investigate how those corrections influence the accuracy of binding free energy predictions for sodium-water clusters. We find that the dual-corrected ωB97X-D functional gives cluster binding energies closest to high-level ab initio methods (CCSD(T)). Binding energy decomposition shows that the ωB97X-D functional predicts the smallest ion-water (pairwise) interaction energy and larger multibody contributions for a four-water cluster than most other functionals - a trend consistent with CCSD(T) results. Also, ωB97X-D produces the smallest amounts of charge transfer and the least polarizable waters of the density functionals studied, which mimics the lower polarizability of CCSD. When compared with experimental binding free energies, however, the exchange-corrected CAM-B3LYP functional performs best (error <1 kcal/mol), possibly because of its parametrization to experimental formation enthalpies. For clusters containing more than four waters, "split-shell" coordination must be considered to obtain accurate free energies in comparison with experiment.

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

    International Nuclear Information System (INIS)

    Iglesias, Y.J.

    2002-01-01

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

  6. Depolymerization of cellulose into high-value chemicals by using synergy of zinc chloride hydrate and sulfate ion promoted titania catalyst.

    Science.gov (United States)

    Wei, Weiqi; Wu, Shubin

    2017-10-01

    Experiments for cellulose depolymerization by synergy of zinc chloride hydrate (ZnCl 2 ·RH 2 O) and sulfated titania catalyst (SO 4 2- /TiO 2 ) were investigated in this study. The results showed the introduction of sulfate into the TiO 2 significantly enhanced the catalyst acid amount, especially for Brønsted acid site, which is beneficial for subsequent cellulose depolymerization. ZnCl 2 ·RH 2 O hydrate, only a narrow composition range of water, specifically 3.0≤R≤4.0, can dissolve cellulose, which finally resulted the cellulose with low crystallinity and weak intrachain and interchain hydrogen bond network. Coupling of ZnCl 2 ·RH 2 O hydrate and SO 4 2- /TiO 2 catalyst as a mixed reaction system promoted cellulose depolymerization, and the products can be adjusted by the control of reaction conditions, the low temperature (80-100°C) seemed beneficial for glucose formation (maximal yield 50.5%), and the high temperature (120-140°C) favored to produce levulinic acid (maximal yield 43.1%). Besides, the addition of organic co-solvent making HMF as the main product (maximal yield 38.3%). Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

    Doll, D.W.; Trester, P.W.; Staley, H.G.

    1981-10-01

    In the Doublet III (D-III) neutral beam injectors, cast, rigid-epoxy insulators are joined to the AISI 304 stainless steel corona rings with semi-rigid epoxy adhesive. Selected mechanical properties of these materials were measured between 11 0 C and 65 0 C, well below the material temperature limits, to identify the trends and to confirm adequate mechanical strength for the insulators. Significant creep deformation was measured at 22 0 C. Empirical relationships were developed to predict long term strain over a range of stress and temperature of design interest. Delayed failure was observed in bonded specimens at stress levels well below the ultimate strength. In order to protect the D-III neutral beam ion source epoxy from elevated temperature effects, a chill was installed in the cooling water circuit. Outgassing measurements of the insulator epoxy were made and found to be low and primarily H 2 O

  8. Guided ion beam and theoretical studies of the bond energy of SmS+

    Science.gov (United States)

    Armentrout, P. B.; Demireva, Maria; Peterson, Kirk A.

    2017-12-01

    Previous work has shown that atomic samarium cations react with carbonyl sulfide to form SmS+ + CO in an exothermic and barrierless process. To characterize this reaction further, the bond energy of SmS+ is determined in the present study using guided ion beam tandem mass spectrometry. Reactions of SmS+ with Xe, CO, and O2 are examined. Results for collision-induced dissociation processes with all three molecules along with the endothermicity of the SmS+ + CO → Sm+ + COS exchange reaction are combined to yield D0(Sm+-S) = 3.37 ± 0.20 eV. The CO and O2 reactions also yield a SmSO+ product, with measured endothermicities that indicate D0(SSm+-O) = 3.73 ± 0.16 eV and D0(OSm+-S) = 1.38 ± 0.27 eV. The SmS+ bond energy is compared with theoretical values characterized at several levels of theory, including CCSD(T) complete basis set extrapolations using all-electron basis sets. Multireference configuration interaction calculations with explicit spin-orbit calculations along with composite thermochemistry using the Feller-Peterson-Dixon method and all-electron basis sets were also explored for SmS+, and for comparison, SmO, SmO+, and EuO.

  9. Tracking metal ions with polypyrrole thin films adhesively bonded to diazonium-modified flexible ITO electrodes.

    Science.gov (United States)

    Lo, Momath; Diaw, Abdou K D; Gningue-Sall, Diariatou; Aaron, Jean-Jacques; Oturan, Mehmet A; Chehimi, Mohamed M

    2018-05-09

    Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb 2+ , Cu 2+ , and Cd 2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu 2+ , Cd 2+ , and Pb 2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu 2+ , Cd 2+ , and Pb 2+ , respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

  10. Structure and bonding in compounds containing the NpO2+ and NpO22+ ions

    International Nuclear Information System (INIS)

    Musikas, C.; Burns, J.H.

    1975-01-01

    Studies of oxo cations of Np(V) and Np(VI) were made on single crystals using X-ray diffraction and spectroscopic methods. Quantitative measurements of the geometry of the triatomic ion and its uranyl(VI) analog made it possible to assess the effects on bond lengths of the nature of equatorial secondary bonds, the change in valence from V to VI, and the actinide contraction. Absorption spectra showed marked changes in the solid state compared to the same ion in solution, especially anisotropy with crystal orientation (dichroism). The compounds analyzed were Na 4 NpO 2 (O 2 ) 3 .9H 2 O, Na 4 UO 2 (O 2 ) 3 .9H 2 O, K 4 NpO 2 (CO 3 ) 3 , and BaNpO 2 (H 3 C 2 O 2 ).2H 2 O. All actinyl ions were found to be linear. The largest difference in M=O bond lengths is between 1.776 in the compound having the relatively weak secondary linkage to carbonate, and 1.843 A in which the peroxide forms much stronger covalent bonds. Between compounds identical except for change of U to Np the M=O bond length contracts by only about 0.01 A. However an elongation of about 0.11A is observed when neptunium(VI) is reduced to neptunium(V) without change in the equatorial ligand. (U.S.)

  11. Associative Ionization of Excited Sodium Species with Various Ligands: Assessing Relative Bonding Strengths of Ion-ligand Interactions

    Czech Academy of Sciences Publication Activity Database

    Gilligan, J. J.; McCunn, L. R.; Leskiw, B. D.; Herman, Zdeněk; Castleman Jr., A. W.

    2001-01-01

    Roč. 204, 1/3 (2001), s. 247-253 ISSN 1387-3806 Institutional research plan: CEZ:AV0Z4040901 Keywords : associative ionization * cluster ions * sodium bonding energies Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.176, year: 2001

  12. CO2 solubility in aqueous solutions containing Na+, Ca2+, Cl−, SO42− and HCO3-: The effects of electrostricted water and ion hydration thermodynamics

    International Nuclear Information System (INIS)

    Gilbert, Kimberly; Bennett, Philip C.; Wolfe, Will; Zhang, Tongwei; Romanak, Katherine D.

    2016-01-01

    Dissolution of CO 2 into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO 2 entering the atmosphere. Ions in solution partially control the amount of CO 2 that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO 2 solubility is difficult to predict. In this study, CO 2 solubility was experimentally determined in water, NaCl, CaCl 2 , Na 2 SO 4, and NaHCO 3 solutions and a mixed brine similar to the Bravo Dome natural CO 2 reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO 2 pressures to 35.5 MPa. Increasing ionic strength decreased CO 2 solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO 2 solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO 2 was strongly correlated (R 2  = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO 2 solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO 2 solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl 2 brine and a natural Na + , Ca 2+ , Cl − type brine with minor amounts of Mg 2+ , K + , Sr 2+ and Br − ). - Highlights: • Measured CO 2 solubility in Na + , Cl − , HCO 3 - , Ca 2+ and SO 4 2− solutions at high PCO 2 . • A new equation calculates electrostricted water (mol/kgw) from hydration number. • CO 2 solubility strongly correlates (R 2  = 0.96) to electrostricted water. • Ion electrostriction of water limits its availability for CO 2 caging and solvation. • Correlations predict CO 2 solubility of several mixed brines to within 1–9%.

  13. The O-H Bond Dissociation Energies of Substituted Phenols and Proton Affinities of Substituted Phenoxide Ions: A DFT Study

    Directory of Open Access Journals (Sweden)

    Tadafumi Uchimaru

    2002-04-01

    Full Text Available Abstract: The accurate O-H bond dissociation enthalpies for a series of meta and para substituted phenols (X-C6H4-OH, X=H, F, Cl, CH3, OCH3, OH, NH2, CF3, CN, and NO2 have been calculated by using the (ROB3LYP procedure with 6-311G(d,p and 6-311++G(2df,2p basis sets. The proton affinities of the corresponding phenoxide ions (XC6H4-O- have also been computed at the same level of theory. The effect of change of substituent position on the energetics of substituted phenols has been analyzed. The correlations of Hammett’s substituent constants with the bond dissociation enthalpies of the O-H bonds of phenols and proton affinities of phenoxide ions have been explored.

  14. 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.

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

    International Nuclear Information System (INIS)

    Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin

    2015-01-01

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

  16. Structural and spectroscopic features of proton hydrates in the crystalline state. Solid-state DFT study on HCl and triflic acid hydrates

    Science.gov (United States)

    Vener, M. V.; Chernyshov, I. Yu.; Rykounov, A. A.; Filarowski, A.

    2018-01-01

    Crystalline HCl and CF3SO3H hydrates serve as excellent model systems for protonated water and perfluorosulphonic acid membranes, respectively. They contain characteristic H3O+, H5О+2, H7О+3 and H3O+(H2O)3 (the Eigen cation) structures. The properties of these cations in the crystalline hydrates of strong monobasic acids are studied by solid-state density function theory (DFT). Simultaneous consideration of the HCl and CF3SO3H hydrates reveals the impact of the size of a counter ion and the crystalline environment on the structure and infrared active bands of the simplest proton hydrates. The H7O+3 structure is very sensitive to the size of the counter ion and symmetry of the local environment. This makes it virtually impossible to identify the specific features of H7O+3 in molecular crystals. The H3O+ ion can be treated as the Eigen-like cation in the crystalline state. Structural, infrared and electron-density features of H5О+2 and the Eigen cation are virtually insensitive to the size of the counter ion and the symmetry of the local crystalline environment. These cations can be considered as the simplest stable proton hydrates in the condensed phase. Finally, the influence of the Grimme correction on the structure and harmonic frequencies of the molecular crystals with short (strong) intermolecular O-H···O bonds is discussed.

  17. Application of empirical hydration distribution functions around polar atoms for assessing hydration structures of proteins

    International Nuclear Information System (INIS)

    Matsuoka, Daisuke; Nakasako, Masayoshi

    2013-01-01

    Highlights: ► Empirical distribution functions of water molecules in protein hydration are made. ► The functions measure how hydrogen-bond geometry in hydration deviate from ideal. ► The functions assess experimentally identified hydration structures of protein. - Abstract: To quantitatively characterize hydrogen-bond geometry in local hydration structures of proteins, we constructed a set of empirical hydration distribution functions (EHDFs) around polar protein atoms in the main and side chains of 11 types of hydrophilic amino acids (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 113 (2009) 11274). The functions are the ensemble average of possible hydration patterns around the polar atoms, and describe the anisotropic deviations from ideal hydrogen bond geometry. In addition, we defined probability distribution function of hydration water molecules (PDFH) over the hydrophilic surface of a protein as the sum of EHDFs of solvent accessible polar protein atoms. The functions envelop most of hydration sites identified in crystal structures of proteins (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 114 (2010) 4652). Here we propose the application of EHDFs and PDFHs for assessing crystallographically identified hydration structures of proteins. First, hydration water molecules are classified with respect to the geometry in hydrogen bonds in referring EHDFs. Difference Fourier electron density map weighted by PDFH of protein is proposed to identify easily density peaks as candidates of hydration water molecules. A computer program implementing those ideas was developed and used for assessing hydration structures of proteins

  18. Selective peptide bond hydrolysis of cysteine peptides in the presence of Ni(II) ions.

    Science.gov (United States)

    Protas, Anna Maria; Bonna, Arkadiusz; Kopera, Edyta; Bal, Wojciech

    2011-01-01

    Recently, we described a sequence-specific R1-(Ser/Thr) peptide bond hydrolysis reaction in peptides of a general sequence R1-(Ser/Thr)-Xaa-His-Zaa-R, which occurs in the presence of Ni(II) ions [A. Krężel, E. Kopera, A. M. Protas, A. Wysłouch-Cieszyńska, J. Poznański, W. Bal, J. Am. Chem. Soc. 132 (2010) 3355-3366]. In this study we explored the possibility of substituting the Ser/Thr and the His residues, necessary for the reaction to occur according to the Ni(II)-assisted acyl shift reaction mechanism, with Cys residues. We tested this concept by synthesizing three homologous peptides: R1-Ser-Arg-Cys-Trp-R2, R1-Cys-Arg-His-Trp-R2, and R1-Cys-Arg-Cys-Trp-R2, and the R1-Ser-Arg-His-Trp-R2 peptide as comparator (R1 and R2 were CH3CO-Gly-Ala and Lys-Phe-Leu-NH2, respectively). We studied their hydrolysis in the presence of Ni(II) ions, under anaerobic conditions and in the presence of TCEP as a thiol group antioxidant. We measured hydrolysis rates using HPLC and identified products of reaction using electrospray mass spectrometry. Potentiometry and UV-vis spectroscopy were used to assess Ni(II) complexation. We demonstrated that Ni(II) is not compatible with the Cys substitution of the Ser/Thr acyl acceptor residue, but the substitution of the Ni(II) binding His residue with a Cys yields a peptide susceptible to Ni(II)-related hydrolysis. The relatively high activity of the R1-Ser-Arg-Cys-Trp-R2 peptide at pH 7.0 suggests that this peptide and its Cys-containing analogs might be useful in practical applications of Ni(II)-dependent peptide bond hydrolysis. Copyright © 2010 Elsevier Inc. All rights reserved.

  19. K+ congeners that do not compromise Na+ activation of the Na+,K+-ATPase: hydration of the ion binding cavity likely controls ion selectivity.

    Science.gov (United States)

    Mahmmoud, Yasser A; Kopec, Wojciech; Khandelia, Himanshu

    2015-02-06

    The Na(+),K(+)-ATPase is essential for ionic homeostasis in animal cells. The dephosphoenzyme contains Na(+) selective inward facing sites, whereas the phosphoenzyme contains K(+) selective outward facing sites. Under normal physiological conditions, K(+) inhibits cytoplasmic Na(+) activation of the enzyme. Acetamidinium (Acet(+)) and formamidinium (Form(+)) have been shown to permeate the pump through the outward facing sites. Here, we show that these cations, unlike K(+), are unable to enter the inward facing sites in the dephosphorylated enzyme. Consistently, the organic cations exhibited little to no antagonism to cytoplasmic Na(+) activation. Na(+),K(+)-ATPase structures revealed a previously undescribed rotamer transition of the hydroxymethyl side chain of the absolutely conserved Thr(772) of the α-subunit. The side chain contributes its hydroxyl to Na(+) in site I in the E1 form and rotates to contribute its methyl group toward K(+) in the E2 form. Molecular dynamics simulations to the E1·AlF4 (-)·ADP·3Na(+) structure indicated that 1) bound organic cations differentially distorted the ion binding sites, 2) the hydroxymethyl of Thr(772) rotates to stabilize bound Form(+) through water molecules, and 3) the rotamer transition is mediated by water traffic into the ion binding cavity. Accordingly, dehydration induced by osmotic stress enhanced the interaction of the congeners with the outward facing sites and profoundly modified the organization of membrane domains of the α-subunit. These results assign a catalytic role for water in pump function, and shed light on a backbone-independent but a conformation-dependent switch between H-bond and dispersion contact as part of the catalytic mechanism of the Na(+),K(+)-ATPase. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

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

    International Nuclear Information System (INIS)

    Kumar, Ashok; Thota, Subhash; Deva, Dinesh; Kumar, Jitendra

    2014-01-01

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

  1. 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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Anodic carbon-boron bond cleavage through the intermediacy of electrogenerated bromonium ion

    International Nuclear Information System (INIS)

    Shi Deqing; Gitkis, Anna; Becker, James Y.

    2007-01-01

    The electrochemical properties of a series of cyclic arylboronic esters, XC 6 H 4 B(OR) 2 [RR = CH 2 CH 2 ; X = H (1a); p-Me (1b); p-OMe (1c); p-Cl (1d); p-Ph (1e); m-Cl (1f); m-OMe (1g); CF 3 (1h); OMe (1i); 2,6-dimethyl (1j); 1b with RR = (CH 2 ) 3 , (1k); 1b with RR = CMe 2 CMe 2 , (1m)] has been studied in acetonitrile by cyclic voltammetry (CV) and controlled-potential electrolysis (CPE). The CV of representative examples of aryl borates with different substituents show one irreversible oxidation wave on a Pt cathode, at 1.8-1.9 V (vs. Ag/AgCl), with a negligible substituent effect. The cathodic CPE process led to small amounts of biaryls only, whereas the direct anodic CPE could not be carried out practically due to low currents. However, in the presence of electrogenerated bromonium (or iodonium) ions a C-B bond cleavage does take place to yield the corresponding bromoaryls, brominated phenols, and arylboronic acids as the major products

  3. Anodic carbon-boron bond cleavage through the intermediacy of electrogenerated bromonium ion

    Energy Technology Data Exchange (ETDEWEB)

    Shi Deqing; Gitkis, Anna [Department of Chemistry, Ben-Gurion University of the Negev, Beer Sheva 84105 (Israel); Becker, James Y. [Department of Chemistry, Ben-Gurion University of the Negev, Beer Sheva 84105 (Israel)], E-mail: becker@bgu.ac.il

    2007-12-31

    The electrochemical properties of a series of cyclic arylboronic esters, XC{sub 6}H{sub 4}B(OR){sub 2} [RR = CH{sub 2}CH{sub 2}; X = H (1a); p-Me (1b); p-OMe (1c); p-Cl (1d); p-Ph (1e); m-Cl (1f); m-OMe (1g); CF{sub 3} (1h); OMe (1i); 2,6-dimethyl (1j); 1b with RR = (CH{sub 2}){sub 3}, (1k); 1b with RR = CMe{sub 2}CMe{sub 2}, (1m)] has been studied in acetonitrile by cyclic voltammetry (CV) and controlled-potential electrolysis (CPE). The CV of representative examples of aryl borates with different substituents show one irreversible oxidation wave on a Pt cathode, at 1.8-1.9 V (vs. Ag/AgCl), with a negligible substituent effect. The cathodic CPE process led to small amounts of biaryls only, whereas the direct anodic CPE could not be carried out practically due to low currents. However, in the presence of electrogenerated bromonium (or iodonium) ions a C-B bond cleavage does take place to yield the corresponding bromoaryls, brominated phenols, and arylboronic acids as the major products.

  4. Stopped-flow studies of carbon dioxide hydration and bicarbonate dehydration in H2O and D2O. Acid-base and metal ion catalysis

    International Nuclear Information System (INIS)

    Pocker, Y.; Bjorkquist, D.W.

    1977-01-01

    The approach to equilibrium between carbon dioxide and bicarbonate has been followed by zero-order kinetics both from direction of CO 2 hydration and HCO 3 - dehydration. The rates are monitored at 25.0 0 C using stopped-flow indicator technique in H 2 O as well as D 2 O. The hydration of CO 2 is subject to catalysis by H 2 O (k 0 = 2.9 x 10 -2 s -1 ) and OH - (k/sub OH - / = 6.0 x 10 3 M -1 s -1 ). The value of 0.63 for the ratio k/sub OH - //k/sub OD - / is consistent with a mechanism utilizing a direct nucleophilic attack of OH - on CO 2 . In reverse direction HCO 3 - dehydration is catalyzed predominantly by H 3 O + (k/sub H 3 O + / 4.1 x 10 4 M -1 s -1 ) and to a much lesser degree by H 2 O (k 0 = 2 x 10 -4 s -1 ). The value of 0.56 for ratio k/sub H 3 O + //kD 3 O + / indicates that HCO 3 - may be protonated either in a preequilibrium step or in a rate-determining dehydration step. Both the hydration of CO 2 and the dehydration of bicarbonate are subject to general catalysis. For CO 2 , dibasic phosphate, a zinc imidazole complex, and a copper imidazole complex all enhanced the rate of hydration with respective rate coefficients of 3 x 10 -1 , 6.0, and 2.5 M -1 s -1 . For bicarbonate, monobasic phosphate catalyzed the rate of dehydration (k/sub H 2 PO 4 - / = 1 x 10 -1 M -1 s -1 ). Additionally in going from an ionic strength of 0.1 to 1.0 there was a negligible salt effect for the water-catalyzed hydration of CO 2 . However, the rate constant for the hydronium ion catalyzed dehydration of HCO 3 - was reduced from 4.1 x 10 4 M -1 s -1 to 2.3 x 10 4 M -1 s -1 for the same change in ionic strength. Finally the rate of CO 2 uptake by the complex Co(NH 3 ) 5 OH 2 3+ was followed spectrophotometrically both in H 2 O and D 2 O to determine the solvent isotope effect for a reaction known to involve a nucleophilic attack of a Co(III)-hydroxo complex on CO 2

  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. Ab initio study of electron-ion structure factors in binary liquids with different types of chemical bonding

    International Nuclear Information System (INIS)

    Klevets, Ivan; Bryk, Taras

    2014-01-01

    Electron-ion structure factors, calculated in ab initio molecular dynamics simulations, are reported for several binary liquids with different kinds of chemical bonding: metallic liquid alloy Bi–Pb, molten salt RbF, and liquid water. We derive analytical expressions for the long-wavelength asymptotes of the partial electron-ion structure factors of binary systems and show that the analytical results are in good agreement with the ab initio simulation data. The long-wavelength behaviour of the total charge structure factors for the three binary liquids is discussed

  7. Strong Dependence of Hydration State of F-Actin on the Bound Mg(2+)/Ca(2+) Ions.

    Science.gov (United States)

    Suzuki, Makoto; Imao, Asato; Mogami, George; Chishima, Ryotaro; Watanabe, Takahiro; Yamaguchi, Takaya; Morimoto, Nobuyuki; Wazawa, Tetsuichi

    2016-07-21

    Understanding of the hydration state is an important issue in the chemomechanical energetics of versatile biological functions of polymerized actin (F-actin). In this study, hydration-state differences of F-actin by the bound divalent cations are revealed through precision microwave dielectric relaxation (DR) spectroscopy. G- and F-actin in Ca- and Mg-containing buffer solutions exhibit dual hydration components comprising restrained water with DR frequency f2 (fw). The hydration state of F-actin is strongly dependent on the ionic composition. In every buffer tested, the HMW signal Dhyme (≡ (f1 - fw)δ1/(fwδw)) of F-actin is stronger than that of G-actin, where δw is DR-amplitude of bulk solvent and δ1 is that of HMW in a fixed-volume ellipsoid containing an F-actin and surrounding water in solution. Dhyme value of F-actin in Ca2.0-buffer (containing 2 mM Ca(2+)) is markedly higher than in Mg2.0-buffer (containing 2 mM Mg(2+)). Moreover, in the presence of 2 mM Mg(2+), the hydration state of F-actin is changed by adding a small fraction of Ca(2+) (∼0.1 mM) and becomes closer to that of the Ca-bound form in Ca2.0-buffer. This is consistent with the results of the partial specific volume and the Cotton effect around 290 nm in the CD spectra, indicating a change in the tertiary structure and less apparent change in the secondary structure of actin. The number of restrained water molecules per actin (N2) is estimated to be 1600-2100 for Ca2.0- and F-buffer and ∼2500 for Mg2.0-buffer at 10-15 °C. These numbers are comparable to those estimated from the available F-actin atomic structures as in the first water layer. The number of HMW molecules is roughly explained by the volume between the equipotential surface of -kT/2e and the first water layer of the actin surface by solving the Poisson-Boltzmann equation using UCSF Chimera.

  8. Determining Double Bond Position in Lipids Using Online Ozonolysis Coupled to Liquid Chromatography and Ion Mobility-Mass Spectrometry.

    Science.gov (United States)

    Harris, Rachel A; May, Jody C; Stinson, Craig A; Xia, Yu; McLean, John A

    2018-02-06

    The increasing focus on lipid metabolism has revealed a need for analytical techniques capable of structurally characterizing lipids with a high degree of specificity. Lipids can exist as any one of a large number of double bond positional isomers, which are indistinguishable by single-stage mass spectrometry alone. Ozonolysis reactions coupled to mass spectrometry have previously been demonstrated as a means for localizing double bonds in unsaturated lipids. Here we describe an online, solution-phase reactor using ozone produced via a low-pressure mercury lamp, which generates aldehyde products diagnostic of cleavage at a particular double bond position. This flow-cell device is utilized in conjunction with structurally selective ion mobility-mass spectrometry. The lamp-mediated reaction was found to be effective for multiple lipid species in both positive and negative ionization modes, and the conversion efficiency from precursor to product ions was tunable across a wide range (20-95%) by varying the flow rate through the ozonolysis device. Ion mobility separation of the ozonolysis products generated additional structural information and revealed the presence of saturated species in a complex mixture. The method presented here is simple, robust, and readily coupled to existing instrument platforms with minimal modifications necessary. For these reasons, application to standard lipidomic workflows is possible and aids in more comprehensive structural characterization of a myriad of lipid species.

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

    International Nuclear Information System (INIS)

    Camaioni, D.M.; Colton, N.G.; Bruening, R.L.

    1992-01-01

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

  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. Hydration and Ion Pairing in Aqueous Mg2+ and Zn2+ Solutions: Force-Field Description Aided by Neutron Scattering Experiments and Ab Initio Molecular Dynamics Simulations.

    Science.gov (United States)

    Duboué-Dijon, Elise; Mason, Philip E; Fischer, Henry E; Jungwirth, Pavel

    2018-04-05

    Magnesium and zinc dications possess the same charge and have an almost identical size, yet they behave very differently in aqueous solutions and play distinct biological roles. It is thus crucial to identify the origins of such different behaviors and to assess to what extent they can be captured by force-field molecular dynamics simulations. In this work, we combine neutron scattering experiments in a specific mixture of H 2 O and D 2 O (the so-called null water) with ab initio molecular dynamics simulations to probe the difference in the hydration structure and ion-pairing properties of chloride solutions of the two cations. The obtained data are used as a benchmark to develop a scaled-charge force field for Mg 2+ that includes electronic polarization in a mean field way. We show that using this electronic continuum correction we can describe aqueous magnesium chloride solutions well. However, in aqueous zinc chloride specific interaction terms between the ions need to be introduced to capture ion pairing quantitatively.

  12. Chloral Hydrate

    Science.gov (United States)

    ... if you are allergic to chloral hydrate, aspirin, tartrazine (a yellow dye in some processed foods and ... in, tightly closed, and out of reach of children. Store it at room temperature, away from excess ...

  13. Ion Beam Enhanced Deposition as Alternative Pretreatment for Adhesive Bonding of Aircraft Alloys

    National Research Council Canada - National Science Library

    Koch, Gerhardus

    1994-01-01

    .... The objective of the work described in this paper was to demonstrate the feasibility of applying a non-chemical technique to generate an aluminum oxide surface with adhesive bonding properties...

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

    International Nuclear Information System (INIS)

    Bach, T.T.H.; Chabas, E.; Pochard, I.; Cau Dit Coumes, C.; Haas, J.; Frizon, F.; Nonat, A.

    2013-01-01

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

  15. Charge transfer processes during ion scattering and stimulated desorption of secondary ions from gas-condensed dielectric surfaces

    CERN Document Server

    Souda, R

    2002-01-01

    The ion emission mechanism from weakly-interacting solid surfaces has been investigated. The H sup + ion captures a valence electron via transient chemisorption, so that the ion neutralization probability is related to the nature of bonding of adsorbates. The H sup + ion is scattered from physisorbed Ar at any coverage whereas the H sup + yield from solid H sub 2 O decays considerably due to covalency in the hydrogen bond. In electron- and ion-stimulated desorption, the ion ejection probability is correlated intimately with the physisorption/chemisorption of parent atoms or molecules. The emission of F sup + ions is rather exceptional because they arise from the screened F 2s core-hole state followed by the ionization via the intra-atomic Auger decay after bond breakage. In electron-stimulated desorption of H sub 2 O, hydrated protons are emitted effectively from nanoclusters formed on a solid Ar substrate due to Coulomb repulsion between confined valence holes.

  16. Distribution of species and Ga–N bonds in silicon co-implanted with gallium and nitrogen ions

    International Nuclear Information System (INIS)

    Surodin, S. I.; Nikolitchev, D. E.; Kryukov, R. N.; Belov, A. I.; Korolev, D. S.; Mikhaylov, A. N.; Tetelbaum, D. I.

    2016-01-01

    The concentration profiles of species in silicon subjected to gallium and nitrogen co-implantation and subsequent annealing have been investigated by the method of X-ray photoelectron spectroscopy combined with the layer-by-layer ion etching of the implanted layer. It is shown that practically entire implanted gallium undergoes out-diffusion, but the preliminary implantation of nitrogen for the synthesis of a barrier SiN_x layer makes it possible to avoid the essential loss of gallium. In this case, about 14 % of implanted gallium bond to nitrogen. The obtained data are discussed from the viewpoint of the possibility of ion synthesis of GaN inclusions in silicon matrix.

  17. Distribution of species and Ga–N bonds in silicon co-implanted with gallium and nitrogen ions

    Energy Technology Data Exchange (ETDEWEB)

    Surodin, S. I., E-mail: surodin.bsn@mail.ru; Nikolitchev, D. E.; Kryukov, R. N.; Belov, A. I.; Korolev, D. S.; Mikhaylov, A. N.; Tetelbaum, D. I., E-mail: tetelbaum@phys.unn.ru [Lobachevsky University, 23 Prospekt Gagarina, Nizhny Novgorod, 603950 (Russian Federation)

    2016-06-17

    The concentration profiles of species in silicon subjected to gallium and nitrogen co-implantation and subsequent annealing have been investigated by the method of X-ray photoelectron spectroscopy combined with the layer-by-layer ion etching of the implanted layer. It is shown that practically entire implanted gallium undergoes out-diffusion, but the preliminary implantation of nitrogen for the synthesis of a barrier SiN{sub x} layer makes it possible to avoid the essential loss of gallium. In this case, about 14 % of implanted gallium bond to nitrogen. The obtained data are discussed from the viewpoint of the possibility of ion synthesis of GaN inclusions in silicon matrix.

  18. Abnormal ion content, hydration and granule expansion of the secretory granules from cystic fibrosis airway glandular cells

    International Nuclear Information System (INIS)

    Baconnais, S.; Delavoie, F.; Zahm, J.M.; Milliot, M.; Terryn, C.; Castillon, N.; Banchet, V.; Michel, J.; Danos, O.; Merten, M.; Chinet, T.; Zierold, K.; Bonnet, N.; Puchelle, E.; Balossier, G.

    2005-01-01

    The absence or decreased expression of cystic fibrosis transmembrane conductance regulator (CFTR) induces increased Na + absorption and hyperabsorption of the airway surface liquid (ASL) resulting in a dehydrated and hyperviscous ASL. Although the implication of abnormal airway submucosal gland function has been suggested, the ion and water content in the Cystic Fibrosis (CF) glandular secretory granules, before exocytosis, is unknown. We analyzed, in non-CF and CF human airway glandular cell lines (MM-39 and KM4, respectively), the ion content in the secretory granules by electron probe X-ray microanalysis and the water content by quantitative dark field imaging on freeze-dried cryosections. We demonstrated that the ion content (Na + , Mg 2+ , P, S and Cl - ) is significantly higher and the water content significantly lower in secretory granules from the CF cell line compared to the non-CF cell line. Using videomicroscopy, we observed that the secretory granule expansion was deficient in CF glandular cells. Transfection of CF cells with CFTR cDNA or inhibition of non-CF cells with CFTR inh -172, respectively restored or decreased the water content and granule expansion, in parallel with changes in ion content. We hypothesize that the decreased water and increased ion content in glandular secretory granules may contribute to the dehydration and increased viscosity of the ASL in CF

  19. Cooperativity of hydrogen-bonded networks in 7-azaindole(CH3OH)n (n=2,3) clusters evidenced by IR-UV ion-dip spectroscopy and natural bond orbital analysis.

