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Sample records for dilute salt solutions

  1. Thermodynamics of Dilute Solutions.

    ERIC Educational Resources Information Center

    Jancso, Gabor; Fenby, David V.

    1983-01-01

    Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

  2. Mechanism of Pitting Corrosion Prevention by Nitrite in Carbon Steel Exposed to Dilute Salt Solutions

    SciTech Connect

    Philip E. Zapp; John W. Van Zee

    2002-02-01

    The research has developed a broad fundamental understanding of the inhibition action of nitrite ions in preventing nitrate pitting corrosion of carbon steel tanks containing high-level radioactive waste. This fundamental understanding can be applied to specific situations during waste removal for permanent disposition and waste tank closure to ensure that the tanks are maintained safely. The results of the research provide the insight necessary to develop solutions that prevent further degradation.

  3. Dilute acid/metal salt hydrolysis of lignocellulosics

    DOEpatents

    Nguyen, Quang A.; Tucker, Melvin P.

    2002-01-01

    A modified dilute acid method of hydrolyzing the cellulose and hemicellulose in lignocellulosic material under conditions to obtain higher overall fermentable sugar yields than is obtainable using dilute acid alone, comprising: impregnating a lignocellulosic feedstock with a mixture of an amount of aqueous solution of a dilute acid catalyst and a metal salt catalyst sufficient to provide higher overall fermentable sugar yields than is obtainable when hydrolyzing with dilute acid alone; loading the impregnated lignocellulosic feedstock into a reactor and heating for a sufficient period of time to hydrolyze substantially all of the hemicellulose and greater than 45% of the cellulose to water soluble sugars; and recovering the water soluble sugars.

  4. Dynamics of dilute solutions of poly(aspartic acid) and its sodium salt elucidated from atomistic molecular dynamics simulations with explicit water.

    PubMed

    Ramachandran, Sanoop; Katha, Anki Reddy; Kolake, Subramanya Mayya; Jung, Bokyung; Han, Sungsoo

    2013-11-01

    The use of forward osmosis (FO) process for seawater desalination has attracted tremendous interest in recent years. Besides the manufacture of suitable membranes, the major technical challenge in the efficient deployment of the FO technology lies in the development of a suitable "draw solute". Owing to its inherent advantages, poly(aspartic acid) has arisen to be an attractive candidate for this purpose. However, an investigation of its molecular level properties has not been studied in detail. In this paper, the dynamics of poly(aspartic acid) and its sodium salt in the dilute concentration regime have been reported. The quantification of the polymer conformational properties, its solvation behavior, and the counterion dynamics are studied. The neutral polymer shows a preferentially coiled structure whereas the fully ionized polymer has an extended structure. Upon comparing with poly(acrylic acid) polymer, another polymer which has been used as a draw solute, poly(aspartic acid) forms more number of hydrogen bonds as well as fewer ion pairs. PMID:24099271

  5. Statistical mechanics of sum frequency generation spectroscopy for the liquid-vapor interface of dilute aqueous salt solutions

    SciTech Connect

    Noah-Vanhoucke, Joyce; Smith, Jared D.; Geissler, Phillip L.

    2009-01-02

    We demonstrate a theoretical description of vibrational sum frequency generation (SFG) at the boundary of aqueous electrolyte solutions. This approach identifies and exploits a simple relationship between SFG lineshapes and the statistics of molecular orientation and electric field. Our computer simulations indicate that orientational averages governing SFG susceptibility do not manifest ion-specific shifts in local electric field, but instead, ion-induced polarization of subsurface layers. Counterbalancing effects are obtained for monovalent anions and cations at the same depth. Ions held at different depths induce an imbalanced polarization, suggesting that ion-specific effects can arise from weak, long ranged influence on solvent organization.

  6. Nematic ordering in dilute solutions of rodlike polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Potemkin, Igor I.; Khokhlov, Alexei R.

    2004-06-01

    Quantitative theory of orientational behavior of rodlike polyelectrolytes in dilute solution is developed. We find that in salt-free solutions many-body Coulomb interactions between macro- and counterions favor nematic ordering. It is shown that the orientationally isotropic phase of the solution becomes unstable toward nematic ordering at polymer concentration smaller than the overlap concentration. Our predictions are consistent with experimental observations for synthetic polyelectrolytes poly(p-phenylene)sulfonates in aqueous solutions.

  7. Ammonia Solubility in High Concentration Salt Solutions

    SciTech Connect

    HEDENGREN, D.C.

    2000-02-01

    Solubility data for ammonia in water and various dilute solutions are abundant in the literature. However, there is a noticeable lack of ammonia solubility data for high salt, basic solutions of various mixtures of salts including those found in many of the Hanford Washington underground waste tanks. As a result, models based on solubility data for dilute salt solutions have been used to extrapolate to high salt solutions. These significant extrapolations need to be checked against actual laboratory data. Some indirect vapor measurements have been made. A more direct approach is to determine the ratio of solubility of ammonia in water to its solubility in high salt solutions. In various experiments, pairs of solutions, one of which is water and the other a high salt solution, are allowed to come to equilibrium with a common ammonia vapor pressure. The ratio of concentrations of ammonia in the two solutions is equal to the ratio of the respective ammonia solubilities (Henry's Law constants) at a given temperature. This information can then be used to refine the models that predict vapor space compositions of ammonia. Ammonia at Hanford is of concern because of its toxicity in the environment and its contribution to the flammability of vapor space gas mixtures in waste tanks.

  8. Neutron scattering study of dilute supercritical solutions

    SciTech Connect

    Cochran, H.D.; Wignall, G.D.; Shah, V.M.; Londono, J.D.; Bienkowski, P.R.

    1994-10-01

    Dilute solutions in supercritical solvents exhibit interesting microstructures that are related to their dramatic macroscopic behavior. In typical attractive solutions, solutes are believed to be surrounded by clusters of solvent molecules, and solute molecules are believed to congregate in the vicinity of one another. Repulsive solutions, on the other hand, exhibit a local region of reduced solvent density around the solute with solute-solute congregation. Such microstructures influence solubility, partial molar volume, reaction kinetics, and many other properties. We have undertaken to observe these interesting microstructures directly by neutron scattering experiments on dilute noble gas systems including Ar. The three partial structure factors for such systems and the corresponding pair correlation functions can be determined by using the isotope substitution technique. The systems studied are uniquely suited for our objectives because of the large coherent neutron scattering length of the isotope {sup 36}Ar and because of the accurate potential energy functions that are available for use in molecular simulations and theoretical calculations to be compared with the scattering results. We will describe our experiment, the unique apparatus we have built for it, and the neutron scattering results from our initial allocations of beam time. We will also describe planned scattering experiments to follow those with noble gases, including study of long-chain molecules in supercritical solvents. Such studies will involve hydrocarbon mixtures with and without deuteration to provide contrast.

  9. Electrochromic salts, solutions, and devices

    DOEpatents

    Burrell, Anthony K.; Warner, Benjamin P.; McClesky,7,064,212 T. Mark

    2006-06-20

    Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

  10. Electrochromic Salts, Solutions, and Devices

    DOEpatents

    Burrell, Anthony K.; Warner, Benjamin P.; McClesky, T. Mark

    2008-10-14

    Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

  11. Electrochromic Salts, Solutions, and Devices

    DOEpatents

    Burrell, Anthony K.; Warner, Benjamin P.; McClesky, T. Mark

    2008-11-11

    Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

  12. Protein aggregation in salt solutions

    PubMed Central

    Kastelic, Miha; Kalyuzhnyi, Yurij V.; Hribar-Lee, Barbara; Dill, Ken A.; Vlachy, Vojko

    2015-01-01

    Protein aggregation is broadly important in diseases and in formulations of biological drugs. Here, we develop a theoretical model for reversible protein–protein aggregation in salt solutions. We treat proteins as hard spheres having square-well-energy binding sites, using Wertheim’s thermodynamic perturbation theory. The necessary condition required for such modeling to be realistic is that proteins in solution during the experiment remain in their compact form. Within this limitation our model gives accurate liquid–liquid coexistence curves for lysozyme and γ IIIa-crystallin solutions in respective buffers. It provides good fits to the cloud-point curves of lysozyme in buffer–salt mixtures as a function of the type and concentration of salt. It than predicts full coexistence curves, osmotic compressibilities, and second virial coefficients under such conditions. This treatment may also be relevant to protein crystallization. PMID:25964322

  13. Hydrodynamic behavior and dilute solution properties of Ulva fasciata algae polysaccharide.

    PubMed

    Shao, Ping; Zhu, Yueqiong; Qin, Minpu; Fang, Zhongxiang; Sun, Peilong

    2015-12-10

    Hydrodynamic behavior and dilute solution properties of Ulva fasciata polysaccharides (UFP) were investigated. Experimental results indicated that the variation of hydrodynamic behavior of UFP was affected by the type and concentration of salts. The specific viscosity of UFP in water increased with its increasing concentration. The slopes of the double logarithmic plots in the dilute and semi-dilute solutions were 0.86 and 1.99, respectively. The molecular conformation could be semi-flexible like. Huggins plots of UFP solutions in the presence of salts including Na(+), K(+), Mg(2+) and Ca(2+) showed that the hydrodynamic behavior of the UFP was strongly affected by the types and strength of salt ion. The stiffness parameter of UFP solution was 0.1149, higher than that of other reported polysaccharides, indicating that it could tolerate high salt concentration. Dynamic rheological results suggested that 0.5% UFP solution was a typical characteristic of polymer solution in the dilute region. This work provided some valuable and fundamental information in understanding the physicochemical properties of UFP solution. PMID:26428159

  14. Ionic liquids behave as dilute electrolyte solutions

    PubMed Central

    Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

    2013-01-01

    We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

  15. Terahertz absorption of dilute aqueous solutions

    NASA Astrophysics Data System (ADS)

    Heyden, Matthias; Tobias, Douglas J.; Matyushov, Dmitry V.

    2012-12-01

    Absorption of terahertz (THz) radiation by aqueous solutions of large solutes reports on the polarization response of their hydration shells. This is because the dipolar relaxation of the solute is dynamically frozen at these frequencies, and most of the solute-induced absorption changes, apart from the expulsion of water, are caused by interfacial water. We propose a model expressing the dipolar response of solutions in terms of a single parameter, the interface dipole moment induced in the interfacial water by electromagnetic radiation. We apply this concept to experimental THz absorption of hydrated sugars, amino acids, and proteins. None of the solutes studied here follow the expectations of dielectric theories, which predict a negative projection of the interface dipole on the external electric field. We find that this prediction is not able to describe the available experimental data, which instead suggests a nearly zero interface dipole for sugars and a more diverse pattern for amino acids. Hydrophobic amino acids, similarly to sugars, give rise to near zero interface dipoles, while strongly hydrophilic ones are best described by a positive projection of the interface dipole on the external field. The sign of the interface dipole is connected to the slope of the absorption coefficient with the solute concentration. A positive slope, implying an increase in the solution polarity relative to water, mirrors results frequently reported for protein solutions. We therefore use molecular dynamics simulations of hydrated glucose and lambda repressor protein to calculate the interface dipole moments of these solutes and the concentration dependence of the THz absorption. The absorption at THz frequencies increases with increasing solute concentration in both cases, implying a higher polarity of the solution compared to bulk water. The structure of the hydration layer, extracted from simulations, is qualitatively similar in both cases, with spatial correlations

  16. Absorption spectra of cold dilute solid solutions

    SciTech Connect

    Holland, R.F.; Maier, W.B. II; Freund, S.; Beattie, W.H.

    1983-06-01

    Infrared absorption spectra have been obtained for some compounds trapped in crystalline solids by freezing liquid Xe, Kr, Ar, or CH/sub 4/ solutions. The optical quality of the solid solutions is good, and they have been cooled to approx.80 K in 1.35 cm sample thicknesses to study the absorption in fundamental vibrational bands of the solutes. In the cases discussed, the bands are narrow, with observed full widths at half-maximum absorbance 0.05--0.30 cm/sup -1/ greater than the instrumental resolution (0.18--0.29 cm/sup -1/). The spectra appear to be free of ''multiple site'' and solute aggregate absorptions. Spectra displaying isotropic splitting in bands of natural BCl/sub 3/, SeF/sub 6/, OsO/sub 4/, TiCl/sub 4/, and MoF/sub 6/ are presented, and band frequencies are compared with some results obtained in evaporative matrices, in the gas phase, and in liquid solutions. For this comparison we have obtained some spectra of SeF/sub 6/ and BCl/sub 3/ gas.

  17. Salting-out and Salting-in in Polyelectrolyte Solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Pengfei; Wu, Jianzhong; Wang, Zhen-Gang

    The phase behavior of polyelectrolyte (PE) solutions is governed by complicated interplay involving the mixing entropy, excluded volume, chain connectivity, and electrostatic interactions. Here we study the phase behavior of PE solutions in both salt-free condition and with added salt using a liquid-state (LS) theory based thermodynamic model. The LS model accounts or the hard-core repulsion by the Canahan-Starling equation of state, correlations due to chain connectivity by the first-order thermodynamic perturbation theory, and electrostatic correlations by the mean-spherical approximation. In comparison to the prediction from the well-known Voorn-Overbeek theory, the LS model predicts loop-type binodal curves in the salt-PE concentration diagram at temperatures slightly above the critical temperature of PE solution in salt-free case, consistent with the experimental study. The phase separated region shrinks with increasing temperature. Three scenarios of salting-out and salting-in phenomenon are predicted with addition of salts based, depending on the PE concentration.

  18. SEPARATION OF INORGANIC SALTS FROM ORGANIC SOLUTIONS

    DOEpatents

    Katzin, L.I.; Sullivan, J.C.

    1958-06-24

    A process is described for recovering the nitrates of uranium and plutonium from solution in oxygen-containing organic solvents such as ketones or ethers. The solution of such salts dissolved in an oxygen-containing organic compound is contacted with an ion exchange resin whereby sorption of the entire salt on the resin takes place and then the salt-depleted liquid and the resin are separated from each other. The reaction seems to be based on an anion formation of the entire salt by complexing with the anion of the resin. Strong base or quaternary ammonium type resins can be used successfully in this process.

  19. Radiolysis of paracetamol in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Takács, Erzsébet; Wojnárovits, László

    2012-09-01

    Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O2 is c.a. 10%. The efficiency is 2-3 times higher in the presence of O2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily.

  20. Coordination chemistry in fused-salt solutions

    NASA Technical Reports Server (NTRS)

    Gruen, D. M.

    1969-01-01

    Spectrophotometric work on structural determinations with fused-salt solutions is reviewed. Constraints placed on the method, as well as interpretation of the spectra, are discussed with parallels drawn to aqueous spectrophotometric curves of the same materials.

  1. Motor-mediated microtubule self-organization in dilute and semi-dilute filament solutions.

    SciTech Connect

    Swaminathan, S.; Ziebert, F.; Aranson, I. S.; Karpeev, D.

    2011-01-01

    We study molecular motor-induced microtubule self-organization in dilute and semi-dilute filament solutions. In the dilute case, we use a probabilistic model of microtubule interaction via molecular motors to investigate microtubule bundle dynamics. Microtubules are modeled as polar rods interacting through fully inelastic, binary collisions. Our model indicates that initially disordered systems of interacting rods exhibit an orientational instability resulting in spontaneous ordering. We study the existence and dynamic interaction of microtubule bundles analytically and numerically. Our results reveal a long term attraction and coalescing of bundles indicating a clear coarsening in the system; microtubule bundles concentrate into fewer orientations on a slow logarithmic time scale. In semi-dilute filament solutions, multiple motors can bind a filament to several others and, for a critical motor density, induce a transition to an ordered phase with a nonzero mean orientation. Motors attach to a pair of filaments and walk along the pair bringing them into closer alignment. We develop a spatially homogenous, mean-field theory that explicitly accounts for a force-dependent detachment rate of motors, which in turn affects the mean and the fluctuations of the net force acting on a filament. We show that the transition to the oriented state can be both continuous and discontinuous when the force-dependent detachment of motors is important.

  2. Reusable chelating resins concentrate metal ions from highly dilute solutions

    NASA Technical Reports Server (NTRS)

    Bauman, A. J.; Weetal, H. H.; Weliky, N.

    1966-01-01

    Column chromatographic method uses new metal chelating resins for recovering heavy-metal ions from highly dilute solutions. The absorbed heavy-metal cations may be removed from the chelating resins by acid or base washes. The resins are reusable after the washes are completed.

  3. Process of concentrating ethanol from dilute aqueous solutions thereof

    DOEpatents

    Oulman, C.S.; Chriswell, C.D.

    1981-07-07

    Relatively dilute aqueous solutions of ethanol are concentrated by passage through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. This process permits ethanol to be concentrated from dilute fermentation beers, which may contain from 6 to 10% ethanol, to obtain a concentrate product at very low energy cost having an ethanol concentration in excess of 95%, such as a concentration of from 98 to 99.5%. 5 figs.

  4. Process of concentrating ethanol from dilute aqueous solutions thereof

    DOEpatents

    Oulman, Charles S. [Ames, IA; Chriswell, Colin D. [Slater, IA

    1981-07-07

    Relatively dilute aqueous solutions of ethanol are concentrated by passage through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. This process permits ethanol to be concentrated from dilute fermentation beers, which may contain from 6 to 10% ethanol, to obtain a concentrate product at very low energy cost having an ethanol concentration in excess of 95%, such as a concentration of from 98 to 99.5%.

  5. Separation and concentration of lower alcohols from dilute aqueous solutions

    DOEpatents

    Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

    1991-01-01

    A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

  6. Geophysical methods to support correct water sampling locations for salt dilution gauging

    NASA Astrophysics Data System (ADS)

    Comina, C.; Lasagna, M.; De Luca, D. A.; Sambuelli, L.

    2014-05-01

    To improve water management design, particularly in irrigation areas, it is important to evaluate the baseline state of the water resources, including canal discharge. Discharge measurements, using salt dilution gauging, are a traditional and well-documented technique. The complete mixing of salt used for dilution gauging is required for reliable measurements; this condition is difficult to test or verify and, if not fulfilled, is the largest source of uncertainty in the discharge calculation. In this paper, a geophysical technique (FERT, Fast Electrical Resistivity Tomography) is proposed for imaging the distribution of the salt plume used for dilution gauging at every point along a sampling cross-section. In this way, it is possible to check whether complete mixing has occurred. If the mixing is not complete, the image created by FERT can also provide guidance for selecting water-sampling locations in the sampling cross-section. A water multi-sampling system prototype for the simultaneous sampling of canal water at different points within the cross-section, aimed to potentially take into account concentration variability, is also proposed and tested. Preliminary results of a single test with salt dilution gauging and FERT in a real case are reported. The results show that imaging the passage of the salt plume is possible by means of geophysical controls and that this can potentially help in the selection of water sampling points.

  7. Fluidized bed electrowinning of chromium from very dilute solutions

    SciTech Connect

    Hu, X.; Bautista, R.G.

    1988-10-01

    The Fluidized Bed Electrochemical Reactor (FBER) was used to electrowin chromium from very dilute solutions, ranging in concentration from 0.52 to 3.12 g Cr/1 at pH = 2. The cathode consisted of particulate chromium (450-600 ..mu..m diam.) with a current feeder made of carbon bars and a tubular lead anode in a cylindrical cell. The current efficiency was in the range of 0.08-0.22. The bed expansion, deposition rate, conversion ratio of Cr(VI) to Cr(III) and voltage - current characteristic of the cell were studied. The results indicate that the use of the FBER will make possible the removal of chromium from very dilute solutions without the introduction of other chemicals which would need to be removed or treated further downstream to satisfy environmental abatement codes.

  8. High-throughput ab-initio dilute solute diffusion database

    PubMed Central

    Wu, Henry; Mayeshiba, Tam; Morgan, Dane

    2016-01-01

    We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

  9. High-throughput ab-initio dilute solute diffusion database.

    PubMed

    Wu, Henry; Mayeshiba, Tam; Morgan, Dane

    2016-01-01

    We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

  10. Solubility of uranium in alkaline salt solutions

    SciTech Connect

    Hobbs, D.T.; Edwards, T.B.

    1994-03-29

    The solubility of uranium in alkaline salt solutions was investigated to screen for significant factors and interactions among the major salt components and temperature. The components included in the study were the sodium salts of hydroxide, nitrate, nitrite, aluminate, sulfate, and carbonate. General findings from the study included: (1) uranium solubilities are very low (1-20 mg/L) for all solution compositions at hydroxide concentrations from 0.1 to 17 molar (2) carbonate, sulfate, and aluminate are not effective complexants for uranium at high hydroxide concentration, (3) uranium solubility decreases with increasing temperature for most alkaline salt solutions, and (4) uranium solubility increases with changes in solution chemistry that reflect aging of high level waste (increase in nitrite and carbonate concentrations, decrease in nitrate and hydroxide concentrations). A predictive model for the concentration of uranium as a function of component concentrations and temperature was fitted to the data. All of the solution components and temperature were found to be significant. There is a significant lack of fit for the model, which suggests that the dependence on the uranium solubility over the wide range of solution compositions is non-linear and/or that there are other uncontrolled parameters which are important to the uranium solubility.

  11. Modeling Corrosion Reactions of Steel in a Dilute Carbonate Solution

    NASA Astrophysics Data System (ADS)

    Eliyan, Faysal Fayez; Alfantazi, Akram

    2016-02-01

    This research models the corrosion reactions of a high-strength steel in an aerated, dilute, carbonate solution during a single-cycle voltammetry. Based on a previous study (Eliyan et al. in J Mater Eng Perform 24(6):1-8, 2015) and a literature survey, the corrosion reactions of the cathodic reduction, anodic dissolution, and passivation, as well as the interfacial interactions and the chemistry of the corrosion products are illustrated in schematics. The paper provides a visual guide on the corrosion reactions for steel in carbonate solutions based on the available mechanistic details that were reported and are still being investigated in literature.

  12. Heat-induced formation of myosin oligomer-soluble filament complex in high-salt solution.

    PubMed

    Shimada, Masato; Takai, Eisuke; Ejima, Daisuke; Arakawa, Tsutomu; Shiraki, Kentaro

    2015-02-01

    Heat-induced aggregation of myosin into an elastic gel plays an important role in the water-holding capacity and texture of meat products. Here, we investigated thermal aggregation of porcine myosin in high-salt solution over a wide temperature range by dynamic light scattering experiments. The myosin samples were readily dissolved in 1.0 M NaCl at 25 °C followed by dilution into various salt concentrations. The diluted solutions consistently contained both myosin monomers and soluble filaments. The filament size decreased with increasing salt concentration and temperature. High temperatures above Tm led to at least partial dissociation of soluble filaments and thermal unfolding, resulting in the formation of soluble oligomers and binding to the persistently present soluble filaments. Such a complex formation between the oligomers and filaments has never been observed. Our results provide new insight into the heat-induced myosin gelation in high-salt solution. PMID:25445683

  13. Scattering by solutions of major sea salts.

    PubMed

    Zhang, Xiaodong; Hu, Lianbo; Twardowski, Michael S; Sullivan, James M

    2009-10-26

    Increased scattering by seawater relative to that by pure water is primarily due to additional fluctuation of the refractive index contributed by sea salts. Salts with different ionic weight and sizes, while barely affecting the scattering that is due to density fluctuations, have a significant effect on the scattering that is due to concentration fluctuations. And this explains the major differences of their total scattering that would be observed. Scattering by solutions of NaCl, the major sea salt, is consistently about 6.7% and 4% lower than seawater of the same mass concentration and of the same refractive index, respectively. Because of ionic interactions, the molecular scattering does not follow the simple addition rule that applies to bulk inherent optical properties, with the total less than the summation of the parts. The possible values of scattering by waters of, such as, Dead Sea or Orca Basin, which have different salt composition from seawater, are discussed. PMID:19997177

  14. Americium separations from high salt solutions

    SciTech Connect

    Mary E. Barr; Gordon D. Jarvinen; Louis D. Schulte; Peter C. Stark; Rebecca M. Chamberlin; Kent D. Abney; Thomas E. Ricketts; Yvette E. Valdez; Richard A. Bartsch

    2000-03-01

    Americium (III) exhibits an unexpectedly high affinity for anion-exchange material from the high-salt evaporator bottoms solutions--an effect which has not been duplicated using simple salt solutions. Similar behavior is observed for its lanthanide homologue, Nd(III), in complex evaporator bottoms surrogate solutions. There appears to be no single controlling factor--acid concentration, total nitrate concentration or solution ionic strength--which accounts for the approximately 2-fold increase in retention of the trivalent ions from complex solutions relative to simple solutions. Calculation of species activities (i.e., water, proton and nitrate) in such concentrated mixed salt solutions is difficult and of questionable accuracy, but it is likely that the answer to forcing formation of anionic nitrate complexes of americium lies in the relative activities of water and nitrate. From a practical viewpoint, the modest americium removal needs (ca. 50--75%) from nitric acid evaporator bottoms allow sufficient latitude for the use of non-optimized conditions such as running existing columns filled with older, well-used Reillex HPQ. Newer materials, such as HPQ-100 and the experimental bifunctional resins, which exhibit higher distribution coefficients, would allow for either increased Am removal or the use of smaller columns. It is also of interest that one of the experimental neutral-donor solid-support extractants, DHDECMP, exhibits a similarly high level of americium (total alpha) removal from EV bottoms and is much less sensitive to total acid content than commercially-available material.

  15. HORSMIC. Horizontal Salt Solution Mining Model

    SciTech Connect

    Russo, A.J.

    1994-01-01

    The code HORSMIC was written to solve the problem of calculating the shape of hydrocarbon (gas or liquid) storage caverns formed by solution mining in bedded salt formations. In the past many storage caverns have been formed by vertically drilling into salt dome formations and solution mining large-aspect-ratio, vertically axisymmetric caverns. This approach is generally not satisfactory for shallow salt beds because it would result in geomechanically-unstable, pancake-shaped caverns. In order to produce a high aspect ratio cavern in the horizontal direction a more complicated strategy must be employed. This code was developed to implement such a strategy, and can be used to estimate the shape of the cavern produced by a prescribed leaching schedule. Multiple trials can then be used to investigate the effects of various pipe hole configurations in order to optimize over the cavern shape.

  16. Oscillations in a Linearly Stratified Salt Solution

    ERIC Educational Resources Information Center

    Heavers, Richard M.

    2007-01-01

    Our physics students like to watch a ball bouncing underwater. They do this by dropping a weighted plastic ball into a 1000-ml cylinder filled with a linearly stratified salt-water solution at room temperature. The ball oscillates and comes to rest at about mid-depth. Its motion is analogous to the damped vertical oscillations of a mass hanging…

  17. Stability of dilute solutions of uranium, lead, and thorium ions

    USGS Publications Warehouse

    Milkey, R.G.

    1954-01-01

    Standard solutions and samples containing a few micrograms of metallic ions per milliliter are frequently used in determination of trace elements. It is important to know whether the concentrations of such solutions remain constant from day to day. The stability of dilute solutions of three metallic ions-uranium, lead, and thorium-has been investigated. Solutions containing concentrations of metallic ions, ranging from 1000 to 0.1 ?? per milliliter, were allowed to stand for approximately 2.5 months, and then the metallic ion content of those solutions that had lost strength was determined. Both adsorption and hydrolysis variously influenced the solute loss, but the minimum pH at which loss of concentration of lead and uranium occurred seemed to coincide with the pH at which the hydrolyzed metal ions began to precipitate. No increase in the stability of the solutions was obtained by substituting polyethylene containers for borosilicate glass. The solutions that lost strength could not be restored promptly to the original concentration by manual means, such as shaking them vigorously for several minutes.

  18. Degradation of Sodium-Polyacrylate in Dilute Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Saita, Takao

    1980-12-01

    It is shown using a capillary viscometer that the viscosity of a dilute aqueous solution of sodium-polyacrylate at 20°C decreases gradually for each flow time measurement and also decreases with the time of rest. Assuming that the polymer degradation is caused by shearing stress and oxidation, their effects are discussed with the data obtained using a closed-type capillary viscometer derived for this investigation. It is proved from the results that rupture of the Na-PAA molecule is caused by mechanochemical degradation, and also photo-degradation under the usual illumination and sunlight in a laboratory.

  19. Thermodynamics of suspensions of polymeric chains in dilute solutions

    NASA Astrophysics Data System (ADS)

    Palumbo, Annunziata; Valenti, Antonino; Lebon, Georgy

    2010-07-01

    A model of suspensions of deformable polymeric chains in dilute solutions is proposed. The originality of the model lies in raising the relative motion of polymers with respect to the solvent to the status of independent variables, at the same level of such classical variables as global mass, mass fraction, temperature, and conformation tensor. Such an attitude is typical of extended irreversible thermodynamics. It is shown that the restrictions placed by the second law of thermodynamics leads to the various expressions of the constitutive and evolution equations governing the model. The use of Onsager's reciprocal relations and the criterion of frame indifference is also commented upon.

  20. Degradation of Sodium-Polyacrylate in Dilute Aqueous Solution, II

    NASA Astrophysics Data System (ADS)

    Saita, Takao; Matumura, On

    1983-08-01

    It has been found that Na-PAA molecules in dilute aqueous solution are degraded by shearing stress, oxidation and photolysis during usual viscosity measurements with a capillary viscometer. The results of previous viscosity measurements, mainly about the mechanochemical degradation in air and in air-free conditions, showed that the degradation rate increases with increasing shear stress, and with decreasing polymer concentration. In this work, the effects of the molecular weight and temperature on the degradation rate are measured using a capillary viscometer in air, and the photodegradation of Na-PAA and PAA in aqueous solution irradiated with UV light are studied by viscosity measurements in air, and by UV absorption and ESR methods. The results show that the degradation of molecules is enhanced by an increase in the molecular weight and strongly accelerated by a rise in temperature and by UV irradiation, and is accompanied by free-radical chain reactions.

  1. Molecular dynamics of a dilute solution of hydrogen in palladium

    NASA Astrophysics Data System (ADS)

    Pratt, Lawrence R.; Eckert, J.

    1989-06-01

    Molecular-dynamics results on a dilute solution of H in Pd are presented and compared with available incoherent inelastic neutron-scattering results. The embedded-atom model adopted here does a good job of describing the H-Pd atomic forces probed by incoherent inelastic neutron scattering. The time correlation functions associated with the computed spectra are strongly damped and indicative of the anharmonicity that has been suggested as the principal contribution to the anomalous isotope dependence of the superconducting transition temperature in PdH. These results highlight the fact that the H-atom vibrations in Pd-H solutions are low-frequency, large-amplitude vibrations relative to vibrations of H atoms in usual covalent interactions. The rms displacement of the H atom from its mean position in the center of the Pd octahedron compares favorably with the available neutron-diffraction results.

  2. Extensional behavior of rod suspension in dilute polymer solution

    NASA Astrophysics Data System (ADS)

    Han, Hyejin; Kim, Chongyoup

    2015-08-01

    Extensional viscosity of rod particle suspensions in polymer solutions is studied experimentally. Rod particle suspensions were prepared by dispersing FeOOH rods in polyacrylamide (molecular weight of 5-6 M) solutions in a glycerin-water mixture. The diameter of rod particles was 100 nm and the aspect ratio was 4.3, 8.7 and 15.6. Particle volume fraction was 0.005-0.02. The extensional viscosity was measured by the capillary thinning method using the commercially available CaBER. Under the experimental condition both the polymer solution and particle suspensions are dilute. Particle-particle interaction is neglected in the solutions which are stretched by the extensional flow at the bulk. The result shows that extensional viscosity of the rod suspension in polymer solution decreases with the increase in particle volume fraction. The decrease is ascribed to the change in polymer conformation from the stretched state in the bulk flow to the less stretched state in shear flow developed near the particle to match the no-slip condition at the particle surface.

  3. Electrical conductivity of aqueous solutions of aluminum salts

    NASA Astrophysics Data System (ADS)

    Vila, J.; Rilo, E.; Segade, L.; Cabeza, O.; Varela, L. M.

    2005-03-01

    We present experimental measurements of the specific electrical conductivity (σ) in aqueous solutions of aluminum salts at different temperatures, covering all salt concentrations from saturation to infinite dilution. The salts employed were AlCl3 , AlBr3 , AlI3 , and Al(NO3)3 , which present a 1:3 relationship between the electrical charges of anion and cation. In addition, we have measured the density in all ranges of concentrations of the four aqueous electrolyte solutions at 298.15K . The measured densities show an almost linear behavior with concentration, and we have fitted it to a second order polynomial with very high degree of approximation. The measurement of the specific conductivity at constant temperature reveals the existence of maxima in the conductivity vs concentration curves at molar concentrations around 1.5M for the three halide solutions studied, and at approximately 2M for the nitrate. We present a theoretical foundation for the existence of these maxima, based on the classical Debye-Hückel-Onsager hydrodynamic mean-field framework for electrical transport and its high concentration extensions, and also a brief consideration of ionic frictional coefficients using mode-coupling theory. We also found that the calculated values of the equivalent conductance vary in an approximately linear way with the square root of the concentration at concentrations as high as those where the maximum of σ appears. Finally, and for completeness, we have measured the temperature dependence of the electrical conductivity at selected concentrations from 283to353K , and performed a fit to an exponential equation of the Vogel-Fulcher-Tamman type. The values of the calculated temperatures of null mobility of the four salts are reported.

