Science.gov

Sample records for alkaline salt solutions

  1. 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.

  2. 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.

  3. Nuclear Magnetic Resonance Studies of Aluminosilicate Gels Prepared in High-Alkaline and Salt-Concentrated Solutions

    SciTech Connect

    Wang, Li Q.; Mattigod, Shas V.; Parker, Kent E.; Hobbs, David T.; McCready, David E.

    2005-01-11

    We have examined the formation of aluminosilicate in high alkaline and salt concentrated solutions characteristic of nuclear tank wastes. Information on the mechanism and kinetics of the phase formation under hydrothermal conditions was obtained by characterization the structures of gel phases as a function of time and composition using multinuclear NMR techniques in combination with x-ray diffraction. This work offers a new insight into the aluminum and aluminosilicate chemistry in simulated nuclear tank wastes.

  4. Counter-ion specificity explored in abnormal expansion of supra-molecular aggregates in aqueous solution of alkaline metal salts.

    PubMed

    Huang, Ningdong; Tao, Jiaojiao; Wei, Shenghui; Chen, Mingming; Wei, Chengsha; Li, Liangbin

    2015-09-21

    Ionic effects in aqueous solution of macro-ions showing specificity and unconventional characters, respectively, receive a lot of interests recently; however, the complexity of specific ion effects in unconventional phenomena remains ambiguous. In this study, the effects of univalent ions on aggregation of supra-molecular nano-fibrils with charged carboxylate groups on the surface as a prototype of macro-ions are investigated by Small Angle X-ray Scattering (SAXS) in aqueous solutions of alkaline metal chlorides. It is found that the columnar bundles of charged fibrils are expanded in certain salt concentration range contradicting the conventional screening effects of salts. The degree of expansion is dominated by cations as Na(+) induces drastic effects in comparison to rather gentle changes from K(+) and Cs(+). The specific cations effects observed by SAXS correlate with the pH behavior of the solutions, an indicator of surface charge, or number of carboxylate groups along the supra-molecular fibrils. It is postulated that while Na(+) with stronger affinity to carboxylates apparently reduces the surface charge, K(+) and Cs(+) only weakly interact with carboxylates and induce minor changes, accounting for the cation-sensitive aggregation behavior of fibrils observed by SAXS. By probing the bundling aggregation of charged supra-molecular nano-fibrils in salty water, we provide direct evidence of specific counter-ion effects in unusual expansion caused by univalent salts. PMID:26395732

  5. Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions

    NASA Astrophysics Data System (ADS)

    Sverjensky, Dimitri A.

    2006-05-01

    Despite the fact that the bulk compositions of most low temperature natural surface waters, groundwaters, and porewaters are heavily influenced by alkaline earths, an understanding of the development of proton surface charge in the presence of alkaline earth adsorption on the surfaces of minerals is lacking. In particular, models of speciation at the mineral-water interface in systems involving alkaline earths need to be established for a range of different minerals. In the present study, X-ray standing wave results for Sr 2+ adsorption on rutile as a tetranuclear complex [Fenter, P., Cheng, L., Rihs, S., Machesky, M., Bedyzk, M.D., Sturchio, N.C., 2000. Electrical double-layer structure at the rutile-water interface as observed in situ with small-period X-ray standing waves. J. Colloid Interface Sci.225, 154-165] are used as constraints for all the alkaline earths in surface complexation simulations of proton surface charge, metal adsorption, and electrokinetic experiments referring to wide ranges of pH, ionic strength, surface coverage, and type of oxide. The tetranuclear reaction 4>SOH+M+H2O=(>SOH)2(>SO-)2_M(OH)++3H+ predominates for the large cations Sr 2+ and Ba 2+ (and presumably Ra 2+), consistent with X-ray results. In contrast, the mononuclear reaction >SOH+M+H2O=>SO-_M(OH)++2H+ predominates for the much smaller Mg 2+ (and presumably Be 2+), with minor amounts of the tetranuclear reaction. Both reaction types appear to be important for the intermediate size Ca 2+. For all the alkaline earths on all oxides, the proportions of the different reaction types vary systematically as a function of pH, ionic strength, and surface coverage. The application of Born solvation and crystal-chemical theory enables estimation of the equilibrium constants of adsorption of all the alkaline earths on all oxides. On high dielectric constant solids (rutile, magnetite, manganese dioxide), where the solvation contribution is negligable, ion adsorption correlates with crystal

  6. Removal of plutonium and americium from alkaline waste solutions

    DOEpatents

    Schulz, Wallace W.

    1979-01-01

    High salt content, alkaline waste solutions containing plutonium and americium are contacted with a sodium titanate compound to effect removal of the plutonium and americium from the alkaline waste solution onto the sodium titanate and provide an effluent having a radiation level of less than 10 nCi per gram alpha emitters.

  7. Chemical equilibrium model for interfacial activity of crude oil in aqueous alkaline solution: the effects of pH, alkali and salt

    SciTech Connect

    Chan, M.; Yen, T.F.

    1980-11-01

    A chemical equilibrium model for interfacial activity of crude in aqueous alkaline solution is proposed. The model predicts the observed effects of pH and concentrations of alkali and salt on the interfacial tension (IFT). The model proposed was shown to describe the observed effects of acid content, pH, and sodium ions on the interfacial activity of crude oil in water. Once the pH of the interface reaches the pKa of the acids, sometimes with the help of addition of some salt, the IFT experiences a sudden steep drop to the range of 10/sup -2/ dynes/cm. After that, further addition of sodium either in the form of NaOH or NaCl is going to increase the IFT due to a shift of equilibriumn to the formation of undissociated soap. This was confirmed by the difference in the observed effect of sodium on the IFT of the extracted soap molecules which are dissociated easily and those which are associated highly and precipitated easily. These soap molecules have dissociation constant values ranging from below 10/sup -2/ to above one. 13 references.

  8. Gas phase salt clusters from electrosprayed alkaline earth colloids

    NASA Astrophysics Data System (ADS)

    Pope, R. Marshall; Shen, Nanzhu; Nicoll, Jeremy; Tarnawiecki, Boris; Dejsupa, Chadin; Dearden, David V.

    1997-03-01

    Several distributions of small polynuclear ions of general form [nM + mA + pS]q+ (where M represents an alkaline earth cation (Mg, Ca, Sr or Ba), n = 2-10, A represents a halide, acetate or nitrate counterion originating in the divalent salt, and S represents an acetic acid or methanol adduct) are detected by FTICR when water/methanol solutions of alkaline earth salts are electrosprayed. For example, the largest cluster ion derived from 6.3 mM solutions of calcium acetate acidified with 2%x acetic acid have n= 10, m = 18, p = 5 and q = 2. Characteristics of these solutions suggest the presence of colloidal dispersions. These characteristics include stability upon aging, light scattering response and the requisite pre-etching of the glass containers. Aqueous mixtures of two group II salts produce mixed-salt cluster ions. For instance, from a mixture of calcium and magnesium acetate we trap mixed-cation clusters characterized by a complete set of binary partitions of n, for n = 2-6. Specifically, the manifold of clusters with four cations contains 4:0, 3:1, 2:2, 1:3 and 0:4 ratios of magnesium to calcium. Isolated alkaline earth clusters react with a low-pressure background of 18-crown-6 (C6) by salt abstraction exclusively. In general, the more facile abstraction from a mixed cluster produces a pair of products in which the neutral conforms to the hard-soft acid-base principle. The reactions of C6 with [MgSr(OAc)3]+ provide evidence for the existence of isomeric clusters at m/z 289. This is supported by bimodal kinetics and preliminary results of ab initio calculations.

  9. Technetium recovery from high alkaline solution

    DOEpatents

    Nash, Charles A.

    2016-07-12

    Disclosed are methods for recovering technetium from a highly alkaline solution. The highly alkaline solution can be a liquid waste solution from a nuclear waste processing system. Methods can include combining the solution with a reductant capable of reducing technetium at the high pH of the solution and adding to or forming in the solution an adsorbent capable of adsorbing the precipitated technetium at the high pH of the solution.

  10. Process for extracting technetium from alkaline solutions

    SciTech Connect

    Moyer, B.A.; Sachleben, R.A.; Bonnesen, P.V.

    1994-12-31

    This invention relates generally to a process for extracting technetium from nuclear wastes and more particularly to a process for extracting technetium from alkaline waste solutions containing technetium and high concentrations of alkali metal nitrates. A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate comprises the steps of: contacting the aqueous alkaline solution with a solvent consisting of a crown ether in a diluent, the diluent being a water-immiscible organic liquid in which the crown ether is soluble, for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution into the solvent; separating the solvent containing the technetium values from the aqueous alkaline solution; and stripping the technetium values from the solvent by contacting the solvent with water.

  11. Process for extracting technetium from alkaline solutions

    DOEpatents

    Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

    1995-01-01

    A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

  12. Salt- and alkaline-tolerance are linked in Acacia.

    PubMed

    Bui, Elisabeth N; Thornhill, Andrew; Miller, Joseph T

    2014-07-01

    Saline or alkaline soils present a strong stress on plants that together may be even more deleterious than alone. Australia's soils are old and contain large, sometimes overlapping, areas of high salt and alkalinity. Acacia and other Australian plant lineages have evolved in this stressful soil environment and present an opportunity to understand the evolution of salt and alkalinity tolerance. We investigate this evolution by predicting the average soil salinity and pH for 503 Acacia species and mapping the response onto a maximum-likelihood phylogeny. We find that salinity and alkalinity tolerance have evolved repeatedly and often together over 25 Ma of the Acacia radiation in Australia. Geographically restricted species are often tolerant of extreme conditions. Distantly related species are sympatric in the most extreme soil environments, suggesting lack of niche saturation. There is strong evidence that many Acacia have distributions affected by salinity and alkalinity and that preference is lineage specific. PMID:25079493

  13. 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.

  14. 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.

  15. 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.

  16. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  17. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  18. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  19. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  20. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  1. 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

  2. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  3. Effect of pH alkaline salts of fatty acids on the inhibition of bacteria associated with poultry processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The agar diffusion assay was used to examine the effect of pH on the ability of alkaline salts of three fatty acids (FA) to inhibit growth of bacteria associated with poultry processing. FA solutions were prepared by dissolving 0.5 M concentrations of caprylic, capric, or lauric acid in separate ali...

  4. 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.

  5. 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.

  6. Kinetics of the Fading of Phenolphthalein in Alkaline Solution.

    ERIC Educational Resources Information Center

    Nicholson, Lois

    1989-01-01

    Described is an experiment which illustrates pseudo-first-order kinetics in the fading of a common indicator in an alkaline solution. Included are background information, details of materials used, laboratory procedures, and sample results. (CW)

  7. Measurement of thermophysical properties of molten salts: Mixtures of alkaline carbonate salts

    SciTech Connect

    Araki, N.; Matsuura, M.; Makino, A.; Hirata, T.; Kato, Y.

    1988-11-01

    The purpose of this study is to develop measuring methods for the thermal diffusivity, the specific heat capacity, and the density of molten salts, as well as to measure these properties of mixtures of alkaline carbonate salts. The thermal diffusivity is measured by the stepwise heating method. The sample salt is poured into a thin container, and as a result, a three-layered cell is formed. The thermal diffusivity is obtained from the ratio of temperature rises at different times measured at the rear surface of the cell when the front surface is heated by the stepwise energy from an iodine lamp. The specific heat capacity is measured using an adiabatic scanning calorimeter. The density is measured by Archimedes' principle. Thermal conductivity is determined from the above properties. Measured samples are Li/sub 2/CO/sub 3/-K/sub 2/CO/sub 3/ (42.7-57.3, 50.0-50.0, and 62.0-38.0 mol%).

  8. 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.

  9. 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.

  10. Extraction of the transplutonium elements from alkaline solutions

    SciTech Connect

    Karalova, Z.K.; Bukina, T.I.; Myasoedov, B.F.

    1986-03-01

    This paper investigates the extraction of transplutonium elements (TPE) and other elements using aliquat-336 and alkylpyrocatechol from strongly alkaline solutions in the presence of complexforming substances. It was shown by the methods of NMR and IR spectroscopy that elements can be extracted from alkaline solutions both in the form of coordination-saturated internal complex compounds and in the form of ionic associates, the anionic portion of which consists either of hydroxo-complexes of the cooresponding metals or their compounds with the complex-forming substance. Together with the TPE and REE the authors also studied the extraction of Fe(III), Ru(III), Zr(IV), Pu(IV), Pa(V), Nb(V), U(VI), Cs(I), and Th(IV) from alkaline solutions.

  11. Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

    DOEpatents

    Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.

    2001-01-01

    A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

  12. Alkaline solution absorption of carbon dioxide method and apparatus

    DOEpatents

    Hobbs, D.T.

    1991-01-01

    Disclosed is a method for measuring the concentration of hydroxides (or pH) in alkaline solutions, using the tendency of hydroxides to adsorb CO{sub 2}. The method comprises passing CO{sub 2} over the surface of an alkaline solution in a remote tank before and after measurements of the CO{sub 2} concentration. Comparison of the measurements yields the adsorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to adsorption fraction. A schematic is given of a process system according to a preferred embodiment of the invention. 2 figs.

  13. Qualitative aspects of the degradation of mitomycins in alkaline solution.

    PubMed

    Beijnen, J H; den Hartigh, J; Underberg, W J

    1985-01-01

    The major degradation product in alkaline solution of mitomycin A, mitomycin C and porfiromycin is the corresponding 7-hydroxymitosane. The isolation and the physico-chemical and analytical properties of these compounds and their derivatized analogues are discussed. Data are presented on the degradation of mitomycin C at extremely high pH values. PMID:16867711

  14. Actinide solubility and spectroscopic speciation in alkaline Hanford waste solutions

    SciTech Connect

    Rao, L.; Felmy, A.R.; Rai, D.

    1996-10-01

    Information on the solubility and the speciation of actinide elements, especially plutonium and neptunium, in alkaline solutions is of importance in the development of separation techniques for the Hanford tank HLW supernatant. In the present study, experimental data on the solubilities of plutonium in simulated Hanford tank solutions were analyzed with Pitzer`s specific ion-interaction approach, which is applicable in dilute to highly concentrated electrolyte solutions. In order to investigate the formation of actinide species in alkaline solutions with ligands (e.g., hydroxide, aluminate and carbonate), spectroscopic measurements of neptunium (V), as a chemical analog of plutonium (V), were conducted. Based on the solubility data and available information on both solid and aqueous species, a thermodynamic model was proposed. The applicability and limitations of this model are discussed.

  15. 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

  16. 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.

  17. 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.

  18. 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…

  19. Use of agar diffusion assay to evaluate bactericidal activity of formulations of alkaline salts of fatty acids against bacteria associated with poultry processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The agar diffusion assay was used to examine antibacterial activity of alkaline salts of fatty acids (FA). Wells in agar media seeded with bacteria were filled with FA-potassium hydroxide (KOH) solutions, plates were incubated, and zones of inhibition were measured. The relationship between bacteric...

  20. Bactericidal activity of alkaline salts of fatty acids towards bacteria associated with poultry processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Antibacterial activity of alkaline salts of caproic, caprylic, capric, lauric, and myristic acids were determined using the agar diffusion assay. A 0.5M concentration of each fatty acid (FA) was dissolved in 1.0 M potassium hydroxide (KOH), and pH of the mixtures was adjusted to 10.5 with citric aci...

  1. 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.

  2. Mobilization of Manufactured Gas Plant Tar with Alkaline Flushing Solutions

    PubMed Central

    Hauswirth, Scott C.; Birak, Pamela Schultz; Rylander, Seth C.; Miller, Cass T.

    2011-01-01

    This experimental study investigates the use of alkaline and alkaline-polymer solutions for the mobilization of former manufactured gas plant (FMGP) tars. Tar-aqueous interfacial tensions (IFTs) and contact angles were measured, and column flushing experiments were conducted. NaOH solutions (0.01–1 wt.%) were found to significantly reduce tar-aqueous IFT. Contact angles indicated a shift to strongly water-wet, then to tar-wet conditions as NaOH concentration increased. Column experiments were conducted with flushing solutions containing 0.2, 0.35, and 0.5% NaOH, both with and without xanthan gum (XG). Between 10 and 44% of the residual tar was removed by solutions containing only NaOH, while solutions containing both NaOH and XG removed 81–93% of the tar with final tar saturations as low as 0.018. The mechanism responsible for the tar removal is likely a combination of reduced IFT, a favorable viscosity ratio, and tar bank formation. Such an approach may have practical applications and would be significantly less expensive than surfactant-based methods. PMID:22091957

  3. Combined Utilization of Cation Exchanger and Neutral Receptor to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.

    2004-03-29

    In this report, novel approaches to the selective liquid-liquid extraction separation of sodium hydroxide and sodium nitrate from high-level alkaline tank waste will be discussed. Sodium hydroxide can be successfully separated from alkaline tank-waste supernatants by weakly acidic lipophilic hydroxy compounds via a cation-exchange mechanism referred to as pseudo hydroxide extraction. In a multi-cycle process, as sodium hydroxide in the aqueous phase becomes depleted, it is helpful to have a neutral sodium receptor in the extraction system to exploit the high nitrate concentration in the waste solution to promote sodium removal by an ion-pair extraction process. Simultaneous utilization of an ionizable organic hydroxy compound and a neutral extractant (crown ether) in an organic phase results in the synergistic enhancement of ion exchange and improved separation selectivity due to the receptor's strong and selective sodium binding. Moreover, combination of the hydroxy compound and the crown ether provides for mutually increased solubility, even in a non-polar organic solvent. Accordingly, application of Isopar{reg_sign} L, a kerosene-like alkane solvent, becomes feasible. This investigation involves examination of such dual-mechanism extraction phases for sodium extraction from simulated and actual salt cake waste solutions. Sodium salts can be regenerated upon the contact of the loaded extraction phases with water. Finally, conditions of potential extraction/strip cycling will be discussed.

  4. Salt tea consumption and esophageal cancer: a possible role of alkaline beverages in esophageal carcinogenesis.

    PubMed

    Dar, Nazir Ahmad; Bhat, Gulzar Ahmad; Shah, Idrees Ayoub; Iqbal, Beenish; Rafiq, Rumaisa; Nabi, Sumaiya; Lone, Mohd Maqbool; Islami, Farhad; Boffetta, Paolo

    2015-03-15

    Salt tea is the most commonly used beverage in Kashmir, India, where esophageal squamous cell carcinoma (ESCC) is the most common cancer. Salt tea is brewed in a unique way in Kashmir, usually with addition of sodium bicarbonate, which makes salt tea alkaline. As little information about the association between salt tea drinking and ESCC was available, we conducted a large-scale case-control study to investigate this association in Kashmir. We recruited 703 histologically confirmed cases of ESCC and 1664 controls individually matched to cases for age, sex, and district of residence. Conditional logistic regression models were used to calculate odds ratios (ORs) and 95% confidence intervals (95% CIs). Participants who consumed >1,250 ml day(-1) showed an increased risk of ESCC (OR = 2.60, 95% CIs = 1.68-4.02). Samovar (a special vessel for the beverage preparation) users (OR = 1.77, 95% CIs 1.25-2.50) and those who ate cereal paste with salt tea (OR = 2.14, 95% CIs = 1.55-2.94) or added bicarbonate sodium to salt tea (OR = 2.12, 95% CIs = 1.33-3.39) were at higher risk of ESCC than others. When analysis was limited to alkaline tea drinkers only, those who both consumed cereal paste with salt tea and used samovar vessel were at the highest risk (OR = 4.58, 95% CIs = 2.04-10.28). This study shows significant associations of salt tea drinking and some related habits with ESCC risk. PMID:25209106

  5. Investigation of aluminum gate CMP in a novel alkaline solution

    NASA Astrophysics Data System (ADS)

    Cuiyue, Feng; Yuling, Liu; Ming, Sun; Wenqian, Zhang; Jin, Zhang; Shuai, Wang

    2016-01-01

    Beyond 45 nm, due to the superior CMP performance requirements with the metal gate of aluminum in the advanced CMOS process, a novel alkaline slurry for an aluminum gate CMP with poly-amine alkali slurry is investigated. The aluminum gate CMP under alkaline conditions has two steps: stock polishing and fine polishing. A controllable removal rate, the uniformity of aluminum gate and low corrosion are the key challenges for the alkaline polishing slurry of the aluminum gate CMP. This work utilizes the complexation-soluble function of FA/O II and the preference adsorption mechanism of FA/O I nonionic surfactant to improve the uniformity of the surface chemistry function with the electrochemical corrosion research, such as OCP-TIME curves, Tafel curves and AC impedance. The result is that the stock polishing slurry (with SiO2 abrasive) contains 1 wt.% H2O2,0.5 wt.% FA/O II and 1.0 wt.% FA/O I nonionic surfactant. For a fine polishing process, 1.5 wt.% H2O2, 0.4 wt.% FA/O II and 2.0 wt.% FA/O I nonionic surfactant are added. The polishing experiments show that the removal rates are 3000 ± 50 Å/min and 1600 ± 60 Å/min, respectively. The surface roughnesses are 2.05 ± 0.128 nm and 1.59 ± 0.081 nm, respectively. A combination of the functions of FA/O II and FA/O I nonionic surfactant obtains a controllable removal rate and a better surface roughness in alkaline solution.

  6. Functional characterization of a Glycine soja Ca(2+)ATPase in salt-alkaline stress responses.

    PubMed

    Sun, Mingzhe; Jia, Bowei; Cui, Na; Wen, Yidong; Duanmu, Huizi; Yu, Qingyue; Xiao, Jialei; Sun, Xiaoli; Zhu, Yanming

    2016-03-01

    It is widely accepted that Ca(2+)ATPase family proteins play important roles in plant environmental stress responses. However, up to now, most researches are limited in the reference plants Arabidopsis and rice. The function of Ca(2+)ATPases from non-reference plants was rarely reported, especially its regulatory role in carbonate alkaline stress responses. Hence, in this study, we identified the P-type II Ca(2+)ATPase family genes in soybean genome, determined their chromosomal location and gene architecture, and analyzed their amino acid sequence and evolutionary relationship. Based on above results, we pointed out the existence of gene duplication for soybean Ca(2+)ATPases. Then, we investigated the expression profiles of the ACA subfamily genes in wild soybean (Glycine soja) under carbonate alkaline stress, and functionally characterized one representative gene GsACA1 by using transgenic alfalfa. Our results suggested that GsACA1 overexpression in alfalfa obviously increased plant tolerance to both carbonate alkaline and neutral salt stresses, as evidenced by lower levels of membrane permeability and MDA content, but higher levels of SOD activity, proline concentration and chlorophyll content under stress conditions. Taken together, for the first time, we reported a P-type II Ca(2+)ATPase from wild soybean, GsACA1, which could positively regulate plant tolerance to both carbonate alkaline and neutral salt stresses. PMID:26801329

  7. 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.

  8. Corrosion of silicon nitride in high temperature alkaline solutions

    NASA Astrophysics Data System (ADS)

    Qiu, Liyan; Guzonas, Dave A.; Qian, Jing

    2016-08-01

    The corrosion of silicon nitride (Si3N4) in alkaline solutions was studied at temperatures from 60 to 300 °C. Si3N4 experienced significant corrosion above 100 °C. The release rates of silicon and nitrogen follow zero order reaction kinetics and increase with increasing temperature. The molar ratio of dissolved silicon and nitrogen species in the high temperature solutions is the same as that in the solid phase (congruent dissolution). The activation energy for silicon and nitrogen release rates is 75 kJ/mol which agrees well with that of silica dissolution. At 300 °C, the release of aluminum is observed and follows first order reaction kinetics while other minor constituents including Ti and Y are highly enriched on the corrosion films due to the low solubility of their oxides.

  9. 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

  10. 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

  11. Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification.

    PubMed

    Ji, Bolin; Tang, Peixin; Yan, Kelu; Sun, Gang

    2015-11-01

    1,2,3,4-Butanetetracarboxylic acid (BTCA) reacts with cellulose in two steps with catalysis of alkaline salts such as sodium hypophosphite: anhydride formation and esterification of anhydride with cellulose. The alkali metal ions were found effective in catalyzing formation of BTCA anhydride in a previous report. In this work, catalytic functions of the alkaline salts in the esterification reaction between BTCA anhydride and cellulose were investigated. Results revealed that acid anions play an important role in the esterification reaction by assisting removal of protons on intermediates and completion of the esterification between cellulose and BTCA. Besides, alkaline salts with lower pKa1 values of the corresponding acids are more effective ones for the reaction since addition of these salts could lead to lower pH values and higher acid anion concentrations in finishing baths. The mechanism explains the results of FTIR and wrinkle recovery angles of the fabrics cured under different temperatures and times. PMID:26256345

  12. Singlet-Oxygen Generation in Alkaline Periodate Solution.

    PubMed

    Bokare, Alok D; Choi, Wonyong

    2015-12-15

    A nonphotochemical generation of singlet oxygen ((1)O2) using potassium periodate (KIO4) in alkaline condition (pH > 8) was investigated for selective oxidation of aqueous organic pollutants. The generation of (1)O2 was initiated by the spontaneous reaction between IO4(-) and hydroxyl ions, along with a stoichiometric conversion of IO4(-) to iodate (IO3(-)). The reactivity of in-situ-generated (1)O2 was monitored by using furfuryl alcohol (FFA) as a model substrate. The formation of (1)O2 in the KIO4/KOH system was experimentally confirmed using electron spin resonance (ESR) measurements in corroboration with quenching studies using azide as a selective (1)O2 scavenger. The reaction in the KIO4/KOH solution in both oxic and anoxic conditions initiated the generation of superoxide ion as a precursor of the singlet oxygen (confirmed by using superoxide scavengers), and the presence of molecular oxygen was not required as a precursor of (1)O2. Although hydrogen peroxide had no direct influence on the FFA oxidation process, the presence of natural organic matter, such as humic and fulvic acids, enhanced the oxidation efficiency. Using the oxidation of simple organic diols as model compounds, the enhanced (1)O2 formation is attributed to periodate-mediated oxidation of vicinal hydroxyl groups present in humic and fulvic constituent moieties. The efficient and simple generation of (1)O2 using the KIO4/KOH system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral and near-alkaline conditions. PMID:26594871

  13. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOEpatents

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-24

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  14. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  15. 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.

  16. [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

  17. Lactoperoxidase-125I localization of salt-extractable alkaline phosphatase on the cytoplasmic membrane of Bacillus licheniformis.

    PubMed

    Spencer, D B; Hulett, F M

    1981-02-01

    Previous histochemical and biochemical localizations of alkaline phosphatase in Bacillus licheniformis MC14 have shown that the membrane-associated form of the enzyme is located on the inner surface of the cytoplasmic membrane, and soluble forms are located in the periplasmic space and in the growth medium. The distribution of salt-extractable alkaline phosphatase on the surfaces of the cytoplasmic membrane of B. licheniformis MC14 was determined by using lactoperoxidase-125I labeling techniques. Cells harvested during rapid alkaline phosphatase production were converted to protoplasts or lysed protoplasts and labeled. Analysis of the data obtained indicated that 30% of the salt-extractable, membrane-associated alkaline phosphatase was located on the outer surface of the cytoplasmic membrane, whereas 70% of the membrane-associated enzyme was localized on the inner surface. Controls for protoplast integrity (release of tritiated thymidine or examination of cytoplasmic proteins for label content) indicated excellent protoplast stability. Controls indicated that chemical labeling was not a factor in the apparent distribution of alkaline phosphatase on the membrane. These results support the previously reported histochemical localization of alkaline phosphatase on the membrane inner surface. The presence of alkaline phosphatase on the membrane outer surface is reasonable, considering the soluble forms of the enzyme found in the periplasmic region and in the culture medium. PMID:7462164

  18. Lactoperoxidase-125I localization of salt-extractable alkaline phosphatase on the cytoplasmic membrane of Bacillus licheniformis.

    PubMed Central

    Spencer, D B; Hulett, F M

    1981-01-01

    Previous histochemical and biochemical localizations of alkaline phosphatase in Bacillus licheniformis MC14 have shown that the membrane-associated form of the enzyme is located on the inner surface of the cytoplasmic membrane, and soluble forms are located in the periplasmic space and in the growth medium. The distribution of salt-extractable alkaline phosphatase on the surfaces of the cytoplasmic membrane of B. licheniformis MC14 was determined by using lactoperoxidase-125I labeling techniques. Cells harvested during rapid alkaline phosphatase production were converted to protoplasts or lysed protoplasts and labeled. Analysis of the data obtained indicated that 30% of the salt-extractable, membrane-associated alkaline phosphatase was located on the outer surface of the cytoplasmic membrane, whereas 70% of the membrane-associated enzyme was localized on the inner surface. Controls for protoplast integrity (release of tritiated thymidine or examination of cytoplasmic proteins for label content) indicated excellent protoplast stability. Controls indicated that chemical labeling was not a factor in the apparent distribution of alkaline phosphatase on the membrane. These results support the previously reported histochemical localization of alkaline phosphatase on the membrane inner surface. The presence of alkaline phosphatase on the membrane outer surface is reasonable, considering the soluble forms of the enzyme found in the periplasmic region and in the culture medium. Images PMID:7462164

  19. 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

  20. 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

  1. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.; Bonnesen, Peter V.

    2006-06-01

    The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of low-activity waste immobilization. Principles of ion recognition are being researched toward discovery of liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudohydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Studies at PNNL are directed toward new solvent formulation for the practical sodium pseudohydroxide extraction systems.

  2. 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}).

  3. 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.

  4. Decomposition Studies of Triphenylboron, Diphenylborinic Acid and Phenylboric Acid in Aqueous Alkaline Solutions Containing Copper

    SciTech Connect

    Crawford, C.L.; Peterson, R. A.

    1997-02-11

    This report documents the copper-catalyzed chemical kinetics of triphenylboron, diphenylborinic acid and phenylboric acid (3PB, 2PB and PBA) in aqueous alkaline solution contained in carbon-steel vessels between 40 and 70 degrees C.

  5. Development of alkaline solution separations for potential partitioning of used nuclear fuels

    SciTech Connect

    Jarvinen, Gordon D; Runde, Wolfgang H; Goff, George S

    2009-01-01

    The processing of used nuclear fuel in alkaline solution provides potentially useful new selectivity for separating the actinides from each other and f rom the fission products. Over the ast decade, several research teams around the world have considered dissolution of used fuel in alkaline solution and further partitioning in this medium as an alternative to acid dissolution. The chemistry of the actinides and fission products in alkaline soilltion requires extensive investigation to more carefully evaluate its potential for developing useful separation methods for used nuclear fueI.

  6. Methanol oxidation on Pd/Pt(poly) in alkaline solution

    NASA Astrophysics Data System (ADS)

    Maksic, A.; Rakocevic, Z.; Smiljanic, M.; Nenadovic, M.; Strbac, S.

    2015-01-01

    Bimetallic electrodes prepared by Pd nanoislands spontaneously deposited on polycrystalline platinum, Pt(poly), at submonolayer coverage were explored for methanol oxidation in alkaline media. Characterization of obtained Pd/Pt(poly) nanostructures was performed ex situ by AFM imaging, spectroscopic ellipsometry and by X-ray photoelectron spectroscopy. In situ characterization of the obtained electrodes and subsequent methanol oxidation measurements were performed by cyclic voltammetry in 0.1 M KOH. Platinum surface with 35% Pd coverage exhibited the highest catalytic activity for methanol oxidation in alkaline media, exceeding those of bare Pt and Pd. Both synergistic and electronic effects are responsible for such enhanced catalysis. The origin of the synergistic effect and possible reaction pathways for methanol oxidation were discussed taking into account the activity of obtained bimetallic electrodes for the oxidation of CO and formaldehyde, as the most probable reaction intermediates.

  7. 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.

  8. Effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Hirai, Nobumitsu; Yamamoto, Yui

    2015-10-01

    The effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution has been investigated. It was found that "the specific anodic oxidation peak" appears at the cathodic scan in cyclic voltammogram of lead electrode in sulfuric acid solution containing Li2SO4, K2SO4, Na2SO4, Rb2SO4, or Cs2SO4. The height of the specific anodic oxidation peak varies with the alkaline sulfate in the solution; K2SO4 >> Na2SO4 > Cs2SO4 > Rb2SO4 > Li2SO4. It should be note that alkaline ions exist in lead sulfate formed on lead electrode in sulfuric acid solution containing potassium sulfate when the electrode was immersed in the solution at the rest potential for more than 1 h.

  9. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.; Bonnesen, Peter V.

    2005-06-01

    The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of low-activity waste immobilization. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudohydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties.

  10. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect

    Moyer, Bruce A.; Bonnesen, Peter V.; Custelcean, Radu; Delmau, Laetitia H.; Engle, Nancy L.; Kang, Hyun-Ah; Keever, Tamara J.; Marchand, Alan P.; Gadthula, Srinivas; Gore, Vinayak K.; Huang, Zilin; Sivappa, Rasapalli; Tirunahari, Pavan K.; Levitskaia, Tatiana G.; Lumetta, Gregg J.

    2005-09-26

    The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of vitrification. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudo hydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties.