    Science.gov (United States)

    Sakota, Kenji; Kageura, Yutaka; Sekiya, Hiroshi

    2008-08-07

    IR-UV ion-dip spectra of the 7-azaindole (7AI)(CH(3)OH)(n) (n=1-3) clusters have been measured in the hydrogen-bonded NH and OH stretching regions to investigate the stable structures of 7AI(CH(3)OH)(n) (n=1-3) in the S(0) state and the cooperativity of the H-bonding interactions in the H-bonded networks. The comparison of the IR-UV ion-dip spectra with IR spectra obtained by quantum chemistry calculations shows that 7AI(CH(3)OH)(n) (n=1-3) have cyclic H-bonded structures, where the NH group and the heteroaromatic N atom of 7AI act as the proton donor and proton acceptor, respectively. The H-bonded OH stretch fundamental of 7AI(CH(3)OH)(2) is remarkably redshifted from the corresponding fundamental of (CH(3)OH)(2) by 286 cm(-1), which is an experimental manifestation of the cooperativity in H-bonding interaction. Similarly, two localized OH fundamentals of 7AI(CH(3)OH)(3) also exhibit large redshifts. The cooperativity of 7AI(CH(3)OH)(n) (n=2,3) is successfully explained by the donor-acceptor electron delocalization interactions between the lone-pair orbital in the proton acceptor and the antibonding orbital in the proton donor in natural bond orbital (NBO) analyses.

  20. 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.

  1. 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

    a remarkably similar trend as the exterior OH groups are sequentially solvated or are replaced by methyl substituents. In effect, solvents H-bonding to exterior OH groups act to increase the proton affinity of the water to which they are bound in a roughly additive fashion. We discuss this behavior...

  2. Ultra-low cost and highly stable hydrated FePO4 anodes for aqueous sodium-ion battery

    Science.gov (United States)

    Wang, Yuesheng; Feng, Zimin; Laul, Dharminder; Zhu, Wen; Provencher, Manon; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

    2018-01-01

    The growing demands for large-scale energy storage devices have put a spotlight on aqueous sodium-ion batteries, which possess a number of highly desirable features, such as sodium abundance, low cost and safety over organic electrolytes. While lots of cathode materials were reported, only few candidate materials like active carbon and NaTi2(PO4)3 were proposed as anodes. It is a long-standing common knowledge that the low cost, non-toxicity, and highly reversible FePO4·2H2O is known as an attractive cathode material for non-aqueous lithium- and sodium-ion batteries, but we demonstrate for the first time that nano-size non-carbon coated amorphous FePO4·2H2O can be used as the anode for an aqueous sodium-ion battery. Its optimum operating voltage (∼2.75 V vs. Na+/Na) avoids hydrogen evolution. The capacity is as high as 80 mAh/g at a rate of 0.5 C in a three-electrode system. The full cell, using the Na0.44MnO2 as cathode, maintained 90% of the capacity at 300 cycles at a rate of 3 C. The calculations also show that its volume change during the intercalation of Na ions is below 2%. Its low cost, high safety, along with its outstanding electrochemical performance makes amorphous FePO4·2H2O a promising anode material for aqueous sodium-ion batteries.

  3. Calcium Aluminate Cement Hydration Model

    Directory of Open Access Journals (Sweden)

    Matusinović, T.

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Benard, Ph

    2005-12-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-28

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

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

    International Nuclear Information System (INIS)

    Soniat, Marielle; Rick, Steven W.; Kumar, Revati

    2015-01-01

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

  7. Effect of covalently bonded polysiloxane multilayers on the electrochemical behavior of graphite electrode in lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Qinmin; Jiang, Yinghua [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)

    2008-03-15

    Polysiloxane multilayers were covalently bonded to the surface of natural graphite particles via diazonium chemistry and silylation reaction. The as-prepared graphite exhibited excellent discharge-charge behavior as negative electrode materials in lithium ion batteries. The improvement in the electrochemical performance of the graphite electrodes was attributed to the formation of a stable and flexible passive film on their surfaces. It was also revealed that the chemical compositions of the multilayers exerted influence on the electrochemical behavior of the graphite electrodes. The result of this study presents a new strategy to the formation of elastic and strong passive film on the graphite electrode via molecular design. Owing to the diversity of polysilxoane multilayers, this method also enables researchers to control the surface chemistries of carbonaceous materials with flexibility. (author)

  8. Sandwiched Thin-Film Anode of Chemically Bonded Black Phosphorus/Graphene Hybrid for Lithium-Ion Battery.

    Science.gov (United States)

    Liu, Hanwen; Zou, Yuqin; Tao, Li; Ma, Zhaoling; Liu, Dongdong; Zhou, Peng; Liu, Hongbo; Wang, Shuangyin

    2017-09-01

    A facile vacuum filtration method is applied for the first time to construct sandwich-structure anode. Two layers of graphene stacks sandwich a composite of black phosphorus (BP), which not only protect BP from quickly degenerating but also serve as current collector instead of copper foil. The BP composite, reduced graphene oxide coated on BP via chemical bonding, is simply synthesized by solvothermal reaction at 140 °C. The sandwiched film anode used for lithium-ion battery exhibits reversible capacities of 1401 mAh g -1 during the 200th cycle at current density of 100 mA g -1 indicating superior cycle performance. Besides, this facile vacuum filtration method may also be available for other anode material with well dispersion in N-methyl pyrrolidone (NMP). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

    Science.gov (United States)

    Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

    2015-05-13

    Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

  10. Determination of metal-hydrogen bond dissociation energies by the deprotonation of transition metal hydride ions: application to MnH +

    Science.gov (United States)

    Stevens, Amy E.; Beauchamp, J. L.

    1981-03-01

    ICR trapped ion techniques are used to examine the kinetics of proton transfer from MnH + (formed as a fragment ion from HMn (CO) 5 by electron impact) to bases of varying strength. Deprotonation is rapid with bases whose proton affinity exceeds 196±3 kcal mol -1. This value for PA (Mn) yields the homolytic bond dissociation energy D0(Mn +-H) = 53±5 kcal mol -1.

  11. Structure and transport of aqueous electrolytes: From simple halides to radionuclide ions

    Energy Technology Data Exchange (ETDEWEB)

    Hartkamp, Remco, E-mail: hartkamp@mit.edu; Coasne, Benoit, E-mail: benoit.coasne@enscm.fr [Institut Charles Gerhardt Montpellier, CNRS (UMR 5253), Université Montpellier 2, ENSCM, 8 rue de l’Ecole Normale, 34296 Montpellier Cedex 05 (France); MultiScale Material Science for Energy and Environment, CNRS/MIT (UMI 3466), Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139 (United States)

    2014-09-28

    Molecular simulations are used to compare the structure and dynamics of conventional and radioactive aqueous electrolytes: chloride solutions with sodium, potassium, cesium, calcium, and strontium. The study of Cs{sup +} and Sr{sup 2+} is important because these radioactive ions can be extremely harmful and are often confused by living organisms for K{sup +} and Ca{sup 2+}, respectively. Na{sup +}, Ca{sup 2+}, and Sr{sup 2+} are strongly bonded to their hydration shell because of their large charge density. We find that the water molecules in the first hydration shell around Na{sup +} form hydrogen bonds between each other, whereas molecules in the first hydration shell around Ca{sup 2+} and Sr{sup 2+} predominantly form hydrogen bonds with water molecules in the second shell. In contrast to these three ions, K{sup +} and Cs{sup +} have low charge densities so that they are weakly bonded to their hydration shell. Overall, the structural differences between Ca{sup 2+} and Sr{sup 2+} are small, but the difference between their coordination numbers relative to their surface areas could potentially be used to separate these ions. Moreover, the different decays of the velocity-autocorrelation functions corresponding to these ions indicates that the difference in mass could be used to separate these cations. In this work, we also propose a new definition of the pairing time that is easy to calculate and of physical significance regardless of the problem at hand.

  12. Ultrafast phosphate hydration dynamics in bulk H2O

    International Nuclear Information System (INIS)

    Costard, Rene; Tyborski, Tobias; Fingerhut, Benjamin P.; Elsaesser, Thomas

    2015-01-01

    Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H 2 PO 4 − 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 S (PO 2 − )) and asymmetric (ν AS (PO 2 − )) PO 2 − stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH) 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 S (PO 2 − ) and ν AS (PO 2 − ) transition frequencies with larger frequency excursions for ν AS (PO 2 − ). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO 2 − ) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H 2 PO 4 − /H 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

  13. Ultrafast phosphate hydration dynamics in bulk H2O

    Science.gov (United States)

    Costard, Rene; Tyborski, Tobias; Fingerhut, Benjamin P.; Elsaesser, Thomas

    2015-06-01

    Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H2PO4- 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 S ( PO2 - ) ) and asymmetric ( ν A S ( PO2 - ) ) PO 2- stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH)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 S ( PO2 - ) and ν A S ( PO2 - ) transition frequencies with larger frequency excursions for ν A S ( PO2 - ) . The calculated frequency-time correlation function is in good agreement with the experiment. The ν ( PO2 - ) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H2PO4-/H2O 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.

  14. [Skin hydration and hydrating products].

    Science.gov (United States)

    Duplan, H; Nocera, T

    2018-05-01

    One of the skin's principal functions is to protect the body against its environment by maintaining an effective epidermal barrier, not only against external factors, but also to prevent water loss from the body. Indeed, water homeostasis is vital for the normal physiological functioning of skin. Hydration levels affect not only visible microscopic parameters such as the suppleness and softness of skin, but also molecular parameters, enzyme activities and cellular signalling within the epidermis. The body is continually losing some of its water, but this phenomenon is limited and the optimal hydration gradient in skin is ensured via a set of sophisticated regulatory processes that rely on the functional and dynamic properties of the uppermost level of the skin consisting of the stratum corneum. The present article brings together data recently acquired in the fields of skin hydration and the characterisation of dehydrated or dry skin, whether through study of the regulatory processes involved or as a result of changes in the techniques used for in situ measurement, and thus in optimisation of management. Copyright © 2018. Published by Elsevier Masson SAS.

  15. On the electrolytic generation of hydrated electron

    International Nuclear Information System (INIS)

    Ghosh Mazumdar, A.S.; Guha, S.N.

    1975-01-01

    Investigations on the electrolytic generation of hydrated electron in oxygenated as well as oxygen-free solutions at different pH were undertaken. Since sup(-e)aq is known to react rapidly with O 2 yielding the transient O 2 - ion, the latter was looked for through its interaction with phosphite ions resulting in their oxidation near the cathode. It appears from the results that in electrolytic processes, the primary electron (esup(-)sub(cathode)) probably reacts directly with reactive solutes like oxygen, bypassing the hydration step. Data obtained in oxygen-free solutions, however, support the possible formation of hydrated electron at least in alkaline solutions. (author)

  16. Subcontract Report: Diffusion Mechanisms and Bond Dynamics in Solid Electrolyte Ion-Conductors

    Energy Technology Data Exchange (ETDEWEB)

    Zevgolis, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Hall, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Alvez, T. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehmedovic, Z. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Shea, P. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Varley, J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Wood, B. C. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Adelstein, N. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-10-03

    We employ first-principles molecular dynamics simulations and Maximally Localized Wannier Function (MLWF) analysis to explore how halide substitution and nano-phase microstructures affect diffusivity, through the activation energy barrier - Ea and D0, in the solid electrolyte Li3InBr6-xClx. We find that nano-phase microstructures with x=3 (50-50 Br-Cl) mixed composition have a higher diffusivity compared to x=2 and x=3 solid solutions. There is a positive linear relationship between ln(D0.) and Ea, which suggests that for superionic conductivity optimizing both the activation energy and the D0 is important. Bond frustration due to mismatch in crystal geometry and ideal coordination number leads to especially high diffusivity through a high D0 in the x=3 composition.

  17. Infrared spectroscopy of anionic hydrated fluorobenzenes

    International Nuclear Information System (INIS)

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-01-01

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C 6 F 6 - ·H 2 O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules

  18. Sodium and potassium salts of dichloroisocyanuric acid and their hydrates as antimicrobials agents studied by 35Cl-NQR spectroscopy and DFT calculations

    International Nuclear Information System (INIS)

    Walczak, A.; Brycki, B.; Kaczmarek, M.; Poleshchuk, O.Kh.; Ostafin, M.; Nogaj, B.

    2006-01-01

    The electronic structure of dichloroisocyanuric acid derivatives was analysed by 35 Cl-NQR spectroscopy and DFT calculations. Here we concentrate our attention on three different factors: type of metallic substituent (sodium and potassium), temperature of the sample (liquid nitrogen and room) and degree of hydration (an amount of water molecules attached to analysed compounds). In particular, all the variations in 35 Cl-NQR frequencies upon hydration of salts containing sodium and potassium ions are explained as a consequence of H-bonds formation and accompanied effects of charge redistribution. Our studies can be useful in searching for the derivatives of dichloroisocyanuric acid revealing higher antimicrobial activity

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

    International Nuclear Information System (INIS)

    Chatterjee, Anupam; Higham, Jonathan; Henchman, Richard H.

    2015-01-01

    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

  20. Hydrated electron: a destroyer of perfluorinated carboxylates?

    International Nuclear Information System (INIS)

    Huang Li; Dong Wenbo; Hou Huiqi

    2006-01-01

    showed that fluorine ion was generated in the mixed solution of K 4 Fe(CN) 6 and PFCAs after irradiation. This phenomenon also proved that hydrated electron could attach to PFCAs and followed by efficient dissociation of PFCAs via heterolytic cleavage of C-F bond. Considering that a majority of hydrated electron are generated in the course of radiation and non-thermal plasma, such technologies are believed to be capable of serving to PFCAs abatement. . (authors)

  1. The estimation of H-bond and metal ion-ligand interaction energies in the G-Quadruplex ⋯ Mn+ complexes

    Science.gov (United States)

    Mostafavi, Najmeh; Ebrahimi, Ali

    2018-06-01

    In order to characterize various interactions in the G-quadruplex ⋯ Mn+ (G-Q ⋯ Mn+) complexes, the individual H-bond (EHB) and metal ion-ligand interaction (EMO) energies have been estimated using the electron charge densities (ρs) calculated at the X ⋯ H (X = N and O) and Mn+ ⋯ O (Mn+ is an alkaline, alkaline earth and transition metal ion) bond critical points (BCPs) obtained from the atoms in molecules (AIM) analysis. The estimated values of EMO and EHB were evaluated using the structural parameters, results of natural bond orbital analysis (NBO), aromaticity indexes and atomic charges. The EMO value increase with the ratio of ionic charge to radius, e/r, where a linear correlation is observed between EMO and e/r (R = 0.97). Meaningful relationships are also observed between EMO and indexes used for aromaticity estimation. The ENH value is higher than EOH in the complexes; this is in complete agreement with the trend of N⋯Hsbnd N and O⋯Hsbnd N angles, the E (2) value of nN → σ*NH and nO → σ*NH interactions and the difference between the natural charges on the H-bonded atom and the hydrogen atom of guanine (Δq). In general, the O1MO2 angle becomes closer to 109.5° with the increase in EMO and decrease in EHB in the presence of metal ion.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-15

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

  3. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

    International Nuclear Information System (INIS)

    Sabil, Khalik M.; Roman, Vicente R.; Witkamp, Geert-Jan; Peters, Cor J.

    2010-01-01

    In the present work, experimental data on the equilibrium conditions of mixed CO 2 and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO 2 and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L W ), liquid organic (L V ), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO 2 and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF 2 2 . Among the cations studied, the strength of hydrate inhibition increases in the following order: K + + 2+ 2+ . Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br - > Cl - > F - . Based on the results, it is suggested that the probability of formation and the strength of ionic-hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water

  4. Metallic and/or oxygen ion implantation into AlN ceramics as a method of preparation for its direct bonding with copper

    International Nuclear Information System (INIS)

    Barlak, M.; Borkowska, K.; Olesinska, W.; Kalinski, D.; Piekoszewski, J.; Werner, Z.; Jagielski, J.; Sartowska, B.

    2006-01-01

    Direct bonding (DB) process is recently getting an increasing interest as a method for producing high quality joints between aluminum nitride (AlN) ceramics and copper. The metallic ions were implanted using an MEVVA type TITAN implanter with unseparated beam. Oxygen ions were implanted using a semi-industrial ion implanter without mass separation equipped with a gaseous ion source. The substrate temperature did not exceed 200 o C. Ions were implanted at two acceleration voltages, i.e. 15 and 70 kV. The fluence range was between 1·E16 and 1·E18 cm -2 . After implantation, some of the samples were characterized by the Rutherford backscattering (RBS) method. In conclusion: (a) The investigations performed in the present work confirm an assumption that ion implantation is a very promising technique as a pretreatment of AlN ceramics for the formation of the joints with copper in direct bonding process. (b) It has been shown that titanium implantation gives the best results in comparison to other metals examined (Fe, Cr, Cu) but also in comparison to double Ti+O and O+Ti implantations

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

    KAUST Repository

    Jang, Jaewon; Santamarina, Carlos

    2016-01-01

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

  6. 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.

  7. Is Br2 hydration hydrophobic?

    Science.gov (United States)

    Alcaraz-Torres, A; Gamboa-Suárez, A; Bernal-Uruchurtu, M I

    2017-02-28

    The spectroscopic properties of bromine in aqueous systems suggest it can behave as either hydrophilic or hydrophobic solute. In small water clusters, the halogen bond and the hydrogen-halogen interaction are responsible for its specific way of binding. In water hydrates, it is efficiently hosted by two different cages forming the crystal structure and it has been frequently assumed that there is little or no interaction between the guest and the host. Bromine in liquid solution poses a challenging question due to its non-negligible solubility and the large blue shift measured in its absorption spectra. Using a refined semi-empirical force field, PM3-PIF, we performed a Born-Oppenheimer molecular dynamics study of bromine in liquid water. Here we present a detailed study in which we retrieved the most representative hydration structures in terms of the most frequent positions around bromine and the most common water orientations. Albeit being an approximate description of the total hydration phenomenon, it captures the contribution of the leading molecular interactions in form of the recurrent structures. Our findings confirm that the spectroscopic signature is mainly caused by the closest neighbors. The dynamics of the whole first hydration shell strongly suggests that the external molecules in that structure effectively isolate the bulk from the presence of bromine. The solvation structure fluctuates from a hydrophilic to a hydrophobic-like environment along the studied trajectory.

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

    International Nuclear Information System (INIS)

    Stamm, A.; Schwing, K.; Gerhards, M.

    2014-01-01

    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S 0 ) and cationic (D 0 ) 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 (H 2 O) 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

  9. Novel protonated and hydrated n=1 Ruddlesden-Popper phases, HxNa1-xLaTiO4.yH2O, formed by ion-exchange/intercalation reaction

    International Nuclear Information System (INIS)

    Nishimoto, Shunsuke; Matsuda, Motohide; Miyake, Michihiro

    2005-01-01

    New derivatives of layered perovskite compounds with H 3 O + ions, H + ions and water molecules in the interlayer, H x Na 1-x LaTiO 4 .yH 2 O, were successfully synthesized by an ion-exchange/intercalation reaction with dilute HCl solution, using an n=1 member of Ruddlesden-Popper phase, NaLaTiO 4 . Powder X-ray diffraction revealed that the layered structure changed from space group P4/nmm with a=3.776(1) and c=13.028(5)A to I4/mmm with a=3.7533(3) and c=28.103(4)A after the ion-exchange/intercalation reaction at pH 5. The change of space group indicates that the perovskite layers are transformed from staggered to an eclipsed configuration through the ion-exchange/intercalation reaction. Thermogravimetric analysis and high-temperature powder X-ray diffraction suggested the existence of the secondary hydrated phase by dehydrating H x Na 1-x LaTiO 4 .yH 2 O at 100 o C

  10. Crystal structure of N,N,N′,N′,N′′,N′′-hexamethylguanidinium cyanate 1.5-hydrate

    Directory of Open Access Journals (Sweden)

    Ioannis Tiritiris

    2015-12-01

    Full Text Available The title hydrated salt, C7H18N3+·OCN−.1.5H2O, was synthesized starting from N,N,N′,N′,N′′,N′′-hexamethylguanidinium chloride by a twofold anion-exchange reaction. The asymmetric unit contains two cations, two cyanate anions and three water molecules. 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 guanidinium 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 molecules and the cyanate ions and strong O—H...O hydrogen bonds between the water molecules are present, resulting in a two-dimensional hydrogen bonded network running parallel to the (001 plane. The hexamethylguanidinium ions are packed in between the layers built up by water molecules and cyanate ions.

  11. Study on coordination characteristics of neptunium and uranium ions in calcium nitrate hydrate melt by Raman spectrometry and UV/Vis/NIR spectrometry

    International Nuclear Information System (INIS)

    Fujii, T; Okude, G; Uehara, A; Yamana, H

    2010-01-01

    Extraction behavior of neptunium (Np) by tri-n-butyl phosphate from calcium nitrate hydrate melt was investigated. Distribution ratio of Np was found to increase with the decrease of water content. Adding nitric acid into the system resulted in an increase of the distribution ratio. In order to understand the extraction trends, Np species in the hydrate melt were analyzed by Raman spectrometry and UV/Vis/NIR spectrometry. Major fraction was assigned to be NpO 2 2+ of Np(VI) and small fraction to be NpO 2 + of Np(V). A shift of the v 1 symmetric vibrational frequency of NpO 2 2+ in nitrate media was found in Raman spectra. This suggests a coordination circumstance change of NpO 2 2+ .

  12. Artificial Hydration and Nutrition

    Science.gov (United States)

    ... Crisis Situations Pets and Animals myhealthfinder Food and Nutrition Healthy Food Choices Weight Loss and Diet Plans ... Your Health Resources Healthcare Management Artificial Hydration and Nutrition Artificial Hydration and Nutrition Share Print Patients who ...

  13. Defect Generation for a Hydrated Layer and Thermal Stability Based on Ba0.7Sr0.3TiO3/SiO2 as H+ Sensitive Layer in Ion-Sensitive Field-Effect Transistor Devices

    Science.gov (United States)

    Chen, Chun-Yuan; Chou, Jung-Chuan; Chou, Hsueh-Tao

    2009-04-01

    In this paper, we present a novel sensitive ion-sensitive field-effect transistor (ISFET) membrane based on Ba0.7Sr0.3TiO3 (BST)/SiO2 fabricated by sputtering deposition. The proposed device exhibits a linear shift in acidic solutions in the pH range from 1 to 10. The device sensitivity was about 50-55 mV/pH for different deposition times. We also examined the trapping behavior of the surface hydrated layer using the metal-insulator-semiconductor (MIS) structure. Results show that the hydration layer gives rise to stress polarity dependence of electron injection when immersed in pH buffer solutions. Injection from the gate electrode produces larger positive charges and interface state densities in contrast to the substrate injection, which causes simultaneous positive and negative charge trapping. A physical model that quantitatively describes the asymmetry associated with the hydrated diffusion layer is presented, and the temperature effects of BST/SiO2 ISFET devices in the range from 25 to 65 °C were examined. We observed that pH sensitivity increases with increasing temperature. The temperature coefficient of sensitivity (TCS) can be divided into two different ranges: 0.08 mV/pH °C between 25 and 45 °C, and 0.57 mV/pH °C between 45 and 65 °C. A better thermal stability is produced in the 25 and 45 °C range in comparison with other sensitive layers.

  14. Modeling dissociation behaviour of methane hydrate in porous soil media

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  15. Proton-bound cluster ions in ion mobility spectrometry

    Science.gov (United States)

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

    1999-01-01

    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.

  16. Nanostructured organic electrode materials grown on graphene with covalent-bond interaction for high-rate and ultra-long-life lithium-ion batteries

    Institute of Scientific and Technical Information of China (English)

    Qing Zhao; Jianbin Wang; Chengcheng Chen; Ting Ma; Jun Chen

    2017-01-01

    Nanostructured organic tetralithium salts of 2,5-dihydroxyterephthalic acid (Li4C8H2O6) supported on graphene were prepared via a facile recrystallization method.The optimized composite with 75 wt.% Li4C8H2O6 was evaluated as an anode with redox couples of Li4C8H2OdLi6C8H2O6 and as a cathode with redox couples of Li4C8H2O6/Li2C8H2O6 for Li-ion batteries,exhibiting a high-rate capability (10 C) and long cycling life (1,000 cycles).Moreover,in an all-organic symmetric Li-ion battery,this dual-function electrode retained capacities of 191 and 121 mA.h·g-1 after 100 and 500 cycles,respectively.Density functional theory calculations indicated the presence of covalent bonds between Li4C8H2O6 and graphene,which affected both the morphology and electronic structure of the composite.The special nanostructures,high electronic conductivity of graphene,and covalent-bond interaction between Li4C8H2O6 and graphene contributed to the superior electrochemical properties.Our results indicate that the combination of organic salt molecules with graphene is useful for obtaining high-performance organic batteries.

  17. 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

    results concerning the multi-species action during chloride penetration. In the model the chemical interaction between ions in solids and in pore solution is assumed governed by simple ion exchange processes only. The drawback using this approach is that the chemical part is lacking important physical...... 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...

  18. Gas hydrate in nature

    Science.gov (United States)

    Ruppel, Carolyn D.

    2018-01-17

    Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

  19. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

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

  20. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

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

  1. 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

    Energy Technology Data Exchange (ETDEWEB)

    Hamid, Ahmed M.; El-Shall, M. Samy, E-mail: mselshal@vcu.edu [Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284 (United States); Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G. [Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

    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 C{sub 5}H{sub 5}N{sup +·}(HCN){sub n} and C{sub 4}H{sub 4}N{sub 2}{sup +·}(HCN){sub n} clusters, respectively, with n = 1–4. For comparison, the binding of 1–4 HCN molecules to the protonated pyridine C{sub 5}H{sub 5}NH{sup +}(HCN){sub 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{sup δ+}⋯NCH). Protonated pyridine forms a stronger ionic hydrogen bond with HCN (NH{sup +}⋯NCH) which can be extended to a linear chain with the clustering of additional HCN molecules (NH{sup +}⋯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{sup δ+}⋯NCH) formed between the pyridine or the pyrimidine radical cations and HCN molecules (11–12 kcal/mol) are stronger than the similar (CH{sup δ+}⋯NCH) bonds formed between the benzene radical cation and HCN molecules (9 kcal/mol) indicating that the CH{sup δ+} centers in the pyridine and pyrimidine radical cations have more effective charges than in the benzene radical cation.

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

    International Nuclear Information System (INIS)

    Yokoya, A.; Shikazono, N.; Fujii, K.; Noguchi, M.; Urushibara, A.

    2011-01-01

    To detect multiple single-strand breaks (SSBs) produced in plasmid DNA molecules by direct energy deposition from radiation tracks, we have developed a novel technique using DNA denaturation by which irradiated DNA is analysed as single-strand DNA (SS-DNA). The multiple SSBs that arise in both strands of DNA, but do not induce a double-strand break, are quantified as loss of SS-DNA using agarose gel electrophoresis. We have applied this method to X-ray and 4 He 2+ ion-irradiated samples of fully hydrated pUC18 plasmid DNA. The fractions of both SS-DNA and closed circular DNA (CC-DNA) exponentially decrease with the increasing dose of X rays and 4 He 2+ ions. The efficiency of the loss of SS-DNA was half that of CC-DNA for both types of irradiation, indicating that one of two strands in DNA is not broken when one SSB is produced in CC-DNA by irradiation. Contrary to our initial expectation, these results indicate that SSBs are not multiply induced even by high linear energy transfer radiation distributed in both strands. (authors)

  3. The rotation of NO3− as a probe of molecular ion - water interactions

    Directory of Open Access Journals (Sweden)

    Ogden T.

    2013-03-01

    Full Text Available The hydration dynamics of aqueous nitrate, NO3−(aq, is studied by 2D-IR spectroscopy, UV-IR- and UV-UV transient absorption spectroscopy. The experimental results are compared to Car-Parinello molecular dynamics (MD simulations. The 2D-IR measurements and MD simulations of the non-degenerate asymmetric stretch vibrations of nitrate reveal an intermodal energy exchange occurring on a 0.2 ps time scale related to hydrogen bond fluctuations. The transient absorption measurements find that the nitrate ions rotate in 2 ps. The MD simulations indicate that the ion rotation is associated with the formation of new hydrogen bonds. The 2 ps rotation time thus indicates that the hydration shell of aqueous nitrate is rather labile.

  4. 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.

  5. 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.

  6. Hydration of the lanthanide ions 152Eu(III), 153Gd(III) and 170Tm(III) in aqueous solutions at 298 K and similarity with the transplutonium element ions 254Es(III), 244Cm(III), 241Am(III), 249Cf(III) and 249Bk(III)

    International Nuclear Information System (INIS)

    Ouerfelli, N.; Latrous, H.; Ammar, M.; Das, D.; Oliver, J.

    2013-01-01

    The open-end capillary method is used for the determination of ionic self-diffusion coefficients (D) for trivalent radiotracer, lanthanide and actinide ions are reported in concentrated aqueous solutions of supporting electrolytes of Gd(NO 3 ) 3 -HNO 3 or Nd(ClO 3 ) 4 -HClO 4 up to 1.5 mol.L -1 at 298.15 K and pH 2.50. The data obtained in large range of concentrations, allow deriving the limiting value D°, the validity of the Onsager limiting law and a more extended law. This study contributes to demonstrate similarities in transport and structure properties between 4f and 5f trivalent ions explained by a similar electronic configuration, ionic radius and hydration number. (author)

  7. Unraveling halide hydration: A high dilution approach.

    Science.gov (United States)

    Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

    2014-07-28

    The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

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

    Institute of Scientific and Technical Information of China (English)

    柴瑞鹏; 李隆; 梁良; 庞庆

    2016-01-01

    The EPR parameters of trivalent Er3+ ions doped in hexagonal GaN crystal have been studied by diagonalizing the 364×364 complete energy matrices. The results indicate that the resonance ground states may be derived from the Kramers doubletΓ6. The EPR g-factors may be ascribed to the stronger covalent bonding and nephelauxetic effects compared with other rare-earth doped complexes, as a result of the mismatch of ionic radii of the impurity Er3+ion and the replaced Ga3+ion apart from the intrinsic covalency of host GaN. Furthermore, the J–J mixing effects on the EPR parameters from the high-lying manifolds have been evaluated. It is found that the dominant J–J mixing contribution is from the manifold 2K15/2, which accounts for about 2.5%. The next important J–J contribution arises from the crystal–field mixture between the ground state 4I15/2 and the first excited state 4I13/2, and is usually less than 0.2%. The contributions from the rest states may be ignored.

  9. 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.

  10. Different-ligand boron complexes with gluconate-ions and pentaerythritol and gluconatoborates with B-O-B bridge bond

    International Nuclear Information System (INIS)

    Tel'zhenskaya, P.N.; Shvarts, E.M.; Vitola, I.M.

    1990-01-01

    Borogluconates differing in structure of the complex dimeric borogluconate ion from the described earlier have been synthesized. The results of physicochemical measurements (chemical and thermal analysis, IR-spectroscopy, titration according to Fisher, conductometry) allowed to propose formulas for the studied compounds

  11. Exploration of the Singlet O2 Oxidation of 8-Oxoguanine by Guided-Ion Beam Scattering and Density Functional Theory: Changes of Reaction Intermediates, Energetics, and Kinetics upon Protonation/Deprotonation and Hydration.