  4. Method for preparing salt solutions having desired properties

    DOEpatents

    Ally, Moonis R.; Braunstein, Jerry

    1994-01-01

    The specification discloses a method for preparing salt solutions which exhibit desired thermodynamic properties. The method enables prediction of the value of the thermodynamic properties for single and multiple salt solutions over a wide range of conditions from activity data and constants which are independent of concentration and temperature. A particular application of the invention is in the control of salt solutions in a process to provide a salt solution which exhibits the desired properties.

  5. Application of the Thermodynamic Solution Model of Dilute Binary Systems

    NASA Astrophysics Data System (ADS)

    Luáek, J.

    1997-12-01

    The thermodynamic solution model by Tanaka et al. for liquid binary systems was extended to solid binary systems. On the basis of this extension the activity coefficients of solute elements in the solid phase in infinite dilution for transition metals were calculated in Part I of this paper. The determination of the activity coefficients in both solid and liquid phases can enable one to predict the equilibrium segregation coefficient of the solute elements in transition metal base alloys without the knowledge of equilibrium binary phase diagrams. The model was applied on Ti, Zr and Hf-base dilute alloys at their melting points. The calculated values of equilibrium segregation coefficients are compared with values derived by other methods. The effect of the model parameters on the value of equilibrium segregation coefficients was discussed. Das thermodynamische Modell für flüssige binäre Systeme nach Tanaka wurde auf feste binäre Systeme ausgedehnt. Auf dieser Grundlage wurden die Aktivitätskoeffizienten der gelösten Elemente in der Solidusphase für die Übergangsmetalle in Teil I dieser Arbeit berechnet. Die Bestimmung der Aktivitätskoeffizienten in der Solidus- und Liquidusphase ermöglicht die Vorhersage des Gleichgewichtsverteilungskoeffizienten der gelösten Elemente in den Legierungen der Übergangsmetalle ohne Kenntnis ihrer Zustandsdiagramme. Das Modell wurde auf Ti, Zr und Hf-Legierungen im Bereich der Schmelztemperatur der Hauptkomponente angewandt. Die berechneten Werte der Gleichgewichtsverteilungskoeffizienten wurden mit den Werten anderer Methoden verglichen. Der Einfluss der Eingangsparameter in unserem Modell auf die Werte der Gleichgewichtsverteilungskoeffizienten wurde diskutiert.

  6. Reactions of gaseous, elemental mercury with dilute halogen solutions

    SciTech Connect

    Mendelsohn, M.H.; Livengood, C.D.

    1996-12-31

    Of the trace elements known to exist in fossil fuels, mercury (Hg) has emerged as one of the greatest concerns. Mercury has been found to be emitted from combustion in at least two different chemical forms: elemental Hg and oxidized Hg compounds. Precise identification of the oxidized compounds emitted has not been accomplished to date. However, most workers in this field assume that mercuric chloride should be the predominant oxidized species. Mercuric chloride should be readily removed in a wet scrubber system because of its relatively high solubility in water. However, it has been presumed, and we have shown, that elemental Hg will pass through a wet scrubber system with little or no removal being effected. Therefore, it is important, in order to obtain a high total Hg removal, to study methods that might result in a removal of gaseous, elemental Hg from a flue-gas stream. In this regard, we have been studying the effect of dilute halogen-containing solutions on elemental Hg in gas streams of various compositions. In particular, the results of passing Hg through bubblers containing solutions of iodine, chlorine, and chloric acid are described. Mercury found in the bubbler solutions is an indication of the extent of reaction (oxidation) of elemental Hg with the halogen species, since we have found very little Hg transferred to the liquid phase when only distilled water is used in the bubblers. Results using commercial iodine, sodium hypochlorite, and NOXSORB-solutions are presented and discussed.

  7. Reactions of gaseous, elemental mercury with dilute halogen solutions

    SciTech Connect

    Mendelsohn, M.H.; Livengood, C.D.

    1996-07-01

    Of the trace elements known to exist in fossil fuels, mercury (Hg) has emerged as one of the greatest concerns. Mercury has been found to be emitted from combustion in at least two different chemical forms: elemental Hg and oxidized Hg compounds. Precise identification of the oxidized compounds emitted has not been accomplished to date. However, most workers in this field assume that mercuric chloride should be the predominant oxidized species. Mercuric chloride should be readily removed in a wet scrubber system because of its relatively high solubility in water. However, it has been presumed, and we have shown, that elemental Hg will pass through a wet scrubber system with little or no removal being effected. Therefore, it is important, in order to obtain a high total Hg removal, to study methods that might result in a removal of gaseous, elemental Hg from a flue-gas stream. In this regard, we have been studying the effect of dilute halogen-containing solutions on elemental Hg in gas streams of various compositions. In particular, the results of passing Hg through bubblers containing solutions of iodine, chlorine, and chloric acid are described. Mercury found in the bubbler solutions is an indication of the extent of reaction (oxidation) of elemental Hg with the halogen species, since we have found very little Hg transferred to the liquid phase when only distilled water is used in the bubblers. Results using commercial iodine, sodium hypochlorite, and NOXSORB (sup TM) solutions are presented and discussed.

  8. Ionizing radiation induced degradation of monuron in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

    Kovács, Krisztina; He, Shijun; Míle, Viktória; Földes, Tamás; Pápai, Imre; Takács, Erzsébet; Wojnárovits, László

    2016-07-01

    The decomposition of monuron was investigated in dilute aqueous solutions using pulse radiolysis and γ-radiolysis in order to identify the intermediates and final products. The main reaction takes place between monuron and the hydroxyl radicals yielding hydroxycyclohexadienyl type radicals with a second order rate constant of (7.4±0.2)×109 mol-1 dm3 s-1. In •OH reactions, the aminyl and phenoxyl radicals may also form. Dechlorination was observed in both hydroxyl radical and hydrated electron reactions. The •OH induced dechlorination reactions are suggested to occur through OH substitution or phenoxyl radical formation. The rate of oxidation is very high in the presence of dissolved oxygen. Some of the results are also supported by quantum chemical calculations.

  9. Droplet Size Distributions in Atomization of Dilute Viscoelastic Solutions

    NASA Astrophysics Data System (ADS)

    Keshavarz, Bavand; McKinley, Gareth; Houze, Eric; Moore, John; Pottiger, Michael; Cotts, Patricia; M. I. T. Collaboration; DuPont Collaboration

    2012-11-01

    The droplet size probability distribution functions (PDF) for atomization/fragmentation processes in Newtonian fluids are now generally accepted to be close to Gamma distributions. Despite the great practical importance, little is known about the nature of corresponding distributions for viscoelastic liquids, e.g. polymeric solutions such as pesticide sprays and paints. We present data from air-assisted atomization experiments for model viscoelastic solutions composed of very dilute solutions of polyethylene oxide. Although the addition of small amounts of high molecular weight polymer keeps the fluid shear viscosity and surface tension close to the solvent values, the size distributions are skewed towards higher values of the Sauter mean diameter. We show that the PDF curves for these weakly-elastic fluids are well described by Gamma distributions, but the exponent n is systematically decreased by fluid elasticity. Flow visualization images show that this behavior arises from the non-linear dynamics close to the break-up point which are dominated by an elasto-capillary force balance within the thinning ligaments and the magnitude of the extensional viscosity in the viscoelastic fluid. Mechanical Engineering Department, Cambridge, MA.

  10. Alyssum homolocarpum seed gum: Dilute solution and some physicochemical properties.

    PubMed

    Hesarinejad, M A; Razavi, Seyed M A; Koocheki, A

    2015-11-01

    The objective of this study was to investigate the effect of various temperatures (25-65°C) on some dilute solution properties of Alyssum homolocarpum seed gum (AHSG) as a novel potential source of hydrocolloid. Monosaccharide composition, FTIR analysis and molecular parameters were determined to provide more structural information. The results indicated that AHSG had a low molecular weight (3.66×10(5)Da), medium intrinsic viscosity (18.34dl/g) at 25°C, relatively flexible chain with a chain flexibility parameter of 618.54, and activation energy of 0.51×10(7)J/kgmol. With rise in temperature from 25 to 55°C, the intrinsic viscosity decreased as well as coil radius and volume of AHSG. The shape factor of AHSG macromolecule was spherical at all temperatures. The electrostatic interaction and particle size of AHSG solution were -25.81mV (at neutral pH) and 225.36nm, respectively. The results revealed that AHSG had high total sugar content (85.33%), small amount of uronic acids (5.63%) and it is likely a galactan-type polysaccharide. The FTIR spectra showed that AHSG behaved like a typical polyelectrolyte because of the presence of carboxyl and hydroxyl groups. PMID:26277752

  11. Nonequilibrium thermodynamics of dilute polymer solutions in flow

    SciTech Connect

    Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M.

    2014-11-07

    Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

  12. SOLUTION MINING IN SALT DOMES OF THE GULF COAST EMBAYMENT

    SciTech Connect

    Griswold, G. B.

    1981-02-01

    Following a description of salt resources in the salt domes of the gulf coast embayment, mining, particularly solution mining, is described. A scenario is constructed which could lead to release of radioactive waste stored in a salt dome via inadvertent solution mining and the consequences of this scenario are analyzed.

  13. Solubility of pllutonium in alkaline salt solutions

    SciTech Connect

    Hobbs, D.T.; Edwards, T.B.

    1993-02-26

    Plutonium solubility data from several studies have been evaluated. For each data set, a predictive model has been developed where appropriate. In addition, a statistical model and corresponding prediction intervals for plutonium solubility as a quadratic function of the hydroxide concentration have been developed. Because of the wide range of solution compositions, the solubility of plutonium can vary by as much as three orders of magnitude for any given hydroxide concentration and still remain within the prediction interval. Any nuclear safety assessments that depend on the maximum amount of plutonium dissolved in alkaline salt solutions should use concentrations at least as great as the upper prediction limits developed in this study. To increase the confidence in the prediction model, it is recommended that additional solubility tests be conducted at low hydroxide concentrations and with all of the other solution components involved. To validate the model for application to actual waste solutions, it is recommended that the plutonium solubilities in actual waste solutions be determined and compared to the values predicted by the quadratic model.

  14. Chitosan sorbents for platinum sorption from dilute solutions

    SciTech Connect

    Guibal, E.; Larkin, A.; Vincent, T.; Tobin, J.M.

    1999-10-01

    Chitosan has proved efficient at removing platinum in dilute effluents. The maximum uptake capacity reaches 300 mg/g (almost 1.5 mmol/g). The optimum pH for sorption is pH 2. A glutaraldehyde cross-linking pretreatment is necessary to stabilize the biopolymer in acidic solutions. Sorption isotherms have been studied as a function of pH, sorbent particle size, and the cross-linking ratio. Surprisingly, the extent of the cross-linking (determined by the concentration of the cross-linking agent in the treatment bath) has no significant influence on uptake capacity. Competitor anions such as chloride or nitrate induce a large decrease in the sorption efficiency. Sorption kinetics show also that uptake rate is not significantly changed by increasing either the cross-linking ratio or the particle size of the sorbent. Mass transfer rates are significantly affected by the initial platinum concentration and by the conditioning of the biopolymer. Gel-bead conditioning appears to reduce the sorption rate. While for molybdate and vanadate ions, mass transfer was governed by intraparticle mass transfer, for platinum, both external and intraparticle diffusion control the uptake rate. In contrast with the former ions, platinum does not form polynuclear hydrolyzed species, which are responsible for steric hindrance of diffusion into the polymer network.

  15. Static and dynamic light scattering studies on dilute polyrotaxane solutions

    NASA Astrophysics Data System (ADS)

    Kume, Tetsuya; Araki, Jun; Sakai, Yasuhiro; Mayumi, Koichi; Kidowaki, Masatoshi; Yokoyama, Hideaki; Ito, Kohzo

    2009-08-01

    Static and dynamic light scattering measurements were performed for dilute polyrotaxane solutions in different types of solvent systems, i.e. dimethylacetamide (DMAc) or dimethylformamide (DMF) containing 1-6 wt% lithium chloride (LiCl), 1 M aqueous sodium hydroxide (NaOH) and dimethylsulfoxide (DMSO). No aggregation of the polyrotaxane in DMF/LiCl was confirmed in the present study. Radius of gyration of the dissolved polyrotaxane was largest in NaOHaq., followed by values in amide solvents/LiCl and that in DMSO, and was probably dominated not by Coulombic repulsion but by the mutual affinity between solvent and polyrotaxane. Ratio of radius of gyration to hydrodynamic radius suggested the flexible random-coiled conformation in DMSO and relatively more extended, semi-flexible ones in amide solvents/LiCl and NaOHaq. The obtained values of second virial coefficient and weight average molecular weight seemed to be affected by a potential change in differential refractive index increments, caused by selective macrocationization or ionization.

  16. Coalescence of silver clusters by immersion in diluted HF solution

    SciTech Connect

    Milazzo, R. G.; Mio, A. M.; D’Arrigo, G.; Spinella, C.; Grimaldi, M. G.; Rimini, E.

    2015-07-14

    The galvanic displacement deposition of silver on H-terminated Si (100) in the time scale of seconds is instantaneous and characterized by a cluster density of 10{sup 11}-10{sup 12} cm{sup −2}. The amount of deposited Ag follows a t{sup 1/2} dependence in agreement with a Cottrell diffusion limited mechanism. At the same time, during the deposition, the cluster density reduces by a factor 5. This behavior is in contrast with the assumption of immobile clusters. We show in the present work that coalescence and aggregation occur also in the samples immersed in the diluted hydrofluoric acid (HF) solution without the presence of Ag{sup +}. Clusters agglomerate according to a process of dynamic coalescence, typical of colloids, followed by atomic redistribution at the contact regions with the generation of multiple internal twins and stacking-faults. The normalized size distributions in terms of r/r{sub mean} follow also the prediction of the Smoluchowski ripening mechanism. No variation of the cluster density occurs for samples immersed in pure H{sub 2}O solution. The different behavior might be associated to the strong attraction of clusters to oxide-terminated Si surface in presence of water. The silver clusters are instead weakly bound to hydrophobic H-terminated Si in presence of HF. HF causes then the detachment of clusters and a random movement on the silicon surface with mobility of about 10{sup −13} cm{sup 2}/s. Attractive interaction (probably van der Waals) among particles promotes coarsening.

  17. Collapse of sodium polyacrylate chains in calcium salt solutions

    NASA Astrophysics Data System (ADS)

    Schweins, R.; Huber, K.

    The sodium salt of polyacrylic acid (NaPA) precipitates in the presence of Ca^{2+}-ions. This phase behaviour can be represented by a phase diagram where the critical NaPA concentration is plotted versus the critical Ca^{2+} concentration resulting in a straight line as a phase boundary. The location of this phase boundary is influenced by the presence of an inert monovalent salt like NaCl. The present contribution focuses on the coil dimensions of NaPA chains in dilute aqueous solution corresponding to the one phase region of such a phase diagram. A variety of parameters with which the size and shape of the polyelectrolyte chains can be modulated are revealed. Approaching the phase boundary by decreasing the NaPA concentration at a constant Ca^{2+} content leads to a collapse of the NaPA chains. Combined static and dynamic light scattering suggests a compact spherical shape as the final state of this transition, both in 0.1 M NaCl and in 0.01 M NaCl. In the lower NaCl concentration, indication is presented for the existence of a cigar or pearl necklace like intermediate. Most strikingly, the collapsed chains can be reexpanded by increasing the concentration of inert NaCl at constant content of NaPA and Ca^{2+}. Clearly, excessive Na+-ions displace the Ca^{2+}-ions from the NaPA chains.

  18. Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions

    SciTech Connect

    Choi, Jun-Ho; Lim, Sohee; Chon, Bonghwan; Cho, Minhaeng; Kim, Heejae; Kim, Seongheun

    2015-05-28

    The vibrational frequency, frequency fluctuation dynamics, and transition dipole moment of the O—D stretch mode of HDO molecule in aqueous solutions are strongly dependent on its local electrostatic environment and hydrogen-bond network structure. Therefore, the time-resolved vibrational spectroscopy the O—D stretch mode has been particularly used to investigate specific ion effects on water structure. Despite prolonged efforts to understand the interplay of O—D vibrational dynamics with local water hydrogen-bond network and ion aggregate structures in high salt solutions, still there exists a gap between theory and experiment due to a lack of quantitative model for accurately describing O—D stretch frequency in high salt solutions. To fill this gap, we have performed numerical simulations of Raman scattering and IR absorption spectra of the O—D stretch mode of HDO in highly concentrated NaCl and KSCN solutions and compared them with experimental results. Carrying out extensive quantum chemistry calculations on not only water clusters but also ion-water clusters, we first developed a distributed vibrational solvatochromic charge model for the O—D stretch mode in aqueous salt solutions. Furthermore, the non-Condon effect on the vibrational transition dipole moment of the O—D stretch mode was fully taken into consideration with the charge response kernel that is non-local polarizability density. From the fluctuating O—D stretch mode frequencies and transition dipole vectors obtained from the molecular dynamics simulations, the O—D stretch Raman scattering and IR absorption spectra of HDO in salt solutions could be calculated. The polarization effect on the transition dipole vector of the O—D stretch mode is shown to be important and the asymmetric line shapes of the O—D stretch Raman scattering and IR absorption spectra of HDO especially in highly concentrated NaCl and KSCN solutions are in quantitative agreement with experimental results. We

  19. Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions.

    PubMed

    Choi, Jun-Ho; Kim, Heejae; Kim, Seongheun; Lim, Sohee; Chon, Bonghwan; Cho, Minhaeng

    2015-05-28

    The vibrational frequency, frequency fluctuation dynamics, and transition dipole moment of the O-D stretch mode of HDO molecule in aqueous solutions are strongly dependent on its local electrostatic environment and hydrogen-bond network structure. Therefore, the time-resolved vibrational spectroscopy the O-D stretch mode has been particularly used to investigate specific ion effects on water structure. Despite prolonged efforts to understand the interplay of O-D vibrational dynamics with local water hydrogen-bond network and ion aggregate structures in high salt solutions, still there exists a gap between theory and experiment due to a lack of quantitative model for accurately describing O-D stretch frequency in high salt solutions. To fill this gap, we have performed numerical simulations of Raman scattering and IR absorption spectra of the O-D stretch mode of HDO in highly concentrated NaCl and KSCN solutions and compared them with experimental results. Carrying out extensive quantum chemistry calculations on not only water clusters but also ion-water clusters, we first developed a distributed vibrational solvatochromic charge model for the O-D stretch mode in aqueous salt solutions. Furthermore, the non-Condon effect on the vibrational transition dipole moment of the O-D stretch mode was fully taken into consideration with the charge response kernel that is non-local polarizability density. From the fluctuating O-D stretch mode frequencies and transition dipole vectors obtained from the molecular dynamics simulations, the O-D stretch Raman scattering and IR absorption spectra of HDO in salt solutions could be calculated. The polarization effect on the transition dipole vector of the O-D stretch mode is shown to be important and the asymmetric line shapes of the O-D stretch Raman scattering and IR absorption spectra of HDO especially in highly concentrated NaCl and KSCN solutions are in quantitative agreement with experimental results. We anticipate that this

  20. Separation processes using expulsion from dilute supercritical solutions

    DOEpatents

    Cochran, Jr., Henry D.

    1993-01-01

    A process for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

  1. Separation processes using expulsion from dilute supercritical solutions

    DOEpatents

    Cochran, H.D. Jr.

    1993-04-20

    A process is described for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

  2. The electrochemistry of SIMFUEL in dilute alkaline hydrogen peroxide solutions

    NASA Astrophysics Data System (ADS)

    Goldik, Jon

    The work described in this thesis is a study of the electrochemistry of SIMFUEL (SIMulated nuclear FUEL) in dilute, alkaline hydrogen peroxide solutions. In the first set of experiments, the reaction of H2O 2 on SIMFUEL electrodes was studied electrochemically and under open circuit conditions in 0.1 mol L-1 NaCl solutions at pH 9.8. The composition of the oxidized UO2 surface was determined by X-ray photoelectron spectroscopy. Hydrogen peroxide reduction was found to be catalyzed by the formation of a mixed UIV/UV (UO 2+x) surface layer, but to be blocked by the accumulation of UVI species (UO3· yH2O or adsorbed (UO2)2+) on the electrode surface. The formation of this UVI layer blocks both H2O2 reduction and oxidation, thereby inhibiting the potentially rapid H2O2 decomposition reaction to H2O and O2. Decomposition is found to proceed at a rate controlled by the desorption of the adsorbed (UO2)2+ or reduction of adsorbed O2 species. Reduction of (O2) ads is coupled to the slow oxidative dissolution of UO2 and formation of a corrosion product deposit of UO3· yH2O. In the second series of experiments, the electrochemical reduction of hydrogen peroxide on SIMFUEL was studied using the steady-state polarization technique. Kinetic parameters for the reaction, such as Tafel slopes and reaction orders, were determined. The results were interpreted in terms of a chemical-electrochemical mechanism involving UIV/UV donor-acceptor reduction sites. The large values of the Tafel slopes and the fractional reaction orders with respect to H2O2 can be understood in terms of the potential-dependent surface coverage of active sites, similar to that observed in the reduction of hydrogen peroxide on oxidized copper surfaces. The effects of pH over the range 10-13 were also investigated. The H2O 2 reduction currents were nearly independent of pH in the range 10-11, but were slowed at more alkaline values. The change in pH dependence appears to be related to the acid-base properties

  3. [Structure and Activity of Fungal Lipases in Bile Salt Solutions].

    PubMed

    Bogdanova, L R; Bakirova, D R; Valiullina, Yu A; Idiyatullin, B Z; Faizullin, D A; Zueva, O S; Zuev, Yu F

    2016-01-01

    The changes in structure and catalytic properties of fungal lipases (Candida rugosa, Rhizomucor miehei, Mucor javanicus) were investigated in micellar solutions of bile salts that differ in hydrophilic-lypophilic balance and reaction medium properties. The methods of circular dichroism and tryptophan fluorescence were applied to estimate the changes in peptide structure within complexes with bile salt micelles. Bile salts do not exert a significant influence on the structure of the enzymes under study: in Rh. miehei and M. javanicus lipases the alpha helix content slightly decreased, the influence of bile salts on the C. rugosa structure was not revealed. Despite negligible structural modifications in the enzymes, in bile salt solutions a considerable change in their catalytic properties was observed: an abrupt decrease in catalytic effectiveness. Substrate-bile salts micelles complex formation was demonstrated by the NMR self-diffusion method. The model of a regulation of fungal lipase activity was proposed. PMID:27192825

  4. Surface viscoelasticity of concentrated salt solutions: specific ion effects.

    PubMed

    Safouane, Mahassine; Langevin, Dominique

    2009-01-12

    Herein, we study the viscoelastic response of concentrated salt solutions using surface waves excited by electrocapillarity. We show that the hydrodynamic behaviour of the solutions is similar to that of water at concentrations up to 2 m-well above the concentration C*, at which inhibition of bubble coalescence occurs in these solutions. This result excludes the occurrence of changes in the slip conditions at C*, postulated to explain this inhibition. Our study is carried out on salts that both increase and decrease the surface tension. We observe that the salt that decreases the tension does not change the surface behaviour at all, whereas the other two salts essentially produce negative contributions to the surface viscoelasticity at very high salt concentrations. The effects observed are quite large and remain to be explained. PMID:19072821

  5. Salt extraction from hydrogen-sulfide scrubber solution using electrodialysis

    SciTech Connect

    Jamaluddin, A.K.M.; Kennedy, M.W.; McManus, D.; Nazarko, T.W.

    1995-05-01

    The buildup of undesirable sulfur compounds (sulfates and thiosulfates) reduces the scrubbing effectiveness of the LO-CAT I autocirculation sulfur recovery process from acid-gas stream. Among various processes, withdrawing and disposing of a portion of the scrubber solution and replacing this blowdown with fresh solution have been the practice in the industry. The application of the electrodialysis system to recycle the blowdown is presented. Experiments were carried out using electrodialysis to separate salts (sulfates and thiosulfates) from the LO-CAT I autocirculation scrubber solution containing organic chelating agents, iron, and various alkali-metal inorganic salts. The results indicated that the electrodialysis was successful in removing 50% of the salts from the scrubber solution with less than 8% loss of organic and 8% loss of carbonates. The fluxes of the undesired salt species were high even at low current densities (200 to 400 A/m{sup 2}).

  6. Salt effects in extraction of ethanol, 1-butanol and acetone from aqueous solutions

    SciTech Connect

    Malinowski, J.J.; Daugulis, A.J. . Dept. of Chemical Engineering)

    1994-09-01

    Experimental studies were performed to assess the effect of salt addition on the extraction of 1-butanol, ethanol and acetone from dilute aqueous solutions using cyclopentanol, n-valeraldehyde, tert-amyl alcohol, and Adol 85NF as extractants. The liquid-liquid partitioning was examined for a few strong electrolytes in a broad range of concentrations. Results demonstrate that the distribution coefficient and selectivity in systems with reduced water activity resulting from salt addition were markedly increased. These observations can be qualitatively explained on the basis of the hydration theory. It was also determined that strong electrolytes added to the aqueous feed reduced extractant solubility in the aqueous phase, thus contributing to lower solvent losses. The results showed that the extraction efficiency was not significantly affected by increasing salt content beyond a level that reduces the water activity to a value of 0.92.

  7. Radiation induced degradation of ketoprofen in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

    Illés, Erzsébet; Takács, Erzsébet; Dombi, András; Gajda-Schrantz, Krisztina; Gonter, Katalin; Wojnárovits, László

    2012-09-01

    The intermediates and final products of ketoprofen degradation were investigated in 0.4 mmol dm-3 solution by pulse radiolysis and gamma radiolysis. For observation of final products UV-vis spectrophotometry and HPLC separation with diode array detection were used, and for identification MS was used. The reactions of •OH lead to hydroxycyclohexadienyl type radical intermediates, in their further reactions hydroxylated derivatives of ketoprofen form as final products. The hydrated electron is scavenged by the carbonyl oxygen and the electron adduct protonates to ketyl radical •OH is more effective in decomposing ketoprofen than hydrated electron. Chemical oxygen demand and total organic carbon content measurements on irradiated aerated solutions showed that using irradiation technology ketoprofen can be mineralised. The initial toxicity of the solution monitored by the Daphnia magna test steadily decreases with irradiation. Using 5 kGy dose no toxicity of the solution was detected with this test.

  8. A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media

    NASA Astrophysics Data System (ADS)

    de Barros, F. P. J.; Fiori, A.; Boso, F.; Bellin, A.

    2015-04-01

    Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data.

  9. A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media.

    PubMed

    de Barros, F P J; Fiori, A; Boso, F; Bellin, A

    2015-01-01

    Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data. PMID:25795562

  10. Conformation of ionizable poly Para phenylene ethynylene in dilute solutions

    DOE PAGESBeta

    Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; Grest, Gary S.

    2015-11-03

    The conformation of dinonyl poly para phenylene ethynylenes (PPEs) with carboxylate side chains, equilibrated in solvents of different quality is studied using molecular dynamics simulations. PPEs are of interest because of their tunable electro-optical properties, chemical diversity, and functionality which are essential in wide range of applications. The polymer conformation determines the conjugation length and their assembly mode and affects electro-optical properties which are critical in their current and potential uses. The current study investigates the effect of carboxylate fraction on PPEs side chains on the conformation of chains in the dilute limit, in solvents of different quality. The dinonylmore » PPE chains are modeled atomistically, where the solvents are modeled both implicitly and explicitly. Dinonyl PPEs maintained a stretched out conformation up to a carboxylate fraction f of 0.7 in all solvents studied. The nonyl side chains are extended and oriented away from the PPE backbone in toluene and in implicit good solvent whereas in water and implicit poor solvent, the nonyl side chains are collapsed towards the PPE backbone. Thus, rotation around the aromatic ring is fast and no long range correlations are seen within the backbone.« less

  11. Microfluidics Meets Dilute Solution Viscometry: An Undergraduate Laboratory to Determine Polymer Molecular Weight Using a Microviscometer

    ERIC Educational Resources Information Center

    Pety, Stephen J.; Lu, Hang; Thio, Yonathan S.

    2011-01-01

    This paper describes a student laboratory experiment to determine the molecular weight of a polymer sample by measuring the viscosity of dilute polymer solutions in a PDMS microfluidic viscometer. Sample data are given for aqueous solutions of poly(ethylene oxide) (PEO). A demonstration of shear thinning behavior using the microviscometer is…

  12. The grand partition function of dilute biregular solutions

    NASA Astrophysics Data System (ADS)

    Nagamori, Meguru; Ito, Kimihisa; Tokuda, Motonori

    1994-10-01

    It has been demonstrated that the grand partition function (GPF) of biregular solutions contains in one single equation such thermodynamic principles as Henry's law, Raoult's law, the Gibbs-Duhem relation, Raoultian activity coefficients and their finite power series, Wagner's rec-iprocity, Schenck-Frohberg-Steinmetz's interchange, Lupis-Elliott's additivity, Mori-Morooka's disparity, and Darken's quadratic formalism. The logarithm of the Raoultian activity coefficient of species i, In γi should not be expressed by the Taylor series expansion, lest its truncation infringe the Gibbs-Duhem equation. The GPF methodology establishes that In γi, is not a vector but a scalar point function, free from any path dependence. While Darken's quadratic formalism employs three parameters to describe a ternary solution, the present biregularity approximation offers an alternative using seven empirical parameters, in case better accuracy is needed.

  13. A new class of draw solutions for minimizing reverse salt flux to improve forward osmosis desalination.

    PubMed

    Nguyen, Hau Thi; Nguyen, Nguyen Cong; Chen, Shiao-Shing; Ngo, Huu Hao; Guo, Wenshan; Li, Chi-Wang

    2015-12-15

    The applications of forward osmosis (FO) have been hindered because of the lack of an optimal draw solution. The reverse salt flux from the draw solution not only reduces the water flux but also increases the cost of draw solute replenishment. Therefore, in this study, Tergitol NP7 and NP9 with a long straight carbon chain and low critical micelle concentration (CMC) were coupled with highly charged ethylenediaminetetraacetic acid (EDTA) as an innovative draw solution to minimize reverse salt diffusion in FO for the first time. The results showed that the lowest reverse salt flux of 0.067 GMH was observed when 0.1M EDTA-2Na coupled with 15mM NP7 was used as a draw solution and deionized water was used as a feed solution in FO mode (active layer facing with the feed solution). This is due to the hydrophobic interaction between the tails of NP7 and the FO membrane, thus creating layers on the membrane surface and constricting the FO membrane pores. Moreover, 1M EDTA-2Na coupled with 15mM NP7 is promising as an optimal draw solution for brackish water and sea water desalination. Average water fluxes of 7.68, 6.78, and 5.95 LMH were achieved when brackish water was used as a feed solution (5, 10, and 20g/L NaCl), and an average water flux of 3.81 LMH was achieved when sea water was used as a feed solution (35g/L NaCl). The diluted draw solution was recovered using a nanofiltration (NF-TS80) membrane with a high efficiency of 95% because of the high charge and large size of the draw solution. PMID:26298255

  14. Form and stability of aluminum hydroxide complexes in dilute solution

    USGS Publications Warehouse

    Hem, John David; Roberson, Charles Elmer

    1967-01-01

    Laboratory studies of solutions 4.53 x 10 -4 to 4.5 x 10 -5 molal (12.2-1.2 ppm) in aluminum, in 0.01 molal sodium perchlorate, were conducted to obtain information as to the probable behavior of aluminum in natural water. When the solutions were brought to pH 7.5-9.5 and allowed to stand for 24 hours, a precipitate was obtained which was virtually amorphous as shown by X-rays, and which had a solubility equivalent to that of boehmite. This precipitate had a hydrolysis constant (*Ks4) of 1.93 x 10 -13a. When solutions were allowed to stead at this pH range for 10 days, their precipitates gave the X-ray pattern of bayerite (*Ks4 = 1.11 > (10- 4). These hydrolysis constants were obtained at 25?C. and corrected to zero ionic strength and are in close agreement with other published values. The predominant dissolved form in this pH range is Al(OH) -4. Below neutral pH (7.0) the dissolved aluminum species consist of octahedral units in which each aluminum ion is surrounded by six water molecules or hydroxide ions. Single units such as Al(OH2)6 + 3 and AlOH(OH2)5+2 are most abundant below pH 5.0, and where the molar ratio (r) of combined hydroxide to total dissolved aluminum is low. When r is greater than 1.0, polymerization of the octahedral units occurs. When r is between 2.0 and 3.0, solutions aged for 10 days or more contained colloidal particles between 0.10 and 0.45 ? in diameter. Particles whose diameters were greater than 0.10 ? were identified by X-ray diffraction as gibbsite. Particles smaller than 0.10 ? were also present and were shown by means of the electron microscope to have a hexagonal crystal pattern. Structured material consisting of sheets of coalesced six-membered rings of aluminum ions held together by double OH bridges has a distinctive kinetic behavior. This property was used to determine amounts of polymerized material in solutions having r between 1.0 and 3.0 after aging times ranging from a few hours to more than 4 months. Aging increased the

  15. Semi-dilute galactomannan solutions: observations on viscosity scaling behavior of guar gum.

    PubMed

    Pollard, Michael A; Fischer, Peter

    2014-11-19

    Based on experimental work involving evaluation of viscosity enhancement of aqueous solutions by high molecular weight guar gum, we have observed that the shear viscosity scaling exponent b for semi-dilute solutions, ηsp ~ (c[η])(b), is sensitive to molecular weight, being approximately 4.7 for native samples and decreasing progressively as Mw is lowered. The critical overlap parameter demarcating the dilute and semi-dilute regimes also depends on the molecular weight as (c[η])* ~Mw(-0.82). Consequently, viscosity-concentration plots fail to achieve overlap using only specific viscosity and overlap concentration as reducing variables, a commonly accepted empiricism for random-coil polysaccharides. To bridge the gap, we propose to account for water solubility, its temperature dependence and the resulting chain flexibility as additional factors to fully describe the solution behavior of these highly-important raw materials. PMID:25347591

  16. METHOD AND APPARATUS FOR CALCINING SALT SOLUTIONS

    DOEpatents

    Lawroski, S.; Jonke, A.A.; Taecker, R.G.