  11. Technetium removal column flow testing with alkaline, high salt, radioactive tank waste

    SciTech Connect

    Blanchard, D.L. Jr.; Kurath, D.E.; Golcar, G.R.; Conradson, S.D.

    1996-09-30

    This report describes two bench-scale column tests conducted to demonstrate the removal of Tc-99 from actual alkaline high salt radioactive waste. The waste used as feed for these tests was obtained from the Hanford double shell tank AW-101, which contains double shell slurry feed (DSSF). The tank sample was diluted to approximately 5 M Na with water, and most of the Cs-137 was removed using crystalline silicotitanates. The tests were conducted with two small columns connected in series, containing, 10 mL of either a sorbent, ABEC 5000 (Eichrom Industries, Inc.), or an anion exchanger Reillex{trademark}-HPQ (Reilly Industries, Inc.). Both materials are selective for pertechnetate anion (TcO{sub 4}{sup -}). The process steps generally followed those expected in a full-scale process and included (1) resin conditioning, (2) loading, (3) caustic wash to remove residual feed and prevent the precipitation of Al(OH){sub 3}, and (4) elution. A small amount of Tc-99m tracer was added as ammonium pertechnetate to the feed and a portable GEA counter was used to closely monitor the process. Analyses of the Tc-99 in the waste was performed using ICP-MS with spot checks using radiochemical analysis. Technetium x-ray absorption spectroscopy (XAS) spectra of 6 samples were also collected to determine the prevalence of non-pertechnetate species [e.g. Tc(IV)].

  12. 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.

  13. 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

    focusing on the major elemental composition as well as on minor elements. In general, the alkali metal and alkaline earth metal elements were clearly detectable in the LIBS spectra in the 280-900 nm region. This allowed for a good distinction between different frozen solutions. Also the oxygen and hydrogen lines gave good signal-to-noise ratios. On the other hand, in particular, sulphur, as known, is difficult to detect in this spectral range as only weak sulphur lines are apparent in this region. The experiments demonstrate the capability of LIBS for detection and identification of frozen salt solutions under Martian conditions.

  14. 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.

    focusing on the major elemental composition as well as on minor elements. In general, the alkali metal and alkaline earth metal elements were clearly detectable in the LIBS spectra in the 280-900 nm region. This allowed for a good distinction between different frozen solutions. Also the oxygen and hydrogen lines gave good signal-to-noise ratios. On the other hand, in particular, sulphur, as known, is difficult to detect in this spectral range as only weak sulphur lines are apparent in this region. The experiments demonstrate the capability of LIBS for detection and identification of frozen salt solutions under Martian conditions.

  15. 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

  16. Extraction of starch from wheat flour by alkaline solution

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Separation of starch from wheat flour with high purity is very important for the analysis of starch such as amylose and amylopectin determination by size exclusion HPLC (SE-HPLC). A procedure that extracts starch from flour by ethanol precipitation after dissolving flour in KOH and urea solution wa...

  17. Autoclave leaching kinetics of a leucoxene concentrate with alkaline solutions

    NASA Astrophysics Data System (ADS)

    Zablotskaya, Yu. V.; Sadykhov, G. B.; Gocharenko, T. V.

    2015-01-01

    The autoclave leaching kinetics of a leucoxene concentrate from the Yaregskoe deposit (Komi Republic, Russia) with NaOH and Na2SiO3 solutions is studied. The changes in the activation energy and reaction order are determined as a function of the degree of desiliconization of a leucoxene concentrate. A steplike character of quartz leaching is shown: "internal" quartz dissolves at the first stage and then free quartz dissolves.

  18. Solid / solution interaction: The effect of carbonate alkalinity on adsorbed thorium

    NASA Astrophysics Data System (ADS)

    LaFlamme, Brian D.; Murray, James W.

    1987-02-01

    Elevated activities of dissolved Th have been found in Soap Lake, an alkaline lake in Eastern Washington. Dissolved 232Th ranges from less than 0.001 to 4.9 dpm/L compared to about 1.3 × 10 -5 dpm/ L in sea water. The enhanced activity in the lake coincides with an increase in carbonate alkalinity. Experiments were conducted to evaluate the effect of pH, ionic strength and carbonate alkalinity on Th adsorption on goethite. Thorium (10 -13 M total) in the presence of 5.22 mg/L α-FeOOH and 0.1 M NaNO 3 has an adsorption edge from pH 2-5. At pH 9.0 ± 0.6 the percent Th absorbed on the solid began to decrease from 100% at 100 meq/L carbonate alkalinity and exhibited no adsorption above 300 meq/L. The experimental data were modeled to obtain the intrinsic adsorption equilibrium constants for Th hydrolysis species. These adsorption constants were incorporated in the model to interpret the observed effect of carbonate alkalinity on Th adsorption. There are two main effects of the alkalinity. To a significant degree the decrease in Th adsorption is due to competition of HCO -3 and CO 2-3 ions for surface sites. Dissolved Th carbonate complexes also contribute to the increase of Th in solution.

  19. 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.

  20. 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.

  1. 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.

  2. USING CERAMIC MEMBRANES TO RECYCLE TWO NONIONIC ALKALINE METAL-CLEANING SOLUTIONS

    EPA Science Inventory

    One ZrO2 ultrafilter (0.05 um pore size) and two a-Al2O3 microfilters (0.2 and 0.8 um) were used to remove one synthetic ester oil and two polyalphaolefin-based and two petroleum hydrocarbon-based oils and greases from two nonionic alkaline cleaning solutions (e.g., Turco 4215-NC...

  3. Characterization and Oxidation of Chromium(III) by Sodium Hypochlorite in Alkaline Solutions

    SciTech Connect

    Jiang, Huijian; Rao, Linfeng; Zhang, Zhicheng; Rai, Dhanpat

    2006-07-01

    Chromium exists in nuclear waste sludges and is a problematic element in the vitrification process of high-level nuclear wastes. It is therefore necessary to treat the waste sludges to remove chromium prior to vitrification, by caustic leaching or oxidation of Cr(III) to Cr(VI). The objective of this study is to investigate the effect of oligomerization of Cr(III) on its oxidation by hypochlorite in alkaline solutions. Monomeric, dimeric and trimeric Cr(III) species in solution were separated by ion exchange. The kinetics of the oxidation of the separated species by hypochlorite in alkaline solutions was studied by UV/Vis absorption spectroscopy, and compared with the oxidation by hydrogen peroxide previously studied. Results indicate that hypochlorite can oxidize Cr(III) to Cr(VI) in alkaline solutions, but the rate of oxidation by hypochlorite is slower than that by hydrogen peroxide at the same alkalinity and concentrations of oxidants. The rate of oxidation of Cr(III) by both oxidants decreases as the concentration of sodium hydroxide is increased, but the oxidation by hypochlorite seems less affected by the degree of oligomerization of Cr(III) than that by peroxide. Compared with the oxidation by hydrogen peroxide where the major reaction pathway has an inverse order with respect to CNaOH, the oxidation by hypochlorite has a significant reaction pathway independent of [OH?].

  4. Pitting corrosion of iron in weakly alkaline chloride solutions

    SciTech Connect

    Makar, G.L.; Tromans, D.

    1996-04-01

    Chloride-induced pitting corrosion of iron at pH 10.5 and 25 C was examined by conducting quasi-steady-state (potentiostatic) polarization experiments in borate-buffered 0.1 M sodium chloride solutions with buffer concentrations from 0 M to 0.075 M. Values of the film breakdown potential (E{sub b}) were scattered at each buffer concentration, and the scatter band moved to higher potentials with increasing concentrations, indicating increased resistance to pitting. Consistent with this, pitting did not always occur at the higher buffer concentrations. E{sub b} measurements, optical and electron microscopy, X-ray microanalysis, and supplementary polarization experiments in lower-pH borate solutions suggested pitting in the iron -Cl{sup {minus}} system initiated within occluded regions, such as matrix-inclusion interfaces and exposed voids, where pH control was lost because of an inadequate local supply of buffer species. Pitting behavior was consistent with a mechanism dominated by mass transport, in which the presence of Cl{sup {minus}} prevented buffering of occluded regions by the borate specie H{sub 2}BO{sub 3}{sup {minus}}, allowing the ph to be driven into an acidic domain where the solubilities of ferrous hydroxide and ferric hydroxide are high.

  5. Dual fluorescence of naphthylamines in alkaline aqueous solution

    NASA Astrophysics Data System (ADS)

    Ma, Li-Hua; Wen, Zhen-Chang; Lin, Li-Rong; Jiang, Yun-Bao

    2001-10-01

    Dual fluorescence was observed with N-(1-naphthyl)aminoacetate (1-NAA) in aqueous solution of pH 13.0 in the presence of cationic surfactants, cetyltrimethylammonium bromide (CTAB) and chloride (CTAC), below and after the critical micelle concentration (CMC). Similar dual fluorescence was also found with 1- and 2-naphthylamine (1-NA, 2-NA), N-(2-naphthyl)aminoacetate (2-NAA) and (1-naphthyl)ethylenediamine (1-NEDA), in the presence and absence of the cationic surfactants, but not with N, N-disubstituted 1- and 2-NAs. We concluded that the dual fluorescence was due to the excited-state deprotonation of the amino group in these NAs. The p Ka*s of the dual fluorescent NAs were estimated to be around 14 from the dual fluorescence pH titrations. No clear correlation was found for p Ka* with the amino substitution and the presence of cationic micelle.

  6. 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.

  7. 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

  8. [Degradation of the absorbed methyl mercaptan by persulfate in alkaline solution].

    PubMed

    Yang, Shi-Ying; Wang, Lei-Lei; Feng, Lin-Yu; Zhao, La-Juan; Shi, Chao

    2013-11-01

    Methyl mercaptan (CH3SH) is considered to be an important contributor to odors. It is a toxic, corrosive and acid gas. The absorption of CH3SH by alkaline solution is one of the most widely used processes, but the remained solution should be further treated. The degradation of dissolved CH3S- by persulfate (PS) oxidation has not been reported. CH3SH is absorbed in alkaline solution and degraded by PS oxidation using a recycling continuous system for absorption and degradation. The stability of PS under alkaline conditions is discussed. The influence of different reaction conditions on the absorption rate and degradation rate is also studied. It was observed that PS was relatively stability under alkaline conditions and the dissolved CH3S- could be degraded effectively by PS. The absorption rate of CH3SH first increased and then decreased with the increasing concentration of PS. The degradation rate of CH3S- increased with the increasing concentration of PS. It was also observed that the efficiency between absorption and degradation had been significantly increased with the increasing of pH. In the conditions of pH = 12, fixed CH3SH concentration of 80 mg x m(-3) with a fixed gas flow rate of 1.5 L x min(-1), 1.4 g x L(-1) PS, 90% of the dissolved CH3S- can be degraded. PMID:24455922

  9. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  10. 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.

  11. A portable air-aluminum power source with an alkaline electrolytic solution

    NASA Astrophysics Data System (ADS)

    Alekseenko, S. V.; Galkin, P. S.; Kashinskii, O. N.; Markovich, D. M.; Novopashin, S. A.; Randin, V. V.; Kharlamov, S. M.

    2014-04-01

    The results from development of a portable air-aluminum chemical power source (AA CPS) with an alkaline electrolytic solution without any additional service circuits are presented. The feasibility of making air cathodes on the basis of a metal-carbon composite produced by the plasma method has been shown. Special features of the operational conditions of a portable AA CPS have been investigated. It has been found that the aluminum cathode passivation when aluminum hydroxide precipitates from a solution significantly restricts the specific capacity of such power sources. It was shown that it is possible to overcome the anode passivation and to considerably increase the specific capacity of an AA CPS with an alkaline electrolytic solution by means of modifying an anode alloy.

  12. A study on the mechanism of stress corrosion cracking of duplex stainless steels in hot alkaline-sulfide solution

    NASA Astrophysics Data System (ADS)

    Chasse, Kevin Robert

    Duplex stainless steels (DSS) generally have superior strength and corrosion resistance as compared to most standard austenitic and ferritic stainless grades owing to a balanced microstructure of austenite and ferrite. As a result of having favorable properties, DSS have been selected for the construction of equipment in pulp and paper, chemical processing, nuclear, oil and gas as well as other industries. The use of DSS has been restricted in some cases because of stress corrosion cracking (SCC), which can initiate and grow in either the ferrite or austenite phase depending on the environment. Thorough understanding of SCC mechanisms of DSS in chloride- and hydrogen sulfide-containing solutions has been useful for material selection in many environments. However, understanding of SCC mechanisms of DSS in sulfide-containing caustic solutions is limited, which has restricted the capacity to optimize process and equipment design in pulp and paper environments. Process environments may contain different concentrations of hydroxide, sulfide, and chloride, altering corrosion and SCC susceptibility of each phase. Crack initiation and growth behavior will also change depending on the relative phase distribution and properties of austenite and ferrite. The role of microstructure and environment on the SCC of standard grade UNS S32205 and lean grade UNS S32101 in hot alkaline-sulfide solution were evaluated in this work using electrochemical, film characterization, mechanical testing, X-ray diffraction, and microscopy techniques. Microstructural aspects, which included residual stress state, phase distribution, phase ratio, and microhardness, were related to the propensity for SCC crack initiation in different simulated alkaline pulping liquors at 170 °C. Other grades of DSS and reference austenitic and superferritic grades of stainless steel were studied using exposure coupons for comparison to understand compositional effects and individual phase susceptibility

  13. Inhibition of Brass Corrosion by 2-Mercapto-1-methylimidazole in Weakly Alkaline Solution

    NASA Astrophysics Data System (ADS)

    Radovanovic, Milan B.; Antonijevic, Milan M.

    2016-03-01

    The electrochemical behavior of brass and anticorrosion effect of 2-mercapto-1-methylimidazole (2-MMI) in weakly alkaline solution with and without presence of chloride ions was investigated using electrochemical techniques in addition to SEM-EDS analysis. Results show that inhibition efficiency depended on inhibitor concentration and immersion time of brass electrode in inhibitor solution. Inhibition mechanism of 2-mercapto-1-methylimidazole includes adsorption of inhibitor on active sites on electrode surface which was confirmed by SEM-EDS analysis of the brass. Adsorption of the 2-MMI in sodium tetraborate solution obeys Flory-Huggins adsorption isotherm, while in the presence of chloride, ions adsorption of inhibitor obeys Langmuir adsorption isotherm.

  14. 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.

  15. Temperature dependence of the absorbance of alkaline solutions of 4-nitrophenyl phosphate--a potential source of error in the measurement of alkaline phosphatase activity.

    PubMed

    Burtis, C A; Seibert, L E; Baird, M A; Sampson, E J

    1977-09-01

    The absorbance of an alkaline solution of 4-nitrophenyl phosphate is a function of temperature. Quantitative evaluation of this phenomenon indicates that it (a) depends on the concentration of the compound and is independent of source, buffer concentration, and pH above 9.0; (b) is reversible; (c) is not a result of alkaline hydrolysis or 4-nitrophenol contamination; and (d) correlates with a temperature-induced shift of its absorbance spectrum. The phenomenon may represent a potential analytical problem in methods for alkaline phosphatase in which this compound is the substrate. If thermal equilibrium is not reached and maintained during an alkaline phosphatase assay, the thermochromic response will be included in the measured rate. The magnitude of this error depends on the thermal response and control characteristics of each particular instrument and the reaction conditions under which such an analysis is performed. PMID:19164

  16. MODELING AN ION EXCHANGE PROCESS FOR CESIUM REMOVAL FROM ALKALINE RADIOACTIVE WASTE SOLUTIONS

    SciTech Connect

    Smith, F; Luther Hamm, L; Sebastian Aleman, S; Johnston Michael, J

    2008-08-26

    The performance of spherical Resorcinol-Formaldehyde ion-exchange resin for the removal of cesium from alkaline radioactive waste solutions has been investigated through computer modeling. Cesium adsorption isotherms were obtained by fitting experimental data using a thermodynamic framework. Results show that ion-exchange is an efficient method for cesium removal from highly alkaline radioactive waste solutions. On average, two 1300 liter columns operating in series are able to treat 690,000 liters of waste with an initial cesium concentration of 0.09 mM in 11 days achieving a decontamination factor of over 50,000. The study also tested the sensitivity of ion-exchange column performance to variations in flow rate, temperature and column dimensions. Modeling results can be used to optimize design of the ion exchange system.

  17. 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.

  18. 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)

  19. Decontamination of alkaline solution from technetium and other fission products and from some actinides by reductive coprecipitation and sorption on metals

    SciTech Connect

    Peretrukhin, V.F.; Silin, V.I.; Tananaev, I.G.; Kareta, A.V.; Trushina, V.E.

    1997-09-01

    Effective decontamination of alkaline solutions and Hanford Site tank waste simulants from technetium has been accomplished by reductive coprecipitation with iron(III) hydroxide. Addition of 1 M (NH{sub 4}){sub 2}Fe(SO{sub 4}){sub 2} to 0.5 to 4.0 M NaOH to a final concentration of 0.1 to 0.15 M coprecipitates more than 99% of the technetium. from 0.5 to 1.0 M NaOH and 98 to 96% from 2.0 to 4.0 M NaOH. Similar results were obtained by reduction of Tc(VII) with 0.1 to 0.15 M hydrazine and subsequent addition of FeCl{sub 3} to a final concentration of 0.15 M. Inclusion of four complex-forming agents [0.01 M phosphate, 0.1 M EDTA (ethylenediaminetetraacetate), 0.03 M citrate, and 0.1 M glycolate (HOCH{sub 2}CO{sub 2}{sup -})] to the alkaline solution decreases technetium coprecipitation with iron hydroxide to 85% under otherwise similar conditions. Inclusion of 0.04 M Na{sub 2}CrO{sub 4} drastically decreases reductive coprecipitation of Tc(VII) in 0.5 to 4.0 M NaOH. Iron(II) salt, added to a 0.07 M excess over that of chromate, completely reduces chromate and provides greater than 99% coprecipitation of technetium with product iron(III) and chromium(III) hydroxides. Technetium(VII) reduction by hydrazine is slow in the presence of chromate in alkaline solution, and technetium coprecipitation is incomplete in these conditions. Decontamination of an alkaline Hanford Site tank waste simulant, containing 0.04M chromate and eleven salts and complex-forming agents, by adding 1 M iron(II) salt solution was studied. Coprecipitation of 15 to 28% of the technetium and more than 99% of the plutonium occurred in the Fe/Cr(III) hydroxide precipitate produced by adding 0.05 to 0.10 M iron(II). Chromate reduction was incomplete. About 75% of the technetium was coprecipitated, and the chromate was completely reduced, after adding 0.2 M iron(II) salt.

  20. The effects of 2% alkaline glutaraldehyde solution on the elastic properties of elastomeric chain.

    PubMed

    Jeffries, C L; von Fraunhofer, J A

    1991-01-01

    The effect of two proprietary alkaline gluteraldehyde solutions on the strength (failure load) and the required displacement or stretching to achieve a force of 500g was studied for six types of elastomeric chains. The effect of disinfection (short-term exposure) and sterilization (long-term exposure) as well as repeated immersion cycles on these parameters was evaluated. The findings showed that exposure to gluteraldehyde solution affected the strength and the distention required to deliver a force of 500g of certain elastomeric chains. However, the resultant changes were relatively small and are probably insignificant in the clinical setting. PMID:1901464

  1. 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

  2. Reduction and alkaline hydrolysis of 5-oxoindeno(1,2-b)pyridinium salts

    SciTech Connect

    Mutsenietse, D.Kh.; Zandersons, A.Z.; Lusis, V.K.; Dubur, G.Ya.

    1987-07-01

    5,9b-dihydro derivatives of indeno(1,2-b)pyridine were obtained by the reduction of the corresponding 1,2-dimethyl-4-acryl-5-oxoindeno(1,2-b)pyridinium perchlorates. 1,2-dimethyl-3-ethoxycarbonyl-4-phenyl-5-oxoindeno(1,2-b)pyridinium perchlorate forms in alkaline medium with splitting, recyclization and deamination products.

  3. Complex formation of alkaline-earth cations with crown ethers and cryptands in methanol solutions

    SciTech Connect

    Buschman, H.J.

    1986-06-01

    The complexation of alkaline-earth cations by different crown ethers, azacrown ethers, and cryptands has been studied in methanol solutions by means of calorimetric and potentiometric titrations. The smallest monocyclic ligands examined from 2:1 complexes (ratio of ligand to cation) with cations which are too large to fit into the ligand cavity. With the smallest cryptand, only Sr/sup 2 +/ and Ba/sup 2 +/ ions are able to form exclusive complexes. In the case of the reaction of cryptand (211) with Ca/sup 2 +/, a separate estimation of stability constants for the formation of exclusive and inclusive complexes was possible for the first time. Higher values for stability constants are found for the reaction of alkaline-earth cations with cryptands compared to the reaction with alkali ions. This increase is only caused by favorable entropic contributions.

  4. Interactions of N,N'-dimethylaminoethanol with steel surfaces in alkaline and chlorine containing solutions

    NASA Astrophysics Data System (ADS)

    Welle, A.; Liao, J. D.; Kaiser, K.; Grunze, M.; Mäder, U.; Blank, N.

    1997-10-01

    Formulations based on dilute aqueous solutions of N,N'-dimethylethanolamine (DMEA) are used to protect reinforcement steel bars ('rebar') in concrete from corrosion. In a previous paper we discussed the usefulness of X-ray photoelectron spectroscopy (XPS) to detect DMEA adsorbed from solution and the application of secondary neutral mass spectrometry (SNMS) to study migration of DMEA through a cement matrix. In this report we present XPS data of DMEA adsorbed on steel surfaces from alkaline and chlorine containing solutions of variable concentration range and discuss models for the interaction of DMEA with the oxidized steel surface and the mechanism of corrosion inhibition of DMEA. DMEA is strongly bonded to the steel surface and displaces ionic species from the substrate/solution interface hence protecting the ironoxide surface from ionic attack.

  5. Alleviating salt stress in tomato seedlings using Arthrobacter and Bacillus megaterium isolated from the rhizosphere of wild plants grown on saline-alkaline lands.

    PubMed

    Fan, Pengfei; Chen, Daitao; He, Yanan; Zhou, Qingxia; Tian, Yongqiang; Gao, Lihong

    2016-11-01

    Salt-induced soil degradation is common in farmlands and limits the growth and development of numerous crop plants in the world. In this study, we isolated salt-tolerant bacteria from the rhizosphere of Tamarix chinensis, Suaeda salsa and Zoysia sinica, which are common wild plants grown on a saline-alkaline land, to test these bacteria's efficiency in alleviating salt stress in tomato plants. We screened out seven strains (TF1-7) that are efficient in reducing salt stress in tomato seedlings. The sequence data of 16S rRNA genes showed that these strains belong to Arthrobacter and Bacillus megaterium. All strains could hydrolyze casein and solubilize phosphate, and showed at least one plant growth promotion (PGP)-related gene, indicating their potential in promoting plant growth. The Arthrobacter strains TF1 and TF7 and the Bacillus megaterium strain TF2 and TF3 could produce indole acetic acid under salt stress, further demonstrating their PGP potential. Tomato seed germination, seedling length, vigor index, and plant fresh and dry weight were enhanced by inoculation of Arthrobacter and B. megaterium strains under salt stress. Our results demonstrated that salt-tolerant bacteria isolated from the rhizosphere of wild plants grown on saline-alkaline lands could be used for alleviating salt stress in crop plants. PMID:27196364

  6. Recovering lead from cathode ray tube funnel glass by mechano-chemical extraction in alkaline solution.

    PubMed

    Zhang, Chenglong; Wang, Jingwei; Bai, Jianfeng; Guan, Jie; Wu, Wenjie; Guo, Cuixiang

    2013-07-01

    This study evaluates the efficiency of lead (Pb) extraction from cathode ray tube (CRT) funnel glass in strongly alkaline solution using mechanical activation in a ball mill as the chemical breakage and defects formed in the inner structures will contribute to the easy dissolution of the activated Pb glass. The combination of mechanical activation and a chemical leaching process in a single operation (mechano-chemical leaching) is more effective than the mechanical activation and subsequent chemical leaching. More than 97% of Pb in the CRT funnel glass can be extracted with a stirring ball mill leaching process in 5 M sodium hydroxide at 70°C. The diameter of the stainless steel balls as the activation medium is 5 mm; the mass ratio of ball to raw materials is 25:1. Pb powder with a purity of 97% can be obtained by electrowinning from the leaching solution. The Pb-depleted solution can be recycled into the leaching step. After Pb is removed, the solid leaching residues can be used for preparation of foam glass. Thus, a novel hydrometallurgical process for recovering Pb from CRT funnel glass in alkaline solution is proposed. PMID:23592759

  7. 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.

  8. Use of agar diffusion assay to measure bactericidal activity of alkaline salts of fatty acids against bacteria associated with poultry processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The agar diffusion assay was used to examine antibacterial activity of alkaline salts of caproic, caprylic, capric, lauric, and myristic acids. A 0.5M concentration of each fatty acid was dissolved in 1.0 M potassium hydroxide (KOH), and pH of the mixtures was adjusted to 10.5 with citric acid. Solu...

  9. Actinides in Hanford Tank Waste Simulants: Chemistry of Selected Species in Oxidizing Alkaline Solutions

    SciTech Connect

    Nash, Kenneth L.; Laszak, Ivan; Borkowski, Marian; Hancock, Melissa; Rao, Linfeng; Reed, Wendy

    2004-03-30

    To enhance removal of selected troublesome nonradioactive matrix elements (P, Cr, Al, S) from the sludges in radioactive waste tanks at the Hanford site, various chemical washing procedures have been evaluated. It is intended that leaching should leave the actinides in the residual sludge phase for direct vitrification. Oxidative treatment with strongly alkaline solutions has emerged as the best approach to accomplishing this feat. However, because the most important actinide ions in the sludge can exist in multiple oxidation states, it is conceivable that changes in actinide oxidation state speciation could interfere with hopes and plans for actinide insolubility. In this presentation, we discuss both the impact of oxidative alkaline leachants on actinide oxidation state speciation and the chemistry of oxidized actinide species in the solution phase. Actinide oxidation does occur during leaching, but the solubility behavior is complex. Mixed ligand complexes may dominate solution phase speciation of actinides under some circumstances. This work was supported by the U.S. Department of Energy, Offices of Science and Waste Management, Environmental Management Science Program under Contract DEAC03- 76SF0098 at Lawrence Berkeley National Laboratory and Contract W-31-109- ENG-38 at Argonne National Laboratory.

  10. Sulfate Separation from Aqueous Alkaline Solutions by Selective Crystallization of Alkali Metal Coordination Capsules

    SciTech Connect

    Rajbanshi, Arbin; Moyer, Bruce A; Custelcean, Radu

    2011-01-01

    Self-assembly of a tris(urea) anion receptor with Na{sub 2}SO{sub 4} or K{sub 2}SO{sub 4} yields crystalline capsules held together by coordinating Na{sup +} or K{sup +} cations and hydrogen-bonding water bridges, with the sulfate anions encapsulated inside urea-lined cavities. The sodium-based capsules can be selectively crystallized in excellent yield from highly competitive aqueous alkaline solutions ({approx}6 M Na{sup +}, pH 14), thereby providing for the first time a viable approach to sulfate separation from nuclear wastes.

  11. Kinetics of leaching of the aluminum hydroxide in bauxites by alkaline solutions at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Burtsev, A. V.; Lainer, Yu. A.; Gorichev, I. G.; Kipriyanov, N. A.; Izotov, A. D.

    2011-11-01

    The kinetics of leaching of the aluminum hydroxide from the gibbsite bauxites of Guinea (Kindia deposit) is studied under atmospheric conditions. The activation energy of the process is found to be 34.75 kJ/mol, which indicates that the process proceeds in a kinetic mode. The leaching of the aluminum hydroxide from bauxite in an alkaline solution is simulated using acid-base equilibria (ion exchange) and the electrochemical theory of the structure of a double electrical layer (Gram-Parsons theory).

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments

    NASA Astrophysics Data System (ADS)

    Szecsody, Jim E.; Truex, Mike J.; Qafoku, Nikolla P.; Wellman, Dawn M.; Resch, Tom; Zhong, Lirong

    2013-08-01

    This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH 2) resulted in a rapid (< 10 h) increase in aqueous carbonate (with Ca2 +, Mg2 +) and phosphate and a slow (100 s of hours) increase in silica, Al3 +, and K+, likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH 13) resulted in a rapid (< 10 h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity.

  17. Influence of Acidic and Alkaline Waste Solution Properties on Uranium Migration in Subsurface Sediments

    SciTech Connect

    Szecsody, James E.; Truex, Michael J.; Qafoku, Nikolla; Wellman, Dawn M.; Resch, Charles T.; Zhong, Lirong

    2013-08-01

    This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments has significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH 2) resulted in a rapid (< 10 h) increase in aqueous carbonate (with Ca2+, Mg2+) and phosphate and a slow (100s of hours) increase in silica, Al3+, and K+, likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH 13) resulted in a rapid (< 10 h) increase in carbonate, followed by a slow (10s to 100s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity.

  18. Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments.

    PubMed

    Szecsody, Jim E; Truex, Mike J; Qafoku, Nikolla P; Wellman, Dawn M; Resch, Tom; Zhong, Lirong

    2013-08-01

    This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH2) resulted in a rapid (<10 h) increase in aqueous carbonate (with Ca(2+), Mg(2+)) and phosphate and a slow (100 s of hours) increase in silica, Al(3+), and K(+), likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH13) resulted in a rapid (<10h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity. PMID:23851265

  19. Alkaline deoxygenated graphene oxide as adsorbent for cadmium ions removal from aqueous solutions.

    PubMed

    Liu, Jun; Du, Hongyan; Yuan, Shaowei; He, Wanxia; Yan, Pengju; Liu, Zhanhong

    2015-01-01

    Alkaline deoxygenated graphene oxide (aGO) was prepared through alkaline hydrothermal treatment and used as adsorbent to remove Cd(II) ions from aqueous solutions for the first time. The characterization results of transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and Fourier transform infrared (FT-IR) spectra indicate that aGO was successfully synthesized. The batch adsorption experiments showed that the adsorption kinetics could be described by the pseudo-second-order kinetic model, and the isotherms equilibrium data were well fitted with the Langmuir model. The maximum adsorption capacity of Cd(II) on aGO was 156 mg/g at pH 5 and T=293 K. The adsorption thermodynamic parameters indicated that the adsorption process was a spontaneous and endothermic reaction. The mainly adsorption mechanism speculated from FT-IR results may be attributed to the electrostatic attraction between Cd2+ and negatively charged groups (-CO-) of aGO and cation-π interaction between Cd2+ and the graphene planes. The findings of this study demonstrate the potential utility of the nanomaterial aGO as an effective adsorbent for Cd(II) removal from aqueous solutions. PMID:26038925

  20. 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.

  1. On the complex structural diffusion of proton holes in nanoconfined alkaline solutions within slit pores

    PubMed Central

    Muñoz-Santiburcio, Daniel; Marx, Dominik

    2016-01-01

    The hydroxide anion OH−(aq) in homogeneous bulk water, that is, the solvated proton hole, is known to feature peculiar properties compared with excess protons solvated therein. In this work, it is disclosed that nanoconfinement of such alkaline aqueous solutions strongly affects the key structural and dynamical properties of OH−(aq) compared with the bulk limit. The combined effect of the preferred hypercoordinated solvation pattern of OH−(aq), its preferred perpendicular orientation relative to the confining surfaces, the pronounced layering of nanoconfined water and the topology of the hydrogen bond network required for proton hole transfer lead to major changes of the charge transport mechanism, in such a way that the proton hole migration mechanism depends exquisitely on the width of the confined space that hosts the water film. Moreover, the anionic Zundel complex, which is of transient nature in homogeneous bulk solutions, can be dynamically trapped as a shallow intermediate species by suitable nanoconfinement conditions. PMID:27550616

  2. On the complex structural diffusion of proton holes in nanoconfined alkaline solutions within slit pores.

    PubMed

    Muñoz-Santiburcio, Daniel; Marx, Dominik

    2016-01-01

    The hydroxide anion OH(-)(aq) in homogeneous bulk water, that is, the solvated proton hole, is known to feature peculiar properties compared with excess protons solvated therein. In this work, it is disclosed that nanoconfinement of such alkaline aqueous solutions strongly affects the key structural and dynamical properties of OH(-)(aq) compared with the bulk limit. The combined effect of the preferred hypercoordinated solvation pattern of OH(-)(aq), its preferred perpendicular orientation relative to the confining surfaces, the pronounced layering of nanoconfined water and the topology of the hydrogen bond network required for proton hole transfer lead to major changes of the charge transport mechanism, in such a way that the proton hole migration mechanism depends exquisitely on the width of the confined space that hosts the water film. Moreover, the anionic Zundel complex, which is of transient nature in homogeneous bulk solutions, can be dynamically trapped as a shallow intermediate species by suitable nanoconfinement conditions. PMID:27550616

  3. Surface charge density on silica in alkali and alkaline earth chloride electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Dove, Patricia M.; Craven, Colin M.