    Science.gov (United States)

    Sun, Yan; Lu, Wenchao; Liu, Jianbo

    2017-02-09

    8-Oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) is one of the most common DNA lesions resulting from reactive oxygen species and ionizing radiation, and is involved in mutagenesis, carcinogenesis, and cell death. Notably, 8-oxodGuo is more reactive toward singlet (a 1 Δ g ) O 2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the 1 O 2 oxidation of free base 8-oxoguanine (8-oxoG) was investigated at different initial conditions including protonated [8-oxoG + H] + , deprotonated [8-oxoG - H] - , and their monohydrates. Experiment was carried out on a guided-ion beam scattering tandem mass spectrometer. Measurements include the effects of collision energy (E col ) on reaction cross sections over a center-of-mass E col range from 0.1 to 0.5 eV. The aim of this study is to quantitatively probe the sensitivity of the early stage of 8-oxoG oxidation to ionization and hydration. Density functional theory and Rice-Ramsperger-Kassel-Marcus calculations were performed to identify the intermediates and the products along reaction pathways and locate accessible reaction potential energy surfaces, and to rationalize reaction outcomes from energetic and kinetic points of view. No product was observed for the reaction of [8-oxoG + H] + ·W 0,1 (W = H 2 O) because insurmountable barriers block the addition of 1 O 2 to reactant ions. Neither was [8-oxoG - H] - reactive with 1 O 2 , in this case due to the rapid decay of transient intermediates to starting reactants. However, the nonreactivity of [8-oxoG - H] - was inverted by hydration; as a result, 4,5-dioxetane of [8-oxoG - H] - was captured as the main oxidation product. Reaction cross section for [8-oxoG - H] - ·W + 1 O 2 decreases with increasing E col and becomes negligible above 0.3 eV, indicating that the reaction is exothermic and has no barriers above reactants. The contrasting oxidation behaviors of [8-oxoG + H] + ·W 0,1 and [8-oxoG - H] - ·W 0

  12. Vibrational spectra of halide-water dimers: Insights on ion hydration from full-dimensional quantum calculations on many-body potential energy surfaces

    Science.gov (United States)

    Bajaj, Pushp; Wang, Xiao-Gang; Carrington, Tucker; Paesani, Francesco

    2018-03-01

    Full-dimensional vibrational spectra are calculated for both X-(H2O) and X-(D2O) dimers (X = F, Cl, Br, I) at the quantum-mechanical level. The calculations are carried out on two sets of recently developed potential energy functions (PEFs), namely, Thole-type model energy (TTM-nrg) and many-body energy (MB-nrg), using the symmetry-adapted Lanczos algorithm with a product basis set including all six vibrational coordinates. Although both TTM-nrg and MB-nrg PEFs are derived from coupled-cluster single double triple-F12 data obtained in the complete basis set limit, they differ in how many-body effects are represented at short range. Specifically, while both models describe long-range interactions through the combination of two-body dispersion and many-body classical electrostatics, the relatively simple Born-Mayer functions employed in the TTM-nrg PEFs to represent short-range interactions are replaced in the MB-nrg PEFs by permutationally invariant polynomials to achieve chemical accuracy. For all dimers, the MB-nrg vibrational spectra are in close agreement with the available experimental data, correctly reproducing anharmonic and nuclear quantum effects. In contrast, the vibrational frequencies calculated with the TTM-nrg PEFs exhibit significant deviations from the experimental values. The comparison between the TTM-nrg and MB-nrg results thus reinforces the notion that an accurate representation of both short-range interactions associated with electron density overlap and long-range many-body electrostatic interactions is necessary for a correct description of hydration phenomena at the molecular level.

  13. Experimental and theoretical investigation of the production of cations containing C-N bonds in the reaction of benzene with atomic nitrogen ions

    International Nuclear Information System (INIS)

    Di Stefano, Marco; Rosi, Marzio; Sgamellotti, Antonio; Ascenzi, Daniela; Bassi, Davide; Franceschi, Pietro; Tosi, Paolo

    2003-01-01

    In the last few years, astronomical spectra have revealed the presence of aromatic and polyaromatic molecules in extraterrestrial environments, near carbon stars, in molecular clouds and meteorites. Moreover, the recent observation of benzene in interstellar space has noticeably increased the interest in the entire class of molecules and in their chemical behavior. In this work, we have investigated the reaction between the benzene molecule and the atomic nitrogen cation and, in particular, the mechanisms by which the reactants are converted into cationic products containing at least one C-N bond, according to the general scheme C 6 H 6 +N + →H m C n N + +C x H y . We have measured the energy dependence of the cross section in a guided ion beam tandem mass spectrometer. Relevant stationary points of the potential energy surface have been studied by using the density functional theory hybrid functional B3LYP with the 6-31G* basis set. Thermochemical calculations, and the comparison with experimental results, allow us to distinguish between exoergic and endoergic processes and to obtain a detailed description of the reaction mechanisms. We show that aromatic hydrocarbons may be converted into organic-nitrogen compounds via the insertion of N + into the benzene ring and the formation of C-N bonds from C-C ring reactants

  14. Effect of hydration on the organo-noble gas molecule HKrCCH: role of krypton in the stabilization of hydrated HKrCCH complexes.

    Science.gov (United States)

    Biswas, Biswajit; Singh, Prashant Chandra

    2015-11-11

    The effect of hydration on the fluorine free organo-noble gas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes.

  15. Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

    Science.gov (United States)

    Camilleri, J; Sorrentino, F; Damidot, D

    2015-04-01

    high calcium ion release early, which was maintained over the 28-day period as opposed to MTA Angelus, which demonstrated low early calcium ion release which increased as the material aged. The mineralogical composition of BioAggregate was different to MTA Angelus. As opposed to MTA Angelus, BioAggregate did not contain aluminium and contained additives such as calcium phosphate and silicon dioxide. As a consequence, BioAggregate reacted more slowly and formation of calcium hydroxide and leaching of calcium ions in solution were not evident as the material aged. The additives in BioAggregate modify the kinetics and the end products of hydration. Although newer generation tricalcium silicate-based materials contain similar constituents to MTA, they do not undergo the same setting reactions, and thus, their clinical performance will not be comparable to that of MTA.

  16. Ion conduction mechanisms and thermal properties of hydrated and anhydrous phosphoric acids studied with 1H, 2H, and 31P NMR.

    Science.gov (United States)

    Aihara, Yuichi; Sonai, Atsuo; Hattori, Mineyuki; Hayamizu, Kikuko

    2006-12-14

    To understand the behaviors of phosphoric acids in fuel cells, the ion conduction mechanisms of phosphoric acids in condensed states without free water and in a monomer state with water were studied by measuring the ionic conductivity (sigma) using AC impedance, thermal properties, and self-diffusion coefficients (D) and spin-lattice relaxation times (T1) with multinuclear NMR. The self-diffusion coefficient of the protons (H+ or H3O+), H2O, and H located around the phosphate were always larger than the diffusion coefficients of the phosphates and the disparity increased with increasing phosphate concentration. The diffusion coefficients of the samples containing D2O paralleled those in the protonated samples. Since the 1H NMR T1 values exhibited a minimum with temperature, it was possible to determine the correlation times and they were found to be of nanosecond order for a distance of nanometer order for a flip. The agreement of the ionic conductivities measured directly and those calculated from the diffusion coefficients indicates that the ion conduction obeys the Nernst-Einstein equation in the condensed phosphoric acids. The proton diffusion plays a dominant role in the ion conduction, especially in the condensed phosphoric acids.

  17. Hydration rate of obsidian.

    Science.gov (United States)

    Friedman, I; Long, W

    1976-01-30

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

  18. Methane Hydrates: Chapter 8

    Science.gov (United States)

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

    2008-01-01

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

  19. 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.

  20. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.; Yoon, S.; Wentzcovitch, R. M.; Monteiro, P. J. M.

    2014-01-01

    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.

  1. Charge accumulation in the buried oxide of SOI structures with the bonded Si/SiO2 interface under γ-irradiation: effect of preliminary ion implantation

    International Nuclear Information System (INIS)

    Naumova, O V; Fomin, B I; Ilnitsky, M A; Popov, V P

    2012-01-01

    In this study, we examined the effect of preliminary boron or phosphorous implantation on charge accumulation in the buried oxide of SOI-MOSFETs irradiated with γ-rays in the total dose range (D) of 10 5 –5 × 10 7 rad. The buried oxide was obtained by high-temperature thermal oxidation of Si, and it was not subjected to any implantation during the fabrication process of SOI structures. It was found that implantation with boron or phosphorous ions, used in fabrication technologies of SOI-MOSFETs, increases the concentration of precursor traps in the buried oxide of SOI structures. Unlike in the case of boron implantation, phosphorous implantation leads to an increased density of states at the Si/buried SiO 2 interface during subsequent γ-irradiation. In the γ-irradiated SOI-MOSFETs, the accumulated charge density and the density of surface states in the Si/buried oxide layer systems both vary in proportion to k i ln D. The coefficients k i for as-fabricated and ion-implanted Si/buried SiO 2 systems were evaluated. From the data obtained, it was concluded that a low density of precursor hole traps was a factor limiting the positive charge accumulation in the buried oxide of as-fabricated (non-implanted) SOI structures with the bonded Si/buried SiO 2 interface. (paper)

  2. Hydration of Portland cement with additions of calcium sulfoaluminates

    International Nuclear Information System (INIS)

    Le Saoût, Gwenn; Lothenbach, Barbara; Hori, Akihiro; Higuchi, Takayuki; Winnefeld, Frank

    2013-01-01

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

    African Journals Online (AJOL)

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

  4. Possible mechanisms for the interaction of polymeric composite resins with Cu(II) ions in aqueous solution

    International Nuclear Information System (INIS)

    El-Zahhhar, A.A.; Abdel-Aziz, H.M.; Siyam, T.

    2005-01-01

    The interaction between the active groups of polymeric composite resins such as Poly(acrylamide-acrylic acid)-ethylenediaminetetra acetic acid disodium salt P(AM-AA)EDTANa 2 , Poly(acrylamide-acrylic acid)- montmorillonite P(AM-AA)-montmorillonite, and Poly(acrylamide-acrylic acid)-potassium nickel hexacyanoferrate P(AM-AA)-KNiHCF, with copper sulfate as a test ion has been studied. The spectroscopic studies show that the mechanism of interaction between polymeric composite resins and copper sulfate is a bond formation between the active groups of polymeric chains and copper ion. The bond formation depends on nature of polymeric chains. It was also found that the amide groups form complexes with hydrated cations, while carboxylate group interact by ion exchange mechanism through complex formation. Montmorillonite and hexacyanoferrate of the resins interact with metal ions by ion exchange mechanism

  5. Solvation numbers and hydration constant for thorium(IV) in ethanol-water medium

    International Nuclear Information System (INIS)

    Sedaira, H.; Idriss, K.A.; Hashem, E.Y.

    1996-01-01

    The solvation number and hydration constant of Th 4+ in ethanol-water medium were determined at 25 degrees C using UV-spectral and electrochemical measurements. A solvate formation equilibrium is demonstrated and characterized. Three molecules of ethanol (S) can bond to the metal cation with strengths comparable to that for H 2 O to form ThS 3 (H 2 O) 3 4+ . Formation of thorium monochelate with lawsone (2-hydroxy-1.4-naphthoquinone) eliminates bonding with alcohol molecules. The dissociation constant of the chelating agent s K a and the formation contant of the monochelated metal ion s K f * that are essentially independent of the solution composition are evaluated. Hydration titrations involving thorium-lawsone monochlate are performed and the data obtained from the changes of pH with solvent composition are analyzed. The solution independent constant, s K f * for thorium-lawsone complex formation in mixed aqueous ethanol is given by log x K f * =vpK a + log s K h - log [LH] - vpH + 3 log v where vpK a is the dissociation constant of the chelating agent LH in the solvent system of v volume fraction of water and s K h is the solution-independent hydration constant of thorium (IV) in the solvent system. Log-values for the constants s K h , s K f * and s K z * are found to be 7.8 ±0.02, 11.38±0.04 and -0.753, respectively

  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. Influence of Lithium Carbonate on C3A Hydration

    Directory of Open Access Journals (Sweden)

    Weiwei Han

    2018-01-01

    Full Text Available Lithium salts, known to ameliorate the effects of alkali-silica reaction, can make significant effects on cement setting. However, the mechanism of effects on cement hydration, especially the hydration of C3A which is critical for initial setting time of cement, is rarely reported. In this study, the development of pH value of pore solution, conductivity, thermodynamics, and mineralogical composition during hydration of C3A with or without Li2CO3 are investigated. The results demonstrate that Li2CO3 promotes C3A hydration through high alkalinity, due to higher activity of lithium ion than that of calcium ion in the solution and carbonation of C3A hydration products resulted from Li2CO3. Li2CO3 favors the C3A hydration in C3A-CaSO4·2H2O-Ca(OH2-H2O hydration system and affects the mineralogical variation of the ettringite phase(s.

  8. Phase equilibrium condition of marine carbon dioxide hydrate

    International Nuclear Information System (INIS)

    Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

    2013-01-01

    Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

  9. Precise structural analysis of methane hydrate by neutron diffraction

    International Nuclear Information System (INIS)

    Igawa, Naoki; Hoshikawa, Akinori; Ishii, Yoshinobu

    2006-01-01

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

  10. Reactions of N+ ions with ethylene: a theoretical study on the addition mechanism into the olefin double bond

    International Nuclear Information System (INIS)

    Di Stefano, Marco; Rosi, Marzio; Sgamellotti, Antonio

    2004-01-01

    The potential energy surface of the reaction between ethylene molecules and N + ions is investigated by using the DFT hybrid functional B3LYP with the 6-31G* basis set. The addition channel leading to the intermediate C 2 NH 4 + is considered. We study eighteen structures of the triplet C 2 NH 4 + cations and the transition states for their isomerizations. Then, we consider the release of a H atom to form the doublet C 2 NH 3 + cations. To obtain more accurate values of reaction energetics and barrier heights, coupled cluster CCSD(T) calculations with the 6-311G** basis set are performed on the B3LYP/6-31G* optimized geometries. The addition of N + into C 2 H 4 is computed as a barrierless process leading to the triplet 1-aziridynil cation which, by ring opening, can easily evolve into the 2-azaallyl isomer. This species can then release a hydrogen atom to form the 2-azaallene cation, process that is computed to be the most likely channel

  11. Chemical alteration of cement hydrates by dissolution

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari; Nakanishi, Kiyoshi

    2000-01-01

    Cementitious material is a potential waste packaging and backfilling material for the radioactive waste disposal, and is expected to provide both physical and chemical containment. In particular, the sorption of radionuclides onto cementitious material and the ability to provide a high pH condition are very important parameters when considering the release of radionuclides from radioactive wastes. For the long term, in the geological disposal environment, cement hydrates will be altered by, for example, dissolution, chemical reaction with ions in the groundwater, and hydrothermal reaction. Once the composition or crystallinity of the constituent minerals of a cement hydrate is changed by these processes, the pH of the repository buffered by cementitious material and its sorption ability might be affected. However, the mechanism of cement alteration is not yet fully understood. In this study, leaching experiments of some candidate cements for radioactive waste disposal were carried out. Hydrated Ordinary Portland Cement (OPC), Blast Furnace Slag blended cement (OPC/BFS) and Highly containing Flyash and Silicafume Cement (HFSC) samples were contacted with distilled water at liquid:solid ratios of 10:1, 100:1 and 1000:1 at room temperature for 200 days. In the case of OPC, Ca(OH) 2 dissolved at high liquid:solid ratios. The specific surface area of all cement samples increased by leaching process. This might be caused by further hydration and change of composition of constituent minerals. A model is presented which predicts the leaching of cement hydrates and the mineral composition in the hydrated cement solid phase, including the incongruent dissolution of CSH gel phases and congruent dissolution of Ca(OH) 2 , Ettringite and Hydrotalcite. Experimental results of dissolution of Ca-O-H and Ca-Si-O-H phases were well predicted by this model. (author)

  12. An ab initio and AIM investigation into the hydration of 2-thioxanthine

    Directory of Open Access Journals (Sweden)

    Fossey John S

    2010-03-01

    Full Text Available Abstract Background Hydration is a universal phenomenon in nature. The interactions between biomolecules and water of hydration play a pivotal role in molecular biology. 2-Thioxanthine (2TX, a thio-modified nucleic acid base, is of significant interest as a DNA inhibitor yet its interactions with hydration water have not been investigated either computationally or experimentally. Here in, we reported an ab initio study of the hydration of 2TX, revealing water can form seven hydrated complexes. Results Hydrogen-bond (H-bond interactions in 1:1 complexes of 2TX with water are studied at the MP2/6-311G(d, p and B3LYP/6-311G(d, p levels. Seven 2TX...H2O hydrogen bonded complexes have been theoretically identified and reported for the first time. The proton affinities (PAs of the O, S, and N atoms and deprotonantion enthalpies (DPEs of different N-H bonds in 2TX are calculated, factors surrounding why the seven complexes have different hydrogen bond energies are discussed. The theoretical infrared and NMR spectra of hydrated 2TX complexes are reported to probe the characteristics of the proposed H-bonds. An improper blue-shifting H-bond with a shortened C-H bond was found in one case. NBO and AIM analysis were carried out to explain the formation of improper blue-shifting H-bonds, and the H-bonding characteristics are discussed. Conclusion 2TX can interact with water by five different H-bonding regimes, N-H...O, O-H...N, O-H...O, O-H...S and C-H...O, all of which are medium strength hydrogen bonds. The most stable H-bond complex has a closed structure with two hydrogen bonds (N(7-H...O and O-H...O, whereas the least stable one has an open structure with one H-bond. The interaction energies of the studied complexes are correlated to the PA and DPE involved in H-bond formation. After formation of H-bonds, the calculated IR and NMR spectra of the 2TX-water complexes change greatly, which serves to identify the hydration of 2TX.

  13. HYDRATE CORE DRILLING TESTS

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-11-01

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

  14. 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.

  15. Theoretical modeling of magnesium ion imprints in the Raman scattering of water.

    Science.gov (United States)

    Kapitán, Josef; Dracínský, Martin; Kaminský, Jakub; Benda, Ladislav; Bour, Petr

    2010-03-18

    Hydration envelopes of metallic ions significantly influence their chemical properties and biological functioning. Previous computational studies, nuclear magnetic resonance (NMR), and vibrational spectra indicated a strong affinity of the Mg(2+) cation to water. We find it interesting that, although monatomic ions do not vibrate themselves, they cause notable changes in the water Raman signal. Therefore, in this study, we used a combination of Raman spectroscopy and computer modeling to analyze the magnesium hydration shell and origin of the signal. In the measured spectra of several salts (LiCl, NaCl, KCl, MgCl(2), CaCl(2), MgBr(2), and MgI(2) water solutions), only the spectroscopic imprint of the hydrated Mg(2+) cation could clearly be identified as an exceptionally distinct peak at approximately 355 cm(-1). The assignment of this band to the Mg-O stretching motion could be confirmed on the basis of several models involving quantum chemical computations on metal/water clusters. Minor Raman spectral features could also be explained. Ab initio and Fourier transform (FT) techniques coupled with the Car-Parrinello molecular dynamics were adapted to provide the spectra from dynamical trajectories. The results suggest that even in concentrated solutions magnesium preferentially forms a [Mg(H(2)O)(6)](2+) complex of a nearly octahedral symmetry; nevertheless, the Raman signal is primarily associated with the relatively strong metal-H(2)O bond. Partially covalent character of the Mg-O bond was confirmed by a natural bond orbital analysis. Computations on hydrated chlorine anion did not provide a specific signal. The FT techniques gave good spectral profiles in the high-frequency region, whereas the lowest-wavenumber vibrations were better reproduced by the cluster models. Both dynamical and cluster computational models provided a useful link between spectral shapes and specific ion-water interactions.

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

    Directory of Open Access Journals (Sweden)

    Hong Sun

    2015-01-01

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

  17. Experimental determination of methane hydrate formation in the presence of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Dong, T.B.; Wang, L.Y.; Liu, A.X.; Guo, X.Q.; Chen, G.J.; Ma, Q.L.; Li, G.W. [China Univ. of Petroleum, Beijng (China). State Key Laboratory of Heavy Oil Processing

    2008-07-01

    Gas hydrates are non-stoichiometric inclusion compounds that are created by a lattice of water molecules. The host molecule has a strong hydrogen bond and encages low molecular weight gases or volatile liquids. The guest molecules favor hydrate formation. Historically, gas hydrates have been thought to be problematic during natural gas transportation because the formed solid hydrate can block pipelines and cause tubing and casing collapse. However, the discovery of huge deposits of gas hydrates in deep-sea sediments and in permafrost has renewed interest in gas hydrates as a new energy resource. This paper discussed a study that is a part of an ongoing experimental and computational program dealing with the thermodynamics of gas hydrate formation in ammonia-water systems. The purpose of the study was to develop a new method to separate and recycle the vent gas of ammonia synthesis by forming or dissociating hydrate. The hydrate-forming conditions of methane in ammonia and water system were studied and reported in this paper with reference to the experimental apparatus and procedure. The materials and preparation of samples were also explained. The experimental results showed that the ammonia had an inhibitive effect on the hydrate formation. 26 refs., 2 tabs., 3 figs.

  18. Hydration Control of the Mechanical and Dynamical Properties of Cellulose

    Energy Technology Data Exchange (ETDEWEB)

    Petridis, Loukas; O’Neill, Hugh M.; Johnsen, Mariah [Ripon College, Ripon, Wisconsin 54971, United States; Fan, Bingxin [Department; Schulz, Roland [Department; Mamontov, Eugene; Maranas, Janna [Department; Langan, Paul [Department; Smith, Jeremy C. [Department

    2014-10-13

    The mechanical and dynamical properties of cellulose, the most abundant biomolecule on earth, are essential for its function in plant cell walls and advanced biomaterials. Cellulose is almost always found in a hydrated state, and it is therefore important to understand how hydration influences its dynamics and mechanics. Here, the nanosecond-time scale dynamics of cellulose is characterized using dynamic neutron scattering experiments and molecular dynamics (MD) simulation. The experiments reveal that hydrated samples exhibit a higher average mean-square displacement above ~240 K. The MD simulation reveals that the fluctuations of the surface hydroxymethyl atoms determine the experimental temperature and hydration dependence. The increase in the conformational disorder of the surface hydroxymethyl groups with temperature follows the cellulose persistence length, suggesting a coupling between structural and mechanical properties of the biopolymer. In the MD simulation, 20% hydrated cellulose is more rigid than the dry form, due to more closely packed cellulose chains and water molecules bridging cellulose monomers with hydrogen bonds. This finding may have implications for understanding the origin of strength and rigidity of secondary plant cell walls. The detailed characterization obtained here describes how hydration-dependent increased fluctuations and hydroxymethyl disorder at the cellulose surface lead to enhancement of the rigidity of this important biomolecule.

  19. Characterizing heterogeneous dynamics at hydrated electrode surfaces

    Science.gov (United States)

    Willard, Adam P.; Limmer, David T.; Madden, Paul A.; Chandler, David

    2013-05-01

    In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

  20. Characterizing heterogeneous dynamics at hydrated electrode surfaces.

    Science.gov (United States)

    Willard, Adam P; Limmer, David T; Madden, Paul A; Chandler, David

    2013-05-14

    In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

  1. 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…

  2. Hydrogen bonding in ionic liquids.

    Science.gov (United States)

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-07

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

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

    Science.gov (United States)

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

    2009-01-01

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

  4. Second harmonic generation microscopy investigation of the crystalline ultrastructure of three barley starch lines affected by hydration

    DEFF Research Database (Denmark)

    Cisek, Richard; Tokarz, Danielle; Steup, Martin

    2015-01-01

    Second harmonic generation (SHG) microscopy is employed to study changes in crystalline organization due to altered gene expression and hydration in barley starch granules. SHG intensity and susceptibility ratio values (R’SHG) are obtained using reduced Stokes-Mueller polarimetric microscopy...... by ordered hydrogen and hydroxyl bond networks which increase with hydration of starch granules....

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

    International Nuclear Information System (INIS)

    Kawai, Koji; Kawakami, Hayato; Narushima, Takashi; Yonezawa, Tetsu

    2015-01-01

    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. Historical methane hydrate project review

    Science.gov (United States)

    Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

    2013-01-01

    In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas 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 gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas 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 gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

  7. 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

  8. N-Benzyl-N-[2-(N-benzyl-N′,N′,N′′,N′′-tetramethylguanidiniumylethyl]-N′,N′,N′′,N′′-tetramethylguanidinium dibromide 1.5-hydrate

    Directory of Open Access Journals (Sweden)

    Ioannis Tiritiris

    2016-01-01

    Full Text Available The asymmetric unit of the hydrated title compound, C26H42N62+·2Br−·1.5H2O, comprises one cation, two bromide anions and one and a half water molecules, as one water molecule is fully occupied and the other is only half occupied [0.500 (6]. Both bromide ions are disordered over two sites with refined occupancies of 0.938 (3:0.062 (3 and 0.520 (9:0.480 (9. The C—N bond lengths in both central C3N units of the bisguanidinium ion range between 1.336 (3 and 1.349 (3 Å, indicating a degree of double-bond character. The central C atoms are bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charges are delocalized in both CN3 planes. The crystal structure is stabilized by a three-dimensional network of O—H...O, O—H...Br and C—H...Br hydrogen bonds.

  9. Overview: Nucleation of clathrate hydrates.

    Science.gov (United States)

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

    2016-12-07

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

  10. Formation of submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Soloviev, V.; Ginsburg, G.D. (Reserch Institute of Geology and Mineral Resources of the Ocean ' ' VNII Okeangeologia' ' , St. Petersburg (Russian Federation))

    1994-03-01

    Submarine gas hydrates have been discoverd in the course of deep-sea drilling (DSDP and ODP) and bottom sampling in many offshore regions. This paper reports on expeditions carried out in the Black, Caspian and Okhotsk Seas. Gas hydrate accumulations were discovered and investigated in all these areas. The data and an analysis of the results of the deep-sea drilling programme suggest that the infiltration of gas-bearing fluids is a necessary condition for gas hydrate accumulation. This is confirmed by geological observations at three scale levels. Firstly, hydrates in cores are usually associated with comparatively coarse-grained, permeable sediments as well as voids and fractures. Secondly, hydrate accumulations are controlled by permeable geological structures, i.e. faults, diapirs, mud volcanos as well as layered sequences. Thirdly, in the worldwide scale, hydrate accumulations are characteristic of continental slopes and rises and intra-continental seas where submarine seepages also are widespread. Both biogenic and catagenic gas may occur, and the gas sources may be located at various distances from the accumulation. Gas hydrates presumably originate from water-dissolved gas. The possibility of a transition from dissolved gas into hydrate is confirmed by experimental data. Shallow gas hydrate accumulations associated with gas-bearing fluid plumes are the most convenient features for the study of submarine hydrate formation in general. These accumulations are known from the Black, Caspian and Okhotsk Seas, the Gulf of Mexico and off northern California. (au) (24 refs.)

  11. 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.

  12. Dehydration behaviour of hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Dette, S.S.; Stelzer, T.; Jones, M.J.; Ulrich, J. [Martin-Luther-Universitaet Halle-Wittenberg, Zentrum fuer Ingenieurwissenschaften, Verfahrenstechnik/TVT, 06099 Halle (Germany)

    2010-07-15

    Immersing a crystalline solvate in a suitable anti-solvent can induce phase transformation to solvent-free solid phase. In certain cases the solvent-mediated phase transition results in the generation of hollow, tubular structures. Both the tube dimensions of sodium-2-keto-L-gulonate anhydrate (skga) and the dehydration kinetics of sodium-2-keto-L-gulonate monohydrate (skgm) can be modified by the antisolvent employed. An explanation for the variable dehydration behaviour of skgm in the antisolvents is presented here. Furthermore, other crystalline hydrates were dehydrated in dry methanol. Providing an operational window can be found, any hydrate material could possibly find use in the production of tubes (micro- or nanotubes for different applications). The experimental conditions selected (dry methanol as antisolvent, dehydration temperature at 25 C) for the dehydration did not lead to the anhydrate tube growth for all hydrates investigated. Based upon the results presented here a first hypothesis is presented to explain this effect. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    International Nuclear Information System (INIS)

    Wang, Liping; Mou, Chengxu; Sun, Yang; Liu, Wei; Deng, Qijiu; Li, Jingze

    2015-01-01

    Graphical Abstract: Effects of hydration water in calcium terephthalates anodes on the structure, operational voltage and electrochemical performance are systematically studied. Display Omitted -- Highlights: •Metal organic frameworks CaC 8 H 4 O 4 ·3H 2 O and CaC 8 H 4 O 4 are applied as anodes for lithium ion batteries. •Appearance of hydration water leads different crystallography structures and electrochemical performance. •Anhydrous CaC 8 H 4 O 4 has a spacious ordered layer structure, a higher Ca-O chemical bonding interaction and a higher transparent lithium ion diffusion coefficient, delivering a higher capacity, better cycling performance and rate performance than CaC 8 H 4 O 4 ·3H 2 O. -- Abstract: Metal organic frameworks have attracted considerable interest as electrode materials for lithium ion batteries. In this paper, the metal organic frameworks hydrated calcium terephthalate (CaC 8 H 4 O 4 ·3H 2 O) and anhydrous calcium terephthalate (CaC 8 H 4 O 4 ) as anodes for lithium ion batteries are comparatively studied. Crystallography and local chemical bond analysis are combined to interpret the structure-property of calcium terephthalates. Results show that the anhydrous CaC 8 H 4 O 4 has a spacious ordered layer structure and a higher Ca-O chemical bonding interaction, delivering a higher capacity, better cycling performance and rate performance than CaC 8 H 4 O 4 ·3H 2 O

  14. Molecular dynamics simulation, ab initio calculation, and size-selected anion photoelectron spectroscopy study of initial hydration processes of calcium chloride.

    Science.gov (United States)

    He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin

    2018-06-14

    To understand the initial hydration processes of CaCl 2 , we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl 2 (H 2 O) n - (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl-Ca ion pair is investigated in CaCl 2 (H 2 O) n - anions, where the first Ca-Cl ionic bond required 4 water molecules, and both Ca-Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl 2 (H 2 O) n clusters, breaking of the first Ca-Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl 2 (H 2 O) n requires fewer water molecules than those for MgCl 2 (H 2 O) n . Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.

  15. Gas hydrate cool storage system

    Science.gov (United States)

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

    1984-09-12

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

  16. THERMODYNAMIC MODEL OF GAS HYDRATES

    OpenAIRE

    Недоступ, В. И.; Недоступ, О. В.

    2015-01-01

    The interest to gas hydrates grows last years. Therefore working out of reliable settlement-theoretical methods of definition of their properties is necessary. The thermodynamic model of gas hydrates in which the central place occupies a behaviour of guest molecule in cell is described. The equations of interaction of molecule hydrate formative gas with cell are received, and also an enthalpy and energy of output of molecule from a cell are determined. The equation for calculation of thermody...

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

    International Nuclear Information System (INIS)

    Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

    2002-01-01

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  18. 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.

  19. Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

    Science.gov (United States)

    Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

    2015-09-23

    The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

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

    Directory of Open Access Journals (Sweden)

    Katharina Fucke

    2010-07-01

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

  1. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina; Yamauchi, Kazuo; Li, Zongjin; Zhang, Xixiang; Ma, Hongyan; Ge, Shenguang

    2017-01-01

    The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10

  2. Differential Deformability of the DNA Minor Groove and Altered BI/BII Backbone Conformational Equilibrium by the Monovalent Ions Li+, Na+, K+ and Rb+ via Water-Mediated Hydrogen Bonding

    Science.gov (United States)

    Savelyev, Alexey; MacKerell, Alexander D.