    1961-10-31

    A method is given for converting uranyl nitrate solution into solid UO/ sub 3/, The solution is sprayed horizontally into a fluidized bed of UO/sub 3/ particles at 310 to 350 deg C by a nozzle of the coaxial air jet type at about 26 psig, Under these conditions the desired conversion takes place, and caking in the bed is avoided.

  17. Pulsed field capillary electrophoresis of multikilobase length nucleic acids in dilute methyl cellulose solutions.

    PubMed

    Kim, Y; Morris, M D

    1994-10-01

    Pulsed field capillary gel electrophoresis in dilute methyl cellulose solutions is used to separate nucleic acid fragments in the size range 75-23,000 base pairs. Field inversion is shown to increase resolution for fragments longer than about 500 base pairs. Methyl cellulose solutions as dilute as 0.01% can be used. Intermolecular hydrogen bonding is suggested as the cause of apparent cellulose fiber entanglement at concentrations below the calculated entanglement limit. The 1-kb DNA ladder and the lambda DNA/HindIII restriction fragment mixtures are each baseline resolved in a 28-cm capillary in less than 9 min at 180 V/cm (dc component). PMID:7978303

  18. Hydration of Kr(aq) in dilute and concentrated solutions

    DOE PAGESBeta

    Chaudhari, Mangesh I.; Sabo, Dubravko; Pratt, Lawrence R.; Rempe, Susan B.

    2014-10-13

    Molecular dynamics simulations of water with both multi-Kr and single Kr atomic solutes are carried out to implement quasi-chemical theory evaluation of the hydration free energy of Kr(aq). This approach obtains free energy differences reflecting Kr–Kr interactions at higher concentrations. Those differences are negative changes in hydration free energies with increasing concentrations at constant pressure. The changes are due to a slight reduction of packing contributions in the higher concentration case. The observed Kr–Kr distributions, analyzed with the extrapolation procedure of Krüger et al., yield a modestly attractive osmotic second virial coefficient, B2 ≈ -60 cm3/mol. Moreover, the thermodynamic analysismore » interconnecting these two approaches shows that they are closely consistent with each other, providing support for both approaches.« less

  19. Hydration of Kr(aq) in dilute and concentrated solutions

    SciTech Connect

    Chaudhari, Mangesh I.; Sabo, Dubravko; Pratt, Lawrence R.; Rempe, Susan B.

    2014-10-13

    Molecular dynamics simulations of water with both multi-Kr and single Kr atomic solutes are carried out to implement quasi-chemical theory evaluation of the hydration free energy of Kr(aq). This approach obtains free energy differences reflecting Kr–Kr interactions at higher concentrations. Those differences are negative changes in hydration free energies with increasing concentrations at constant pressure. The changes are due to a slight reduction of packing contributions in the higher concentration case. The observed Kr–Kr distributions, analyzed with the extrapolation procedure of Krüger et al., yield a modestly attractive osmotic second virial coefficient, B2 ≈ -60 cm3/mol. Moreover, the thermodynamic analysis interconnecting these two approaches shows that they are closely consistent with each other, providing support for both approaches.

  20. Stability of Diluted Adenosine Solutions in Polyolefin Infusion Bags

    PubMed Central

    Almagambetova, Elise; Hutchinson, David; Blais, Danielle M.; Zhao, Fang

    2013-01-01

    Background: Intravenous or intracoronary adenosine is used in the cardiac catherization lab to achieve maximal coronary blood flow and determine fractional flow reserve. Objective: To determine the stability of adenosine 10 and 50 µg/mL in either 0.9% sodium chloride injection or 5% dextrose injection in polyolefin infusion bags stored at 2 temperatures, refrigeration (2°C-8°C) or controlled room temperature (20°C-25°C). Methods: Adenosine 10 µg/mL and 50 µg/mL solutions were prepared in 50 mL polyolefin infusion bags containing 0.9% sodium chloride injection or 5% dextrose injection and stored at controlled room temperature or under refrigeration. Each combination of concentration, diluent, and storage was prepared in triplicate. Samples were assayed using stability-indicating, reversed-phase high-performance liquid chromatography immediately at time 0 and at 24 hours, 48 hours, 7 days, and 14 days. Stability was defined as retaining 90% to 110% of the initial adenosine concentration. The samples were also visually inspected against a light background for clarity, color, and the presence of particulate matter. Results: After 14 days, all samples retained 99% to 101% of the initial adenosine concentration. No considerable change in pH or visual appearance was noted. The stability data indicated no significant loss of drug due to chemical degradation or physical interactions during storage. Conclusion: Adenosine solutions of 10 and 50 µg/mL were stable for at least 14 days in 50 mL polyolefin infusion bags of 0.9% sodium chloride injection or 5% dextrose injection stored at controlled room temperature and refrigerated conditions. PMID:24421510

  1. The diffusion of dissolved silica in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

    Applin, Kenneth R.

    1987-08-01

    The diffusion coefficient of dissolved silica at 25.5 ± .5° C was determined as a function of concentration using a non-steady-state method whereby agar-gelled solutions containing dissolved silica from 0.09 to 1.50 mM ( pH = 5.5) were placed in contact with distilled water in glass cells. Diffusion coefficients were obtained by measuring the dissolved silica content of the distilled water after a given length of time. The measured diffusion coefficients decreased as a function of increasing dissolved silica concentration, which is thought to reflect an increase in dimeric silica according to the equilibrium: 2 Si( OH) 4 = Si2O( OH) 6 + H2O. The tracer diffusion coefficients for Si(OH) 4 and Si 2O(OH) 6 and an association constant for the above reaction were determined by fitting the following equation to the experimental data: Dobs = αDmonomer + (1 - α) Ddimer where α is the fraction of total dissolved silica which is Si(OH) 4. The best fit yielded tracer D's for Si(OH) 4 and Si 2O(OH) 6 of 2.2 and 1.0 (in units of 10 -5 cm 2 sec -1), respectively, and an association constant of 330.

  2. Solvation Phenomena in Dilute Solutions: Formal, Experimental Evidence, and Modeling Implications

    SciTech Connect

    Chialvo, Ariel A

    2013-01-01

    We review the fundamentals underlying a general molecular-based formalism for the microscopic interpretation of the solvation phenomena involving sparingly soluble solutes in compressible media, an approach that hinges around the unambiguous splitting of the species correlation function integrals into short-(finite) and long-ranged (diverging) contributions at infinite dilution, where this condition is taken as the reference system for the derivation of composition expansions. Then, we invoke the formalism (a) to illustrate the well-behaved nature of the solvation contributions to the mechanical partial molecular properties of solutes at infinite dilution, (b) to guide the development of, and provide molecular-based support to, the macroscopic modeling of high-temperature dilute aqueous-electrolyte solutions, (c) to study solvation effects on the kinetic rate constants of reactions in near-critical solvents in an attempt to understand from a microscopic perspective the macroscopic evidence regarding the thermodynamic pressure effects, and (d) to interpret the microscopic mechanism behind synergistic solvation effects involving either co-solutes or co-solvents, and provide a molecular argument on the unsuitability of the van der Waals one-fluid (vdW-1f) mixing rules for the 2 description of weakly attractive solutes in compressible solvents. Finally, we develop thermodynamically consistent perturbation expansions, around the infinite dilution reference, for the species residual properties in binary and ternary mixtures, and discuss the theoretical and modeling implications behind ad hoc first-order truncated expansions.

  3. Protein–Protein Interactions in Dilute to Concentrated Solutions: α-Chymotrypsinogen in Acidic Conditions

    PubMed Central

    2015-01-01

    Protein–protein interactions were investigated for α-chymotrypsinogen by static and dynamic light scattering (SLS and DLS, respectively), as well as small-angle neutron scattering (SANS), as a function of protein and salt concentration at acidic conditions. Net protein–protein interactions were probed via the Kirkwood–Buff integral G22 and the static structure factor S(q) from SLS and SANS data. G22 was obtained by regressing the Rayleigh ratio versus protein concentration with a local Taylor series approach, which does not require one to assume the underlying form or nature of intermolecular interactions. In addition, G22 and S(q) were further analyzed by traditional methods involving fits to effective interaction potentials. Although the fitted model parameters were not always physically realistic, the numerical values for G22 and S(q → 0) were in good agreement from SLS and SANS as a function of protein concentration. In the dilute regime, fitted G22 values agreed with those obtained via the osmotic second virial coefficient B22 and showed that electrostatic interactions are the dominant contribution for colloidal interactions in α-chymotrypsinogen solutions. However, as protein concentration increases, the strength of protein–protein interactions decreases, with a more pronounced decrease at low salt concentrations. The results are consistent with an effective “crowding” or excluded volume contribution to G22 due to the long-ranged electrostatic repulsions that are prominent even at the moderate range of protein concentrations used here (<40 g/L). These apparent crowding effects were confirmed and quantified by assessing the hydrodynamic factor H(q → 0), which is obtained by combining measurements of the collective diffusion coefficient from DLS data with measurements of S(q → 0). H(q → 0) was significantly less than that for a corresponding hard-sphere system and showed that hydrodynamic nonidealities can lead to qualitatively incorrect

  4. Pinch-off dynamics, extensional viscosity and relaxation time of dilute and ultradilute aqueous polymer solutions

    NASA Astrophysics Data System (ADS)

    Biagioli, Madeleine; Dinic, Jelena; Jimenez, Leidy Nallely; Sharma, Vivek

    Free surface flows and drop formation processes present in printing, jetting, spraying, and coating involve the development of columnar necks that undergo spontaneous surface-tension driven instability, thinning, and pinch-off. Stream-wise velocity gradients that arise within the thinning neck create and extensional flow field, which induces micro-structural changes within complex fluids that contribute elastic stresses, changing the thinning and pinch-off dynamics. In this contribution, we use dripping-onto-substrate (DoS) extensional rheometry technique for visualization and analysis of the pinch-off dynamics of dilute and ultra-dilute aqueous polyethylene oxide (PEO) solutions. Using a range of molecular weights, we study the effect of both elasticity and finite extensibility. Both effective relaxation time and the transient extensional viscosity are found to be strongly concentration-dependent even for highly dilute solutions.

  5. Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight, second virial coefficient, and intermolecular structure factor

    PubMed Central

    Muthukumar, M.

    2012-01-01

    Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism. PMID:22830728

  6. Influence of Deacetylation on the Rheological Properties of Xanthan-Guar Interactions in Dilute Aqueous Solutions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An oscillating capillary rheometer was used to investigate the effects of xanthan deacetylation on the viscoelastic properties and intrinsic viscosity of xanthan and guar mixtures in dilute aqueous solutions. Deacetylated xanthan exhibited a stronger synergistic interaction with guar than native xan...

  7. Properties of alkali-halide salt solutions about polarizable nanoparticle solutes for different ion models

    NASA Astrophysics Data System (ADS)

    Wynveen, Aaron; Bresme, Fernando

    2010-10-01

    We investigate the distributions of various salts about large hydrophobic polarizable solutes in aqueous electrolyte solutions. The solutes are modeled as nanometer-sized cylindrical objects, a scale relevant to biomolecules and nanomaterials, and particularly high aspect ratio nanoparticles. Interactions, including image charge forces arising from the finite polarizability of the solute, between explicit solvent/ions and the solute are computed explicitly using a molecular dynamics simulation methodology we have recently introduced. Comparisons are made between several salt species and different models of the force fields for each ionic component of the salt. We find evidence that both small cations, Li+, and large anions, I-, adsorb at hydrophobic interfaces. Our results indicate that the ion structure about the solute is strongly dependent on the force field investigated, suggesting that ion selectivity is quite sensitive to the respective parameters defining the ion's size and binding energy as well as to the polarizability of the solute.

  8. Dynamics and scaling of polymers in a dilute solution: Analytical treatment in two and higher dimensions

    NASA Astrophysics Data System (ADS)

    Punkkinen, O.; Falck, E.; Vattulainen, I.; Ala-Nissila, T.

    2005-03-01

    We consider the dynamical scaling of a single polymer chain in good solvent. In the case of two-dimensional systems, Shannon and Choy [Phys. Rev. Lett. 79, 1455 (1997)] have suggested that the dynamical scaling for a dilute polymer solution breaks down. Using scaling arguments and analytical calculations based on the Zimm model, we show that the dynamical scaling of a dilute two-dimensional polymer system holds when the relevant dynamical quantities are properly extracted from finite systems. Most important, the polymer diffusion coefficient in two dimensions scales logarithmically with system size, in excellent agreement with our extensive computer simulations. This scaling is the reason for the failure of the previous attempts to resolve the dynamical scaling of dilute two-dimensional polymer systems. In three and higher dimensions our analytic calculations are in agreement with previous results in the literature.

  9. Dynamics in Perturbed Very Dilute Aqueous Solutions: Theory and Experimental Evidence

    NASA Astrophysics Data System (ADS)

    Yinnon, Tamar A.; Elia, Vittorio

    2013-02-01

    Perturbed very dilute aqueous solutions are investigated by analyzing their electric conductivity (χ). Foci include titrations and quasi-periodic oscillations of χ spanning several months. The χ data reflect persistent dissipative supramolecular self-organization. This paper's successful consistent explanations of the χ measurements corroborate earlier quantum field theoretical predictions. For example: (1) Permanent polarization results from quantum electro-dynamical interactions mediated auto-ordering of water molecules and molecular aggregates which have electric dipole moments. (2) The aggregates are created by exciting very dilute aqueous solutions, generating long lasting (cold) vortices in crystalline-like-structured super-fluidic domains. These domains are only present when the concentration (C) is lower than a solute dependent transitions concentration (Ctrans). Typically, Ctrans is of the order of 10-4 M or below.

  10. Dilution Confusion: Conventions for Defining a Dilution

    ERIC Educational Resources Information Center

    Fishel, Laurence A.

    2010-01-01

    Two conventions for preparing dilutions are used in clinical laboratories. The first convention defines an "a:b" dilution as "a" volumes of solution A plus "b" volumes of solution B. The second convention defines an "a:b" dilution as "a" volumes of solution A diluted into a final volume of "b". Use of the incorrect dilution convention could affect…

  11. Salt Effects on Surface Tethered Peptides in Solution

    PubMed Central

    Feng, Jun; Wong, Ka-Yiu; Lynch, Gillian C.; Gao, Xiaolian; Pettitt, B. Montgomery

    2009-01-01

    The capability to manipulate proteins/peptide fragments at liquid-solid interfaces has led to tremendous applications in detectors and biotechnology. Therefore, understanding the detailed molecular behavior of proteins and peptides tethered on a hard material surface is an interesting and important topic. The inhomogeneity presented by surfaces as well as ions in the solution plays an important role in the thermodynamics and kinetics of the tethered proteins. In this study, we perform a series of molecular dynamics simulations of a pentapeptide RHSVV, a p53 epitope, tethered on a prepared microarray surface in various salt concentrations (0 M, 0.14 M, 0.5 M, and 1M NaCl), as well as free in ionic solution (0M, 0.5M, and 1M). The conformational space the tethered peptide visits largely overlaps with the free peptide in solution. However, surface tethering as well as the salt concentration changes both the thermodynamics and kinetics of the peptide. Frequent conformational changes are observed during the simulations, and tend to be slowed down by both increasing the salt concentration and surface tethering. The local composition of ions at different salt concentrations is also compared between the tethered and free peptide. PMID:19548651

  12. The flow of dilute polymer solution in a narrow channel. II. Plane Poiseuille flow

    NASA Astrophysics Data System (ADS)

    Goh, C. J.; Atkinson, J. D.; Phan-Thien, N.

    1985-04-01

    As an extension of the previous paper, we derive a similar theory for the plane Poiseuille flow of a dilute polymer solution. The strict enforcement of reflective boundary conditions allows an approximate solution to the Fokker-Planck-Kolmogorov equation to be obtained which is found to be consistent with solutions obtained by Galerkin methods and Monte Carlo simulation. The approximate theory also allows us to derive analytical expressions for the slip velocity and the effective viscosity which are again consistent with the plane Couette flow results derived in the previous paper. The theory is also extended to the nonlinear Warner spring model via Monte Carlo simulation.

  13. Rheological behaviors in the regimes from dilute to concentrated in cellulose solutions dissolved at low temperature.

    PubMed

    Lue, Ang; Zhang, Lina

    2009-05-13

    Cellulose was dissolved rapidly in 9.5 wt.-% NaOH/4.5 wt.-% thiourea aqueous solution pre-cooled to -5 degrees C to prepare cellulose solution with different concentrations. The rheological properties of the cellulose solutions in wide concentration regimes from dilute (0.008 wt.-%) to concentrated (4.0 wt.-%) at 25 degrees C were investigated. On the basis of data from the steady-shear flow test, the critical overlap (c*), the entanglement (c(e)) and the gel (c(g)) concentrations of the cellulose solution at 25 degrees C were determined, respectively, to be 0.10 wt.-%, 0.53 wt.-% and 2.50 wt.-%, in accordance with the results of storage modulus (G') versus c by dynamic test. Moreover, the Cox-Merz deviation at relatively low concentrations was in good agreement with the micro-gel particles in dilute regime. As the cellulose concentration increased, a homogeneous 3-dimensional network formed in the cellulose solution in the concentrated regime, and further increasing of the concentration led to micro-phase separation as determined by the time-temperature superposition (tTS). So far, this complex cellulose solution has been successfully described by the concentration regime theory for the first time, and the relatively molecular morphologies in each regime have been determined, providing useful information for the applications of the cellulose solution systems. PMID:19039777

  14. Photoionization of Sodium Salt Solutions in a Liquid Jet

    SciTech Connect

    Grieves, G. A.; Petrik, Nikolay G.; Herring-Captain, J.; Olanrewaju, B.; Aleksandrov, A.; Tonkyn, Russell G.; Barlow, Stephan E.; Kimmel, Gregory A.; Orlando, Thomas M.

    2008-06-05

    A liquid microjet was employed to examine the gas/liquid interface of aqueous sodium halide (Na+X-, X=Cl, Br, I) salt solutions. Laser excitation at 193 nm produced and removed cations of the form H+(H2O)n and Na+(H2O)m from liquid jet surfaces containing either NaCl, NaBr or NaI. The protonated water cluster yield varied inversely with increasing salt concentration, while the solvated sodium ion cluster yield varied by anion type. The distribution of H+(H2O)n at low salt concentration is identical to that observed from low-energy electron irradiated amorphous ice and the production of these clusters can be accounted for using a localized ionization/Coulomb expulsion model. Production of Na+(H2O)m is not accounted for by this model but requires ionization of solvation shell waters and a contact ion/Coulomb expulsion mechanism. The reduced yields of Na+(H2O)m from high concentration (10-2 and 10-1 M) NaBr and NaI solutions indicate a propensity for Br- and I- at the solution surfaces and interfaces. This is supported by the observation of multiphoton induced production and desorption of Br+ and I+ from the 10-2 and 10-1 M solution surfaces.

  15. CRITICALITY SAFETY OF PROCESSING SALT SOLUTION AT SRS

    SciTech Connect

    Stephens, K; Davoud Eghbali, D; Michelle Abney, M

    2008-01-15

    High level radioactive liquid waste generated as a result of the production of nuclear material for the United States defense program at the Savannah River Site has been stored as 36 million gallons in underground tanks. About ten percent of the waste volume is sludge, composed of insoluble metal hydroxides primarily hydroxides of Mn, Fe, Al, Hg, and most radionuclides including fission products. The remaining ninety percent of the waste volume is saltcake, composed of primarily sodium (nitrites, nitrates, and aluminates) and hydroxides. Saltcakes account for 30% of the radioactivity while the sludge accounts for 70% of the radioactivity. A pilot plant salt disposition processing system has been designed at the Savannah River Site for interim processing of salt solution and is composed of two facilities: the Actinide Removal Process Facility (ARPF) and the Modular Caustic Side Solvent Extraction Unit (MCU). Data from the pilot plant salt processing system will be used for future processing salt at a much higher rate in a new salt processing facility. Saltcake contains significant amounts of actinides, and other long-lived radioactive nuclides such as strontium and cesium that must be extracted prior to disposal as low level waste. The extracted radioactive nuclides will be mixed with the sludge from waste tanks and vitrified in another facility. Because of the presence of highly enriched uranium in the saltcake, there is a criticality concern associated with concentration and/or accumulation of fissionable material in the ARP and MCU.

  16. Fabrication of CPA Salt Pill with Circulating Solution Method

    NASA Astrophysics Data System (ADS)

    Hoshino, A.; Tokoi, K.; Ishisaki, Y.; Shinozaki, K.; McCammon, D.

    2008-05-01

    We report results on fabrication of a Chromium Potassium Alum (CPA) salt pill. CPA is a typical paramagnetic salt used as refrigerant of Adiabatic Demagnetization Refrigerator (ADR) because of its low Curie point, 4 11 mK. We made an test model of CPA salt pill by fast crystallizing method, namely circulating solution between 36°C and 15°C. The crystallizing rate was 0.5 g h-1, and 40 g of CPA crystal was obtained inside a stainless steel cylinder equipped with 160 copper wires. The cooling test was operated utilizing a commercial ADR system. We attached three thermometers and four heaters to the salt pill, in order to measure thermal conductance among different parts of the pill. It is confirmed that our salt pill was cooled down from B/ T=4 T/2 K to 64 mK at zero magnetic field. We suspect the cause of limiting the cooling temperature in the present level to be the dehydration of CPA, non-uniformity of magnetic field, and stainless steel of the pill which has large heat capacity below 0.1 K.

  17. Effect of Corrosion by Diluted HCL Solution on the Zno:. AL Texture

    NASA Astrophysics Data System (ADS)

    Shi, Mingji; Wang, Ping; Chen, Lanli

    2012-08-01

    High quality textured ZnO: Al electrode can improve the energy conversion efficiency of silicon based thin film solar cells. ZnO: Al films were deposited under 200W. Different textured surfaces were got when etching ZnO: Al films with diluted HCl solutions of 0.5% for different times. The transmission spectrum, square resistance and atomic force microscopy (AFM) images of the samples were measured. The dependence of corrosion time on the resistivity, transmittance and surface texture of the samples were studied. With the increasing of the corrosion time, the resistivity increased, the transmittance decreased, the root-mean-square roughness first increases, then decreases. High quality textured ZnO: Al electrode was obtained when etching the ZnO: Al film deposited under 200W of sputtering power with diluted HCl solution of 0.5%.

  18. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

  19. Renal failure and corrosive airway and gastrointestinal injury after ingestion of diluted diquat solution.

    PubMed

    Tanen, D A; Curry, S C; Laney, R F

    1999-10-01

    A 66-year-old man ingested 200 mL of Dexol Industries Weed and Grass Killer Concentrate (Torrance, CA), which contains 1.84% diquat dibromide, a herbicide structurally similar to paraquat. He remained asymptomatic for 8 hours, and then a sore throat and vomiting developed. Twenty hours after ingestion, esophagitis, mucositis, epiglottitis, and acute renal failure developed, from which he slowly recovered. This is the first report of systemic diquat toxicity from ingestion of a diluted diquat solution. PMID:10499956

  20. Capillary electrophoretic separation of DNA restriction fragments using dilute polymer solutions

    SciTech Connect

    Braun, B.; Blanch, W.; Prausnitz, J.M.

    1997-02-01

    Because the mechanism of DNA separation in capillary electrophoresis is not well understood, selection of polymers is a {open_quotes}trial-and-error{close_quotes} procedure. We investigated dilute-solution DNA separations by capillary electrophoresis using solutions of four polymers that differ in size, shape and stiffness. Hydroxyethylcellulose of high molecular weight provides excellent separation of large DNA fragments (2027 bp - 23130 bp). Polyvinylpyrrolidone separates DNA from 72 bp to 23 kbp and star-(polyethylene oxide), like linear poly (ethylene oxide), provides separation of fragments up to 1353 bp.

  1. Scaling Equations for a Biopolymer in Salt Solution

    NASA Astrophysics Data System (ADS)

    Geissler, Erik; Hecht, Anne-Marie; Horkay, Ferenc

    2007-12-01

    The effect of the simultaneous presence of monovalent and divalent cations on the thermodynamics of polyelectrolyte solutions is an incompletely solved problem. In physiological conditions, combinations of these ions affect structure formation in biopolymer systems. Dynamic light scattering measurements of the collective diffusion coefficient D and the osmotic compressibility of semidilute hyaluronan solutions containing different ratios of sodium and calcium ions are compared with simple polyelectrolyte models. Scaling relationships are proposed in terms of polymer concentration and ionic strength J of the added salt. Differences in the effects of sodium and calcium ions are found to be expressed only through J.

  2. SODIUM ALUMINOSILICATE FOULING AND CLEANING OF DECONTAMINATED SALT SOLUTION COALESCERS

    SciTech Connect

    Poirier, M; Thomas Peters, T; Fernando Fondeur, F; Samuel Fink, S

    2008-10-28

    During initial non-radioactive operations at the Modular Caustic Side Solvent Extraction Unit (MCU), the pressure drop across the decontaminated salt solution coalescer reached {approx}10 psi while processing {approx}1250 gallons of salt solution, indicating possible fouling or plugging of the coalescer. An analysis of the feed solution and the 'plugged coalescer' concluded that the plugging was due to sodium aluminosilicate solids. MCU personnel requested Savannah River National Laboratory (SRNL) to investigate the formation of the sodium aluminosilicate solids (NAS) and the impact of the solids on the decontaminated salt solution coalescer. Researchers performed developmental testing of the cleaning protocols with a bench-scale coalescer container 1-inch long segments of a new coalescer element fouled using simulant solution. In addition, the authors obtained a 'plugged' Decontaminated Salt Solution coalescer from non-radioactive testing in the MCU and cleaned it according to the proposed cleaning procedure. Conclusions from this testing include the following: (1) Testing with the bench-scale coalescer showed an increase in pressure drop from solid particles, but the increase was not as large as observed at MCU. (2) Cleaning the bench-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (11 g of bayerite if all aluminum is present in that form or 23 g of sodium aluminosilicate if all silicon is present in that form). (3) Based on analysis of the cleaning solutions from bench-scale test, the 'dirt capacity' of a 40 inch coalescer for the NAS solids tested is calculated as 450-950 grams. (4) Cleaning the full-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (60 g of aluminum and 5 g of silicon). (5) Piping holdup in the full-scale coalescer system caused the pH to differ from the target value. Comparable hold-up in the facility could lead to less effective

  3. Modeling Sucrose Hydrolysis in Dilute Sulfuric Acid Solutions at Pretreatment Conditions for Lignocellulosic Biomass

    SciTech Connect

    Bower, S.; Wickramasinghe, R.; Nagle, N. J.; Schell, D. J.

    2008-01-01

    Agricultural and herbaceous feedstocks may contain appreciable levels of sucrose. The goal of this study was to evaluate the survivability of sucrose and its hydrolysis products, fructose and glucose, during dilute sulfuric acid processing at conditions typically used to pretreat lignocellulose biomass. Solutions containing 25 g/l sucrose with 0.1-2.0% (w/w) sulfuric acid concentrations were treated at temperatures of 160-200 C for 3-12 min. Sucrose was observed to completely hydrolyze at all treatment conditions. However, appreciable concentrations of fructose and glucose were detected and glucose was found to be significantly more stable than fructose. Different mathematical approaches were used to fit the kinetic parameters for acid-catalyzed thermal degradation of these sugars. Since both sugars may survive dilute acid pretreatment, they could provide an additional carbon source for production of ethanol and other bio-based products.

  4. Recovery of uranium from dilute solution using liquid emulsion membrane system

    SciTech Connect

    Mukhopadhyay, S.; Ghosh, S.K.; Juvekar, V.A.

    2008-07-01

    The liquid emulsion membrane (LEM) technique has great potential for application in the nuclear industry for large interfacial area, low consumption of organics, and high recovery from dilute streams. A LEM system composed DEHPA-kerosene-SPAN80-HNO{sub 3} has been developed for recovery of uranium from dilute nitrate solution, which gives 98% extraction and 88% stripping in a single stage. An attempt has been made to understand the mechanism of the LEM process, in which phenomena like per-traction, occlusion, swelling, and leakage occur simultaneously. The effect of various parameters on these phenomena has been described with a mathematical model, which is able to explain the experimental findings. (authors)

  5. Three-terminal capacitance cell for stopped-flow measurements of very dilute solutions

    NASA Astrophysics Data System (ADS)

    Tjahjono, Martin; Davis, Thomas; Garland, Marc

    2007-02-01

    A capacitance cell has been designed, constructed, and tested for stopped-flow measurements of very dilute low-relative permittivity liquid solutions. The capacitance cell utilizes a three-terminal design and is connected to ultrahigh sensitivity capacitance bridge. The cell was designed for operating conditions T ≈243.15-373.15K and P ≈0-1MPa and tested with pure anhydrous cyclohexane and with dilute acetone/cyclohexane solutions at 298.15K and 0.1MPa under an argon blanket in a thermostated bath with a temperature variation of <0.001K. Details of the design and materials of construction are reported. The measured relative permittivity of cyclohexane was 2.015 565, in agreement with the literature, and the long term variation of the measurement was ±5×10-6. The relative permittivities of the acetone/cyclohexane solutions were very linear (R2=0.9997) in the measured interval of 0.001-0.008mole fraction. These measurements confirm that the design specifications for stability and resolution/sensitivity of better than 1×10-5 have been realized. Finally, the present online capacitance cell was connected online to an ultrasensitive densitometer and ultrasensitive refractometer and binary acetone/cyclohexane solutions were measured. The measurements of density, refractive index, and relative permittivity were combined to provide a dipole moment of acetone of 2.750±0.005D, which is in good agreement with literature.

  6. Simulation of osmotic pressure in concentrated aqueous salt solutions.

    SciTech Connect

    Luo, Y.; Roux, B.; Univ. of Chicago

    2010-01-01

    Accurate force fields are critical for meaningful simulation studies of highly concentrated electrolytes. The ion models that are widely used in biomolecular simulations do not necessarily reproduce the correct behavior at finite concentrations. In principle, the osmotic pressure is a key thermodynamic property that could be used to test and refine force field parameters for concentrated solutions. Here we describe a novel, simple, and practical method to compute the osmotic pressure directly from molecular dynamics (MD) simulation of concentrated aqueous solutions by introducing an idealized semipermeable membrane. Simple models for Na+, K+, and Cl- are tested and calibrated to accurately reproduce the experimental osmotic pressure at high salt concentration, up to the solubility limit of 4-5 M. The methodology is general and can be extended to any type of solute as well as nonadditive polarizable force fields.

  7. Dilute solution properties of canary seed (Phalaris canariensis) starch in comparison to wheat starch.

    PubMed

    Irani, Mahdi; Razavi, Seyed M A; Abdel-Aal, El-Sayed M; Hucl, Pierre; Patterson, Carol Ann

    2016-06-01

    Dilute solution properties of an unknown starch are important to understand its performance and applications in food and non-food industries. In this paper, rheological and molecular properties (intrinsic viscosity, molecular weight, shape factor, voluminosity, conformation and coil overlap parameters) of the starches from two hairless canary seed varieties (CO5041 & CDC Maria) developed for food use were evaluated in the dilute regime (Starch dispersions in DMSO (0.5g/dl)) and compared with wheat starch (WS). The results showed that Higiro model is the best among five applied models for intrinsic viscosity determination of canary seed starch (CSS) and WS on the basis of coefficient of determination (R(2)) and root mean square error (RMSE). WS sample showed higher intrinsic viscosity value (1.670dl/g) in comparison to CSS samples (1.325-1.397dl/g). Berry number and the slope of master curve demonstrated that CSS and WS samples were in dilute domain without entanglement occurrence. The shape factor suggested spherical and ellipsoidal structure for CO5041 starch and ellipsoidal for CDC Maria starch and WS. The molecular weight, coil radius and coil volume of CSSs were smaller than WS. The behavior and molecular characterization of canary seed starch showed its unique properties compared with wheat starch. PMID:26902890

  8. Selective recovery of uranium and thorium ions from dilute aqueous solutions by animal biopolymers.

    PubMed

    Ishikawa, Shin-ichi; Suyama, Kyozo; Arihara, Keizo; Itoh, Makoto

    2002-06-01

    Selective actinide ion recovery from dilute, aqueous, multication waste streams is an important problem. The recovery of uranium (U) and thorium (Th) by various animal biopolymers was examined. Of four species of biopolymers tested, a high uptake of uranium and thorium was found in hen eggshell membrane (ESM) and silk proteins, with the maximum uranium and thorium recovery exceeding 98% and 79%, respectively. The uptake of U and Th was significantly affected by the pH of the solution. The optimum pH values were 6 and 3 for the uptake of U and Th, respectively. The effect of temperature differed with the metal. The uptake of U decreased with increasing temperature (30-50 degrees C), whereas the Th uptake increased with increasing temperature. Selective recovery of U and Th from dilute aqueous binary and multimetal solutions was also examined. ESM and silk proteins tested were effective and selective for removing each metal by controlling the pH and temperature of the solution. In multimetal systems, the order of sorption of ESM proteins was preferential: U > Cu > Cd > Mn > Pb > Th > Ni > Co > Zn at pH 6 and Th > U > Cu > Pb > Cd > Mn > Co > Ni = Zn at pH 3. These biopolymers appear to have potential for use in a commercial process for actinide recovery from actinide-containing wastewater. PMID:12019520

  9. Dynamics and scaling of two-dimensional polymers in a dilute solution

    NASA Astrophysics Data System (ADS)

    Falck, E.; Punkkinen, O.; Vattulainen, I.; Ala-Nissila, T.