    2005-11-01

    The surface charge density of colloidal SiO 2 (Aerosil 380) was measured in alkali chloride (0.067 and 0.20 M LiCl, NaCl, and KCl) and alkaline earth chloride (0.067 M MgCl 2, CaCl 2, SrCl 2, BaCl 2) solutions. Measurements were conducted at 25°C by potentiometric titrations using the constant ionic medium method in a CO 2-free system. The experimental design measured surface charge for solutions with constant ionic strength as well as constant cation concentration. Alkali chloride solutions promote negative surface charge density in the order LiCl < NaCl < KCl to give the "regular" lyotropic behavior previously reported. In contrast, the alkaline earth chloride solutions exhibit a reversed lyotropic trend with increasing crystallographic radius where increasing negative charge is promoted in the order BaCl 2 < SrCl 2 < CaCl 2 < MgCl 2. The origin of the opposing affinity trends is probed by testing the hypothesis that this reversal is rooted in the differing solvent structuring characteristics of the IA and IIA cations at the silica-water interface. This idea arises from earlier postulations that solvent structuring effects increase entropy through solvent disordering and these gains must be much greater than the small, positive enthalpy associated with electrostatic interactions. By correlating measured charge density with a proxy for the solvent-structuring ability of cations, this study shows that silica surface charge density is maximized by those electrolytes that have the strongest effects on solvent structuring. We suggest that for a given solid material, solvation entropy has a role in determining the ionic specificity of electrostatic interactions and reiterate the idea that the concept of lyotropy is rooted in the solvent-structuring ability of cations at the interface.

  4. Arsenophilic Bacterial Processes in Searles Lake: A Salt-saturated, Arsenic-rich, Alkaline Soda Lake.

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Kulp, T. R.; Hoeft, S. E.; Miller, L. G.; Swizer Blum, J.; Stolz, J. F.

    2005-12-01

    Searles Lake, located in the Mojave Desert of California, is essentially a chemically-similar, concentrated version of Mono Lake, but having a much higher salinity (e.g., 340 vs. 90 g/L) and a greater dissolved inorganic arsenic content in its brine (e.g., 3.9 vs. 0.2 mM). The source of all this arsenic ultimately comes from hydrothermal spring inputs, thereby underscoring the importance of volcanic and fluvial processes in transporting this toxic element into these closed basin lakes. Nonetheless, the presence of microbial activities with regard to respiration of arsenate oxyanions under anaerobic conditions and the oxidation of arsenite oxyanions under aerobic conditions can be inferred from porewater profiles taken from handcores retrieved beneath Searles Lake's salt crust. Sediment slurry incubations confirmed biological arsenate respiration and arsenite oxidation, with the former processes notably enhanced by provision of the inorganic electron donor sulfide or H2. Hence, arsenic-linked chemo-autotrophy appears to be an important means of carbon fixation in this system. Subsequent efforts using 73As-arsenate as radiotracer detected dissimilatory arsenate reduction activity down the length of the core, but we were unable to detect any evidence for sulfate-reduction using 35S-sulfate. An extremely halophilic anaerobic bacterium of the order Haloanaerobiales [strain SLAS-1] was isolated from the sediments that grew via arsenate respiration using lactate or sulfide as its electron donors. These results show that, unlike sulfate-reduction, arsenic metabolism (i.e., both oxidation of arsenite and dissimilatory reduction of arsenate) is operative and even vigorous under the extreme conditions of salt-saturation and high pH. The occurrence of arsenophilic microbial processes in Searles Lake is relevant to the search for extant or extinct microbial life on Mars. It is evident from surface imagery that Mars had past episodes of volcanism, fluvial transport, and most

  5. Hexavalent uranium diffusion into soils from concentrated acidic and alkaline solutions

    SciTech Connect

    Tokunaga, Tetsu K.; Wan, Jiamin; Pena, Jasquelin; Sutton, Stephen R.; Newville, Matthew

    2004-03-29

    Uranium contamination of soils and sediments often originates from acidic or alkaline waste sources, with diffusion being a major transport mechanism. Measurements of U(VI) diffusion from initially pH 2 and pH 11 solutions into a slightly alkaline Altamont soil and a neutral Oak Ridge soil were obtained through monitoring uptake from boundary reservoirs and from U concentration profiles within soil columns. The soils provided pH buffering, resulting in diffusion at nearly constant pH. Micro x-ray absorption near edge structure spectra confirmed that U remained in U(VI) forms in all soils. Time trends of U(VI) depletion from reservoirs, and U(VI) concentration profiles within soil columns yielded K{sub d} values consistent with those determined in batch tests at similar concentrations ({approx} 1 mM), and much lower than values for sorption at much lower concentrations (nM to {mu}M). These results show that U(VI) transport at high concentrations can be relatively fast at non-neutral pH, with negligible surface diffusion, because of weak sorption.

  6. XANES Demonstrates the Release of Calcium Phosphates from Alkaline Vertisols to Moderately Acidified Solution.

    PubMed

    Andersson, Karl O; Tighe, Matthew K; Guppy, Christopher N; Milham, Paul J; McLaren, Timothy I; Schefe, Cassandra R; Lombi, Enzo

    2016-04-19

    Calcium phosphate (CaP) minerals may comprise the main phosphorus (P) reserve in alkaline soils, with solubility dependent on pH and the concentration of Ca and/or P in solution. Combining several techniques in a novel way, we studied these phenomena by progressively depleting P from suspensions of two soils (low P) using an anion-exchange membrane (AEM) and from a third soil (high P) with AEM together with a cation-exchange membrane. Depletions commenced on untreated soil, then continued as pH was manipulated and maintained at three constant pH levels: the initial pH (pHi) and pH 6.5 and 5.5. Bulk P K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the main forms of inorganic P in each soil were apatite, a second more soluble CaP mineral, and smectite-sorbed P. With moderate depletion of P at pHi or pH 6.5, CaP minerals became more prominent in the spectra compared to sorbed species. The more soluble CaP minerals were depleted at pH 6.5, and all CaP minerals were exhausted at pH 5.5, showing that the CaP species present in these alkaline soils are soluble with decreases of pH in the range achievable by rhizosphere acidification. PMID:26974327

  7. A chelating ion exchanger for gallium recovery from alkaline solution using 5-palmitoyl-8-hydroxyquinoline immobilized on a nonpolar adsorbent

    SciTech Connect

    Filik, H.; Apak, R.

    1998-06-01

    The recently developed method of gallium recovery from alkaline solution by alkanoyl oxine/chloroform extraction has been improved by immobilizing palmitoyl oxine on hydrophobic macroporous styrene-divinylbenzene copolymer Amberlite XAD-2 and passing the GA-containing alkaline solution of pH 13.5 through the synthesized resin column. The developed column showed reasonable efficiency after successive passages, and the selectivity of Ga over Al was very high, suggesting the utilizibility of the method in Ga recovery from the basic aluminate liquor of the Bayer process. The Ga capacity of the oxine-based resin was 3.94 {micro}mol/g. Two mg Ga retained on 10 g resin could be eluted with 25 mL of 2 N HCl at a throughput rate of 2 mL/min. The developed process has prospective use in Ga separation from Al in a strongly alkaline solution.

  8. 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

  9. 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

  10. Oxygen Reduction on Ag(100) in Alkaline Solutions--A Theoretical Study.

    PubMed

    Goduljan, Aleksej; de Campos Pinto, Leandro Moreira; Juarez, Fernanda; Santos, Elizabeth; Schmickler, Wolfgang

    2016-02-16

    Silver is much more reactive to oxygen than gold; nevertheless, in alkaline solutions, the rates of oxygen reduction on both metals are similar. To explain this phenomenon, the first, rate-determining step of oxygen reduction on Ag(100) is determined by a combination of DFT, molecular dynamics, and electrocatalysis theory. In vacuum, oxygen is adsorbed on Ag(100), but in the electrochemical environment, the adsorption energy is offset by the loss of hydration energy as the molecule approaches the surface. As a result, the first electron transfer should take place in an outer-sphere mode. Previously, the same mechanism for oxygen reduction on Au(100) has been predicted, and these calculations have been repeated by using a more advanced version of the electrocatalysis theory discussed herein to confirm previous conclusions. The theoretical results compare well with experimental data. PMID:26698629

  11. Development of anion-conducting ionomer binder solutions for electrodes of solid alkaline fuel cells.

    PubMed

    Shin, Mun-Sik; Kang, Moon-Sung; Park, Jin-Soo

    2014-10-01

    For solid alkaline fuel cell applications, membrane-electrode assemblies (MEAs) should be prepared. Thus, in this study, anion-conducting ionomer binder was prepared for electrodes of MEAs. Specifically, we synthesized water soluble anionic binder solutions based on quaternized chitosan derivatives (QCDs) and cross-linked QCDs and prepared a novel electrode. The electrochemical and physicochemical properties of ionomer binder and electrode were investigated by FT-IR, NMR and ionic conductivity. The ionic conductivity of these cross-linked QCDs was 9.7 x 10(-3) S cm(-1) in deionized water at room temperature. The membrane electrode assemblies (MEAs) were prepared by a spray method and were investigated in terms of cyclic voltammetry, impedance and fuel cell performance. The MEA with the 35 wt% QCD ionomer showed the highest performance and confirmed the successful formation of ionomer binder at the electrode of the MEA by the on-site crosslinking reaction. PMID:25942868

  12. Purification and concentration of alkaline phosphatase by selective permeabilization of Escherichia coli using reverse micellar solutions.

    PubMed

    Bansal-Mutalik, Ritu; Gaikar, Vilas G

    2003-01-01

    Recovery of alkaline phosphatase (AP) from the periplasm of Escherichia coli using reverse micellar solutions (RMSs) of sodium dioctyl sulfosuccinate (AOT) in aliphatic hydrocarbons has been attempted. A variety of surface-active agents, solvents, and reverse micellar conditions were screened, and an excellent recovery of the enzyme in a concentrated form, with a high purification factor, was obtained in a single-step process. The permeabilization process strongly depended on the water content of the RMS as well as on the amount of water coating the microbial cell surface. The product was almost free from nucleic acids. In addition, because of the low affinity of AOT and the organic solvent for the aqueous phase, contamination by the permeabilizing agents would also be negligible. PMID:14656146

  13. Speciation and the structure of lead(II) in hyper-alkaline aqueous solution.

    PubMed

    Bajnóczi, Eva G; Pálinkó, István; Körtvélyesi, Tamás; Bálint, Szabolcs; Bakó, Imre; Sipos, Pál; Persson, Ingmar

    2014-12-14

    The identity of the predominating lead(ii) species in hyper-alkaline aqueous solution has been determined by Raman spectroscopy, and ab initio quantum chemical calculations and its structure has been determined by EXAFS. The observed and calculated Raman spectra for the [Pb(OH)3](-) complex are in agreement while they are different for two-coordinated complexes and complexes containing Pb[double bond, length as m-dash]O double bonds. Predicted bond lengths are also consistent with the presence of [Pb(OH)3](-) and exclude the formation of Pb[double bond, length as m-dash]O double bond(s). These observations together with experimentally established analogies between lead(ii) and tin(ii) in hyper-alkaline aqueous solutions suggest that the last stepwise hydroxido complex of lead(ii) is [Pb(OH)3](-). The Pb-O bond distance in the [Pb(OH)3](-) complex as determined is remarkably short, 2.216 Å, and has low symmetry as no multiple back-scattering is observed. The [Pb(OH)3](-) complex has most likely trigonal pyramidal geometry as all reported three-coordinated lead(ii) complexes in the solid state. From single crystal X-ray data, the bond lengths for O-coordinated lead(ii) complexes with low coordination numbers are spread over an unusually wide interval, 2.216-2.464 Å for N = 3. The Pb-O bond distance is at the short side and within the range of three coordinated complexes, as also observed for the trihydroxidostannate(ii) complex indicating that the hydroxide ion forms short bonds with d(10)s(2) metal ions with occupied anti-bonding orbitals. PMID:25347136

  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. Reactive transport modeling of column experiments on the evolution of saline alkaline waste solutions

    NASA Astrophysics Data System (ADS)

    Zheng, Zuoping; Zhang, Guoxiang; Wan, Jiamin

    2008-04-01

    Leakage of saline-alkaline tank waste solutions often creates a serious environmental contamination problem. To better understand the mechanisms controlling the fate of such waste solutions in the Hanford vadose zone, we simulated reactive transport in columns designed to represent local site conditions. The Pitzer ion interaction module was used, with principal geochemical processes considered in the simulation including quartz dissolution, precipitation of brucite, calcite, and portlandite, multi-component cation exchange, and aqueous complexation reactions. Good matches were observed between the simulated and measured column data at ambient temperature (˜ 21 °C). Relatively good agreement was also obtained at high temperature (˜ 70 °C). The decrease of pH at the plume front is examined through formation of secondary mineral phases and/or quartz dissolution. Substantial formation of secondary mineral phases resulting from multi-component cation exchange suggests that these phases are responsible for a decrease in pH within the plume front. In addition, a sensitivity analysis was conducted with respect to cation exchange capacity, selectivity coefficient, mineral assemblage, temperature, and ionic strength. This study could serve as a useful guide to subsequent experimental work, to thermodynamic models developed for the concentrated solutions at high ionic strength and to other types of waste plume studies.

  16. Reactive transport modeling of column experiments on the evolution of saline-alkaline waste solutions.

    PubMed

    Zheng, Zuoping; Zhang, Guoxiang; Wan, Jiamin

    2008-04-01

    Leakage of saline-alkaline tank waste solutions often creates a serious environmental contamination problem. To better understand the mechanisms controlling the fate of such waste solutions in the Hanford vadose zone, we simulated reactive transport in columns designed to represent local site conditions. The Pitzer ion interaction module was used, with principal geochemical processes considered in the simulation including quartz dissolution, precipitation of brucite, calcite, and portlandite, multi-component cation exchange, and aqueous complexation reactions. Good matches were observed between the simulated and measured column data at ambient temperature ( approximately 21 degrees C). Relatively good agreement was also obtained at high temperature ( approximately 70 degrees C). The decrease of pH at the plume front is examined through formation of secondary mineral phases and/or quartz dissolution. Substantial formation of secondary mineral phases resulting from multi-component cation exchange suggests that these phases are responsible for a decrease in pH within the plume front. In addition, a sensitivity analysis was conducted with respect to cation exchange capacity, selectivity coefficient, mineral assemblage, temperature, and ionic strength. This study could serve as a useful guide to subsequent experimental work, to thermodynamic models developed for the concentrated solutions at high ionic strength and to other types of waste plume studies. PMID:18313795

  17. 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.

  18. Americium/Lanthanide Separations in Alkaline Solutions for Advanced Nuclear Fuel Cycles

    SciTech Connect

    Goff, George S.; Long, Kristy Marie; Reilly, Sean D.; Jarvinen, Gordon D.; Runde, Wolfgang H.

    2012-06-11

    Project goals: Can used nuclear fuel be partitioned by dissolution in alkaline aqueous solution to give a solution of uranium, neptunium, plutonium, americium and curium and a filterable solid containing nearly all of the lanthanide fission products and certain other fission products? What is the chemistry of Am/Cm/Ln in oxidative carbonate solutions? Can higher oxidation states of Am be stabilized and exploited? Conclusions: Am(VI) is kinetically stable in 0.5-2.0 M carbonate solutions for hours. Aliquat 336 in toluene has been successfully shown to extract U(VI) and Pu(VI) from carbonate solutions. (Stepanov et al 2011). Higher carbonate concentration gives lower D, SF{sub U/Eu} for = 4 in 1 M K{sub 2}CO{sub 3}. Experiments with Am(VI) were unsuccessful due to reduction by the organics. Multiple sources of reducing organics...more optimization. Reduction experiments of Am(VI) in dodecane/octanol/Aliquat 336 show that after 5 minutes of contact, only 30-40% of the Am(VI) has been reduced. Long enough to perform an extraction. Shorter contact times, lower T, and lower Aliquat 336 concentration still did not result in any significant extraction of Am. Anion exchange experiments using a strong base anion exchanger show uptake of U(VI) with minimal uptake of Nd(III). Experiments with Am(VI) indicate Am sorption with a Kd of 9 (10 minute contact) but sorption mechanism is not yet understood. SF{sub U/Nd} for = 7 and SF{sub U/Eu} for = 19 after 24 hours in 1 M K{sub 2}CO{sub 3}.

  19. 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.

  20. Purification of alkaline solutions and wastes from actinides and technetium by coprecipitation with some carriers using the method of appearing reagents: Final Report

    SciTech Connect

    Peretrukhin, V.F.; Silin, V.I.; Kareta, A.V.; Gelis, A.V.; Shilov, V.P.; German, K.E.; Firsova, E.V.; Maslennikov, A.G.; Trushina, V.E.

    1998-09-01

    The coprecipitation of transuranium elements (TRU) and technetium from alkaline solutions and from simulants of Hanford Site tank wastes has been studied in reducing and oxidizing conditions on uranium(IV,VI) hydroxocompounds, tetraalkylammonium perrhenate and perchlorate, and on hydroxides of Fe(III), Co(III), Mn(II), and Cr(III) using the method of appearing reagents (MAR). Coprecipitations in alkaline solution have been shown to give high decontamination factors (DF) at low content of carrier and in the presence of high salt concentrations. Uranium(IV) hydroxide in concentrations higher than 3 {times} 10{sup {minus}3} M coprecipitates Pu and Cm in any oxidation state from 0.2 to 4 M NaOH with DFs of 110 to 1000 and Np and Tc with DFs of 51 to 176. Technetium (VII) coprecipitates with (5 to 8) {times} 10{sup {minus}4} M tetrabutylammonium (TBA) perrhenate in 0.01 to 0.02 M TBA hydroxide from 0.5 to 1.5 M NaOH to give DFs of 150 to 200. Coprecipitations of Np and Pu with Co(OH){sub 3}, Fe(OH){sub 3}, Cr(OH){sub 3}, and Mn(OH){sub 2} obtained by the MAR from precursors in the range from pH 10.5 to 0.4 M NaOH give DFs from 80 to 400.

  1. Addition and elimination kinetics in OH radical induced oxidation of phenol and cresols in acidic and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Roder, M.; Wojnárovits, L.; Földiák, G.; Emmi, S. S.; Beggiato, G.; D'Angelantonio, M.

    1999-05-01

    The rates of the two consecutive reactions, OH radical addition and H 2O/OH - elimination, were studied by pulse radiolysis in highly acidic (pH=1.3-1.9) and alkaline (pH≈11) solutions, respectively, for phenol and for the three cresol isomers. The rate coefficient of the addition as measured by the build-up of phenoxyl radical absorbance and by a competitive method is the same (1.4±0.1)×10 10 mol -1 dm 3 s -1 both in acidic and alkaline solution. The rate coefficient of the H 2O elimination in acidic solution is (1.6±0.2)×10 6 s -1, whereas the coefficient of the OH - elimination in alkaline solutions is 6-8 times higher. The kinetics of the phenoxyl radical formation was described by the two-exponential equation of the consecutive reactions: the first exponential is related to the pseudo-first-order addition, while the second to the elimination reaction. No considerable structure dependence was found in the rate coefficients, indicating that the methyl substitutent in these highly acidic or alkaline solutions influences neither the addition nor the elimination rate.

  2. Technetium in alkaline, high-salt, radioactive tank waste supernate: Preliminary characterization and removal

    SciTech Connect

    Blanchard, D.L. Jr.; Brown, G.N.; Conradson, S.D.

    1997-01-01

    This report describes the initial work conducted at Pacific Northwest National Laboratory to study technetium (Tc) removal from Hanford tank waste supernates and Tc oxidation state in the supernates. Filtered supernate samples from four tanks were studied: a composite double shell slurry feed (DSSF) consisting of 70% from Tank AW-101, 20% from AP-106, and 10% from AP-102; and three complexant concentrate (CC) wastes (Tanks AN-107, SY-101, ANS SY-103) that are distinguished by having a high concentration of organic complexants. The work included batch contacts of these waste samples with Reillex{trademark}-HPQ (anion exchanger from Reilly Industries) and ABEC 5000 (a sorbent from Eichrom Industries), materials designed to effectively remove Tc as pertechnetate from tank wastes. A short study of Tc analysis methods was completed. A preliminary identification of the oxidation state of non-pertechnetate species in the supernates was made by analyzing the technetium x-ray absorption spectra of four CC waste samples. Molybdenum (Mo) and rhenium (Re) spiked test solutions and simulants were tested with electrospray ionization-mass spectrometry to evaluate the feasibility of the technique for identifying Tc species in waste samples.

  3. 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.

  4. Experimentally determined swelling pressures and geochemical interactions of compacted Wyoming bentonite with highly alkaline solutions

    NASA Astrophysics Data System (ADS)

    Karnland, Ola; Olsson, Siv; Nilsson, Ulf; Sellin, Patrik

    The estimated quantity of cement for construction and sealing purposes is around 9E5 kg in the planned Swedish KBS3 repository for nuclear waste. The highly alkaline cement pore fluid (pH > 12) may affect other components in the repository, and especially the bentonite buffer is of concern. In this study, we simulated possible interactions between cement and bentonite by contacting highly compacted bentonite with high molar hydroxide solutions in a series of laboratory experiments. Wyoming bentonite (MX-80) and purified homo-ionic Na- and Ca-montmorillonite were used for tests with 0.1, 0.3 and 1.0 M NaOH, and saturated Ca(OH) 2 solutions. Pressure cells with permeable filters were loaded with compacted discs of bentonite at the proposed buffer density (2000 kg/m 3 at full water saturation). A hydroxide solution was circulated on one side of the cell and an isotonic chloride solution on the other during a minimum of 45 days. Swelling pressure and solution pH were monitored during the tests and the change in the solution composition and bentonite mineralogy were determined after completed tests. No effect on swelling pressure was observed in tests with 0.1 M NaOH (pH 12.9) or saturated Ca(OH) 2 solutions (pH 12.4) and the mineralogical/chemical changes of the clay were minimal. The bentonite swelling pressure was significantly reduced in the tests with 0.3 (pH 13.3) and 1.0 M (pH 13.8) NaOH solutions. The reduction seems to be due to an instant osmotic effect, and to a continuous dissolution of silica minerals, resulting in mass loss and, consequently, a decrease in density. At these high pH, the release of silica was dominating and the CEC of the clay increased by 20-25%. The structural formula of the smectite and X-ray diffraction tests for non-expandability (Greene-Kelly test) provided strong evidence that the dissolution of montmorillonite proceeds incongruently through an initial step of beidellitization. The calculated rate of silica release from

  5. 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.

  6. 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

  7. 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)

  8. Mercury(II) Complex Formation With Glutathione in Alkaline Aqueous Solution

    SciTech Connect

    Mah, V.; Jalilehvand, F.

    2009-05-19

    The structure and speciation of the complexes formed between mercury(II) ions and glutathione (GSH = L-glutamyl-L-cysteinyl-glycine) have been studied for a series of alkaline aqueous solutions (C{sub Hg{sup 2+}} {approx} 18 mmol dm{sup -3} and C{sub GSH} = 40-200 mmol dm{sup -3} at pH {approx} 10.5) by means of extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy at ambient temperature. The dominant complexes are [Hg(GS){sub 2}]{sup 4-} and [Hg(GS){sub 3}]{sup 7-}, with mean Hg-S bond distances of 2.32(1) and 2.42(2) {angstrom} observed in digonal and trigonal Hg-S coordination, respectively. The proportions of the Hg{sup 2+}-glutathione complexes were evaluated by fitting linear combinations of model EXAFS oscillations representing each species to the experimental EXAFS spectra. The [Hg(GS){sub 4}]{sup 10-} complex, with four sulfur atoms coordinated at a mean Hg-S bond distance of 2.52(2) {angstrom}, is present in minor amounts (<30%) in solutions containing a large excess of glutathione (C{sub GSH} {ge} 160 mmol dm{sup -3}). Comparable alkaline mercury(II) cysteine (H{sub 2}Cys) solutions were also investigated and a reduced tendency to form higher complexes was observed, because the deprotonated amino group of Cys{sup 2-} allows the stable [Hg(S,N-Cys){sub 2}]{sup 2-} chelate to form. The effect of temperature on the distribution of the Hg{sup 2+}-glutathione complexes was studied by comparing the EXAFS spectra at ambient temperature and at 25 K of a series of glycerol/water (33/67, v/v) frozen glasses with and C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3} and C{sub GSH} = 16-81 mmol dm{sup -3}. Complexes with high Hg-S coordination numbers, [Hg(GS){sub 3}]{sup 7-} and [Hg(GS){sub 4}]{sup 10-}, became strongly favored when just a moderate excess of glutathione (C{sub GSH} {ge} 28 mmol dm{sup -3}) was used in the glassy samples, as expected for a stepwise exothermic bond formation. Addition of glycerol had no effect on the Hg

  9. 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.

  10. 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.

  11. Recovery of MnO2 from a spent alkaline battery leach solution via ozone treatment

    NASA Astrophysics Data System (ADS)

    Cruz-Díaz, Martín R.; Arauz-Torres, Yennifer; Caballero, Francisco; Lapidus, Gretchen T.; González, Ignacio

    2015-01-01

    This work investigates the reaction rate of Mn(II) to generate solid manganese dioxide (MnO2) as a function of the gaseous ozone mass flow rate (27.5-77 g h-1). The experimental studies were carried out in a semi-continuous reactor, using a synthetic solution (300 mL of 1 M H2SO4 with 6000 ppm of Mn(II) added as MnSO4) that simulated the composition of an acid leaching solution from spent alkaline battery material (SBM). It was observed that at 1.3-1.45 V/SHE and pH < 1.0 a selective formation of MnO2 powder was obtained; at values greater than 1.45 V/SHE, permanganate ion (MnO41-) was formed. On the other hand, a linear relation was perceived between the volumetric mass transfer coefficient (kLa) and the ozone mass flow rate (19.3-77 g h-1 in 600 mL of the 1 M H2SO4 solution). The rate constant (k) was determined in the presence and absence of nonporous plastic spheres (D = 3 mm). In both cases the rate of Mn(II) conversion increased proportionally with the ozone mass flow rate, although the conversions obtained with non-porous plastic spheres (x = 82%) were always higher than those without non-porous plastic spheres (x = 72%). A pseudo-homogenous mass transfer model adequately approximated the experimental data.

  12. Uranium mobility during interaction of rhyolitic glass with alkaline solutions: dissolution of glass

    USGS Publications Warehouse

    Zielinski, Robert A.

    1977-01-01

    This report concerns investigations designed to identify the important physical and chemical parameters influencing the rate of release of uranium from glass shards of rhyolitic air-fall ash. Oxidizing, silica undersaturated, alkaline solutions are eluted through a column of rhyolitic glass shards at a carefully controlled temperature, pressure, and flow rate. The solutions are monitored for the concentration of uranium and selected additional elements (Si, K, Li, F), and the glass is recovered and examined for physical and/or chemical evidence of attack. The flushing mode is designed to mimic leaching of glass shards by intermittent, near-surface waters with which the glass is not in equilibrium. Reported rates are applicable only to the experimental conditions (120?C, 7,000 psi), but it is assumed that the reaction mechanisms and the relative importance of rate-influencing parameters remain unchanged, at reduced temperature and pressure. Results of the above experiment indicate that silica and uranium are released from glass shards at comparable rates, while lithium and potassium are released faster and fluorine slower than either Si or U. Rates of release of silica and uranium correlate positively with the surface area of the shards. Rhyolitic shards release uranium at faster rates than rhyodacitic shards of comparable surface area. Changes in the shards resulting from experimental treatment and observed in the original glass separates from an Oligocene ash (compared to a Pleistocene ash) include; surface pitting, increased surface area, devitrification rinds (<1l micron wide) and reduced lithium contents. Future investigations will study the effect of temperature, pressure, solution composition, and flow rate on the relative mobility of U, Si, Li, F, and K.

  13. 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.

  14. 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

  15. Reuse of ozonated alkaline solutions as fermentation brines in Spanish green table olives.

    PubMed

    Segovia-Bravo, K A; Arroyo-López, F N; García-García, P; Durán-Quintana, M C; Garrido-Fernández, A

    2007-05-01

    The water used to reduce the excess NaOH after the immersion of green olives in lye becomes a heavily polluted, alkaline wastewater (AW) once it has come into contact with the fruits. Its treatment with ozonated air for 72 h (TAW) destroyed all polyphenols in the solution. A comparison of the microbial, physicochemical, and organoleptic characteristics of olives processed in the traditional way (W) and those reusing AW or TAW was made. The reuse of TAW or diluted TAW (TAW + W) as fermentation brines led to a shorter lag phase, higher maximum specific growth of lactobacillus, and higher lactic acid accumulation (in TAW) than the traditional process; differences among other physicochemical characteristics were not relevant, except that reused brines (AW) always had higher polyphenol contents. The organoleptic panel test did not detect significant differences among treatments in acidic taste, firmness, pit detachment, or olive color. Overall quality was fairly similar for olives from the traditional process and those from the reused TAW. Direct (or diluted) reuse of AW was also possible but produced a more bitter tasting olive. PMID:17995780

  16. Critical anomalies of alkaline fading of phenolphthalein in the critical solution of 2-butoxyethanol + water.

    PubMed

    Du, Zhongyu; Yin, Handi; Hao, Zhiguo; Zheng, Peizhu; Shen, Weiguo

    2013-12-14

    We have used three-wavelength UV-spectrophotometry to study the reaction of the alkaline fading of phenolphthalein in the critical solution of 2-butoxyethanol + water. It was found that when the temperature was far away from the critical point, the values of the natural logarithm of the rate constant k and the natural logarithm of the chemical equilibrium K determined in our experiments had good linear relationships with the reciprocal of temperature, which served as the backgrounds and were used for correcting k and K in the critical region. The critical slowing down of the reaction and the critical anomaly of the chemical equilibrium were detected near the critical point. The value of the critical exponent characterizing the slowing down effect of the reaction rate was obtained to be 0.156, which was close to the value 0.11 associated with the heat capacity divergence and agreed with the theoretical prediction. The experimental result also confirmed the theoretical prediction of 0.11 for the critical exponent characterizing the weak divergence of the singularity of the chemical equilibrium. PMID:24329072

  17. Phase Stability of Chromium(III) Oxide Hydroxide in Alkaline Sodium Phosphate Solutions

    SciTech Connect

    S.E. Ziemniak; E.P. Opalka

    2003-07-08

    Grimaldiite ({alpha}-CrOOH) is shown to transform to a sodium-chromium(III)-hydroxyphosphate compound (SCHP) in alkaline sodium phosphate solutions at elevated temperatures via CrOOH(s) + 4Na{sup +} + 2HPO{sub 4}{sup 2-} = Na{sub 4}Cr(OH)(PO{sub 4}){sub 2}(s) + H{sub 2}O. X-ray diffraction analyses indicate that SCHP possesses an orthorhombic lattice having the same space group symmetry (Ibam, No.72) as sodium ferric hydroxyphosphate. A structurally-consistent designation for SCHP is Na{sub 3}Cr(PO{sub 4}){sub 2} {center_dot} NaOH; the molar volume of SCHP is estimated to be 1552 cm{sup 3}. The thermodynamic equilibrium for the above reaction was defined in the system Na{sub 2}O-P{sub 2}O{sub 5}-Cr{sub 2}O{sub 3}-H{sub 2}O for Na/P molar ratios between 2.0 and 2.4. On the basis of observed reaction threshold values for sodium phosphate concentration and temperature, the standard molar entropy (S{sup o}), heat capacity (C{sub p}{sup o}) and free energy of formation ({Delta}G{sub f}{sup o}) for SCHP were calculated to be 690 J/(mol-K), 622 J/(mol-K) and -3509.97 kJ/mol, respectively.

  18. The inhibition of the spongy electrocrystallization of zinc from doped flowing alkaline zincate solutions

    NASA Astrophysics Data System (ADS)

    Wen, Yue-hua; Cheng, Jie; Zhang, Li; Yan, Xu; Yang, Yu-sheng

    The effects of the presence of additives like lead and tungstate ions in flowing alkaline zincate solutions on suppressing spongy zinc electrogrowth are examined. The results show that the two additives with optimal concentrations in flowing electrolytes can suppress spongy zinc initiation and propagation. And, the two additives can bring about more uniform and compact deposits and, thereby, reduce spongy zinc growth. The influence of lead and tungstate ions on the zinc deposition/dissolution is evaluated by cyclic voltammetry. It also shows that the addition of the two additives is largely a blocking action, and the co-deposition of lead and zinc ions may occur. The performance of the zinc-air flow battery with zinc regeneration electrolysis is determined. It shows that by the addition of 0.6 M Na 2WO 4 or 10 -4 M to 10 -3 M lead, compact or mixed compact-spongy zinc deposits are created and the favorable charge/discharge performance of the battery is achieved with an energy efficiency of approximately 60%.