    2015-01-01

    Recently, we reported the differential impact of the monovalent cations Li+, Na+, K+ and Rb+ on DNA conformational properties. These were identified from variations in the calculated solution-state X-ray DNA spectra as a function of the ion type in the solvation buffer in MD simulations using our recently developed polarizable force field based on the classical Drude oscillator. Changes in the DNA structure were found to mainly involve variations in the minor groove width. Because minor groove dimensions vary significantly in protein-DNA complexes and have been shown to play a critical role in both specific and nonspecific DNA readout, understanding the origins of the observed differential DNA modulation by the first-group monovalent ions is of great biological importance. In the present study we show that the primary microscopic mechanism for the phenomenon is the formation of the water-mediated hydrogen bonds between solvated cations located inside the minor groove and simultaneously to two DNA strands, a process whose intensity and impact on DNA structure depends on both the type of the ion and DNA sequence. Additionally, it is shown that formation of such ion-DNA hydrogen bond complexes appreciably modulates the conformation of the backbone by increasing the population of the BII substate. Notably, the differential impact of the ions on DNA conformational behavior is only predicted by the Drude polarizable model for DNA, with virtually no effect observed from MD simulations utilizing the additive CHARMM36 model. Analysis of dipole moments of the water shows the Drude SWM4 model to possess high sensitivity to changes in the local environment, which indicates the important role of electronic polarization in the salt-dependent conformational properties. This also suggests that inclusion of polarization effects is required to model even relatively simple biological systems such as DNA in various ionic solutions. PMID:26575937

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

    International Nuclear Information System (INIS)

    Eslamimanesh, Ali

    2012-01-01

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

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

    Science.gov (United States)

    Zhang, Zhengcai; Guo, Guang-Jun

    2017-07-26

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

  5. Theoretical study of the mechanism of formation of a chemical bond between two ions: A+ and B+. Application to CO++. Interpretation of N2O++ photo-dissociation mechanisms

    International Nuclear Information System (INIS)

    Levasseur, Nathalie

    1989-01-01

    This research thesis reports the theoretical study of the mechanism of formation of a chemical bond between two positively charged species, within the frame of the valence-bond theory and in the CO model case. The analysis in terms of orthogonal and non orthogonal orbitals leads to two very different interpretations, and allows potential curves of doubly charged diatomic ions to be simply explained, the generally evoked model to be put into question again, and a predictive model to be developed. The theoretical determination of N 2 O potential energy surfaces and of the first states of N 2 O ++ ( 3 Σ - , 1 Δ, 1 Σ + et 3 Π) allowed experimental results of N 2 O ++ photo-dissociation to be at least qualitatively understood and interpreted. Moreover, the study of electronic configurations involved in dissociation, showed that the model elaborated for a diatomic molecule is also valid for a triatomic system [fr

  6. 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

  7. Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

    Science.gov (United States)

    De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

    2017-12-01

    A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

  8. Hydration of ammonia, methylamine, and methanol in amorphous solid water

    Science.gov (United States)

    Souda, Ryutaro

    2016-02-01

    Interactions of polar protic molecules with amorphous solid water (ASW) have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. The ammonia and methylamine are incorporated into the interior of porous ASW films. They are caged by water molecules and are released during water crystallization. In contrast, the methanol-water interaction is not influenced by pores of ASW. The methanol additives tend to survive water crystallization and are released during ASW film evaporation. The hydration of n-hexane in ASW is influenced significantly by methanol additives because n-hexane is accommodated in a methanol-induced hydration shell.

  9. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-15

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

  11. 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.

  12. Ductile flow of methane hydrate

    Science.gov (United States)

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

    2003-01-01

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

  13. Cations form sequence selective motifs within DNA grooves via a combination of cation-pi and ion-dipole/hydrogen bond interactions.

    Science.gov (United States)

    Stewart, Mikaela; Dunlap, Tori; Dourlain, Elizabeth; Grant, Bryce; McFail-Isom, Lori

    2013-01-01

    The fine conformational subtleties of DNA structure modulate many fundamental cellular processes including gene activation/repression, cellular division, and DNA repair. Most of these cellular processes rely on the conformational heterogeneity of specific DNA sequences. Factors including those structural characteristics inherent in the particular base sequence as well as those induced through interaction with solvent components combine to produce fine DNA structural variation including helical flexibility and conformation. Cation-pi interactions between solvent cations or their first hydration shell waters and the faces of DNA bases form sequence selectively and contribute to DNA structural heterogeneity. In this paper, we detect and characterize the binding patterns found in cation-pi interactions between solvent cations and DNA bases in a set of high resolution x-ray crystal structures. Specifically, we found that monovalent cations (Tl⁺) and the polarized first hydration shell waters of divalent cations (Mg²⁺, Ca²⁺) form cation-pi interactions with DNA bases stabilizing unstacked conformations. When these cation-pi interactions are combined with electrostatic interactions a pattern of specific binding motifs is formed within the grooves.

  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. 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.

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

    Science.gov (United States)

    Sutton, Rebecca; Sposito, Garrison

    2002-01-01

    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.

  17. Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

    Science.gov (United States)

    Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

    2017-01-01

    Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

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

    Science.gov (United States)

    Perrier, Erica T

    2017-01-01

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

  19. 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.

  20. 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.

  1. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

  2. 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.

  3. Preliminary report on the economics of gas production from natural gas hydrates

    International Nuclear Information System (INIS)

    Walsh, M.; Wilson, S.; Patil, S.; Moridis, G.; Boswell, R.; Koh, C.; Sloan, D.

    2008-01-01

    Gas hydrates are solid crystalline compounds in which gas molecules reside inside cages that are formed by hydrogen-bonded water molecules in a crystal lattice. At particularly low temperatures and high pressures, a guest molecule will combine with water to form gas hydrates. Gas hydrates are found in two different settings in which the temperature and pressure conditions are suitable for their existence, notably in Arctic permafrost regions and below the seafloor. Because of the size of this possible future resource, if any of the gas in hydrates can be proven to be economically recoverable, then production from gas hydrates could become an important portion of the world's energy portfolio as demand for natural gas increases along with the technology to compress and distribute natural gas to distant markets. This paper presented a compilation of economic research that was conducted on the resource potential of gas hydrates. The paper reported a preliminary estimate of the price of natural gas that may lead to economically-viable production from North American Arctic region hydrates. The paper also discussed the implications of a recent study on the production of class 3 marine hydrate deposits from the Gulf of Mexico. The state of the art technologies and methods in hydrate reservoir modeling and hydrate reservoir production and petrophysical testing were also discussed. It was concluded that the somewhat optimistic results presented in this report should be interpreted with caution, however, the economically-viable gas production from hydrates was not an unreasonable scenario. 23 refs., 2 tabs., 10 figs

  4. Contribution to the systemic study of energetic systems including electrochemical devices: Bond Graph formalism applied to modelling fuel cells, lithium-ion batteries and sun-racer; Contribution a l'etude systemique de dispositifs energetiques a composants electrochimiques. Formalisme Bond Graph applique aux piles a combustible, accumulateurs lithium-ion, vehicule solaire

    Energy Technology Data Exchange (ETDEWEB)

    Saisset, R.

    2004-04-01

    This thesis is a contribution to the study of electric power conversion systems including electrochemical devices. A systemic approach draws advantage of the unified Bond Graph formalism in order to model every component as well as the whole system. A state of the art of electrochemical devices for decentralized electric energy generation and storage put emphasis on common phenomena with the aim of developing 'system oriented' generic models. Solid Oxide and Proton Exchange Fuel Cells (SOFC, PEMFC), as well as Lithium Ion batteries, have been modelled through an efficient work with electrochemistry specialists. These models involve an explicit representation, at a macroscopic level, of conversion and irreversible phenomena linked to the chemical reaction and coupled together both in the hydraulic, chemical, thermodynamic, electric and thermal fields. These models are used to study the modularity of the components, particularly the electric and thermal imbalances in the series and parallel fuel cells associations. The systemic approach is also applied to the study of architectures and energy management of electric power generating units involving PEMFC and battery or super-capacitors storage. Different working conditions for the fuel cells are defined and studied, consisting in either voltage or current or power imposed by means of the storage and static converters environment. Identification of parameters and working tests are performed on specially developed test benches so as to validate theoretical results. At last, the method is applied to study a 'sun-racer', an original complex system with embedded photovoltaic generator, electrochemical storage and brush-less wheel motor, wholly modelled in order to compare various energy management onboard the solar vehicle 'Solelhada'. (author)

  5. Innovative Approaches To Improving The Bond Between Concrete and Steel Surfaces

    National Research Council Canada - National Science Library

    Day, Donna C; Carrasquillo, Mariangelica; Weiss, Jr., Charles A; Sykes, Melvin C; Baugher, Jr., Earl H; Malone, Philip G

    2006-01-01

    A reactive silicate layer fused onto the surface of reinforcing steel provides a coupling layer that allows a very strong bond to develop between hydrating Portland cement paste and the surface of the steel...

  6. Alcohol cosurfactants in hydrate antiagglomeration.

    Science.gov (United States)

    York, J Dalton; Firoozabadi, Abbas

    2008-08-28

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

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

    Roč. 407, č. 17 (2015), s. 5175-5188 ISSN 1618-2642 R&D Projects: GA ČR GAP206/12/0750 Institutional support: RVO:61388963 Keywords : double bond * gas-phase chemistry * lipidomics * olive oil * vernix caseosa Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.125, year: 2015

  8. Structure and Hydrogen Bonding of 2-aminopyridine·(H2O)n (n=1,2) Studied by Infrared Ion Depletion Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Wu, R.; Nachtigall, Petr; Brutschy, B.

    2004-01-01

    Roč. 6, č. 3 (2004), s. 515-521 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : hydrogen bonding * electronic and vibrational spectra * spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.076, year: 2004

  9. A QUANTUM MECHANICAL STUDY OF THE PROTONATION AND COVALENT HYDRATION OF QUINAZOLINE IN THE PRESENCE OF METAL CATIONS

    Science.gov (United States)

    We have investigated the protonation and reversible covalent hydration of quinazoline in the presence of Li+, Na+, and Ca2+ ions using ab initio quantum mechanical calculations at the MP2/6-31G**//HF/6-31G*level of theory. Proton affinities, enthalpies of hydration at 298.15K (DH...

  10. Suspension hydration of tricalcium silicate at constant pH. I. Variation of particle size and tricalcium silicate content

    NARCIS (Netherlands)

    McCurdy, K.G.; Stein, H.N.

    1973-01-01

    Calcium and silicate ion concentrations during suspension hydration of C3S indicate that at pH 11.5 an equilibrium is established between one of the hydrates and the solution during about 80 minutes. The concentrations found in this period are indipendent of the particle size of the C3S and (within

  11. How the shape of an H-bonded network controls proton-coupled water activation in HONO formation.

    Science.gov (United States)

    Relph, Rachael A; Guasco, Timothy L; Elliott, Ben M; Kamrath, Michael Z; McCoy, Anne B; Steele, Ryan P; Schofield, Daniel P; Jordan, Kenneth D; Viggiano, Albert A; Ferguson, Eldon E; Johnson, Mark A

    2010-01-15

    Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)-bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

  12. Bone bonding bioactivity of Ti metal and Ti-Zr-Nb-Ta alloys with Ca ions incorporated on their surfaces by simple chemical and heat treatments.

    Science.gov (United States)

    Fukuda, A; Takemoto, M; Saito, T; Fujibayashi, S; Neo, M; Yamaguchi, S; Kizuki, T; Matsushita, T; Niinomi, M; Kokubo, T; Nakamura, T

    2011-03-01

    Ti15Zr4Nb4Ta and Ti29Nb13Ta4.6Zr, which do not contain the potentially cytotoxic elements V and Al, represent a new generation of alloys with improved corrosion resistance, mechanical properties, and cytocompatibility. Recently it has become possible for the apatite forming ability of these alloys to be ascertained by treatment with alkali, CaCl2, heat, and water (ACaHW). In order to confirm the actual in vivo bioactivity of commercially pure titanium (cp-Ti) and these alloys after subjecting them to ACaHW treatment at different temperatures, the bone bonding strength of implants made from these materials was evaluated. The failure load between implant and bone was measured for treated and untreated plates at 4, 8, 16, and 26 weeks after implantation in rabbit tibia. The untreated implants showed almost no bonding, whereas all treated implants showed successful bonding by 4 weeks, and the failure load subsequently increased with time. This suggests that a simple and economical ACaHW treatment could successfully be used to impart bone bonding bioactivity to Ti metal and Ti-Zr-Nb-Ta alloys in vivo. In particular, implants heat treated at 700 °C exhibited significantly greater bone bonding strength, as well as augmented in vitro apatite formation, in comparison with those treated at 600 °C. Thus, with this improved bioactive treatment process these advantageous Ti-Zr-Nb-Ta alloys can serve as useful candidates for orthopedic devices. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  13. 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.

  14. Obsidian hydration dates glacial loading?

    Science.gov (United States)

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

    1973-05-18

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

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

    International Nuclear Information System (INIS)

    Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

    2006-01-01

    Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C 3 S, C 2 S) and aluminates (C 3 A, C 4 AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm -1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1 H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  17. Hydration structure of Ti(III) and Cr(III): Monte Carlo simulation ...

    African Journals Online (AJOL)

    Classical Monte Carlo simulations were performed to investigate the solvation structures of Ti(III) and Cr(III) ions in water with only ion-water pair interaction potential and by including three-body correction terms. The hydration structures were evaluated in terms of radial distribution functions, coordination numbers and ...

  18. Ion radical rupture of the carbon-carbon bond in oxidation of 1,3,1',3'-tetramethyl-2,3,2',3'- tetrahydro-2,2'-diperimidinyl

    International Nuclear Information System (INIS)

    Sabanov, V.Kh.; Kibizova, A.Yu.; Klimov, E.S.; Berberova, N.T.; Okhlobystin, O.Yu.

    1987-01-01

    Electrochemical and chemical oxidation of 1,3,1',3'-tetramethyl-2,3,2',3'-tetrahydro-2,2'-dipyriminyl takes place with rupture of the C-C bond in the initially formed cation radical. In the oxidation of the compound with aluminum chloride in nitrobenzene, ESR revealed a cation radical with an unresolved hyperfine structure. Oxidation of the dihydrodimer with nitrosonium perchlorate in nitrobenzene or nitromethane resulted in the same spectra. Cyclic volt-ampere diagrams are included

  19. Hydration dependent dynamics in RNA

    International Nuclear Information System (INIS)

    Olsen, Greg L.; Bardaro, Michael F.; Echodu, Dorothy C.; Drobny, Gary P.; Varani, Gabriele

    2009-01-01

    The essential role played by local and collective motions in RNA function has led to a growing interest in the characterization of RNA dynamics. Recent investigations have revealed that even relatively simple RNAs experience complex motions over multiple time scales covering the entire ms-ps motional range. In this work, we use deuterium solid-state NMR to systematically investigate motions in HIV-1 TAR RNA as a function of hydration. We probe dynamics at three uridine residues in different structural environments ranging from helical to completely unrestrained. We observe distinct and substantial changes in 2 H solid-state relaxation times and lineshapes at each site as hydration levels increase. By comparing solid-state and solution state 13 C relaxation measurements, we establish that ns-μs motions that may be indicative of collective dynamics suddenly arise in the RNA as hydration reaches a critical point coincident with the onset of bulk hydration. Beyond that point, we observe smaller changes in relaxation rates and lineshapes in these highly hydrated solid samples, compared to the dramatic activation of motion occurring at moderate hydration

  20. Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds

    Directory of Open Access Journals (Sweden)

    Alankriti Bajpai

    2016-11-01

    Full Text Available Hydrates are technologically important and ubiquitous yet they remain a poorly understood and understudied class of molecular crystals. In this work, we attempt to rationalize propensity towards hydrate formation through crystallization studies of molecules that lack strong hydrogen-bond donor groups. A Cambridge Structural Database (CSD survey indicates that the statistical occurrence of hydrates in 124 molecules that contain five- and six-membered N-heterocyclic aromatic moieties is 18.5%. However, hydrate screening experiments on a library of 11 N-heterocyclic aromatic compounds with at least two acceptor moieties and no competing hydrogen-bond donors or acceptors reveals that over 70% of this group form hydrates, suggesting that extrapolation from CSD statistics might, at least in some cases, be deceiving. Slurrying in water and exposure to humidity were found to be the most effective discovery methods. Electrostatic potential maps and/or analysis of the crystal packing in anhydrate structures was used to rationalize why certain molecules did not readily form hydrates.

  1. 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.

  2. Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms.

    Science.gov (United States)

    Yu, Haoyu; Truhlar, Donald G

    2015-07-14

    Although many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. However, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree-Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive

  3. 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.

  4. Bonds Boom.

    Science.gov (United States)

    Reynolds, Cathryn

    1989-01-01

    The combined effect of the "Serrano" decision and Proposition 13 left California school districts with aging, overcrowded facilities. Chico schools won a $18.5 million general obligation bond election for facilities construction. With $11 billion needed for new school construction, California will need to tap local sources. A sidebar…

  5. Cage occupancies of natural gas hydrates encaging methane and ethane

    Energy Technology Data Exchange (ETDEWEB)

    Kida, M.; Hachikubo, A.; Sakagami, H.; Minami, H.; Krylov, A.; Yamashita, S.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan); Kida, M. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan); Khlystov, O. [Limnological Inst., Irkutsk (Russian Federation). Siberian Branch of the Russian Academy of Sciences; Poort, J. [Ghent Univ., Ghent (Belgium). Renard Centre of Marine Geology; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan)

    2008-07-01

    Natural gas hydrates are crystalline compounds that contain large amounts of natural gas in its structure and are expected to provide natural gas resources in the future. The gas species are trapped in different types of polyhedral cages which consist of hydrogen bonded water molecules. Three main types of crystallographic structures exist, notably structure 1, structure 2 and structure H (sH). The crystallographic structure of natural gas hydrates depends on the encaged gas components. The cage occupancy is the ratio of the number of cages occupied by guest molecules to the number of total cages. It is also important to estimate the amount of natural gas, since it depends on the condition of the hydrate formation such as gas composition. The cages of natural gas hydrates mainly contain methane. However, other heavier hydrocarbons such as ethane (C{sub 2}H{sub 6}), propane (C{sub 3}H{sub 8}), and isobutane (i-C{sub 4}H{sub 1}0) may be encaged together with CH{sub 4}. Little is known about cage occupancies of natural gas hydrates including CH{sub 4} and heavier hydrocarbons. This paper discussed a study that developed cage occupancy estimations of natural gas hydrates encaging heavier hydrocarbons. 13C nuclear magnetic resonance (NMR) measurements were conducted. The assignments of resonance lines were based on 13C chemical shifts obtained by artificial sample measurements. The paper presented the experimental data and discussed the results of the study. The large cages were almost fully occupied with CH{sub 4} and C{sub 2}H{sub 6} molecules, whereas the small cage occupancies of CH{sub 4} were below 0.8. The distribution of CH{sub 4} and C{sub 2}H{sub 6} in each cage were similar to that of synthetic CH{sub 4} + C{sub 2}H{sub 6} hydrate. It was concluded that these results should be useful for optimal estimation of the amount of natural gas in gas hydrates. 18 refs., 1 tab., 3 figs.

  6. A high yield process for hydrate formation

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F. [Univ. of Roma La Sapienza, Roma (Italy). Dept. of Chemical Engineering

    2008-07-01

    Due to the large quantities of natural gas stored in deep ocean hydrates, hydrate reservoirs are a substantial energy resource. Hydrates concentrate methane by as much as a factor of 164. As such, several natural gas transportation and storage systems using gas hydrates have been studied, and many of them are nearing practical use. In these systems, the hydrate is produced as a slurry by a spray process at approximately 7 megapascal (MPa), and then shaped into pellets. The use of a spray process, instead of a conventional stirred vessel is necessary in order to reach high hydrate concentrations in the hydrate-ice system. This paper presented a new procedure to produce a bulk of concentrated methane hydrate in a static traditional reactor at moderate pressure, controlling pressure and temperature in the interval between ice melting and the hydrate equilibrium curve. This paper discussed the experimental procedure which included formation of methane hydrate at approximately 5 MPa and 2 degrees Celsius in a reaction calorimeter at a volume of two liters. Results were also discussed. It was concluded that the procedure seemed suitable for the development of a gas hydrate storage and transport technology. It was found that the spray procedure took more time, but could be sped up and made continuous by using two vessels, one for hydrate formation and the other for hydrate concentration. The advantage was the production of a concentrated hydrate, using a simpler equipment and working at lower pressures respect to the spray process. 9 refs., 5 figs.

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

    Czech Academy of Sciences Publication Activity Database

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

    2002-01-01

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

  8. 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.

  9. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

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

    1999-01-01

    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......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...

  10. Storage capacity of hydrogen in gas hydrates

    International Nuclear Information System (INIS)

    Tsuda, Takaaki; Ogata, Kyohei; Hashimoto, Shunsuke; Sugahara, Takeshi; Sato, Hiroshi; Ohgaki, Kazunari

    2010-01-01

    The storage capacity of H 2 in the THF, THT, and furan hydrates was studied by p-V-T measurements. We confirmed that the storage and release processes of H 2 in all hydrates could be performed reversibly by pressure swing without destroying of hydrate cages. H 2 absorption in both THT and furan hydrates is much faster than THF hydrate in spite of same unit-cell structure. On the other hand, the storage amounts of H 2 are coincident in the all additive hydrates and would reach at about 1.0 mass% asymptotically.

  11. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.

    1976-01-01

    A method is described for joining beryllium to beryllium by diffusion bonding. At least one surface portion of at least two beryllium pieces is coated with nickel. A coated surface portion is positioned in a contiguous relationship with another surface portion and subjected to an environment having an atmosphere at a pressure lower than ambient pressure. A force is applied on the beryllium pieces for causing the contiguous surface portions to abut against each other. The contiguous surface portions are heated to a maximum temperature less than the melting temperature of the beryllium, and the applied force is decreased while increasing the temperature after attaining a temperature substantially above room temperature. A portion of the applied force is maintained at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions

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

    International Nuclear Information System (INIS)

    Buanam-Om, C.

    1981-01-01

    The chapter of reviews presents in particular the Badger-Bauer-rule, distance and angle dependence of O-H...Y hydrogen bond and the structure of aqueous electrolyte solutions. A chapter of vibrational spectroscopic investigations of crystalline hydrates - metal perchlorate hydrates follows. Two further chapters just so investigate metal halide hydrates and some sulfate hydrates and related systems. The following chapter describes near infrared spectroscopic investigations of HOD(D 2 O) and its electrolyte solutions. The concluding chapter contains thermodynamic consequences and some properties of electrolyte solutions from vibrational spectroscopic investigations. (SPI) [de

  13. Gas hydrates forming and decomposition conditions analysis

    Directory of Open Access Journals (Sweden)

    А. М. Павленко

    2017-07-01

    Full Text Available The concept of gas hydrates has been defined; their brief description has been given; factors that affect the formation and decomposition of the hydrates have been reported; their distribution, structure and thermodynamic conditions determining the gas hydrates formation disposition in gas pipelines have been considered. Advantages and disadvantages of the known methods for removing gas hydrate plugs in the pipeline have been analyzed, the necessity of their further studies has been proved. In addition to the negative impact on the process of gas extraction, the hydrates properties make it possible to outline the following possible fields of their industrial use: obtaining ultrahigh pressures in confined spaces at the hydrate decomposition; separating hydrocarbon mixtures by successive transfer of individual components through the hydrate given the mode; obtaining cold due to heat absorption at the hydrate decomposition; elimination of the open gas fountain by means of hydrate plugs in the bore hole of the gushing gasser; seawater desalination, based on the hydrate ability to only bind water molecules into the solid state; wastewater purification; gas storage in the hydrate state; dispersion of high temperature fog and clouds by means of hydrates; water-hydrates emulsion injection into the productive strata to raise the oil recovery factor; obtaining cold in the gas processing to cool the gas, etc.

  14. Femtosecond study of the effects of ions and hydrophobes on the dynamics of water.

    Science.gov (United States)

    van der Post, Sietse T; Tielrooij, Klaas-Jan; Hunger, Johannes; Backus, Ellen H G; Bakker, Huib J

    2013-01-01

    We study the effects of ions and hydrophobic molecular groups on the orientational dynamics of water using THz dielectric relaxation (THz-DR) and polarization-resolved femtosecond infrared (fs-IR) pump-probe spectroscopy. We measure the dynamics of water in solutions of NaI, NaCl, CsCl, guanidinium chloride (GndCl) and tetramethyl guanidinium chloride (TMGndCl) of different the static dipoles of their surrounding water molecules. With fs-IR we find that concentrations. With THz-DR we observe that strongly hydrated cations align the OD groups that form hydrogen bonds to halide anions reorient with two distinct time constants of 2 +/- 0.3 ps and 9 +/- 1 ps. The fast process is assigned to a wobbling motion of the OD group that keeps the hydrogen bond with the anion intact. The amplitude of this wobbling motion depends on the nature of both the anion and the counter cation. The replacement of four of the six hydrogen atoms of the weakly hydrated cation guanidinium by hydrophobic methyl groups leads to an exceptionally strong slowing down of the water dynamics. Hydrophobic groups thus appear to have a much stronger effect on the dynamics of water than ions. These findings give new insights in the mechanism of protein denaturation by GndCl and TMGndCl.

  15. Possible mechanisms for interaction of poly electrolytes with ions in aqueous solution

    International Nuclear Information System (INIS)

    Siyam, T.

    1995-01-01

    The interaction between the active groups of water soluble poly electrolytes such as polyacrylamide 'neutral polymers PAM', poly sodium acrylate 'anionic polymer PAANA', polyacrylamide-diallyamine-hydrochloride 'cationic polymer PAM-DAA-HCl and polyacrylamide-diallylethylamine-hydrochloride 'cationic polymer PAM-DAEA-HCl' with copper sulphate has been carried out under different experimental conditions. Spectroscopic studies show that the mechanism of the flock formation due to interaction between the polymer and copper sulphate is a bond formation between the active group of polymeric chains and copper sulphate. This bond formation depends on the nature of polymer chain. It was also found that the amide groups form complexes with hydrated cations, while both carboxylate-and ammonium groups interact by ion-exchange mechanism. The same studies were applied on polyacrylamideacrylic acid resin 'PAM-AA' resin and copper sulphate. The obtained results show that the resin interacts by the same mechanism, where the amide groups form a complex with hydrated cations, while the carboxylic group interacts by ion-exchange mechanism. 1 fig., 1 tab

  16. Energy landscapes for mobile ions in ion conducting solids

    Indian Academy of Sciences (India)

    molecular dynamics (MD) simulations yields quantitative predictions of the ion transport characteristics. As ... Solid electrolytes; bond valence analysis; ion transport in glasses. 1. .... clusters are considered to contribute only to a.c. conduc-.

  17. 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.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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 2 SO 4 –H 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. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina

    2017-05-13

    The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10 was conducted for tricalcium silicate (C3S) to interpret long-term hydration process and investigate the formation, structure and properties of C-S-H. Based on results from XRD, IR, SEM, NMR and so forth, loose and dense clusters of C-S-H with analogous C/S ratio were obtained along with the corresponding chemical formulae proposed as Ca5Si4O13∙6.2H2O. Crystalline structure inside C-S-H was observed by TEM, which was allocated at the foil-like proportion as well as the edge of wrinkles of the product. The long-term hydration process of C3S in dilute suspension could be sketchily described as migration of calcium hydroxide and in-situ growth of C-S-H with equilibrium silicon in aqueous solution relatively constant and calcium varied.

  20. Formation of an Ion-Pair Molecule with a Single NH+...Cl- Hydrogen Bond: Raman spectra of 1,1,3,3-Tetramethylguanidinium chloride in the solid state, in solution and in the vapor phase

    DEFF Research Database (Denmark)

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

    2008-01-01

    Some ionic compounds (salts) form liquids when heated to temperatures in the range of 200-300 °C. They may be referred to as moderate temperature ionic liquids. An example of such a compound is the 1,1,3,3- tetramethylguanidinium chloride, [TMGH]Cl, melting at ∼212 °C. The chemistry of this compo......Some ionic compounds (salts) form liquids when heated to temperatures in the range of 200-300 °C. They may be referred to as moderate temperature ionic liquids. An example of such a compound is the 1,1,3,3- tetramethylguanidinium chloride, [TMGH]Cl, melting at ∼212 °C. The chemistry...... and the dimeric chloride ion-pair salt converged to give geometries near the established crystal structure of [TMGH]Cl. The structures and their binding energies are given as well as calculated vibrational harmonic normal modes (IR and Raman band wavenumbers and intensities). Experimentally obtained Raman...... scattering spectra are presented and assigned, by comparing to the quantum mechanical calculations. It is concluded that dimeric molecular ion pairs with four N-H+ · · · Cl- hydrogen bonds probably exist in the solutions and are responsible for the relatively high solubility of the “salt” in ethanol...

  1. Impacts of Hydrate Distribution on the Hydro-Thermo-Mechanical Properties of Hydrate-Bearing Sediments

    Science.gov (United States)

    Dai, S.; Seol, Y.

    2015-12-01

    In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.

  2. Electronic structures in ion-surface interactions

    International Nuclear Information System (INIS)

    Kiuchi, Masato; Takeuchi, Takae; Yamamoto, Masao.

    1997-01-01

    A chemical bond generated by the interaction between low energy ion and base was investigated by ab initio molecular orbital method. The effects of ion charge were studied by calculation of this method. When carbon ion approached to graphite base (C 24 H 12 ), the positive ion and the neutral atom covalently bonded, but the negative ion did not combine with it. When carbon ion was injected into h-BN base (B 12 N 12 H 12 , hexagonal system boron nitride), the positive ion and the neutron atom formed covalent bond and the van der Waals binding, and the negative ion interacted statically with it. (S.Y.)

  3. 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

  4. The impact of kosmotropes and chaotropes on bulk and hydration shell water dynamics in a model peptide solution

    International Nuclear Information System (INIS)

    Russo, Daniela

    2008-01-01

    Kosmotropic (order-making) and chaotropic (order-breaking) co-solvents influence stability and biochemical equilibrium in aqueous solutions of proteins, acting indirectly through the structure and dynamics of the hydration water that surrounds the protein molecules. We have investigated the influence of kosmotropic and chaotropic co-solvents on the hydrogen bonding network dynamics of both bulk water and hydration water. To this end the evolution of bulk water and hydration water dynamics of a prototypical hydrophobic amino acid with polar backbone, N-acetyl-leucine-methylamide (NALMA), has been studied by quasielastic neutron scattering as a function of solvent composition. The results show that bulk water and hydration water dynamics, apart from a dynamical suppression that depends on the NALMA solute, exhibit the same dependence on addition of co-solvent for all of the co-solvents studied (urea, glycerol, MgSO 4 , and dimethyl sulfoxide). The hydrophobic solute and the high concentration water-structuring additive have the same effect on the water hydrogen bonding network. Water remains the preferential hydration of the hydrophobic side chain and backbone. We also find that the reorganization of the bulk water hydrogen bond network, upon addition of kosmotrope and chaotrope additives, is not dynamically perturbed, and that the hydrogen bond lifetime is maintained at 1 ps as in pure bulk water. On the other hand the addition of NALMA to the water/co-solvent binary system causes reorganization of the hydrogen bonds, resulting in an increased hydrogen bond lifetime. Furthermore, the solute's side chain dynamics is not affected by high concentrations of co-solvent. We shall discuss the hydration dynamics results in the context of protein folding and protein-solvent interactions

  5. How Sodium Chloride Salt Inhibits the Formation of CO2 Gas Hydrates.

    Science.gov (United States)

    Holzammer, Christine; Finckenstein, Agnes; Will, Stefan; Braeuer, Andreas S

    2016-03-10

    We present an experimental Raman study on how the addition of sodium chloride to CO2-hydrate-forming systems inhibits the hydrate formation thermodynamically. For this purpose, the molar enthalpy of reaction and the molar entropy of reaction for the reaction of weakly hydrogen-bonded water molecules to strongly hydrogen bonded water molecules are determined for different salinities from the Raman spectrum of the water-stretching vibration. Simultaneously, the influence of the salinity on the solubility of CO2 in the liquid water-rich phase right before the start of hydrate formation is analyzed. The results demonstrate that various mechanisms contribute to the inhibition of gas hydrate formation. For the highest salt concentration of 20 wt % investigated, the temperature of gas hydrate formation is lowered by 12 K. For this concentration the molar enthalpy and entropy of reaction become smaller by 50 and 20%, respectively. Concurrently, the solubility of carbon dioxide is reduced by 70%. These results are compared with data in literature for systems of sodium chloride in water (without carbon dioxide).

  6. Molecular dynamics study of methane hydrate formation at a water/methane interface.

    Science.gov (United States)

    Zhang, Junfang; Hawtin, R W; Yang, Ye; Nakagava, Edson; Rivero, M; Choi, S K; Rodger, P M

    2008-08-28

    We present molecular dynamics simulation results of a liquid water/methane interface, with and without an oligomer of poly(methylaminoethylmethacrylate), PMAEMA. PMAEMA is an active component of a commercial low dosage hydrate inhibitor (LDHI). Simulations were performed in the constant NPT ensemble at temperatures of 220, 235, 240, 245, and 250 K and a pressure of 300 bar. The simulations show the onset of methane hydrate growth within 30 ns for temperatures below 245 K in the methane/water systems; at 240 K there is an induction period of ca. 20 ns, but at lower temperatures growth commences immediately. The simulations were analyzed to calculate hydrate content, the propensity for hydrogen bond formation, and how these were affected by both temperature and the presence of the LDHI. As expected, both the hydrogen bond number and hydrate content decreased with increasing temperature, though little difference was observed between the lowest two temperatures considered. In the presence of PMAEMA, the temperature below which sustained hydrate growth occurred was observed to decrease. Some of the implications for the role of PMAEMA in LDHIs are discussed.