    2003-11-01

    The breakdown of dynamical scaling for a dilute polymer solution in two dimensions has been suggested by Shannon and Choy [Phys. Rev. Lett. 79, 1455 (1997)]. However, we show here through extensive computer simulations that dynamical scaling holds when the relevant dynamical quantities are properly extracted from finite systems. To verify dynamical scaling, we present results based on mesoscopic simulations in two dimensions for a polymer chain in a good solvent with full hydrodynamic interactions. We also present analytical arguments for the size dependence of the diffusion coefficient and find excellent agreement with the present large-scale simulations.

  10. An investigation of the critical liquid-vapor properties of dilute KCl solutions

    USGS Publications Warehouse

    Potter, R.W., II; Babcock, R.S.; Czamanske, G.K.

    1976-01-01

    The three parameters that define the critical point, temperature, pressure, and volume have been experimentally determined by means of filling studies in a platinum-lined system for five KCl solutions ranging from 0.006 to 0.568 m. The platinum-lined vessels were used to overcome the problems with corrosion experienced by earlier workers. The critical temperature (tc), pressure (Pc), and volume (Vc) were found to fit the equations {Mathematical expression} from infinite dilution to 1.0 m. ?? 1976 Plenum Publishing Corporation.

  11. Formation of 3He droplets in dilute 3He-4He solid solutions

    NASA Astrophysics Data System (ADS)

    Huan, Chao; Candela, Don; Kim, Sung; Yin, Liang; Xia, Jiang-Sheng; Sullivan, Neil

    2015-03-01

    We review the different stages of the formation of 3He droplets in dilute solid 3He-4He solutions. The studies are interesting because the phase separation in isotopic helium mixtures is a first-order transition with a conserved order parameter. The rate of growth of the droplets as observed in NMR studies is compared with the rates expected for homogeneous nucleation followed by a period of coarsening known as Ostwald ripening. Work suported by the National Science Foundation - DMR-1303599 and DMR- 1157490 (National High Magnetic Field Laboratory).

  12. Blending Of Radioactive Salt Solutions In Million Gallon Tanks

    SciTech Connect

    Leishear, Robert A.; Lee, Si Y.; Fowley, Mark D.; Poirier, Michael R.

    2012-12-10

    Research was completed at Savannah River National Laboratory (SRNL) to investigate processes related to the blending of radioactive, liquid waste, salt solutions in 4920 cubic meter, 25.9 meter diameter storage tanks. One process was the blending of large salt solution batches (up to 1135 ? 3028 cubic meters), using submerged centrifugal pumps. A second process was the disturbance of a settled layer of solids, or sludge, on the tank bottom. And a third investigated process was the settling rate of sludge solids if suspended into slurries by the blending pump. To investigate these processes, experiments, CFD models (computational fluid dynamics), and theory were applied. Experiments were performed using simulated, non-radioactive, salt solutions referred to as supernates, and a layer of settled solids referred to as sludge. Blending experiments were performed in a 2.44 meter diameter pilot scale tank, and flow rate measurements and settling tests were performed at both pilot scale and full scale. A summary of the research is presented here to demonstrate the adage that, ?One good experiment fixes a lot of good theory?. Experimental testing was required to benchmark CFD models, or the models would have been incorrectly used. In fact, CFD safety factors were established by this research to predict full-scale blending performance. CFD models were used to determine pump design requirements, predict blending times, and cut costs several million dollars by reducing the number of required blending pumps. This research contributed to DOE missions to permanently close the remaining 47 of 51 SRS waste storage tanks.

  13. Blending of Radioactive Salt Solutions in Million Gallon Tanks - 13002

    SciTech Connect

    Leishear, Robert A.; Lee, Si Y.; Fowley, Mark D.; Poirier, Michael R.

    2013-07-01

    Research was completed at Savannah River National Laboratory (SRNL) to investigate processes related to the blending of radioactive, liquid waste, salt solutions in 4920 cubic meter, 25.9 meter diameter storage tanks. One process was the blending of large salt solution batches (up to 1135 - 3028 cubic meters), using submerged centrifugal pumps. A second process was the disturbance of a settled layer of solids, or sludge, on the tank bottom. And a third investigated process was the settling rate of sludge solids if suspended into slurries by the blending pump. To investigate these processes, experiments, CFD models (computational fluid dynamics), and theory were applied. Experiments were performed using simulated, non-radioactive, salt solutions referred to as supernates, and a layer of settled solids referred to as sludge. Blending experiments were performed in a 2.44 meter diameter pilot scale tank, and flow rate measurements and settling tests were performed at both pilot scale and full scale. A summary of the research is presented here to demonstrate the adage that, 'One good experiment fixes a lot of good theory'. Experimental testing was required to benchmark CFD models, or the models would have been incorrectly used. In fact, CFD safety factors were established by this research to predict full-scale blending performance. CFD models were used to determine pump design requirements, predict blending times, and cut costs several million dollars by reducing the number of required blending pumps. This research contributed to DOE missions to permanently close the remaining 47 of 51 SRS waste storage tanks. (authors)

  14. Investigation of effects of dilute oxygen solute on nucleation of zirconium

    NASA Astrophysics Data System (ADS)

    Wert, Melissa Jane

    Classical nucleation theory is the foundation of considerations of the freezing of liquids. The presence of a dilute solute has been shown to affect nucleation, however, classical theory does not account for the rates seen experimentally. This work investigates the effects of a dilute amount of oxygen solute on the nucleation of solidification in otherwise pure zirconium. Undercooling distributions were obtained for mid and high purity zirconium samples via electrostatic levitation experiments and the critical work of formation, DeltaG*, and kinetic prefactor, log Kv, were determined using statistical analysis. Oxygen content of each sample was determined using glow discharge mass spectrometry. Both kinetic parameters were seen to increase with increasing sample purity. In order to examine these effects of oxygen, a sharp interface model was assumed to allow separation of total free energy change accompanying nucleation into volume free energy and interfacial free energy components. It was shown that dilute amounts of oxygen (<0.2 at %) had a minimal effect on the volume free energy change for this system. Thus, the interfacial free energy term was found to be the dominant factor in the total free energy change for nucleation. Spaepen and Turnbull's temperature-dependent reduced interfacial free energy, alpha, was used to examine the interfacial free energy which arises as a result of the decrease in configurational entropy at the interface. Experimentally-determined values for alpha were significantly less than theoretical predictions of their negentropic model, which assumed an infinite planar interface between a pure liquid and pure close-packed crystal. The interface configurational entropy is greater than the theoretical prediction due to the curvature of the interface and the presence of oxygen. The addition of oxygen increases the number of available configurations, increasing the configurational entropy at the interface, decreasing the interfacial free

  15. Extensional Relaxation Times and Pinch-off Dynamics of Dilute Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Dinic, Jelena; Zhang, Yiran; Jimenez, Leidy; Sharma, Vivek

    2015-11-01

    We show that visualization and analysis of capillary-driven thinning and pinch-off dynamics of the columnar neck in an asymmetric liquid bridge created by dripping-onto-substrate can be used for characterizing the extensional rheology of complex fluids. Using a particular example of dilute, aqueous PEO solutions, we show the measurement of both the extensional relaxation time and extensional viscosity of weakly elastic, polymeric complex fluids with low shear viscosity η< 20 mPa .s and relatively short relaxation time, λ <1 ms. Characterization of elastic effects and extensional relaxation times in these dilute solutions is beyond the range measurable in the standard geometries used in commercially available shear and extensional rheometers (including CaBER, capillary breakup extensional rheometer). As the radius of the neck that connects a sessile drop to a nozzle is detected optically, and the extensional response for viscoelastic fluids is characterized by analyzing their elastocapillary self-thinning, we refer to this technique as optically-detected elastocapillary self-thinning dripping-onto-substrate (ODES-DOS) extensional rheometry.

  16. Polysaccharide-based polyanion--polycation--polyanion ternary systems. A preliminary analysis of interpolyelectrolyte interactions in dilute solutions.

    PubMed

    Donati, Ivan; Feresini, Massimo; Travan, Andrea; Marsich, Eleonora; Lapasin, Romano; Paoletti, Sergio

    2011-11-14

    The present contribution deals with the preparation and characterization of ternary mixtures of polysaccharides with potential applications in the field of tissue engineering. Two natural polyanions, i.e., alginate and hyaluronic acid, and a polycation, a lactose-modified chitosan (chitlac), were mixed in dilute conditions. The miscibility between the three components was explored in the presence of different amounts of supporting simple salt. These analyses allowed to identify the experimental conditions avoiding polymer phase separation and leading to either solution of independent polymers or soluble nonstoichiometric interpolyelectrolyte complexes. The characterization of the interpolyelectrolyte complexes was tackled by means of viscometry, light scattering, fluorescence quenching, and energy transfer. The electrostatic interactions taking place among the different polyelectrolytes led to synergistic effects on the viscosity of the polymer mixtures which strongly depend on the ionic strength. It has been found that, starting from binary soluble complexes of alginate and chitlac, the addition of hyaluronan led to the dissolution of the complexes. At variance, the addition of alginate to a phase-separated binary mixture of hyaluronan and chitlac led to the formation of soluble complexes composed of all three polysaccharides and, eventually, to their dissolution. In addition, the results showed that at low ionic strength the overall properties of the ternary mixtures depend on their order of mixing. PMID:21995461

  17. Surface Potential of DPPC Monolayers on Concentrated Aqueous Salt Solutions.

    PubMed

    Casper, Clayton B; Verreault, Dominique; Adams, Ellen M; Hua, Wei; Allen, Heather C

    2016-03-01

    The presence and exchange of electrical charges on the surfaces of marine aerosols influence their ability to act as cloud condensation nuclei and play a role in thundercloud electrification. Although interactions exist between surface-active inorganic ions and organic compounds, their role in surface charging of marine aerosols is not well understood. In this study, the surface potential of dipalmitoylphosphatidylcholine (DPPC) monolayers, a zwitterionic phospholipid found in the sea surface microlayer, is measured on concentrated (0.3-2.0 M) chloride salt solutions containing marine-relevant cations (Na(+), K(+), Mg(2+), Ca(2+)) to model and elucidate the electrical properties of organic-covered marine aerosols. Monovalent cations show only a weak effect on the surface potential of DPPC monolayers in the condensed phase compared to water. In contrast, Mg(2+) and Ca(2+) increase the surface potential, indicating different cation binding modes and affinities for the PC headgroup. Moreover, it is found that for divalent chloride salt solutions, the PC headgroup and interfacial water molecules make the largest dipolar contribution to the surface potential. This study shows that for equal charge concentrations, divalent cations impact surface potential of DPPC monolayers more strongly than monovalents likely through changes in the PC headgroup orientation induced by their complexation along with the lesser ordering of interfacial water molecules caused by phosphate group charge screening. PMID:26761608

  18. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    SciTech Connect

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  19. Enhancing wastewater reuse by forward osmosis with self-diluted commercial fertilizers as draw solutes.

    PubMed

    Zou, Shiqiang; He, Zhen

    2016-08-01

    Using fertilizers as draw solutes in forward osmosis (FO) can accomplish wastewater reuse with elimination of recycling draw solute. In this study, three commercial fast-release all-purpose solid fertilizers (F1, F2 and F3) were examined as draw solutes in a submerged FO system for water extraction from either deionized (DI) water or the treated wastewater. Systematic optimizations were conducted to enhance water extraction performance, including operation modes, initial draw concentrations and in-situ chemical fouling control. In the mode of the active layer facing the feed (AL-F or FO), a maximum of 324 mL water was harvested using 1-M F1, which provided 41% of the water need for fertilizer dilution for irrigation. Among the three fertilizers, F1 containing a lower urea content was the most favored because of a higher water extraction and a lower reverse solute flux (RSF) of major nutrients. Using the treated wastewater as a feed solution resulted in a comparable water extraction performance (317 mL) to that of DI water in 72 h and a maximum water flux of 4.2 LMH. Phosphorus accumulation on the feed side was mainly due to the FO membrane solute rejection while total nitrogen and potassium accumulation was mainly due to RSF from the draw solute. Reducing recirculation intensity from 100 to 10 mL min(-1) did not obviously decrease water flux but significantly reduced the energy consumption from 1.86 to 0.02 kWh m(-3). These results have demonstrated the feasibility of using commercial solid fertilizers as draw solutes for extracting reusable water from wastewater, and challenges such as reverse solute flux will need to be further addressed. PMID:27174605

  20. Defect and solute properties in dilute Fe-Cr-Ni austenitic alloys from first principles

    NASA Astrophysics Data System (ADS)

    Klaver, T. P. C.; Hepburn, D. J.; Ackland, G. J.

    2012-05-01

    We present results of an extensive set of first-principles density functional theory calculations of point defect formation, binding, and clustering energies in austenitic Fe with dilute concentrations of Cr and Ni solutes. A large number of possible collinear magnetic structures were investigated as appropriate reference states for austenite. We found that the antiferromagnetic single- and double-layer structures with tetragonal relaxation of the unit cell were the most suitable reference states and highlighted the inherent instabilities in the ferromagnetic states. Test calculations for the presence and influence of noncollinear magnetism were performed but proved mostly negative. We calculate the vacancy formation energy to be between 1.8 and 1.95 eV. Vacancy cluster binding was initially weak at 0.1 eV for divacancies but rapidly increased with additional vacancies. Clusters of up to six vacancies were studied and a highly stable octahedral cluster and stacking fault tetrahedron were found with total binding energies of 2.5 and 2.3 eV, respectively. The <100> dumbbell was found to be the most stable self-interstitial with a formation energy of between 3.2 and 3.6 eV and was found to form strongly bound clusters, consistent with other fcc metals. Pair interaction models were found to be capable of capturing the trends in the defect cluster binding energy data. Solute-solute interactions were found to be weak in general, with a maximal positive binding of 0.1 eV found for Ni-Ni pairs and maximum repulsion found for Cr-Cr pairs of -0.1 eV. Solute cluster binding was found to be consistent with a pair interaction model, with Ni-rich clusters being the most stable. Solute-defect interactions were consistent with Ni and Cr being modestly oversized and undersized solutes, respectively, which is exactly opposite to the experimentally derived size factors for Ni and Cr solutes in type 316 stainless steel and in the pure materials. Ni was found to bind to the vacancy and

  1. Results of Hg speciation testing on MCU strip effluent hold tank (SEHT) and decontaminated salt solution hold tank (DSSHT) materials

    SciTech Connect

    Bannochie, C. J.

    2015-09-17

    The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team.i,ii The tenth shipment of samples was designated to include Modular Caustic Side Solvent Extraction Unit (MCU) Strip Effluent Hold Tank (SEHT) and MCU Decontaminated Salt Solution Hold Tank (DSSHT) materials from processing Salt Batch 7b. The MCU SEHT (MCU-15-722) and DSSHT (MCU-15-709) samples were pulled on June 15, 2015. All MCU samples were received at SRNL on June 16, 2015. The DSSHT sample was moved the same day to refrigeration, while the SEHT sample was placed in the Shielded Cells. On July 9, 2015 it was opened and an aliquot diluted 1:100 with Eurofins deionized water and a portion of the diluted sample transferred to a Teflon® bottle prior to moving it to refrigeration that same day. All samples were kept in the dark and refrigerated until final dilutions were prepared for shipment to Eurofins.

  2. Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

    NASA Astrophysics Data System (ADS)

    Schuler, Thomas; Nastar, Maylise

    2016-06-01

    We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

  3. Effect of dilute amounts of oxygen solute on nucleation of zirconium

    NASA Astrophysics Data System (ADS)

    Wert, M. J.; Hofmeister, W. H.; Bayuzick, R. J.

    2003-03-01

    Classical nucleation theory was used as the basis for investigating the effects of dilute oxygen solute on the nucleation behavior of pure zirconium. Undercooling distributions were obtained for zirconium samples via electrostatic levitation experiments and kinetic parameters were determined using statistical analysis. Oxygen and residual impurity content were determined using glow discharge mass spectrometry. The work of formation of a critical nucleus, ΔG*, and the kinetic prefactor, Kv, increased with decreasing oxygen content. To examine the effects of oxygen on ΔG*, a sharp interface model was assumed to allow separation of volume free energy and interfacial free energy components. Dilute oxygen has a minimal effect on the volume free energy. A temperature-dependent reduced interfacial free energy, αm, was used to examine the effect of oxygen on interfacial free energy. Experimentally derived values for αm and the corresponding interface configurational entropy values varied significantly from theoretical predictions for "pure" zirconium. Oxygen compositional effects increased the configurational entropy of the interface atoms, resulting in a decrease in the reduced interfacial free energy.

  4. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

    NASA Technical Reports Server (NTRS)

    Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

    1994-01-01

    We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

  5. Breakdown of Dynamical Scaling for Dilute Polymer Solutions in 2D?

    NASA Astrophysics Data System (ADS)

    Falck, Emma; Punkkinen, Olli; Ala-Nissila, Tapio; Vattulainen, Ilpo

    2004-03-01

    The breakdown of dynamical scaling for a dilute polymer solution in 2D has been suggested by Shannon and Choy [1]. However, we show here through extensive computer simulations that dynamical scaling holds when the relevant dynamical quantities are properly extracted from finite systems. To verify dynamical scaling, we present results based on mesoscopic simulations in 2D for a polymer chain in a good solvent with full hydrodynamic interactions. We also present analytical arguments for the size-dependence of the diffusion coefficient and find excellent agreement with the present large-scale simulations. 1. S. R. Shannon and T. C. Choy, Phys. Rev. Lett. 79, 1455 (1997). 2. E. Falck et al., Phys. Rev. E 68, 050102 (2003).

  6. Temperature dependence of the activity of Al in dilute Ni(Al) solid solutions

    SciTech Connect

    Jiang Yong; Smith, J. R.; Evans, A. G.

    2006-12-01

    Activities of dilute Al solid solutions in Ni are determined from a first-principles approach. Both thermal lattice vibration and electronic contributions to free energies are considered and compared. Vibrational contributions tend to dominate the temperature dependencies of the free energies, though electron thermal effects are significant. Calculations show opposing temperature trends for the formation enthalpies and entropies, leading to a partial cancellation of their role in the overall energetics. Nevertheless, their remaining temperature effects are strong. Over the temperature range, 400 K

  7. Tuning supramolecular structuring at the nanoscale level: nonstoichiometric soluble complexes in dilute mixed solutions of alginate and lactose-modified chitosan (chitlac).

    PubMed

    Donati, Ivan; Borgogna, Massimiliano; Turello, Esther; Cesàro, Attilio; Paoletti, Sergio

    2007-05-01

    Two oppositely charged polysaccharides, alginate and a lactose-modified chitosan (chitlac), have been used to prepare dilute binary polymer mixtures at physiological pH (7.4). Because of the negative charge on the former polysaccharide and the positive charge on the latter, polyanion-polycation complex formation occurred. A complete miscibility between the two polysaccharides was attained in the presence of both high (0.15 M) and low (0.015 M) concentrations of simple 1:1 supporting salt (NaCl), as confirmed by turbidity measurements; phase separation occurred for intermediate values of the ionic strength (I). The binary solutions were further characterized by means of light scattering, specific viscosity, and fluorescence quenching measurements. All of these techniques pointed out the fundamental role of the electrostatic interactions between the two oppositely charged polysaccharides in the formation of nonstoichiometric polyelectrolyte soluble complexes in dilute solution. Fluorescence depolarization (P) experiments showed that the alginate chain rotational mobility was impaired by the presence of the cationic polysaccharide when 0.015 M NaCl was used. Moreover, upon addition of calcium, the P values of the binary polymer mixture in 0.015 M NaCl increased more rapidly than that of an alginate solution without chitlac, suggesting an efficient crowding of the negatively charged alginate chains caused by the polycation. PMID:17417904

  8. Column chromatographic boron isotope separation at 5 and 17 MPa with diluted boric acid solution.

    PubMed

    Musashi, Masaaki; Oi, Takao; Matsuo, Motoyuki; Nomura, Masao

    2008-08-01

    Boron isotopic fractionation factor (S) between boron taken up in strongly basic anion exchange resin and boron in aqueous solution was determined by breakthrough column chromatography at 5 and 17 MPa at 25 degrees C, using 0.1 mM boric acid solution as feed solution. The S values obtained were 1.018 and 1.012, respectively, which were smaller than the value reported by using the same chromatographic method at the atmospheric pressure at 25 degrees C with the boron concentration of 10mM, but were larger than the values under the same condition with much higher concentration of 100 and 501 mM. Calculations based on the theory of isotope distribution between two phases estimated that 21% (5 MPa) and 47% (17 MPa) of boron taken up in the resin phase was in the three-coordinated B(OH)(3)-form, instead of in the four-coordinated B(OH)(4)-form, at high pressures even with a very diluted boric acid solution. We discussed the present results by introducing (1) hydration and (2) a partial molar volume difference between isotopic molecules. Borate may have been partially dehydrated upon transfer from the solution phase to the resin phase at high pressures, which resulted in smaller S values compared with those at the atmospheric pressure. Instead, it may be possible that the difference in the isotopic partial molar volume difference between B(OH)(3) and B(OH)(4)(-) caused the S value to decrease with increasing pressure. PMID:18585727

  9. Polyimide Composites from 'Salt-Like' Solution Precursors

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J.; Hou, Tan H.; Weiser, Erik S.; SaintClair, Terry L.

    2001-01-01

    Four NASA Langley-developed polyimide matrix resins, LaRC(TM)-IA, LaRC(TM)-IAX, LaRC(TM)-8515 and LaRC(TM)-PETI-5, were produced via a 'saltlike' process developed by Unitika Ltd. The salt-like solutions (65% solids in NMP) were prepregged onto Hexcel IM7 carbon fiber using the NASA LaRC multipurpose tape machine. Process parameters were determined and composite panels fabricated. The temperature dependent volatile depletion rates, the thermal crystallization behavior and the resin rheology were characterized. Composite molding cycles were developed which consistently yielded well consolidated, void-free laminated parts. Composite mechanical properties such as the short beam shear strength; the longitudinal and transverse flexural strength and flexural modulus; the longitudinal compression strength and modulus; and the open hole compression strength and compression after impact strength were measured at room temperature and elevated temperatures. The processing characteristics and the composite mechanical properties of the four intermediate modulus carbon fiber/polyimide matrix composites were compared to existing data on the same polyimide resin systems and IM7 carbon fiber manufactured via poly(amide acid) solutions (30-35% solids in NMP). This work studies the effects of varying the synthetic route on the processing and mechanical properties of the polyimide composites.

  10. The effect of divalent salt in chondroitin sulfate solutions

    NASA Astrophysics Data System (ADS)

    Aranghel, D.; Badita, C. R.; Radulescu, A.; Moldovan, L.; Craciunescu, O.; Balasoiu, M.

    2016-03-01

    Chondroitin-4 sulfate (CS4) is the main glycosaminoglycan extracted from bovine trachea. CS4 play an important role in osteoarthritis treatment, anticoagulant activity, reduces the degradation of cartilage matrix components, reduces necrosis and apoptosis of chondrocytes and reduces the activity of collagenase. Chondroitin sulfate is also responsible for proteoglycans degradation. Chondroitin sulfate can bind calcium ions with different affinities, depending on their sulfation position. The purpose of this study was to determine the structural properties and the influence of Ca2+ cations. We carried out measurements on CS4 solutions and mixtures of liquid CS4 with Ca2+ by Small-Angle Neutron Scattering (SANS). CS4 have a mass fractal behavior and the addition of a salt (CaCl2) in CS4 solutions generates the appearance of a correlation peak due to local ordering between adjacent chains with inter-chain distances between 483 Å and 233 Å for a calcium concentration of 0.01% w/w.

  11. The Surface Structure of Concentrated Aqueous salt Solutions

    SciTech Connect

    Sloutskin,E.; Baumert, J.; Ocko, B.; Kuzmenko, I.; Checco, A.; Tamam, L.; Ofer, E.; Gog, T.; Deutsch, M.

    2007-01-01

    The surface-normal electron density profile {rho}{sub s}(z) of concentrated aqueous salt solutions of RbBr, CsCl, LiBr, RbCl, and SrCl{sub 2} was determined by x-ray reflectivity (XR). For all but RbBr and SrCl{sub 2} {rho}{sub s}(z) increases monotonically with depth z from {rho}{sub s}(z)=0 in the vapor (z<0) to {rho}{sub s}(z) = {rho}{sub b} of the bulk (z>0) over a width of a few angstroms. The width is commensurate with the expected interface broadening by thermally excited capillary waves. Anomalous (resonant) XR of RbBr reveals a depletion at the surface of Br{sup -} ions to a depth of {approx}10 A. For SrCl{sub 2}, the observed {rho}{sub s}(z)>{rho}{sub b} may imply a similar surface depletion of Cl{sup -} ions to a depth of a few angstroms. However, as the deviations of the XRs of RbBr and SrCl{sub 2} from those of the other solutions are small, the evidence for a different ion composition in the surface and the bulk is not strongly conclusive. Overall, these results contrast earlier theoretical and simulational results and nonstructural measurements, where significant surface layering of alternate, oppositely charged, ions is concluded.

  12. Rheological observation of glassy dynamics of dilute polymer solutions near the coil-stretch transition in elongational flows.

    PubMed

    Sridhar, T; Nguyen, D A; Prabhakar, R; Prakash, J Ravi

    2007-04-20

    It has long been conjectured that the macroscopic dynamics of dilute polymer solutions may exhibit a glasslike slowdown caused by ergodicity breaking, in the vicinity of the coil-stretch transition in elongational flows. We report experimental observations using a filament stretching rheometer that confirm the existence of such glassy states. It is observed that different time-dependent elongational strain-rate profiles lead to a pronounced history dependence and aging effects within a narrow range of strain rates. The results have a direct bearing on the analysis and design of processes employing dilute polymer solutions, such as ink-jet printing, surface coating, and turbulent-drag reduction. PMID:17501464

  13. Analytical approaches to the OH radical induced degradation of sulfonamide antibiotics in dilute aqueous solutions.

    PubMed

    Sági, Gyuri; Csay, Tamás; Szabó, László; Pátzay, György; Csonka, Emil; Takács, Erzsébet; Wojnárovits, László

    2015-03-15

    By combining a large variety of analytical techniques this study aimed at elaborating methods to follow up the degradation of sulfonamides in an advanced oxidation process (AOP): irradiation with ionizing radiation in dilute aqueous solution. In this process, besides other radicals, hydroxyl radicals are produced. As pulse radiolysis experiments show the basic initial reaction is hydroxyl radical addition to the benzene ring, forming cyclohexadienyl radical intermediates. In aerated solutions these radicals transform to peroxy radicals. Among the first formed products aromatic molecules hydroxylated in the benzene rings or in some cases in the heterocyclic rings were observed by LC-MS/MS. Chemical oxygen demand (COD) measurements indicate that at the early reaction period of degradation one hydroxyl radical induces incorporation of 1.5 O atoms into the products. Comparison of the COD and TOC (total organic carbon content) results shows gradual oxidation. Simultaneously with hydroxylation ring opening also takes place. The kinetics of inorganic SO4(2-) and NH4(+) formation, analyzed by ion chromatography, is similar to the kinetics of ring degradation (UV spectroscopy), however, there is a delayed formation of NO3(-). The latter ions may be produced in oxidative degradation of smaller N containing fragments. The S atoms of the sulfonamides remain in the solution (ICP-MS measurements) after degradation, whereas some part of the N atoms leaves the solution probably in the form of N2 (total nitrogen content (TN) measurements). Degradation is accompanied by a high pH drop due to formation of SO4(2-), NO3(-) and smaller organic acids. The degradation goes through many simultaneous and consecutive reactions, and with the applied methods the different stages of degradation can be characterized. PMID:25266558

  14. A statistical theory of cosolvent-induced coil-globule transitions in dilute polymer solution

    NASA Astrophysics Data System (ADS)

    Budkov, Yu. A.; Kolesnikov, A. L.; Georgi, N.; Kiselev, M. G.

    2014-07-01

    We present a statistical model of a dilute polymer solution in good solvent in the presence of low-molecular weight cosolvent. We investigate the conformational changes of the polymer induced by a change of the cosolvent concentration and the type of interaction between the cosolvent and the polymer. We describe the polymer in solution by the Edwards model, where the partition function of the polymer chain with a fixed radius of gyration is described in the framework of the mean-field approximation. The contributions of polymer-cosolvent and the cosolvent-cosolvent interactions in the total free energy are treated also within the mean-field approximation. For convenience we separate the system volume on two parts: the volume occupied by the polymer chain expressed through its gyration volume and the bulk solution. Considering the equilibrium between the two subvolumes we obtain the total free energy of the solution as a function of radius of gyration and the cosolvent concentration within gyration volume. After minimization of the total free energy with respect to its arguments we obtain a system of coupled equations with respect to the radius of gyration of the polymer chain and the cosolvent concentration within the gyration volume. Varying the interaction strength between polymer and cosolvent we show that the polymer collapse occurs in two cases—either when the interaction between polymer and cosolvent is repulsive or when the interaction is attractive. The reported effects could be relevant for different disciplines where conformational transitions of macromolecules in the presence of a cosolvent are of interest, in particular in biology, chemistry, and material science.

  15. Visualizing phase transition behavior of dilute stimuli responsive polymer solutions via Mueller matrix polarimetry.

    PubMed

    Narayanan, Amal; Chandel, Shubham; Ghosh, Nirmalya; De, Priyadarsi

    2015-09-15

    Probing volume phase transition behavior of superdiluted polymer solutions both micro- and macroscopically still persists as an outstanding challenge. In this regard, we have explored 4 × 4 spectral Mueller matrix measurement and its inverse analysis for excavating the microarchitectural facts about stimuli responsiveness of "smart" polymers. Phase separation behavior of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and pH responsive poly(N,N-(dimethylamino)ethyl methacrylate) (PDMAEMA) and their copolymers were analyzed in terms of Mueller matrix derived polarization parameters, namely, depolarization (Δ), diattenuation (d), and linear retardance (δ). The Δ, d, and δ parameters provided useful information on both macro- and microstructural alterations during the phase separation. Additionally, the two step action ((i) breakage of polymer-water hydrogen bonding and (ii) polymer-polymer aggregation) at the molecular microenvironment during the cloud point generation was successfully probed via these parameters. It is demonstrated that, in comparison to the present techniques available for assessing the hydrophobic-hydrophilic switch over of simple stimuli-responsive polymers, Mueller matrix polarimetry offers an important advantage requiring a few hundred times dilute polymer solution (0.01 mg/mL, 1.1-1.4 μM) at a low-volume format. PMID:26287499

  16. A new method to determine the yield stress of diluted polymeric solutions

    NASA Astrophysics Data System (ADS)

    Soto, Enrique; Ruiz, Servando; Cordova Aguilar, Maria Soledad

    2012-11-01

    A new method to measure the yield stress for diluted polymeric solutions is presented. The tested solutions exhibit shear thinning behavior a once the critical yield stress is overcame. In rheology, these fluids are known as Herschel-Buckley. The yield stress phenomenon and its relation with bubble motion is an important issue for different industries, for example, personal care, paints and some others. As a result of the yield stress, small bubbles remain trapped in the fluid bulk, but above a critical volume, which is related with the characteristic yield stress, the bubbles flow in the liquid. In order to change the bubble volume, the liquid is placed in a cylindrical container whose pressure is decreased by a vacuum pump. The bubble growths as the pressure decreases and keeps its position until it reaches the critical volume. The bubble shape changes with volume and velocity, and a competition among surface, gravitational, inertial and viscous forces is discussed. The yield stress determined value is higher than the obtained from simple shear measurements due to the complex flow around the bubble.

  17. Structural Dynamics of Star-Shaped Weak Polyelectrolytes in Dilute Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Qu, Chen; Zhu, Y. Elaine

    Weak polyelectrolyte (PE) bearing tunable charges along their backbones show great potential as ``smart'' polymer materials for diverse applications from drug delivery to energy storage. With the introduction of branched topology, the local counterion distribution in the vicinity to the polyelectrolyte segments becomes highly inhomogeneous. To experimentally investigate the interplay between structural dynamics and local electric environment of a branched polyelectrolyte, in this work we custom synthesized star-shaped poly(2-vinylpyridine) (P2VP) using reversible addition fragmentation chain transfer (RAFT) polymerization and labeled P2VP stars with pH-sensitive fluorophore precisely either in the center or periphery. By employing fluorescence correlation spectroscopy (FCS) with photon counts histogram (PCH) analysis, we observed gradual stretched-to-collapses conformational transition with increasing solution pH for both P2VP stars of different fluorophore labeling locations. However, the measured local pH, or local proton concentration, shows strong dependence of the fluorophore labeling locations. Higher electric potential yet lower ionization degree was observed in the core of P2VP star than that in the periphery. Ongoing work is carried out to examine the scaling behaviors of P2VP star sizes with varied number of arms, arm lengths and counterion concentrations in dilute aqueous solutions.