  19. Effect of carbon nanofiber surface functional groups on oxygen reduction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Zhong, Ren-Sheng; Qin, Yuan-Hang; Niu, Dong-Fang; Tian, Jing-Wei; Zhang, Xin-Sheng; Zhou, Xin-Gui; Sun, Shi-Gang; Yuan, Wei-Kang

    2013-03-01

    Carbon nanofibers (CNFs) with different content of surface functional groups which are carboxyl groups (CNF-OX), carbonyl groups (CNF-CO) and hydroxyl groups (CNF-OH) and nitrogen-containing groups (CNF-ON) are synthesized, and their electrocatalytic activities toward oxygen reduction reaction (ORR) in alkaline solution are investigated. The result of X-ray photoelectron spectroscopy (XPS) characterization indicates that a higher concentration of carboxyl groups, carbonyl groups and hydroxyl groups are imported onto the CNF-OX, CNF-CO and CNF-OH, respectively. Cyclic voltammetry shows that both the oxygen- and nitrogen-containing groups can improve the electrocatalytic activity of CNFs for ORR. The CNF-ON/GC electrode, which has nitrogen-containing groups, exhibits the highest current density of ORR. Rotating disk electrode (RDE) characterization shows that the oxygen reduction on CNF-ON/GC electrode proceeds almost entirely through the four-electron reduction pathway, the CNF-OX/GC, CNF-CO/GC and CNF-OH/GC electrodes proceed a two-electron reduction pathway at low potentials (-0.2 V to -0.6 V) followed by a gradual four-electron reduction pathway at more negative potentials, while the untreated carbon nanofiber (CNF-P/GC) electrode proceeds predominantly by a two-electron reduction pathway within the whole range of potential studied.

  20. Two new frameworks of potassium saccharate obtained from acidic and alkaline solution

    SciTech Connect

    Lv, Yao-Kang; Feng, Yun-Long; Liu, Ji-Wei; Jiang, Zhan-Guo

    2011-05-15

    Two chiral K(I) complexes based on D-saccharic acid (H{sub 2}sac), [K(Hsac)]{sub n} (1) and [K{sub 2}(sac)]{sub n} (2) were obtained from acidic and alkaline solution. The 3D framework of 1 includes K(I) polyhedral rods and typical pairwise coaxial right- and left-handed helical chains, and displays binodal 6-connected pcu topology. 2 contains 2D polyhedral sheets consisting of left-handed helical chains, and generates 3D network with an unprecedented (7,11)-connected net. Cyclic voltammetry tests and charge-discharge tests indicate that the addition of complex 2 to the electrolyte could improve the electrochemical properties of the nickel hydroxide electrode. -- Graphical abstract: Two K(I) complexes based on D-saccharic acid (H{sub 2}sac), [K(Hsac)]{sub n} (1) and [K{sub 2}(sac)]{sub n} (2) were obtained and characterized. Electrochemical studies indicate the potential use of 2 in Ni-MH battery. Display Omitted highlights: > Two novel chiral K(I) frameworks based on D-saccharic acid were obtained. > The structure of 1 includes K(I) polyhedral rods and typical helical chains. > 2 contains 2D polyhedral sheets and generates an unprecedented (7,11)-connected net. > Addition of 2 to electrolyte could improve the nickel hydroxide electrode's property.

  1. 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

  2. The alkaline solution to the emergence of life: energy, entropy and early evolution.

    PubMed

    Russell, Michael J

    2007-01-01

    The Earth agglomerates and heats. Convection cells within the planetary interior expedite the cooling process. Volcanoes evolve steam, carbon dioxide, sulfur dioxide and pyrophosphate. An acidulous Hadean ocean condenses from the carbon dioxide atmosphere. Dusts and stratospheric sulfurous smogs absorb a proportion of the Sun's rays. The cooled ocean leaks into the stressed crust and also convects. High temperature acid springs, coupled to magmatic plumes and spreading centers, emit iron, manganese, zinc, cobalt and nickel ions to the ocean. Away from the spreading centers cooler alkaline spring waters emanate from the ocean floor. These bear hydrogen, formate, ammonia, hydrosulfide and minor methane thiol. The thermal potential begins to be dissipated but the chemical potential is dammed. The exhaling alkaline solutions are frustrated in their further attempt to mix thoroughly with their oceanic source by the spontaneous precipitation of biomorphic barriers of colloidal iron compounds and other minerals. It is here we surmise that organic molecules are synthesized, filtered, concentrated and adsorbed, while acetate and methane--separate products of the precursor to the reductive acetyl-coenzyme-A pathway-are exhaled as waste. Reactions in mineral compartments produce acetate, amino acids, and the components of nucleosides. Short peptides, condensed from the simple amino acids, sequester 'ready-made' iron sulfide clusters to form protoferredoxins, and also bind phosphates. Nucleotides are assembled from amino acids, simple phosphates carbon dioxide and ribose phosphate upon nanocrystalline mineral surfaces. The side chains of particular amino acids register to fitting nucleotide triplet clefts. Keyed in, the amino acids are polymerized, through acid-base catalysis, to alpha chains. Peptides, the tenuous outer-most filaments of the nanocrysts, continually peel away from bound RNA. The polymers are concentrated at cooler regions of the mineral compartments through

  3. 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.

  4. 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.

  5. Electrolyte salts for power sources

    DOEpatents

    Doddapaneni, N.; Ingersoll, D.

    1995-11-28

    Electrolyte salts are disclosed for power sources comprising salts of phenyl polysulfonic acids and phenyl polyphosphonic acids. The preferred salts are alkali and alkaline earth metal salts, most preferably lithium salts. 2 figs.

  6. 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.

  7. 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

  8. Screening Evaluation of Sodium Nonatitanate for Strontium and Actinide Removal from Alkaline Salt Solution

    SciTech Connect

    Hobbs, D.T.

    2001-02-13

    This report describes results from screening tests evaluating strontium and actinide removal characteristics of a sodium titanate material developed by Clearfield and coworkers at Texas A and M University and offered commercially by Honeywell. Sodium nonatitanate may exhibit improved actinide removal kinetics and filtration characteristics compared to MST and thus merit testing.

  9. Enhancement of palladium-porphyrin room temperature phosphorescence by alkaline earth metal in deoxycholate aggregates solution.

    PubMed

    Wang, Ying-Te; Wang, Xiang-Wei; Zhang, Yong

    2011-01-01

    Room temperature phosphorescence (RTP) of three palladium (Pd)-phorphyrins in air-saturated solution of sodium deoxycholate (NaDC) aggregates was measured. RTP of Pd-meso-tetrakis (4-carboxyphenyl) porphyrin (Pd-TCPP) was obviously enhanced in NaDC-aggregates mediated by alkaline earth metal (AEM). Under the same experimental conditions, Ca(2+), Ba(2+) and Mg(2+) induced 200, 90 and 24 times greater enhancement in RTP of Pd-TCPP, respectively. It is ascribed to form the complex of NaDC-aggregate/AEM/Pd-TCPP in the system. The positively charged AEM has a strong capability of co-ordination with negatively charged carboxyl groups of NaDC and Pd-TCPP. The phosphor Pd-TCPP is confined in rigid NaDC-aggregates/AEM system by the coordination which decreases the probability of collision of phosphor with quenchers such as dissolved oxygen molecules and prolongs the lifetime of the phosphor on the triplet state. Long excited-state lifetimes resulted in great enhancement of Pd-TCPP phosphorescence. Observations by optical microscope showed that specific fan-like structures of NaDC were formed under the influence of AEM. Surface tension measurements supported a close interaction between Ca(2+) ions and anion aggregates of NaDC with 1:1 stoichiometric ratio. Due to its outstanding RTP behavior in NaDC-aggregates induced by Ca(2+), Pd-TCPP was used as a RTP probe to detect bovine serum albumin (BSA). A broad linear range from 1.0 × 10(-9) to 9.0 × 10(-7) g mL(-1) was obtained. Detection limit is 2.6 × 10(-11) g mL(-1), the relative standard deviation (n = 6) is 2.3% for 2.0 × 10(-9) g mL(-1) BSA. PMID:21438880

  10. Molecular Characterization of a Thermophilic and Salt- and Alkaline-Tolerant Xylanase from Planococcus sp. SL4, a Strain Isolated from the Sediment of a Soda Lake.

    PubMed

    Huang, Xiaoyun; Lin, Juan; Ye, Xiuyun; Wang, Guozeng

    2015-05-01

    To enrich the genetic resource of microbial xylanases with high activity and stability under alkaline conditions, a xylanase gene (xynSL4) was cloned from Planococcus sp. SL4, an alkaline xylanase-producing strain isolated from the sediment of soda lake Dabusu. Deduced XynSL4 consists of a putative signal peptide of 29 residues and a catalytic domain (30-380 residues) of glycosyl hydrolase family 10, and shares the highest identity of 77% with a hypothetical protein from Planomicrobium glaciei CHR43. Phylogenetic analysis indicated that deduced XynSL4 is closely related with thermophilic and alkaline xylanases from Geobacillus and Bacillus species. The gene xynSL4 was expressed heterologously in Escherichia coli and the recombinant enzyme showed some superior properties. Purified recombinant XynSL4 (rXynSL4) was highly active and stable over the neutral and alkaline pH range from 6 to 11, with maximum activity at pH 7 and more than 60% activity at pH 11. It had an apparent temperature optimum of 70°C and retained stable at this temperature in the presence of substrate. rXynSL4 was highly halotolerant, retaining more than 55% activity with 0.25-3.0 M NaCl and was stable at the concentration of NaCl up to 4M. The enzyme activity was significantly enhanced by β-mercaptoethanol and Ca(2+) but strongly inhibited by heavy-metal ions and SDS. This thermophilic and alkaline- and salt-tolerant enzyme has great potential for basic research and industrial applications. PMID:25381738

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. CO adsorption and kinetics on well-characterized Pd films on Pt(111) in alkaline solutions

    SciTech Connect

    Arenz, M.; Stamenkovic, V.; Wandelt, K.; Ross, P.N.; Markovic, N.M.

    2002-01-01

    The electrochemistry of CO on a bare Pt(111) electrode as well as a Pt(111) electrode modified with pseudomorphic thin palladium films has been studied in alkaline solution by means of Fourier transform infrared (FTIR) spectroscopy. First Pd films were prepared and well characterized in UHV and subsequently transferred into the electrochemical cell for the registration of the voltammetric profiles. The charge corresponding to the formation of underpotentially deposited hydrogen (H{sub upd}) on these Pt(111)-xPd surfaces was established in sulfuric acid solution as a function of x (0 {le} x {le} 1 Pd monolayer (ML)). All subsequent measurements were then performed on electrochemically deposited palladium films using the above H{sub upd}-charge vs. Pd coverage relationship to evaluate the amount of electrochemically deposited palladium. FTIR spectra for CO adsorbed on one monolayer and a submonolayer coverage are compared to those of the unmodified Pt(111) surface, all surfaces having identical 2D lattice structures. Infrared absorption bands of CO bound on either Pt(111) or Pt(111)-1ML Pd are clearly distinguished. Spectra of CO adsorbed on Pd submonolayers show characteristic features of both CO bound to Pt and to Pd, indicating that on Pt(111)-xPd surfaces there is no coupling between Pt-CO{sub ad} and Pd-CO{sub ad} molecules. The kinetics of CO oxidation on these surfaces is determined either by rotating disk electrode (RDE) measurements or by FTIR spectroscopy, monitoring the CO{sub 3}{sup 2-} production. The oxidation of CO{sub ad} on Pt(111) and on Pd modified platinum surfaces starts at the same potential, ca. at 0.2 V. The oxidation rate is, however, considerably lower on the Pt(111)-xPd surfaces than on the Pt(111) surface. The kinetics of CO oxidation appears to be determined by the nature of adsorbed hydroxyl anions (OH{sub ad}), which are more strongly (less active) adsorbed on the highly oxophilic Pd atoms.

  16. 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

  17. Early containment of high-alkaline solution simulating low-level radioactive waste stream in clay-bearing blended cement

    SciTech Connect

    Kruger, A.A.; Olson, R.A.; Tennis, P.D.

    1995-04-01

    Portland cement blended with fly ash and attapulgite clay was mixed with high-alkaline solution simulating low-level radioactive waste stream at a one-to-one weight ratio. Mixtures were adiabatically and isothermally cured at various temperatures and analyzed for phase composition, total alkalinity, pore solution chemistry, and transport properties as measured by impedance spectroscopy. Total alkalinity is characterized by two main drops. The early one corresponds to a rapid removal of phosphorous, aluminum, sodium, and to a lesser extent potassium solution. The second drop from about 10 h to 3 days is mainly associated with the removal of aluminum, silicon, and sodium. Thereafter, the total alkalinity continues descending, but at a lower rate. All pastes display a rapid flow loss that is attributed to an early precipitation of hydrated products. Hemicarbonate appears as early as one hour after mixing and is probably followed by apatite precipitation. However, the former is unstable and decomposes at a rate that is inversely related to the curing temperature. At high temperatures, zeolite appears at about 10 h after mixing. At 30 days, the stabilized crystalline composition Includes zeolite, apatite and other minor amounts of CaCO{sub 3}, quartz, and monosulfate Impedance spectra conform with the chemical and mineralogical data. The normalized conductivity of the pastes shows an early drop, which is followed by a main decrease from about 12 h to three days. At three days, the permeability of the cement-based waste as calculated by Katz-Thompson equation is over three orders of magnitude lower than that of ordinary portland cement paste. However, a further decrease in the calculated permeability is questionable. Chemical stabilization is favorable through incorporation of waste species into apatite and zeolite.

  18. Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

    DOEpatents

    Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

    1994-01-01

    A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

  19. Removal of dissolved actinides from alkaline solutions by the method of appearing reagents

    DOEpatents

    Krot, Nikolai N.; Charushnikova, Iraida A.

    1997-01-01

    A method of reducing the concentration of neptunium and plutonium from alkaline radwastes containing plutonium and neptunium values along with other transuranic values produced during the course of plutonium production. The OH.sup.- concentration of the alkaline radwaste is adjusted to between about 0.1M and about 4M. [UO.sub.2 (O.sub.2).sub.3 ].sup.4- ion is added to the radwastes in the presence of catalytic amounts of Cu.sup.+2, Co.sup.+2 or Fe.sup.+2 with heating to a temperature in excess of about 60.degree. C. or 85.degree. C., depending on the catalyst, to coprecipitate plutonium and neptunium from the radwaste. Thereafter, the coprecipitate is separated from the alkaline radwaste.

  20. 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

  1. Investigation on the co-precipitation of transuranium elements from alkaline solutions by the method of appearing reagents

    SciTech Connect

    Krot, N.; Shilov, V.; Bessonov, A.; Budantseva, N.; Charushnikova, I.; Perminov, V.; Astafurova, L.

    1996-06-06

    Highly alkaline radioactive waste solutions originating from production of plutonium for military purposes are stored in underground tanks at the U.S. Department of Energy Hanford Site. The purification of alkaline solutions from neptunium and plutonium is important in the treatment and disposal of these wastes. This report describes scoping tests with sodium hydroxide solutions, where precipitation techniques were investigated to perform the separation. Hydroxides of iron (III), manganese (II), cobalt (II, III), and chromium (III); manganese (IV) oxide, and sodium uranate were investigated as carriers. The report describes the optimum conditions that were identified to precipitate these carriers homogeneously throughout the solution by reductive, hydrolytic, or catalytic decomposition of alkali-soluble precursor compounds by a technique called the Method of Appearing Reagents. The coprecipitation of pentavalent and hexavalent neptunium and plutonium was investigated for the candidate agents under optimum conditions and is described in this report along with the following results. Plutonium coprecipitated well with all tested materials except manganese (IV) oxide. Neptunium only coprecipitated well with uranate. The report presents a hypothesis to explain these behaviors. Further tests with more complex solution matrices must be performed.

  2. 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.

  3. 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

  4. 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

  5. CHARACTERIZATION OF ACTINIDES IN SIMULATED ALKALINE TANK WASTE SLUDGES AND LEACH SOLUTIONS

    EPA Science Inventory

    The expectation that solubility of actinide ions will be low during alkaline sludge washing to remediate DOE's underground waste tanks is based on minimal experimental evidence, and the application of thermodynamic models of dubious validity to systems that may well be under kine...

  6. Effects of applied potential on the stress corrosion cracking behavior of 7003 aluminum alloy in acid and alkaline chloride solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-yan; Song, Ren-guo; Sun, Bin; Lu, Hai; Wang, Chao

    2016-07-01

    Potentiodynamic polarization tests and slow strain rate test (SSRT) in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking (SCC) behavior of 7003 aluminum alloy (AA7003) in acid and alkaline chloride solutions under various applied potentials ( E a). The results show that AA7003 is to a certain extent susceptible to SCC via anodic dissolution (AD) at open-circuit potential (OCP) and is highly susceptible to hydrogen embrittlement (HE) at high negative E a in the solutions with pH levels of 4 and 11. The susceptibility increases with negative shift in the potential when E a is less than -1000 mV vs. SCE. However, the susceptibility distinctly decreases because of the inhibition of AD when E a is equal to -1000 mV vs. SCE. In addition, the SCC susceptibility of AA7003 in the acid chloride solution is higher than that in the alkaline solution at each potential. Moreover, the effect of hydrogen on SCC increases with increasing hydrogen ion concentration.

  7. Reactivity of Tannic Acid with Common Corrosion Products and Its Influence on the Hydrolysis of Iron in Alkaline Solutions

    NASA Astrophysics Data System (ADS)

    Jaén, J. A.; Araúz, E. Y.; Iglesias, J.; Delgado, Y.

    2003-06-01

    To ascertain the role of tannic acid in the anticorrosive protection of steels, the reaction between 5% tannic acid aqueous solutions with lepidocrocite, goethite, superparamagnetic goethite, akaganeite, poorly crystalline maghemite, magnetite and hematite was studied using color changes, infrared and Mössbauer spectroscopy. After three months of interaction with lepidocrocite, the formation of an iron tannate complex was detected by its dark blue color and confirmed by infrared and Mössbauer analysis. Evidence for the chemical transformation was obtained for goethite in nanoparticles and poorly crystalline maghemite after reaction for six months. The other iron compounds do not transform to another oxide or phase upon treatment with the tannic acid solution. These results showed that lepidocrocite is the most reactive phase and that the size and degree of crystallinity have strong influence on the formation of the tannate complexes. The precipitation of iron phases from alkaline solutions of iron (II) sulfate heptahydrate containing different amount of tannic acid and potassium nitrate as oxidative agent was also studied. Mössbauer and infrared results show that in the absence of tannic acid some common rust components are obtained (viz. goethite, superparamagnetic goethite, maghemite and non-stoichiometric magnetite). The presence of 0.1% tannic acid in a low alkalinity solution results in the precipitation of iron oxyhydroxides and some iron tannates. Concentrations of 1% tannic acid are required for the formation of the tannates complexes as main reaction product.

  8. 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.

  9. Electrolytic recycling of a carbonate salt in a process with a dissolution of spent nuclear fuel in a strong alkaline carbonate media

    SciTech Connect

    Kwang-Wook Kim; In-Tae Kim; Seong-Min Kim; Yeon-Hwa Kim; Eil-Hee Lee; Kwang-Yong Jee

    2007-07-01

    A removal of only uranium from spent nuclear fuel with the concepts of a high proliferation-resistance and a minimal generation of waste is helpful for a spent fuel management in view of a volume reduction of the high level radioactive waste generated from the spent fuel treatment. That can be accomplished by a process using a selective oxidative dissolution of the spent fuel in a carbonate solution of high alkalinity. In this work, an electrolytic method for a de-carbonation and a recovery of CO{sub 2} for recycling the used carbonate solution contaminated with some impurity metal ions generated in such a process with a concept of zero-release of waste solution was studied. A carbonate solution generated from such a system was confirmed to be completely recycled within the system, while the impurity ions being separated from the carbonate solution. (authors)

  10. 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

  11. 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)

  12. 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

  13. 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.

  14. 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.

  15. Effects of Aging on PuO2∙xH2O Particle Size in Alkaline Solution

    SciTech Connect

    Delegard, Calvin H.

    2013-05-01

    Between 1944 and 1989, 54.5 metric tons of the United States’ weapons-grade plutonium and an additional 12.9 metric tons of fuel-grade plutonium were produced and separated from irradiated fuel at the Hanford Site. Acidic high-activity wastes containing around 600 kg of plutonium were made alkaline and discharged to underground storage tanks from separations, isolation, and recycle processes to yield average plutonium concentration of about 0.003 grams per liter (or ~0.0002 wt%) in the ~200 million liter tank waste volume. The plutonium is largely associated with low-solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g., iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO2∙xH2O, could undergo sufficient crystal growth through dissolution and reprecipitation in the alkaline tank waste to potentially become separable from neutron absorbing constituents by settling or sedimentation. Thermodynamic considerations and laboratory studies of systems chemically analogous to tank waste show that the plutonium formed in the alkaline tank waste by precipitation through neutralization from acid solution probably entered as 2–4-nm PuO2∙xH2O crystallite particles that, because of their low solubility and opposition from radiolytic processes, grow from that point at exceedingly slow rates, thus posing no risk of physical segregation.

  16. [Isolation and functional analysis of GsTIFY11b relevant to salt and alkaline stress from Glycine soja].

    PubMed

    Zhu, Dan; Bai, Xi; Zhu, Yan-Ming; Cai, Hua; Li, Yong; Ji, Wei; Chen, Chao; An, Lin; Zhu, Yi

    2012-02-01

    Using homologous cloning and RT-PCR technology, we isolated a novel TIFY family gene, GsTIFY11b, from Glycine soja L. G07256, a species that is tolerant to saline and alkaline environments. Phylogenetic analysis indicated that GsTIFY11b was closely related to AtTIFY11a with 56% similarity in amino acid identity. Protein sequence analysis showed that GsTIFY11b protein also had conserved TIFY domain, N-terminal domain, and a C-terminal Jas motif. Quantitative realtime PCR analysis indicated that the expression of GsTIFY11b was induced by both saline and alkaline stresses. Two homozygous GsTIFY11b over-expressing transgenic Arabidopsis lines were obtained. Phenotypic analysis of the transgenic and wild-type Arabidopsis indicated that over-expressing GsTIFY11b in Arabidopsis did not enhance plant tolerance to saline and alkaline stresses, whereas it showed an increased sensitivity to saline stress during seed germination and seedling development. Expression analysis of saline stress response marker genes in transgenic and wild-type plants under stress condition indicated that GsTIFY11b regulated the expression of RD29B, KIN1, and DREB. The transient expression of a GsTIFY11b-GFP fusion protein in onion epidermal cells showed that GsTIFY11b was localized to the nucleus, suggesting a role as a transcriptional regulator in the saline stress response pathway. PMID:22382065

  17. Evidence for the Formation of Benzacridine Derivatives in Alkaline-Treated Sunflower Meal and Model Solutions.

    PubMed

    Bongartz, Verena; Brandt, Lisa; Gehrmann, Mai Linh; Zimmermann, Benno F; Schulze-Kaysers, Nadine; Schieber, Andreas

    2016-01-01

    Sunflower extraction meal (SEM) is an economically interesting protein source. During alkaline extraction of proteins, the presence of chlorogenic acid (CQA) in the meal gives rise to the formation of o-quinones. Reactions with nucleophiles present in proteins can lead to green discoloration. Although such reactions have been known for a long time, there is a lack of information on the chemical nature of the reaction products. SEM and model systems consisting of amino acids and CQA were subjected to alkaline treatment and, for comparison, to oxidation of CQA by polyphenoloxidase (PPO). Several green trihydroxy benzacridine (TBA) derivatives were tentatively identified in all samples by UHPLC-DAD-MS/MS. Surprisingly, in alkaline-treated samples of particular amino acids as well as in SEM, the same six TBA isomers were detected. In contrast, the enzymatically oxidized samples resulted in only three TBA derivatives. Contrary to previous findings, neither peptide nor amino acid residues were attached to the resultant benzacridine core. The results indicate that the formation of TBA derivatives is caused by the reaction between CQA quinones and free NH2 groups. Further research is necessary to elucidate the structure of the addition products for a comprehensive evaluation of food and feed safety aspects. PMID:26784152

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Enhancement of the absorption of CO{sub 2} in alkaline buffer solutions: Joint action of two enhancers

    SciTech Connect

    Vazquez, G.; Chenlo, F.; Pereira, G.; Vazquez, P.

    1999-05-01

    The authors measured the absorption of CO{sub 2} in alkaline 0.5 M/0.5 M sodium carbonate/bicarbonate buffers containing either saccharose and sodium arsenite or saccharose and formaldehyde. Absorption enhancement increased upon increasing the concentration of either of the catalysts, but the joint action of the two was always less than the sum of their individual effects, the difference being a function of the acidities and concentrations of the catalysts and the pH of the carbonate/bicarbonate buffer solution

  4. 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

  5. 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

  6. 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.

  7. 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

  8. MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

    2013-03-21

    Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results. PMID:23480174

  9. 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

  10. 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.

  11. 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

  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. 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.

  14. 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.

  15. Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

    SciTech Connect

    Lassinantti Gualtieri, Magdalena

    2015-01-15

    Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for construction purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.

  16. Cysteine as a green corrosion inhibitor for Cu37Zn brass in neutral and weakly alkaline sulphate solutions.

    PubMed

    Radovanović, Milan B; Petrović, Marija B; Simonović, Ana T; Milić, Snežana M; Antonijević, Milan M

    2013-07-01

    The aim of this study was to investigate electrochemical properties of brass in neutral and weakly alkaline solutions in the presence of cysteine as a nontoxic and ecological corrosion inhibitor. Potentiodynamic measurements, open circuit potential measurements, as well as chronoamperometric measurements were the methods used during investigation of the inhibitory effect of cysteine on the corrosion behaviour of brass. Potentiodynamic measurements showed that cysteine behaves as a mixed-type inhibitor in the investigated media. Based on polarization curves for brass in a weakly alkaline solution of sodium sulphate at varying cysteine concentrations, an interaction occurs between Cu(+) ions and the inhibitor, resulting in the formation of a protective complex on the electrode surface. The results of chronoamperometric measurements confirm the results obtained by potentiodynamic measurements. Optical microphotography of the brass surface also confirms the formation of a protective film in the presence of a 1 × 10(-4) mol/dm(3) cysteine. Adsorption of cysteine on the brass surface proceeds according to the Langmuir adsorption isotherm. PMID:22836675

  17. 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.

  18. Influence of grain refinement on the electrochemical behavior of AISI 430 ferritic stainless steel in an alkaline solution

    NASA Astrophysics Data System (ADS)

    Fattah-alhosseini, A.; Vafaeian, S.

    2016-01-01

    In this paper, the effect of grain refinement on the electrochemical behavior of AISI 430 ferritic stainless steel in 0.1 M NaOH solution was investigated. Potentiodynamic polarization curves showed that fine-grained samples have less corrosion potential, higher corrosion current density, and less protective passive film in comparison to coarse-grained samples. Electrochemical impedance spectroscopy (EIS) analysis revealed that implementing the thermomechanical operation led to lower polarization resistance. Also, Mott-Schottky analysis revealed that the passive films on both fine-grained and coarse-grained samples behave as n-type and p-type semiconductors and the semiconductor character of the passive films did not change by grain refinement. Moreover, it was found that the calculated donor and acceptor densities increased with grain refinement. Thus, the presented results indicated that grain refinement weakens the corrosion and passivation behavior of AISI 430 stainless steel in this alkaline solution.

  19. Effects of solvent structure on the distribution of silicate anions in mixed aqueous/organic solutions of alkaline tetramethylammonium silicate

    SciTech Connect

    Hendricks, W.M.; Bell, A.T.; Radke, C.J. )

    1991-11-14

    Interest in the physical-chemical processes occurring during zeolite synthesis has stimulated the study of dissolved silicate oligomers in aqueous alkaline solution and their possible link to zeolite nucleation and crystal growth. Effects of solvent structure on the equilibrium distribution of silicate oligomers in mixed organic/aqueous solutions of tetramethylammonium hydroxide (TMAOH) have been investigated by using {sup 29}Si NMR spectroscopy. The results indicate that the presence of organic molecules leads to condensation of the silicates, particularly to double-ring structures. Equilibrium calculations indicate that the observed extent of silicate condensation exceeds what would be expected from mass action. The variety of organic solvents used allowed elucidation of structure effects due to the following: carbon chain length, carbon chain morphology, functional group, and placement of the functional group. The structural effects of organic solvents can be attributed to the ordering of water around the solvent molecules.

  20. 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.

  1. 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.

  2. 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.

  3. Alkaline battery, separator therefore

    NASA Technical Reports Server (NTRS)

    Schmidt, George F. (Inventor)

    1980-01-01

    An improved battery separator for alkaline battery cells has low resistance to electrolyte ion transfer and high resistance to electrode ion transfer. The separator is formed by applying an improved coating to an electrolyte absorber. The absorber, preferably, is a flexible, fibrous, and porous substrate that is resistant to strong alkali and oxidation. The coating composition includes an admixture of a polymeric binder, a hydrolyzable polymeric ester and inert fillers. The coating composition is substantially free of reactive fillers and plasticizers commonly employed as porosity promoting agents in separator coatings. When the separator is immersed in electrolyte, the polymeric ester of the film coating reacts with the electrolyte forming a salt and an alcohol. The alcohol goes into solution with the electrolyte while the salt imbibes electrolyte into the coating composition. When the salt is formed, it expands the polymeric chains of the binder to provide a film coating substantially permeable to electrolyte ion transfer but relatively impermeable to electrode ion transfer during use.

  4. Inefficacy of osmotic backwash induced by sodium chloride salt solution in controlling SWRO membrane fouling

    NASA Astrophysics Data System (ADS)

    Farooque, A. Mohammed; Al-Jeshi, Subhi; Saeed, Mohamed O.; Alreweli, Ali

    2014-12-01

    A study was conducted to evaluate the efficacy of osmotic backwash induced by high salt (NaCl) concentration solution on feed side of seawater reverse osmosis (SWRO) membranes, online and offline, in controlling membrane fouling and therefore minimizing/eliminating the need for chemical cleaning. SWRO membranes were deliberately fouled by feeding seawater from an open intake located on the Arabian Gulf Coast without dosing chemicals. The fouled membranes were subjected to offline cleaning with the salt solution of up to 25 % concentration. Despite the partial removal of foulants from the membrane surface, SWRO membrane performance could not be restored, indicating the ineffectiveness of osmotic backwash in aiding offline salt cleaning. Similarly, online osmotic backwash was found to be not only ineffective in removing foulants from membrane surfaces but actually increased the fouling rate, as indicated by faster fouling rates compared to other cases. Although the driving force required for the osmotic backwash existed, the generated back flow proved to be insufficient to detach foulants from membrane surfaces. During the study period, the average SWRO membrane flux was maintained between 19 and 23 LMH, whereas the average generated back flow flux by high salt concentration solution was only 11 LMH, which was not adequate to remove foulants from membrane surfaces. Moreover, it seems that the membrane configuration as well as inherent microstructure of SWRO membrane places certain constraints on the osmotic backwash process and renders osmotic backwash ineffective in tackling SWRO membrane fouling. Hence, chemical cleaning is essential to restore SWRO membrane performance whenever fouling occurs, and the use of highly concentrated salt solution does not have any significant benefit. Membrane autopsy revealed only an insignificant accumulation of biofouling layer despite the absence of disinfection. However, it was shown that culturable biofilm bacteria species

  5. Silica precipitation in acidic solutions: mechanism, pH effect, and salt effect.

    PubMed

    Gorrepati, Elizabeth A; Wongthahan, Pattanapong; Raha, Sasanka; Fogler, H Scott

    2010-07-01

    This study is the first to show that silica precipitation under very acidic conditions ([HCl] = 2-8 M) proceeds through two distinct steps. First, the monomeric form of silica is quickly depleted from solution as it polymerizes to form primary particles approximately 5 nm in diameter. Second, the primary particles formed then flocculate. A modified Smoluchowski equation that incorporates a geometric population balance accurately describes the exponential growth of silica flocs. Variation of the HCl concentration between 2 and 8 M further showed that polymerization to form primary particles and subsequent particle flocculation become exponentially faster with increasing acid concentration. The effect of salt was also studied by adding 1 M chloride salts to the solutions; it was found that salts accelerated both particle formation and growth rates in the order: AlCl(3) > CaCl(2) > MgCl(2) > NaCl > CsCl > no salt. It was also found that ionic strength, over cation identity, determines silica polymerization and particle flocculation rates. This research reveals that precipitation of silica products from acid dissolution of minerals can be studied apart from the mineral dissolution process. Thus, silica product precipitation from mineral acidization follows a two-step process--formation of 5 nm primary particles followed by particle flocculation--which becomes exponentially faster with increasing HCl concentration and with salts accelerating the process in the above order. This result has implications for any study of acid dissolution of aluminosilicate or silicate material. In particular, the findings are applicable to the process of acidizing oil-containing rock formations, a common practice of the petroleum industry where silica dissolution products encounter a low-pH, salty environment within the oil well. PMID:20536253

  6. Copper Catalyzed Sodium Tetraphenylborate, Triphenylborane, Diphenylborinic Acid and Phenylboronic Acid Decomposition Kinetic Studies in Aqueous Alkaline Solutions

    SciTech Connect

    Crawford, C.L.