  7. Hydration modeling of calcium sulphates

    NARCIS (Netherlands)

    de Korte, A.C.J.; Brouwers, H.J.H.; Al-Mattarneh, Hashem; Mustapha, Kamal N.; Nuruddin, Muhd Fadhil

    2008-01-01

    The CEMHYD3D model has been extended at the University of Twente in the last ten years [1,2]. At present the cement hydration model is extended for the use of gypsum. Although gypsum was present in the model already, the model was not suitable for high contents of gypsum and did not include the

  8. Shear bond strengths of tooth coating materials including the experimental materials contained various amounts of multi-ion releasing fillers and their effects for preventing dentin demineralization.

    Science.gov (United States)

    Arita, Shoko; Suzuki, Masaya; Kazama-Koide, Miku; Shinkai, Koichi

    2017-10-01

    We examined shear bond strengths (SBSs) of various tooth-coating-materials including the experimental materials to dentin and demineralization resistance of a fractured adhesive surface after the SBS testing. Three resin-type tooth-coating-materials (BC, PRG Barrier Coat; HC, Hybrid Coat II; and SF, Shield force plus) and two glass-ionomer-type tooth-coating-materials (CV, Clinpro XT Varnish; and FJ, Fuji VII) were selected. The experimental PRG Barrier Coat containing 0, 17, and 33 wt% S-PRG filler (BC0, BC17, and BC33, respectively) were developed. Each tooth-coating-material was applied to flattened dentin surfaces of extracted human teeth for SBS testing. After storing in water for 32 days with 4000 thermal cycling, the specimens were subjected to the SBS test. Specimens after SBS testing were subjected to a pH cycling test, and then, demineralization depths were measured using a polarized-light microscope. ANOVA and Tukey's HSD test were used for statistical analysis. The SBS value of FJ and CV was significantly lower than those of other materials except for BC (p coating-materials demonstrated significantly higher SBS for dentin than the glass-ionomer-type tooth-coating-materials; however, they were inferior to the glass ionomer-type tooth-coating-materials in regards to the acid resistance of the fractured adhesion surface.

  9. Room temperature Cu-Cu direct bonding using surface activated bonding method

    International Nuclear Information System (INIS)

    Kim, T.H.; Howlader, M.M.R.; Itoh, T.; Suga, T.

    2003-01-01

    Thin copper (Cu) films of 80 nm thickness deposited on a diffusion barrier layered 8 in. silicon wafers were directly bonded at room temperature using the surface activated bonding method. A low energy Ar ion beam of 40-100 eV was used to activate the Cu surface prior to bonding. Contacting two surface-activated wafers enables successful Cu-Cu direct bonding. The bonding process was carried out under an ultrahigh vacuum condition. No thermal annealing was required to increase the bonding strength since the bonded interface was strong enough at room temperature. The chemical constitution of the Cu surface was examined by Auger electron spectroscope. It was observed that carbon-based contaminations and native oxides on copper surface were effectively removed by Ar ion beam irradiation for 60 s without any wet cleaning processes. An atomic force microscope study shows that the Ar ion beam process causes no surface roughness degradation. Tensile test results show that high bonding strength equivalent to bulk material is achieved at room temperature. The cross-sectional transmission electron microscope observations reveal the presence of void-free bonding interface without intermediate layer at the bonded Cu surfaces

  10. Growth of hydrated gel layers in nuclear waste glasses

    International Nuclear Information System (INIS)

    Sullivan, T.M.; Machiels, A.J.

    1984-01-01

    The hydration kinetics of waste glasses in contact with an aqueous solution has been studied by using three different approaches. Emphasis has been placed on modeling processes in the transition zone defined as the region in which the nature of the glass changes from the original dry glass to an open hydrated structure. The first model relies on concentration-dependent diffusion coefficients to obtain a transition zone in which the ions mobility is extremely low compared to that in the gel layer. In the second model, the transition zone and hydrated layer are treated as distinct phases and it is assumed that ion exchange at their common boundary is the rate-controlling process. The third model treats the transition zone as a thin film of constant thickness and low diffusivity. In the absence of appreciable network dissolution, all three models indicate that growth of the gel layer becomes eventually proportional to the square root of time; however, as long as processes in the transition zone are rate controlling, growth is linearly proportional to time

  11. Ab initio studies on the solvation, electronic structures and intracluster reactions in M(+)L(n), with M(+)=magnesium and calcium singly-charged ions, L=water, methanol, ammonia, and n=1-6, and the elimination of a hydrogen atom in H atom in hydrated sodium clusters

    Science.gov (United States)

    Chan, Ka Wai

    The solvation and electronic structures of M+Ln, with M+ = Mg+ and Cat, L = H2O, CH 3OH and NH3, n=1-6 were investigated by ab initio calculations using G03 package and density functional theory based ab initio molecular dynamics (AIMD) simulations with projector augmented-wave (PAW) method and a planewave basis set using Vienna Ab initio Simulation Package (VASP). Furthermore, ab initio studies on the intracluster reactions of Mg+ and Ca+ ions with different solvent molecules, H2O, CH3OH and NH3, were also done using G03 package. Finally, the elimination of a H atom in Na(H2O)n was studied. Such studies on the interactions and reactivity in gas clusters can provide insights into their analogies existing in condense phase. Interactions of Mg+ and Ca+ ions in different solvent molecules, H2O, CH3OH and NH3, were calculated with B3LYP and MP2 methods with basis sets 6-31+g** and 6-311+g**. A systematic comparison on the structures and reactivities of these clusters should provide a better understanding on the interplay of the ion-solvent, solvent-solvent, and electron-solvent interactions. It can provide a better understanding on the structures and bonding of complexes having analogies to those existing in condense phase. For Mg+(CH3OH)n and Ca+(CH 3OH)n, both H-elimination from OH/CH bond and CH3-elimination were investigated. H-elimination from O---H bond becomes more accessible for large cluster due to the diffusion of electron density to O---H bond. Studies on the H-elimination in Mg+(NH3)n and H-elimination from C---H bond in Mg+(CH3OH) n show that the reaction barriers flatten above 20 kcal/mol as n reaches 4 and above. These calculation results prove that the source of loss of H atom in ground state Mg+(CH3OH)n should be through the O---H bond rather than through the C---H bond. Compared to Mg+(CH3OH)n, the reaction barriers for H-elimination in Mg+(NH3)n is much larger, which is in consistent with the experimental observation of little H-elimination for Mg

  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. DNA hydration studied by neutron fiber diffraction

    International Nuclear Information System (INIS)

    Fuller, W.; Forsyth, V.T.; Mahendrasingam, A.; Langan, P.; Pigram, W.J.

    1994-01-01

    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

  14. An Examination of the Prediction of Hydrate Formation Conditions in the Presence of Thermodynamic Inhibitors

    Directory of Open Access Journals (Sweden)

    Carollina de M. Molinari O. Antunes

    Full Text Available Abstract Gas hydrates are crystalline compounds, solid structures where water traps small guest molecules, typically light gases, in cages formed by hydrogen bonds. They are notorious for causing problems in oil and gas production, transportation and processing. Gas hydrates may form at pressures and temperatures commonly found in natural gas and oil production pipelines, thus causing partial or complete pipe blockages. In order to inhibit hydrate formation, chemicals such as alcohols (e.g., ethanol, methanol, mono-ethylene glycol and salts (sodium, magnesium or potassium chloride are injected into the produced stream. The purpose of this work is to briefly review the literature on hydrate formation in mixtures containing light gases (hydrocarbons and carbon dioxide and water in the presence of thermodynamic inhibitors. Four calculation methods to predict hydrate formation in those systems were examined and compared. Three commercial packages (Multiflash®, PVTSim® and CSMGem and a hydrate prediction routine in Fortran90 using the van der Waals and Platteeuw theory and the Peng-Robinson equation of state were tested. Predictions given by the four methods were compared to independent experimental data from the literature. In general, the four methods were found to be reasonably accurate. CSMGem and Multiflash® showed the best results.

  15. α-chymotrypsin in water-acetone and water-dimethyl sulfoxide mixtures: Effect of preferential solvation and hydration.

    Science.gov (United States)

    Sirotkin, Vladimir A; Kuchierskaya, Alexandra A

    2017-10-01

    We investigated water/organic solvent sorption and residual enzyme activity to simultaneously monitor preferential solvation/hydration of protein macromolecules in the entire range of water content at 25°C. We applied this approach to estimate protein destabilization/stabilization due to the preferential interactions of bovine pancreatic α-chymotrypsin with water-acetone (moderate-strength H-bond acceptor) and water-DMSO (strong H-bond acceptor) mixtures. There are three concentration regimes for the dried α-chymotrypsin. α-Chymotrypsin is preferentially hydrated at high water content. The residual enzyme activity values are close to 100%. At intermediate water content, the dehydrated α-chymotrypsin has a higher affinity for acetone/DMSO than for water. Residual enzyme activity is minimal in this concentration range. The acetone/DMSO molecules are preferentially excluded from the protein surface at the lowest water content, resulting in preferential hydration. The residual catalytic activity in the water-poor acetone is ∼80%, compared with that observed after incubation in pure water. This effect is very small for the water-poor DMSO. Two different schemes are operative for the hydrated enzyme. At high and intermediate water content, α-chymotrypsin exhibits preferential hydration. However, at intermediate water content, in contrast to the dried enzyme, the initially hydrated α-chymotrypsin possesses increased preferential hydration parameters. At low water content, no residual enzyme activity was observed. Preferential binding of DMSO/acetone to α-chymotrypsin was detected. Our data clearly demonstrate that the hydrogen bond accepting ability of organic solvents and the protein hydration level constitute key factors in determining the stability of protein-water-organic solvent systems. © 2017 Wiley Periodicals, Inc.

  16. Observed gas hydrate morphologies in marine sediment

    Energy Technology Data Exchange (ETDEWEB)

    Holland, M.; Schultheiss, P.; Roberts, J.; Druce, M. [Geotek Ltd., Daventry, Northamptonshire (United Kingdom)

    2008-07-01

    The morphology of gas hydrate in marine sediments determines the basic physical properties of the sediment-hydrate matrix and provides information regarding the formation of gas hydrate deposits, and the nature of the disruption that will occur on dissociation. Small-scale morphology is useful in estimating the concentrations of gas hydrate from geophysical data. It is also important for predicting their response to climate change or commercial production. Many remote techniques for gas hydrate detection and quantification depend on hydrate morphology. In this study, morphology of gas hydrate was examined in HYACINTH pressure cores from recent seagoing expeditions. Visual and infrared observations from non-pressurized cores were also used. The expeditions and pressure core analysis were described in detail. This paper described the difference between two types of gas hydrate morphologies, notably pore-filling and grain-displacing. Last, the paper addressed the impact of hydrate morphology. It was concluded that a detailed morphology of gas hydrate is an essential component for a full understanding of the past, present, and future of any gas hydrate environment. 14 refs., 4 figs.

  17. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K

    1996-12-31

    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.

  18. 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.

  19. Influence of fluorosurfactants on hydrate formation rates

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  20. Investigation of the Methane Hydrate Formation by Cavitation Jet

    Science.gov (United States)

    Morita, H.; Nagao, J.

    2015-12-01

    Methane hydrate (hereafter called "MH") is crystalline solid compound consisting of hydrogen-bonded water molecules forming cages and methane gas molecules enclosed in the cage. When using MH as an energy resource, MH is dissociated to methane gas and water and collect only the methane gas. The optimum MH production method was the "depressurization method". Here, the production of MH means dissociating MH in the geologic layers and collecting the resultant methane gas by production systems. In the production of MH by depressurization method, MH regeneration was consider to important problem for the flow assurance of MH production system. Therefore, it is necessary to clarify the effect of flow phenomena in the pipeline on hydrate regeneration. Cavitation is one of the flow phenomena which was considered a cause of MH regeneration. Large quantity of microbubbles are produced by cavitation in a moment, therefore, it is considered to promote MH formation. In order to verify the possible of MH regeneration by cavitation, it is necessary to detailed understanding the condition of MH formation by cavitation. As a part of a Japanese National hydrate research program (MH21, funded by METI), we performed a study on MH formation using by cavitation. The primary objective of this study is to demonstrate the formation MH by using cavitation in the various temperature and pressure condition, and to clarify the condition of MH formation by using observation results.

  1. Dynamics of Permafrost Associated Methane Hydrate in Response to Climate Change

    Science.gov (United States)

    You, K.; Flemings, P. B.

    2014-12-01

    The formation and melting of methane hydrate and ice are intertwined in permafrost regions. A shortage of methane supply leads to formation of hydrate only at depth, below the base of permafrost. We consider a system with the ground surface initially at 0 oC with neither ice nor hydrate present. We abruptly decrease the temperature from 0 to -10 oC to simulate the effect of marine regression/ global cooling. A low methane supply rate of 0.005 kg m-2 yr-1 from depth leads to distinct ice and hydrate layers: a 100 m continuous hydrate layer is present beneath 850 m at 80 k.y.. However, a high methane supply rate of 0.1 kg m-2 yr-1 leads to 50 m ice-bonded methane hydrate at the base of permafrost, and the hydrate layer distributes between the depth of 350 and 700 m at 80 k.y.. We apply our model to illuminate future melting of hydrate at Mallik, a known Arctic hydrate accumulation. We assume a 600 m thick ice saturated (average 90%) layer extending downward from the ground surface. We increase the surface temperature linearly from -6 to 0 oC for 300 yr and then keep the surface temperature at 0 oC to reflect future climate warming caused by doubling of CO2. Hydrate melting is initiated at the base of the hydrate layer after 15 k.y.. Methane gas starts to vent to the atmosphere at 38 k.y. with an average flux of ~ 0.35 g m-2 yr-1. If the 600 m thick average ice saturation is decreased to half (45%) (or to zero), methane gas starts to vent to the atmosphere at 29 k.y. (or at 20 k.y.) with the same average flux. These results are found by a newly-developed fully-coupled multiphase multicomponent fluid flow and heat transport model. Our thermodynamic equilibrium-based model emphasizes the role of salinity in both ice and hydrate dynamics.

  2. Phenylmercuric hydroxide. A highly selective reagent for the hydration of nonconjugated terminal alkynes

    International Nuclear Information System (INIS)

    Janout, V.; Regen, S.L.

    1982-01-01

    This article describes an unusual and highly selective method for hydrating nonconjugated terminal alkynes based on the use of phenylmercuric hydroxide as a reagent. Unlike classical mercury catalyzed procedures, sigma-bonded mercury acetylides are formed initially as stable intermediates and subsequently reacted with water under neutral pH to form the corresponding methyl ketone. Isolated yields which have been obtained by using this approach lie in the range of 49-65%. The high selectivity toward nonconjugated terminal alkynes which characterizes the procedure described herein should make it a useful supplement to existing hydration methods

  3. 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.

  4. Molecular structure of self-assembled chiral nanoribbons and nanotubules revealed in the hydrated state.

    Science.gov (United States)

    Oda, Reiko; Artzner, Franck; Laguerre, Michel; Huc, Ivan

    2008-11-05

    A detailed molecular organization of racemic 16-2-16 tartrate self-assembled multi-bilayer ribbons in the hydrated state is proposed where 16-2-16 amphiphiles, tartrate ions, and water molecules are all accurately positioned by comparing experimental X-ray powder diffraction and diffraction patterns derived from modeling studies. X-ray diffuse scattering studies show that molecular organization is not fundamentally altered when comparing the flat ribbons of the racemate to chirally twisted or helical ribbons of the pure tartrate enantiomer. Essential features of the three-dimensional molecular organizations of these structures include interdigitation of alkyl chains within each bilayer and well-defined networks of ionic and hydrogen bonds between cations, anions, and water molecules between bilayers. The detailed study of diffraction patterns also indicated that the gemini headgroups are oriented parallel to the long edge of the ribbons. The structure thus possesses a high cohesion and good crystallinity, and for the first time, we could relate the packing of the chiral molecules to the expression of the chirality at a mesoscopic scale. The organization of the ribbons at the molecular level sheds light on a number of their macroscopic features. Among these are the reason why enantiomerically pure 16-2-16 tartrate forms ribbons that consist of exactly two bilayers, and a plausible mechanism by which a chirally twisted or helical shape may emerge from the packing of chiral tartrate ions. Importantly, the distinction between commonly observed helical and twisted morphologies could be related to a subtle symmetry breaking. These results demonstrate that accurately solving the molecular structure of self-assembled soft materials--a process rarely achieved--is within reach, that it is a valid approach to correlate molecular parameters to macroscopic properties, and thus that it offers opportunities to modulate properties through molecular design.

  5. Properties of clusters in the gas phase: V. Complexes of neutral molecules onto negative ions

    International Nuclear Information System (INIS)

    Keesee, R.G.; Lee, N.; Castleman, A.W. Jr.

    1980-01-01

    Ion--molecules association reactions of the form A - (B)/sub n1/-+B=A - (B)/sub n/ were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl - , I - , and NO 2 - with n ranging from one to three or four, and onto SO 2 - and SO 3 - with n equal to one; and (2) carbon dioxide onto Cl - , I - , NO 2 - , CO 3 - , and SO 3 - with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions. For any given ion, the relative order of the addition enthalpies among the neutrals was found to be dependent on the polarizabilities of the neutrals and on the covalency in the ion-neutral bond. Dispersion of charge via covalent bonding was found to affect significantly the succeeding clustering steps

  6. Hydration patterns and salting effects in sodium chloride solution.

    Science.gov (United States)

    Li, Weifeng; Mu, Yuguang

    2011-10-07

    The salting effects of 2M sodium chloride electrolyte are studied based on a series of model solutes with properties ranging from hydrophobic to hydrophilic. Generally, hydrophobic solutes will be salted out and hydrophilic solutes will be salted in by NaCl solution. The solvation free energy changes are highly correlated with Kirkwood-Buff integrals. The underlying mechanism resorts to the preferential binding of ions and water to solutes. Our results demonstrate that the salting effect not only depends on the salt's position in Hofmeister series, but also on the solutes' specifics. Taking the hydration free energies of solutes and ions as independent variables, a schematic diagram of salting effects is suggested. The resolved multifaceted salting effects rely on the sensitive balance of the tripartite interaction among solutes, ions, and water. © 2011 American Institute of Physics

  7. Bond strength of masonry

    NARCIS (Netherlands)

    Pluijm, van der R.; Vermeltfoort, A.Th.

    1992-01-01

    Bond strength is not a well defined property of masonry. Normally three types of bond strength can be distinguished: - tensile bond strength, - shear (and torsional) bond strength, - flexural bond strength. In this contribution the behaviour and strength of masonry in deformation controlled uniaxial

  8. Fire extinction utilizing carbon dioxide hydrate

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  9. 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......Solid-state, magic-angle spinning (MAS) NMR spectroscopy represents a valuable tool for structural investigations on the nanoscale of the most important phases in anhydrous and hydrated Portland cements and of various admixtures. This is primarily due to the fact that the method reflects the first......- and second-coordination spheres of the spin nucleus under investigation while it is less sensitive to long-range order. Thus, crystalline as well as amorphous phases can be detected in a quantitative manner by solid-state NMR. In particular the structure of the calcium-silicate-hydrate (C-S-H) phase have...

  10. 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.

  11. 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.

  12. Bond energies of ThO{sup +} and ThC{sup +}: A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O{sub 2} and CO

    Energy Technology Data Exchange (ETDEWEB)

    Cox, Richard M; Citir, Murat; Armentrout, P. B., E-mail: armentrout@chem.utah.edu [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850 (United States); Battey, Samuel R.; Peterson, Kirk A. [Department of Chemistry, Washington State University, Pullman, Washington 99164-4630 (United States)

    2016-05-14

    Kinetic energy dependent reactions of Th{sup +} with O{sub 2} and CO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO{sup +} in the reaction of Th{sup +} with O{sub 2} is observed to be exothermic and barrierless with a reaction efficiency at low energies of k/k{sub LGS} = 1.21 ± 0.24 similar to the efficiency observed in ion cyclotron resonance experiments. Formation of ThO{sup +} and ThC{sup +} in the reaction of Th{sup +} 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 D{sub 0}(Th{sup +}–O) = 8.57 ± 0.14 eV and D{sub 0}(Th{sup +}–C) = 4.82 ± 0.29 eV. The present value of D{sub 0} (Th{sup +}–O) is within experimental uncertainty of previously reported experimental values, whereas this is the first report of D{sub 0} (Th{sup +}–C). Both BDEs are observed to be larger than those of their transition metal congeners, TiL{sup +}, ZrL{sup +}, and HfL{sup +} (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{sup +}, ThO, and ThO{sup +}, 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{sup +} BDE is compared to other actinide (An) oxide cation BDEs and a simple model utilizing An{sup +} promotion energies to the reactive state is used to estimate AnO{sup +} and AnC{sup +} BDEs. For AnO{sup +}, this model yields predictions that are typically within experimental uncertainty and performs better than density functional theory calculations presented previously.

  13. The effect of bond characteristics between steel slag fine aggregate and cement paste on mechanical properties of concrete and mortar

    International Nuclear Information System (INIS)

    Yuji, W.

    1988-01-01

    The ordinary fine aggregate in concrete has been replaced by ground and sieved steel slag fine aggregate, treated and exposed to air for three months. Compared with concrete made from natural sand, properties such as compressive strength, flexural strength, elastic modules, permeability and abrasion resistance are considerably improved. The improvement increases with a decrease in w/c ratio, an increase in curing time and an increase in the replacement weight of sand. These results are due to the fact that the steel slag contains some active minerals such as C/sub 3/S, C/sub 2/S, C/sub 4/AF, etc., and shows favorable surface physical characteristics that improve the bond between steel slag particles and cement paste. The results of XRD, SEM and EPM microhardness showed that there are heavier concentration of ions, with finer crystals and a lower degree of CH orientation at the interfacial zone between steel slag particles and cement paste. The study also found small cementitious and fibrous C-S-H crystals growing from the fine aggregate, which are linked with hydrated products form cement paste making the bond and structural characteristic more favorable with cement. The steel slag fine aggregate is an active mineral similar to cement. The bond between the aggregate and cement paste is strengthened both physically and chemically

  14. NMR spectroscopic determination of an equilibrium isotope effect on the hydration of cobalt(II)

    International Nuclear Information System (INIS)

    Evilia, R.F.; Saunders, M.

    1985-01-01

    A recently reported NMR method for the measurement of deuterium equilibrium isotope effects is applied to the hydration of the paramagnetic cobalt(II) ion. An isotope effect of about 1.3% is measured. A substantial difference between the intrinsic shift of H 2 O and D 2 O when coordinated to cobalt is also measured

  15. Tensile strength of hydrated cement paste phases assessed by microbending tests and nanoindentation

    Czech Academy of Sciences Publication Activity Database

    Němeček, J.; Králík, V.; Šmilauer, V.; Polívka, Leoš; Jäger, Aleš

    2016-01-01

    Roč. 73, Oct (2016), 164-173 ISSN 0958-9465 R&D Projects: GA ČR GBP108/12/G043 Institutional support: RVO:68378271 Keywords : cement * hydration products * micro-beam * tensile strength * fracture energy * nanoindentation * focused ion beam Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.265, year: 2016

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  17. 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....

  18. 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 D.

    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.

  19. Polyethylene glycol drilling fluid for drilling in marine gas hydrates-bearing sediments: an experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, G.; Liu, T.; Ning, F.; Tu, Y.; Zhang, L.; Yu, Y.; Kuang, L. [China University of Geosciences, Faculty of Engineering, Wuhan (China)

    2011-07-01

    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{sub 2}CO{sub 3}, 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 {sup o}C to 15 {sup o}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. (authors)

  20. 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.

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

    Science.gov (United States)

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

    2013-07-01

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

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

    Science.gov (United States)

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

    2017-12-01

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

  3. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    Undervisningsmateriale. A bond is a debt security, similar to an ”I Owe You document” (IOU). When you purchase a bond, you are lending money to a government, municipality, corporation, federal agency or other entity known as the issuer. In return for the loan, the issuer promises to pay you...... a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...... securities and foreign government bonds....

  4. Monitoring early hydration of reinforced concrete structures using structural parameters identified by piezo sensors via electromechanical impedance technique

    Science.gov (United States)

    Talakokula, Visalakshi; Bhalla, Suresh; Gupta, Ashok

    2018-01-01

    Concrete is the most widely used material in civil engineering construction. Its life begins when the hydration process is activated after mixing the cement granulates with water. In this paper, a non-dimensional hydration parameter, obtained from piezoelectric ceramic (PZT) patches bonded to rebars embedded inside concrete, is employed to monitor the early age hydration of concrete. The non-dimensional hydration parameter is derived from the equivalent stiffness determined from the piezo-impedance transducers using the electro-mechanical impedance (EMI) technique. The focus of the study is to monitor the hydration process of cementitious materials commencing from the early hours and continue till 28 days using single non-dimensional parameter. The experimental results show that the proposed piezo-based non-dimensional hydration parameter is very effective in monitoring the early age hydration, as it has been derived from the refined structural impedance parameters, obtained by eliminating the PZT contribution, and using both the real and imaginary components of the admittance signature.

  5. Nonlinear fluid dynamics of nanoscale hydration water layer

    Science.gov (United States)

    Jhe, Wonho; Kim, Bongsu; Kim, Qhwan; An, Sangmin

    In nature, the hydration water layer (HWL) ubiquitously exists in ambient conditions or aqueous solutions, where water molecules are tightly bound to ions or hydrophilic surfaces. It plays an important role in various mechanisms such as biological processes, abiotic materials, colloidal interaction, and friction. The HWL, for example, can be easily formed between biomaterials since most biomaterials are covered by hydrophilic molecules such as lipid bilayers, and this HWL is expected to be significant to biological and physiological functions. Here (1) we present the general stress tensor of the hydration water layer. The hydration stress tensor provided the platform form for holistic understanding of the dynamic behaviors of the confined HWL including tapping and shear dynamics which are until now individually studied. And, (2) through fast shear velocity ( 1mm/s) experiments, the elastic turbulence caused by elastic property of the HWL is indirectly observed. Our results may contribute to a deeper study of systems where the HWL plays an important role such as biomolecules, colloidal particles, and the MEMS. This work was supported by the National Research Foundation of Korea(NRF) Grant funded by the Korea government(MSIP) (2016R1A3B1908660).

  6. Physical Properties of Gas Hydrates: A Review

    Energy Technology Data Exchange (ETDEWEB)

    Gabitto, Jorge [Prairie View A& M University; Tsouris, Costas [ORNL

    2010-01-01

    Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

  7. Accelerated hydration of high silica cements

    International Nuclear Information System (INIS)

    Walker, Colin; Yui, Mikazu

    2012-01-01

    Current Japanese designs for high level radioactive waste (HLW) repositories anticipate the use of both bentonite (buffer and backfill material) and cement based materials. Using hydrated Ordinary Portland Cement (OPC) as a grouting material is undesirable because the associated high pH buffer will have an undisputed detrimental effect on the performance of the bentonite buffer and backfill and of the host rock by changing its porosity. Instead, hydrated low pH cement (LopHC) grouting materials are being developed to provide a pH inferior or equal to 11 to reduce these detrimental effects. LopHC grouting materials use mixtures of superfine OPC (SOPC) clinker and silica fume (SF), and are referred as high silica cements (HSC). The focus of the present study was to identify the development of the unhydrated and hydrated mineral assemblage and the solution chemistry during the hydration of HSC. Since hydration experiments of cementitious materials are notably slow, a ball mill was used to accelerate hydration. This was done for two reasons. Firstly, to develop a method to rapidly hydrate cement based materials without the need for higher temperatures (which can alter the mineral assemblage), and secondly, to ensure that the end point of hydration was reached in a reasonable time frame and so to realize the final mineralogy and solution chemistry of hydrated HSC

  8. Microstructure of natural hydrate host sediments

    International Nuclear Information System (INIS)

    Jones, K.W.; Kerkar, P.B.; Mahajan, D.; Lindquist, W.B.; Feng, H.

    2007-01-01

    There is worldwide interest in the study of natural gas hydrate because of its potential impact on world energy resources, control on seafloor stability, significance as a drilling hazard and probable impact on climate as a reservoir of a major greenhouse gas. Gas hydrates can (a) be free floating in the sediment matrix (b) contact, but do not cement, existing sediment grains, or (c) actually cement and stiffen the bulk sediment. Seismic surveys, often used to prospect for hydrates over a large area, can provide knowledge of the location of large hydrate concentrations because the hydrates within the sediment pores modify seismic properties. The ability to image a sample at the grain scale and to determine the porosity, permeability and seismic profile is of great interest since these parameters can help in determining the location of hydrates with certainty. We report here on an investigation of the structure of methane hydrate sediments at the grain-size scale using the synchrotron radiation-based computed microtomography (CMT) technique. Work has started on the measurements of the changes occurring as tetrahydrofuran hydrate, a surrogate for methane hydrate, is formed in the sediment

  9. THE ROLE OF HYDRATION IN THE HYDROLYSIS OF PYROPHOSPHATE - A MONTE-CARLO SIMULATION WITH POLARIZABLE-TYPE INTERACTION POTENTIALS

    NARCIS (Netherlands)

    STMARTIN, H; ORTEGABLAKE, [No Value; LES, A; ADAMOWICZ, L

    1994-01-01

    The exchange of energy in biochemical reactions involves, in a majority of cases, the hydrolysis of phosphoanhydrides (P-O-P). This discovery has lead to a long discussion about the origin of the high energy of such bonds, and to a proposal that hydration plays a major role in the energetics of the

  10. Structures and the Hydrogen Bonding Abilities of Estrogens Studied by Supersonic Jet/laser Spectroscopy

    Science.gov (United States)

    Morishima, Fumiya; Inokuchi, Yoshiya; Ebata, Takayuki

    2013-06-01

    Estrone, estradiol, estriol are known as endogenous estrogen which have the same steroidal frame with different substituent, leading to difference of physiological activity upon the formation of hydrogen bond with estrogen receptor. In the present study, structures of estrogens and their hydrated clusters in a supersonic jet have been studied by various laser spectroscopic techniques and density functional theory calculation to study how the difference of substituents affects their hydrogen bonding ability. Infrared spectra in the OH stretching region indicate a formation of intramolecular hydrogen-bond in estriol, which may lead to weaker physiological activity among the three estrogens. We also measured electronic and infrared spectra of 1:1 hydrated clusters of estrogen. The results show a switch of stable hydration site from the phenolic OH group to the five member ring by substituting one more OH group.

  11. 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…

  12. Effect of cations on the hydrated proton.

    Science.gov (United States)

    Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J

    2014-09-17

    We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

  13. 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...

  14. 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...... produces an elongation of 0.102 (7) Angstrom of the Co-N bond to the 1,4,7-triazacyclononane N atom in the trans position. This relatively small trans influence is presumably a result of the triamine ligand forming strong bonds to the Co-III atom....

  15. Vibrational transitions in hydrogen bonded bimolecular complexes – A local mode perturbation theory approach to transition frequencies and intensities

    DEFF Research Database (Denmark)

    Mackeprang, Kasper; Kjærgaard, Henrik Grum

    2017-01-01

    The local mode perturbation theory (LMPT) model was developed to improve the description of hydrogen bonded XH-stretching transitions, where X is typically O or N. We present a modified version of the LMPT model to extend its application from hydrated bimolecular complexes to hydrogen bonded...

  16. Differential scanning calorimetric study of the binding between native DNA and its primary water of hydration.

    Science.gov (United States)

    Marlowe, R. L.; Lukan, A. M.; Lee, S. A.; Anthony, L.; Rupprecht, A.