  18. Dilute and Semidilute Solutions of a Nonionic, Rigid, Water-soluble Polymer

    NASA Astrophysics Data System (ADS)

    Russo, Paul; Huberty, Wayne; Zhang, Donghui; Water-Soluble Rodlike Polymer Team Collaboration

    2014-03-01

    The solution physics of random polymer chains was established largely on the behavior of commercial polymers such as polystyrene for organic solvents or nonionic poly(ethyleneoxide) for aqueous solvents. Not only are these materials widely available for industrial use, they can be synthesized to be essentially monodisperse. When it comes to stiff polymers, good choices are few and less prone to be used in industrial applications. Much was learned from polypeptides such as poly(benzylglutamate) or poly(stearylglutamate) in polar organic solvents and nonpolar organic solvents, respectively, but aqueous systems generally require charge. Poly(Nɛ-2-[2-(2-Methoxyethoxy) ethoxy]acetyl-L-Lysine) a.k.a. PEGL was pioneered by Deming and coworkers. In principle, PEGL provides a convenient platform from which to study stiff polymer behavior--phase relations, dynamics, liquid crystal formation and gelation--all with good molecular weight control and uniformity and without electrical charge. Still, a large gap in knowledge exists between PEGL and traditional rodlike polymer systems. To narrow this gap, dynamic and static scattering, circular dichroism, and viscosity measurements have been made in dilute and semidilute solutions as necessary preliminaries for lyotropic liquid crystalline and gel phases. Supported by NSF DMR 1306262. Department of Chemistry and Macromolecular Studies Group. Current address: Georgia Institute of Technology, School of Materials Science and Engineering.

  19. Superhydrophobic surfaces as smart platforms for the analysis of diluted biological solutions.

    PubMed

    Gentile, Francesco; Coluccio, Maria Laura; Coppedè, Nicola; Mecarini, Federico; Das, Gobind; Liberale, Carlo; Tirinato, Luca; Leoncini, Marco; Perozziello, Gerardo; Candeloro, Patrizio; De Angelis, Francesco; Di Fabrizio, Enzo

    2012-06-27

    The aim of this paper is to expound on the rational design, fabrication and development of superhydrophobic surfaces (SHSs) for the manipulation and analysis of diluted biological solutions. SHSs typically feature a periodic array or pattern of micropillars; here, those pillars were modified to incorporate on the head, at the smallest scales, silver nanoparticles aggregates. These metal nanoclusters guarantee superior optical properties and especially SERS (surface enhanced Raman scattering) effects, whereby a molecule, adsorbed on the surface, would reveal an increased spectroscopy signal. On account of their two scale-hybrid nature, these systems are capable of multiple functions which are (i) to concentrate a solution, (ii) to vehicle the analytes of interest to the active areas of the substrate and, therefore, (iii) to measure the analytes with exceptional sensitivity and very low detection limits. Forasmuch, combining different technologies, these devices would augment the performance of conventional SERS substrates and would offer the possibility of revealing a single molecule. In this work, similar SHSs were used to detect Rhodamine molecules in the fairly low atto molar range. The major application of this novel family of devices would be the early detection of tumors or other important pathologies, with incredible advances in medicine. PMID:22620470

  20. Dynamic wetting of dilute polymer solutions: the case of impacting droplets.

    PubMed

    Bertola, V

    2013-06-01

    The moving contact line of a dilute polymer solution that advances over, or recedes from a solid substrate, is a fundamental problem of fluid dynamics with important practical applications. In particular, the case of droplets impacting on hydrophobic surfaces received much attention in the recent past. Experiments show that while the advancing motion proceeds as with Newtonian liquids, recession is severely inhibited. This phenomenon was initially understood as an effect of elongational viscosity, which was believed to cause large energy dissipation in the fluid. Later on, a hydrodynamic mechanism was proposed to suggest that the slowing down of the contact line is due to non-Newtonian normal stresses generated near the moving droplet edge. Recent experiments however ruled out the role of elongational viscosity, showing that the fluid velocity measured inside the droplet during retraction is the same in water drops and polymer solution drops. Direct visualization of fluorescently stained λ-DNA molecules showed that polymer molecules are stretched perpendicularly to the contact line as the drop edge sweeps the substrate, which suggests an effective friction arises locally at the drop edge, causing the contact line to slow down. PMID:23597730

  1. Characterization of nanoparticles in diluted clear solutions for Silicalite-1 zeolite synthesis using liquid 29Si NMR, SAXS and DLS.

    PubMed

    Follens, L R A; Aerts, A; Haouas, M; Caremans, T P; Loppinet, B; Goderis, B; Vermant, J; Taulelle, F; Martens, J A; Kirschhock, C E A

    2008-09-28

    Clear solutions for colloidal Silicalite-1 synthesis were prepared by reacting tetraethylorthosilicate in aqueous tetrapropylammonium hydroxide solution. A dilution series with water resulting in clear solutions with a TEOS ratio TPAOH ratio H2O molar ratio of 25 : 9 : 152 up to 25 : 9 : 15,000 was analysed using liquid 29Si nuclear magnetic resonance (NMR), synchrotron small angle X-ray scattering (SAXS) and dynamic light scattering (DLS). Particle sizes were derived independently from DLS and from the combination of SAXS and NMR. NMR allowed quantitative characterization of silicon distributed over nanoparticles and dissolved oligomeric silicate polyanions. In all samples studied, the majority of silicon (78-90%) was incorporated in the nanoparticle fraction. In concentrated suspensions, silicate oligomers were mostly double-ring species (D3R, D4R, D5R, D6R). Dilution with water caused their depolymerisation. Contrarily, the internal condensation and size of nanoparticles increased with increasing dilution. SAXS revealed a decrease of effective nanoparticle surface charge upon dilution, reducing the effective particle interactions. With DLS, the reduction of nanoparticle interactions could be confirmed monitoring the collective diffusion mode. The observed evolution of nanoparticle characteristics provides insight in the acceleration of the Silicalite-1 crystallization upon dilution, in view of different crystallization models proposed in the literature. PMID:18956092

  2. A novel method of non-violent dissolution of sodium metal in a concentrated aqueous solution of Epsom salt

    NASA Astrophysics Data System (ADS)

    Lakshmanan, A. R.; Prasad, M. V. R.; Ponraju, D.; Krishnan, H.

    2004-10-01

    A new technique of non-violent and fast dissolution of sodium metal in a concentrated aqueous solution of Epsom salt (MgSO4.7H2O) at room temperature (RT) has been developed. The dissolution process is mildly exothermic but could be carried out even in a glass beaker in air under swift stirring condition. The reaction products consist of mixed salts of MgSO4 and Na2SO4 as well as Mg(OH)2 which are only mildly alkaline and hence are non-corrosive and non-hazardous unlike NaOH. A 50 mL solution having Epsom salt concentration of 2 M was found to give the optimal composition for disposal of 1 g of sodium. Supersaturated (>2.7 M), as well as dilute (<1.1 M) solutions, however, cause violent reactions and hence should be avoided. Repeated sodium dissolution in Epsom solution produced a solid waste of 4.7 g per g of sodium dissolved which is comparable with the waste (4 g) produced in 8 M NaOH solution. A 1.4 M Epsom solution sprayed with a high-pressure jet cleaner at RT in air easily removed the sodium blocked inside a metal pipe made of mild steel. The above jet also dissolved peacefully residual sodium collected on the metal tray after a sodium fire experiment. No sodium fire or explosion was observed during this campaign. The Epsom solution spray effectively neutralized the minor quantity of sodium aerosol produced during this campaign. This novel technique would hence be quite useful for draining sodium from fast breeder reactor components and bulk processing of sodium as well as for sodium fire fighting.

  3. Modeling of electro-osmosis of dilute electrolyte solutions in silica microporous media

    NASA Astrophysics Data System (ADS)

    Wang, Moran; Kang, Qinjun; Viswanathan, Hari; Robinson, Bruce A.

    2010-10-01

    Physicochemical transport due to electro-osmosis of dilute electrolyte solutions (<1 × 10-3 mol/L) through microporous media with granular random microstructures has been modeled in this work by our three-step numerical framework. First, the three-dimensional microstructures of porous media are reproduced by a random generation growth method. Second, the effects of chemical adsorption and electrical dissociation at the solid-liquid interfaces are modeled to determine the electrical boundary conditions, which vary with the ionic concentration, pH, and temperature. Finally, the nonlinear governing equations for electrokinetic transport are solved using a highly efficient lattice Poisson-Boltzmann algorithm. The simulation results indicate that the electro-osmotic permeability through the granular microporous media increases monotonically with the porosity, ionic concentration, pH, and temperature. When the surface electric potential is higher than about -50 mV, the electro-osmotic permeability exponentially increases with the electric potential. The electro-osmotic permeability increases with the bulk ionic concentration even though the surface zeta potential decreases correspondingly, which deviates from the conclusions based on the thin layer model. The electro-osmotic permeability increases exponentially with pH and linearly with temperature. The present modeling results improve our understanding of hydrodynamic and electrokinetic transport in geophysical systems and help guide the design of porous electrodes in microenergy systems.

  4. Elastic turbulence in Taylor-Couette Flow of Dilute Polymeric Solutions: A Direct Numerical Simulation Study

    NASA Astrophysics Data System (ADS)

    Liu, Nansheng; Khomami, Bamin

    2011-11-01

    Despite tremendous progress in development of numerical techniques and constitutive theories for polymeric fluids in the past decade, Direct Numerical Simulation (DNS) of elastic turbulence has posed tremendous challenges to researchers engaged in developing first principles models and simulations that can accurately and robustly predict the dynamical behavior of polymeric flows. In this presentation, we report the first DNS of elastic turbulence in the Taylor-Couette (TC) flow. Specifically, our computations with prototypical constitutive equations for dilute polymeric solutions, such as the FENE-P model are capable of reproducing the essential features of the experimentally observed elastic turbulence in TC flow of this class of fluids, namely, randomly fluctuating fluid motion excited in a broad range of spatial and temporal scales, and a significant increase of the flow resistance. Moreover, the experimentally measured Power Spectral Density of radial velocity fluctuations, i.e., two contiguous regions of power-law decay, -1.1 at lower frequencies and -2.2 at high-frequencies is accurately computed. We would like to thank NSF through grant CBET-0755269 and NSFC through grant NO. 10972211 for supporting of this work.

  5. Chain-length heterogeneity allows for the assembly of fatty acid vesicles in dilute solutions.

    PubMed

    Budin, Itay; Prwyes, Noam; Zhang, Na; Szostak, Jack W

    2014-10-01

    A requirement for concentrated and chemically homogeneous pools of molecular building blocks would severely restrict plausible scenarios for the origin of life. In the case of membrane self-assembly, models of prebiotic lipid synthesis yield primarily short, single-chain amphiphiles that can form bilayer vesicles only at very high concentrations. These high critical aggregation concentrations (cacs) pose significant obstacles for the self-assembly of single-chain lipid membranes. Here, we examine membrane self-assembly in mixtures of fatty acids with varying chain lengths, an expected feature of any abiotic lipid synthesis. We derive theoretical predictions for the cac of mixtures by adapting thermodynamic models developed for the analogous phenomenon of mixed micelle self-assembly. We then use several complementary methods to characterize aggregation experimentally, and find cac values in close agreement with our theoretical predictions. These measurements establish that the cac of fatty acid mixtures is dramatically lowered by minor fractions of long-chain species, thereby providing a plausible route for protocell membrane assembly. Using an NMR-based approach to monitor aggregation of isotopically labeled samples, we demonstrate the incorporation of individual components into mixed vesicles. These experiments suggest that vesicles assembled in dilute, mixed solutions are depleted of the shorter-chain-length lipid species, a finding that carries implications for the composition of primitive cell membranes. PMID:25296310

  6. Chain-Length Heterogeneity Allows for the Assembly of Fatty Acid Vesicles in Dilute Solutions

    PubMed Central

    Budin, Itay; Prwyes, Noam; Zhang, Na; Szostak, Jack W.

    2014-01-01

    A requirement for concentrated and chemically homogeneous pools of molecular building blocks would severely restrict plausible scenarios for the origin of life. In the case of membrane self-assembly, models of prebiotic lipid synthesis yield primarily short, single-chain amphiphiles that can form bilayer vesicles only at very high concentrations. These high critical aggregation concentrations (cacs) pose significant obstacles for the self-assembly of single-chain lipid membranes. Here, we examine membrane self-assembly in mixtures of fatty acids with varying chain lengths, an expected feature of any abiotic lipid synthesis. We derive theoretical predictions for the cac of mixtures by adapting thermodynamic models developed for the analogous phenomenon of mixed micelle self-assembly. We then use several complementary methods to characterize aggregation experimentally, and find cac values in close agreement with our theoretical predictions. These measurements establish that the cac of fatty acid mixtures is dramatically lowered by minor fractions of long-chain species, thereby providing a plausible route for protocell membrane assembly. Using an NMR-based approach to monitor aggregation of isotopically labeled samples, we demonstrate the incorporation of individual components into mixed vesicles. These experiments suggest that vesicles assembled in dilute, mixed solutions are depleted of the shorter-chain-length lipid species, a finding that carries implications for the composition of primitive cell membranes. PMID:25296310

  7. Morphological study of cationic polymer-anionic surfactant complex precipitated in solution during the dilution process.

    PubMed

    Miyake, M; Kakizawa, Y

    2010-01-01

    We investigated the phase diagrams and the morphology of the complexes that were formed by cationic polymers, cationic cellulose (CC) and cationic dextran (CD), and by anionic surfactant-based sodium poly(oxyethylene) lauryl ether sulfate (LES). The anionic charge of the LES-based surfactants was changed by adding an amphoteric surfactant, lauryl amidopropyl betaine acetate (LPB), or a nonionic surfactant, polyoxyethylene stearyl ether (C18EO25). We discuss the relationship between the complex aggregation process and the morphology of the precipitated complexes. The morphologies of CC complex aggregates, which precipitated during the dilution process in a model shampoo solution, changed from membranous forms to mesh-like forms by decreasing the charges of both the CC and the surfactant. Their touch on hair in the rinsing process changed from sticky to smooth and velvety, corresponding to their rheological properties. In contrast, CD complex aggregates had a membranous form and a smooth touch independently of the charges on the polymer and surfactant. These results suggested that the control of the charges of both the polymer and surfactant and the choice of polymer structure are important for excellent conditioning effects upon rinsing with shampoo. PMID:20716437

  8. Lagrange thermodynamic potential and intrinsic variables for He-3 He-4 dilute solutions

    NASA Technical Reports Server (NTRS)

    Jackson, H. W.

    1983-01-01

    For a two-fluid model of dilute solutions of He-3 in liquid He-4, a thermodynamic potential is constructed that provides a Lagrangian for deriving equations of motion by a variational procedure. This Lagrangian is defined for uniform velocity fields as a (negative) Legendre transform of total internal energy, and its primary independent variables, together with their thermodynamic conjugates, are identified. Here, similarities between relations in classical physics and quantum statistical mechanics serve as a guide for developing an alternate expression for this function that reveals its character as the difference between apparent kinetic energy and intrinsic internal energy. When the He-3 concentration in the mixtures tends to zero, this expression reduces to Zilsel's formula for the Lagrangian for pure liquid He-4. An investigation of properties of the intrinsic internal energy leads to the introduction of intrinsic chemical potentials along with other intrinsic variables for the mixtures. Explicit formulas for these variables are derived for a noninteracting elementary excitation model of the fluid. Using these formulas and others also derived from quantum statistical mechanics, another equivalent expression for the Lagrangian is generated.

  9. Recovery of propylene glycol from dilute aqueous solutions via reversible reaction with aldehydes

    SciTech Connect

    Broekhuis, R.R.; Lynn, S.; King, C.J. )

    1994-12-01

    The recovery of propylene glycol from dilute aqueous solutions via reaction with formaldehyde to form 4-methyl-1,3-dioxolane or with acetaldehyde to form 2,4-dimethyl-1,3-dioxolane was studied experimentally. The equilibrium and kinetics of the reaction with formaldehyde were studied in systems catalyzed by Amberlite IR-120 ion exchange resin. The equilibrium constant ranged from 5.9 to 8.7 in the temperature range from 25 to 85 C, with no obvious trend with respect to temperature. The kinetics was found to be first-order in the concentrations of propylene glycol, formaldehyde, and Amberlite IR-120, with an activation energy of 102 kJ/mol. In the reaction with acetaldehyde, the equilibrium constant decreased from 18.1 at 40 C to 8.5 at 83 C. The kinetics was faster than with formaldehyde. The volatilities of 4-methyl-1,3-dioxolane and 2,4-dimethyl-1,3-dioxolane relative to water were 100 and 33, respectively. Of several solvents screened, aromatic hydrocarbons exhibited the highest distribution of 2,4-dimethyl-1,3-dioxolane from the aqueous into the organic phase. Recovery of propylene glycol by reactive distillation with formaldehyde or acetaldehyde is hampered by unfavorable chemical and phase equilibria. A process combining reaction and extraction into an organic solvent appears to be more attractive and substantially reduces the energy requirement, in comparison with a triple-effect evaporation process.

  10. Controlled formation of ag nanoparticles by means of long-chain sodium polyacrylates in dilute solution.

    PubMed

    Huber, Klaus; Witte, Thomas; Hollmann, Jutta; Keuker-Baumann, Susanne

    2007-02-01

    A new tool is presented to control formation of Ag nanoparticles. Small amounts of silver ions were added to dilute solutions of long-chain sodium polyacrylates (NaPA). Four NaPA samples covering a molar mass regime of 97 kD < or = Mw < or = 650 kD have been used. With amounts of added Ag(+) as low as 1-2% of the COO(-) groups of the polyanionic chains, significant changes could already be induced in the NaPA coils with 650 kD. If the NaPA concentration was kept below 0.1 g/L, the coils with 650 kD exhibited a significant coil shrinking in stable solutions. At larger NaPA concentrations, addition of Ag+ initiates an aggregation of the polyacrylate coils toward compact structures. Coil shrinking and aggregation was revealed by means of time-resolved static light scattering. If exposed to UV-radiation, small Ag particles formed within the shrunken anionic polyacrylate coils. The Ag nanoparticles were identified by means of an enhanced light scattering and a characteristic plasmon absorption band around 410 nm. No such Ag particle formation could be observed even at 5 times larger concentrations of Ag(+) and NaPA if the two smallest polyacrylate samples have been used under otherwise equal conditions. This molar mass sensitive response of NaPA to Ag(+)-addition suggests an interesting phenomenon: if the coil size of the NaPa chains, which act as Ag(+) collectors, is large enough, local Ag(+) concentration in these coil-shaped Ag(+) containers exceeds a critical value, and irradiation with UV generates Ag nanoparticles. PMID:17263389

  11. ISOPAR L Release Rates from Saltstone Using Simulated Salt Solutions

    SciTech Connect

    Bronikowski, M

    2006-02-06

    The Modular Caustic-Side Solvent Extraction (CSSX) Unit (MCU) and the Salt Waste Processing Facility (SWPF) will produce a Deactivated Salt Solution (DSS) that will go to the Saltstone Production Facility (SPF). Recent information indicates that solvent entrainment in the DSS is larger than expected. The main concern is with Isopar{reg_sign} L, the diluent in the solvent mixture, and its flammability in the saltstone vault. If it is assumed that all the Isopar{reg_sign} L is released instantaneously into the vault from the curing grout before each subsequent pour; the Isopar{reg_sign} L in the vault headspace is well mixed; and each pour displaces an equivalent volume of headspace, the allowable concentration of Isopar{reg_sign} L in the DSS sent to SPF has been calculated at approximately 4 ppm. The amount allowed would be higher, if the release from grout were significantly less. The Savannah River National Laboratory was tasked with determining the release of Isopar{reg_sign} L from saltstone prepared with a simulated DSS with Isopar{reg_sign} L concentrations ranging from 50 mg/L to 200 mg/L in the salt fraction and with test temperatures ranging from ambient to 95 C. The results from the curing of the saltstone showed that the Isopar{reg_sign} L release data can be treated as a percentage of initial concentration in the concentration range studied. The majority of the Isopar{reg_sign} L that was released over the test duration was released in the first few days. The release of Isopar{reg_sign} L begins immediately and the rate of release decreases over time. At higher temperatures the immediate release is larger than at lower temperatures. In one test at 95 C essentially all of the Isopar{reg_sign} L was released in three months. Initial curing temperature was found to be very important as slight variations during the first few days affected the final Isopar{reg_sign} L amount released. Short scoping tests at 95 C with solvent containing all components (Isopar

  12. ISOPAR L RELEASE RATES FROM SALTSTONE USING SIMULATED SALT SOLUTIONS

    SciTech Connect

    Zamecnik, J; Michael Bronikowski, M; Alex Cozzi, A; Russell Eibling, R; Charles Nash, C

    2008-07-31

    The Modular Caustic-Side Solvent Extraction (CSSX) Unit (MCU) and the Salt Waste Processing Facility (SWPF) will produce a Decontaminated Salt Solution (DSS) that will go to the Saltstone Production Facility (SPF). Recent information indicates that solvent entrainment in the DSS is larger than expected. The main concern is with Isopar{reg_sign} L, the diluent in the solvent mixture, and its flammability in the saltstone vault. If it is assumed that all the Isopar{reg_sign} L is released instantaneously into the vault from the curing grout before each subsequent pour, the Isopar{reg_sign} L in the vault headspace is well mixed, and each pour displaces an equivalent volume of headspace, the maximum concentration of Isopar{reg_sign} L in the DSS to assure 25% of the lower flammable limit is not exceeded has been determined to be about 4 ppm. The amount allowed would be higher if the release from grout were significantly less. The Savannah River National Laboratory was tasked with determining the release of Isopar{reg_sign} L from saltstone prepared with a simulated DSS with Isopar{reg_sign} L concentrations ranging from 50 to 200 mg/L in the salt fraction and with test temperatures ranging from ambient to 95 C. The results from the curing of the saltstone showed that the amount of Isopar{reg_sign} L released versus time can be treated as a percentage of initial amount present; there was no statistically significant dependence of the release rate on the initial concentration. The majority of the Isopar{reg_sign} L that was released over the test duration was released in the first few days. The release of Isopar{reg_sign} L begins immediately and the rate of release decreases over time. At higher temperatures the immediate release rate is larger than at lower temperatures. Initial curing temperature was found to be very important as slight variations during the first few hours or days had a significant effect on the amount of Isopar{reg_sign} L released. Short scoping

  13. Aggregation in dilute aqueous tert-butyl alcohol solutions: Insights from large-scale simulations

    NASA Astrophysics Data System (ADS)

    Gupta, Rini; Patey, G. N.

    2012-07-01

    possible nature of microheterogeneity in dilute TBA-water solutions, and of the associated long correlation lengths. It is clear that system size can be a very important factor in simulations of these solutions, and must be taken into account in the evaluation and development of TBA-water force fields.

  14. A Study of Novel Hexavalent Phosphazene Salts as Draw Solutes in Forward Osmosis

    SciTech Connect

    Mark L. Stone; Aaron D. Wilson; Mason K. Harrup; Frederick F. Stewart

    2013-03-01

    Two novel multi-valent salts based on phosphazene chemistry have been synthesized and characterized as forward osmosis (FO) draw solutes. Commercially obtained hexachlorocyclotriphosphazene was reacted with the sodium salt of 4-ethylhydroxybenzoate to yield hexa(4-ethylcarboxylatophenoxy)phosphazene. Hydrolysis, followed by and neutralization with NaOH or LiOH, of the resulting acidic moieties yielded water soluble sodium and lithium phosphazene salts, respectively. Degrees of dissociation were determined through osmometry over the range of 0.05-0.5 m, giving degrees of 3.08-4.95 per mole, suggesting a high osmotic potential. The Li salt was found to be more ionized in solution than the sodium salt, and this was reflected in FO experiments where the Li salt gave higher initial fluxes (~ 7 L/m2h) as compared to the sodium salt (~6 L/m2h) at identical 0.07 m draw solution concentrations at 30 °C. Longer term experiments revealed no detectable degradation of the salts; however some hydrolysis of the cellulose acetate membrane was observed, presumably due to the pH of the phosphazene salt draw solution (pH = ~8).

  15. Salt weathering in Egyptian limestone after laboratory simulations with continuous flow of salt solutions at different temperatures

    NASA Astrophysics Data System (ADS)

    Aly, Nevin; Gomez-Heras, Miguel; Hamed, Ayman; Alvarez de Buergo, Monica

    2013-04-01

    weathering in Egyptian limestone after laboratory simulations with continuous flow of salt solutions at different temperatures Nevin Aly Mohamed (1), Miguel Gomez - Heras(2), Ayman Hamed Ahmed (1), and Monica Alvarez de Buergo(2). (1) Faculty of Pet. & Min. Engineering- Suez Canal University, Suez, Egypt, (2) Instituto de Geociencias (CSIC-UCM) Madrid. Spain. Limestone is one of the most frequent building stones in Egypt and is used since the time of ancient Egyptians and salt weathering is one of the main threats to its conservation. Most of the limestone used in historical monuments in Cairo is a biomicrite extracted from the Mid-Eocene Mokattam Group. During this work, cylindrical samples (2.4 cm diameter and approx. 4.8 cm length) were subjected, in a purpose-made simulation chamber, to simulated laboratory weathering tests with fixed salt concentration (10% weight NaCl solution), at different temperatures, which were kept constant throughout each test (10, 20, 30, 40 oC). During each test, salt solutions flowed continuously imbibing samples by capilarity. Humidity within the simulation chamber was reduced using silica gel to keep it low and constant to increase evaporation rate. Temperature, humidity inside the simulation chamber and samples weight were digitally monitored during each test. Results show the advantages of the proposed experimental methodology using a continuous flow of salt solutions and shed light on the effect of temperature on the dynamics of salt crystallization on and within samples. Research funded by mission sector of high education ministry, Egypt and Geomateriales S2009/MAT-1629.

  16. Concentration and precipitation of NaCl and KCl from salt cake leach solutions by electrodialysis

    SciTech Connect

    Sreenivasarao, K; Patsiogiannis, F.; Hryn, J.N.

    1997-02-09

    Electrodialysis was investigated for cost-effective recovery of salt from salt cake leach solutions. (Salt cake is a waste stream generated by the aluminum industry during treatment of aluminum drosses and scrap.) We used a pilot-scale electrodialysis stack of 5 membrane pairs, each with an effective area of 0.02 m{sup 2}. The diluate stream contained synthetic NaCl, KCl,mixtures of NaCl and KCl, and actual salt cake leach solutions (mainly NaCl and KCl, with small amounts of MgCl{sub 2}). We concentrated and precipitated NaCl and KCl salts from the concentrate steam when the initial diluate stream concentration was 21.5 to 28.8 wt% NaCl and KCl. We found that water transferring through the membranes was a significant factor in overall efficiency of salt recovery by electrodialysis.

  17. MTBE Hydrolysis in Dilute Aqueous Solution Using Heterogeneous Strong Acid Catalysts

    NASA Astrophysics Data System (ADS)

    Rixey, W. G.

    2003-12-01

    The objective of this research has been the development of a potential in situ catalytic process for the hydrolysis of methyl tertiary butyl ether (MTBE) to tertiary butyl alcohol (TBA) and methanol in ground water. Bench-scale batch reactor studies were conducted over a temperature range of 23 deg C to 50 deg C with several heterogeneous strong acid catalysts to obtain rates of hydrolysis of MTBE to TBA and methanol at dilute concentrations in water. Continuous flow experiments were then conducted to obtain kinetic data over a temperature range of 15 deg C to 50 deg C for various flow rates for the most active catalysts. It was found that the batch and continuous flow experiments yielded similar intrinsic kinetic rate constants when sorption of MTBE to the catalyst was accounted for. Additional fixed-bed experiments were conducted with deionized water and 0.005 M CaCl2 feed solutions containing 100 mg/L MTBE, respectively, to assess the deactivation of the catalyst, and deactivation was found to be controlled by ion exchange of H+ in the catalyst with Ca+2 in the feed. Our results indicate that, for low to moderate groundwater velocities and cation concentrations at ambient temperatures, an in situ reactive barrier process using the most active catalysts studied in this research could be a viable process in terms of both suitable conversion of MTBE and catalyst life. Although application to in situ remediation is emphasized, the results of this research are also applicable to ex-situ groundwater treatment.

  18. Simulation of dilute solutions of linear and star-branched polymers by dissipative particle dynamics.

    PubMed

    Nardai, M M; Zifferer, G

    2009-09-28

    A most promising off-lattice technique in order to simulate not only static but in addition dynamic behavior of linear and star-branched chains is the dissipative particle dynamics (DPD) method. In this model the atomistic representation of polymer molecules is replaced by a (coarse-grained) equivalent chain consisting of beads which are repulsive for each other in order to mimic the excluded volume effect (successive beads in addition are linked by springs). Likewise solvent molecules are combined to beads which in turn are repulsive for each other as well as for the polymer segments. The system is relaxed by molecular dynamics solving Newton's laws under the influence of short ranged conservative forces (i.e., repulsion between nonbonded beads and a proper balance of repulsion and attraction between bonded segments) and dissipative forces due to friction between particles, the latter representing the thermostat in conjunction with proper random forces. A variation of the strength of the repulsion between different types of beads allows the simulation of any desired thermodynamic situation. Static and dynamic properties of isolated linear and star-branched chains embedded in athermal, exothermal, and endothermal solvent are presented and theta conditions are examined. The generally accepted scaling concept for athermal systems is fairly well reproduced by linear and star-branched DPD chains and theta conditions appear for a unique parameter independent of functionality as in the case of Monte Carlo simulations. Furthermore, the correspondence between DPD and Monte Carlo data referring to the shape of chains and stars is fairly well, too. For dilute solutions the Zimm behavior is expected for dynamic properties which is indeed realized in DPD systems. PMID:19791917

  19. Solvent controlled ion association in structured copolymers: Molecular dynamics simulations in dilute solutions

    NASA Astrophysics Data System (ADS)

    Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

    2015-09-01

    Tailoring the nature of individual segments within ion containing block co-polymers is one critical design tool to achieve desired properties. The local structure including the size and distribution of the ionic blocks, as well as the long range correlations, are crucial for their transport ability. Here, we present molecular dynamics simulations on the effects of varying the concentrations of the ionizable groups on the conformations of pentablock ionomer that consist of a center block of ionic sulfonated styrene tethered to polyethylene and terminated by a bulky substituted styrene in dilute solutions. Sulfonation fractions f (0 ≤ f ≤ 0.55), spanning the range from ionomer to polyelectrolytes, were studied. Results for the equilibrium conformation of the chains in water and a 1:1 mixture of cyclohexane and heptane are compared to that in implicit poor solvents with dielectric constants ɛ = 1.0 and 77.73. In water, the pentablock collapses with the sulfonated groups on the outer surface. As f increases, the ionic, center block increasingly segregates from the hydrophobic regions. In the 1:1 mixture of cyclohexane and heptane, the flexible blocks swell, while the center ionic block collapses for f > 0. For f = 0, all blocks swell. In both implicit poor solvents, the pentablock collapses into a nearly spherical shape for all f. The sodium counterions disperse widely throughout the simulation cell for both water and ɛ = 77.73, whereas for ɛ = 1.0 and mixture of cyclohexane and heptane, the counterions largely condense onto the collapsed pentablock.

  20. Testing of stripping columns for the removal of benzene from aqueous radioactive salt solution

    SciTech Connect

    Georgeton, G.K.; Taylor, G.A.; Gaughan, T.P.

    1995-06-27

    Radioactive high level wastes (HLW) generated from production of special nuclear materials at the Savannah River Site (SRS) are held in interim storage in 51 underground, million gallon tanks. Radioactive cesium ({sup 137}Cs) is segregated by evaporation of aqueous waste solution for interim storage in a salt matrix comprised of Na and K salts or in concentrated salt solution. The saltcake will be dissolved and {sup 137}Cs will be separated from the nonradioactive salts in solution in the In-Tank Precipitation (ITP) Process. The cesium will be combined with other radioactive species and glass formers to be melted and poured into stainless steel canisters in the Defense Waste Processing Facility (DWPF). The salt solution remaining after decontamination in the ITP process will be incorporated into grout for disposal at the site`s Saltstone facility. In the ITP facility, sodium tetraphenylborate (STPB) will be added to precipitate the cesium. Potassium in the waste solution also reacts with STPB and precipitates. Due to radiolytic and chemical degradation of the tetraphenylborate (TPB) precipitate, benzene is generated. The benzene dissolves into the decontaminated salt solution (DSS) and into water (WW) used to {open_quotes}wash{close_quotes} the precipitate to lower the soluble salt content of the slurry. Safety and processing requirements for disposal of the DSS and for temporary storage of the WW dictate that the benzene concentration be reduced.