    1999-03-15

    This work studied the kinetics of copper-catalyzed decomposition of tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid (NaTPB, 3PB, 2PB and 1PB, respectively) in aqueous alkaline solution over the temperature range of 25 to 70 degrees C. The statistically designed test matrices added copper sulfate to maximum concentrations of 10 mg/L. The relative rates of decomposition increase in the order of NaTPB < 1PB {tilde} 3PB < 2PB. Dependence of decomposition on the amount of added copper increases in the order of 3PB {tilde} 2PB < 1PB {tilde} NaTPB. Activation energies ranged from 82 to 143 kJ/mole over the temperature range studied. Final decomposition products predominately involved benzene and phenol. All 3PB, 2PB and 1PB intermediate phenylborate species proved relatively stable (< 8 percent decomposition over {tilde} 500 h) towards thermal hydrolysis in 1.5 M NaOH when contained in carbon-steel vessels sealed under air at ambient temperature (23 - 25 degrees C) with no added copper. Measurable (> 10-7 Mh-1) thermal hydrolysis of the phenylborate species occurs at 55 to 70 degrees C in alkaline (0.6-2.3 M OH-, 2-4.7 M Na+) solution with no added copper. The experiments suggest an important role for oxygen in copper-catalyzed phenylborate decomposition. NaTPB decomposes promptly under anoxic conditions while 3PB, 2PB and 1PB decompose faster in aerobic solutions. Benzene and phenol form as the predominant end-products from alkaline copper catalysis in static systems sealed under air. Both 2PB and 1PB decompose with near equal rates and quantitatively produce phenol under flowing air-purge conditions at 25 to 60 degrees C. Mechanisms for copper-catalyzed phenylborate decomposition likely involve a redox process giving loss of a phenyl group from the phenylborate with reduction of cupric ion, or dephenylation by reduced cuprous ion involving a phenylated copper intermediate.

  7. Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

    A process is described for stripping uranium for a pregnant organic extractant comprising an alkyl pyrophosphoric acid dissolved in a substantially water-immiscible organic diluent. The organic extractant contains tetravalent uranium and an alcohol or phenol modifier in a quantity sufficient to retain substantially all the unhydrolyzed alkyl pyrophosphoric acid in solution in the diluent during stripping. The process comprises adding an oxidizing agent to the organic extractant and thereby oxidizing the tetravalent uranium to the +6 state in the organic extractant, and contacting the organic extractant containing the uranium in the +6 state with a stripping solution comprising an aqueous solution of an alkali metal or ammonium carbonate or hydroxide thereby stripping uranium from the organic extractant into the stripping solution. The resulting barren organic extractant containing substantially all of the unhydrolyzed alkyl pyrophosphoric acid dissolved in the diluent is separated from the stripping solution containing the stripped uranium, the barren extractant being suitable for recycle.

  8. Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

    A process is described for stripping uranium from a pregnant organic extractant comprising an alkyl pyrophosphoric acid dissolved in a substantially water-immiscible organic diluent. The organic extractant contains tetravalent uranium and an alcohol or phenol modifier in a quantity sufficient to retain substantially all the unhydrolyzed alkyl pyrophosphoric acid in solution in the diluent during stripping. The process comprises adding an oxidizing agent to the organic extractant to and thereby oxidizing the tetravalent uranium to the +6 state in the organic extractant, and contacting the organic extractant containing the uranium in the +6 state with a stripping solution comprising an aqueous solution of an alkali metal or ammonium carbonate, nonsaturated in uranium. The uranium is stripped from, the organic extractant into the stripping solution, and the resulting barren organic extractant containing substantially all of the unhydrolyzed alkyl pyrophosphoric acid dissolved in the diluent is separated from the stripping solution containing the stripped uranium, the barren extractant being suitable for recycle.

  9. Reductive atmospheric acid leaching of spent alkaline batteries in H2SO4/Na2SO3 solutions

    NASA Astrophysics Data System (ADS)

    Morcali, Mehmet Hakan

    2015-07-01

    This work studies the optimum reductive leaching process for manganese and zinc recovery from spent alkaline battery paste. The effects of reducing agents, acid concentration, pulp density, reaction temperature, and leaching time on the dissolution of manganese and zinc were investigated in detail. Manganese dissolution by reductive acidic media is an intermediate-controlled process with an activation energy of 12.28 kJ·mol-1. After being leached, manganese and zinc were selectively precipitated with sodium hydroxide. The zinc was entirely converted into zincate (Zn(OH){4/2-}) ions and thus did not co-precipitate with manganese hydroxide during this treatment (2.0 M NaOH, 90 min, 200 r/min, pH > 13). After the manganese was removed from the solution, the Zn(OH){4/2-} was precipitated as zinc sulfate in the presence of sulfuric acid. The results indicated that this process could be effective in recovering manganese and zinc from alkaline batteries.

  10. Ice crystallization in ultrafine water-salt aerosols: nucleation, ice-solution equilibrium, and internal structure.

    PubMed

    Hudait, Arpa; Molinero, Valeria

    2014-06-01

    Atmospheric aerosols have a strong influence on Earth's climate. Elucidating the physical state and internal structure of atmospheric aqueous aerosols is essential to predict their gas and water uptake, and the locus and rate of atmospherically important heterogeneous reactions. Ultrafine aerosols with sizes between 3 and 15 nm have been detected in large numbers in the troposphere and tropopause. Nanoscopic aerosols arising from bubble bursting of natural and artificial seawater have been identified in laboratory and field experiments. The internal structure and phase state of these aerosols, however, cannot yet be determined in experiments. Here we use molecular simulations to investigate the phase behavior and internal structure of liquid, vitrified, and crystallized water-salt ultrafine aerosols with radii from 2.5 to 9.5 nm and with up to 10% moles of ions. We find that both ice crystallization and vitrification of the nanodroplets lead to demixing of pure water from the solutions. Vitrification of aqueous nanodroplets yields nanodomains of pure low-density amorphous ice in coexistence with vitrified solute rich aqueous glass. The melting temperature of ice in the aerosols decreases monotonically with an increase of solute fraction and decrease of radius. The simulations reveal that nucleation of ice occurs homogeneously at the subsurface of the water-salt nanoparticles. Subsequent ice growth yields phase-segregated, internally mixed, aerosols with two phases in equilibrium: a concentrated water-salt amorphous mixture and a spherical cap-like ice nanophase. The surface of the crystallized aerosols is heterogeneous, with ice and solution exposed to the vapor. Free energy calculations indicate that as the concentration of salt in the particles, the advance of the crystallization, or the size of the particles increase, the stability of the spherical cap structure increases with respect to the alternative structure in which a core of ice is fully surrounded by

  11. Aqueous Biphasic Systems Based on Salting-Out Polyethylene Glycol or Ionic Solutions: Strategies for Actinide or Fission Product Separations

    SciTech Connect

    Rogers, Robin D.; Gutowski, Keith E.; Griffin, Scott T.; Holbrey, John D.

    2004-03-29

    Aqueous biphasic systems can be formed by salting-out (with kosmotropic, waterstructuring salts) water soluble polymers (e.g., polyethylene glycol) or aqueous solutions of a wide range of hydrophilic ionic liquids based on imidazolium, pyridinium, phosphonium and ammonium cations. The use of these novel liquid/liquid biphases for separation of actinides or other fission products associated with nuclear wastes (e.g., pertechnetate salts) has been demonstrated and will be described in this presentation.

  12. An empirical correlation between the enthalpy of solution of aqueous salts and their ability to form hydrates

    SciTech Connect

    Pandelov, S.; Werhahn, Jasper C.; Pilles, Bert M.; Xantheas, Sotiris S.; Iglev, H.

    2010-09-30

    The ability of aqueous salt solutions to form hydrates by cooling them at ambient pressure is probed by infrared (IR) spectroscopy by examining the structure of the spectra in the hydrogen-bonding region (3,000 - 3,800 cm-1). A collection of 75 organic and inorganic salts in saturated solutions are examined. We have found a correlation between the enthalpy of solution of the salt and its ability to form a hydrate, namely that the salt’s enthalpy of solution is lower than the standard enthalpy of fusion of ice (6 kJ/mol). This observation can serve as an empirical rule that determines whether a salt will form a hydrate upon cooling from its aqueous solution.

  13. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    DOE PAGESBeta

    Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A.

    2014-12-04

    We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over themore » equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less

  14. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    SciTech Connect

    Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A.

    2014-12-04

    We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.

  15. RECENT STUDIES OF URANIUM AND PLUTONIUM CHEMISTRY IN ALKALINE RADIOACTIVE WASTE SOLUTIONS

    SciTech Connect

    King, W; Bill Wilmarth, B; David Hobbs, D; Tommy Edwards, T

    2006-06-13

    Solubility studies of uranium and plutonium in a caustic, radioactive Savannah River Site tank waste solution revealed the existence of uranium supersaturation in the as-received sample. Comparison of the results to predictions generated from previously published models for solubility in these waste types revealed that the U model poorly predicts solubility while Pu model predictions are quite consistent with experimental observations. Separate studies using simulated Savannah River Site evaporator feed solution revealed that the known formation of sodium aluminosilicate solids in waste evaporators can promote rapid precipitation of uranium from supersaturated solutions.

  16. Alkaline titrations of poly(dG-dC).poly(dG-dC): microemulsion versus solution behavior.

    PubMed

    Airoldi, Marta; Gennaro, Giuseppe; Giomini, Marcello; Giuliani, Anna Maria; Giustini, Mauro

    2007-06-01

    PolyGC was titrated with a strong base in the presence of increasing concentrations of NaCl (from 0.00 to 0.60M) either in water solution or with the polynucleotide solubilized in the aqueous core of reverse micelles, i.e., the cationic quaternary water-in-oil microemulsion CTAB/n-hexane/n-pentanol/water. The results for matched samples in the two media were compared. CD and UV spectroscopies and, for the solution experiments, pH measurements were used to follow the course of deprotonation. In both media the primary effect of the addition of base was denaturation of the polynucleotide, reversible by back-titration with a strong acid. In solution, the apparent pK(a) of the transition decreases with increasing the salt concentration and a roughly linear dependence of pK(a) on p[NaCl] has been found. A parallel monotonic decay with ionic strength has been found in solution for R(OH), defined as the number of hydroxyl ions required per monomeric unit of polyGC to reach half-transition. By contrast, in microemulsion, R(OH) has been found to be independent of the NaCl concentration (and 10 to 50 times lower than in solution). This result is proposed as an indirect evidence of the independence of pK(a) on the salt concentration in microemulsion, where the pH cannot be measured. A sort of buffering effect of the positive charges on the micellar wall and of their counter-ions on the ionic strength could well explain this discrepancy of behavior in the two media. PMID:17508778

  17. CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.

    PubMed

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-09-01

    This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char. PMID:23880130

  18. Cross-linked anion exchange membranes with pendent quaternary pyrrolidonium salts for alkaline polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Lan, Chunhua; Fang, Jun; Guan, Yingjie; Zhou, Huili; Zhao, Jinbao

    2015-11-01

    Novel anion-exchange membranes based on two kinds of pyrrolidonium type ionic liquids, N-methyl-N-vinyl-pyrrolidonium (NVMP) and N-ethyl-N-vinyl-pyrrolidonium (NVEP), have been synthesized via polymerization and crosslinking treatment, followed by membrane casting. The covalent cross-linked structures of these membranes are confirmed by FT-IR. The obtained membranes are also characterized in terms of water uptake, ion exchange capacity (IEC), ionic conductivity as well as thermal, dimensional and chemical stability. The membranes display hydroxide conductivity of above 10-2 S cm-1 at 25 °C. Excellent thermal stability with onset degradation temperature above 235 °C, good alkaline stability in 6 mol L-1 NaOH at 60 °C for 168 h and remarkable dimensional stability of the resulting membranes have been proved. H2/air single fuel cells employed membrane M3 and N3 show the open-circuit voltage (OCV) of 0.953 V and 0.933 V, and the maximum power density of 88.90 mW cm-2 and 81.90 mW cm-2 at the current density of 175 mA cm-2 and 200 mA cm-2 at 65 °C, respectively.

  19. Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution.

    PubMed

    Zhan, Yi; Du, Guojun; Yang, Shiliu; Xu, Chaohe; Lu, Meihua; Liu, Zhaolin; Lee, Jim Yang

    2015-06-17

    Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER-ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO). The good performance was attributed to the nanosizing of Co(OH)2 and the synergistic interaction between Co(OH)2 and N-rGO. A zinc-air cell assembled with a Co(OH)2-air electrode also showed a performance comparable to that of the state-of-the-art zinc-air cells. The combination of bifunctional activity and operational stability establishes Co(OH)2 as an effective low-cost alternative to the platinum group metal catalysts. PMID:25997179

  20. In situ generated highly active copper oxide catalysts for the oxygen evolution reaction at low overpotential in alkaline solutions.

    PubMed

    Liu, Xiang; Cui, Shengsheng; Qian, Manman; Sun, Zijun; Du, Pingwu

    2016-04-25

    Developing efficient water oxidation catalysts made up of earth-abundant elements has attracted much attention as a step toward for future clean energy production. Herein we report a simple one-step method to generate a low cost copper oxide catalyst film in situ from a copper(ii) ethylenediamine complex. The resulting catalyst has excellent activity toward the oxygen evolution reaction in alkaline solutions. A catalytic current density of 1.0 mA cm(-2) and 10 mA cm(-2) for the catalyst film requires the overpotentials of only ∼370 mV and ∼475 mV in 1.0 M KOH, respectively. This catalytic performance shows that the new catalyst is one of the best Cu-based heterogeneous OER catalysts to date. PMID:27020763

  1. Facile synthesis of PbTe nanoparticles and thin films in alkaline aqueous solution at room temperature

    SciTech Connect

    Wang, Y.Y.; Cai, K.F.; Yao, X.

    2009-12-15

    A novel, simple, and cost-effective route to PbTe nanoparticles and films is reported in this paper. The PbTe nanoparticles and films are fabricated by a chemical bath method, at room temperature and ambient pressure, using conventional chemicals as starting materials. The average grain size of the nanoparticles collected at the bottom of the bath is {approx}25 nm. The film deposited on glass substrate is dense, smooth, and uniform with silver gray metallic luster. The film exhibits p-type conduction and has a moderate Seebeck coefficient value ({approx}147 muV K{sup -1}) and low electrical conductivity ({approx}0.017 S cm{sup -1}). The formation mechanism of the PbTe nanoparticles and films is proposed. - PbTe nanoparticles and films were fabricated at room temperature and ambient pressure in an alkaline aqueous solution by a chemical bath method.

  2. USING MINED SPACE FOR LONG-TERM RETENTION OF NONRADIOACTIVE HAZARDOUS WASTE. VOLUME 2. SOLUTION MINED SALT CAVERNS

    EPA Science Inventory

    This two-volume report assesses the current status of using mined-space for long-term retention of nonradioactive hazardous waste. Volume 2 expands the definition of mined space to include that created by solution mining of salt. This report examines the extent of salt deposits i...

  3. Molecular Thermodynamics for Swelling of a Mesoscopic Ionomer Gelin 1:1 Salt Solutions

    SciTech Connect

    Victorov, Alexey; Radke, Clayton; Prausnitz,John

    2005-06-15

    For a microphase-separated diblock copolymer ionic gel swollen in salt solution, a molecular-thermodynamic model is based on the self-consistent field theory in the limit of strongly segregated copolymer subchains. The geometry of microdomains is described using the Milner generic wedge construction neglecting the packing frustration. Thermodynamic functions are expressed analytically for gels of lamellar, bicontinuous, cylindrical and spherical morphologies. Molecules are characterized by chain composition, length, rigidity, degree of ionization, and by effective polymer-polymer and polymer-solvent interaction parameters. The model predicts equilibrium solvent uptakes and the equilibrium microdomain spacing for gels swollen in salt solutions. Results are given for details of the gel structure: distribution of mobile ions and polymer segments, and the electric potential across microdomains. Apart from effects obtained by coupling classical Flory-Rehner theory with Donnan equilibria, viz., increased swelling with polyelectrolyte charge and shrinking of gel upon addition of salt, the model predicts the effects of microphase morphology on swelling.

  4. Molecular dynamics study of salt–solution interface: Solubility and surface charge of salt in water

    SciTech Connect

    Kobayashi, Kazuya; Liang, Yunfeng E-mail: matsuoka@earth.kumst.kyoto-u.ac.jp; Matsuoka, Toshifumi E-mail: matsuoka@earth.kumst.kyoto-u.ac.jp; Sakka, Tetsuo

    2014-04-14

    The NaCl salt–solution interface often serves as an example of an uncharged surface. However, recent laser-Doppler electrophoresis has shown some evidence that the NaCl crystal is positively charged in its saturated solution. Using molecular dynamics (MD) simulations, we have investigated the NaCl salt–solution interface system, and calculated the solubility of the salt using the direct method and free energy calculations, which are kinetic and thermodynamic approaches, respectively. The direct method calculation uses a salt–solution combined system. When the system is equilibrated, the concentration in the solution area is the solubility. In the free energy calculation, we separately calculate the chemical potential of NaCl in two systems, the solid and the solution, using thermodynamic integration with MD simulations. When the chemical potential of NaCl in the solution phase is equal to the chemical potential of the solid phase, the concentration of the solution system is the solubility. The advantage of using two different methods is that the computational methods can be mutually verified. We found that a relatively good estimate of the solubility of the system can be obtained through comparison of the two methods. Furthermore, we found using microsecond time-scale MD simulations that the positively charged NaCl surface was induced by a combination of a sodium-rich surface and the orientation of the interfacial water molecules.

  5. Protein-protein and protein-salt interactions in aqueous protein solutions containing concentrated electrolytes

    SciTech Connect

    Curtis, R.A.; Blanch, H.W.; Prausnitz, J.M.

    1998-01-05

    Protein-protein and protein-salt interactions have been obtained for ovalbumin in solutions of ammonium sulfate and for lysozyme in solutions of ammonium sulfate, sodium chloride, potassium isothiocyanate, and potassium chloride. The two-body interactions between ovalbumin molecules in concentrated ammonium-sulfate solutions can be described by the DLVO potentials plus a potential that accounts for the decrease in free volume available to the protein due to the presence of the salt ions. The interaction between ovalbumin and ammonium sulfate is unfavorable, reflecting the kosmotropic nature of sulfate anions. Lysozyme-lysozyme interactions cannot be described by the above potentials because anion binding to lysozyme alters these interactions. Lysozyme-isothiocyanate complexes are strongly attractive due to electrostatic interactions resulting from bridging by the isothiocyanate ion. Lysozyme-lysozyme interactions in sulfate solutions are more repulsive than expected, possibly resulting from a larger excluded volume of a lysozyme-sulfate bound complex or perhaps, hydration forces between the lysozyme-sulfate complexes.

  6. A chronoamperometric screen printed carbon biosensor based on alkaline phosphatase inhibition for W(IV) determination in water, using 2-phospho-L-ascorbic acid trisodium salt as a substrate.

    PubMed

    Alvarado-Gámez, Ana Lorena; Alonso-Lomillo, María Asunción; Domínguez-Renedo, Olga; Arcos-Martínez, María Julia

    2015-01-01

    This paper presents a chronoamperometric method to determine tungsten in water using screen-printed carbon electrodes modified with gold nanoparticles and cross linked alkaline phosphatase immobilized in the working electrode. Enzymatic activity over 2-phospho-l-ascorbic acid trisodium salt, used as substrate, was affected by tungsten ions, which resulted in a decrease of chronoamperometric current, when a potential of 200 mV was applied on 10 mM of substrate in a Tris HCl buffer pH 8.00 and 0.36 M of KCl. Calibration curves for the electrochemical method validation, give a reproducibility of 5.2% (n = 3), a repeatability of 9.4% (n = 3) and a detection limit of 0.29 ± 0.01 µM. Enriched tap water, purified laboratory water and bottled drinking water, with a certified tungsten reference solution traceable to NIST, gave a recovery of 97.1%, 99.1% and 99.1% respectively (n = 4 in each case) and a dynamic range from 0.6 to 30 µM. This study was performed by means of a Lineweaver-Burk plot, showing a mixed kinetic inhibition. PMID:25621602

  7. A Chronoamperometric Screen Printed Carbon Biosensor Based on Alkaline Phosphatase Inhibition for W(VI) Determination in Water, Using 2-Phospho-l-Ascorbic Acid Trisodium Salt as a Substrate

    PubMed Central

    Alvarado-Gámez, Ana Lorena; Alonso-Lomillo, María Asunción; Domínguez-Renedo, Olga; Arcos-Martínez, María Julia

    2015-01-01

    This paper presents a chronoamperometric method to determine tungsten in water using screen-printed carbon electrodes modified with gold nanoparticles and cross linked alkaline phosphatase immobilized in the working electrode. Enzymatic activity over 2-phospho-l-ascorbic acid trisodium salt, used as substrate, was affected by tungsten ions, which resulted in a decrease of chronoamperometric current, when a potential of 200 mV was applied on 10 mM of substrate in a Tris HCl buffer pH 8.00 and 0.36 M of KCl. Calibration curves for the electrochemical method validation, give a reproducibility of 5.2% (n = 3), a repeatability of 9.4% (n = 3) and a detection limit of 0.29 ± 0.01 μM. Enriched tap water, purified laboratory water and bottled drinking water, with a certified tungsten reference solution traceable to NIST, gave a recovery of 97.1%, 99.1% and 99.1% respectively (n = 4 in each case) and a dynamic range from 0.6 to 30 μM. This study was performed by means of a Lineweaver–Burk plot, showing a mixed kinetic inhibition. PMID:25621602

  8. On the decay of the ozonide radical in aqueous alkaline solutions

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, P. K.; Saini, R. D.

    1982-11-01

    In flash photolysis of an oxygenated aqueous potassium persulphate solution at pH 12.5 the decay of the ozonide radical has been found to follow 3/2 order kinetics which has been explained by reactions O -3 + O - ⇌ 2 O -2 and O -3 + HO 2 → 2 O 2 + OH -

  9. Spray washing carcasses with alkaline solutions of lauric acid to reduce bacterial contamination

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The ability of lauric acid (LA)-potassium hydroxide (KOH) solutions to reduce carcass bacterial contamination was examined. Skin of carcasses was inoculated with a cecal paste containing antibiotic resistant strains of Escherichia coli, Salmonella Typhimirum, and Campylobacter coli. In one trial, in...

  10. Alkaline iron(III) reduction by a novel alkaliphilic, halotolerant, Bacillus sp. isolated from salt flat sediments of Soap Lake.

    PubMed

    Pollock, Jarrod; Weber, Karrie A; Lack, Joe; Achenbach, Laurie A; Mormile, Melanie R; Coates, John D

    2007-12-01

    A halotolerant, alkaliphilic dissimilatory Fe(III)-reducing bacterium, strain SFB, was isolated from salt flat sediments collected from Soap Lake, WA. 16S ribosomal ribonucleic acid gene sequence analysis identified strain SFB as a novel Bacillus sp. most similar to Bacillus agaradhaerens (96.7% similarity). Strain SFB, a fermentative, facultative anaerobe, fermented various hexoses including glucose and fructose. The fructose fermentation products were lactate, acetate, and formate. Under fructose-fermenting conditions in a medium amended with Fe(III), Fe(II) accumulated concomitant with a stoichiometric decrease in lactate and an increase in acetate and CO(2). Strain SFB was also capable of respiratory Fe(III) reduction with some unidentified component(s) of Luria broth as an electron donor. In addition to Fe(III), strain SFB could also utilize nitrate, fumarate, or O(2) as alternative electron acceptors. Optimum growth was observed at 30 degrees C and pH 9. Although the optimal salinity for growth was 0%, strain SFB could grow in a medium with up to 15% NaCl by mass. These studies describe a novel alkaliphilic, halotolerant organism capable of dissimilatory Fe(III) reduction under extreme conditions and demonstrate that Bacillus species can contribute to the microbial reduction of Fe(III) in environments at elevated pH and salinity, such as soda lakes. PMID:17943280

  11. Ionic conductivity of dual-phase polymer electrolytes comprised of NBR/SBR latex films swollen with lithium salt solutions

    SciTech Connect

    Matsumoto, Morihiko; Ichino, Toshihiro; Rutt, J.S.; Nishi, Shiro . NTT Interdisciplinary Research Lab.)

    1994-08-01

    Dual-phase polymer electrolytes (DPE) with high ionic conductivity and good mechanical strength were prepared by swelling poly(acrylonitrile-co-butadiene) rubber (NBR) and poly(styrene-co-butadiene) rubber (SBR) mixed latex films with lithium salt solutions (e.g., 1M LiClO[sub 4]/[gamma]-butyrolactone). The latex films retain particle morphology in the solid state. The NBR phase (formed from fused NBR latex particles) is polar and is impregnated selectively with polar lithium salt solutions, yielding ion-conductive channels, whereas the SBR phase (formed from fused SBR latex particles) is nonpolar and is not impregnated, providing a mechanically supportive matrix. The ionic conductivity of the DPE increased dramatically with increasing content of lithium salt solution, and higher amounts of solution were imbibed with increasing content of NBR relative to SBR. Several factors which affect the ionic conductivity of this system were examined, and the highest ionic conductivity (>10[sup [minus]3] S/cm) was obtained when either an NBR/SBR 70/30 (w/w) or a 50/50 (w/w) latex film was saturated with 1M LiClO[sub 4]/[gamma]-BL solution or 1M LiClO[sub 4]/[gamma]-BL/DME solution. Ion-conductive behavior changed critically with increasing lithium salt solution uptake. At low levels of lithium salt solution uptake, evidence suggested that ionic conductivity of the absorbed lithium salt solution was strongly influenced by the presence of the NBR in the ion-conductive channel, but at higher levels, the effects of the NBR were reduced and free'' lithium salt solution was present.

  12. Association-dissociation and denaturation behaviour of an oligomeric seed protein alpha-globulin of Sesamum indicum L. in acid and alkaline solutions.

    PubMed

    Prakash, V; Nandi, P K

    1977-01-01

    The association-dissociation and denaturation behaviour of the major protein fraction, alpha-globulin of sesame seed (Sesamum indicum L.), in acid and alkaline solutions in the ranges of pH 4.2-1.5 and pH 7-12 have been studied. The results of gel filtration, fluorescence and viscosity measurements indicate dissociation and denaturation of the protein up to pH approximately 3. The difference spectrum in this region arises from a combination of dissociation, denaturation and charge effect on the chromophore. In still stronger acid solution, reassociation of the dissociated fraction takes place by hydrophobic interaction. In alkaline solution dissociation takes place around pH 8, and above pH 10 dissociation and denaturation proceed simultaneously as has been evidenced by sedimentation, fluorescence, spectral change, optical rotation and viscosity measurements. The phenolic group (pKInt=10.6) in the protein is abnormal and denaturation in alkaline solution is irreversible. Above pH 11.5 further dissociation of the protein takes place. Characteristic pH values of transition from 10.6-10.8 indicate that the transition of the protein involves a single step in alkaline solution. PMID:19367

  13. RESULTS OF ANALYSES OF MACROBATCH 3 DECONTAMINATED SALT SOLUTION (DSS) COALESCER AND PRE-FILTERS

    SciTech Connect

    Peters, T.; Fondeur, F.; Fink, S.

    2012-06-13

    SRNL analyzed the pre-filter and Decontamination Salt Solution (DSS) coalescer from MCU by several analytical methods. The results of these analyses indicate that overall there is light to moderate solids fouling of both the coalescer and pre-filter elements. The majority of the solids contain aluminum, sodium, silicon, and titanium, in oxide and/or hydroxide forms that we have noted before. The titanium is presumably precipitated from leached, dissolved monosodium titanate (MST) or fines from MST at ARP, and the quantity we find is significantly greater than in the past. A parallel report discusses potential causes for the increased leaching rate of MST, showing that increases in free hydroxide concentration of the feed solutions and of chemical cleaning solutions lead to faster leaching of titanium.

  14. Iron salts in solid state and in frozen solutions as dosimeters for low irradiation temperatures.

    PubMed

    Martínez, T; Lartigue, J; Ramos-Bernal, S; Ramos, A; Mosqueira, G F; Negrón-Mendoza, A

    2005-01-01

    The aim of this work is to study the irradiation of iron salts in solid state (heptahydrated ferrous sulfate) and in frozen acid solutions. The study is focused on finding their possible use as dosimeters for low temperature irradiations and high doses. The analysis of the samples was made by UV-visible and Mössbauer spectroscopies. The output signal was linear from 0 to 10 MGy for the solid samples, and 0-600 Gy for the frozen solutions. The obtained data is reproducible and easy to handle. For these reasons, heptahydrate iron sulfate is a suitable dosimeter for low temperature and high irradiation doses, in solid state, and in frozen solution. PMID:15985374

  15. Faraday Discussion 160 Introductory Lecture: Interpreting and Predicting Hofmeister Salt Ion and Solute Effects on Biopolymer and Model Processes Using the Solute Partitioning Model

    PubMed Central

    Record, M. Thomas; Guinn, Emily; Pegram, Laurel; Capp, Michael

    2013-01-01

    Understanding how Hofmeister salt ions and other solutes interact with proteins, nucleic acids, other biopolymers and water and thereby affect protein and nucleic acid processes as well as model processes (e.g solubility of model compounds) in aqueous solution is a longstanding goal of biophysical research. Empirical Hofmeister salt and solute “m-values” (derivatives of the observed standard free energy change for a model or biopolymer process with respect to solute or salt concentration m3) are equal to differences in chemical potential derivatives: m-value = Δ(dμ2/dm3) = Δμ23 which quantify the preferential interactions of the solute or salt with the surface of the biopolymer or model system (component 2) exposed or buried in the process. Using the SPM, we dissect μ23 values for interactions of a solute or Hofmeister salt with a set of model compounds displaying the key functional groups of biopolymers to obtain interaction potentials (called α-values) that quantify the interaction of the solute or salt per unit area of each functional group or type of surface. Interpreted using the SPM, these α-values provide quantitative information about both the hydration of functional groups and the competitive interaction of water and the solute or salt with functional groups. The analysis corroborates and quantifies previous proposals that the Hofmeister anion and cation series for biopolymer processes are determined by ion-specific, mostly unfavorable interactions with hydrocarbon surfaces; the balance between these unfavorable nonpolar interactions and often-favorable interactions of ions with polar functional groups determine the series null points. The placement of urea and glycine betaine (GB) at opposite ends of the corresponding series of nonelectrolytes results from the favorable interactions of urea, and unfavorable interactions of GB, with many (but not all) biopolymer functional groups. Interaction potentials and local-bulk partition coefficients

  16. The Role of Oxygen in the Copper-Catalyzed Decomposition of Phenylborates in Aqueous Alkaline Solutions

    SciTech Connect

    Hyder, M.L.

    1997-03-17

    The effect of oxygen on the copper-catalyzed hydrolysis of phenyl borates containing from one to four phenyl groups was studied in 1 M aqueous sodium hydroxide solution at 59 degrees C. The results are tentatively explained if the effective catalyst for each of the reactions is either cupric or cuprous ion, with the latter being present in significant concentration only in the absence of air.

  17. Decontamination of Dissolved Salt Solution from Tank 19F Using Duolite CS-100 and Amberlite IRC-718 Resins

    SciTech Connect

    Lee, L.M.

    2001-10-17

    In this study actual Savannah River Plant liquid supernate solutions were processed to refine and verify these synthetic solution studies. The main objectives were: (1) confirm high decontamination factors (DFs) for cesium-137 and strontium-90 using Duolite CS-100 and Amberlite IRC-718 ion exchange resins, (2) obtain DFs for other minor radioactive isotopes such as plutonium, technetium and ruthenium, (3) provide ion exchange elutriant containing cesium-137, strontium-90 and other radioactive isotopes for ''hot'' melter studies, (4) determine the quality of the decontaminated salt solution, and (5) provide actual decontaminated salt solution for saltcrete development programs.

  18. Evaluating Battery-like Reactions to Harvest Energy from Salinity Differences using Ammonium Bicarbonate Salt Solutions.

    PubMed

    Kim, Taeyoung; Rahimi, Mohammad; Logan, Bruce E; Gorski, Christopher A

    2016-05-10

    Mixing entropy batteries (MEBs) are a new approach to generate electricity from salinity differences between two aqueous solutions. To date, MEBs have only been prepared from solutions containing chloride salts, owing to their relevance in natural salinity gradients created from seawater and freshwater. We hypothesized that MEBs could capture energy using ammonium bicarbonate (AmB), a thermolytic salt that can be used to convert waste heat into salinity gradients. We examined six battery electrode materials. Several of the electrodes were unstable in AmB solutions or failed to produce expected voltages. Of the electrode materials tested, a cell containing a manganese oxide electrode and a metallic lead electrode produced the highest power density (6.3 mW m(-2) ). However, this power density is still low relative to previously reported NaCl-based MEBs and heat recovery systems. This proof-of-concept study demonstrated that MEBs could indeed be used to generate electricity from AmB salinity gradients. PMID:27030080

  19. Equilibrium, kinetic and thermodynamic study of cesium adsorption onto nanocrystalline mordenite from high-salt solution.