    1996-03-01

    Differential scanning calorimetry was used to measure the binding strength between calf-thymus DNA and its primary water of hydration. The specific heat of wet-spun films was found to have a broad endothermic transition near 80 ^oC and a sharp exothermic transition near 250 ^oC. The broad transition is believed to be mainly due to the breaking of the bonds of the strongly bound water of hydration. This transition was found to be reversible, as expected. Kissinger analysis indicates that the activation barrier for breaking the bonds of these water molecules is about 0.6 eV. The sharp transition appeared to be an indication of a thermal decomposition of the DNA. Samples taken above this transition lost mass, showed evidence of having melted, and had turned black in color. This transition is irreversible.

  17. 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.

  18. Hydrogen speciation in hydrated layers on nuclear waste glass

    International Nuclear Information System (INIS)

    Aines, R.D.; Weed, H.C.; Bates, J.K.

    1987-01-01

    The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 and 165, and PNL 76-68), which were leached at 90 0 C (all glasses) or hydrated in a vapor-saturated atmosphere at 202 0 C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was found in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 μm layer on SRL-131 glass formed by leaching at 90 0 C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H + interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups

  19. Gas Hydrates | Alaska Division of Geological & Geophysical Surveys

    Science.gov (United States)

    Preliminary Report - Cascadia Margin Gas Hydrates, Volume 204 Initial Report Mallik 2002 GSC Bulletin 585 : Scientific results from the Mallik 2002 gas hydrate production well program Offshore gas hydrate sample

  20. Simulation and Characterization of Methane Hydrate Formation

    Science.gov (United States)

    Dhakal, S.; Gupta, I.

    2017-12-01

    The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate

  1. 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

  2. Influence of polymeric excipient properties on crystal hydrate formation kinetics of caffeine in aqueous slurries.

    Science.gov (United States)

    Gift, Alan D; Southard, Leslie A; Riesberg, Amanda L

    2012-05-01

    The influence of polymeric excipients on the hydrate transformation of caffeine (CAF) was studied. Anhydrous CAF was added to aqueous solutions containing different additives and the transformation to the hydrate form was monitored using in-line Raman spectroscopy. Various properties of two known inhibitors of CAF hydrate formation, polyacrylic acid (PAA) and polyvinyl alcohol (PVA), were investigated. For inhibition by PAA, a pH dependence was observed: at low pH, the inhibition was greatest, whereas no inhibitory effects were observed at pH above 6.5. For PVA, grades with high percent hydrolysis were the most effective at inhibiting the transformation. In addition, PVA with higher molecular weight showed slightly more inhibition than the shorter chain PVA polymers. A variety of other hydroxyl containing compounds were examined but none inhibited the CAF anhydrate-to-hydrate transformation. The observed inhibitory effects of PAA and PVA are attributed to the large number of closely spaced hydrogen bond donating groups of the polymer molecule, which can interact with the CAF hydrate crystal. Copyright © 2012 Wiley Periodicals, Inc.

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

    Directory of Open Access Journals (Sweden)

    Carugo Oliviero

    2011-10-01

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

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

    International Nuclear Information System (INIS)

    Bouchemoua, A.

    2012-01-01

    CO 2 capture and sequestration represent a major industrial and scientific challenge of this century. There are different methods of CO 2 separation and capture, such as solid adsorption, amines adsorption and cryogenic fractionation. Although these processes are well developed at industrial level, they are energy intensive. Hydrate formation method is a less energy intensive and has an interesting potential to separate carbon dioxide. Gas hydrates are Document crystalline compounds that consist of hydrogen bonded network of water molecules trapping a gas molecule. Gas hydrate formation is favored by high pressure and low temperature. This study was conducted as a part of the SECOHYA ANR Project. The objective is to study the thermodynamic and kinetic conditions of the process to capture CO 2 by gas hydrate crystallization. Firstly, we developed an experimental apparatus to carry out experiments to determine the thermodynamic and kinetic formation conditions of CO 2 -N 2 gas hydrate mixture in water as liquid phase. We showed that the operative pressure may be very important and the temperature very low. For the feasibility of the project, we used TBAB (Tetrabutylammonium Bromide) as thermodynamic additive in the liquid phase. The use of TBAB may reduce considerably the operative pressure. In the second part of this study, we presented a thermodynamic model, based on the van der Waals and Platteeuw model. This model allows the estimation of thermodynamic equilibrium conditions. Experimental equilibrium data of CO 2 -CH 4 and CO 2 -N 2 mixtures are presented and compared to theoretical results. (author)

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    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 V E as a function of ethanol mole fraction X 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. Role of interatomic bonding in the mechanical anisotropy and interlayer cohesion of CSH crystals

    Energy Technology Data Exchange (ETDEWEB)

    Dharmawardhana, C.C. [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States); Misra, A. [Department of Civil, Environmental, and Architectural Engineering, University of Kansas, Lawrence, KS 66045 (United States); Aryal, S.; Rulis, P. [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States); Ching, W.Y., E-mail: ccdxz8@mail.umkc.edu [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States)

    2013-10-15

    Atomic scale properties of calcium silicate hydrate (CSH), the main binding phase of hardened Portland cement, are not well understood. Over a century of intense research has identified almost 50 different crystalline CSH minerals which are mainly categorized by their Ca/Si ratio. The electronic structure and interatomic bonding in four major CSH crystalline phases with structures close to those found in hardened cement are investigated via ab initio methods. Our result reveals the critical role of hydrogen bonding and importance of specifying precise locations for water molecules. Quantitative analysis of contributions from different bond types to the overall cohesion shows that while the Si-O covalent bonds dominate, the hydrogen bonding and Ca-O bonding are also very significant. Calculated results reveal the correlation between bond topology and interlayer cohesion. The overall bond order density (BOD) is found to be a more critical measure than the Ca/Si ratio in classifying different CSH crystals.

  7. The effects of mucopolysaccharide polysulphate on hydration and elasticity of human skin.

    Science.gov (United States)

    Wanitphakdeedecha, Rungsima; Eimpunth, Sasima; Manuskiatti, Woraphong

    2011-01-01

    Background. Mucopolysaccharide polysulphate (MPS) has been used in medicine as an anti-inflammatory and antithrombotic agent for over 50 years. Its chemical structure permits considerable hydrogen bonding with adjacent water molecules, which effectively leads to hydration of the surrounding tissue. In addition, it stimulates endogenous hyaluronate synthesis, resulting in an increase in water-binding capacity and viscoelasticity of the skin. Objective. To study the efficacy of 0.1% MPS on hydration and elasticity of human skin. Methods. The first part of this study was a randomized double blind placebo-controlled study which included 60 female volunteers aged 30-45 years with dry skin, defined by Corneometer CM 825. The volunteers were treated with either 0.1% MPS or vehicle control. All subjects were asked to apply 1 g of cream to their face twice daily for a total period of 4 weeks. Skin hydration and elasticity were measured at baseline and week 4 with Corneometer CM 825 and cutometer MPA 580, respectively, at forehead and both cheeks. The second part of this study focused on the efficacy of 0.1% MPS on skin hydration after single application. 20 female volunteers aged 30-45 years with dry skin, defined by Corneometer CM 825, were recruited to the study. All subjects were asked to apply 2 g of 0.1% MPS cream on entirely randomly selected forearm. Skin hydration at the middle of both forearms was measured at baseline, immediately after application, and every 1 hour after application for a period of 10 hours. Results. 57 subjects (28 in vehicle control group, 29 in MPS) completed treatment protocol. The baseline skin hydration of both groups was not significantly different (P = 0.47). Hower, there was a statistically significant difference in skin hydration at 4 weeks between MPS and placebo group (P = 0.01). Skin elasticity was significantly improved at week 4 in both groups (vehicle-control, P skin elasticity between MPS and vehicle-control group

  8. Free energy of hydration of niobium oxide

    International Nuclear Information System (INIS)

    Plodinec, M.J.

    1996-01-01

    Some of the glasses being formulated by SRTC researchers contain niobium oxide. In this report, the free energy of hydration of the oxide is calculated from the free energies of formation of the oxide, the hydroxide, and water. This value can be used in calculations of the free energy of hydration of glasses containing niobium

  9. 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)

  10. 75 FR 9886 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2010-03-04

    ... DEPARTMENT OF ENERGY Methane Hydrate Advisory Committee AGENCY: Department of Energy, Office of Fossil Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane... the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice on potential...

  11. 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....

  12. Multicomponent modelling of Portland cement hydration reactions

    NARCIS (Netherlands)

    Ukrainczyk, N.; Koenders, E.A.B.; Van Breugel, K.

    2012-01-01

    The prospect of cement and concrete technologies depends on more in depth understanding of cement hydration reactions. Hydration reaction models simulate the development of the microstructures that can finally be used to estimate the cement based material properties that influence performance and

  13. 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

  14. Experimental Setup to Characterize Bentonite Hydration Processes

    International Nuclear Information System (INIS)

    Bru, A.; Casero, D.; Pastor, J. M.

    2001-01-01

    We present an experimental setup to follow-up the hydration process of a bentonite. Clay samples, of 2 cm x 12 cm x 12 cm, were made and introduced in a Hele-Shaw cell with two PMM windows and two steel frames. In hydration experiments, a fluid enters by an orifice in the frame, located both at the top and the bottom of the cell, to perform hydration in both senses. To get a uniform hydration we place a diffuser near the orifice. Volume influxes in hydration cells are registered in time. The evolution of the developed interface was recorded on a videotape. The video cameras was fixed to a holder so that the vertical direction in the monitor was the same as the direction of the larger extension of the cell. (Author) 6 refs

  15. Volume of hydration in terminal cancer patients.

    Science.gov (United States)

    Bruera, E; Belzile, M; Watanabe, S; Fainsinger, R L

    1996-03-01

    In this retrospective study we reviewed the volume and modality of hydration of consecutive series of terminal cancer patients in two different settings. In a palliative care unit 203/290 admitted patients received subcutaneous hydration for 12 +/- 8 days at a daily volume of 1015 +/- 135 ml/day. At the cancer center, 30 consecutive similar patients received intravenous hydration for 11.5 +/- 5 days (P > 0.2) but at a daily volume of 2080 +/- 720 ml/day (P palliative care unit patients required discontinuation of hydration because of complications. Hypodermoclysis was administered mainly as a continuous infusion, an overnight infusion, or in one to three 1-h boluses in 62 (31%), 98 (48%) and 43 (21%) patients, respectively. Our findings suggest that, in some settings, patients may be receiving excessive volumes of hydration by less comfortable routes such as the intravenous route. Increased education and research in this area are badly needed.

  16. Hydration shells exchange charge with their protein

    DEFF Research Database (Denmark)

    Abitan, Haim; Lindgård, Per-Anker; Nielsen, Bjørn Gilbert

    2010-01-01

    . In our experiments, the amplitude of an ultrasonic pressure wave is gradually increased (0–20 atm) while we simultaneously measure the Raman spectra from the hydrated protein (β-lactoglobulin and lysozyme). We detected two types of spectral changes: first, up to 70% increase in the intensity......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...... the presence of an ultrasonic pressure, a protein and its hydration shells are in thermodynamic and charge equilibrium, i.e. a protein and its hydration shells exchange charges. The ultrasonic wave disrupts these equilibria which are regained within 30–45 min after the ultrasonic pressure is shut off....

  17. Modeling of Cation Binding in Hydrated 2:1 Clay Minerals - Final Report

    International Nuclear Information System (INIS)

    Smith, David E.

    2000-01-01

    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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-28

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

  19. Direct current-induced electrogenerated chemiluminescence of hydrated and chelated Tb(III) at aluminum cathodes

    International Nuclear Information System (INIS)

    Hakansson, M.; Jiang, Q.; Spehar, A.-M.; Suomi, J.; Kotiranta, M.; Kulmala, S.

    2005-01-01

    Cathodic DC polarization of oxide-covered aluminum produces electrogenerated chemiluminescence from hydrated and chelated Tb(III) ions in aqueous electrolyte solutions. At the moment of cathodic voltage onset, a strong cathodic flash is observed, which is attributed to a tunnel emission of hot electrons into the aqueous electrolyte solution and the successive chemical reactions with the luminophores. However, within a few milliseconds the insulating oxide film is damaged and finally dissolved due to (i) indiffusion of protons or alkali metal ions into the thin oxide film, (ii) subsequent hydrogen evolution at the aluminum/oxide interface and (iii) alkalization of the electrode surface induced by hydrogen evolution reaction. When the alkalization of the electrode surface has proceeded sufficiently, chemiluminescence is generated with increasing intensity. Aluminum metal, short-lived Al(II), Al(I) or atomic hydrogen and its conjugated base form, hydrated electron, can act as highly reducing species in addition to the less energetic heterogeneously transferred electrons from the aluminum electrode. Tb(III) added as a hydrated ion in the solution probably luminesces in the form of Tb(OH) 3 or Tb(OH) 4 - by direct redox reactions of the central ion whereas multidentate aromatic ligand chelated Tb(III) probably luminesces by ligand sensitized chemiluminescence mechanism in which ligand is first excited by one-electron redox reactions, which is followed by intramolecular energy transfer to the central ion which finally emits light

  20. Ion bonding in organic scaffolding promotes biomineralization

    NARCIS (Netherlands)

    Hamers, L.; Sommerdijk, N.A.J.M.

    2015-01-01

    The seashells you pick up at the beach might not seem extraordinary, but they’re a source of inspiration for researchers, whether seeking new routes to making materials or searching for efficient ways to store extra atmospheric carbon. Through a process called biomineralization, organisms like

  1. 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

  2. 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.

  3. Protein Stabilization and Enzyme Activation in Ionic Liquids: Specific Ion Effects

    Science.gov (United States)

    Zhao, Hua

    2015-01-01

    There are still debates on whether the hydration of ions perturbs the water structure, and what is the degree of such disturbance; therefore, the origin of Hofmeister effect on protein stabilization continues being questioned. For this reason, it is suggested to use the ‘specific ion effect’ instead of other misleading terms such as Hofmeister effect, Hofmeister series, lyotropic effect, and lyotropic series. In this review, we firstly discuss the controversial aspect of inorganic ion effects on water structures, and several possible contributors to the specific ion effect of protein stability. Due to recent overwhelming attraction of ionic liquids (ILs) as benign solvents in many enzymatic reactions, we further evaluate the structural properties and molecular-level interactions in neat ILs and their aqueous solutions. Next, we systematically compare the specific ion effects of ILs on enzyme stability and activity, and conclude that (a) the specificity of many enzymatic systems in diluted aqueous IL solutions is roughly in line with the traditional Hofmeister series albeit some exceptions; (b) however, the specificity follows a different track in concentrated or neat ILs because other factors (such as hydrogen-bond basicity, nucelophilicity, and hydrophobicity, etc) are playing leading roles. In addition, we demonstrate some examples of biocatalytic reactions in IL systems that are guided by the empirical specificity rule. PMID:26949281

  4. Hydrogen-bond coordination in organic crystal structures: statistics, predictions and applications.

    Science.gov (United States)

    Galek, Peter T A; Chisholm, James A; Pidcock, Elna; Wood, Peter A

    2014-02-01

    Statistical models to predict the number of hydrogen bonds that might be formed by any donor or acceptor atom in a crystal structure have been derived using organic structures in the Cambridge Structural Database. This hydrogen-bond coordination behaviour has been uniquely defined for more than 70 unique atom types, and has led to the development of a methodology to construct hypothetical hydrogen-bond arrangements. Comparing the constructed hydrogen-bond arrangements with known crystal structures shows promise in the assessment of structural stability, and some initial examples of industrially relevant polymorphs, co-crystals and hydrates are described.

  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. Can hydrate dissolution experiments predict the fate of a natural hydrate system?

    Energy Technology Data Exchange (ETDEWEB)

    Hester, K.C.; Peltzer, E.T.; Dunk, R.M.; Walz, P.M.; Brewer, P.G. [Monterey Bay Aquarium Research Inst., Moss Landing, CA (United States); Dendy Sloan, E. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

    2008-07-01

    Gas hydrates are naturally occurring compounds found in permafrost regions and in oceans. In the natural environment, sufficient temperature and pressure conditions for hydrate formation exist over a significant portion of the ocean. However, in addition to pressure and temperature, the chemical potential of the gas in the hydrate must be equal to the surrounding waters. If the concentration of the gas in surrounding water is under-saturated with respect to the gas in the hydrate, the hydrate will dissolve to drive the system towards chemical equilibrium. This paper presented a dissolution study of exposed hydrate from outcrops at Barkley Canyon, located off Vancouver Island, British Columbia. A previous field experiment on synthetic methane hydrate samples had demonstrated that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. An in-situ dissolution experiment was performed on two distinct natural hydrate fabrics in order to help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate. The paper presented a map of Barkley Canyon and discussed the field measurements and methods for the study. Exposed outcrops of gas hydrates were cored using a specially constructed stainless steel coring device and a hydraulic ram was located inside the corer. Hydrate samples were cored directly using the a manipulator arm and then injected into a sampling cell. The hydrate was then added to an open mesh exposure container, which allowed for exposure to ambient benthic currents with minimal disturbance. As well, in order to observe the slow dissolution of the hydrate in seawater at Barkley Canyon, time-lapse photography was employed. Last, the paper presented the results of the hydrate fabric porosities and hydrate dissolution rates. It was

  7. 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

  8. Calcium and magnesium silicate hydrates

    International Nuclear Information System (INIS)

    Lothenbach, B.; L'Hopital, E.; Nied, D.; Achiedo, G.; Dauzeres, A.

    2015-01-01

    Deep geological disposals are planed to discard long-lived intermediate-level and high-level radioactive wastes. Clay-based geological barriers are expected to limit the ingress of groundwater and to reduce the mobility of radioelements. In the interaction zone between the cement and the clay based material alteration can occur. Magnesium silicate hydrates (M-S-H) have been observed due to the reaction of magnesium sulfate containing groundwater with cements or in the interaction zone between low-pH type cement and clays. M-S-H samples synthesized in the laboratory showed that M-S-H has a variable composition within 0.7 ≤ Mg/Si ≤ 1.5. TEM/EDS analyses show an homogeneous gel with no defined structure. IR and 29 Si NMR data reveal a higher polymerization degree of the silica network in M-S-H compared to calcium silicate hydrates (C-S-H). The presence of mainly Q 3 silicate tetrahedrons in M-S-H indicates a sheet like or a triple-chain silica structure while C-S-H is characterised by single chain-structure. The clear difference in the silica structure and the larger ionic radius of Ca 2+ (1.1 Angstrom) compared to Mg 2+ (0.8 Angstrom) make the formation of an extended solid solution between M-S-H and C-S-H gel improbable. In fact, the analyses of synthetic samples containing both magnesium and calcium in various ratios indicate the formation of separate M-S-H and C-S-H gels with no or very little uptake of magnesium in CS-H or calcium in M-S-H

  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. Basics of development of gas hydrate deposits

    Energy Technology Data Exchange (ETDEWEB)

    Makogon, Yuri F.; Holditch, Stephen A.; Makogon, Taras Y.

    2005-07-01

    Natural gas hydrate deposits could possibly be an important energy resource during this century. However, many problems associated with producing these deposits must first be solved. The industry must develop new technologies to produce the gas, to forecast possible tectonic cataclysms in regions of gas hydrate accumulations, and to prevent damage to the environment. These global issues must be addressed by every company or country who wants to produce gas hydrate deposits. Cooperative research between industry and universities can lead to technology breakthroughs in coming years. This paper reviews the Messoyakha field and the Blake Ridge and Nankai areas to explain a methodology for estimating how much gas might be producible from gas hydrate deposits (GHDs) under various conditions. The Messoyakha field is located on land, while the Blake Ridge and Nankai areas are offshore. Messoyakha is the first and the only GHD where gas production from hydrates has reached commercial flow rates. The Blake Ridge GHD has been studied for 20 years and 11 wells have been drilled to collect gas-hydrate samples. The potential resources of gas (gas in place) from Blake Ridge is estimated at 37.7Oe10{sup 12} m{sup 3} (1.330 Tcf) in hydrate form and 19.3Oe10{sup 12}m{sup 3} (681 Bcf) [5] in free gas. To estimate how much of the potential resource can be produced we need a thorough understanding of both the geologic and the thermodynamic characteristics of the formations. (Author)

  11. Gas hydrate exploration activities in Korea

    Energy Technology Data Exchange (ETDEWEB)

    Keun-Pil Park, K.P. [Korea Inst. of Geoscience and Mineral Resources, Gas Hydrate R and D Organization, Ministry of Knowledge Economy, Yuseong-gu, Daejeon (Korea, Republic of)

    2008-07-01

    Korea's first gas hydrate research project was launched in 1996 to study the gas hydrate potential in the Ulleung Basin of the East Sea. It involved a series of laboratory experiments followed by a preliminary offshore seismic survey and regional reconnaissance geophysical and marine geological surveys. The bottom simulating reflector (BSR) was interpreted to show wide area distribution in the southern part of the Ulleung Basin, and its average burial depth was 187 m below the sea floor in the East Sea. A three-phase 10-year National Gas Hydrate Development Program was launched in 2004 to estimate the potential reserves in the East Sea. It will involve drilling to identify natural gas hydrates and to determine the most optimized production methods. Drilling sites were proposed based on five indicators that imply gas hydrate occurrence, notably BSR, gas vent, enhanced seismic reflection, acoustic blanking and gas seeping structure. The UBGH-X-01 gas hydrate expedition in the East Sea Ulleung Basin involved 5 logging while drilling (LWD) surveys at three high priority sites. One wire line logging was implemented at the site of the UBGH09. A total 334 m of non-pressurized conventional cores and 16 pressure cores were obtained in late 2007. The UBGH-X-01 was successfully completed, recovering many natural samples of gas hydrate from 3 coring sites in the East Sea. 7 refs., 12 figs.

  12. 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.

  13. Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

    Science.gov (United States)

    Braun, Doris E.; Griesser, Ulrich J.

    2018-01-01

    The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III) differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products. PMID:29520359

  14. 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.

  15. Hydration of Atmospheric Molecular Clusters: Systematic Configurational Sampling.

    Science.gov (United States)

    Kildgaard, Jens; Mikkelsen, Kurt V; Bilde, Merete; Elm, Jonas

    2018-05-09

    We present a new systematic configurational sampling algorithm for investigating the potential energy surface of hydrated atmospheric molecular clusters. The algo- rithm is based on creating a Fibonacci sphere around each atom in the cluster and adding water molecules to each point in 9 different orientations. To allow the sam- pling of water molecules to existing hydrogen bonds, the cluster is displaced along the hydrogen bond and a water molecule is placed in between in three different ori- entations. Generated redundant structures are eliminated based on minimizing the root mean square distance (RMSD) of different conformers. Initially, the clusters are sampled using the semiempirical PM6 method and subsequently using density func- tional theory (M06-2X and ωB97X-D) with the 6-31++G(d,p) basis set. Applying the developed algorithm we study the hydration of sulfuric acid with up to 15 water molecules. We find that the additions of the first four water molecules "saturate" the sulfuric acid molecule and are more thermodynamically favourable than the addition of water molecule 5-15. Using the large generated set of conformers, we assess the performance of approximate methods (ωB97X-D, M06-2X, PW91 and PW6B95-D3) in calculating the binding energies and assigning the global minimum conformation compared to high level CCSD(T)-F12a/VDZ-F12 reference calculations. The tested DFT functionals systematically overestimates the binding energies compared to cou- pled cluster calculations, and we find that this deficiency can be corrected by a simple scaling factor.

  16. Submarine slope failures in the Beaufort Sea; Influence of gas hydrate decomposition

    Science.gov (United States)

    Grozic, J. L.; Dallimore, S.

    2012-12-01

    The continental shelf of the Beaufort Sea is composed of complex of marine and non-marine sequences of clay, silt, and sand. In many areas of the shelf these sediments contain occurrences of ice-bonded permafrost and associated pressure and temperature conditions that are conducive to the occurrence of methane gas hydrates. This complex environment is undergoing dramatic warming, where changes in sea level, ocean bottom temperatures, and geothermal regimes are inducing permafrost thawing and gas hydrate decomposition. Decomposition is inferred to be occurring at the base and top of the gas hydrate stability zone, which will cause sediment weakening and the generation of excess water and free gas. In such settings, the overlying permafrost cap may act as a permeability barrier, which could result in significant excess pore pressures and reduction in sediment stability. The shelf to slope transition is thought to be an area of extensive regional instability with acoustic records indicating there is upwards of 500 km of slumps and glides extending over the entire Beaufort margin. Some of these slide regions are coincident with up-dip limit of the permafrost gas hydrate stability zone. In this paper, a two dimensional model of the Beaufort shelf was constructed to examine the influence of gas hydrate decomposition on slope stability. The model relies on available data on the Beaufort sediments generated from offshore hydrocarbon exploration in the 1980s and 90s, as well as knowledge available from multidisciplinary marine research programs conducted in the outer shelf area. The slope stability model investigates the influence of marine transgression and ocean bottom warming by coupling soil deformation with hydrate dissociation during undrained conditions. By combining mechanical and thermal loading of the sediment, a more accurate indication of slope stability was obtained. The stability analysis results indicate a relatively low factor of safety for the Beaufort

  17. Tapping methane hydrates for unconventional natural gas

    Science.gov (United States)

    Ruppel, Carolyn

    2007-01-01

    Methane hydrate is an icelike form of concentrated methane and water found in the sediments of permafrost regions and marine continental margins at depths far shallower than conventional oil and gas. Despite their relative accessibility and widespread occurrence, methane hydrates have never been tapped to meet increasing global energy demands. With rising natural gas prices, production from these unconventional gas deposits is becoming economically viable, particularly in permafrost areas already being exploited for conventional oil and gas. This article provides an overview of gas hydrate occurrence, resource assessment, exploration, production technologies, renewability, and future challenges.

  18. Emergence of a Stern Layer from the Incorporation of Hydration Interactions into the Gouy-Chapman Model of the Electrical Double Layer.

    Science.gov (United States)

    Brown, Matthew A; Bossa, Guilherme Volpe; May, Sylvio

    2015-10-27

    In one of the most commonly used phenomenological descriptions of the electrical double layer, a charged solid surface and a diffuse region of mobile ions are separated from each other by a thin charge-depleted Stern layer. The Stern layer acts as a capacitor that improves the classical Gouy-Chapman model by increasing the magnitude of the surface potential and limiting the maximal counterion concentration. We show that very similar Stern-like properties of the diffuse double layer emerge naturally from adding a nonelectrostatic hydration repulsion to the electrostatic Coulomb potential. The interplay of electrostatic attraction and hydration repulsion of the counterions and the surface leads to the formation of a diffuse counterion layer that remains well separated from the surface. In addition, hydration repulsions between the ions limit and control the maximal ion concentration and widen the width of the diffuse double layer. Our mean-field model, which we express in terms of electrostatic and hydration potentials, is physically consistent and conceptually similar to the classical Gouy-Chapman model. It allows the incorporation of ion specificity, accounts for hydration properties of charged surfaces, and predicts Stern layer properties, which we analyze in terms of the effective size of the hydrated counterions.

  19. Bonding with Your Baby

    Science.gov (United States)

    ... the future bonding of the child and parent. Adoptive parents may be concerned about bonding with their ... general emotional support. And it's OK to ask family members and friends for help in the days — ...

  20. Experimental Investigation of Effect on Hydrate Formation in Spray Reactor

    Directory of Open Access Journals (Sweden)

    Jianzhong Zhao

    2015-01-01

    Full Text Available The effects of reaction condition on hydrate formation were conducted in spray reactor. The temperature, pressure, and gas volume of reaction on hydrate formation were measured in pure water and SDS solutions at different temperature and pressure with a high-pressure experimental rig for hydrate formation. The experimental data and result reveal that additives could improve the hydrate formation rate and gas storage capacity. Temperature and pressure can restrict the hydrate formation. Lower temperature and higher pressure can promote hydrate formation, but they can increase production cost. So these factors should be considered synthetically. The investigation will promote the advance of gas storage technology in hydrates.

  1. Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

    Science.gov (United States)

    Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

    2007-12-01

    A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

  2. Australia's Bond Home Bias

    OpenAIRE

    Anil V. Mishra; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  3. A Hydrate Database: Vital to the Technical Community

    Directory of Open Access Journals (Sweden)

    D Sloan

    2007-06-01

    Full Text Available Natural gas hydrates may contain more energy than all the combined other fossil fuels, causing hydrates to be a potentially vital aspect of both energy and climate change. This article is an overview of the motivation, history, and future of hydrate data management using a CODATA vehicle to connect international hydrate databases. The basis is an introduction to the Gas Hydrate Markup Language (GHML to connect various hydrate databases. The accompanying four articles on laboratory hydrate data by Smith et al., on field hydrate data by L?wner et al., on hydrate modeling by Wang et al., and on construction of a Chinese gas hydrate system by Xiao et al. provide details of GHML in their respective areas.

  4. Theoretical understanding on the v(1)-SO4(2-) band perturbed by the formation of magnesium sulfate ion pairs.

    Science.gov (United States)

    Zhang, Hao; Zhang, Yun-Hong; Wang, Feng

    2009-02-01

    The factors determining the spectroscopic characteristics of the v(1)-SO4(2-) band of the MgSO4 ion pairs are discussed via ab initio calculation, including coupling effect, hydrogen bonding effect, and direct contact effect of Mg2+ with SO4(2-). With the calculation of the heavy water hydrated contact ion pairs (CIP), the overlap between the librations of water and the v(1)-SO4(2-) band can be separated, and thus the coupling effect is abstracted, and this coupling effect leads to a blue shift for the v(1)-SO4(2-) band of 5.6 cm(-1) in the monodentate CIP and 3.6 cm(-1) in the bidentate CIP. The hydrogen bonding between each water molecule without relation to Mg2+ and the sulfate ion makes the v(1)-SO4(2-) band blue shift of 3.7 cm(-1). When the outer-sphere water around Mg2+ are hydrogen bonded between SO4(2-) and Mg2+, it will make the largest disturbance to the v(1)-SO4(2-) band. Moreover, the inner-sphere water can affect the v(1)-SO4(2-) band conjunct with the direct contact of Mg2+ with SO4(2-), showing a blue shift of 14.4 cm(-1) in the solvent-shared ion pair, 22.6 cm(-1) in the monodentate CIP, 4.3 cm(-1) in the bidentate CIP, and 21.4 cm(-1) in the tridentate CIP. At last, the Raman spectral evolution in the efflorescence production process is tried to be rationalized. The shoulder at 995 cm(-1) is attributed to the monodentate CIP with 2-3 outer-sphere water molecules, whereas the new peak at 1021 cm(-1) at high concentration is assigned to the formation of aqueous triple ion.

  5. Hydration interactions and stability of soluble microbial products in aqueous solutions.

    Science.gov (United States)

    Wang, Ling-Ling; Wang, Long-Fei; Ye, Xiao-Dong; Yu, Han-Qing

    2013-10-01

    Soluble microbial products (SMP) are organic compounds excreted by microorganisms in their metabolism and decay and the main constituents in effluent from biological wastewater treatment systems. They also have an important contribution to the dissolved organic matters in natural aqueous systems. So far the interactions between SMP colloids have not been well explored. In this work, the interactions between SMP colloids in water and salt solutions were studied by using a combination of static and dynamic light scattering, Fourier transform infrared spectra, Zeta potential and acid-base titration techniques. The second osmotic virial coefficient had a larger value in a 750-mM salt solution than that in a 50-mM solution, indicating that repulsion between SMP colloids increased with an increase in salt concentration, which is contrary with the classic Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory. Such a repulsion was attributed to water structuring and enhanced by the accumulation of hydrophilic counter ions around SMP colloids and the formed hydration force. The repulsion and hydration effect led to the dispersing and deeper draining structure, accompanied by a decreased hydrodynamic radius and increased diffusion coefficient. This hydration force was related to so-called ion specific effect, and electrolyte sodium chloride had a more substantial effect on hydration force than KCl, CsCl, NaBr and NaI. Our results provide an experimental approach to explore the SMP structures, inter-colloid interactions and confirm the non-DLVO forces. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Phenylacetylene and H bond

    Indian Academy of Sciences (India)

    ... all resembling H bonds. Non-linear H bonds due to secondary interactions. C-H stretching frequency shows blue shift. Heavy atom distances are longer than the sum of van der Waals radii. Formed a task group through IUPAC to come up with a modern definition of H bond. 15 international experts including Desiraju.