  1. Molecular imaging of shear-induced polymer migration near a surface in dilute and semidilute solutions

    NASA Astrophysics Data System (ADS)

    Fang, Lin

    The goal of our research is to optically visualize shear-induced polymer migration near a surface on the single molecular level, and to enhance current understanding of interactions between flowing polymer solutions with surfaces. By using epi-fluorescence microscopy, we measured the mean fractional stretch and concentrations of lambda-phage DNA molecules above a glass surface in shear flows in a microchannel and a torsional shear cell. We find that DNA molecules are driven away to create a depletion layer near the surface. The shear-induced migration is enhanced with a larger depletion layer at high Weissenberg number (Wi), in qualitative agreement with theories. We proposed a simple mechanism for this shear-induced migration based on hydrodynamic interaction (HI) between the surface and polymer chains. We find that the thickness of depletion layer of lambda-phage DNA molecules is about 10mum at Wi = 10.3, which is thinner than in the predictions for the FENE-P dumbbell model [Ma and Graham (2005)] and in Brownian dynamics simulations. The discrepancies suggest that current theoretical models of the polymer migration phenomenon are incomplete. We find that the time scale of DNA migration is on the order of the diffusion time over the distance of depletion layer, and that the mean fractional stretch of DNA molecules decreases near the surface over this same time scale. Experiments with deliberately fragmented DNA indicate that the decrease in mean fractional stretch near the surface might be caused by the selective retention of fragments in the DNA solution owing to weaker HI effects between the surface and shorter polymer chains. The shear-induced migration of DNA molecules exists in diminished form up to 3.0 c* (c* is the overlap concentration), implying that: in the traditionally defined dilute regime (c < c*), screening of wall hydrodynamics occurs over DNA concentration from 0.1 c* to 1.0 c*; and in the semidilute regime (c > c*); while the chains are

  2. Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries

    SciTech Connect

    Doe, RE; Han, R; Hwang, J; Gmitter, AJ; Shterenberg, I; Yoo, HD; Pour, N; Aurbach, D

    2014-01-01

    Herein the first inorganic magnesium salt solution capable of highly reversible magnesium electrodeposition is presented. Synthesized by acid-base reaction of MgCl2 and Lewis acidic compounds such as AlCl3, this salt class demonstrates upwards of 99% Coulombic efficiency, deposition overpotential of <200 mV, and anodic stability of 3.1 V.

  3. MECHANISM OF PITTING CORROSION PREVENTION BY NITRITE IN CARBON STEEL EXPOSED TO DILUTE SALT SOLUTIONS

    EPA Science Inventory

    The overall goal of this project is to develop a fundamental understanding of the role of nitrite in preventing the breakdown of protective oxide coating on steel and the onset of pitting. A fundamental understanding of the materials science and electrochemistry of the nitrite ro...

  4. Location of microseismic swarms induced by salt solution mining

    NASA Astrophysics Data System (ADS)

    Kinscher, J.; Bernard, P.; Contrucci, I.; Mangeney, A.; Piguet, J. P.; Bigarre, P.

    2015-01-01

    Ground failures, caving processes and collapses of large natural or man-made underground cavities can produce significant socio-economic damages and represent a serious risk envisaged by the mine managements and municipalities. In order to improve our understanding of the mechanisms governing such a geohazard and to test the potential of geophysical methods to prevent them, the development and collapse of a salt solution mining cavity was monitored in the Lorraine basin in northeastern France. During the experiment, a huge microseismic data set (˜50 000 event files) was recorded by a local microseismic network. 80 per cent of the data comprised unusual swarming sequences with complex clusters of superimposed microseismic events which could not be processed through standard automatic detection and location routines. Here, we present two probabilistic methods which provide a powerful tool to assess the spatio-temporal characteristics of these swarming sequences in an automatic manner. Both methods take advantage of strong attenuation effects and significantly polarized P-wave energies at higher frequencies (>100 Hz). The first location approach uses simple signal amplitude estimates for different frequency bands, and an attenuation model to constrain the hypocentre locations. The second approach was designed to identify significantly polarized P-wave energies and the associated polarization angles which provide very valuable information on the hypocentre location. Both methods are applied to a microseismic data set recorded during an important step of the development of the cavity, that is, before its collapse. From our results, systematic spatio-temporal epicentre migration trends are observed in the order of seconds to minutes and several tens of meters which are partially associated with cyclic behaviours. In addition, from spatio-temporal distribution of epicentre clusters we observed similar epicentre migration in the order of hours and days. All together, we

  5. Students' Misconceptions in Electrochemistry: Current Flow in Electrolyte Solutions and the Salt Bridge.

    ERIC Educational Resources Information Center

    Sanger, Michael J.; Greenbowe, Thomas J.

    1997-01-01

    Examines students' misconceptions and proposed mechanisms related to current flow in electrolyte solutions and the salt bridge. Confirms reported misconceptions and identifies several new ones. Discusses probable sources of misconceptions and some methods for preventing them. Contains 27 references. (JRH)

  6. Nuclear magnetic resonance in water solutions of inorganic salts in vitreous and liquid states

    SciTech Connect

    Lundin, A. G. Koryavko, N. A.; Chichikov, S. A.

    2013-05-15

    Peculiarities of the behavior of water solutions of inorganic salts at temperatures of {approx}(120-150) K are examined. At these temperatures the solutions are in the vitreous state. At higher temperatures (up to 240 K) the solutions may be in metastable liquid, crystalline, or usual liquid states.

  7. Materials and methods for stabilizing nanoparticles in salt solutions

    DOEpatents

    Robinson, David Bruce; Zuckermann, Ronald; Buffleben, George M.

    2013-06-11

    Sequence-specific polymers are proving to be a powerful approach to assembly and manipulation of matter on the nanometer scale. Ligands that are peptoids, or sequence-specific N-functional glycine oligomers, allow precise and flexible control over the arrangement of binding groups, steric spacers, charge, and other functionality. We have synthesized short peptoids that can prevent the aggregation of gold nanoparticles in high-salt environments including divalent salt, and allow co-adsorption of a single DNA molecule. This degree of precision and versatility is likely to prove essential in bottom-up assembly of nanostructures and in biomedical applications of nanomaterials.

  8. Effects of dilute aqueous NaCl solution on caffeine aggregation

    SciTech Connect

    Sharma, Bhanita; Paul, Sandip

    2013-11-21

    The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogen bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl.

  9. Effects of dilute aqueous NaCl solution on caffeine aggregation

    NASA Astrophysics Data System (ADS)

    Sharma, Bhanita; Paul, Sandip

    2013-11-01

    The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogen bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl.

  10. Enthalpies of the dissolution and dilution of aqueous solutions of rubidium and cesium diclofenac at 293.15-318.15 K

    NASA Astrophysics Data System (ADS)

    Manin, N. G.; Perlovich, G. L.; Fini, A.

    2014-03-01

    Enthalpies of the dissolution and dilution of aqueous solutions of rubidium and cesium diclofenac (RbDC and CsDC) are measured at 293.15, 298.15, 308.15, and 318.15 K at concentrations of water of less than 0.1 mol/kg. The heat capacity of RbDC and CsDC crystal salts is determined. Changes in the thermodynamic properties of both a solution and its components vs. concentration and temperature is considered. An increase in the endothermicity of the dissolution of RbDC and CsDC with a rise in temperature is noted. It is shown that the dissolution of both RbDC and CsDC electrolytes in water is determined by the contribution from entropy. It is shown that in aqueous solutions of RbDC and CsDC, the degree of binding of water molecules is higher than in pure water at temperatures below 303.15 K.

  11. Determination of the viscosity number of thermoplastics in dilute solution; polyamides (PA)

    NASA Technical Reports Server (NTRS)

    1985-01-01

    This West German Standard presents a test used to determine the viscosity number of polyamides and copolyamides which are easily diluted in sulfuric acid, and for other polyamides which are less easily diluted in sulfuric acid, and which are diluted in m-cresol. As formic acid is often used in industry instead of sulfuric acid, this solvent is also presented as an alternative, however, sulfuric acid is preferred because of the thermodynamic solubility characteristics of the polyamides and the handling safety. In addition, it is shown which solvent should be used for each polyamide. Finally, determinations concerning the preparation of the samples are presented. Using the viscosity number, a determination of the molar mass of the polyamides is possible.

  12. Salt-Finger Convection in a Stratified Fluid Layer Induced by Thermal and Solutal Capillary Motion

    NASA Technical Reports Server (NTRS)

    Chen, Chuan F.; Chan, Cho Lik

    1996-01-01

    Salt-finger convection in a double-diffusive system is a motion driven by the release of gravitational potential due to different diffusion rates. Normally, when the gravitational field is reduced, salt-finger convection together with other convective motions driven by buoyancy forces will be rapidly suppressed. However, because the destabilizing effect of the concentration gradient is amplified by the Lewis number, with values varying from 10(exp 2) for aqueous salt solutions to 10 (exp 4) for liquid metals, salt-finger convection may be generated at much reduced gravity levels. In the microgravity environment, the surface tension gradient assumes a dominant role in causing fluid motion. In this paper, we report on some experimental results showing the generation of salt-finger convection due to capillary motio on the surface of a stratified fluid layer. A numerical simulation is presented to show the cause of salt-finger convection.

  13. Pesticide Removal from Aqueous Solutions by Adding Salting Out Agents

    PubMed Central

    Moscoso, Fátima; Deive, Francisco J.; Esperança, José M. S. S.; Rodríguez, Ana

    2013-01-01

    Phase segregation in aqueous biphasic systems (ABS) composed of four hydrophilic ionic liquids (ILs): 1-butyl-3-methylimidazolium methylsulfate and 1-ethyl-3-methylimidazolium methylsulfate (CnC1im C1SO4, n = 2 and 4), tributylmethyl phosphonium methylsulfate (P4441 C1SO4) and methylpyridinium methylsulfate (C1Py C1SO4) and two high charge density potassium inorganic salts (K2CO3 and K2HPO4) were determined by the cloud point method at 298.15 K. The influence of the addition of the selected inorganic salts to aqueous mixtures of ILs was discussed in the light of the Hofmeister series and in terms of molar Gibbs free energy of hydration. The effect of the alkyl chain length of the cation on the methylsulfate-based ILs has been investigated. All the solubility data were satisfactorily correlated to several empirical equations. A pesticide (pentachlorophenol, PCP) extraction process based on the inorganic salt providing a greater salting out effect was tackled. The viability of the proposed process was analyzed in terms of partition coefficients and extraction efficiencies. PMID:24145747

  14. Ion aggregation in high salt solutions: Ion network versus ion cluster

    SciTech Connect

    Kim, Seongheun; Kim, Heejae; Choi, Jun-Ho; Cho, Minhaeng

    2014-09-28

    The critical aggregation phenomena are ubiquitous in many self-assembling systems. Ions in high salt solutions could also spontaneously form larger ion aggregates, but their effects on hydrogen-bond structures in water have long been controversial. Here, carrying out molecular dynamics (MD) simulation studies of high salt solutions and comparing the MD simulation results with infrared absorption and pump-probe spectroscopy of O–D stretch mode of HDO in highly concentrated salt solutions and {sup 13}C-NMR chemical shift of S{sup 13}CN{sup −} in KSCN solutions, we find evidence on the onset of ion aggregate and large-scale ion-ion network formation that concomitantly breaks water hydrogen-bond structure in certain salt solutions. Despite that these experimental results cannot provide direct evidence on the three-dimensional morphological structures of ion aggregates, they serve as reference data for verifying MD simulation methods. The MD results suggest that disrupted water hydrogen-bond network is intricately intertwined with ion-ion network. This further shows morphological variation of ion aggregate structures from ion cluster to ion network in high salt solutions that are interrelated to the onset of macroscopic aggregate formation and the water hydrogen-bond structure making and breaking processes induced by Hofmeister ions.

  15. Ion aggregation in high salt solutions: Ion network versus ion cluster

    NASA Astrophysics Data System (ADS)

    Kim, Seongheun; Kim, Heejae; Choi, Jun-Ho; Cho, Minhaeng

    2014-09-01

    The critical aggregation phenomena are ubiquitous in many self-assembling systems. Ions in high salt solutions could also spontaneously form larger ion aggregates, but their effects on hydrogen-bond structures in water have long been controversial. Here, carrying out molecular dynamics (MD) simulation studies of high salt solutions and comparing the MD simulation results with infrared absorption and pump-probe spectroscopy of O-D stretch mode of HDO in highly concentrated salt solutions and 13C-NMR chemical shift of S13CN- in KSCN solutions, we find evidence on the onset of ion aggregate and large-scale ion-ion network formation that concomitantly breaks water hydrogen-bond structure in certain salt solutions. Despite that these experimental results cannot provide direct evidence on the three-dimensional morphological structures of ion aggregates, they serve as reference data for verifying MD simulation methods. The MD results suggest that disrupted water hydrogen-bond network is intricately intertwined with ion-ion network. This further shows morphological variation of ion aggregate structures from ion cluster to ion network in high salt solutions that are interrelated to the onset of macroscopic aggregate formation and the water hydrogen-bond structure making and breaking processes induced by Hofmeister ions.

  16. Length Scale Dependence of the Dynamic Properties of Hyaluronic Acid Solutions in the Presence of Salt

    SciTech Connect

    Horkay, Ferenc; Falus, Peter; Hecht, Anne-Marie; Geissler, Erik

    2010-12-07

    In solutions of the charged semirigid biopolymer hyaluronic acid in salt-free conditions, the diffusion coefficient D{sub NSE} measured at high transfer momentum q by neutron spin echo is more than an order of magnitude smaller than that determined by dynamic light scattering, D{sub DLS}. This behavior contrasts with neutral polymer solutions. With increasing salt content, D{sub DLS} approaches D{sub NSE}, which is independent of ionic strength. Contrary to theoretical expectation, the ion-polymer coupling, which dominates the low q dynamics of polyelectrolyte solutions, already breaks down at distance scales greater than the Debye-Hueckel length.

  17. Preparation of silver nanoparticles in solution from a silver salt by laser irradiation.

    PubMed

    Abid, J P; Wark, A W; Brevet, P F; Girault, H H

    2002-04-01

    A new method is proposed for the fabrication of a well-defined size and shape distribution of silver nanoparticles in solution; the method employs direct laser irradiation of an aqueous solution containing a silver salt and a surfactant in the absence of reducing agents. PMID:12119726

  18. Fluid-loading solutions and plasma volume: Astro-ade and salt tablets with water

    NASA Technical Reports Server (NTRS)

    Fortney, Suzanne M.; Seinmann, Laura; Young, Joan A.; Hoskin, Cherylynn N.; Barrows, Linda H.

    1994-01-01

    Fluid loading with salt and water is a countermeasure used after space flight to restore body fluids. However, gastrointestinal side effects have been frequently reported in persons taking similar quantities of salt and water in ground-based studies. The effectiveness of the Shuttle fluid-loading countermeasure (8 gms salt, 0.97 liters of water) was compared to Astro-ade (an isotonic electrolyte solution), to maintain plasma volume (PV) during 4.5 hrs of resting fluid restriction. Three groups of healthy men (n=6) were studied: a Control Group (no drinking), an Astro-ade Group, and a Salt Tablet Group. Changes in PV after drinking were calculated from hematocrit and hemoglobin values. Both the Salt Tablet and Astro-ade Groups maintained PV at 2-3 hours after ingestion compared to the Control Group, which had a 6 percent decline. Side effects (thirst, stomach cramping, and diarrhea) were noted in at least one subject in both the Astro-ade and Salt Tablet Groups. Nausea and vomiting were reported in one subject in the Salt Tablet Group. It was concluded that Astro-ade may be offered as an alternate fluid-loading countermeasure but further work is needed to develop a solution that is more palatable and has fewer side effects.

  19. Temperature- and salt-responsive polyoxometalate-poly(N-isopropylacrylamide) hybrid macromolecules in aqueous solution.

    PubMed

    Zhou, Jing; Yin, Panchao; Chen, Xinyue; Hu, Lang; Liu, Tianbo

    2015-11-14

    Polyoxometalate (POM) polar head groups were covalently functionalized with poly(N-isopropylacrylamide) (PNIPAM) tails. The macromolecular hybrid demonstrates solution behavior of hydrophilic macroions by self-assembling into blackberry structures at room temperature. The hybrid behaves like an amphiphilic surfactant by forming a vesicular structure when the temperature is above the phase transition of PNIPAM. The reversible self-assembly is also salt-sensitive and the salt-induced smaller vesicular formation results from counterion-association. PMID:26383608

  20. Isoconversional Kinetics of Nonisothermal Crystallization of Salts from Solutions.

    PubMed

    Stanford, Victoria L; McCulley, Calla M; Vyazovkin, Sergey

    2016-06-30

    In this study, differential scanning calorimetry (DSC) has been applied to measure the kinetics of nonisothermal crystallization of potassium nitrate and ammonium perchlorate from unsaturated and saturated aqueous solutions. DSC data have been analyzed by an advanced isoconversional method that demonstrates that the process is represented by negative values of the effective activation energy, which varies with the progress of crystallization. The classical nucleation model can be used to predict and understand the experimentally observed variation in the effective activation energy. The saturated and unsaturated solutions have demonstrated distinctly different crystallization kinetics. It is suggested that the unsaturated solutions undergo a change in crystallization mechanism from homogeneous to heterogeneous nucleation. PMID:27305831

  1. Laser etching of metals in neutral salt solutions

    NASA Astrophysics Data System (ADS)

    Datta, M.; Romankiw, L. T.; Vigliotti, D. R.; von Gutfeld, R. J.

    1987-12-01

    We report new findings that relate to rapid maskless laser etching of steel and stainless steel in neutral solutions of sodium chloride, sodium nitrate, and potassium sulfate. Etch rates have been determined as a function of laser power, laser on-time, and solution concentration. The morphology of laser-etched holes obtained in these solutions was compared with holes obtained in pure water. Results indicate that some controlled melting occurs under certain laser conditions in addition to the metal dissolution process induced by the locally intense heat of the laser beam.

  2. Conformational changes of bovine plasma albumin prior to the salting-out of protein in concentrated salt solution.

    PubMed

    Sogami, M; Inouye, H; Nagaoka, S; Era, S

    1982-09-01

    By working at very low protein concentration (ca. 0.003%), it is possible to measure tryptophyl fluorescence intensity at 350 nm (F350) of bovine plasma albumin (BPA) as a function of pH under precipitating conditions (acidic concentrated salt solutions). Under such conditions, distinct changes in F350 were seen before the starting of precipitation of BPA and no further changes in F350 over the precipitating pH range. Comparison of pH-profiles monitored by F350 with those by solubility in the presence of various salts at various concentrations indicated that the change of solubility is observed after definite changes in conformation of the protein. PMID:7129758

  3. Tracer-dilution experiments and solute-transport simulations for a mountain stream, Saint Kevin Gulch, Colorado. Water resources investigation

    SciTech Connect

    Broshears, R.E.; Bencala, K.E.; Kimball, B.A.; McKnight, D.M.

    1993-01-01

    In 1986, the U.S. Geological Survey began an investigation to characterize within-stream hydrologic, chemical, and biological processes that influence the distribution and transport of hazardous constituents in the headwaters of the Arkansas River. The report describes the results of tracer-dilution experiments and associated solute-transport simulations for a 1804-meter stretch of Saint Kevin Gulch, a stream affected by acid mine drainage in Lake County, Colorado. The report describes transient changes in tracer (lithium chloride) concentration at six instream sites.

  4. The Solidification Velocity of Undercooled Nickel and Titanium Alloys with Dilute Solute

    NASA Technical Reports Server (NTRS)

    Algoso, Paul R.; Altgilbers, A. S.; Hofmeister, William H.; Bayuzick, Robert J.

    2003-01-01

    The study of solidification velocity is important for two reasons. First, understanding the manner in which the degree of undercooling of the liquid and solidification velocity affect the microstructure of the solid is fundamental. Second, there is disagreement between theoretical predictions of the relationship between undercooling and solidification velocity and experimental results. Thus, the objective of this research is to accurately and systematically quantify the solidification velocity as a function of undercooling for dilute nickel-and titanium-based alloys. The alloys chosen for study cover a wide range of equilibrium partition coefficients, and the results are compared to current theory.

  5. Frequency of OH in solutions of n-butanol in carbon tetrachloride: effect of dilution

    NASA Astrophysics Data System (ADS)

    Srivastava, P. K.; Rai, D. K.; Rai, S. B.

    2000-06-01

    It is noted that the 1←0 transition for νOH shows a blue shift as the relative concentration of n-butanol in a CCl 4- n-butanol is reduced. The magnitude of the shift decreases for the 2←0 transition and there is almost no shift for the 3←0 transition. These observations are consistent with the observed red shift [Y. Mizugai, F. Takimoto, M. Katayama, Chem. Phys. Lett. 76 (1980) 615] on dilution for the 5←0 transition in n-butanol. The observations have been interpreted on the basis of formation of O-H. . . . Cl hydrogen bond.

  6. Scaling of dynamics in 2d semi-dilute polymer solutions

    NASA Astrophysics Data System (ADS)

    Cicuta, P.; Hopkinson, I.

    2004-10-01

    We consider the dynamics of thermal concentration fluctuations in polymer Langmuir monolayers, probed with surface light scattering. We present data on the proteins β-lactoglobulin and β-casein and on the synthetic polymers Poly(vinyl acetate) and Poly(4-hydroxystyrene). We show that for all these systems, in the semi-dilute concentration regime, there is a power law dependency of both the elastic and viscous components of the dilational modulus on the concentration. We find that for all the systems considered, the viscosity scales with a power that is double that of the elasticity. A simple explanation for this universal dynamical behavior in semidilute polymer monolayers is suggested.

  7. Selective removal of copper from multication dilute aqueous solutions using the membrane-electrode process

    SciTech Connect

    Gopal, V.; April, G.C.; Schrodt, V.N.

    1998-03-01

    The presence of metallic contaminants (in the form of cations) in wastewater streams has long been a source of concern to process industries. Conventional methods of removal of metallic components from wastewater result in products which have little or no further use and are subsequently landfilled. This research involves developing a method, i.e., the membrane-electrode (M-E) process, to selectively recover heavy metals from dilute aqueous waste streams (cation concentrations less than 1000 ppm) in forms that can be recycled. Preliminary results for copper-nickel systems are presented to demonstrate the selectivity of this new treatment method.

  8. Solvation phenomena in dilute multicomponent solutions I. Formal results and molecular outlook.

    PubMed

    Chialvo, Ariel A; Chialvo, Sebastian; Simonson, J Michael; Kalyuzhnyi, Yu V

    2008-06-01

    We derive second-order thermodynamically consistent truncated composition expansions for the species residual partial molar properties--including volume, enthalpy, entropy, and Gibbs free energy--of dilute ternary systems aimed at the molecular account of solvation phenomena in compressible media. Then, we provide explicit microscopic interpretation of the expansion coefficients in terms of direct and total correlation function integrals over the microstructure of the corresponding infinite dilution reference system, as well as their pressure and temperature derivatives, allowing for the direct prediction of the species partial molar properties from the knowledge of the effective intermolecular interactions. Finally, we apply these formal results (a) to derive consistent expressions for the corresponding properties of the binary system counterparts, (b) to illustrate how the formal expressions converge, at the zero density limit, to those for multicomponent mixtures of imperfect gases obeying the virial equation of state Z = 1 + BPkT, and (c) to discuss, and highlight with examples from the literature, the thermodynamic inconsistencies encountered in the currently available first-order truncated expansions, by pinpointing the mathematical origin and physical meaning of the inconsistencies that render the first-order truncated expansions invalid. PMID:18537438

  9. Solvaton Phenomena in Dilute Multicomponent Solutions I. Formal Results and Molecular Outlook

    SciTech Connect

    Chialvo, Ariel A; Chialvo, Sebastian; Simonson, J Michael {Mike}; Kalyuzhnyi, Yu

    2008-01-01

    We derive 2nd-order thermodynamically consistent truncated composition-expansions for the species residual partial molar properties ⎯ including volume, enthalpy, entropy, and Gibbs free energy ⎯ of dilute ternary systems aimed at the molecular account of solvation phenomena in compressible media. Then, we provide explicit microscopic interpretation of the expansion coefficients in terms of direct and total correlation function integrals over the microstructure of the corresponding infinite dilution reference system, as well as their pressure and temperature derivatives, allowing for the direct prediction of the species partial molar properties from the knowledge of the effective intermolecular interactions. Finally, we apply these formal results (a) to derive consistent expressions for the corresponding properties of the binary system counterparts, (b) to illustrate how the formal expressions converge, at the zero density limit, to those for multicomponent mixtures of imperfect gases obeying the virial equation of state Z=1+BP/kT, and (c) to discuss, and highlight with examples from the literature, the thermodynamic inconsistencies encountered in the currently available 1st-order truncated expansions, by pinpointing the mathematical origin and physical meaning of the inconsistencies that render the 1st-order truncated expansions invalid.

  10. Continuous electrolytic decarbonation and recovery of a carbonate salt solution from a metal-contaminated carbonate solution.

    PubMed

    Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-Yoon; Lee, Eil-Hee; Song, Kyusuk; Song, Kee-Chan

    2009-11-15

    This work studied the characteristic changes of a continuous electrolytic decarbonation and recovery of a carbonate salt solution from a metal-contaminated carbonate solution with changes of operational variables in an electrolytic system which consisted of a cell-stacked electrolyzer equipped with a cation exchange membrane and a gas absorber. The system could completely recover the carbonate salt solution from a uranyl carbonato complex solution in a continuous operation. The cathodic feed rate could control the carbonate concentration of the recovered solution and it affected the most transient pH drop phenomenon of a well type within the gas absorber before a steady state was reached, which caused the possibility of a CO(2) gas slip from the gas absorber. The pH drop problem could be overcome by temporarily increasing the OH(-) concentration of the cathodic solution flowing down within the gas absorber only during the time required for a steady state to be obtained in the case without the addition of outside NaOH. An overshooting peak of the carbonate concentration in the recovered solution before a steady state was observed, which was ascribed to the decarbonation of the initial solution filled within the stacked cells by a redundant current leftover from the complete decarbonation of the feeding carbonate solution. PMID:19604641

  11. Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Nam, Hyo On; Morgan, Dane

    2015-10-01

    Molten salts technology is of significant interest for nuclear, solar, and other energy systems. In this work, first-principles molecular dynamics (FPMD) was used to model the solute behavior in eutectic LiCl-KCl and FLiBe (Li2BeF4) melts at 773 K and 973 K, respectively. The thermo-kinetic properties for solute systems such as the redox potential, solute diffusion coefficients and structural information surrounding the solute were predicted from FPMD modeling and the calculated properties are generally in agreement with the experiments. In particular, we formulate an approach to model redox energetics vs. chlorine (or fluorine) potential from first-principles approaches. This study develops approaches for, and demonstrates the capabilities of, FPMD to model solute properties in molten salts.

  12. Evaluation of a commercial integrating sphere setup for the determination of absolute photoluminescence quantum yields of dilute dye solutions.

    PubMed

    Würth, Christian; Lochmann, Cornelia; Spieles, Monika; Pauli, Jutta; Hoffmann, Katrin; Schüttrigkeit, Tanja; Franzl, Thomas; Resch-Genger, Ute

    2010-07-01

    The commercial availability of stand-alone setups for the determination of absolute photoluminescence quantum yields (Phi(f)) in conjunction with the increasing use of integrating sphere accessories for spectrofluorometers is expected to have a considerable influence not only on the characterization of chromophore systems for use in optical and opto-electronic devices, but also on the determination of this key parameter for (bio)analytically relevant dyes and functional luminophores. Despite the huge potential of systems measuring absolute Phi(f) values and the renewed interest in dependable data, evaluated protocols for even the most elementary case, the determination of the fluorescence quantum yield of transparent dilute solutions of small organic dyes with integrating sphere methods, are still missing. This encouraged us to evaluate the performance and sources of uncertainty of a simple commercial integrating sphere setup with dilute solutions of two of the best characterized fluorescence quantum yield standards, quinine sulfate dihydrate and rhodamine 101, strongly differing in spectral overlap between absorption and emission. Special attention is dedicated to illustrate common pitfalls of this approach, thereby deriving simple procedures to minimize measurement uncertainties and improve the comparability of data for the broad community of users of fluorescence techniques. PMID:20615286

  13. Using temperature-programmed reaction for kinetic analysis of reactions in dilute aqueous solutions at high pressure

    SciTech Connect

    Brown, L.F.; Robinson, B.A.

    1986-01-01

    The technique of temperature-programmed reaction (TPR) is shown to be a practical experimental method for determining reaction-rate expressions and kinetics parameters for reactions in dilute aqueous solutions under high ambient pressure. By sampling and measuring the extent of reaction during a rise in temperature, information normally obtained from a series of isothermal batch kinetics experiments can be found in a single TPR test. The use of nonlinear least-squares regression eliminates the need to achieve a constant rate of temperature rise, simplifies the experimental requirements for TPR results, and gives more accurate answers than does a linear analysis of TPR results. Numerical simulations of TPR tests in the presence of random concentration-measurement error is used to assess the accuracy of the technique and to identify the best values of crucial operating parameters. The results of two TPR experiments measuring the alkaline hydrolysis of ethyl acetate demonstrate the applicability of the technique to reactions in dilute aqueous solutions at high pressure. These preliminary experimental results, along with numerical simulations, allow us to chart a course for future TPR kinetics experiments on a large number of similar reactions. 16 refs., 6 figs., 8 tabs.

  14. Solution by dilution?--A review on the pollution status of the Yangtze River.

    PubMed

    Floehr, Tilman; Xiao, Hongxia; Scholz-Starke, Björn; Wu, Lingling; Hou, Junli; Yin, Daqiang; Zhang, Xiaowei; Ji, Rong; Yuan, Xingzhong; Ottermanns, Richard; Roß-Nickoll, Martina; Schäffer, Andreas; Hollert, Henner

    2013-10-01

    The Yangtze River has been a source of life and prosperity for the Chinese people for centuries and is a habitat for a remarkable variety of aquatic species. But the river suffers from huge amounts of urban sewage, agricultural effluents, and industrial wastewater as well as ship navigation wastes along its course. With respect to the vast amounts of water and sediments discharged by the Yangtze River, it is reasonable to ask whether the pollution problem may be solved by simple dilution. This article reviews the past two decades of published research on organic pollutants in the Yangtze River and several adjacent water bodies connected to the main stream, according to a holistic approach. Organic pollutant levels and potential effects of water and sediments on wildlife and humans, measured in vitro, in vivo, and in situ, were critically reviewed. The contamination with organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans, polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and others, of water and sediment along the river was described. Especially Wuhan section and the Yangtze Estuary exhibited stronger pollution than other sections. Bioassays, displaying predominantly the endpoints mutagenicity and endocrine disruption, applied at sediments, drinking water, and surface water indicated a potential health risk in several areas. Aquatic organisms exhibited detectable concentrations of toxic compounds like PCBs, OCPs, PBDEs, and PFCs. Genotoxic effects could also be assessed in situ in fish. To summarize, it can be stated that dilution reduces the ecotoxicological risk in the Yangtze River, but does not eliminate it. Keeping in mind an approximately 14 times greater water discharge compared to the major European river Rhine, the absolute pollution mass transfer of the Yangtze River is of severe concern for

  15. Acemetacin cocrystals and salts: structure solution from powder X-ray data and form selection of the piperazine salt

    PubMed Central

    Sanphui, Palash; Bolla, Geetha; Nangia, Ashwini; Chernyshev, Vladimir

    2014-01-01

    Acemetacin (ACM) is a non-steroidal anti-inflammatory drug (NSAID), which causes reduced gastric damage compared with indomethacin. However, acemetacin has a tendency to form a less soluble hydrate in the aqueous medium. We noted difficulties in the preparation of cocrystals and salts of acemetacin by mechanochemical methods, because this drug tends to form a hydrate during any kind of solution-based processing. With the objective to discover a solid form of acemetacin that is stable in the aqueous medium, binary adducts were prepared by the melt method to avoid hydration. The coformers/salt formers reported are pyridine carboxamides [nicotinamide (NAM), isonicotinamide (INA), and picolinamide (PAM)], caprolactam (CPR), p-aminobenzoic acid (PABA), and piperazine (PPZ). The structures of an ACM–INA cocrystal and a binary adduct ACM–PABA were solved using single-crystal X-ray diffraction. Other ACM cocrystals, ACM–PAM and ACM–CPR, and the piperazine salt ACM–PPZ were solved from high-resolution powder X-ray diffraction data. The ACM–INA cocrystal is sustained by the acid⋯pyridine heterosynthon and N—H⋯O catemer hydrogen bonds involving the amide group. The acid⋯amide heterosynthon is present in the ACM–PAM cocrystal, while ACM–CPR contains carboxamide dimers of caprolactam along with acid–carbonyl (ACM) hydrogen bonds. The cocrystals ACM–INA, ACM–PAM and ACM–CPR are three-dimensional isostructural. The carboxyl⋯carboxyl synthon in ACM–PABA posed difficulty in assigning the position of the H atom, which may indicate proton disorder. In terms of stability, the salts were found to be relatively stable in pH 7 buffer medium over 24 h, but the cocrystals dissociated to give ACM hydrate during the same time period. The ACM–PPZ salt and ACM–nicotinamide cocrystal dissolve five times faster than the stable hydrate form, whereas the ACM–PABA adduct has 2.5 times faster dissolution rate. The pharmaceutically acceptable piperazine

  16. A salt-bridge structure in solution revealed by 2D-IR spectroscopy.

    PubMed

    Huerta-Viga, Adriana; Domingos, Sérgio R; Amirjalayer, Saeed; Woutersen, Sander

    2014-08-14

    Salt bridges are important interactions for the stability of protein conformations, but up to now it has been difficult to determine salt-bridge geometries in solution. Here we characterize the spatial structure of a salt bridge between guanidinium (Gdm(+)) and acetate (Ac(-)) using two-dimensional vibrational (2D-IR) spectroscopy. We find that as a result of salt bridge formation there is a significant change in the infrared response of Gdm(+) and Ac(-), and cross peaks between them appear in the 2D-IR spectrum. From the 2D-IR spectrum we determine the relative orientation of the transition-dipole moments of the vibrational modes of Gdm(+) and Ac(-), as well as the coupling between them. PMID:24676430

  17. Thermodynamics of extraction by solutions of amines and salts of substituted ammonium bases

    NASA Astrophysics Data System (ADS)

    Ochkin, A. V.; Sergievskii, V. V.