    PubMed

    Lee, Keun-Young; Park, Minsung; Kim, Jimin; Oh, Maengkyo; Lee, Eil-Hee; Kim, Kwang-Wook; Chung, Dong-Yong; Moon, Jei-Kwon

    2016-05-01

    In this study, the equilibrium, kinetics and thermodynamics of cesium adsorption by nanocrystalline mordenite were investigated under cesium contamination with high-salt solution, simulating the case of an operation and decommissioning of nuclear facilities or an accident during the processes. The adsorption rate constants were determined using a pseudo second-order kinetic model. The kinetic results strongly demonstrated that the cesium adsorption rate of nano mordenite is extremely fast, even in a high-salt solution, and much faster than that of micro mordenite. In the equilibrium study, the Langmuir isotherm model fit the cesium adsorption data of nano mordenite better than the Freundlich model, which suggests that cesium adsorption onto nano mordenite is a monolayer homogeneous adsorption process. The obtained thermodynamic parameters indicated that the adsorption involved a very stable chemical reaction. In particular, the combination of rapid particle dispersion and rapid cesium adsorption of the nano mordenite in the solution resulted in a rapid and effective process for cesium removal without stirring, which may offer great advantages for low energy consumption and simple operation. PMID:26683820

  20. Thermodynamic Model for ThO2(am) Solubility in Alkaline Silica Solutions

    SciTech Connect

    Rai, D; Yui, Mikazu; Moore, Dean A.; Lumetta, Gregg J.; Rosso, Kevin M.; Xia, Yuanxian; Felmy, Andrew R.; Skomurski, Frances N.

    2008-10-11

    literature, agreed closely with the extensive experimental data and showed that under alkaline conditions aqueous Si makes very strong complexes with Th.

  1. Cosolute effect on crystallization of two dinucleotide complexes of bovine seminal ribonuclease from concentrated salt solutions

    NASA Astrophysics Data System (ADS)

    Sica, Filomena; Adinolfi, Salvatore; Vitagliano, Luigi; Zagari, Adriana; Capasso, Sante; Mazzarella, Lelio

    1996-10-01

    Two complexes of bovine seminal ribonuclease with dinucleotides, uridylyl(2'-5')adenosine (UpA) and 2'-deoxycytidylyl(3'-5')-2'-deoxyadenosine (d(CpA)), were crystallized under unusual conditions involving a liquid-liquid phase separation. This phenomenon was induced by adding small aliquots of organic cosolutes to highly concentrated ammonium sulfate solutions. The liquid-liquid interface acts as a source of nucleation centers for growth of large crystals. Among the cosolutes tested in these salt-mediated crystallizations, 2-methyl-2,4-pentanediol was found to be the most efficient.

  2. Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

    PubMed Central

    2013-01-01

    Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO. PMID:24059434

  3. Super-absorbency and phase transition of gels in physiological salt solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Yong-Qing; Tanaka, Toyoichi; Shibayama, Mitsuhiro

    1992-11-01

    IONIC gels with the ability to absorb many times their dry weight of water have found widespread use as absorbents in medical, chemical and agricultural applications1. The dramatic swelling power of these super-absorbent gels results from both the electrostatic repulsion between the charges on the polymer chains, and the osmotic pressure of the counter-ions2. In salt solutions such as saline, urine or blood, however, excess Na+ and Cl- ions screen the polymer charges and eliminate the osmotic imbalance, effectively changing the properties of the material to that of a non-ionic gel3: this greatly diminishes the swelling power, and hence the utility of these materials under physiological conditions. Here we report the development of a system combining a non-ionic gel with ionized surfactants, which shows super-absorbent behaviour even in the presence of salt. In water, the hydrophobic gel facilitates the formation of spherical surfactant micelles, which mimic the charged sites of an ionic gel. As the salt concentration is increased, the micelles become rod-like, maintaining the electrostatic repulsion along the polymer chains and thereby preserving the swelling power of the gel.

  4. The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: II. Vapor-liquid water equilibration of mixed salt solutions from 50 to 100°C and geochemical implications

    NASA Astrophysics Data System (ADS)

    Horita, Juske; Cole, David R.; Wesolowski, David J.

    1993-10-01

    The difference between oxygen and hydrogen isotope activity and composition ratios of water in mixed salt solutions in the system Na-K-Mg-Ca-Cl-SO 4-H 2O was determined by means of a vaporliquid water equilibration method over the temperature range of 50 to 100°C. The observed isotope salt effects in complex mixed salt solutions to very high ionic strengths agree quantitatively with calculations based on the assumption of a simple additive property of the isotope salt effects of the individual salts in the solutions. SOFER and GAT (1972, 1975) and HORITA and GAT (1989) also observed that this simple mixing rule applies to synthetic and natural chloride-mixed salt solutions at room temperature. Equations to convert between the isotope activity and composition scales for brines and fractionation factors between brines and other substances are presented. For most geochemical interactions between brines and other phases (vapor, gases, minerals) such as evaporation/boiling, mineral precipitation, and mineral/rock alteration, the isotope activity scale should be used. The isotope composition scale, on the other hand, is most useful for studies of mixing of different brines and formation of brines by mineral dissolution. Misusage of the two isotopic scales of brines will, and probably in the literature has, lead to incorrect conclusions in many isotopic studies of brine-dominated systems (origin of brines, temperature of mineral formation, isotope ratios of fossil fluids).

  5. Preparation, stability, and structural characterization of plutonium(VII) in alkaline aqueous solution.

    PubMed

    Antonio, Mark R; Williams, C W; Sullivan, James A; Skanthakumar, S; Hu, Yung-Jin; Soderholm, L

    2012-05-01

    A freshly prepared solution of Pu(VI) in 2 M NaOH was oxidized to Pu(VII), via ozonolysis, while simultaneously collecting X-ray absorption spectra. Analyses of the XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) data, acquired throughout the in situ experiments, show a dioxo coordination environment for Pu(VI), PuO(2)(2+), typical for it and the hexavalent actinyl species of U and Np, and its evolution into a tetraoxo-coordination environment for Pu(VII), PuO(4)(-), like that known for Np(VII). The EXAFS data provide average Pu-O distances of 1.79(1) and 1.88(1) Å, respectively. The second coordination shells, also fit as O atoms, provide Pu-O distances of 2.29-2.32 Å that are independent of the Pu oxidation state. The coordination numbers for the distant O atoms in sums with those for the nearest O atoms are consistent with 6-O environments for both Pu(VI) and Pu(VII) ions in accordance with their previously proposed speciation as [Pu(VI)O(2)(OH)(4)](2-) and [Pu(VII)O(4)(OH)(2)](3-), respectively. This solution speciation accounts precisely for the Pu(VI) and Pu(VII) coordination environments reported in various solid state structures. The Pu(VII) tetraoxo-dihydroxo anion was found to have a half-life of 3.7 h. Its instability is attributed to spontaneous reduction to Pu(VI) and not to a measurable extent of disproportionation. We found no direct evidence for Pu(VIII) in the X-ray data and, furthermore, the stoichiometry of the oxidation of Cr(III) by Pu is consistent with that expected for a valence-pure Pu(VII) preparation by ozonation and, in turn, stoichiometrically equivalent to the established Np(VII)/Cr(III) redox reaction. PMID:22524489

  6. Evaluation of poly (aspartic acid sodium salt) as a draw solute for forward osmosis.

    PubMed

    Gwak, Gimun; Jung, Bokyung; Han, Sungsoo; Hong, Seungkwan

    2015-09-01

    Poly (aspartic acid sodium salt) (PAspNa) was evaluated for its potential as a novel draw solute in forward osmosis (FO). The inherent advantages of PAspNa, such as good water solubility, high osmotic pressure, and nontoxicity, were first examined through a series of physicochemical analyses and atomic-scale molecular dynamics simulations. Then, lab-scale FO tests were performed to evaluate its suitability in practical processes. Compared to other conventional inorganic solutes, PAspNa showed comparable water flux but significantly lower reverse solute flux, demonstrating its suitability as a draw solute. Moreover, fouling experiments using synthetic wastewater as a feed solution demonstrated that PAspNa reversely flowed to the feed side reduced inorganic scaling on the membrane active layer. The recyclability of PAspNa was studied using both nanofiltration (NF) and membrane distillation (MD) processes, and the results exhibited its ease of recovery. This research reported the feasibility and applicability of FO-NF or FO-MD processes using PAspNa for wastewater reclamation and brackish water desalination. PMID:26005789

  7. Composite Properties of Polyimide Resins Made From "Salt-Like" Solution Precursors

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J.; Weiser, Erik S.; SaintClair, Terry L.; Echigo, Yoshiaki; Kaneshiro, Hisayasu

    1997-01-01

    Recent work in high temperature materials at NASA Langley Research Center (LaRC (trademark)) have led to the development of new polyimide resin systems with very attractive properties. The majority of the work done with these resin systems has concentrated on determining engineering mechanical properties of composites prepared from a poly(amide acid) precursor. Three NASA Langley-developed polyimide matrix resins, LaRC (trademark) -IA, LaRC (trademark) -IAX, and LaRC (trademark) -8515, were produced via a salt-like process developed by Unitika Ltd. The 'salt-like' solutions (sixty-five percent 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. Mechanical properties are presented for these three intermediate modulus carbon fiber/polyimide matrix composites and compared to existing data on the same polyimide resin systems and IM7 carbon fiber manufactured via poly(amide acid) solutions (thirty-five percent solids in NMP). This work studies the effects of varying the synthetic route on the processing and mechanical properties of polyimide composites.

  8. Comparison of peak shape in hydrophilic interaction chromatography using acidic salt buffers and simple acid solutions.

    PubMed

    Heaton, James C; Russell, Joseph J; Underwood, Tim; Boughtflower, Robert; McCalley, David V

    2014-06-20

    The retention and peak shape of neutral, basic and acidic solutes was studied on hydrophilic interaction chromatography (HILIC) stationary phases that showed both strong and weak ionic retention characteristics, using aqueous-acetonitrile mobile phases containing either formic acid (FA), ammonium formate (AF) or phosphoric acid (PA). The effect of organic solvent concentration on the results was also studied. Peak shape was good for neutrals under most mobile phase conditions. However, peak shapes for ionised solutes, particularly for basic compounds, were considerably worse in FA than AF. Even neutral compounds showed deterioration in performance with FA when the mobile phase water concentration was reduced. The poor performance in FA cannot be entirely attributed to the negative impact of ionic retention on ionised silanols on the underlying silica base materials, as results using PA at lower pH (where their ionisation is suppressed) were inferior to those in AF. Besides the moderating influence of the salt cation on ionic retention, it is likely that salt buffers improve peak shape due to the increased ionic strength of the mobile phase and its impact on the formation of the water layer on the column surface. PMID:24813934

  9. Interaction of lead(II) with beta-cyclodextrin in alkaline solutions.

    PubMed

    Norkus, Eugenijus; Grinciene, Giedre; Vaitkus, Rimantas

    2002-10-01

    Polarographic and UV-spectrophotometric investigations of Pb(II) complex formation with beta-cyclodextrin have showed that the complexation of Pb(II) ions begins at pH >10. The formation of lead(II) 1:1 complex with the beta-cyclodextrin anion was observed at pH 10-11.5. The logarithm of the stability constant of this complex compound is 15.9+/-0.3 (20 degrees C, ionic strength 1.0), and the molar extinction coefficient value is ca. 5500 (lambda(max)=260 nm). With further increase in solution pH the Pb-beta-cyclodextrin complex decomposes and converts to Pb(OH)(2) or Pb(OH)(3)(-) hydroxy-complexes. This process occurs with a decrease in Pb(II) complexation degree. The latter result could be explained by a decrease in the beta-cyclodextrin anion activity. Neither Pb(OH)(2) nor Pb(OH)(3)(-) encapsulation into beta-CD cavity was observed. PMID:12423967

  10. Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability

    NASA Astrophysics Data System (ADS)

    Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.

    2014-11-01

    This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.

  11. Separating nano graphene oxide from the residual strong-acid filtrate of the modified Hummers method with alkaline solution

    NASA Astrophysics Data System (ADS)

    Hu, Xuebing; Yu, Yun; Wang, Yongqing; Zhou, Jianer; Song, Lixin

    2015-02-01

    In the modified Hummers method for preparing graphene oxide, the yellow slurry can be obtained. After filtering through a quantitative filter paper, the strong-acid filtrate containing the unprecipitated nano graphene oxide was gained. The corresponding filtrate was added gradually with an alkaline (NaOH or KOH) solution at room temperature. The unprecipitated nano graphene oxide could undergo fast aggregation when the pH value of the filtrate was about 1.7 and formed the stable floccules. X-ray diffraction analysis shows the dominant peak of the floccules is about 11°, which accords to the peak of graphene oxide. Spectra of X-ray photoelectron spectroscopy confirm the presence in the floccules of an abundance of oxygen functional groups and the purified graphene oxide floccules can be obtained. Atomic force microscopy measurement shows the graphene oxide floccules consists of sheet-like objects, mostly containing only a few layers (about 5 layers). Zeta potential analysis demonstrates the surface charge of the graphene oxide is pH-sensitive and its isoelectric point is ∼1.7. The flocculation mechanism of graphene oxide ascribes to the acid-base interaction with the surface functional groups of the carbon layers.

  12. Implications of alkaline solutions-induced etching on optical and minority carrier lifetime features of monocrystalline silicon

    NASA Astrophysics Data System (ADS)

    Bachtouli, N.; Aouida, S.; Laajimi, R. Hadj; Boujmil, M. F.; Bessais, B.

    2012-09-01

    In this work, we search to optimize the surface textures of monocrystalline silicon (c-Si) intended to be used in silicon solar cells. For this purpose, we studied the morphology of formed etch hillocks during anisotropic etching of silicon using alkaline solutions based on sodium hydroxide (NaOH), potassium hydroxide (KOH) and tetramethylammonium hydroxide (TMAH). Such treatments lead to the formation of various pyramids-like textures that can be well optimized to improve the photocurrent of c-Si-based solar cells. The produced textures were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-visible optical reflectivity and minority carrier lifetime measurements. These investigations allow evaluating the size and density of the formed pyramidal textures; the apex angles vary between 75° and 82°, while the heights and bases of the pyramids range from a few hundred nanometers to several micrometers. A minimum reflectivity value of about 6% was obtained at specific conditions using NaOH, whereas it was found that the apparent effective minority carrier lifetime (τeff) is sensitive to the injection level (Δn), which shows an apparent increase from 1.2 μs to 2.4 μs for a minority carrier density of about Δn = 21014 cm-3.

  13. Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions

    SciTech Connect

    Lima,F.; Zhang, J.; Shao, M.; Sasaki, K.; Vukmirovic, M.; Ticianelli, E.; Adzic, R.

    2007-01-01

    We determined, by the rotating disk electrode technique, the kinetics of the oxygen-reduction reaction (ORR) on the surfaces of single crystals of Au(111), Ag(111), Pd(111), Rh(111), Ir(111), and Ru(0001), on Pt monolayers deposited on their surfaces, and also on nanoparticles of these metals dispersed on high-surface-area carbon. Plotting the correlation between the experimentally determined activities of these three types of electrocatalysts with the calculated metal d-band center energies,{var_epsilon}{sub d}, revealed a volcano-type dependence. In all cases, the electronic properties of the metal electrocatalysts, represented by the {var_epsilon}{sub d} value, were used for elucidating the metal-dependent catalytic activities, and establishing their electronic properties-the ORR kinetics relationship. Pt(111), Pt/C, and Pt/Pd(111) were found to top their corresponding volcano plots. Pd in alkaline solutions showed particularly high activity, suggesting it may offer potential replacement for Pt in fuel cells.

  14. Kinetic study on the degradation of meclophenoxate hydrochloride in alkaline aqueous solutions by high performance liquid chromatography.

    PubMed

    El-Bardicy, Mohammad Galal; Lotfy, Hayam Mahmoud; El-Sayed, Mohammad Abdalla; El-Tarras, Mohammad Fayez

    2007-01-01

    A high performance liquid chromatographic method was developed and validated for determination of meclophenoxate hydrochloride (I) in the presence of its degradation product (p-chlorophenoxy acetic acid) (II). Separation of (I) from (II) was performed using a ZORBAX ODS column with a mobile phase consisting of 0.2% triethylamine in 0.01 M ammonium carbonate: acetonitrile (70:30 v/v). The method showed high sensitivity with good linearity over the concentration range of 50 to 400 mug/ml. The method was successfully applied to the analysis of a pharmaceutical formulation containing (I) with excellent recovery. A kinetics investigation of the alkaline hydrolysis of (I) was carried out in sodium hydroxide solutions of 1, 1.5 and 2 N by monitoring the parent compound itself. The reaction order of (I) followed pseudo-first order kinetics. The activation energy could be estimated from the Arrhenius plot and it was found to be 12.331 kcal/mole. PMID:17202800

  15. Graphene-based non-noble-metal Co/N/C catalyst for oxygen reduction reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Niu, Kexing; Yang, Baoping; Cui, Jinfeng; Jin, Jutao; Fu, Xiaogang; Zhao, Qiuping; Zhang, Junyan

    2013-12-01

    This study develops a promising catalyst for oxygen reduction reaction (ORR) via a simple two-step heat treatment of a mixture of cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O), polyethyleneimine (PEI), and graphene oxide (GO), firstly in argon atmosphere and then in ammonia atmosphere. X-ray photoemission spectroscopy (XPS) result reveals that the catalyst has pyridinic N-dominant (46% atomic concentration among all N components) on the surface. The kinetics measurement of the catalyst in 0.1 M KOH solution using a rotating disk electrode (RDE) reveals that the catalyst (Co/N/rGO(NH3)) has high activity. Furthermore, the number of electrons exchanged during the ORR with the catalyst is determined to be ˜3.9, suggesting that the ORR is dominated by a 4e- reduction of O2 to H2O. The catalyst has good stability, and its performance is superior to the commercial Pt/C(20%) catalyst in alkaline condition, making the material a promising substitute to noble metal ORR electrocatalyst on the cathode side of fuel cells.

  16. Products of pertechnetate radiolysis in highly alkaline solution: structure of TcO2 x xH2O.

    PubMed

    Lukens, Wayne W; Bucher, Jerome I; Edelstein, Norman M; Shuh, David K

    2002-03-01

    The chemistry of technetium in certain high-level nuclear waste (HLW) tanks at the Hanford Site complicates the treatment and vitrification of HLW. A major problem is the presence, in certain tanks, of unidentified, lower-valent technetium species, which are difficult to remove from the waste by current separation processes. Radiolytic reduction of TcO4- in alkaline solutions containing selected organic compounds, approximating the conditions in HLW, was investigated to determine the classes of compounds that can be formed under these conditions. Insoluble TcO2 x xH2O is the primary radiolysis product with the majority of organic compounds investigated, including citrate, dibutyl phosphate, and aminopolycarboxylates. X-ray absorption fine structure (XAFS) measurements show that TcO2 x xH2O has a one-dimensional chain structure consisting of edge-sharing TcO6 octahedra with bridging oxide and trans water ligands. When diols, such as ethylene glycol, are present, only soluble, Tc(IV) alkoxide compounds are produced. The XAFS and UV-visible spectra of these compounds provide evidence for a binuclear structure similar to (H2EDTA)2Tc2(mu-O)2. The properties of the Tc(IV) alkoxide complexes were determined and are consistent with those observed for the soluble, lower-valent technetium complexes that complicate the treatment of HLW at the Hanford site. PMID:11918000

  17. Kinetics of reduction of plutonium(VI) and neptunium(VI) by sulfide in neutral and alkaline solutions

    USGS Publications Warehouse

    Nash, K.L.; Cleveland, J.M.; Sullivan, J.C.; Woods, M.

    1986-01-01

    The rate of reduction of plutonium(VI) and neptunium(VI) by bisulfide ion in neutral and mildly alkaline solutions has been investigated by the stopped-flow technique. The reduction of both of these ions to the pentavalent oxidation state appears to occur in an intramolecular reaction involving an unusual actinide(VI)-hydroxide-bisulfide complex. For plutonium the rate of reduction is 27.4 (??4.1) s-1 at 25??C with ??H* = +33.2 (??1.0) kJ/mol and ??S* = -106 (??4) J/(mol K). The apparent stability constant for the transient complex is 4.66 (??0.94) ?? 103 M-1 at 25??C with associated thermodynamic parameters of ??Hc = +27.7 (??0.4) kJ/mol and ??Sc = +163 (??2) J/(mol K). The corresponding rate and stability constants are determined for the neptunium system at 25??C (k3 = 139 (??30) s-1, Kc. = 1.31 (??0.32) ?? 103 M-1), but equivalent parameters cannot be determined at reduced temperatures. The reaction rate is decreased by bicarbonate ion. At pH > 10.5, a second reaction mechanism, also involving a sulfide complex, is indicated. ?? 1986 American Chemical Society.

  18. The relationship between coefficient of restitution and state of charge of zinc alkaline primary LR6 batteries [Bouncing alkaline batteries: A basic solution

    SciTech Connect

    Bhadra, S.; Hertzberg, B. J.; Croft, M.; Gallaway, J. W.; Van Tassell, B. J.; Chamoun, M.; Erdonmez, C.; Zhong, Z.; Steingart, D. A.

    2015-03-13

    The coefficient of restitution of alkaline batteries had been shown to increase as a function of depth of discharge. In this work, using non-destructive mechanical testing, the change in coefficient of restitution is compared to in situ energy-dispersive x-ray diffraction data to determine the cause of the macroscopic change in coefficient of restitution. The increase in coefficient of restitution correlates to the formation of a percolation pathway of ZnO within the anode of the cell, and that the coefficient of restitution saturates at a value of 0.63 ± .05 at 50% state if charge when the anode has densified into porous ZnO solid. Of note is the sensitivity of coefficient of restitution to the amount of ZnO formation that rivals the sensitivity on in situ energy-dispersive x-ray diffraction spectroscopy.

  19. The relationship between coefficient of restitution and state of charge of zinc alkaline primary LR6 batteries [Bouncing alkaline batteries: A basic solution

    DOE PAGESBeta

    Bhadra, S.; Hertzberg, B. J.; Croft, M.; Gallaway, J. W.; Van Tassell, B. J.; Chamoun, M.; Erdonmez, C.; Zhong, Z.; Steingart, D. A.

    2015-03-13

    The coefficient of restitution of alkaline batteries had been shown to increase as a function of depth of discharge. In this work, using non-destructive mechanical testing, the change in coefficient of restitution is compared to in situ energy-dispersive x-ray diffraction data to determine the cause of the macroscopic change in coefficient of restitution. The increase in coefficient of restitution correlates to the formation of a percolation pathway of ZnO within the anode of the cell, and that the coefficient of restitution saturates at a value of 0.63 ± .05 at 50% state if charge when the anode has densified intomore » porous ZnO solid. Of note is the sensitivity of coefficient of restitution to the amount of ZnO formation that rivals the sensitivity on in situ energy-dispersive x-ray diffraction spectroscopy.« less

  20. A fuel-cell reactor for the direct synthesis of hydrogen peroxide alkaline solutions from H(2) and O(2).

    PubMed

    Yamanaka, Ichiro; Onisawa, Takeshi; Hashimoto, Toshikazu; Murayama, Toru

    2011-04-18

    The effects of the type of fuel-cell reactors (undivided or divided by cation- and anion-exchange membranes), alkaline electrolytes (LiOH, NaOH, KOH), vapor-grown carbon fiber (VGCF) cathode components (additives: none, activated carbon, Valcan XC72, Black Pearls 2000, Seast-6, and Ketjen Black), and the flow rates of anolyte (0, 1.5, 12 mL h(-1)) and catholyte (0, 12 mL h(-1)) on the formation of hydrogen peroxide were studied. A divided fuel-cell system, O(2) (g)|VGCF-XC72 cathode|2 M NaOH catholyte|cation-exchange membrane (Nafion-117)|Pt/XC72-VGCF anode|2 M NaOH anolyte at 12 mL h(-1) flow|H(2) (g), was effective for the selective formation of hydrogen peroxide, with 130 mA cm(-2) , a 2 M aqueous solution of H(2)O(2)/NaOH, and a current efficiency of 95 % at atmospheric pressure and 298 K. The current and formation rate gradually decreased over a long period of time. The cause of the slow decrease in electrocatalytic performance was revealed and the decrease was stopped by a flow of catholyte. Cyclic voltammetry studies at the VGCF-XC72 electrode indicated that fast diffusion of O(2) from the gas phase to the electrode, and quick desorption of hydrogen peroxide from the electrode to the electrolyte were essential for the efficient formation of solutions of H(2)O(2)/NaOH. PMID:21400665

  1. Effect of Protein-Lipid-Salt Interactions on Sodium Availability in the Mouth and Consequent Perception of Saltiness: In Solutions.

    PubMed

    Yucel, Umut; Peterson, Devin G

    2015-09-01

    The influence of protein-sodium interactions on the availability of sodium in the aqueous phase of liquid samples and consequently on the perception of saltiness was investigated. The aqueous effluents of casein and casein emulsion-salt solutions were monitored for sodium availability from a tongue column system. In the aqueous protein-salt solutions, increasing the protein/salt ratio from 1:1 to 5:1 or 10:1 significantly decreased the initial salt concentration in the effluent and resulted in a higher salt concentration in the effluent over time. Sensory analysis was in agreement. Samples with increased protein were rated as having significantly lower initial saltiness and a higher salty aftertaste. However, when casein was formulated as an emulsion, the initial release of sodium in the effluent was enhanced (compared to nonemulsified protein). Increasing the emulsion interfacial area (more hydrophilic segments of the protein were structured into the aqueous phase) resulted in a higher salt concentration in the aqueous phase and greater perceived saltiness intensity. In summary, protein interactions, specifically ionic, were reported as food interactions that influence salt perception and provide a basis to develop higher flavor quality low-sodium food products. PMID:26255631

  2. Water Uptake by Mars Salt Analogs: An Investigation of Stable Aqueous Solutions Using Raman Microscopy

    NASA Astrophysics Data System (ADS)

    Nuding, Danielle L.

    Liquid water processes that may occur on the surface and near-subsurface of Mars have important implications for the present-day water cycle, habitability, and planetary protection policies. The presence of salts on Mars plays a role in surface-atmosphere interactions as salts enhance the soil's ability to retain water. This thesis explores the phase transitions of water upon interaction with Mars relevant salt analogs. Water uptake and loss properties of a single and complex Mars analog are examined using a Raman microscope equipped with an environmental cell. The effect of the hygroscopic salts on bacterial spores was evaluated with a focus on potential terrestrial contamination on outbound spacecraft and its influence on planetary protection concerns. Calcium perchlorate (Ca(ClO4)2) is a highly deliquescent salt that may exist on the surface of present-day Mars. Here, we quantify the deliquescent relative humidity (DRH) and efflorescent relative humidity (ERH) of Ca(ClO4)2 as a function of temperature (223 K to 273 K) to elucidate its behavior on the surface of Mars. Mars relevant temperature and relative humidity (RH) conditions were simulated and deliquescence (solid to aqueous) and efflorescence (aqueous to solid) phase transitions of Ca(ClO4)2 were characterized. Experimental DRH values were compared to a thermodynamic model for three hydration states of Ca(ClO 4)2. Calcium perchlorate was found to supersaturate, with lower ERH values than DRH values. Additionally, we conducted a 17-hour experiment to simulate a subsurface relative humidity and temperature diurnal cycle. This demonstrated that aqueous Ca(ClO4)2 solutions can persist without efflorescing for the majority of a martian sol, up to 17 hours under Mars temperature heating rates and RH conditions. Applying these experimental results to martian surface and subsurface heat and mass transfer models, we find that aqueous Ca(ClO4)2 solutions could persist for most of the martian sol under present

  3. Hydrology of the Bonneville Salt Flats, northwestern Utah, and simulation of ground-water flow and solute transport in the shallow-brine aquifer

    USGS Publications Warehouse

    Mason, James L.; Kipp, Kenneth L.

    1998-01-01

    This report describes the hydrologic system of the Bonneville Salt Flats with emphasis on the mechanisms of solute transport. Variable-density, three-dimensional computer simulations of the near-surface part of the ground-water system were done to quantify both the transport of salt dissolved in subsurface brine that leaves the salt-crust area and the salt dissolved and precipitated on the land surface. The study was designed to define the hydrology of the brine ground-water system and the natural and anthropogenic processes causing salt loss, and where feasible, to quantify these processes. Specific areas of study include the transport of salt in solution by ground-water flow and the transport of salt in solution by wind-driven ponds and the subsequent salt precipitation on the surface of the playa upon evaporation or seepage into the subsurface. In addition, hydraulic and chemical changes in the hydrologic system since previous studies were documented.

  4. Self-organization of poly(ethylene oxide) on the surface of aqueous salt solutions.

    PubMed

    Fuchs, Christian; Hussain, Hazrat; Amado, Elkin; Busse, Karsten; Kressler, Joerg

    2015-01-01

    It is demonstrated that stable Langmuir films of poly(ethylene oxide) (PEO) can be formed up to surface pressures of 30 mN m(-1) when potassium carbonate K2CO3 is added to the aqueous subphase. Generally, PEO homopolymer cannot stay on the water surface at a surface pressure ≥10 mN m(-1) due to its high water solubility. To prepare stable monolayer films, PEO can be modified with hydrophobic moieties. However, by exploiting the salting out effect by adding certain salts (K2CO3 or MgSO4) into the aqueous subphase, not only very stable films but also unusual self-organization can be achieved by the PEO homopolymer on the surface of the aqueous solution. Thus, a series of OH-terminated PEOs is found to form a stable monolayer at K2CO3 concentrations of 2 M and above in the aqueous subphase, and the stability of the film increases with an increase in K2CO3 concentration. Hysteresis experiments are also carried out. During the phase transition induced by progressive compression, self-organization into well-defined domains with sizes in the micrometer range are observed, and with further compression and holding of the film for 30 min and above the microdomains transform into a crystalline morphology as visualized by Brewster angle microscopy. PMID:25269665

  5. Hydrogen generation in microbial reverse-electrodialysis electrolysis cells using a heat-regenerated salt solution.

    PubMed

    Nam, Joo-Youn; Cusick, Roland D; Kim, Younggy; Logan, Bruce E

    2012-05-01

    Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m(3) H(2)/m(3)·d, with a hydrogen yield of 3.4 mol H(2)/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes. PMID:22463373

  6. Light Emission from Porous Silicon Photoetched in Aqueous Alkali Salt Solutions

    NASA Astrophysics Data System (ADS)

    Adachi, Sadao; Miyazaki, Takayuki; Inoue, Kazufumi; Sodezawa, Shingo

    2007-07-01

    An interband-transition model was applied to explain the emission mechanism in porous silicon (PSi) fabricated by photoetching in aqueous HF and salt (NaF and KF) solutions. The HF-formed samples show a yellow photoluminescence band at ˜2 eV. The salt-formed samples, on the other hand, show an ultraviolet (UV) emission peak at ˜3.3 eV with a spectral width of ˜0.1 eV, together with a broad emission band at ˜2.7 eV. The broad emission bands at ˜2 and ˜2.7 eV can be explained by the quantum-mechanical confinement effect, i.e., a relaxation of the momentum conservation at and above the indirect-absorption edge (supra-EgID emission). This effect may also lead to a change in the E1 critical point (CP) from the two-dimensional M0 to the zero-dimensional CP with decreasing nanocrystalline size. The change in the E1-CP dimensionality makes possible an emission in the UV region with a narrow spectral width.

  7. In situ X-ray microprobe study of salt layers during anodic dissolution of stainless steel in chloride solution

    SciTech Connect

    Isaacs, H.S.; Cho, J.H.; Rivers, M.L.; Sutton, S.R.

    1995-04-01

    Salt layers play an important role in many electrochemical dissolution processes. The composition of salt films formed on austenitic stainless steel have, for the first time, been determined using in situ energy dispersive X-ray fluorescence microanalysis during dissolution in a chloride solution. The electrode was the cross section of a nickel/chromium steel foil sandwiched between plastic sheets. The foil was electrochemically dissolved producing a pit 1.6 mm deep. The electrode configuration simulated localized corrosion with a one-dimensional diffusion geometry. X-ray fluorescence intensities of chromium K{sub {alpha}}, iron K{sub {alpha}}, an nickel K{sub {beta}} energies were measured as the steel/solution interface traversed a 6 {mu}m, polychromatic, high-intensity X-ray beam. Qualitative determinations were made of the composition of the salt layer and the composition of the saturated solution. Salt layer thickness was found to increase with increased applied potentials. The salt layer was found to be rich in iron and depleted in nickel and, particularly, chromium. The effective diffusion coefficients of the dissolved species were determined from the composition of the saturated solution at the interface. Nickel showed the highest and chromium the lowest effective diffusion coefficient.

  8. Electrophysical methods of separation of metal cations in the moving salts solution

    NASA Astrophysics Data System (ADS)

    Gofman, V. N.; Tuksov, I. V.; Timchenko, S. N.; Shamanin, I. V.; Poberezhnikov, A. D.; Kazaryan, M. A.

    2016-07-01

    The results of experiments on the excitation of the phenomenon of selective drift of solvated ions under the influence of an external "asymmetric" electric field to the circulating solution of calcium chloride and magnesium salts in a polar liquid dielectric - water are shown. The purpose of the experiments was to determine the influence of the field frequency and amplitude of the field strength on the excitation phenomenon, and the study of the operating characteristics of the testing apparatus - a dividing cell. The dependences of the separation efficiency of solvated cations from the frequency of the external field and the excitation threshold of the phenomenon from the field strength in the separation cell are defined.