  7. Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

    Science.gov (United States)

    Avdellidou, C.; Delbo', M.; Fienga, A.

    2018-04-01

    Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

  8. Description and classification of uranium oxide hydrate sheet topologies

    International Nuclear Information System (INIS)

    Miller, M.L.; Burns, P.C.; Ewing, R.C.; Finch, R.J.

    1996-01-01

    The uranyl oxide hydrates (UOH) are important corrosion products of uraninite and UO 2 in spent nuclear fuel under oxidizing conditions. However, the systematics of the crystal chemistry, thermodynamic parameters, and solubilities of this mineral group are poorly understood. With the exception of the synthetic UO 2 (OH) 2 polymorphs, all UOH crystal structures are based on sheets of edge-sharing 5 and 4-coordinated uranyl dipyramids. This structural similarity suggests that it is possible to develop a model by which to estimate the thermodynamic behavior of UOHs from data on structural endmember phases. Toward this end, a method of quantitatively describing all known UOH sheets has been developed. Only four structural unit chains are required to construct the uranyl oxide hydrate sheets (as well as the structurally similar U 3 O 8 sheets). The H-chain is restricted to α-UO 2 (OH) 2 and is made up of hexagonally coordinated uranyl ions sharing opposing edges. The arrowhead chain composed of pentagonal dipyramids sharing edges and alternating with trigonal vacancies is present in all other UOH sheets. These arrowhead chains are directed and can occur in both an Up-arrow and Down-arrow sense within a single sheet. The P-chain consists of edge-sharing pentagonal dipyramids forming a zigzag chain. The P-chain is flanked on both sides by arrowhead chains of the same sense. The remaining structural unit is a discontinuous chain of rhombic dipyramids. This R-chain is produced when nested adjacent Up-arrow and Down-arrow arrowhead chains are translated by a diagonal shift. This chain occurs in sheets which contain only 4-coordinate uranyl ion and those containing both 4- and 5-coordinate uranyl ions

  9. 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

  10. Oceanic hydrates: more questions than answers

    International Nuclear Information System (INIS)

    Laherrere, Jean

    2000-01-01

    Methane hydrates create problems by blocking pipelines and casing; they are also accused of contributing to environmental problems (e.g. global warming). Methane hydrates are also found in permafrost areas and in oceanic sediments where the necessary temperature and pressure for stability occur. Claims for the widespread occurrence in thick oceanic deposits are unfounded: apparently indirect evidence from seismic reflectors, seismic hydrocarbon indicators, logs and free samples is unreliable. At one time, hydrate was seen as a static, biogenic, continuous, huge resource but that view is changing to one of a dynamic, overpressurised, discontinuous and unreliable resource. Only Japan and India are currently showing any serious interest in hydrates. Academic research has raised more questions than answers. It is suggested that more hard exploratory evidence rather than theoretical study is required

  11. 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.)

  12. 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 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...... volumes and the needs for high pressure. The process could be interesting for concentration of heat sensitive, high value products...

  13. 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.

  14. ConocoPhillips Gas Hydrate Production Test

    Energy Technology Data Exchange (ETDEWEB)

    Schoderbek, David [ConocoPhillips Co., Houston, TX (United States); Farrell, Helen [ConocoPhillips Co., Houston, TX (United States); Howard, James [ConocoPhillips Co., Houston, TX (United States); Raterman, Kevin [ConocoPhillips Co., Houston, TX (United States); Silpngarmlert, Suntichai [ConocoPhillips Co., Houston, TX (United States); Martin, Kenneth [ConocoPhillips Co., Houston, TX (United States); Smith, Bruce [ConocoPhillips Co., Houston, TX (United States); Klein, Perry [ConocoPhillips Co., Houston, TX (United States)

    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.

  15. 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.

  16. 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

  17. Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

    Science.gov (United States)

    Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

    2012-12-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the

  18. Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

    Directory of Open Access Journals (Sweden)

    Doris E. Braun

    2018-02-01

    Full Text Available The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis, gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations. Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (dehydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules and (form III differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products.

  19. 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.

  20. Heavy ion beam measurement of the hydration of cementitious materials

    International Nuclear Information System (INIS)

    Livingston, R.A.; Schweitzer, J.S.; Rolfs, C.; Becker, H.-W.; Kubsky, S.; Spillane, T.; Zickefoose, J.; Castellote, M.; Viedma, P.G. de; Cheung, J.

    2010-01-01

    The setting and development of strength of Portland cement concrete depends upon the reaction of water with various phases in the Portland cement. Nuclear resonance reaction analysis (NRRA) involving the 1 H( 15 N,α,γ) 12 C reaction has been applied to measure the hydrogen depth profile in the few 100 nm thick surface layer that controls the early stage of the reaction. Specific topics that have been investigated include the reactivity of individual cementitious phases and the effects of accelerators and retarders.

  1. Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores

    Science.gov (United States)

    Yang, Guomin; Neretnieks, Ivars; Holmboe, Michael

    2017-08-01

    During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and

  2. Bonding topologies in diamondlike amorphous-carbon films

    Energy Technology Data Exchange (ETDEWEB)

    Siegal, M. P. [Sandia National Laboratories, Albuquerque, New Mexico 87185-1421 (United States); Provencio, P. N. [Sandia National Laboratories, Albuquerque, New Mexico 87185-1421 (United States); Tallant, D. R. [Sandia National Laboratories, Albuquerque, New Mexico 87185-1421 (United States); Simpson, R. L. [Sandia National Laboratories, Albuquerque, New Mexico 87185-1421 (United States); Kleinsorge, B. [Department of Engineering, Cambridge University, Cambridge CB2 1PZ, (United Kingdom); Milne, W. I. [Department of Engineering, Cambridge University, Cambridge CB2 1PZ, (United Kingdom)

    2000-04-10

    The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces; their thicknesses increase with deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies <60 eV and increases for films grown using ion energies >160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of {sigma}- to {pi}-bonded carbon atoms. (c) 2000 American Institute of Physics.

  3. Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

    Science.gov (United States)

    Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

    2018-06-01

    The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

  4. Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

    Science.gov (United States)

    Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

    2018-05-07

    Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

  5. Skin hydration: interplay between molecular dynamics, structure and water uptake in the stratum corneum.

    Science.gov (United States)

    Mojumdar, Enamul Haque; Pham, Quoc Dat; Topgaard, Daniel; Sparr, Emma

    2017-11-16

    Hydration is a key aspect of the skin that influences its physical and mechanical properties. Here, we investigate the interplay between molecular and macroscopic properties of the outer skin layer - the stratum corneum (SC) and how this varies with hydration. It is shown that hydration leads to changes in the molecular arrangement of the peptides in the keratin filaments as well as dynamics of C-H bond reorientation of amino acids in the protruding terminals of keratin protein within the SC. The changes in molecular structure and dynamics occur at a threshold hydration corresponding to ca. 85% relative humidity (RH). The abrupt changes in SC molecular properties coincide with changes in SC macroscopic swelling properties as well as mechanical properties in the SC. The flexible terminals at the solid keratin filaments can be compared to flexible polymer brushes in colloidal systems, creating long-range repulsion and extensive swelling in water. We further show that the addition of urea to the SC at reduced RH leads to similar molecular and macroscopic responses as the increase in RH for SC without urea. The findings provide new molecular insights to deepen the understanding of how intermediate filament organization responds to changes in the surrounding environment.

  6. 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.

  7. In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

    Science.gov (United States)

    Peltzer, E. T.; White, S. N.; Dunk, R. M.; Brewer, P. G.; Sherman, A. D.; Schmidt, K.; Hester, K. C.; Sloan, E. D.

    2004-12-01

    During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in

  8. 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.

  9. Internal hydration of a metal-transporting ATPase is controlled by membrane lateral pressure

    Energy Technology Data Exchange (ETDEWEB)

    Fahmy, Karim [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Fischermeier, E. [Technische Univ. Dresden (Germany); Pospisil, P. [A.S.C. R., Prague (Czech Republic). J. Heyrovsky Inst. Physical Chemistry; Solioz, M. [Bern Univ. (Switzerland); Sayed, A.; Hof, M.

    2017-07-01

    The active transport of ions across biological mem branes requires their hydration shell to interact with the interior of membrane proteins. However, the influence of the external lipid phase on internal dielectric dynamics is hard to access by experiment. Using the octahelical transmembrane architecture of the copper-transporting P{sub 1B}-type ATPase from Legionella pneumophila (LpCopA) as a model structure, we have established the site-specific labeling of internal cysteines with a polarity-sensitive fluorophore. This enabled dipolar relaxation studies in a solubilized form of the protein and in its lipid-embedded state in nano-discs (NDs). Time-dependent fluorescence shifts revealed the site-specific hydration and dipole mobility around the conserved ion-binding motif. The spatial distribution of both features is shaped significantly and independently of each other by membrane lateral pressure.

  10. Internal hydration of a metal-transporting ATPase is controlled by membrane lateral pressure

    International Nuclear Information System (INIS)

    Fahmy, Karim; Pospisil, P.; Sayed, A.; Hof, M.

    2017-01-01

    The active transport of ions across biological mem branes requires their hydration shell to interact with the interior of membrane proteins. However, the influence of the external lipid phase on internal dielectric dynamics is hard to access by experiment. Using the octahelical transmembrane architecture of the copper-transporting P_1_B-type ATPase from Legionella pneumophila (LpCopA) as a model structure, we have established the site-specific labeling of internal cysteines with a polarity-sensitive fluorophore. This enabled dipolar relaxation studies in a solubilized form of the protein and in its lipid-embedded state in nano-discs (NDs). Time-dependent fluorescence shifts revealed the site-specific hydration and dipole mobility around the conserved ion-binding motif. The spatial distribution of both features is shaped significantly and independently of each other by membrane lateral pressure.

  11. Influence of pozzolana on C4AF hydratio n and the effects of chloride and sulfate io ns on the hydrates formed

    Directory of Open Access Journals (Sweden)

    RIMVYDAS KAMINSKAS

    2011-09-01

    Full Text Available This study investigated the influence of natural pozzolana additive on the hydration of C4AF (aluminoferrite and the effects of chloride and sulfate ions on the hydrates formed. In the samples, 25% (by weight of the C4AF was replaced with pozzolana. The mixture was then hardened for 28 days in water, soaked in a saturated NaCl solution for 3 months, and then soaked in a 5% Na2SO4 solution for 3 months at 20°C. It is estimated that under normal conditions, pozzolana additive accelerates the formation of CO32-–AFm (monocarboaluminate and gibbsite, however, impede the formation of cubic aluminum hydrates. Also, part of the amorphous SiO2 penetrates into the structure of hydrates of C4AF and initiates the formation of hydrated alumino-silicate (gismondine. Monocarboaluminate affected by NaCl becomes unstable and takes part in reactions producing Ca2Al(OH6Cl·2H2O (hydrocalumite-M. After samples were transferred from a saturated NaCl solution to a 5% Na2SO4 solution, hydrocalumite-M was the source of aluminates for the formation of ettringite. In samples with pozzolana additive, the hydrated alumino-silicate and gibbsite compounds that were formed remained stable in an environment containing chloride and sulfate ions and retarded the corrosion reaction of C4AF hydrates.

  12. Stabilization of ammonia-rich hydrate inside icy planets.

    Science.gov (United States)

    Naden Robinson, Victor; Wang, Yanchao; Ma, Yanming; Hermann, Andreas

    2017-08-22

    The interior structure of the giant ice planets Uranus and Neptune, but also of newly discovered exoplanets, is loosely constrained, because limited observational data can be satisfied with various interior models. Although it is known that their mantles comprise large amounts of water, ammonia, and methane ices, it is unclear how these organize themselves within the planets-as homogeneous mixtures, with continuous concentration gradients, or as well-separated layers of specific composition. While individual ices have been studied in great detail under pressure, the properties of their mixtures are much less explored. We show here, using first-principles calculations, that the 2:1 ammonia hydrate, (H 2 O)(NH 3 ) 2 , is stabilized at icy planet mantle conditions due to a remarkable structural evolution. Above 65 GPa, we predict it will transform from a hydrogen-bonded molecular solid into a fully ionic phase O 2- ([Formula: see text]) 2 , where all water molecules are completely deprotonated, an unexpected bonding phenomenon not seen before. Ammonia hemihydrate is stable in a sequence of ionic phases up to 500 GPa, pressures found deep within Neptune-like planets, and thus at higher pressures than any other ammonia-water mixture. This suggests it precipitates out of any ammonia-water mixture at sufficiently high pressures and thus forms an important component of icy planets.

  13. 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.

  14. The influence of Na2O on the hydration of C3A II. Suspension hydration

    NARCIS (Netherlands)

    Spierings, G.A.C.M.; Stein, H.N.

    1976-01-01

    The influence of Na2O on the hydration of C3A was studied in suspensions from the start of the reaction onwards. The heat evolution rate in very early stages of the hydration, measured at varying NaOH concentrations, and SEM, indicate that at NaOH concentrations larger then 0.1 M the reaction

  15. Distinguishing between hydrated, partially hydrated or unhydrated clinker in hardened concrete using microscopy

    NARCIS (Netherlands)

    Valcke, S.L.A.; Rooij, M.R. de; Visser, J.H.M.; Nijland, T.G.

    2010-01-01

    Hydration of clinker particles is since long a topic of interest in both designing and optimizing cement composition and its quantity used in concrete. The interest for carefully observing and also quantifying the type or stage of clinker hydration in hardened cement paste is twofold. Firstly, the

  16. Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator

    International Nuclear Information System (INIS)

    Li, Gang; Li, Xiao-Sen; Li, Bo; Wang, Yi

    2014-01-01

    The combination forms of the hydrate dissociation methods in different well systems are divided into 6 main patterns. Dissociation processes of methane hydrate in porous media using the inverted five-spot water flooding method (Pattern 4) are investigated by the experimental observation and numerical simulation. In situ methane hydrate is synthesized in the Cubic Hydrate Simulator (CHS), a 5.832-L cubic reactor. A center vertical well is used as the hot water injection well, while the four vertical wells at the corner are the gas and water production wells. The gas production begins simultaneously with the hot water injection, while after approximately 20 min of compression, the water begins to be produced. One of the common characteristics of the inverted five-spot water flooding method is that both the gas and water production rates decrease with the reduction of the hydrate dissociation rate. The evaluation of the energy efficiency ratio might indicate the inverted five-spot water flooding as a promising gas producing method from the hydrate reservoir. - Highlights: • A three-dimensional 5.8-L cubic pressure vessel is developed. • Gas production of hydrate using inverted five-spot flooding method is studied. • Water/gas production rate and energy efficiency ratio are evaluated. • Temperature distributions of numerical simulation and experiment agree well. • Hydrate dissociation process is a moving boundary problem in this study

  17. Controls on Gas Hydrate Formation and Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  18. Physical chemistry of portland-cement hydrate, radioactive-waste hosts: Final report, January 16, 1987--December 31, 1987

    International Nuclear Information System (INIS)

    Grutzeck, M.W.

    1989-01-01

    This is a final report summarizing the results of a study of the physical and crystal chemistry of potential hydroxylated radioactive waste hosts compatible with portland cement. Research has focussed on the identification and evaluation of hydrated host phases for four ions: cesium, strontium, iodine and boron. These ions were chosen because they are among the most long lived of the radioactive waste ions as well as the most difficult to immobilize with cement-based materials. Results show that such phases do indeed exist, and that they are excellent host phases for the above ions

  19. 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.

  20. Calcium silicate-based sealers: Assessment of physicochemical properties, porosity and hydration.

    Science.gov (United States)

    Marciano, Marina Angélica; Duarte, Marco Antonio Hungaro; Camilleri, Josette

    2016-02-01

    Investigation of hydration, chemical, physical properties and porosity of experimental calcium silicate-based sealers. Experimental calcium silicate-based sealers with calcium tungstate and zirconium oxide radio-opacifiers were prepared by mixing 1g of powder to 0.3 mL of 80% distilled water and 20% propylene glycol. MTA and MTA Fillapex were used as controls. The raw materials and set sealers were characterized using a combination of scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Physical properties were analyzed according to ANSI/ADA. The pH and calcium ion release were assessed after 3, 24, 72 and 168 h. The porosity was assessed using mercury intrusion porosimetry. The analysis of hydration of prototype sealers revealed calcium hydroxide as a by-product resulting in alkaline pH and detection of calcium ion release, with high values in initial periods. The radiopacity was similar to MTA for the sealers containing high amounts of radio-opacifiers (p>0.05). Flowability was higher and film thickness was lower for resinous MTA Fillapex sealer (p0.05). The prototype sealers presented adequate hydration, elevated pH and calcium ion release. Regarding physical properties, elevated proportions of radio-opacifiers were necessary to accomplish adequate radiopacity, enhance flowability and reduce film thickness. All the tested sealers presented water sorption and porosity similar to MTA. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  1. Discrete element modeling of calcium-silicate-hydrate

    International Nuclear Information System (INIS)

    Chandler, Mei Qiang; Peters, John F; Pelessone, Daniele

    2013-01-01

    The discrete element method (DEM) was used to model calcium-silicate-hydrate (C-S-H) at the nanoscale. The C-S-H nanoparticles were modeled as spherical particles with diameters of approximately 5 nm. Interparticle forces included traditional mechanical contact forces, van der Waals forces and ionic correlation forces due to negatively charged C-S-H nanoparticles and ion species in the nanopores. Previous work by the authors demonstrated the DEM method was feasible in studying the properties of the C-S-H nanostructures. In this work, the simulations were performed to look into the effects of nanoparticle packing, nanoparticle morphology, interparticle forces and nanoparticle properties on the deformation mechanisms and mechanical properties of the C-S-H matrix. This work will provide insights into possible ways to improve the properties of the C-S-H matrix. (paper)

  2. Kinetics of the reactions of hydrated electrons with metal complexes

    International Nuclear Information System (INIS)

    Korsse, J.

    1983-01-01

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  3. Radiation response of hydrated urea evaluated using 14N nuclear quadrupole resonance

    International Nuclear Information System (INIS)

    Hintenlang, D.E.

    1992-01-01

    In this paper Nitrogen-14 nuclear quadrupole resonance is utilized to detect radiation-induced changes in urea over the 0- to 300-Gy dose range. The spin-spin relaxation time exhibits a consistent change as a function of delivered dose in hydrated urea under exposure to 60 Co gamma radiation. No changes to the spin-spin relaxation time are observed in urea samples that were not hydrated. The radiation-induced changes are attributed to indirect radiation interactions with the water surrounding the urea molecules and are explained by the formation of subtle changes in the electron bonding configurations surrounding the 14 N nuclei, not major structural rearrangements. These subtle changes may provide additional insight into the effects of ionizing radiation on biological systems

  4. Unique Bond Breaking in Crystalline Phase Change Materials and the Quest for Metavalent Bonding.

    Science.gov (United States)

    Zhu, Min; Cojocaru-Mirédin, Oana; Mio, Antonio M; Keutgen, Jens; Küpers, Michael; Yu, Yuan; Cho, Ju-Young; Dronskowski, Richard; Wuttig, Matthias

    2018-05-01

    Laser-assisted field evaporation is studied in a large number of compounds, including amorphous and crystalline phase change materials employing atom probe tomography. This study reveals significant differences in field evaporation between amorphous and crystalline phase change materials. High probabilities for multiple events with more than a single ion detected per laser pulse are only found for crystalline phase change materials. The specifics of this unusual field evaporation are unlike any other mechanism shown previously to lead to high probabilities of multiple events. On the contrary, amorphous phase change materials as well as other covalently bonded compounds and metals possess much lower probabilities for multiple events. Hence, laser-assisted field evaporation in amorphous and crystalline phase change materials reveals striking differences in bond rupture. This is indicative for pronounced differences in bonding. These findings imply that the bonding mechanism in crystalline phase change materials differs substantially from conventional bonding mechanisms such as metallic, ionic, and covalent bonding. Instead, the data reported here confirm a recently developed conjecture, namely that metavalent bonding is a novel bonding mechanism besides those mentioned previously. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Hydrates on tap: scientists say natural gas hydrates may be tough nut to crack

    Energy Technology Data Exchange (ETDEWEB)

    Mahoney, J.

    2001-12-01

    Gas hydrates are methane molecules trapped in cages of water molecules, yielding a substance with a slushy, sherbet-like consistency. Drilling for hydrates is similar to conventional oil and gas drilling, however, the secret to economic production still remains hidden. Hydrates exist in abundance in such places as deep ocean floor and below ground in some polar regions. The real challenge lies in producing gas from this resource, inasmuch as there is no existing technology for production of gas specifically from methane hydrates. This paper describes an international research program, involving a five-country partnership to spud the first of three wells into the permafrost of the Mackenzie River Delta in the Northwest Territories. The project, worth about $15 million, has brought together public funding and expertise from Japan, Germany, India as well as the Canadian and US Geological Surveys and the US Dept. of Energy in an effort to gain information on the production response of gas hydrates. The operator of the project is Japan Petroleum Exploration Company of Canada, a subsidiary of Japan National Oil Corporation. Since Japan is poor in domestic hydrocarbon resources, but is surrounded by deep water that contains potential for gas hydrates, Japan has a great deal riding on the success of this project. Germany and the United States are also very much interested. Current thinking is that gas is in contact with the hydrates and that it should be possible to develop a free gas reservoir as if it were a conventional deposit. As the free gas is drawn off, the pressure is reduced on the hydrates in contact with it , the hydrates dissociate from the gas and replenish the conventional reservoir. So far this is still only a theory, but it appears to be a sensible approach to hydrate production. 1 photo.

  6. Experimental Determination of Refractive Index of Gas Hydrates

    DEFF Research Database (Denmark)

    Bylov, Martin; Rasmussen, Peter

    1997-01-01

    . For methane hydrate (structure I) the refractive index was found to be 1.346 and for natural gas hydrate (structure II) it was found to be 1.350. The measurements further suggest that the gas hydrate growth rate increases if the water has formed hydrates before. The induction time, on the other hand, seems......The refractive indexes of methane hydrate and natural gas hydrate have been experimentally determined. The refractive indexes were determined in an indirect manner making use of the fact that two non-absorbing materials will have the same refractive index if they cannot be distinguished visually...

  7. Development of hydrate risk quantification in oil and gas production

    Science.gov (United States)

    Chaudhari, Piyush N.

    Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

  8. 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

  9. Experimental investigation of methane release from hydrate formation in sandstone through both hydrate dissociation and CO{sub 2} sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Husebo, J.; Graue, A.; Kvamme, B. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology; Stevens, J.; Howard, J.J. [ConocoPhillips, Ponca City, OK (United States); Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States)

    2008-07-01

    Large amounts of natural gas trapped in hydrate reservoirs are found in Arctic regions and in deep offshore locations around the world. Natural gas production from hydrate deposits offer significant potential for future energy needs. However, research is needed in order to propose potential production schemes for natural gas hydrates. Natural gas molecules can be freed from hydrate structured cages by depressurization, by heating and by exposing the hydrate to a substance that will form a thermodynamically more stable hydrate structure. This paper provided a comparison of two approaches for releasing methane from methane hydrate in porous sandstone. The study scope covered the dissociation rate of methane hydrate in porous media through depressurization, and also referred to previous work done on producing methane from hydrates in sandstone while sequestering carbon dioxide (CO{sub 2}). The study was conducted in a laboratory setting. The paper discussed the experimental design which included the placing of a pressure- and temperature-controlled sample holder inside the bore of a magnetic resonance imager. The experimental procedures were then outlined, with reference to hydrate formation; carbon dioxide sequestration; hydrate dissociation experiments with constant volume; and hydrate dissociation experiments at constant pressure. The constant volume experiments demonstrated that in order to dissociate a large amount of hydrate, the initial depressurization had to be significantly lower than the hydrate stability pressure. 9 refs., 9 figs.

  10. Strength Estimation for Hydrate-Bearing Sediments From Direct Shear Tests of Hydrate-Bearing Sand and Silt

    Science.gov (United States)

    Liu, Zhichao; Dai, Sheng; Ning, Fulong; Peng, Li; Wei, Houzhen; Wei, Changfu

    2018-01-01

    Safe and economic methane gas production, as well as the replacement of methane while sequestering carbon in natural hydrate deposits, requires enhanced geomechanical understanding of the strength and volume responses of hydrate-bearing sediments during shear. This study employs a custom-made apparatus to investigate the mechanical and volumetric behaviors of carbon dioxide hydrate-bearing sediments subjected to direct shear. The results show that both peak and residual strengths increase with increased hydrate saturation and vertical stress. Hydrate contributes mainly the cohesion and dilatancy constraint to the peak strength of hydrate-bearing sediments. The postpeak strength reduction is more evident and brittle in specimens with higher hydrate saturation and under lower stress. Significant strength reduction after shear failure is expected in silty sediments with high hydrate saturation Sh ≥ 0.65. Hydrate contribution to the residual strength is mainly by increasing cohesion at low hydrate saturation and friction at high hydrate saturation. Stress state and hydrate saturation are dominating both the stiffness and the strength of hydrate-bearing sediments; thus, a wave velocity-based peak strength prediction model is proposed and validated, which allows for precise estimation of the shear strength of hydrate-bearing sediments through acoustic logging data. This method is advantageous to geomechanical simulators, particularly when the experimental strength data of natural samples are not available.

  11. 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)

  12. Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

    Science.gov (United States)

    Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

    2014-12-01

    The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E

  13. BONDING ALUMINUM METALS

    Science.gov (United States)

    Noland, R.A.; Walker, D.E.

    1961-06-13

    A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

  14. Effect of overpressure on gas hydrate distribution

    Energy Technology Data Exchange (ETDEWEB)

    Bhatnagar, G.; Chapman, W.G.; Hirasaki, G.J. [Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering; Dickens, G.R.; Dugan, B. [Rice Univ., Houston, TX (United States). Dept. of Earth Sciences

    2008-07-01

    Natural gas hydrate systems can be characterized by high sedimentation rates and/or low permeability sediments, which can lead to pore pressure higher than hydrostatic. This paper discussed a study that examined this effect of overpressure on gas hydrate and free gas distribution in marine sediments. A one-dimensional numerical model that coupled sedimentation, fluid flow, and gas hydrate formation was utilized. In order to quantify the relative importance of sedimentation rates and low permeability sediments, a dimensionless sedimentation-compaction group (scN) was defined, that compared the absolute permeability of the sediments to the sedimentation rate. Higher values of scN mean higher permeability or low sedimentation rate which generally yield hydrostatic pore pressure while lower values of scN normally create pore pressure greater than hydrostatic. The paper discussed non-hydrostatic consolidation in gas hydrate systems, including mass balances; constitutive relationships; normalized variables; and dimensionless groups. A numerical solution to the problem was presented. It was concluded that simulation results demonstrated that decreasing scN not only increased pore pressure above hydrostatic values, but also lowered the lithostatic stress gradient and gas hydrate saturation. This occurred because overpressure resulted in lower effective stress, causing higher porosity and lower bulk density of the sediment. 16 refs., 5 figs., 1 appendix.

  15. Methane hydrates in quaternary climate change

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  16. Blue LED irradiation to hydration of skin

    Science.gov (United States)

    Menezes, Priscila F. C.; Requena, Michelle B.; Lizarelli, Rosane F., Z.; Bagnato, Vanderlei S.

    2015-06-01

    Blue LED system irradiation shows many important properties on skin as: bacterial decontamination, degradation of endogenous skin chromophores and biostimulation. In this clinical study we prove that the blue light improves the skin hydration. In the literature none authors reports this biological property on skin. Then this study aims to discuss the role of blue light in the skin hydration. Twenty patients were selected to this study with age between 25-35 years old and phototype I, II and III. A defined area from forearm was pre determined (A = 4.0 cm2). The study was randomized in two treatment groups using one blue light device (power of 5.3mW and irradiance of 10.8mW/cm2). The first treatment group was irradiated with 3J/cm2 (277seconds) and the second with 6J/cm2 (555 seconds). The skin hydration evaluations were done using a corneometer. The measurements were collected in 7, 14, 21 and 30 days, during the treatment. Statistical test of ANOVA, Tukey and T-Student were applied considering 5% of significance. In conclusion, both doses were able to improve the skin hydration; however, 6J/cm2 has kept this hydration for 30 days.

  17. 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...

  18. GROUT-CONCRETE INTERFACE BOND PERFORMANCE: EFFECT OF INTERFACE MOISTURE ON THE TENSILE BOND STRENGTH AND GROUT MICROSTRUCTURE.

    Science.gov (United States)

    De la Varga, I; Muñoz, J F; Bentz, D P; Spragg, R P; Stutzman, P E; Graybeal, B A

    2018-05-01

    Bond between two cementitious materials is crucial in applications such as repairs, overlays, and connections of prefabricated bridge elements (PBEs), to name just a few. It is the latter that has special interest to the authors of this paper. After performing a dimensional stability study on grout-like materials commonly used as connections between PBEs, it was observed that the so-called 'non-shrink' cementitious grouts showed a considerable amount of early-age shrinkage. This might have negative effects on the integrity of the structure, due not only to the grout material's early degradation, but also to a possible loss of bond between the grout and the prefabricated concrete element. Many factors affect the bond strength between two cementitious materials (e.g., grout-concrete), the presence of moisture at the existing concrete substrate surface being one of them. In this regard, pre-moistening the concrete substrate surface prior to the application of the grout material is sometimes recommended for bond enhancement. This topic has been the focus of numerous research studies in the past; however, there is still controversy among practitioners on the real benefits that this practice might provide. This paper evaluates the tensile bond performance of two non-shrink cementitious grouts applied to the exposed aggregate surface of a concrete substrate, and how the supply of moisture at the grout-concrete interface affects the bond strength. "Pull-off" bond results show increased tensile bond strength when the concrete surface is pre-moistened. Reasons to explain the observed increased bond strength are given after a careful microstructural analysis of the grout-concrete interface. Interfaces where sufficient moisture is provided to the concrete substrate such that moisture movement from the grout is prevented show reduced porosity and increased hydration on the grout side of the interface, which is thought to directly contribute to the increased tensile bond

  19. Effects of Nanosilica on Early Age Stages of Cement Hydration

    Directory of Open Access Journals (Sweden)

    Forood Torabian Isfahani

    2017-01-01

    Full Text Available Effects of nanosilica on cement hydration have been broadly investigated in the literature and early age cement hydration, as a whole, has been mainly considered, disregarding the substages of the hydration. The hydration of cement is characterized by different substages and nanosilica effect on the hydration could be a result of diverse, even contradictory, behavior of nanosilica in individual stages of the hydration. In this study, effects of nanosilica on different substages of cement hydration are investigated. Isothermal calorimetry results show that at early ages (initial 72 hours the effects of nanosilica depend on the phenomenon by which the hydration is governed: when the hydration is chemically controlled, that is, during initial reaction, dormant period, and acceleratory period, the hydration rate is accelerated by adding nanosilica; when the hydration is governed by diffusion process, that is, during postacceleratory period, the hydration rate is decelerated by adding nanosilica. The Thermal Gravimetric Analysis on the samples at the hardened state (after 28 days of curing reveals that, after adding nanosilica, the hydration degree slightly increased compared to the plain paste.

  20. Morphology studies on gas hydrates interacting with silica gel

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  1. 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

  2. Fuel cell membrane hydration and fluid metering

    Science.gov (United States)

    Jones, Daniel O.; Walsh, Michael M.

    1999-01-01

    A hydration system includes fuel cell fluid flow plate(s) and injection port(s). Each plate has flow channel(s) with respective inlet(s) for receiving respective portion(s) of a given stream of reactant fluid for a fuel cell. Each injection port injects a portion of liquid water directly into its respective flow channel in order to mix its respective portion of liquid water with the corresponding portion of the stream. This serves to hydrate at least corresponding part(s) of a given membrane of the corresponding fuel cell(s). The hydration system may be augmented by a metering system including flow regulator(s). Each flow regulator meters an injecting at inlet(s) of each plate of respective portions of liquid into respective portion(s) of a given stream of fluid by corresponding injection port(s).