    1989-09-01

    Extraction systems containing amines and their salts are widely used to concentrate and separate metals. From the theoretical viewpoint, these systems are among the most complex, because of the variety of intermolecular interactions in the organic phase. The explanation and quantitative description of the observed regularities of extraction became possible only as a result of progress in the study of the thermodynamics of binary and multicomponent solutions of salts of substituted ammonium bases in non-polar organic solvents, which make it possible to distinguish the contribution of each type of interaction to the non-ideal character of the solutions. All known "anomalous" features are due to the influence of the hydration of the salts of the substituted ammonium bases on their activity. The bibliography contains 113 references.

  18. Elastic properties of swollen polyelectrolyte gels in aqueous salt solutions.

    PubMed

    Sasaki, Shigeo

    2006-03-01

    The elastic relaxation responding to a uniaxially stretched poly(acrylic acid) rodlike gel in the aqueous NaCl solution was investigated. The relaxation elucidated the shear (mu) and bulk (K) moduli and the frictional coefficients (sigma) of the fully ionized gel at pH above 9 as functions of the degree of swelling, which was controlled by the NaCl concentration (C(S)) of the solution. Two gels, cross-linked chains of which consist of 500 (GelA500) and 50 (GelA50) monomeric units, were examined to investigate the effect of the chain length on the elastic behavior. The moduli of GelA500 increased with swelling at C(S) below 100 mM and decreased at C(S) above it. The mu values of both gels can be characterized by the power function of gel diameter, d as mu proportional, variantd(beta). The beta values being -1 at C(S) above 100 mM transitionally changed to 1.2 at C(S) about 100 mM. That is, the dimensionality of space for the chains to distribute, n(dim) [= (beta+5)/(beta+2) according to the conventional theory [Sasaki et al., J. Chem. Phys. 102, 5694 (1995)

  19. Electrosorption of inorganic salts from aqueous solution using carbon aerogels.

    PubMed

    Gabelich, Christopher J; Tran, Tri D; Suffet, I H Mel

    2002-07-01

    Capacitive deionization (CDI) with carbon aerogels has been shown to remove various inorganic species from aqueous solutions, though no studies have shown the electrosorption behavior of multisolute systems in which ions compete for limited surface area. Several experiments were conducted to determine the ion removal capacity and selectivity of carbon aerogel electrodes, using both laboratory and natural waters. Although carbon aerogel electrodes have been treated as electrical double-layer capacitors, this study showed that ion sorption followed a Langmuir isotherm, indicating monolayer adsorption. The sorption capacity of carbon aerogel electrodes was approximately 1.0-2.0 x 10(-4) equiv/g aerogel, with ion selectivity being based on ionic hydrated radius. Monovalent ions (e.g., sodium) with smaller hydrated radii were preferentially removed from solution over multivalent ions (e.g., calcium) on a percent or molar basis. Because of the relatively small average pore size (4-9 nm) of the carbon aerogel material, only 14-42 m2/g aerogel surface area was available for ion sorption. Natural organic matter may foul the aerogel surface and limit CDI effectiveness in treating natural waters. PMID:12144279

  20. Conformation and Phase Separation of Oligo (ethylene glycol) Grafted Polystyrene in Dilute Aqueous Solutions

    SciTech Connect

    Cheng, Gang; Melnichenko, Yuri B; Wignall, George D; Hua, Fengjun; Hong, Kunlun; Mays, Jimmy

    2007-01-01

    Temperature induced conformational changes of poly(p-oligo(ethylene glycol) styrene) (POEGS) in aqueous solutions were investigated by small angle neutron scattering (SANS), neutron transmission and dynamic light scattering (DLS). The molecular weight of the polymer studied was 9400 g/mol with a polydispersity index of 1.18 and each repeat unit of the polymer had four ethylene glycol monomer segments. The polymer was water soluble due to the hydrophilicity of the OEG side chains and these solutions showed lower critical solution temperature (LCST) depending on the concentration of the polymer. Measurements of solution behavior were made as a function of temperature in the range of 25-55 C for three polymer concentrations (0.1 wt%, 0.3 wt%, and 1.8 wt%). Neutron transmission measurements were used to monitor the amount of polymer which precipitated or remained in solution above the cloud point temperature (T{sub CP}). DLS revealed the presence of large clusters in all solutions both below and above T{sub CP} while SANS provided information on the structure and interactions between individual chains. It was found that in the homogeneous region below T{sub CP} the shape of individual polymers in solution was close to ellipsoidal with the dimensions R{sub a} = 37 Angstroms and R{sub b} = 14 Angstroms and was virtually independent of temperature. The SANS data taken for the most concentrated solution studied (1.8 wt%) were fit to the ellipsoidal model with attractive interactions which were approximated by the Ornstein-Zernike function with a temperature-dependent correlation length in the range of 24-49 Angstroms. The collapse of individual polymers to spherical globules with the radius of 15 Angstroms above TCP was observed.

  1. Conformation of ionizable poly Para phenylene ethynylene in dilute solutions

    SciTech Connect

    Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; Grest, Gary S.

    2015-11-03

    The conformation of dinonyl poly para phenylene ethynylenes (PPEs) with carboxylate side chains, equilibrated in solvents of different quality is studied using molecular dynamics simulations. PPEs are of interest because of their tunable electro-optical properties, chemical diversity, and functionality which are essential in wide range of applications. The polymer conformation determines the conjugation length and their assembly mode and affects electro-optical properties which are critical in their current and potential uses. The current study investigates the effect of carboxylate fraction on PPEs side chains on the conformation of chains in the dilute limit, in solvents of different quality. The dinonyl PPE chains are modeled atomistically, where the solvents are modeled both implicitly and explicitly. Dinonyl PPEs maintained a stretched out conformation up to a carboxylate fraction f of 0.7 in all solvents studied. The nonyl side chains are extended and oriented away from the PPE backbone in toluene and in implicit good solvent whereas in water and implicit poor solvent, the nonyl side chains are collapsed towards the PPE backbone. Thus, rotation around the aromatic ring is fast and no long range correlations are seen within the backbone.

  2. Results of Analysis of Macrobatch 3 Decontaminated Salt Solution Coalescer from May 2010

    SciTech Connect

    Peters, T. B.; Fink, S. D.

    2012-12-18

    SRNL analyzed the Decontamination Salt Solution (DSS) coalescer from MCU by several analytical methods. This unit was removed from service in May 2010. The results of these analyses indicate that there is very little evidence of fouling via excessive solids, either from the leaching studies or X-Ray Diffraction (XRD) analysis.

  3. Methods for predicting properties and tailoring salt solutions for industrial processes

    NASA Technical Reports Server (NTRS)

    Ally, Moonis R.

    1993-01-01

    An algorithm developed at Oak Ridge National Laboratory accurately and quickly predicts thermodynamic properties of concentrated aqueous salt solutions. This algorithm is much simpler and much faster than other modeling schemes and is unique because it can predict solution behavior at very high concentrations and under varying conditions. Typical industrial applications of this algorithm would be in manufacture of inorganic chemicals by crystallization, thermal storage, refrigeration and cooling, extraction of metals, emissions controls, etc.

  4. Solute trapping in rapid solidification of a binary dilute system: a phase-field study.

    PubMed

    Galenko, P K; Abramova, E V; Jou, D; Danilov, D A; Lebedev, V G; Herlach, D M

    2011-10-01

    The phase-field model of Echebarria, Folch, Karma, and Plapp [Phys. Rev. E 70, 061604 (2004)] is extended to the case of rapid solidification in which local nonequilibrium phenomena occur in the bulk phases and within the diffuse solid-liquid interface. Such an extension leads to the fully hyperbolic system of equations given by the atomic diffusion equation and the phase-field equation of motion. This model is applied to the problem of solute trapping, which is accompanied by the entrapment of solute atoms beyond chemical equilibrium by a rapidly moving interface. The model predicts the beginning of complete solute trapping and diffusionless solidification at a finite solidification velocity equal to the diffusion speed in bulk liquid. PMID:22181123

  5. Separation of compounds with multiple -OH groups from dilute aqueous solutions via complexation with organoboronate

    SciTech Connect

    Chow, Tina Kuo Fung

    1992-05-01

    The complexing extractant agent investigated in this work is 3-nitrophenylboronic acid (NPBA) in its anionic form (NPB). NPBA and Aliquat 336 (quaternary amine) is dissolved in 2-ethyl-l-hexanol, and the extractant is contacted with aq. NaOH. Solutes investigated were 1,2-propanediol, glycerol, fructose, sorbitol and lactic acid. Batch extraction experiments were performed at 25{degree}C. Partition coefficients, distribution ratios and loadings are reported for varying concentrations of solute and NPB. All solutes complexed with NPB{sup {minus}}, with all complexes containing only one NPB{sup {minus}} per complex. The 1:1 complexation constants for the solutes glycerol, fructose and sorbitol follow trends similar to complexation with B(OH){sub 4}{sup {minus}} (aq.), i.e. the complexation constants increase with increasing number of {minus}OH groups available for complexation. Assumption of 1:1 complex is not valid for 1, 2-propanediol, which showed overloading (more than one mole of solute complexed to one mole NPB{sup {minus}}) at higher concentrations. The {minus}OH group on the NPB{sup {minus}} which is left uncomplexed after one solute molecule had bound to the other two {minus}OH groups may be responsible for the overloading. Overloading is also observed in extraction of tactic acid, but through a different mechanism. It was found that TOMA{sup +} can extract lactic acid to an extent comparable to the uptake of lactic acid by NPB{sup {minus}}. The complexation is probably through formation of an acid-base ion pair. Losses of NPBA into the aqueous phase could lead to problems, poor economics in industrial separation processes. One way of overcoming this problem would be to incorporate the NPBA onto a solid support.

  6. Long-term degradation of dilute polyacrylamide solutions in turbulent pipe flow

    SciTech Connect

    Choi, U.S.; Kasza, K.E.

    1989-05-01

    The long-term degradation behavior of 200 wppM polyacrylamide solution was studied experimentally in a closed recirculatory flow loop at temperatures of 7.2, 25 and 87.8/degree/C. The degradation behavior was found to be strongly dependent on temperature. The results indicate that, with flow shear similar to that encountered in practical DHC pipe flow, polyacrylamide solutions are highly effective and have a reasonable lifetime at chilled water temperature of 7.2/degree/C. 9 refs., 4 figs.

  7. Effect of aging on aluminum hydroxide complexes in dilute aqueous solutions

    USGS Publications Warehouse

    Smith, Ross Wilbert; Hem, John David

    1972-01-01

    Aqueous aluminum solutions containing 4?10 -5 mole/liter aluminum and a constant total ionic strength of 10 -2, but with varying ratios of hydroxide to aluminum (OH:Al), were prepared. Progress of these solutions toward equilibrium conditions over aging periods of as much as 2 years was studied by determining the composition and pH of the solutions at various time intervals. The solutions, after mixing, were supersaturated with respect to both crystalline and amorphous forms of aluminum oxides and aluminum hydroxides. The compositions of the solutions were determined by use of a timed colorimetric analytical procedure which allowed the estimation of three separate forms of aluminum that have been designated Al a, Al b, and Al c. Form Al a appeared to be composed of monomeric species such as Al(H20)6+3, Al(OH)(H20)5+2, Al(OH)2(H20)4 +I and Al(OH)4-. Form Al b was polynuclear material containing perhaps 20-400 aluminum atoms per structure. It appeared to be a metastable material. Form Al c was composed of relatively large, microcrystalline, clearly solid AI(OH)3 particles. For each OH :Al ratio, the concentration of Al a remained constant with aging time, Al b decreased, and Al c increased. It appeared that Al b particles were increasing in size and ultimately were converted to Al c particles. After a few weeks' aging, Al c particles had the structure of gibbsite. In all solutions, equilibrium was only very slowly achieved, and the time required depended on the OH:Al ratio and how rapidly the solution was initially prepared (mixing time). Lower ratios caused a slower approach to equilibrium; sometimes equilibrium was not achieved even after several years' aging. The more slowly base was initially added (to obtain the proper OH:Al ratio), the more slowly was equilibrium approached. Ultimate equilibrium values of dissolved aluminum concentration and pH were consistent with known thermodynamic data on monomeric aluminum species. From data determined during the aging

  8. Hydration structure of salt solutions from ab initio molecular dynamics

    NASA Astrophysics Data System (ADS)

    Bankura, Arindam; Carnevale, Vincenzo; Klein, Michael L.

    2013-01-01

    The solvation structures of Na^+, K^+, and Cl^- ions in aqueous solution have been investigated using density functional theory (DFT) based Car-Parrinello (CP) molecular dynamics (MD) simulations. CPMD trajectories were collected for systems containing three NaCl or KCl ion pairs solvated by 122 water molecules using three different but commonly employed density functionals (BLYP, HCTH, and PBE) with electron correlation treated at the level of the generalized gradient approximation (GGA). The effect of including dispersion forces was analyzed through the use of an empirical correction to the DFT-GGA scheme. Special attention was paid to the hydration characteristics, especially the structural properties of the first solvation shell of the ions, which was investigated through ion-water radial distribution functions, coordination numbers, and angular distribution functions. There are significant differences between the present results obtained from CPMD simulations and those provided by classical MD based on either the CHARMM force field or a polarizable model. Overall, the computed structural properties are in fair agreement with the available experimental results. In particular, the observed coordination numbers 5.0-5.5, 6.0-6.4, and 6.0-6.5 for Na^+, K^+, and Cl^-, respectively, are consistent with X-ray and neutron scattering studies but differ somewhat from some of the many other recent computational studies of these important systems. Possible reasons for the differences are discussed.

  9. pH in physiological salt solutions: direct measurements.

    PubMed

    Abrahamsen, J; Norrie, B; Andersen, P K; Stokke, D B; Nedergaard, O A

    1990-11-01

    Calculations of pH in modified Krebs solutions by inserting PCO2 and total-CO2 in the Henderson-Hasselbalch (H.-H.) equation are obvious as the equation originally served for this purpose. An exact calculation of the relation between pH and PCO2 is complicated as the concentration of bicarbonate, the dissociation constant and the solubility of CO2 change. Furthermore, the dissociation constant in the H.-H. equation is constant only if activities are used in the equation instead of stoichiometric concentrations. We therefore investigated the influence of different carbon dioxide tensions and bicarbonate concentrations on directly measured pH of organ baths aerated with mass-spectrometric analyzed O2-CO2 gases. For reference precision buffers were used. The measured pH values differed distinctly from calculated pH values in the acidic and alkaline parts of the pH interval investigated (6.57-8.15). Measurements of actual pH with proper calibration standards therefore seem mandatory. PMID:2177306

  10. Hydration structure of salt solutions from ab initio molecular dynamics

    SciTech Connect

    Bankura, Arindam; Carnevale, Vincenzo; Klein, Michael L.

    2013-01-07

    The solvation structures of Na{sup +}, K{sup +}, and Cl{sup -} ions in aqueous solution have been investigated using density functional theory (DFT) based Car-Parrinello (CP) molecular dynamics (MD) simulations. CPMD trajectories were collected for systems containing three NaCl or KCl ion pairs solvated by 122 water molecules using three different but commonly employed density functionals (BLYP, HCTH, and PBE) with electron correlation treated at the level of the generalized gradient approximation (GGA). The effect of including dispersion forces was analyzed through the use of an empirical correction to the DFT-GGA scheme. Special attention was paid to the hydration characteristics, especially the structural properties of the first solvation shell of the ions, which was investigated through ion-water radial distribution functions, coordination numbers, and angular distribution functions. There are significant differences between the present results obtained from CPMD simulations and those provided by classical MD based on either the CHARMM force field or a polarizable model. Overall, the computed structural properties are in fair agreement with the available experimental results. In particular, the observed coordination numbers 5.0-5.5, 6.0-6.4, and 6.0-6.5 for Na{sup +}, K{sup +}, and Cl{sup -}, respectively, are consistent with X-ray and neutron scattering studies but differ somewhat from some of the many other recent computational studies of these important systems. Possible reasons for the differences are discussed.

  11. Hydration structure of salt solutions from ab initio molecular dynamics.

    PubMed

    Bankura, Arindam; Carnevale, Vincenzo; Klein, Michael L

    2013-01-01

    The solvation structures of Na(+), K(+), and Cl(-) ions in aqueous solution have been investigated using density functional theory (DFT) based Car-Parrinello (CP) molecular dynamics (MD) simulations. CPMD trajectories were collected for systems containing three NaCl or KCl ion pairs solvated by 122 water molecules using three different but commonly employed density functionals (BLYP, HCTH, and PBE) with electron correlation treated at the level of the generalized gradient approximation (GGA). The effect of including dispersion forces was analyzed through the use of an empirical correction to the DFT-GGA scheme. Special attention was paid to the hydration characteristics, especially the structural properties of the first solvation shell of the ions, which was investigated through ion-water radial distribution functions, coordination numbers, and angular distribution functions. There are significant differences between the present results obtained from CPMD simulations and those provided by classical MD based on either the CHARMM force field or a polarizable model. Overall, the computed structural properties are in fair agreement with the available experimental results. In particular, the observed coordination numbers 5.0-5.5, 6.0-6.4, and 6.0-6.5 for Na(+), K(+), and Cl(-), respectively, are consistent with X-ray and neutron scattering studies but differ somewhat from some of the many other recent computational studies of these important systems. Possible reasons for the differences are discussed. PMID:23298049

  12. Explicit-water theory for the salt-specific effects and Hofmeister series in protein solutions

    NASA Astrophysics Data System (ADS)

    Kalyuzhnyi, Yuriy V.; Vlachy, Vojko

    2016-06-01

    Effects of addition of salts on stability of aqueous protein solutions are studied theoretically and the results are compared with experimental data. In our approach, all the interacting species, proteins, ions, and water molecules, are accounted for explicitly. Water molecules are modeled as hard spheres with four off-center attractive square-well sites. These sites serve to bind either another water or to solvate the ions or protein charges. The ions are represented as charged hard spheres, and decorated by attractive sites to allow solvation. Spherical proteins simultaneously possess positive and negative groups, represented by charged hard spheres, attached to the surface of the protein. The attractive square-well sites, mimicking the protein-protein van der Waals interaction, are located on the surface of the protein. To obtain numerical results, we utilized the energy route of Wertheim's associative mean spherical approximation. From measurable properties, we choose to calculate the second virial coefficient B2, which is closely related to the tendency of proteins to aggregate and eventually crystalize. Calculations are in agreement with experimental trends: (i) For low concentration of added salt, the alkali halide salts follow the inverse Hofmeister series. (ii) At higher concentration of added salt, the trend is reversed. (iii) When cations are varied, the salts follow the direct Hofmeister series. (iv) In contrast to the colloidal theories, our approach correctly predicts the non-monotonic behavior of B2 upon addition of salts. (v) With respect to anions, the theory predicts for the B2 values to follow different sequences below and above the iso-ionic point, as also confirmed experimentally. (vi) A semi-quantitative agreement between measured and calculated values for the second virial coefficient, as functions of pH of solution and added salt type and concentration, is obtained.

  13. Explicit-water theory for the salt-specific effects and Hofmeister series in protein solutions.

    PubMed

    Kalyuzhnyi, Yuriy V; Vlachy, Vojko

    2016-06-01

    Effects of addition of salts on stability of aqueous protein solutions are studied theoretically and the results are compared with experimental data. In our approach, all the interacting species, proteins, ions, and water molecules, are accounted for explicitly. Water molecules are modeled as hard spheres with four off-center attractive square-well sites. These sites serve to bind either another water or to solvate the ions or protein charges. The ions are represented as charged hard spheres, and decorated by attractive sites to allow solvation. Spherical proteins simultaneously possess positive and negative groups, represented by charged hard spheres, attached to the surface of the protein. The attractive square-well sites, mimicking the protein-protein van der Waals interaction, are located on the surface of the protein. To obtain numerical results, we utilized the energy route of Wertheim's associative mean spherical approximation. From measurable properties, we choose to calculate the second virial coefficient B2, which is closely related to the tendency of proteins to aggregate and eventually crystalize. Calculations are in agreement with experimental trends: (i) For low concentration of added salt, the alkali halide salts follow the inverse Hofmeister series. (ii) At higher concentration of added salt, the trend is reversed. (iii) When cations are varied, the salts follow the direct Hofmeister series. (iv) In contrast to the colloidal theories, our approach correctly predicts the non-monotonic behavior of B2 upon addition of salts. (v) With respect to anions, the theory predicts for the B2 values to follow different sequences below and above the iso-ionic point, as also confirmed experimentally. (vi) A semi-quantitative agreement between measured and calculated values for the second virial coefficient, as functions of pH of solution and added salt type and concentration, is obtained. PMID:27276970

  14. Mixed solvent systems for recovery of ethanol from dilute aqueous solution by liquid-liquid extraction

    SciTech Connect

    Mitchell, R.J.; Arrowsmith, A.; Ashton, N.

    1987-01-01

    Distribution coefficients and selectivities of a number of mixed solvent systems have been determined in order to assess their suitability in preferentially extracting ethanol from aqueous solution. The measured values of distribution coefficients and selectivities differ substantially from the values estimated by interpolating between the pure solvents. (Refs. 10).

  15. A traditional Japanese-style salt field is a niche for haloarchaeal strains that can survive in 0.5% salt solution

    PubMed Central

    Fukushima, Tadamasa; Usami, Ron; Kamekura, Masahiro

    2007-01-01

    Background Most of the haloarchaeal strains have been isolated from hypersaline environments such as solar evaporation ponds, salt lakes, or salt deposits, and they, with some exceptions, lyse or lose viability in very low-salt concentrations. There are no salty environments suitable for the growth of haloarchaea in Japan. Although Natrialba asiatica and Haloarcula japonica were isolated many years ago, the question, "Are haloarchaea really thriving in natural environments of Japan?" has remained unanswered. Results Ten strains were isolated from a traditional Japanese-style salt field at Nie, Noto Peninsula, Japan by plating out the soil samples directly on agar plates containing 30% (w/v) salts and 0.5% yeast extract. They were most closely related to strains of three genera, Haladaptatus, Halococcus, and Halogeometricum. Survival rates in 3% and 0.5% SW (Salt Water, solutions containing salts in approximately the same proportions as found in seawater) solutions at 37°C differed considerably depending on the strains. Two strains belonging to Halogeometricum as well as the type strain Hgm. borinquense died and lysed immediately after suspension. Five strains that belonged to Halococcus and a strain that may be a member of Halogeometricum survived for 1–2 days in 0.5% SW solution. Two strains most closely related to Haladaptatus possessed extraordinary strong tolerance to low salt conditions. About 20 to 34% of the cells remained viable in 0.5% SW after 9 days incubation. Conclusion In this study we have demonstrated that haloarchaea are really thriving in the soil of Japanese-style salt field. The haloarchaeal cells, particularly the fragile strains are suggested to survive in the micropores of smaller size silt fraction, one of the components of soil. The inside of the silt particles is filled with concentrated salt solution and kept intact even upon suspension in rainwater. Possible origins of the haloarchaea isolated in this study are discussed. PMID

  16. Modeling Solute Thermokinetics in LiCI-KCI Molten Salt for Nuclear Waste Separation

    SciTech Connect

    Morgan, Dane; Eapen, Jacob

    2013-10-01

    Recovery of actinides is an integral part of a closed nuclear fuel cycle. Pyrometallurgical nuclear fuel recycling processes have been developed in the past for recovering actinides from spent metallic and nitride fuels. The process is essentially to dissolve the spent fuel in a molten salt and then extract just the actinides for reuse in a reactor. Extraction is typically done through electrorefining, which involves electrochemical reduction of the dissolved actinides and plating onto a cathode. Knowledge of a number of basic thermokinetic properties of salts and salt-fuel mixtures is necessary for optimizing present and developing new approaches for pyrometallurgical waste processing. The properties of salt-fuel mixtures are presently being studied, but there are so many solutes and varying concentrations that direct experimental investigation is prohibitively time consuming and expensive (particularly for radioactive elements like Pu). Therefore, there is a need to reduce the number of required experiments through modeling of salt and salt-fuel mixture properties. This project will develop first-principles-based molecular modeling and simulation approaches to predict fundamental thermokinetic properties of dissolved actinides and fission products in molten salts. The focus of the proposed work is on property changes with higher concentrations (up to 5 mol%) of dissolved fuel components, where there is still very limited experimental data. The properties predicted with the modeling will be density, which is used to assess the amount of dissolved material in the salt; diffusion coefficients, which can control rates of material transport during separation; and solute activity, which determines total solubility and reduction potentials used during electrorefining. The work will focus on La, Sr, and U, which are chosen to include the important distinct categories of lanthanides, alkali earths, and actinides, respectively. Studies will be performed using LiCl-KCl salt

  17. The adsorption stability & inhibition by allyl-thiourea of bulk nanocrystalline ingot iron in dilute HCl solution

    NASA Astrophysics Data System (ADS)

    Shen, C. B.; Wang, S. G.; Yang, H. Y.; Long, K.; Wang, F. H.

    2006-12-01

    The inhibitive effect of thiourea's (TU) alkyl derivative—allyl-thiourea (ATU) on the corrosion behaviors of bulk nanocrystalline and conventional polycrystalline ingot iron (BNII & CPII) was tested. Results indicate that BNII is less prone to get corrosive than its coarse grain counterpart in blank 1 mol L -1 HCl at room temperature. When CPII and BNII were immersed for a very short time in the corrosive solution inhibited by ATU, namely, 5 min, no inductive loop appears at different concentrations. When time became prolonged, for BNII, a Warburg impedance appeared. Inhibited by ATU, the electrodes composed of the samples are polarized anodically during the potentiodynamic polarization tests, the phenomena of desorption happens at the concentration of 100 mg L -1, but the variation between potential Edes is obvious. The inhibition effect of ATU for BNII is very limited by comparison with CPII in dilute HCl.

  18. Salt-water-freshwater transient upconing - An implicit boundary-element solution

    USGS Publications Warehouse

    Kemblowski, M.

    1985-01-01

    The boundary-element method is used to solve the set of partial differential equations describing the flow of salt water and fresh water separated by a sharp interface in the vertical plane. In order to improve the accuracy and stability of the numerical solution, a new implicit scheme was developed for calculating the motion of the interface. The performance of this scheme was tested by means of numerical simulation. The numerical results are compared to experimental results for a salt-water upconing under a drain problem. ?? 1985.

  19. Fracture Fabrication of a Multi-scale, Channel Device that Efficiently Captures and Linearizes DNA from Dilute Solutions

    PubMed Central

    Kim, Byoung Choul; Weerappuli, Priyan; Thouless; Takayama, Shuichi

    2015-01-01

    This paper describes a simple technique for patterning channels on elastomeric substrates, at two distinct scales of depth, through the use of controlled fracture. Control of channel depth is achieved by the careful use of different layers of PDMS, where the thickness and material properties of each layer, and the position of layers relative to one another, dictate the depth of the channels formed. The system created in this work consists of a single ‘deep’ channel, whose width can be adjusted between the micron- and nano-scale by the controlled application or removal of a uniaxial strain, and an array of ‘shallow’ nano-scale channels oriented perpendicular to the ‘deep’ channel. The utility of this system is demonstrated through the successful capture and linearization of DNA from a dilute solution, by executing a two-step ‘concentrate-then-linearize’ procedure. When the ‘deep’ channel is in its open state, and a voltage is applied across the channel network, an overlapping electric double layer forms within the ‘shallow’ channel array. This overlapping electric double layer is used to prevent passage of DNA into the ‘shallow’ channels when the DNA molecules migrate into the junctional region by electrophoresis. Release of the applied strain then allows the ‘deep’ channel to return to its closed state, reducing the cross-sectional area of this channel from the micro- to the nano-scale. The resulting hydrodynamic flow and nano-confinement effects then combine to efficiently uncoil and trap the DNA in its linearized form. By adopting this strategy, we were able to overcome the entropic barriers associated with capturing and linearizing DNA derived from a dilute solution. PMID:25589471

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

    PubMed

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

    2016-08-11

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

  1. Solution Asymmetry and Salt Expand Fluid-Fluid Coexistence Regions of Charged Membranes.

    PubMed

    Kubsch, Bastian; Robinson, Tom; Lipowsky, Reinhard; Dimova, Rumiana

    2016-06-21

    Liquid-liquid phase separation in giant unilamellar vesicles (GUVs) leads to the formation of intramembrane domains. To mimic charged biological membranes, we studied phase separation and domain formation in GUVs of ternary lipid mixtures composed of egg sphingomyelin, cholesterol, and the negatively charged lipid dioleoylphosphatidylglycerol. The GUVs were exposed to solutions of sucrose and high-saline buffer. The phase diagram was determined using epifluorescence microscopy for vesicle populations with symmetric and asymmetric solution compositions across the membranes. Trans-membrane solution asymmetry was found to affect the membrane phase state. Furthermore, compared to the case of salt-free conditions, the phase diagram in the presence of high-saline buffer (both symmetrically or asymmetrically present across the membrane) was found to exhibit a significantly extended region of liquid-ordered and liquid-disordered coexistence. These observations were confirmed on single GUVs using microfluidics and confocal microscopy. Moreover, we found that the miscibility temperatures markedly increased for vesicles in the presence of symmetric and asymmetric salt solutions. Our results demonstrate a substantial effect of salt and solution asymmetry on the phase behavior of charged membranes, which has direct implications for protein adsorption onto these membranes and for the repartitioning of proteins within the membrane domains. PMID:27288275

  2. Films, Preimpregnated Tapes and Composites Made from Polyimide "Salt-Like" Solutions

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J. (Inventor); Weiser, Erik S. (Inventor); St.Clair, Terry L. (Inventor); Echigo, Yoshiaki (Inventor); Kaneshiro, Hisayasu (Inventor)

    2001-01-01

    High quality films, preimpregnated tape (prepegs), and composites have been fabricated from polyimide precursor 'saltlike' solutions. These salt-like solutions have a low viscosity (5,000 to 10,000 cp) and a high solids content (50-65% by weight) and can be coated onto reinforcing fiber to produce prepegs with excellent tack and drape at 12-15% residual solvent (approximately 4-6% water from thermal imidization reaction). The processing of these types of prepegs significantly overcomes solvent removal problems and allows excellent fiber wet out. In addition, the physical characteristics of the polyimide precursor salt-like solutions permits processing into high-performance materials through the use of standard prepregging and composite fabrication equipment. The resultant composites are of high quality.

  3. Solution-derived sodalite made with Si- and Ge-ethoxide precursors for immobilizing electrorefiner salt

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Lepry, William C.; Crum, Jarrod V.

    2016-01-01

    Chlorosodalite has the general form of Na8(AlSiO4)6Cl2 and this paper describes experiments conducted to synthesize sodalite with a solution-based approach to immobilize a simulated spent electrorefiner salt solution containing a mixture of alkali, alkaline earth, and lanthanide chlorides. The reactants used were the salt solution, NaAlO2, and either Si(OC2H5)4 or Ge(OC2H5)4. Additionally, seven different glass sintering aids (at loadings of 5 mass%) were evaluated as sintering aids for consolidating the as-made powders using a cold-press-and-sinter technique. This process of using alkoxide additives for the Group IV component can be used to produce large quantities of sodalite at near-room temperature as compared to a method where colloidal silica was used as the silica source. However, the small particle sizes inhibited densification during heat treatments.

  4. Molecular dynamics simulations of the surface tension and structure of salt solutions and clusters.

    PubMed

    Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

    2012-03-15

    Sodium halides, which are abundant in sea salt aerosols, affect the optical properties of aerosols and are active in heterogeneous reactions that cause ozone depletion and acid rain problems. Interfacial properties, including surface tension and halide anion distributions, are crucial issues in the study of the aerosols. We present results from molecular dynamics simulations of water solutions and clusters containing sodium halides with the interatomic interactions described by a conventional force field. The simulations reproduce experimental observations that sodium halides increase the surface tension with respect to pure water and that iodide anions reach the outermost layer of water clusters or solutions. It is found that the van der Waals interactions have an impact on the distribution of the halide anions and that a conventional force field with optimized parameters can model the surface tension of the salt solutions with reasonable accuracy. PMID:22352372

  5. Conversion of borate-based glass scaffold to hydroxyapatite in a dilute phosphate solution.

    PubMed

    Liu, Xin; Pan, Haobo; Fu, Hailuo; Fu, Qiang; Rahaman, Mohamed N; Huang, Wenhai

    2010-02-01

    Porous scaffolds of a borate-based glass (composition in mol%: 6Na2O, 8K2O, 8MgO, 22CaO, 36B2O3, 18SiO2, 2P2O5), with interconnected porosity of approximately 70% and pores of size 200-500 microm, were prepared by a polymer foam replication technique. The degradation of the scaffolds and conversion to a hydroxyapatite-type material in a 0.02 M K2HPO4 solution (starting pH = 7.0) at 37 degrees C were studied by measuring the weight loss of the scaffolds, as well as the pH and the boron concentration of the solution. X-ray diffraction, scanning electronic microscopy and energy dispersive x-ray analysis showed that a hydroxyapatite-type material was formed on the glass surface within 7 days of immersion in the phosphate solution. Cellular response to the scaffolds was assessed using murine MLO-A5 cells, an osteogenic cell line. Scanning electron microscopy showed that the scaffolds supported cell attachment and proliferation during the 6 day incubation. The results indicate that this borate-based glass could provide a promising degradable scaffold material for bone tissue engineering applications. PMID:20057014

  6. Laser flash photolysis and integral equation theory to investigate reactions of dilute solutes with oxygen in supercritical fluids

    SciTech Connect

    Roberts, C.B.; Zhang, J.; Chateauneuf, J.E.; Brennecke, J.F.