  9. Molecular dynamics study of charged dendrimers in salt-free solution: Effect of counterions

    NASA Astrophysics Data System (ADS)

    Gurtovenko, Andrey A.; Lyulin, Sergey V.; Karttunen, Mikko; Vattulainen, Ilpo

    2006-03-01

    Polyamidoamine dendrimers, being protonated under physiological conditions, represent a promising class of nonviral, nanosized vectors for drug and gene delivery. We performed extensive molecular dynamics simulations of a generic model dendrimer in a salt-free solution with dendrimer's terminal beads positively charged. Solvent molecules as well as counterions were explicitly included as interacting beads. We find that the size of the charged dendrimer depends nonmonotonically on the strength of electrostatic interactions demonstrating a maximum when the Bjerrum length equals the diameter of a bead. Many other structural and dynamic characteristics of charged dendrimers are also found to follow this pattern. We address such a behavior to the interplay between repulsive interactions of the charged terminal beads and their attractive interactions with oppositely charged counterions. The former favors swelling at small Bjerrum lengths and the latter promotes counterion condensation. Thus, counterions can have a dramatic effect on the structure and dynamics of charged dendrimers and, under certain conditions, cannot be treated implicitly.

  10. Factors influencing the formation of polybromide monoanions in solutions of ionic liquid bromide salts.

    PubMed

    Easton, Max E; Ward, Antony J; Chan, Bun; Radom, Leo; Masters, Anthony F; Maschmeyer, Thomas

    2016-03-01

    Six different bromide salts - tetraethylammonium bromide ([N2,2,2,2]Br, Br), 1-ethyl-1-methylpiperidinium bromide ([C2MPip]Br, Br), 1-ethyl-1-methylpyrrolidinium bromide ([C2MPyrr]Br, Br), 1-ethyl-3-methylimidazolium bromide ([C2MIm]Br, Br), 1-ethylpyridinium bromide ([C2Py]Br, Br), and 1-(2-hydroxyethyl)pyridinium bromide ([C2OHPy]Br, Br) - were studied in regards to their capacity to form polybromide monoanion products on addition of molecular bromine in acetonitrile solutions. Using complementary spectroscopic and computational methods for the examination of tribromide and pentabromide anion formation, key factors influencing polybromide sequestration were identified. Here, we present criteria for the targeted synthesis of highly efficient bromine sequestration agents. PMID:26890026

  11. Designing voltage multipliers with nanofluidic diodes immersed in aqueous salt solutions.

    PubMed

    Ramirez, P; Gomez, V; Verdia-Baguena, C; Nasir, S; Ali, M; Ensinger, W; Mafe, S

    2016-02-01

    Membranes with nanofluidic diodes allow the selective control of molecules in physiological salt solutions at ambient temperature. The electrical coupling of the membranes with conventional electronic elements such as capacitors suggests opportunities for the external monitoring of sensors and actuators. We demonstrate experimentally and theoretically the voltage multiplier functionality of simple electrical networks composed of membranes with conical nanopores coupled to load capacitors. The robust operation of half and full wave voltage multipliers is achieved in a broad range of experimental conditions (single pore and multipore membranes, electrolyte concentrations, voltage amplitudes, and solid-state capacitances). The designed voltage multipliers operate in the liquid state and can be used in sensing devices because different electrical, optical, and chemical inputs are known to modulate the individual nanofluidic diode resistances in the electrical network. PMID:26771033

  12. Micro-Arc oxidation of Ti in a solution of sulfuric acid and Ti +3 salt

    NASA Astrophysics Data System (ADS)

    Ragalevičius, Rimas; Stalnionis, Giedrius; Niaura, Gediminas; Jagminas, Arūnas

    2008-01-01

    A comparative study was performed on the behavior of titanium electrode in a sulfuric acid solution with and without Ti +3 during micro-arc oxidation under the constant current density control regime. The composition and microstructure of the obtained micro-arc films were analyzed using scanning electron microscopy, glancing-angle X-ray diffractometry, Raman and energy-dispersive X-ray spectroscopies. We have shown that addition of a Ti +3 salt extends the region of current densities ( ja) can be used for micro-arc oxidation of Ti and results in an obvious change of sparking behavior from extensive, large and long-played sparks to numerous, small and short sparks. As a consequence, the titania films formed in the Ti +3-containing solutions are relatively thick, more uniform, composed of almost pure crystalline anatase and rutile phases of TiO 2, and contain a network of evenly distributed small pores. It has also been shown that these films are promising for applications in catalysis, sensors and optoelectronics. The Raman spectra indicate that an increase in the electrolysis time of titanium in the Ti +3-containing solution leads to the increase in rutile content, as expected.

  13. Mechanical Behavior of Salt Caverns: Closed-Form Solutions vs Numerical Computations

    NASA Astrophysics Data System (ADS)

    Wang, Linlin; Bérest, Pierre; Brouard, Benoît

    2015-11-01

    Creep closure and structural stability of a cylindrical elongated cavern leached out from a salt formation are discussed. The Norton-Hoff creep law, or "power law", is used to capture the main features of salt rheological behavior. Two failure criteria are considered: (1) shear stresses must not be larger than a certain fraction of the mean stress (dilation criterion); and (2) the effective stress at the cavern wall (actual stress plus cavern fluid pressure) must not be tensile. The case of a brine-filled cavern whose pressure is kept constant is discussed first. It is proved that creep closure reaches a steady state such that stresses in the rock mass remain constant. However, decades are needed to reach such a state. During the transient phase that results from the slow redistribution of stresses in the rock mass, deviatoric stresses decrease at the vicinity of the cavern wall, and onset of dilation is less and less likely. At this point, the case of a rapid brine pressure increase, typical of a tightness test, is considered. It is proved that during such a swift pressure increase, cavern behavior is almost perfectly elastic; there is no risk of dilation onset. However, even when cavern pressure remains significantly smaller than geostatic, the effective stress at cavern wall can become tensile. These results, obtained through numerical computations, are confirmed by closed-form solutions obtained in the case of an idealized perfectly cylindrical cavern; these solutions provide a better insight into the main structural features of the behavior of the cavern.

  14. An assessment of the long-term environmental impacts of reusing alkaline clay on coal refuse piles with a dynamic solute transport model at a watershed scale

    NASA Astrophysics Data System (ADS)

    Xu, Y.; Liang, X.; Davis, T. W.; Patterson, J.; Jaw, F. K.; Koranchie-Boah, P.

    2011-12-01

    Coal refuse piles play a significant role in producing acid mining drainage (AMD) that deteriorates water quality at a watershed scale. The waste produced from coal refuse piles results in a decrease of the pH value in soil water and river flow. Metal compounds, such as ferric and ferrous solutions, are also continuously released from the coal pile due to the extensive and complicated chemical reactions in the acidic environment. Alkaline clay, a byproduct of alumina refining process, has a high residual pH in the material. If the alkaline clay is used innovatively with the coal mine refuse, the problems associated with each (e.g., high and low pH values) are likely to be effectively resolved. In addition, the solubility of the sulfur and iron will be reduced significantly. This will effectively eliminate the AMD problem at the coal refuse pile and improve the water quality at the watershed scale. This study investigates the long-term impacts of the combined mixture (i.e., alkaline clay + coal refuse) on the environment (e.g., in the soil column and in the river system) through systematic modeling simulations in a combination with field measurements. In particular, a dynamic solute transport model that accounts for processes of the pyrite oxidation, oxygen diffusion, absorption, desorption, and advection is developed and is coupled with the Distributed Hydrology Soil and Vegetation Model (DHSVM) to assess the environmental impacts at the watershed scale. The model-simulated sulfur and iron concentrations are compared with field observations and the long-term impacts of the combined mixture (i.e., alkaline clay + coal refuse) on the environment are investigated. This study paves the way for monitoring and assessing the impacts of the reuse of the alkaline clay and refuse mixture on the environment at a watershed scale.

  15. Spectrophotometric determination of copper in alkaline solutions and evaluation of some hydroxy-substituted 1,10-phenanthrolines as chromogenic reagents.

    PubMed

    Dunbar, W E; Schilt, A A

    1972-09-01

    Seven new hydroxy-substituted 1,10-phenanthroline derivatives have been evaluated as chromogenic reagents for the determination of copper in strongly alkaline solution. The most sensitive of these, 2,9-dimethyl-4,7-dihydroxy-1,10-phenanthroline, has proven to be highly effective in a simple, rapid procedure for determining trace amounts of copper in sodium hydroxide, potassium carbonate, sodium phosphate or ammonium hydroxide. PMID:18961151

  16. Enzymatically mediated bioprecipitation of heavy metals from industrial wastes and single ion solutions by mammalian alkaline phosphatase.

    PubMed

    Chaudhuri, Gouri; Shah, Gaurav A; Dey, Pritam; S, Ganesh; Venu-Babu, P; Thilagaraj, W Richard

    2013-01-01

    The study was aimed at investigating the potential use of calf intestinal alkaline phosphatase (CIAP) enzyme in the removal of heavy metals (Cd(2+), Ni(2+), Co(2+) and Cr(3+/6+)) from single ion solutions as well as tannery and electroplating effluents. CIAP mediated bioremediation (white biotechnology) is a novel technique that is eco-friendly and cost effective unlike the conventional chemical technologies. Typical reactions containing the enzyme (CIAP) and p-nitrophenyl phosphate (pNPP) as substrate in Tris-HCl buffer (pH 8 and 11) and either single ion metal solutions (250 ppm and 1000 ppm) or effluents from tannery or electroplating industry were incubated at 37°C for 30 min, 60 min and 120 min. The inorganic phosphate (P(i)) generated due to catalytic breakdown of pNPP complexes free metal ions as metal-phosphate and the amount of metal precipitated was derived by estimating the reduction in the free metal ion present in the supernatant of reactions employing atomic absorption spectrophotometer (AAS). Better precipitation of metal was obtained at pH 11 than at pH 8 and between the two concentrations of different metals tested, an initial metal concentration of 250 ppm in the reaction gave more precipitation than with 1000 ppm. Experimental data showed that at pH 11, the percentage of removal of metal ions (for an initial concentration of 250 ppm) was in the following order: Cd(2+) (80.99%) > Ni(2+) (64.78%) > Cr(3+) > (46.15%) > Co(2+) (36.47%) > Cr(6+) (32.33%). The overall removal of Cr(3+) and Cr(6+) from tannery effluent was 32.77% and 37.39% respectively in 120 min at pH 11. Likewise, the overall removal of Cd(2+), Co(2+) and Ni(2+) from electroplating effluent was 50.42%, 13.93% and 38.64% respectively in 120 min at pH 11. The study demonstrates that bioprecipitation by CIAP may be a viable and environmental friendly method for clean-up of heavy metals from tannery and electroplating effluents. PMID:23030390

  17. Chain dimensions in free and immobilized brush states of polysulfobetaine in aqueous solution at various salt concentrations

    NASA Astrophysics Data System (ADS)

    Terayama, Y.; Arita, H.; Ishikawa, T.; Kikuchi, M.; Mitamura, K.; Kobayashi, M.; Yamada, N. L.; Takahara, A.

    2011-01-01

    The chain dimensions of free and immobilized polysulfobetaine in aqueous solution at various salt concentrations were investigated by size-exclusion chromatography with multiangle light scattering and neutron reflectivity measurement, respectively. The dependence of the z-average mean square radius of gyration (z1/2) on the weight-average molecular weight (Mw) of free poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfo-nate) (MAPS) in aqueous solution at salt concentrations of 74, 100, 200, and 500 mM was described by the perturbed wormlike chain model using the chain stiffness parameter λ-1 the molar mass per unit contour length ML, and the excluded volume effect B. B increased from 0 to 1.8 nm with increasing salt concentration to 500 mM due to the screening of attractive electrostatic interaction between ammonium cations and sulfonyl anions by salt ions. The swollen structure of the poly(MAPS) brush in D2O changed from a shrunken state to a relatively extended state with increasing salt concentration from 0 to 500 mM NaCl/D2O solution. The thickness of the swollen poly(MAPS) brush in 500 mM NaCl/D2O was 9.0 times greater than 2z1/2 of free poly(MAPS) due to high osmotic pressure generated by the excluded volume effect of densely grafted polymer chains.

  18. Structure of salts solution in polar dielectric liquids and electrically induced separation of solvated ions

    NASA Astrophysics Data System (ADS)

    Shamanin, Igor V.; Kazaryan, Mishik A.; Sachkov, Victor I.

    2015-12-01

    The aim of study is to demonstrate that separation of solvated ions in solution of mix of salts under the action of external periodic electric field happens because of around ions there are formed clusters consisting of molecules of solvent and the sizes of such clusters have dimensions ~ 0.1 μm. In investigations the sizes of clusters theoretically were defined and experimentally value of frequency of external electric field which action excites the effect of separation of the solvated ions was defined. Experiments were done in the Technical Physics Chair of the National Research Tomsk Polytechnic University. At theoretical determination of the dimensions of clusters Poisson's equation was solved and was considered that polar molecules of solvent are oriented under the action of electric field of an ion. The chemical composition of samples of solutions was determined by means of the spectrophotometry and he X-ray excited fluorescent radiation analysis method. Theoretical estimates and results of experiments confirmed the assumption that clusters which are formed around ions in solutions have the dimensions ~ 0.1 μm. Results of investigation testify that placing of volume distributed electric charge of ion in dielectric liquid is accompanied by formation of the supramolecular particles, which we called "clusters", linear sizes of which is significantly more than first and second radiuses of solvation (~ 1 Angstrom) and reach size ~ 0.1 μm. At such sizes inertial properties of clusters and their natural frequencies give the chance to operate their movement by means of action of external electric field on solution.

  19. Influence of acid and alkaline sources on optical, structural and photovoltaic properties of CdSe nanoparticles precipitated from aqueous solution

    NASA Astrophysics Data System (ADS)

    Coria-Monroy, C. Selene; Sotelo-Lerma, Mérida; Hu, Hailin

    2016-06-01

    CdSe is a widely researched material for photovoltaic applications. One of the most important parameters of the synthesis is the pH value, since it determines the kinetics and the mechanism of the reaction and in consequence, the optical and morphological properties of the products. We present the synthesis of CdSe in solution with strict control of pH and the comparison of ammonia and KOH as alkaline sources and diluted HCl as acid medium. CdSe formation was monitored with photoluminescence emission spectra (main peak in 490 nm, bandgap of CdSe nanoparticles). XRD patterns indicated that CdSe nanoparticles are mainly of cubic structure for ammonia and HCl, but the hexagonal planes appear with KOH. Product yield decreases with pH and also decreases with KOH at constant pH value since ammonia has a double function, as complexing agent and alkaline source. Changes in morphology were observed in SEM images as well with the different alkaline source. The effect of alkaline sources on photovoltaic performance of hybrid organic solar cells with CdSe and poly(3-hexylthiophene) as active layers was clearly observed, indicating the importance of synthesis conditions on optoelectronic properties of promising semiconductor nanomaterials for solar cell applications.

  20. Cryochemical method for forming spherical metal oxide particles from metal salt solutions

    DOEpatents

    Tinkle, M.C.

    1973-12-01

    A method is described of preparing small metal oxide spheres cryochemically utilizing metal salts (e.g., nitrates) that cannot readily be dried and calcined without loss of sphericity of the particles. Such metal salts are cryochemically formed into small spheres, partially or completely converted to an insoluble salt, and dried and calcined. (Official Gazette)

  1. Development of an analytical technique for the detection of alteration minerals formed in bentonite by reaction with alkaline solutions

    NASA Astrophysics Data System (ADS)

    Sakamoto, H.; Shibata, M.; Owada, H.; Kaneko, M.; Kuno, Y.; Asano, H.

    A multibarrier system consisting of cement-based backfill, structures and support materials, and a bentonite-based buffer material has been studied for the TRU waste disposal concept being developed in Japan, the aim being to restrict the migration of radionuclides. Concern regarding bentonite-based materials in this disposal environment relates to long-term alteration under hyper-alkaline conditions due to the presence of cementitious materials. In tests simulating the interaction between bentonite and cement, formation of secondary minerals due to alteration reactions under the conditions expected for geological disposal of TRU waste (equilibrated water with cement at low liquid/solid ratio) has not been observed, although alteration was observed under extremely hyper-alkaline conditions with high temperatures. This was considered to be due to the fact that analysis of C-S-H gel formed at the interface as a secondary mineral was difficult using XRD, because of its low crystallinity and low content. This paper describes an analytical technique for the characterization of C-S-H gel using a heavy liquid separation method which separates C-S-H gel from Kunigel V1 bentonite (bentonite produced in Japan) based on the difference in specific gravity between the crystalline minerals constituting Kunigel V1 and the secondary C-S-H gel. For development of C-S-H gel separation methods, simulated alteration samples were prepared by mixing 990 mg of unaltered Kunigel V1 and 10 mg of C-S-H gel synthesized using pure chemicals at a ratio of Ca/Si = 1.2. The simulated alteration samples were dispersed in bromoform-methanol mixtures with specific gravities ranging from 2.00 to 2.57 g/cm 3 and subjected to centrifuge separation to recover the light density fraction. Subsequent XRD analysis to identify the minerals was complemented by dissolution in 0.6 N hydrochloric acid to measure the Ca and Si contents. The primary peak (2 θ = 29.4°, Cu Kα) and secondary peaks (2 θ = 32.1

  2. Adaptive resolution simulation of an atomistic DNA molecule in MARTINI salt solution

    NASA Astrophysics Data System (ADS)

    Zavadlav, J.; Podgornik, R.; Melo, M. N.; Marrink, S. J.; Praprotnik, M.

    2016-07-01

    We present a dual-resolution model of a deoxyribonucleic acid (DNA) molecule in a bathing solution, where we concurrently couple atomistic bundled water and ions with the coarse-grained MARTINI model of the solvent. We use our fine-grained salt solution model as a solvent in the inner shell surrounding the DNA molecule, whereas the solvent in the outer shell is modeled by the coarse-grained model. The solvent entities can exchange between the two domains and adapt their resolution accordingly. We critically asses the performance of our multiscale model in adaptive resolution simulations of an infinitely long DNA molecule, focusing on the structural characteristics of the solvent around DNA. Our analysis shows that the adaptive resolution scheme does not produce any noticeable artifacts in comparison to a reference system simulated in full detail. The effect of using a bundled-SPC model, required for multiscaling, compared to the standard free SPC model is also evaluated. Our multiscale approach opens the way for large scale applications of DNA and other biomolecules which require a large solvent reservoir to avoid boundary effects.

  3. The deliquescence behaviour, solubilities, and densities of aqueous solutions of five methyl- and ethyl-aminium sulphate salts

    NASA Astrophysics Data System (ADS)

    Clegg, Simon L.; Qiu, Chong; Zhang, Renyi

    2013-07-01

    We report measured solubilities of five aminium (i.e., monomethyl, dimethyl, trimethyl, diethyl, and triethyl) sulphate salts in water at 24 °C, and the densities of their aqueous solutions. Using these results, we have converted hygroscopic growth factors determined by Qiu and Zhang (Environ. Sci. Technol. 2012, 46, 4474-4480) to a moles of water per mole of solute basis, and obtained the relationships between concentration and equilibrium relative humidity (water activity) for solutions of the five salts. The results are compared with values predicted using the Extended Aerosol Inorganics Model (E-AIM) of Clegg and co-workers (J. Geophys. Res. 2002, 107, D14, Art. No. 4207). It is assumed in this model that ion and water activities in the solutions are the same as those for aqueous (NH4)2SO4 at the same molality. The experimental and modelled growth factors agree well in all cases, within the uncertainties of the data, which supports this assumption. Equations for the apparent molar volumes of the aminium sulphate salts in aqueous solutions are presented (based upon the measured densities and literature data), and also activity products of the salts in saturated aqueous solutions (based upon the measured solubilities and assumption of similarity with (NH4)2SO4). Simulations of the deliquescence curves of 1:1 and 1:9 mass ratio mixtures of monomethyl and dimethyl aminium sulphate with (NH4)2SO4 are shown to agree well with the measurements. The treatment of amines and aminium salts in the E-AIM model is described.

  4. Rubidium-87 NMR studies of rubidium salts and complexes with 18-crown-6 and cryptand-222 in solutions

    NASA Astrophysics Data System (ADS)

    Khazaeli, Sadegh; Dye, James L.; Popov, Alexander I.

    Rubidium-87 NMR measurements were used to study the behavior of the Rb + ion in water, methanol, and propylene carbonate solutions. In aqueous solutions the 87Rb chemical shift varies linearly with the mean activity of the salt. In methanol and propylene carbonate solutions the relationship is linear only at high salt concentrations. The resonance lines are broad and vary from ˜ 150 Hz (at half height) in water to ˜ 1000 Hz in propylene carbonate. Additions of macrocyclic ligands 18C6 and C222 to Rb + solutions in the three solvents result in further broadening of the resonance line so that variations in the resonance frequency cannot be measured with a reasonable precision.

  5. REAL-TIME MONITORING OF A SALT SOLUTION MINING CAVERN: FROM PRECURSORY SIGNS TO GENERAL COLLAPSE

    NASA Astrophysics Data System (ADS)

    Klein, E.; Contrucci, I.; Cao, N.; Bigarré, P.

    2009-12-01

    In order to improve our understanding in brutal large scale ground failure phenomenon, a salt solution mining cavern was instrumented in 2004 previously to its expected collapse as part of its mining scheme. A permanent early warning system was set up, including a high resolution microseismic monitoring network linked to a surface field displacement measurement system. The important amount of data collected during this 5 years experiment offered real-time insight of the evolution of the geological system. The complete data set recorded during the experiment made it possible to track with precision the main stages in the evolution of the cavern. The early signs of failure were detected by high resolution microseismic monitoring during spring 2008: a shift in microseismic background regime as well as recurrent microseismic episodes were undoubtedly associated to a general process of rock failure due to the salt cavern extending up to a critical size. This was accompanied by a few episodes of massive roof falls while the upper part of the overburden remained elastic, with no ground surface movement detected. During a second and last stage of evolution, on-line processing and analysis of a sudden intense microseismic activity allowed the interpretation of the rapid, energetic failure of a thin and very stiff bed rock underlying 120 meters deep. After this failure, the ground surface measurements indicated an irreversible acceleration of the subsidence up to the general collapse 24 hours later. As it will be shown, the in-depth analysis of the whole data set enables to characterize the dynamic process of rupture and its associated precursory signs. It provides also essential knowledge and feedback experience for operational monitoring of underground operations carried out on other sensitive mining sites.

  6. Estimation of salt water upconing using a steady-state solution for partial completion of a pumped well.

    PubMed

    Garabedian, Stephen P

    2013-01-01

    A new steady-state analytical solution to the two-dimensional radial-flow equation was developed for drawdown (head) conditions in an aquifer with constant transmissivity, no-flow conditions at the top and bottom, constant head conditions at a known radial distance, and a partially completed pumping well. The solution was evaluated for accuracy by comparison to numerical simulations using MODFLOW. The solution was then used to estimate the rise of the salt water-fresh water interface (upconing) that occurs under a pumping well, and to calculate the critical pumping rate at which the interface becomes unstable, allowing salt water to enter the pumping well. The analysis of salt water-fresh water interface rise assumed no significant effect on upconing by recharge; this assumption was tested and supported using results from a new steady-state analytical solution developed for recharge under two-dimensional radial-flow conditions. The upconing analysis results were evaluated for accuracy by comparison to those from numerical simulations using SEAWAT for salt water-fresh water interface positions under mild pumping conditions. The results from the equation were also compared with those of a published numerical sharp-interface model applied to a case on Cape Cod, Massachusetts. This comparison indicates that estimating the interface rise and maximum allowable pumping rate using the analytical method will likely be less conservative than the maximum allowable pumping rate and maximum stable interface rise from a numerical sharp-interface model. PMID:23336341

  7. Saturated salt solution method: a useful cadaver embalming for surgical skills training.

    PubMed

    Hayashi, Shogo; Homma, Hiroshi; Naito, Munekazu; Oda, Jun; Nishiyama, Takahisa; Kawamoto, Atsuo; Kawata, Shinichi; Sato, Norio; Fukuhara, Tomomi; Taguchi, Hirokazu; Mashiko, Kazuki; Azuhata, Takeo; Ito, Masayuki; Kawai, Kentaro; Suzuki, Tomoya; Nishizawa, Yuji; Araki, Jun; Matsuno, Naoto; Shirai, Takayuki; Qu, Ning; Hatayama, Naoyuki; Hirai, Shuichi; Fukui, Hidekimi; Ohseto, Kiyoshige; Yukioka, Tetsuo; Itoh, Masahiro

    2014-12-01

    This article evaluates the suitability of cadavers embalmed by the saturated salt solution (SSS) method for surgical skills training (SST). SST courses using cadavers have been performed to advance a surgeon's techniques without any risk to patients. One important factor for improving SST is the suitability of specimens, which depends on the embalming method. In addition, the infectious risk and cost involved in using cadavers are problems that need to be solved. Six cadavers were embalmed by 3 methods: formalin solution, Thiel solution (TS), and SSS methods. Bacterial and fungal culture tests and measurement of ranges of motion were conducted for each cadaver. Fourteen surgeons evaluated the 3 embalming methods and 9 SST instructors (7 trauma surgeons and 2 orthopedists) operated the cadavers by 21 procedures. In addition, ultrasonography, central venous catheterization, and incision with cauterization followed by autosuture stapling were performed in some cadavers. The SSS method had a sufficient antibiotic effect and produced cadavers with flexible joints and a high tissue quality suitable for SST. The surgeons evaluated the cadavers embalmed by the SSS method to be highly equal to those embalmed by the TS method. Ultrasound images were clear in the cadavers embalmed by both the methods. Central venous catheterization could be performed in a cadaver embalmed by the SSS method and then be affirmed by x-ray. Lungs and intestines could be incised with cauterization and autosuture stapling in the cadavers embalmed by TS and SSS methods. Cadavers embalmed by the SSS method are sufficiently useful for SST. This method is simple, carries a low infectious risk, and is relatively of low cost, enabling a wider use of cadavers for SST. PMID:25501070

  8. Saturated Salt Solution Method: A Useful Cadaver Embalming for Surgical Skills Training

    PubMed Central

    Hayashi, Shogo; Homma, Hiroshi; Naito, Munekazu; Oda, Jun; Nishiyama, Takahisa; Kawamoto, Atsuo; Kawata, Shinichi; Sato, Norio; Fukuhara, Tomomi; Taguchi, Hirokazu; Mashiko, Kazuki; Azuhata, Takeo; Ito, Masayuki; Kawai, Kentaro; Suzuki, Tomoya; Nishizawa, Yuji; Araki, Jun; Matsuno, Naoto; Shirai, Takayuki; Qu, Ning; Hatayama, Naoyuki; Hirai, Shuichi; Fukui, Hidekimi; Ohseto, Kiyoshige; Yukioka, Tetsuo; Itoh, Masahiro

    2014-01-01

    Abstract This article evaluates the suitability of cadavers embalmed by the saturated salt solution (SSS) method for surgical skills training (SST). SST courses using cadavers have been performed to advance a surgeon's techniques without any risk to patients. One important factor for improving SST is the suitability of specimens, which depends on the embalming method. In addition, the infectious risk and cost involved in using cadavers are problems that need to be solved. Six cadavers were embalmed by 3 methods: formalin solution, Thiel solution (TS), and SSS methods. Bacterial and fungal culture tests and measurement of ranges of motion were conducted for each cadaver. Fourteen surgeons evaluated the 3 embalming methods and 9 SST instructors (7 trauma surgeons and 2 orthopedists) operated the cadavers by 21 procedures. In addition, ultrasonography, central venous catheterization, and incision with cauterization followed by autosuture stapling were performed in some cadavers. The SSS method had a sufficient antibiotic effect and produced cadavers with flexible joints and a high tissue quality suitable for SST. The surgeons evaluated the cadavers embalmed by the SSS method to be highly equal to those embalmed by the TS method. Ultrasound images were clear in the cadavers embalmed by both the methods. Central venous catheterization could be performed in a cadaver embalmed by the SSS method and then be affirmed by x-ray. Lungs and intestines could be incised with cauterization and autosuture stapling in the cadavers embalmed by TS and SSS methods. Cadavers embalmed by the SSS method are sufficiently useful for SST. This method is simple, carries a low infectious risk, and is relatively of low cost, enabling a wider use of cadavers for SST. PMID:25501070

  9. Salt-enhanced removal of 2-ethyl-1-hexanol from aqueous solutions by adsorption on activated carbon.

    PubMed

    Chang, Ganggang; Bao, Zongbi; Zhang, Zhiguo; Xing, Huabin; Su, Baogen; Yang, Yiwen; Ren, Qilong

    2013-12-15

    2-Ethyl-1-hexanol has extensive industrial applications in solvent extraction, however, in view of its potential pollution to environment, the removal and recovery of 2-ethyl-1-hexanol is considered an essential step toward its sustainable use in the future. In this work, we report the removal of 2-ethyl-1-hexanol from aqueous solutions containing salts in high concentrations by adsorption on a coal-based activated carbon. Adsorption thermodynamics showed that the experimental isotherms were conformed well to the Langmuir equation. Also it was found that inorganic salts, i.e. MgCl2 and CaCl2 in high concentration significantly enhanced the adsorption capacity from 223 mg/g in the deionized water to 277 mg/g in a saline water. This phenomenon of adsorption enhancement could be ascribed to the salt-out effect. Kinetic analysis indicated that adsorption kinetics follows the pseudo-second-order equation and the adsorption rate constants increase with the salt concentration. The dynamic breakthrough volume and adsorbed amount of 2-ethyl-1-hexanol were significantly elevated when the salt is present in the water. The dynamic saturated adsorption amount increased from 218.3mg/g in the deionized water to 309.5mg/g in a salt lake brine. The Tomas model was well applied to predict the breakthrough curves and determine the characteristics parameters of the adsorption column. PMID:24144367

  10. The on-line removal of non-regenerable salts from amine solutions using the UCARSEP{reg_sign} Process

    SciTech Connect

    Burns, D.; Gregory, R.A.

    1995-11-01

    Amine unit contamination with non-regenerable salts, whether as a result of acid or inorganic salt incursion, or solvent degradation, is a common industry problem. In MEA systems this is usually addressed by the use of a reclaimer but this is not a practical solution for DEA, MDEA or formulated solvents. Similarly, the old approach of purging solvent is no longer economically or environmentally justifiable. Neutralization of amine salts with a strong base can significantly prolong the useful life of the amine solution but eventually some of the salt may have to be removed, especially if mechanical losses are low. Electrodialysis (ED) has recently been applied to this problem and has been found to overcome many of the disadvantages of vacuum distillation and ion exchange technologies, both of which have been used in recent years for solvent clean-up. Union Carbide adapted ED technology to the unique conditions encountered in an amine system and developed the UCARSEP{reg_sign} Process. A mobile UCARSEP{reg_sign} unit has been built to achieve on-line salt removal rates of 40 lbmol/day (about 3,300 lb/day). This has been successfully used to clean up UCARSOL{reg_sign} solvents as well as DEA. Case studies are presented and the relative merits of this and other clean-up options are discussed.

  11. SAVANNAH RIVER SITE INCIPIENT SLUDGE MIXING IN RADIOACTIVE LIQUID WASTE STORAGE TANKS DURING SALT SOLUTION BLENDING

    SciTech Connect

    Leishear, R.; Poirier, M.; Lee, S.; Steeper, T.; Fowley, M.; Parkinson, K.

    2011-01-12

    This paper is the second in a series of four publications to document ongoing pilot scale testing and computational fluid dynamics (CFD) modeling of mixing processes in 85 foot diameter, 1.3 million gallon, radioactive liquid waste, storage tanks at Savannah River Site (SRS). Homogeneous blending of salt solutions is required in waste tanks. Settled solids (i.e., sludge) are required to remain undisturbed on the bottom of waste tanks during blending. Suspension of sludge during blending may potentially release radiolytically generated hydrogen trapped in the sludge, which is a safety concern. The first paper (Leishear, et. al. [1]) presented pilot scale blending experiments of miscible fluids to provide initial design requirements for a full scale blending pump. Scaling techniques for an 8 foot diameter pilot scale tank were also justified in that work. This second paper describes the overall reasons to perform tests, and documents pilot scale experiments performed to investigate disturbance of sludge, using non-radioactive sludge simulants. A third paper will document pilot scale CFD modeling for comparison to experimental pilot scale test results for both blending tests and sludge disturbance tests. That paper will also describe full scale CFD results. The final paper will document additional blending test results for stratified layers in salt solutions, scale up techniques, final full scale pump design recommendations, and operational recommendations. Specifically, this paper documents a series of pilot scale tests, where sludge simulant disturbance due to a blending pump or transfer pump are investigated. A principle design requirement for a blending pump is UoD, where Uo is the pump discharge nozzle velocity, and D is the nozzle diameter. Pilot scale test results showed that sludge was undisturbed below UoD = 0.47 ft{sup 2}/s, and that below UoD = 0.58 ft{sup 2}/s minimal sludge disturbance was observed. If sludge is minimally disturbed, hydrogen will not be

  12. Fundamental Properties of Salts

    SciTech Connect

    Toni Y Gutknecht; Guy L Fredrickson

    2012-11-01

    Thermal properties of molten salt systems are of interest to electrorefining operations, pertaining to both the Fuel Cycle Research & Development Program (FCR&D) and Spent Fuel Treatment Mission, currently being pursued by the Department of Energy (DOE). The phase stability of molten salts in an electrorefiner may be adversely impacted by the build-up of fission products in the electrolyte. Potential situations that need to be avoided, during electrorefining operations, include (i) fissile elements build up in the salt that might approach the criticality limits specified for the vessel, (ii) electrolyte freezing at the operating temperature of the electrorefiner due to changes in the liquidus temperature, and (iii) phase separation (non-homogenous solution). The stability (and homogeneity) of the phases can be monitored by studying the thermal characteristics of the molten salts as a function of impurity concentration. Simulated salt compositions consisting of the selected rare earth and alkaline earth chlorides, with a eutectic mixture of LiCl-KCl as the carrier electrolyte, were studied to determine the melting points (thermal characteristics) using a Differential Scanning Calorimeter (DSC). The experimental data were used to model the liquidus temperature. On the basis of the this data, it became possible to predict a spent fuel treatment processing scenario under which electrorefining could no longer be performed as a result of increasing liquidus temperatures of the electrolyte.