  3. Hydration dynamics of hyaluronan and dextran.

    Science.gov (United States)

    Hunger, Johannes; Bernecker, Anja; Bakker, Huib J; Bonn, Mischa; Richter, Ralf P

    2012-07-03

    Hyaluronan is a polysaccharide, which is ubiquitous in vertebrates and has been reported to be strongly hydrated in a biological environment. We study the hydration of hyaluronan in solution using the rotational dynamics of water as a probe. We measure these dynamics with polarization-resolved femtosecond-infrared and terahertz time-domain spectroscopies. Both experiments reveal that a subensemble of water molecules is slowed down in aqueous solutions of hyaluronan amounting to ∼15 water molecules per disaccharide unit. This quantity is consistent with what would be expected for the first hydration shell. Comparison of these results to the water dynamics in aqueous dextran solution, a structurally similar polysaccharide, yields remarkably similar results. This suggests that the observed interaction with water is a common feature for hydrophilic polysaccharides and is not specific to hyaluronan. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  4. Thermal expansion properties of calcium aluminate hydrates

    International Nuclear Information System (INIS)

    Song, Tae Woong

    1986-01-01

    In order to eliminate the effect of impurities and aggregates on the thermomechanical properties of the various calcium aluminate hydrates, and to prepare clinkers in which all calcium aluminates are mixed homogeneously, chemically pure CaO and Al 2 O 3 were weighed, blended and heated in various conditions. After quantitative X-ray diffractometry(QXRD), the synthesized clinker was hydrated and cured under the conditions of 30 deg C, W/C=0.5, relative humidity> 90% respectively during 24 hours. And then differential thermal analysis(DTA), thermogravimetry(TG), micro calorimetry, thermomechanical analysis(TMA) and scanning electron microanalysis(SEM) were applied to examine the thermal properties of samples containing, calcium aluminate hydrates in various quantity. (Author)

  5. THz characterization of hydrated and anhydrous materials

    Science.gov (United States)

    Sokolnikov, Andre

    2011-06-01

    The characterization of anhydrous and hydrated forms of materials is of great importance to science and industry. Water content poses difficulties for successful identification of the material structure by THz radiation. However, biological tissues and hydrated forms of nonorganic substances still may be investigated by THz radiation. This paper outlines the range of possibilities of the above characterization, as well as provides analysis of the physical mechanism that allows or prevents penetration of THz waves through the substance. THz-TDS is used to measure the parameters of the characterization of anhydrous and hydrated forms of organic and nonorganic samples. Mathematical methods (such as prediction models of time-series analysis) are used to help identifying the absorption coefficient and other parameters of interest. The discovered dependencies allow designing techniques for material identification/characterization (e.g. of drugs, explosives, etc. that may have water content). The results are provided.

  6. Relaxation mechanism of the hydrated electron.

    Science.gov (United States)

    Elkins, Madeline H; Williams, Holly L; Shreve, Alexander T; Neumark, Daniel M

    2013-12-20

    The relaxation dynamics of the photoexcited hydrated electron have been subject to conflicting interpretations. Here, we report time-resolved photoelectron spectra of hydrated electrons in a liquid microjet with the aim of clarifying ambiguities from previous experiments. A sequence of three ultrashort laser pulses (~100 femtosecond duration) successively created hydrated electrons by charge-transfer-to-solvent excitation of dissolved anions, electronically excited these electrons via the s→p transition, and then ejected them into vacuum. Two distinct transient signals were observed. One was assigned to the initially excited p-state with a lifetime of ~75 femtoseconds, and the other, with a lifetime of ~400 femtoseconds, was attributed to s-state electrons just after internal conversion in a nonequilibrated solvent environment. These assignments support the nonadiabatic relaxation model.

  7. Bonding topologies in diamondlike amorphous-carbon films

    International Nuclear Information System (INIS)

    Siegal, M. P.; Provencio, P. N.; Tallant, D. R.; Simpson, R. L.; Kleinsorge, B.; Milne, W. I.

    2000-01-01

    The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces; their thicknesses increase with deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies 160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of σ- to π-bonded carbon atoms. (c) 2000 American Institute of Physics

  8. Ground movements associated with gas hydrate production

    International Nuclear Information System (INIS)

    Siriwardane, H.J.; Kutuk, B.

    1992-03-01

    This report deals with a study directed towards a modeling effort on production related ground movements and subsidence resulting from hydrate dissociation. The goal of this research study was to evaluate whether there could be subsidence related problems that could be an impediment to hydrate production. During the production of gas from a hydrate reservoir, it is expected that porous reservoir matrix becomes more compressible which may cause reservoir compression (compaction) under the influence of overburden weight. The overburden deformations can propagate its influence upwards causing subsidence near the surface where production equipment will be located. In the present study, the reservoir compaction is modeled by using the conventional ''stress equilibrium'' approach. In this approach, the overburden strata move under the influence of body force (i.e. self weight) in response to the ''cavity'' generated by reservoir depletion. The present study is expected to provide a ''lower bound'' solution to the subsidence caused by hydrate reservoir depletion. The reservoir compaction anticipated during hydrate production was modeled by using the finite element method, which is a powerful computer modeling technique. The ground movements at the reservoir roof (i.e. reservoir compression) cause additional stresses and disturbance in the overburden strata. In this study, the reservoir compaction was modeled by using the conventional ''stress equilibrium'' approach. In this approach, the overburden strata move under the influence of body force (i.e. self weight) in response to the ''cavity'' generated by reservoir depletion. The resulting stresses and ground movements were computed by using the finite element method. Based on the parameters used in this investigation, the maximum ground subsidence could vary anywhere from 0.50 to 6.50 inches depending on the overburden depth and the size of the depleted hydrate reservoir

  9. Irrigation port hydration in phacoemulsification surgery

    Directory of Open Access Journals (Sweden)

    Suzuki H

    2018-01-01

    Full Text Available Hisaharu Suzuki,1 Yoichiro Masuda,2 Yuki Hamajima,1 Hiroshi Takahashi3 1Department of Ophthalmology, Nippon Medical School Musashikosugi Hospital, Kawasaki City, Kanagawa, 2Department of Ophthalmology, The Jikei University, Katsushika Medical Center, Tokyo, 3Department of Ophthalmology, Nippon Medical School, Tokyo, Japan Background: In most cases, hydration is performed by water injection into the stromal tissue with a needle. The technique is simple, however it is sometimes troublesome.Purpose: We describe a simple technique for hydrating the corneal stroma in cataract surgery using an irrigation port.Patients and methods: The technique began by pushing the irrigation port against the corneal stroma for a few seconds during phacoemulsification, which generated edema in the corneal incision that subsequently prevented leakage. This procedure is called the hydration using irrigation port (HYUIP technique. A total of 60 eyes were randomized and placed in two groups, 30 eyes underwent surgeries using the HYUIP technique (HYUIP group and 30 eyes underwent surgeries without the HYUIP technique (control. The three points evaluated during each surgery included 1 the occurrence of anterior chamber collapse during the pulling out of the I/A tip after inserting the intraocular lens, 2 the need for conventional hydration, and 3 watertight completion at the end stage of surgery.Results: The anterior chamber collapse and the need for conventional hydration were significantly smaller in the HYUIP group compared to the control group. Regarding the self-sealing completion, no significant difference was observed between the two groups.Conclusion: The HYUIP technique is an effective method for creating self-sealing wound. In addition, this technique helps to prevent anterior chamber collapse. Keywords: cataract surgery, hydration, irrigation and aspiration, phacoemulsification, wound, self-sealing 

  10. Hydration and nutrition knowledge in adolescent swimmers. Does water intake affect urine hydration markers after swimming?

    Directory of Open Access Journals (Sweden)

    Cesare Altavilla

    2017-12-01

    Full Text Available Little data exists regarding nutritional knowledge and hydration in adolescent swimmers. The aim of this study was to assess the level of nutrition and hydration knowledge and to describe the fluid balance in adolescent swimmers during training. A study was carried out with a cross-sectional descriptive part and a longitudinal part with repeated measurements over five swimming sessions. Eighty-six adolescent swimmers completed a questionnaire to assess their sport nutrition and hydration knowledge. Fluid balance and urine hydration markers were studied during training. Swimmers showed a limited nutrition knowledge (33.26 % ± SD 12.59 and meagre hydration knowledge (28.61 % ± SD 28.59. Females showed lower scores than male swimmers in nutrition and hydration knowledge. Based on urine specific gravity, swimmers started the training close to the euhydrated threshold (1.019 g/mL ± SD 0.008. Although urine specific gravity and urine colour were reduced after the training, there were minimal changes in body mass (-0.12 Kg ± SD 0.31. Sweat loss (2.67 g/min ± SD 3.23 and the net changes in the fluid balance (-0.22 % ± SD 0.59 were low. The poor knowledge in nutrition and hydration encountered in the swimmers can justify the development of a strategy to incorporate nutritional education programmes for this group. Body water deficit from swimming activity seems to be easily replaced with the water intake to maintain hydration. After the training, the urine of swimmers was diluted regardless of their water intake. Dilution of urine did not reflect real hydration state in swimming.

  11. n-Electrons of heteroatoms in hydrogen bond and luminescence

    International Nuclear Information System (INIS)

    Karyakin, A.V.

    1985-01-01

    Hydrogen bond energy in the process of interaction between water molecules, water molecules and heteroatoms of organic solvents, water molecules and inorganic compounds, is determined, its mechanism being studied. On the basis of X-ray structure and IR-spectroscopic data water state in easily hydrolized compounds of zirconium and hafnium, including sulfates, nitrates, oxychlorides etc. is analyzed. Water state in uranyl nitrate hydrates, the structure of the compounds and their behaviour when they are extracted by TBP, are considered. The reasons for stability of uranyl nitrate hydrates are discussed. The effect of n-electrons of heteroatoms of simple aromatic compound on structural spectra of luminescence in aliphatic and inorganic matrices is investigated

  12. Thermal decomposition of uranyl sulphate hydrate

    International Nuclear Information System (INIS)

    Sato, T.; Ozawa, F.; Ikoma, S.

    1980-01-01

    The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)

  13. Nanostructure of Calcium Silicate Hydrates in Cements

    KAUST Repository

    Skinner, L. B.; Chae, S. R.; Benmore, C. J.; Wenk, H. R.; Monteiro, P. J. M.

    2010-01-01

    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.

  14. 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.

  15. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...

  16. Spectral Decomposition and Other Seismic Attributes for Gas Hydrate Prospecting

    Energy Technology Data Exchange (ETDEWEB)

    McConnell, Dan

    2018-02-25

    Studying the sediments at the base of gas hydrate stability is ideal for determining the seismic response to gas hydrate saturation. First, assuming gas migration to the shallow section, this area is more likely to have concentrated gas hydrate because it encompasses the zone in which upward moving buoyant gas transitions to form immobile gas hydrate deposits. Second, this zone is interesting because these areas have the potential to show a hydrate filled zone and a gas filled zone within the same sediments. Third, the fundamental measurement within seismic data is impedance contrasts between velocity*density layers. High saturation gas hydrates and free gas inhabit opposite ends of these measurements making the study of this zone ideal for investigating the seismic characteristics of gas hydrate and, hence, the investigation of other seismic attributes that may indicate gas hydrate fill.

  17. The rates measurement of methane hydrate formation and dissociation using micro-drilling system application for gas hydrate exploration

    Energy Technology Data Exchange (ETDEWEB)

    Bin Dou [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)]|[Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Reinicke, K.M. [Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Guosheng Jiang; Xiang Wu; Fulong Ning [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)

    2006-07-01

    When drilling through gas hydrate bearing formations, the energy supplied by virtue of the drilling process may lead to a destabilization of the hydrates surrounding the wellbore. Therefore, as the number of oil and gas fields being development in deepwater and onshore arctic environments increases, greater emphasis should be placed on quantifying the risks, gas hydrates pose to drilling operations. The qualification of these risks requires a comprehensive understanding of gas hydrate-formation and dissociation as a result of drilling induced processes. To develop the required understanding of gas hydrat formation and dissociation, the authors conducted laboratory experiments by using a micro-drilling system, to study the dissociation rates of methane hydrates contained in a tank reactor. The test facility used is a development of China University of Geosciences. The rates of methane hydrate formation and dissociation in the tank reactor were measured at steady-state conditions at pressures ranging from 0.1 to 25 MPa and temperatures ranging from -5 to 20 C. The experimental results show that the rate of hydrate formation is strongly influenced by the fluid system used to form the hydrates, pressure and temperature, with the influence of the temperature on methane hydrate dissociation being stronger than that of the pressure. Drilling speed, drilling fluids and hydrate dissociation inhibitors were also shown to influence hydrate dissociation rate. The derived results have been used to predict hydrate drilling stability for several drilling fluid systems.

  18. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  19. New Composite Sorbents for Caesium and Strontium Ions Sorption

    Directory of Open Access Journals (Sweden)

    Mykola Kartel

    2017-06-01

    Full Text Available Composite lignocellulose-inorganic sorbents derived from plant residues of agriculture and food industry, modified with ferrocyanides of d-metals and hydrated antimony pentoxide were prepared. Caesium and strontium ions removal from water was tested by radiotracer method. Sorption of heavy metal ions, methylene blue, gelatin, vitamin B12 was also studied.

  20. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yongling [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Bo, Maolin [Yangtze Normal University, College of Mechanical and Electrical Engineering, Chongqing 408100 (China); Wang, Yan [School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Liu, Yonghui [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Sun, Chang Q. [NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Huang, Yongli, E-mail: huangyongli@xtu.edu.cn [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China)

    2017-02-28

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O{sup 2−} lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta{sup +} electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta{sup +}; the sp{sup 3}-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent

  1. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    International Nuclear Information System (INIS)

    Guo, Yongling; Bo, Maolin; Wang, Yan; Liu, Yonghui; Sun, Chang Q.; Huang, Yongli

    2017-01-01

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O"2"− lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta"+ electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta"+; the sp"3-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent insight into the

  2. Marine Gas Hydrates - An Untapped Non-conventional Energy ...

    Indian Academy of Sciences (India)

    Table of contents. Marine Gas Hydrates - An Untapped Non-conventional Energy Resource · Slide 2 · Slide 3 · Slide 4 · Gas Hydrate Stability Zone · Slide 6 · Slide 7 · Exploration of gas hydrates (seismic) · Characteristics of BSR · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Distribution of Gas Hydrates in KG ...

  3. Dynamics of hydrated mucopolysaccharides in cartilaginous tissues treated by laser radiation

    Science.gov (United States)

    Omelchenko, Alexander I.; Sobol, Emil N.; Ignatieva, Natalia Y.; Lunin, Valerii V.; Jumel, Kornelia; Harding, Stephen E.; Jones, Nicholas

    2001-05-01

    Dynamic mechanical properties of hydrated mucopolysaccharides have been studied in heated solutions by means of molecular hydrodynamic and acoustic techniques. These experiments model the thermal condition used for laser reshaping of cartilage. It has been shown that elastic modulus and internal friction depends on concentration of chondroitine sulphate in the solution and temperature. Maximum of internal friction was revealed at about 40 degree(s)C that corresponds to temperature of breakdown of hydrophobic bonds. Temperature dependence of internal friction manifests structural changes in polysaccharides molecules under laser heating.

  4. Hydration of excess electrons trapped in charge pockets on molecular surfaces

    Science.gov (United States)

    Jalbout, Abraham F.; Del Castillo, R.; Adamowicz, Ludwik

    2007-01-01

    In this work we strive to design a novel electron trap located on a molecular surface. The process of electron trapping involves hydration of the trapped electron. Previous calculations on surface electron trapping revealed that clusters of OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), while the hydrogen atoms on the opposite side of the surface form pockets of positive charge that can attract extra negative charge. The excess electron density on such surfaces can be further stabilized by interactions with water molecules. Our calculations show that these anionic systems are stable with respect to vertical electron detachment (VDE).

  5. Oxidation potentials, Gibbs energies, enthalpies and entropies of actinide ions in aqueous solutions

    International Nuclear Information System (INIS)

    1977-01-01

    The values of the Gibbs energy, enthalpy, and entropy of different actinide ions, thermodynamic characteristics of the processes of hydration of these ions, and the presently known ionization potentials of actinides are given. The enthalpy and entropy components of the oxidation potentials of actinide elements are considered. The curves of the dependence of the Gibbs energy of ion formation on the atomic number of the element and the Frost diagrams are analyzed. The diagram proposed by Frost represents the graphical dependence of the Gibbs energy of hydrated ions on the degree of oxidation of the element. Using the Frost diagram it is easy to establish whether a given ion is stable to disproportioning

  6. Standardization and software infrastructure for gas hydrate data communications

    Energy Technology Data Exchange (ETDEWEB)

    Kroenlein, K.; Chirico, R.D.; Kazakov, A.; Frenkel, M. [National Inst. of Standards and Technology, Boulder, CO (United States). Physical and Chemical Properties Div.; Lowner, R. [GeoForschungsZentrum Potsdam (Germany); Wang, W. [Chinese Academy of Science, Beijing (China). Computer Network Information Center; Smith, T. [MIT Systems, Flushing, NY (United States); Sloan, E.D. [Colorado School of Mines, Golden, CO (United States). Centre for Hydrate Research

    2008-07-01

    The perceived value of gas hydrates as an energy resource for the future has led to extensive hydrate research studies and experiments. The hydrate deposits are widely dispersed throughout the world, and many countries are now investigating methods of extracting gas hydrate resources. This paper described a gas hydrates markup language (GHML) developed as an international standard for data transfer and storage within the gas hydrates community. The language is related to a hydrates database developed to facilitate a greater understanding of naturally occurring hydrate interactions with geophysical processes, and aid in the development of hydrate technologies for resource recovery and storage. Recent updates to the GHML included the addition of ThermoML, a communication standard for thermodynamic data into the GHML schema. The standard will be used to represent all gas hydrates thermodynamic data. A new element for the description of crystal structures has also been developed, as well as a guided data capture tool. The tool is available free of charge and is publicly licensed for use by gas hydrate data producers. A web service has also been provided to ensure that access to GHML files for gas hydrates and data files are available for users. It was concluded that the tool will help to ensure data quality assurance for the conversion of data and meta-data within the database. 28 refs., 9 figs.

  7. Small angle X-ray scattering from hydrating tricalcium silicate

    International Nuclear Information System (INIS)

    Vollet, D.

    1983-01-01

    The small-angle X-ray scattering technique was used to study the structural evolution of hydrated tricalcium silicate at room temperature. The changes in specific area of the associated porosity and the evolution of density fluctuations in the solid hydrated phase were deduced from the scattering data. A correlation of these variations with the hydration mechanism is tried. (Author) [pt

  8. 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)

  9. Gas hydrate resource quantification in Uruguay

    International Nuclear Information System (INIS)

    Tomasini, J.; De Santa Ana, H.; Veroslavsky, G.

    2012-01-01

    The gas hydrates are crystalline solids formed by natural gas (mostly methane) and water, which are stable in thermobaric conditions given under high pressures and low temperatures. These conditions are given in permafrost zones and continental margin basins offshore in the nature

  10. Pentagonal dodecahedron methane hydrate cage and methanol ...

    Indian Academy of Sciences (India)

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

  11. A new approach to model mixed hydrates

    Czech Academy of Sciences Publication Activity Database

    Hielscher, S.; Vinš, Václav; Jäger, A.; Hrubý, Jan; Breitkopf, C.; Span, R.

    2018-01-01

    Roč. 459, March (2018), s. 170-185 ISSN 0378-3812 R&D Projects: GA ČR(CZ) GA17-08218S Institutional support: RVO:61388998 Keywords : gas hydrate * mixture * modeling Subject RIV: BJ - Thermodynamics Impact factor: 2.473, year: 2016 https://www.sciencedirect.com/science/article/pii/S0378381217304983

  12. [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...

  13. Hydration dynamics near a model protein surface

    International Nuclear Information System (INIS)

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

    2003-01-01

    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

  14. 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...

  15. Gold(III)-Catalyzed Hydration of Phenylacetylene

    Science.gov (United States)

    Leslie, J. Michelle; Tzeel, Benjamin A.

    2016-01-01

    A guided inquiry-based experiment exploring the regioselectivity of the hydration of phenylacetylene is described. The experiment uses an acidic gold(III) catalyst in a benign methanol/water solvent system to introduce students to alkyne chemistry and key principles of green chemistry. The experiment can be easily completed in approximately 2 h,…

  16. [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 sh...

  17. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, Jos

    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

  18. Hydrogeochemical and isotopic signatures of gas hydrate-forming fluids offshore NE Sakhalin (the sea of Okhotsk): Results from the CHAOS-2003 cruises

    International Nuclear Information System (INIS)

    Mazurenko, Leonid; Matveeva, Tatiana; Soloviev, Valery; Prasolov, Eduard; Logvina, Elizaveta; Shoji, Hitoshi; Hachikubo, Akihiro; Minami, Hirotsugi; Sakagami, Hirotoshi

    2005-01-01

    During the CHAOS-2003 cruises of R/V Akademik Lavrentyev three new gas hydrate accumulations named the Chaos, the Hieroglyph and the Kitami were discovered offshore NE Sakhalin (the Sea of Okhotsk) in association with fluid venting. The main goal of this paper is to clarify the origin and the composition of gas and water involving the accumulation of vent-related gas hydrates and to reveal their mechanism of formation. Discharging of deeper sourced water is not observed based on data of the major ion distribution. Observed isotope anomalies of hydrogen (up to 2.52%) and oxygen (up to 0.36%) are higher than fractionation coefficient under gas hydrate formation (1.8% and 0.3%, respectively). These features could be explained by two processes: a) an influence of residual water during gas hydrates formation or b) involving to the process of gas hydrate formation of deep-sourced water. The latter process is most probably influence on the isotopic composition of the pore water. Studied pore water samples consist from three end members: Gas hydrate water, seawater (or in situ pore water of the basin) and deep-sourced water. Results of isotopic studies of water testify that discharged fluid is characterized by light (delta)D (up to approx. 0.11% ) and (delta) 18 O (up to approx. 0.12%). Two mechanisms of gas hydrate accumulation are distinguished: Precipitation from infiltrating gas-saturated water and segregation of pore water by diffusing gas. (Author)

  19. Hydrate-melt electrolytes for high-energy-density aqueous batteries

    Science.gov (United States)

    Yamada, Yuki; Usui, Kenji; Sodeyama, Keitaro; Ko, Seongjae; Tateyama, Yoshitaka; Yamada, Atsuo

    2016-10-01

    Aqueous Li-ion batteries are attracting increasing attention because they are potentially low in cost, safe and environmentally friendly. However, their low energy density (water and the limited selection of suitable negative electrodes, is problematic for their future widespread application. Here, we explore optimized eutectic systems of several organic Li salts and show that a room-temperature hydrate melt of Li salts can be used as a stable aqueous electrolyte in which all water molecules participate in Li+ hydration shells while retaining fluidity. This hydrate-melt electrolyte enables a reversible reaction at a commercial Li4Ti5O12 negative electrode with a low reaction potential (1.55 V versus Li+/Li) and a high capacity (175 mAh g-1). The resultant aqueous Li-ion batteries with high energy density (>130 Wh kg-1) and high voltage (˜2.3-3.1 V) represent significant progress towards performance comparable to that of commercial non-aqueous batteries (with energy densities of ˜150-400 Wh kg-1 and voltages of ˜2.4-3.8 V).

  20. 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.

  1. Enthalpy of dissociation and hydration number of methane hydrate from the Clapeyron equation

    International Nuclear Information System (INIS)

    Anderson, Graydon K.

    2004-01-01

    The enthalpies of the reactions in which methane hydrate is dissociated to methane vapor and either (1) water, or (2) ice are determined by a new analysis using the Clapeyron equation. The difference in enthalpies of the two reactions is used to infer the hydration number at the quadruple point where hydrate, ice, liquid water, and methane vapor coexist. By appropriate corrections, the hydration number at points removed from the quadruple point is also determined. The most important feature of the new analysis is the direct use of the Clapeyron equation. The method avoids the use of certain simplifying assumptions that have compromised the accuracy of previous analyses in which the Clausius-Clapeyron equation was used. The analysis takes into account the finite volumes of all phases, the non-ideality of the vapor phase, and the solubility of methane in water. The results show that the enthalpy of dissociation and hydration number are constant within experimental error over the entire (hydrate, liquid, vapor) coexistence region. The results are more accurate than but entirely consistent with almost all previous studies

  2. 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.

  3. MORPHOLOGY OF METHANE HYDRATE HOST SEDIMENTS

    International Nuclear Information System (INIS)

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

    2004-01-01

    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)

  4. Bonding topologies in diamondlike amorphous-carbon films

    Energy Technology Data Exchange (ETDEWEB)

    SIEGAL,MICHAEL P.; PROVENCIO,PAULA P.; TALLANT,DAVID R.; SIMPSON,REGINA L.; KLEINSORGE,B.; MILNE,W.I.

    2000-01-27

    The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces and their thicknesses increase with increasing deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies < 60 eV and increases for films grown using ion energies > 160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of 4-fold to 3-fold coordinated carbon atoms.

  5. Study of the interaction of multiply charged ions and complex systems of biological interest: effects of the molecular environment

    International Nuclear Information System (INIS)

    Capron, Michael

    2011-01-01

    This PhD thesis describes the experimental study of the interaction between slow multiply charged ions (tens of keV) and molecular systems of biological interest (amino acids and nucleobases). It is the aim to identify and to better understand the effect of a molecular environment on different collision induced phenomena. To do so, the time of flight spectra of cationic products emerging from collisions with isolated molecules as well as clusters are compared. It is shown that the molecular environment protects the molecule as it allows to distribute the transferred energies and charges over the whole system (global decrease of the fragmentation and quenching of some fragmentation channels). Furthermore, in the case of adenine clusters, the molecular environment weakens some intramolecular bonds. Moreover, products of chemical reactions are observed concerning proton transfer processes in hydrated cluster of adenine and the formation of peptides bonds between beta-alanine molecules in a cluster. The latter finding is studied as a function of the cluster size and type of the projectile. Some criteria for peptide bond formation, such as flexibility and geometry of the molecule, are investigated for different amino acids. (author)

  6. 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

  7. Bond markets in Africa

    Directory of Open Access Journals (Sweden)

    Yibin Mu

    2013-07-01

    Full Text Available African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on government securities and corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to better institutions and interest rate volatility, and inversely related to smaller fiscal deficits, higher interest rate spreads, exchange rate volatility, and current and capital account openness. Corporate bond market capitalization is directly linked to economic size, the level of development of the economy and financial markets, better institutions, and interest rate volatility, and inversely related to higher interest rate spreads and current account openness. Policy implications follow.

  8. Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

    Science.gov (United States)

    Weber, J. Mathias; Adams, Christopher L.

    2010-06-01

    We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

  9. Molecular rotation-vibration dynamics of low-symmetric hydrate crystal in the terahertz region.

    Science.gov (United States)

    Fu, Xiaojian; Wu, Hongya; Xi, Xiaoqing; Zhou, Ji

    2014-01-16

    The rotational and vibrational dynamics of molecules in copper sulfate pentahydrate crystal are investigated with terahertz dielectric spectra. It is shown that the relaxation-like dielectric dispersion in the low frequency region is related to the reorientation of water molecules under the driving of terahertz electric field, whereas the resonant dispersion can be ascribed to lattice vibration. It is also found that, due to the hydrogen-bond effect, the vibrational mode at about 1.83 THz along [-111] direction softens with decreasing temperature, that is, the crystal expands in this direction when cooled. On the contrary, the mode hardens in the direction perpendicular to [-111] during the cooling process. This contributes to the further understanding of the molecular structure and bonding features of hydrate crystals.

  10. Quinolinium 8-hy-droxy-7-iodo-quinoline-5-sulfonate 0.8-hydrate.

    Science.gov (United States)

    Smith, Graham

    2012-12-01

    In the crystal structure of the title hydrated quinolinium salt of ferron (8-hy-droxy-7-iodo-quinoline-5-sulfonic acid), C9H7N(+)·C9H5INO4S(-)·0.8H2O, the quinolinium cation is fully disordered over two sites (occupancy factors fixed at 0.63 and 0.37) lying essentially within a common plane and with the ferron anions forming π-π-associated stacks down the b axis [minimum ring centroid separation = 3.462 (6) Å]. The cations and anions are linked into chains extending along c through hy-droxy O-H⋯O and quinolinium N-H⋯O hydrogen bonds to sulfonate O-atom acceptors which are also involved in water O-H⋯O hydrogen-bonding inter-actions along b, giving a two-dimensional network.

  11. Quinolinium 8-hydroxy-7-iodoquinoline-5-sulfonate 0.8-hydrate

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2012-12-01

    Full Text Available In the crystal structure of the title hydrated quinolinium salt of ferron (8-hydroxy-7-iodoquinoline-5-sulfonic acid, C9H7N+·C9H5INO4S−·0.8H2O, the quinolinium cation is fully disordered over two sites (occupancy factors fixed at 0.63 and 0.37 lying essentially within a common plane and with the ferron anions forming π–π-associated stacks down the b axis [minimum ring centroid separation = 3.462 (6 Å]. The cations and anions are linked into chains extending along c through hydroxy O—H...O and quinolinium N—H...O hydrogen bonds to sulfonate O-atom acceptors which are also involved in water O—H...O hydrogen-bonding interactions along b, giving a two-dimensional network.

  12. The structure of hydrate bearing fine grained marine sediments

    Energy Technology Data Exchange (ETDEWEB)

    Priest, J.; Kingston, E.; Clayton, C. [Southampton Univ., Highfield (United Kingdom). School of Civil Engineering and the Environment; Schultheiss, P.; Druce, M. [Geotek Ltd., Daventry (United Kingdom)

    2008-07-01

    This paper discussed the structure of naturally occurring methane gas hydrates in fine-grained sediments from core samples recovered using in situ pressures from the eastern margin of the Indian Ocean. High resolution X-ray computed tomography (CT) images were taken of gas hydrate cores. The hydrate structure was examined and comparisons were made between low resolution X-ray images obtained on the cores prior to sub-sectioning and depressurization procedures. The X-ray images showed the presence of high-angle, sub-parallel veins within the recovered sediments. The scans indicated that the hydrates occurred as fracture filing veins throughout the core. Fracture orientation was predominantly sub-vertical. Thick millimetric hydrate veins were composed of sub-millimetric veins with variations in fracture angle. The analysis indicated that hydrate formation was episodic in nature and subject to changes in the stress regime. Results of the study showed that depressurization and subsequent freezing alter the structure of the sediment even when the gas hydrate has not been altered. A large proportion of the hydrate survived when outside of its stability region. The self-preserving behaviour of the hydrate was attributed to the endothermic nature of gas hydrate dissociation. It was concluded that the accurate physical characterization of gas hydrates can only be conducted when the core section remains under in situ stress conditions. 13 refs., 9 figs.

  13. Carbon dioxide hydrate formation in a fixed-bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Fan, S.; Lang, X. [South China Univ. of Technology, Guangzhou (China). Key Laboratory of Enhanced Heat Transfer and Energy Conservation; Wang, Y.; Liang, D. [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Energy Conversion and Guangzhou Center of Natural Gas Hydrate; Sun, X.; Jurcik, B. [Air Liquide Laboratories, Tsukuba (Japan)

    2008-07-01

    Gas hydrates are thermodynamically stable at high pressures and near the freezing temperature of pure water. Methane hydrates occur naturally in sediments in the deep oceans and permafrost regions and constitute an extensive hydrocarbon reservoir. Carbon dioxide (CO{sub 2}) hydrates are of interest as a medium for marine sequestration of anthropogenic carbon dioxide. Sequestering CO{sub 2} as hydrate has potential advantages over most methods proposed for marine CO{sub 2} sequestration. Because this technique requires a shallower depth of injection when compared with other ocean sequestration methods, the costs of CO{sub 2} hydrate sequestration may be lower. Many studies have successfully used different continuous reactor designs to produce CO{sub 2} hydrates in both laboratory and field settings. This paper discussed a study that involved the design and construction of a fixed-bed reactor for simulation of hydrate formation system. Water, river sands and carbon dioxide were used to simulate the seep kind of hydrate formation. Carbon dioxide gas was distributed as small bubbles to enter from the bottom of the fixed-bed reactor. The paper discussed the experimental data and presented a diagram of the gas hydrate reactor system. The morphology as well as the reaction characters of CO{sub 2} hydrate was presented in detail. The results were discussed in terms of experimental phenomena and hydrate formation rate. A mathematical model was proposed for describing the process. 17 refs., 7 figs.

  14. 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.V.; ,

    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.