    1995-06-21

    The absolute reactivity of triplet benzophenone ({sup 3}BP) and benzyl free radical (PhCH{sub 2}) toward molecular oxygen (O{sub 2}) in supercritical CO{sub 2} and CHF{sub 3} has been measured by laser flash photolysis (LFP). The transient reactants may be considered to be infinitely dilute solutes reacting with a gaseous cosolvent in a supercritical fluid mixture. Both reactants were found to undergo kinetically controlled reactivity with O{sub 2} and the measured bimolecular rate constants (k{sub hi}) were found to decrease with a decrease in solvent density at reduced pressures between 1.0 and 2.5. These results are consistent with solute reactivity with a `nonattractive` cosolvent. The results are compared with those previously obtained for the reaction of {sup 3}BP with an `attractive` cosolvent, 1,4-cyclohexadiene, in supercritical CO{sub 2} and CHF{sub 3}, in which enhanced {sup 3}BP reactivity was observed due to preferential cosolvent/solute solvation. Integral equation theory has also been applied to model these ternary systems, and the results indicate how the strengths of local solvation forces can influence kinetically controlled reactions in supercritical fluids. 36 refs., 8 figs., 3 tabs.

  7. Analysis of frozen salt solutions with laser-induced breakdown spectroscopy under Martian conditions

    NASA Astrophysics Data System (ADS)

    Schröder, S.; Pavlov, S. G.; Hübers, H.-W.; Rauschenbach, I.; Jessberger, E. K.

    2010-05-01

    Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique for determining the elemental composition of materials. It can be applied in-situ to geological surfaces on planetary missions. Since pure liquid water is unstable at the current surface conditions on Mars, i.e. low surface pressure and temperatures ranging from 140 K to 300 K, salt solutions or brines are of particular interest. It has been suggested that salts could stabilize liquid water on Mars lowering the freezing point of the solution and suppressing evaporation rates. The appropriate salts have been found on Mars in different locations. In this study LIBS is employed for the investigation of frozen sulphate and chloride solutions under Martian conditions in a dedicated simulation chamber. For the laboratory experiments, various salt solutions were prepared with different concentrations. To produce ice with only little inclusions of air, the samples were degassed before freezing them in a copper container. The measurements were performed at 240 K by cooling with liquid nitrogen and controlled heating. A constant flow of a Martian atmosphere-like gas mixture at a pressure of approximately 6 hPa was maintained through the chamber during the measurements. A Q-switched Nd:YAG laser operating at 1064nm and at 10 Hz was used to ablate material and to generate a plasma on the frozen sample's surface. The emitted light of the plasma was collected into the entrance slit of an echelle spectrometer (LTB Aryelle Butterfly) by a toroid mirror. A time-gated ICCD camera (Andor) at the exit of the spectrometer recorded the plasma emission signal. The laser beam was focused at a new position for each measurement. The delay time and the integration time of the spectrometer have been optimized to obtain good signal-to-noise ratios up to 150 while at the same time not losing signals from fast recombining ions. First, the spectra of several frozen salt solutions were investigated qualitatively

  8. Laser-induced breakdown spectroscopy for analysis of frozen salt solutions under Martian conditions

    NASA Astrophysics Data System (ADS)

    Schröder, Susanne; Pavlov, Sergey; Hübers, Heinz-Wilhelm; Rauschenbach, Isabelle; Jessberger, Elmar K.

    Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique for determin-ing the elemental composition of materials. It can be applied in-situ to geological surfaces on planetary missions. Since pure liquid water is unstable at the current surface conditions on Mars, i.e. low surface pressure and temperatures ranging from 140 K to 300 K, salt solutions or brines are of particular interest. It has been suggested that salts could stabilize liquid water on Mars lowering the freezing point of the solution and suppressing evaporation rates. The ap-propriate salts have been found on Mars in different locations. In this study LIBS is employed for the investigation of frozen sulphate and chloride solutions under Martian conditions in a dedicated simulation chamber. For the laboratory experiments, various salt solutions were prepared with different concen-trations. To produce ice with only little inclusions of air, the samples were degassed before freezing them in a copper container. The measurements were performed at 240 K by cooling with liquid nitrogen and controlled heating. A constant flow of a Martian atmosphere-like gas mixture at a pressure of approximately 6 hPa was maintained through the chamber during the measurements. A Q-switched Nd:YAG laser operating at 1064nm and at 10 Hz was used to ablate material and to generate a plasma on the frozen sample's surface. The emitted light of the plasma was collected into the entrance slit of an echelle spectrometer (LTB Aryelle But-terfly) by a toroid mirror. A time-gated ICCD camera (Andor) at the exit of the spectrometer recorded the plasma emission signal. The laser beam was focused at a new position for each measurement. The delay time and the integration time of the spectrometer have been optimized to obtain good signal-to-noise ratios up to 150 while at the same time not losing signals from fast recombining ions. First, the spectra of several frozen salt solutions were investigated qualitatively

  9. Volumetric Properties of Dilute Aqueous Solutions of 1- and 2-propanol to 50 MPa and 373.15 K

    NASA Astrophysics Data System (ADS)

    Seitz, J.; Bahramian, J.; Blackwell, R.; Inaki, T.; York, D.; Schulte, M. D.

    2014-12-01

    The need to accurately model and understand reactions among organic compounds and biomolecules in solution is necessary to develop realistic chemical models for the reactions leading to the emergence of life and metabolic processes of extremophiles under elevated temperature and pressure conditions. Unfortunately, the scarcity of experimentally determined volumetric (and other) properties for important compounds at high temperatures and pressures leads to uncertainty in the calculation of reaction properties. Experimentally determined volumetric properties of aqueous solutions at non-standard conditions provide direct tests of current estimation methods and aid in the refinement of these methods. The goal of our research is to provide a database of experimentally determined volumetric properties. In previous studies, we have examined important organic molecules and biomolecules such as adenosine, coenzyme M and D-ribose. In this study, we investigate the volumetric properties of the structural isomers 1- and 2-propanol. 1-propanol (n-propanol) is a primary alcohol (CH3CH2CH2OH) and 2-propanol (isopropanol) is the simplest example of a secondary alcohol (CH3CHOHCH3). These compounds differ slightly in structure depending on to which carbon atom the hydroxyl group is bonded and will provide a sensitive test of current estimation methods and lead to more accurate predictions of the properties of complex aqueous systems at elevated temperatures and pressures. We obtained the densities of aqueous solutions of the alchohols using an Anton Paar DMA HP vibrating tube densimeter. Pressure was measured (pressure transducer) to an accuracy of ±0.01% and temperature was measured (integrated platinum thermometer) with an accuracy of ±0.05 K. Experimental uncertainty of density measurements is less than ±0.0001 g·cm-3. The partial molar volumes at infinite dilution (V∞) for 1- and 2-propanol were calculated from the measured densities and are shown in the figure at 0

  10. Selective on site separation and detection of molecules in diluted solutions with super-hydrophobic clusters of plasmonic nanoparticles

    NASA Astrophysics Data System (ADS)

    Gentile, Francesco; Coluccio, Maria Laura; Zaccaria, Remo Proietti; Francardi, Marco; Cojoc, Gheorghe; Perozziello, Gerardo; Raimondo, Raffaella; Candeloro, Patrizio; di Fabrizio, Enzo

    2014-06-01

    Super-hydrophobic surfaces are bio-inspired interfaces with a superficial texture that, in its most common evolution, is formed by a periodic lattice of silicon micro-pillars. Similar surfaces reveal superior properties compared to conventional flat surfaces, including very low friction coefficients. In this work, we modified meso-porous silicon micro-pillars to incorporate networks of metal nano-particles into the porous matrix. In doing so, we obtained a multifunctional-hierarchical system in which (i) at a larger micrometric scale, the super-hydrophobic pillars bring the molecules dissolved in an ultralow-concentration droplet to the active sites of the device, (ii) at an intermediate meso-scale, the meso-porous silicon film adsorbs the low molecular weight content of the solution and, (iii) at a smaller nanometric scale, the aggregates of silver nano-particles would measure the target molecules with unprecedented sensitivity. In the results, we demonstrated how this scheme can be utilized to isolate and detect small molecules in a diluted solution in very low abundance ranges. The presented platform, coupled to Raman or other spectroscopy techniques, is a realistic candidate for the protein expression profiling of biological fluids.Super-hydrophobic surfaces are bio-inspired interfaces with a superficial texture that, in its most common evolution, is formed by a periodic lattice of silicon micro-pillars. Similar surfaces reveal superior properties compared to conventional flat surfaces, including very low friction coefficients. In this work, we modified meso-porous silicon micro-pillars to incorporate networks of metal nano-particles into the porous matrix. In doing so, we obtained a multifunctional-hierarchical system in which (i) at a larger micrometric scale, the super-hydrophobic pillars bring the molecules dissolved in an ultralow-concentration droplet to the active sites of the device, (ii) at an intermediate meso-scale, the meso-porous silicon film

  11. Recovery of propylene glycol from dilute aqueous solutions via reversible reaction with aldehydes

    SciTech Connect

    Broekhuis, R.R.; Lynn, S.; King, C.J. |

    1993-12-01

    A means is proposed for separating propylene glycol and other compounds bearing multiple hydroxyl groups by reversible chemical reaction. Glycols react with aldehydes in cyclic acetalization reactions to form substituted dioxolanes. Propylene glycol reacts with formaldehyde and acetaldehyde to form 4-methyl-1,3-dioxolane and 2,4-dimethyl-1,3-dioxolane. The reaction is catalyzed homogeneously by strong mineral acids or heterogeneously by cation exchange resins in the acid form. Separation processes utilizing this reaction would include an acetalization step, several distillative separation steps and finally a hydrolysis step in which the reaction is reversed. Both reaction steps must be forced to completion by removing the reaction product simultaneously. The equilibrium and kinetics of the reaction with formaldehyde were studied experimentally in systems catalyzed by Amberlite IR-120 ion exchange resin. A number of solvents were screened for their ability to extract 2,4-dimethyl-1,3-dioxolane from aqueous solution. Aromatic hydrocarbons exhibited the highest distribution into the organic phase. To achieve an effective separation of propylene glycol from aqueous solution by combined reaction with formaldehyde and distillation, formaldehyde would have to be present in excess and would be difficult and costly to separate from the aqueous solution. In reactive distillation using acetaldehyde as a reactant this is not a problem. A large flow of acetaldehyde would be necessary to recover the propylene glycol sufficiently in a distillative process. In a process combining reaction and extraction into an organic solvent this problem is avoided. Process simulation indicates the energy input of such a process is less than half of the energy required in a triple-effect evaporation process. This benefit is offset by higher capital costs and increased complexity in the reaction/extraction process.

  12. Identification of frozen salt solutions combining LIBS and multivariate analysis methods

    NASA Astrophysics Data System (ADS)

    Schröder, S.; Pavlov, S.; Jessberger, E.; Hübers, H.

    2012-12-01

    Laser-induced breakdown spectroscopy (LIBS) is an emission spectroscopy technique and relies on evaporating material from the target by focusing radiation from a pulsed laser onto the sample surface. The generated plasma is analyzed spectroscopically and information about the elemental composition is obtained from specific atomic or ionic transitions and the associated emanating photons, which result in characteristic spectral lines. For the geochemical investigation of extraterrestrial surfaces LIBS has been suggested as a powerful analytical tool and is part of the payload on NASA's rover MSL (Mars Science Laboratory), which landed in the Gale crater on Mars in August 2012. This is the first time that LIBS is used for planetary science. In this study, salts, which are considered relevant for Martian geochemistry were investigated, including sulfates, chlorides, and perchlorates. An infrared Nd:YAG laser (1064 nm wavelength, up to 220 mJ, 8 ns pulse duration, 10 Hz repetition rate) generated the plasma at distances < 1 m. The plasma emission was detected with an echelle spectrometer with a time-gated intensified CCD enabling a continuous coverage from 280 nm to 900 nm. The salts were investigated in their pure form and in frozen salt solutions under simulated Martian atmospheric conditions with an appropriate gas mixture composed of 95.55 % Vol. CO2 at a pressure of 7 mbar. The influence of different gating parameters for time-resolved detection of the plasma was studied and parameters best suited for the LIBS analysis of ices were determined. The emission lines of metals are detectable with LIBS with high signal-to-noise ratios, which facilitates a relatively straightforward identification of the type of the cation. Due to weak excitation of the high-energy levels required for efficient radiative transitions of both sulfur and chlorine ions, their emission lines are typically weak and hardly detectable, in particular in the LIBS spectra of the ices. This

  13. Effect of heat stable salts on MDEA solution corrosivity: Part 2

    SciTech Connect

    Rooney, P.C.; DuPart, M.S.; Bacon, T.R.

    1997-04-01

    A comprehensive coupon corrosion testing program was undertaken to address the effect of various heat stable salts on methyldiethanolamine (MDEA) corrosivity to carbon steel and various stainless steels. Corrosion rates of carbon steel, 304SS, 316SS and 410SS liquid and vapor coupons towards MDEA, and MDEA containing various anions, at 180 F and 250 F, were measured in a reactor. Corrosion results of two refinery plant solutions before and after caustic neutralization were also performed. Based on these results, guidelines were determined for heat stable amine salt (HSAS) levels of oxalates, sulfates, formates, acetates and thiosulfates. In addition, caustic neutralization guidelines for MDEA heat stable salts were determined. Ongoing results include MDEA corrosivity with succinates, and malonates, glycolates, SO{sub 2} and ammonia.

  14. Thermodynamic characteristics of the heparin-leucine-CaCl2 system in a diluted physiological solution

    NASA Astrophysics Data System (ADS)

    Nikolaeva, L. S.; Belov, G. V.; Rulev, Yu. A.; Semenov, A. N.

    2013-03-01

    Chemical equilibria in aqueous solutions of high-molecular weight heparin (Na4hep) and leucine (HLeu) are calculated through the mathematical modeling of chemical equilibria based on representative experimental pH titration data. In addition, chemical equilibria in the CaCl2-Na4hep-HLeu-H2O-NaCl system in the presence of 0.154M NaCl background electrolyte at a temperature of 37°C in the range of 2.30 ≤ pH ≤ 10.50 and initial concentrations of basic components n × 10-3 M ( n ≤ 4).

  15. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution: II. Polycondensations

    NASA Technical Reports Server (NTRS)

    Kolb, V.; Orgel, L. E.

    1995-01-01

    We have prepared a [32P]-labeled oligonucleotide probe carrying a ureido (-NH-CO-NH2) function at its 3'-terminus. This labeled oligomer was used to study polycondensations of urea and formaldehyde and of various phenols and formaldehyde in aqueous solution. The formation of formaldehyde copolymers attached to the amido-function of the probe was monitored by gel electrophoresis. Our results are generally in agreement with those obtained using conventional techniques. Our method is suitable for monitoring potentially prebiotic polycondensation reactions involving formaldehyde.

  16. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution. 2: Polycondensations

    NASA Technical Reports Server (NTRS)

    Kolb, Vera; Orgel, Leslie E.

    1995-01-01

    We have prepared a (P-32)-labeled oligonucleotide probe carrying a ureido (-NH-CO-NH2) function at its 3'-terminus. This labeled oligomer was used to study polycondensations of urea and formaldehyde and of various phenols and formaldehyde in aqueous solution. The formation of formaldehyde copolymers attached to the amido-function of the probe was monitored by gel electrophoresis. Our results are generally in agreement with those obtained using conventional techniques. Our method is suitable for monitoring potentially prebiotic polycondensation reactions involving formaldehyde.

  17. Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics

    DOEpatents

    Nguyen, Quang A.; Keller, Fred A.; Tucker, Melvin P.

    2003-12-09

    A process of converting lignocellulosic biomass to ethanol, comprising hydrolyzing lignocellulosic materials by subjecting dried lignocellulosic material in a reactor to a catalyst comprised of a dilute solution of a strong acid and a metal salt to lower the activation energy (i.e., the temperature) of cellulose hydrolysis and ultimately obtain higher sugar yields.

  18. Hausmannite (Mn3O4) conversion to manganite (γ-MnOOH) in dilute oxalate solution

    USGS Publications Warehouse

    Lind, Carol J.

    1988-01-01

    Oxalic acid retards the alteration of Mn3O4 to γ-MnOOH during aging at pH 7.4 ?? 0.2 in well-aerated, abiotic suspensions that contain 4.4 ?? 10-3 M total Mn. In solutions of 1.25 ?? 10-3 M oxalate and greater, about 15% of the initial Mn3O4 altered to ??-MnOOH by day 10, and in solutions of 6.7 ?? 10-4 M oxalate, about 45% altered to ??-MnOOH by day 67. Although precipitation continued through day 365, the degree of conversion remained the same as at day 10 and day 67, respectively. In oxalate-free suspensions, the conversion was about 80% complete by day 67 and 100% by day 109. Oxalate complexed most of the dissolved divalent Mn, lowered the free Mn(II) and MnSO40 concentrations, but increased the total dissolved Mn. Steric hindrance of surface reactions by a suggested manganese oxalate layer on the Mn3O4 surface may explain the blockage of the oxidation cycle.

  19. The aggregation behavior of native collagen in dilute solution studied by intrinsic fluorescence and external probing

    NASA Astrophysics Data System (ADS)

    Wu, Kun; Liu, Wentao; Li, Guoying

    2013-02-01

    The aggregation behavior of type I collagen in acid solutions with the concentrations covering a range of 0.06-1.50 mg/mL was studied utilizing both of the fluorescence resonance energy transfer (FRET) between the phenylalanine and tyrosine residues and the external probing of 1,8-anilinonaphthalene sulfonate (ANS). FRET at 0.30 mg/mL showed the distance among collagen monomers was within 10 nm without the obvious aggregates formed. The predominance of tyrosine fluorescence in FRET in the range of 0.45-0.75 mg/mL identified the existence of collagen aggregates companied with the formation of hydrophobic microdomains revealed by the change of the fluorescence of ANS. The blue-shift of tyrosine fluorescence from 303 to 293 nm for 0.90-1.50 mg/mL dedicated the formation of high order aggregates. The results from the two-phase diagrams of the intrinsic fluorescence for the guanidine hydrochloride-induced unfolding of collagen confirmed these conclusions. By the two-dimensional correlation analysis for the intrinsic fluorescence of collagen solutions of 0.45, 0.75 and 1.05 mg/mL, the probable characteristic fluorescence peaks for the interactions of proline-aromatic (CH ˜ π) among the collagen molecules were found at 298 and 316 nm.

  20. Effects of ion exchange on stream solute fluxes in a basin receiving highway deicing salts

    USGS Publications Warehouse

    Shanley, J.B.

    1994-01-01

    At Fever Brook, a 1260-ha forested basin in central Massachusetts, highway deicing salt application increased the solute flux in streamflow by 120% above background flux (equivalent basis) during a 2-yr period. Attempts to isolate the nonsalt component of stream solute fluxes have commonly subtracted salt contributions based on the net Cl flux (Cl output in streamflow minus Cl input in precipitation). In these studies, any net Na flux in excess of the amount needed to balance the net Cl flux has been attributed to weathering. At Fever Brook, however, the net output of Na was less than the net output of Cl, suggesting a loss of Na within the basin. The Na sink was inferred to be cation exchange of Na for Ca and Mg in the soil. A method was developed to quantify the exchange based on a Na budget, which included an independent estimate of the Na flux from weathering. The amount of exchange was apportioned to Ca and Mg based on their relative concentrations in the stream. The background fluxes of Ca and Mg (i.e., those that would occur in the absence of deicing salts) were calculated by subtracting the amounts from ion exchange plus the much smaller direct contributions in deicing salts from the observed fluxes. Ion exchange and direct salt contributions increased the net output fluxes of Ca and Mg, each by 44% above background. In basins that receive deicing salts, failure to account for cation exchange thus may result in an underestimate of the flux of Na from weathering and overestimates of the fluxes of Ca and Mg from weathering.

  1. The role of saline solution properties on porous limestone salt weathering by magnesium and sodium sulfates

    NASA Astrophysics Data System (ADS)

    Ruiz-Agudo, E.; Mees, F.; Jacobs, P.; Rodriguez-Navarro, C.

    2007-03-01

    Saline solution properties, viscosity in particular, are shown to be critical in salt weathering associated with sodium and magnesium sulfate crystallization in porous limestone. The crystallization of sodium and magnesium sulfate within a porous limestone has been studied at a macro- and microscale using different techniques, including mercury intrusion porosimetry, environmental scanning microscopy and X-ray computed tomography. Such analysis enabled the visualization of the crystallization process in situ, and at high magnification, yielding critical information as to where and how salts crystallize. Sodium sulfate decahydrate (mirabilite) tends to crystallize in large pores as euhedral micron-sized crystals formed at low supersaturation near to the surface of the stone. In contrast, magnesium sulfate heptahydrate (epsomite) tends to precipitate as anhedral wax-like aggregates formed at high supersaturation and distributed homogeneously throughout the stone pore system filling large and small pores. While the former crystallization behavior resulted in scale formation, the latter led to crack development throughout the bulk stone. Ultimately, the contrasting weathering behavior of the two sulfates is explained by considering differences in flow dynamics of solutions within porous materials that are mainly connected with the higher viscosity of magnesium sulfate saturated solution (7.27 cP) when compared with sodium sulfate saturated solution (1.83 cP). On the basis of such results, new ways to tackle salt weathering, particularly in the field of cultural heritage conservation, are discussed.

  2. Conformational study of a single molecule of poly para phenylene ethynylenes in dilute solutions

    NASA Astrophysics Data System (ADS)

    Maskey, Sabina; Pierce, Flint; Perahia, Dvora; Grest, Gary S.

    2011-06-01

    The conformation of single molecules of dialkyl poly para phenylene ethynylenes (PPEs), electro-active polymers, is studied in solutions using molecular dynamics simulations. The conformation of conjugated polymers affects their electro-optical properties and therefore is critical to their current and potential uses, though only limited theoretical knowledge is available regarding the factors that control their configuration. The present study investigates the affects of molecular parameters including molecular weight of the polymer and chemical structure of the side chains of PPEs in different solvents on the conformation of the polymers. The PPEs are modeled atomistically where the solvents are modeled both implicitly and explicitly. The study finds that PPEs assume extended configuration which is affected by the length of the polymer backbone and the nature and length of substituting side chains. While the polymer remains extended, local dynamics is retained and no long range correlations are observed within the backbone. The results are compared with scattering experiments.

  3. Molecular simulations of self-assembly processes of amphiphiles in dilute solutions: the challenge for quantitative modelling

    NASA Astrophysics Data System (ADS)

    Jusufi, Arben

    2013-11-01

    We report on two recent developments in molecular simulations of self-assembly processes of amphiphilic solutions. We focus on the determination of micelle formation of ionic surfactants which exhibit the archetype of self-assembling compounds in solution. The first approach is centred on the challenge in predicting micellisation properties through explicit solvent molecular dynamics simulations. Even with a coarse-grained (CG) approach and the use of highly optimised software packages run on graphics processing unit hardware, it remains in many cases computationally infeasible to directly extract the critical micelle concentration (cmc). However, combined with a recently presented theoretical mean-field model this task becomes resolved. An alternative approach to study self-assembly is through implicit solvent modelling of the surfactants. Here we review some latest results and present new ones regarding capabilities of such a modelling approach in determining the cmc, and the aggregate structures in the dilute regime, that is currently not accessible through explicit solvent simulations, neither through atomistic nor through CG approaches. A special focus is put on surfactant concentration effects and surfactant correlations quantified by scattering intensities that are compared to recently published small-angle X-ray scattering data.

  4. Diluting ferric carboxymaltose in sodium chloride infusion solution (0.9% w/v) in polypropylene bottles and bags: effects on chemical stability

    PubMed Central

    Philipp, Erik; Braitsch, Michaela; Bichsel, Tobias; Mühlebach, Stefan

    2016-01-01

    Objectives This study was designed to assess the physicochemical stability of colloidal ferric carboxymaltose solution (Ferinject) when diluted and stored in polypropylene (PP) bottles and bags for infusion. Methods Two batches of ferric carboxymaltose solution (Ferinject) were diluted (500 mg, 200 mg and 100 mg iron in 100 mL saline) in PP bottles or bags under aseptic conditions. The diluted solutions were stored at 30°C and 75%±5% relative humidity (rH) for 72 h, and samples were withdrawn aseptically at preparation and after 24 h, 48 h and 72 h. Multiple parameters were used to test stability-related measures (pH, total iron and iron (II) content, molecular weight range determination, microbial contamination and particles count ≥10 μm). Results Overall, Ferinject diluted in 0.9% (w/v) NaCl solution and stored in PP bottles and bags was stable within the specifications for the complex and the acceptability limits set for all assays. In both containers, total iron content remained stable, within 10% of the theoretical iron content, and levels of iron (II) remained far below the threshold of acceptability. All preparations were free from sediments, particle numbers were acceptable and there was no microbial contamination. The molecular weight distribution and polydispersity index were also acceptable. Conclusions Under the tested experimental conditions, colloidal ferric carboxymaltose solution (Ferinject) diluted in saline in PP infusion bottles or bags demonstrated physical and chemical stability for up to 72 h at 30°C and 75% rH. Because of the lack of additional clinical data, when using ferric carboxymaltose, physicians/pharmacists should refer to the dilution and storing recommendations given in the product's summary of product characteristics. PMID:26835007

  5. Removal of rhodamine B (a basic dye) and thoron (an acidic dye) from dilute aqueous solutions and wastewater simulants by ion flotation.

    PubMed

    Shakir, Kamal; Elkafrawy, Ahmed Faouzy; Ghoneimy, Hussein Fouad; Elrab Beheir, Shokry Gad; Refaat, Mamdoh

    2010-03-01

    The present work deals with removal, by ion flotation, of two dyes: a basic dye (rhodamine B (RB)) and an acidic one (thoron (TH)) from dilute aqueous solutions and simulated wastewaters. These dyes are widely used for analytical and biological staining purposes. Besides, RB is commonly used in dyeing of various industrial products. Therefore, wastewaters emanating from chemical and radiochemical laboratories, and biomedical and biological research laboratories may be contaminated with RB and TH. Ion flotation of these dyes has been investigated over a wide range of pH using the anionic surfactant, sodium lauryl sulfate (NaLS) and the cationic surfactant, cetyltrimethylammonium bromide (CTAB) as collectors. Successful removals could be achieved for RB and TH with the anionic collector, NaLS, and the cationic collector, CTAB, respectively. In addition to the effects of pH and type of collector on the efficiency of removal of each dye, the effects of collector and dye concentrations, frother dosage, ionic strength, bubbling time period and presence of foreign salts were investigated and the optimal removal conditions have been established. Removals exceeding 99.5 % and 99.9% could be achieved for RB and TH, respectively. The results obtained are discussed with respect to dissociation of dye, type of collector, ionic strength and sign and magnitude of charge of added foreign ions. Kinetics of flotation were also studied. Further studies demonstrate that under optimum conditions the developed flotation processes can be applied for the treatment of dye-contaminated wastewaters simulated to those generated at dyeing industries and radiochemical laboratories. PMID:19942250

  6. Characterization of Swollen States of Polyelectrolyte Brushes in Salt Solution by Neutron Reflectivity

    NASA Astrophysics Data System (ADS)

    Kobayashi, Motoyasu; Mitamura, Koji; Terada, Masami; Yamada, Norifumi L.; Takahara, Atsushi

    2011-01-01

    Cationic and zwitterionic polyelectrolyte brushes on quartz substrate were synthesized by surface-initiated atom transfer radical polymerization of 2-(methacryloyloxy)-ethyltrimethylammonium chloride (MTAC) and 2-(methacryloyloxy)ethyl phosphorylcholine (MPC). The effects of ionic strength on brush structure are investigated by neutron reflectivity (NR) in NaCl deuterium oxide (D2O) solutions. We observed that poly(MTAC) chains were drastically shrunk at concentrations above 0.1 M NaCl/D2O, which may be the change in charge-screening effect against ions on poly(MTAC). On the other hand, effect of salt concentration on a swollen state of poly(MPC) brush was negligible, even at the high concentration (5.0 M) close to saturation. The behaviour of poly(MPC) in salt aqueous solution is completely different from that of poly(MTAC), which may arise from the unique interaction properties, neutral nature, and hydrated water structure of phosphorylcholine units.

  7. Solution-Derived Sodalite Made with Si- and Ge-Ethoxide Precursors for Immobilizing electrorefiner salt

    SciTech Connect

    Riley, Brian J.; Lepry, William C.; Crum, Jarrod V.

    2016-01-01

    Chlorosodalite has the general form of Na8(AlSiO4)6Cl2 and this paper describes experiments conducted to synthesize sodalite to immobilize a mixed chloride salt using solution-based techniques. Sodalites were made using different Group IV contributions from either Si(OC2H5)4 or Ge(OC2H5)4, NaAlO2, and a simulated spent electrorefiner salt solution containing a mixture of alkali, alkaline earth, and lanthanide chlorides. Additionally, 6 glass binders at low loadings of 5 mass% were evaluated as sintering aids for the consolidation process. The approach of using the organic Group IV additives can be used to produce large quantities of sodalite at room temperature and shows promise over a method where colloidal silica is used as the silica source. However, the small particle sizes inhibited densification during pressure-less sintering.

  8. Prediction of subsidence resulting from creep closure of solutioned-mined caverns in salt domes

    SciTech Connect

    Neal, J.T.

    1991-01-01

    The prediction of subsidence rates over a range of areal configurations of solution-mined caverns in salt domes is possible, based on some fifty years of history in solution mining. Several approaches contribute to predictions: site-specific observations obtained from subsidence monitoring; numerical modeling, now becoming more practicable and credible; salt-creep data from testing; and rule-of-thumb methods, based on experience. All of these approaches contribute to understanding subsidence but none are totally reliable alone. The example of subsidence occurring at the Strategic Petroleum Reserve sites demonstrates several principles of cavern creep closure, the main cause of the subsidence, and shows that reliable projections of future subsidence are possible. 13 refs., 6 figs.

  9. Condensation of Self-Assembled Lyotropic Chromonic Liquid Crystal Sunset Yellow in Aqueous Solutions Crowded with Polyethylene Glycol and Doped with Salt

    SciTech Connect

    Park, Heung-Shik; Kang, Shin-Woong; Tortora, Luana; Kumar, Satyendra; Lavrentovich, Oleg D.

    2012-10-10

    We use optical and fluorescence microscopy, densitometry, cryo-transmission electron microscopy (cryo-TEM), spectroscopy, and synchrotron X-ray scattering to study the phase behavior of the reversible self-assembled chromonic aggregates of an anionic dye Sunset Yellow (SSY) in aqueous solutions crowded with an electrically neutral polymer polyethylene glycol (PEG) and doped with the salt NaCl. PEG causes the isotropic SSY solutions to condense into a liquid-crystalline region with a high concentration of SSY aggregates, coexisting with a PEG-rich isotropic (I) region. PEG added to the homogeneous nematic (N) phase causes separation into the coexisting N and I domains; the SSY concentration in the N domains is higher than the original concentration of PEG-free N phase. Finally, addition of PEG to the highly concentrated homogeneous N phase causes separation into the coexisting columnar hexagonal (C) phase and I phase. This behavior can be qualitatively explained by the depletion (excluded volume) effects that act at two different levels: at the level of aggregate assembly from monomers and short aggregates and at the level of interaggregate packing. We also show a strong effect of a monovalent salt NaCl on phase diagrams that is different for high and low concentrations of SSY. Upon the addition of salt, dilute I solutions of SSY show appearance of the condensed N domains, but the highly concentrated C phase transforms into a coexisting I and N domains. We suggest that the salt-induced screening of electric charges at the surface of chromonic aggregates leads to two different effects: (a) increase of the scission energy and the contour length of aggregates and (b) decrease of the persistence length of SSY aggregates.

  10. Self-association of caffeine in aqueous solution. Study of dilute solutions by normal and second derivative UV absorption spectroscopy.

    NASA Astrophysics Data System (ADS)

    Iza, N.; Gil, M.; Montero, J. L.; Morcillo, J.

    1988-05-01

    The concentration dependence of the spectral parameters of caffeine bands at ˜205 and 273 nm has been studied in aqueous solution by normal and second derivative spectroscopy. The concentration range was 5 x 10 -6 - 5 x 10 -3 M and thirty-five different concentrations were used. Discontinuities in parameter variation of these two bands at ˜7.5 x 10 -5, ˜2 x 10 -4, and ˜1 x 10 -3M were observed as concentration was increased. These "limiting" concentrations define three quite differenciated hyper- or hipochromic effects: the first one can be explained as caffeine-water molecule interaction and the second and third as dimer and (dimer + polymer) stacking, respectively. Apparent self-association constants using the isodesmic model have been obtained K= 160 M -1 (for the second hypochromic effect) and K= 13.6 M -1 (for the third hypochromic effect), for the 273 nm band. It is noteworthy that the three "limiting" concentrations coincide with changes in DNA-caffeine interaction modes (H. Lang , 1976) and biological activity (I.B. Syed , 1976).