  13. In vitro corrosion of ZEK100 plates in Hank's Balanced Salt Solution

    PubMed Central

    2012-01-01

    Background In recent years magnesium alloys have been intensively investigated as potential resorbable materials with appropriate mechanical and corrosion properties. Particularly in orthopedic research magnesium is interesting because of its mechanical properties close to those of natural bone, the prevention of both stress shielding and removal of the implant after surgery. Methods ZEK100 plates were examined in this in vitro study with Hank's Balanced Salt Solution under physiological conditions with a constant laminar flow rate. After 14, 28 and 42 days of immersion the ZEK100 plates were mechanically tested via four point bending test. The surfaces of the immersed specimens were characterized by SEM, EDX and XRD. Results The four point bending test displayed an increased bending strength after 6 weeks immersion compared to the 2 week group and 4 week group. The characterization of the surface revealed the presence of high amounts of O, P and Ca on the surface and small Mg content. This indicates the precipitation of calcium phosphates with low solubility on the surface of the ZEK100 plates. Conclusions The results of the present in vitro study indicate that ZEK100 is a potential candidate for degradable orthopedic implants. Further investigations are needed to examine the degradation behavior. PMID:22413949

  14. Protein-salt binding data from potentiometric titrations of lysozyme in aqueous solutions containing KCl

    SciTech Connect

    Engmann, J.; Blanch, H.W.; Prausnitz, J.M. |

    1997-03-01

    An existing method for potentiometric titrations of proteins was improved, tested and applied to titrations of the enzyme hen-egg-white lysozyme in aqueous solutions containing KCl at ionic strengths from 0.1 M to 2.0 M at 25 C. Information about the protein`s net charge dependence on pH and ionic strength were obtained and salt binding numbers for the system were calculated using a linkage concept. For the pH range 2.5--11.5, the net charge slightly but distinctly increases with increasing ionic strength between 0.1 M and 2.0 M. The differences are most distinct in the pH region below 5. Above pH 11.35, the net charge decreases with increasing ionic strength. Preliminary calculation of binding numbers from titration curves at 0.1 M and 1.0 M showed selective association of chloride anions and expulsion of potassium ions at low pH. Ion-binding numbers from this work will be used to evaluate thermodynamic properties and to correlate crystallization or precipitation phase-equilibrium data in terms of a model based on the integral-equation theory of fluids which is currently under development.

  15. Experimental study of natural convection melting of ice in salt solutions

    SciTech Connect

    Fang, L.J.; Cheung, F.B.; Linehan, J.H.; Pedersen, D.R.

    1984-01-01

    The solid-liquid interface morphology and the micro-physical process near the moving phase boundary during natural convection melting of a horizontal layer of ice by an overlying pool of salt solution were studied experimentally. A cathetometer which amplifies the interface region was used to measure the ice melting rate. Also measured were the temperature transients of the liquid pool. Within the temperature and the density ratio ranges explored, the ice melting rate was found to be very sensitive to the ratio of pool-to-ice melt density but independent of pool-to-ice temperature difference. By varying the density ratio, three different flow regimes and morphologies of the solid-liquid interface were observed, with melt streamers emanating from the crests of the wavy interface into the pool in all three cases. The measured wavelengths (spacing) between the streamers for four different pairs of materials were correlated with the density ratio and found to agree favorably with the predictions of Taylor instability theory.

  16. Salt Solutions in Carbon Nanotubes: The Role of Cation- π Interactions

    NASA Astrophysics Data System (ADS)

    Pham, Tuan Anh; Mortuza, Golam; Wood, Brandon; Lau, Edmond; Ogitsu, Tadashi; Buchsbaum, Steven; Siwy, Zuzanna; Fornasiero, Francesco; Schwegler, Eric

    Understanding the structure of aqueous electrolytes at interfaces is essential for predicting and optimizing device performances for a wide variety of emerging energy and environmental technologies. In this work, we investigate the structure of two common salt solutions, NaCl and KCl, at a hydrophobic interface within narrow carbon nanotubes (CNTs). Using a combination of first-principles and classical molecular dynamics simulations, we find that the solvation structure of the cations in the CNTs can deviate substantially from the conventional weakly interacting hydrophobic picture. Instead, interactions between solvated ions and the π-orbitals of the CNTs are found to play a critically important role, with the ion solvation structure ultimately determined by a subtle interplay between cation- π interactions and the intrinsic flexibility of the solvation shell. In the case of K+, these effects result in an unusually strong propensity to partially desolvate and reside closer to the carbon wall than either Na+ and Cl-, in sharp contrast to the known ion ordering at the water-vapor interface. This work was performed under the auspices of the U.S. Department of Energy by LLNL under Contract DE-AC52-07NA27344.

  17. Influence and hydrolysis kinetics in titanyl sulfate solution from the sodium hydroxide molten salt method

    NASA Astrophysics Data System (ADS)

    Wang, Weijing; Chen, Desheng; Chu, Jinglong; Li, Jie; Xue, Tianyan; Wang, Lina; Wang, Dong; Qi, Tao

    2013-10-01

    Hydrated titanium dioxide (HTD) was precipitated by thermal hydrolysis in purified titanyl sulfate solution (TSS) obtained through the sodium hydroxide molten salt clean method. Various factors including the stirring speed and initial concentrations of TiOSO4, sulfuric acid, and sodium ion were studied. The main influence factors in the hydrolysis process were the initial concentrations of TiOSO4 and sulfuric acid. Contrary to the ferrous ion, the sodium ion improved the ionic activity of Ti4+, but did not decrease the crystal size. The Boltzman growth model (x=A2+(A1-A2)/{1+exp[(t-t0)/dt)]}, which focuses on two main parameters (CTiOSO4 and CH2SO4), fits the hydrolysis process well with R2>0.97. An increase in sulfuric acid concentration negatively affected the hydrolysis rates and the value of A2, while t0 increased. An increase in titanyl sulfate concentration directly reduced the hydrolysis rates and particle size of HTD, contrary to the trend for the value of t0. A simulation software called 1stopt was used to observe the relationship between Z (A1, A2, t0, dt) and a, b (CTiO2 and CH2SO4).

  18. Synergistic effects of inorganic salt and surfactant on phenanthrene removal from aqueous solution by sediment.

    PubMed

    Zhang, Xiaoyan; Wu, Yaoguo; Hu, Sihai; Lu, Cong

    2014-01-01

    The economic and effective application of surfactant enhanced remediation (SER) technology in a sediment-freshwater/saline water system was investigated by batch method using the combined effects of inorganic salt (sodium chloride, NaCl) and anionic surfactant (sodium dodecylbenzene sulfonate (SDBS)) on phenanthrene (PHE) removal via sorption by sediment. In all cases, PHE sorption followed a linear equation and partition as the main mechanism for PHE removal from aqueous solution. Separate addition of SDBS (2 mmol L(-1)) and NaCl (2-100 mmol L(-1)) moderately enhanced PHE removal, while with their combined addition the enhancement was substantial, and the removal efficiency achieved a peak of 92.8%. The combined effect expressed a synergy, and the sorption enhancement increased by factors of 2.7, 3.2 and 3.4 when compared with the sum of the separate entities at elevated salinity. This was because the sorbed SDBS, with increasing amount and a high packing conformation at elevated salinity, outcompeted aqueous SDBS for PHE partition. Moreover, a combination of 2 mmol L(-1) SDBS and 2 mmol L(-1) NaCl was optimal for PHE removal. Therefore, SER technology appears more effective for PHE removal in saline water than in freshwater, and preliminary water quality monitoring is essential for economic and efficient SER application. PMID:25353936

  19. Effect of alkali and alkaline-earth chloride addition on electrolytic reduction of UO 2 in LiCl salt bath

    NASA Astrophysics Data System (ADS)

    Sakamura, Yoshiharu

    2011-05-01

    The electrolytic reduction process of actinide oxides in a LiCl salt bath at 923 K has been developed for nuclear fuel reprocessing. Since some salt-soluble fission products, such as Cs, Sr and Ba, accumulate in the LiCl salt bath, their effect on UO 2 reduction was investigated. In the experiments, UO 2 specimens were reduced by potential- or current-controlled electrolysis in various LiCl salt baths containing up to 30 mol% of KCl, CsCl, SrCl 2 or BaCl 2. The rate of UO 2 reduction in a LiCl salt bath was considerably decreased by the addition of alkali metal chlorides (KCl and CsCl) and slightly decreased by BaCl 2 addition. SrCl 2 addition had no appreciable effect. It was suggested that the diffusion of O 2- ions from the inside of UO 2 specimens to the bulk salt determined the reduction rate during the electrolysis and that the effect of salt composition was related to the solubility of O 2- ions in the salt bath.

  20. Extreme ductile deformation of fine-grained salt by coupled solution-precipitation creep and microcracking: Microstructural evidence from perennial Zechstein sequence (Neuhof salt mine, Germany)

    NASA Astrophysics Data System (ADS)

    Závada, Prokop; Desbois, Guillaume; Schwedt, Alexander; Lexa, Ondrej; Urai, Janos L.

    2012-04-01

    Microstructural study revealed that the ductile flow of intensely folded fine-grained salt exposed in an underground mine (Zechstein-Werra salt sequence, Neuhof mine, Germany) was accommodated by coupled activity of solution-precipitation (SP) creep and microcracking of the halite grains. The grain cores of the halite aggregates contain remnants of sedimentary microstructures with straight and chevron shaped fluid inclusion trails (FITs) and are surrounded by two concentric mantles reflecting different events of salt precipitation. Numerous intra-granular or transgranular microcracks originate at the tips of FITs and propagate preferentially along the interface between sedimentary cores and the surrounding mantle of reprecipitated halite. These microcracks are interpreted as tensional Griffith cracks. Microcracks starting at grain boundary triple junctions or grain boundary ledges form due to stress concentrations generated by grain boundary sliding (GBS). Solid or fluid inclusions frequently alter the course of the propagating microcracks or the cracks terminate at these inclusions. Because the inner mantle containing the microcracks is corroded and is surrounded by microcrack-free outer mantle, microcracking is interpreted to reflect transient failure of the aggregate. Microcracking is argued to play a fundamental role in the continuation and enhancement of the SP-GBS creep during halokinesis of the Werra salt, because the transgranular cracks (1) provide the ingress of additional fluid in the grain boundary network when cross-cutting the FITs and (2) decrease grain size by splitting the grains. More over, the ingress of additional fluids into grain boundaries is also provided by non-conservative grain boundary migration that advanced into FITs bearing cores of grains. Described readjustments of the microstructure and mechanical and chemical feedbacks for the grain boundary diffusion flow in halite-brine system are proposed to be comparable to other rock-fluid or

  1. Growth of single crystals of organic salts with large second-order optical nonlinearities by solution processes for devices

    NASA Technical Reports Server (NTRS)

    Leslie, Thomas M.

    1995-01-01

    Data obtained from the electric field induced second harmonic generation (EFISH) and Kurtz Powder Methods will be provided to MSFC for further refinement of their method. A theoretical model for predicting the second-order nonlinearities of organic salts is being worked on. Another task is the synthesis of a number of salts with various counterions. Several salts with promising SHG activities and new salts will be tested for the presence of two crystalline forms. The materials will be recrystallized from dry and wet solvents and compared for SHG efficiency. Salts that have a high SHG efficiency and no tendency to form hydrates will be documented. The synthesis of these materials are included in this report. A third task involves method to aid in the growth of large, high quality single crystals by solution processes. These crystals will be characterized for their applicability in the fabrication of devices that will be incorporated into optical computers in future programs. Single crystals of optimum quality may be obtained by crystal growth in low-gravity. The final task is the design of a temperature lowering single crystal growth apparatus for ground based work. At least one prototype will be built.

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

    PubMed

    Choi, Jun-Ho; Cho, Minhaeng

    2016-05-28

    Dissolved ions in water tend to form polydisperse ion aggregates such as ion pairs, relatively compact ion clusters, and even spatially extended ion networks with increasing salt concentration. Combining molecular dynamics simulation and graph theoretical analysis methods, we recently studied morphological structures of ion aggregates with distinctively different characteristics. They can be distinguished from each other by calculating various spectral graph theoretical properties such as eigenvalues and eigenvectors of adjacency matrices of ion aggregates and water hydrogen-bonding networks, minimum path lengths, clustering coefficients, and degree distributions. Here, we focus on percolation and graph entropic properties of ion aggregates and water hydrogen-bonding networks in high salt solutions. Ion network-forming K(+) and SCN(-) ions at high concentrations show a percolating behavior in their aqueous solutions, but ion cluster-forming ions in NaCl solutions do not show such a transition from isolated ion aggregates to percolating ion-water mixture morphology. Despite that the ion aggregate structures are strikingly different for either cluster- or network-forming ions in high salt solutions, it is interesting that the water structures remain insensitive to the electrostatic properties, such as charge densities and polydentate properties, of dissolved ions, and morphological structures of water H-bonding networks appear to be highly robust regardless of the nature and concentration of salt. We anticipate that the present graph entropy analysis results would be of use in understanding a variety of anomalous behaviors of interfacial water around biomolecules as well as electric conductivities of high electrolyte solutions. PMID:27250298

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

    NASA Astrophysics Data System (ADS)

    Choi, Jun-Ho; Cho, Minhaeng

    2016-05-01

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

  4. Distributions of 14 elements on 60 selected absorbers from two simulant solutions (acid-dissolved sludge and alkaline supernate) for Hanford HLW Tank 102-SY

    SciTech Connect

    Marsh, S.F.; Svitra, Z.V.; Bowen, S.M.

    1993-10-01

    Sixty commercially available or experimental absorber materials were evaluated for partitioning high-level radioactive waste. These absorbers included cation and anion exchange resins, inorganic exchangers, composite absorbers, and a series of liquid extractants sorbed on porous support-beads. The distributions of 14 elements onto each absorber were measured from simulated solutions that represent acid-dissolved sludge and alkaline supernate solutions from Hanford high-level waste (HLW) Tank 102-SY. The selected elements, which represent fission products (Ce, Cs, Sr, Tc, and Y); actinides (U, Pu, and Am); and matrix elements (Cr, Co, Fe, Mn, Zn, and Zr), were traced by radionuclides and assayed by gamma spectrometry. Distribution coefficients for each of the 1680 element/absorber/solution combinations were measured for dynamic contact periods of 30 min, 2 h, and 6 h to provide sorption kinetics information for the specified elements from these complex media. More than 5000 measured distribution coefficients are tabulated.

  5. Kinetics of the alkaline hydrolysis of 2,4,6-trinitrotoluene in aqueous solution and highly contaminated soils

    SciTech Connect

    Emmrich, M.

    1999-11-01

    During the two World Wars, large amounts of TNT were released into the environment. Until today, high concentrations of TNT can be found in the soil of former ammunition plants. To obtain basic data for a novel treatment process for highly contaminated soils, the homogeneous aqueous hydrolysis of TNT in the pH range from 10 to 12 and the alkaline treatment of two contaminated soils at pH 11 and pH 12 were investigated. The experimental data were described for their respective pH values using a pseudo-first-order model. In the homogeneous experiments, 95--97% of the TNT was hydrolyzed. During alkaline hydrolysis, up to two nitrogroups per TNT molecule were released, indicating the irreversible destruction of TNT. Except for the formation of small traces of amino dinitrotoluenes and trinitrobenzenes, no nitroaromatic benzenes or toluenes were detected during GC analysis. For the less contaminated soil, ELBP2, with an initial TNT concentration of 116 mg/kg, a destruction of 99% was achieved. The highly contaminated soil, HTNT2 (16.1 g of TNT/kg), showed a hydrolyzation level of 90-94%. The results show that the alkaline treatment of highly contaminated soils may prove to be effective as an alternative treatment technology.

  6. Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

    PubMed

    Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

    2016-08-26

    A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. PMID:27485150

  7. Immobilization of ultrafine bimetallic Ni-Pt nanoparticles inside the pores of metal-organic frameworks as efficient catalysts for dehydrogenation of alkaline solution of hydrazine.

    PubMed

    Cao, Nan; Yang, Lan; Dai, Hongmei; Liu, Teng; Su, Jun; Wu, Xiaojun; Luo, Wei; Cheng, Gongzhen

    2014-10-01

    We report a facile liquid impregnation approach for immobilization of ultrafine bimetallic Ni-Pt nanoparticles (NPs) inside the pores of MIL-101. The methods of powder X-ray diffraction, N2 physisorption, X-ray photoelectron spectroscopy, transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy were employed to characterize the NiPt@MIL-101 catalysts and further indicated the as-synthesized Ni-Pt NPs were confined in the pores of MIL-101. These as-synthesized bimetallic NiPt@MIL-101 NPs exhibit exceedingly high catalytic activity, selectivity, and durability toward hydrogen generation from alkaline solution of hydrazine. PMID:25197778

  8. Probing the electron-accepting reactivity of isomeric bis(pyrrolidinium) fullerene salts in aqueous solutions

    SciTech Connect

    Guldi, D.M.

    2000-02-24

    A series of water-soluble isomer bis(pyrrolidinium) salts, with C{sub 60}(C{sub 4}H{sub 10}N{sup +}){sub 2} as cationic moiety (2a--2d), were probed in radical- and light-induced reduction studies and compared to bis(carboxylates) C{sub 60}[C(COO{sup {minus}}){sub 2}]{sub 2} and to {gamma}-CD-encapsulated C{sub 60}. Pulse radiolytic reduction of 2a--2d with hydrated electrons and (CH{sub 3}){sub 2}{sup {sm{underscore}bullet}}COH radicals leads to the formation of the fullerene {pi}-radical anion, exhibiting fingerprint absorption characteristics in the near-IR region. Because of the electron-withdrawing nature of the pyrrolidinium groups the electron-acceptor properties of the investigated bis(pyrrolidinium) salts are markedly improved relative to the bis(carboxylates) (C{sub 60}[C(COO{sup {minus}}){sub 2}]{sub 2}) and also relative to C{sub 60}. For example, the rate constants for the fullerene reduction of 2a--2d with hydrated electrons ((0.88--2.2) x 10{sup 10} M{sup {minus}1} s{sup {minus}1}) and (CH{sub 3}){sub 2}{sm{underscore}bullet}COH radicals ((4.7--7.1) x 10{sup 8} M{sup {minus}1} s{sup {minus}1}) are clearly faster than those noted for C{sub 60}[C(COO{sup {minus}}){sub 2}]{sub 2} (e{sub aq}{sup {minus}}: (0.19--0.34) x 10{sup 10} M{sup {minus}1} s{sup {minus}1}; (CH{sub 3}){sub 2}{sup {sm{underscore}bullet}}COH: (0.9--2.2) x 10{sup 8}M{sup {minus}1} s{sup {minus}1}), and C{sub 60} (e{sub aq}{sup {minus}}: 1.8 x 10{sup 10} M{sup {minus}1} s{sup {minus}1}; (CH{sub 3}){sub 2}{sup {sm{underscore}bullet}}COH: 2.7 x 10{sup 8} M{sup {minus}1} s{sup {minus}1}). Photolysis of 2a--2d gives rise to singlet excited state absorptions that closely resemble earlier observations for the pyrrolidine precursor, e.g., C{sub 60}(C{sub 3}H{sub 7}N){sub 2} (1a--1d) in deoxygenated toluene solutions. The triplet lifetimes of 2a--2d, as measured by nanosecond-resolved photolysis, are typically around 33 {mu}s, similar to the triplet lifetimes of truly monomeric fullerene

  9. Electrochemical activation of carbon cloth in aqueous inorganic salt solution for superior capacitive performance

    NASA Astrophysics Data System (ADS)

    Ye, Dong; Yu, Yao; Tang, Jie; Liu, Lin; Wu, Yue

    2016-05-01

    Carbon cloth (CC) is an inexpensive and highly conductive textile with excellent mechanical flexibility and strength; it holds great promise as an electrode material for flexible supercapacitors. However, pristine CC has such a low surface area and poor electrochemical activity that the energy storage capability is usually very poor. Herein, we report a green method, two-step electrochemical activation in an aqueous solution of inorganic salts, to significantly enhance the capacitance of CC for supercapacitor application. Micro-cracks, exfoliated carbon fiber shells, and oxygen-containing functional groups (OFGs) were introduced onto the surface of the carbon filament. This resulted in an enhancement of over two orders of magnitude in capacitance compared to that of the bare CC electrode, reaching up to a maximum areal capacitance of 505.5 mF cm-2 at the current density of 6 mA cm-2 in aqueous H2SO4 electrolyte. Electrochemical reduction of CC electrodes led to the removal of most electrochemically unstable surface OFGs, resulting in superior charging/discharging rate capability and excellent cycling stability. Although the activated CC electrode contained a high-level of surface oxygen functional groups (~15 at%), it still exhibited a remarkable charging-discharging rate capability, retaining ~88% of the capacitance when the charging rate increased from 6 to 48 mA cm-2. Moreover, the activated CC electrode exhibited excellent cycling stability with ~97% capacitance remaining after 10 000 cycles at a current density of 24 mA cm-2. A symmetrical supercapacitor based on the activated CC exhibited an ideal capacitive behavior and fast charge-discharge properties. Such a simple, environment-friendly, and cost-effective strategy to activate CC shows great potential in the fabrication of high-performance flexible supercapacitors.Carbon cloth (CC) is an inexpensive and highly conductive textile with excellent mechanical flexibility and strength; it holds great promise as

  10. Effects of solution mining of salt on wetland hydrology as inferred from tree rings

    USGS Publications Warehouse

    Yanosky, T.M.; Kappel, W.M.

    1997-01-01

    Radial growth and concentrations of selected elements within rings were studied in white pine (Pinus strobus) trees from a wetland in central New York approximately 5 km north of a salt-solution mining field that operated from 1889 to 1988. Trees seemingly document three sequential episodes of mine-induced alterations of groundwater discharge irrigating the wetland during the 100-year period. The radial growth of trees established before the onset of mining declined abruptly in the early 1890s and remained suppressed until about 1960, as did growth of numerous other trees that became established after the onset of mining. Suppressed pre-1960 radial growth coincided with the interval that surface water was injected into the saltbeds, suggesting that losses of injected water to the bedrock and/or unconsolidated deposits increased groundwater flow into the wetland. An abrupt and sustained enhancement of radial growth beginning about 1960 indicates that the wetland became drier, and thus more conducive to tree growth, when injection practices were discontinued in the late 1950s despite the continued pumping of brine. Following the cessation of mining in the late 1980s, head pressures again increased in the upper valley, driving chloride-enriched flow northward along regional bedding-plane fractures and into the wetland. Large concentrations of chloride were detected within the most recently formed rings of some trees. As the result of chloride-enriched irrigation, the radial growth of some trees declined, and some trees died. Thus trees have preserved evidence of a century of hydrologic alterations, unobtainable by other means, where the effects of brine mining have not been documented previously.

  11. The inhibitive effect of some quaternary ammonium salts towards corrosion of aluminium in hydrochloric acid solution

    NASA Astrophysics Data System (ADS)

    Mohamed, A.-M. K.; Al-Nadjm, A.; Fouda, A.-A. S.

    1998-10-01

    The inhibitive action of some quaternary ammonium salts towards the corrosion of aluminium in hydrochloric acid was tested by thermometric, mass loss and polarization measurements. Parallelism between the different methods was established. It is suggested that the tested compounds act as cathodic inhibitors. The inhibitors appear to function through adsorption, following the Temkin adsorption isotherm. The values of free energy of adsorption have been calculated and discussed. The inhibitor character of the additives depends upon the concentration as well as the composition of the inhibitor. Within the given homolegous series the contribution of the functional group to adsorption increases with the length of the chain. The aim of this article is to throw some light on the mechanism of inhibition of these bulky molecules on the corrosion of aluminium in hydrochloric acid. L'action inhibitrice de certains sels d'ammonium quaternaires vis-à-vis de la corrosion de l'aluminium dans l'acide chlorhydrique en solution a été testée par des mesures thermiques de perte de matière et de polarisation. Il est suggéré que les composés testés agissent comme des inhibiteurs cathodiques, fonctionnant par adsorption suivant l'isotherme de Temkin. Les énergies libres d'adsorption ont été calculées et discutées. Le caractère inhibiteur des additifs dépend aussi bien de leur concentration que de leur composition. Pour une série d'inhibiteurs homologues, la contribution à l'adsorption du groupe fonctionnel augmente avec la longueur de la chaîne. Le but de cet article est de mieux comprendre le mécanisme d'inhibition de ces grosses molécules sur la corrosion de l'aluminium dans l'acide chlorhydrique.

  12. Electrochemical activation of carbon cloth in aqueous inorganic salt solution for superior capacitive performance.

    PubMed

    Ye, Dong; Yu, Yao; Tang, Jie; Liu, Lin; Wu, Yue

    2016-05-21

    Carbon cloth (CC) is an inexpensive and highly conductive textile with excellent mechanical flexibility and strength; it holds great promise as an electrode material for flexible supercapacitors. However, pristine CC has such a low surface area and poor electrochemical activity that the energy storage capability is usually very poor. Herein, we report a green method, two-step electrochemical activation in an aqueous solution of inorganic salts, to significantly enhance the capacitance of CC for supercapacitor application. Micro-cracks, exfoliated carbon fiber shells, and oxygen-containing functional groups (OFGs) were introduced onto the surface of the carbon filament. This resulted in an enhancement of over two orders of magnitude in capacitance compared to that of the bare CC electrode, reaching up to a maximum areal capacitance of 505.5 mF cm(-2) at the current density of 6 mA cm(-2) in aqueous H2SO4 electrolyte. Electrochemical reduction of CC electrodes led to the removal of most electrochemically unstable surface OFGs, resulting in superior charging/discharging rate capability and excellent cycling stability. Although the activated CC electrode contained a high-level of surface oxygen functional groups (∼15 at%), it still exhibited a remarkable charging-discharging rate capability, retaining ∼88% of the capacitance when the charging rate increased from 6 to 48 mA cm(-2). Moreover, the activated CC electrode exhibited excellent cycling stability with ∼97% capacitance remaining after 10 000 cycles at a current density of 24 mA cm(-2). A symmetrical supercapacitor based on the activated CC exhibited an ideal capacitive behavior and fast charge-discharge properties. Such a simple, environment-friendly, and cost-effective strategy to activate CC shows great potential in the fabrication of high-performance flexible supercapacitors. PMID:27141910

  13. Geobacter sp. SD-1 with enhanced electrochemical activity in high-salt concentration solutions.

    PubMed

    Sun, Dan; Call, Douglas; Wang, Aijie; Cheng, Shaoan; Logan, Bruce E

    2014-12-01

    An isolate, designated strain SD-1, was obtained from a biofilm dominated by Geobacter sulfurreducens in a microbial fuel cell. The electrochemical activity of strain SD-1 was compared with type strains, G. sulfurreducens PCA and Geobacter metallireducens GS-15, and a mixed culture in microbial electrolysis cells. SD-1 produced a maximum current density of 290 ± 29 A m−3 in a high-concentration phosphate buffer solution (PBS-H, 200 mM). This current density was significantly higher than that produced by the mixed culture (189 ± 44 A m−3) or the type strains (< 70 A m−3). In a highly saline water (SW; 50 mM PBS and 650 mM NaCl), current by SD-1 (158 ± 4 A m−3) was reduced by 28% compared with 50 mM PBS (220 ± 4 A m−3), but it was still higher than that of the mixed culture (147 ± 19 A m−3), and strains PCA and GS-15 did not produce any current. Electrochemical tests showed that the improved performance of SD-1 was due to its lower charge transfer resistance and more negative potentials produced at higher current densities. These results show that the electrochemical activity of SD-1 was significantly different than other Geobacter strains and mixed cultures in terms of its salt tolerance. PMID:25756125

  14. Photochemical intracomplex reaction between [beta]-cyclodextrin and anthraquinone-2,6-disulfonic acid disodium salt in water solution

    NASA Astrophysics Data System (ADS)

    Petrova, S. S.; Kruppa, A. I.; Leshina, T. V.

    2005-05-01

    1D and 2D 1H NMR studies of anthraquinone-2,6-disulfonic acid disodium salt in the β-cyclodextrin solution have identified the inclusion complex formation. The association constant of AQDS-β-CD inclusion complex was determined as 800 ± 100 M -1. The selective intra-complex photo-oxidation of β-cyclodextrin at C6 position was detected by CIDNP method.

  15. highly selective amino acid salt solutions as absorption liquid for CO(2) capture in gas-liquid membrane contactors.

    PubMed

    Simons, Katja; Nijmeijer, Kitty; Mengers, Harro; Brilman, Wim; Wessling, Matthias

    2010-08-23

    The strong anthropogenic increase in the emission of CO(2) and the related environmental impact force the developments towards sustainability and carbon capture and storage (CCS). In the present work, we combine the high product yields and selectivities of CO(2) absorption processes with the advantages of membrane technology in a membrane contactor for the separation of CO(2) from CH(4) using amino acid salt solutions as competitive absorption liquid to alkanol amine solutions. Amino acids, such as sarcosine, have the same functionality as alkanol amines (e.g., monoethanolamine=MEA), but in contrast, they exhibit a better oxidative stability and resistance to degradation. In addition, they can be made nonvolatile by adding a salt functionality, which significantly reduces the liquid loss due to evaporation at elevated temperatures in the desorber. Membrane contactor experiments using CO(2)/CH(4) feed mixtures to evaluate the overall process performance, including a full absorption/desorption cycle show that even without a temperature difference between absorber and desorber, a CO(2)/CH(4) selectivity of over 70 can be easily achieved with the sarcosine salt solution as absorption liquid. This selectivity reaches values of 120 at a temperature difference between absorber and desorber of 35 degrees C, compared to a value of only 60 for MEA under the same conditions. Although CO(2) permeance values are somewhat lower than the values obtained for MEA, the results clearly show the potential of amino acid salt solutions as competitive absorption liquids for the energy efficient removal of CO(2). In addition, due to the low absorption of CH(4) in sarcosine compared to MEA, the loss of CH(4) is reduced and significantly higher CH(4) product yields can be obtained. PMID:20623726

  16. Absorption of 308-nm excimer laser radiation by balanced salt solution, sodium hyaluronate, and human cadaver eyes

    SciTech Connect

    Keates, R.H.; Bloom, R.T.; Schneider, R.T.; Ren, Q.; Sohl, J.; Viscardi, J.J. )

    1990-11-01

    Absorption of the excimer laser radiations of 193-nm argon fluorine and 308-nm xenon chloride in balanced salt solution, sodium hyaluronate, and human cadaver eyes was measured. The absorption of these materials as considerably different for the two wavelengths; we found that 308-nm light experienced much less absorption than the 193-nm light. The extinction coefficient (k) for 308 nm was k = 0.19/cm for balanced salt solution and k = 0.22/cm for sodium hyaluronate. In contrast to this, the extinction coefficient for 193 nm was k = 140/cm for balanced salt solution and k = 540/cm for sodium hyaluronate. Two 1-day-old human phakic cadaver eyes showed complete absorption with both wavelengths. Using aphakic eyes, incomplete absorption was noted at the posterior pole with 308 nm and complete absorption was noted with 193 nm. The extinction in the anterior part of aphakic eyes (the first 6 mm) was 4.2/cm for 308 nm, meaning that the intensity of the light is reduced by a factor of 10 after traveling the first 5.5 mm. However, we observed that the material in the eye fluoresces, meaning the 308 nm is transformed into other (longer) wavelengths that travel through the total eye with minimal absorption. Conclusions drawn from this experiment are that the use of the 308-nm wavelength may have undesirable side effects, while the use of the 193-nm wavelength should be consistent with ophthalmic use on both the cornea and the lens.

  17. Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

    NASA Astrophysics Data System (ADS)

    Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

    2013-03-01

    A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

  18. Modeling of Flow, Transport and Controlled Sedimentation Phenomena during Mixing of Salt Solutions in Complex Porous Formations

    NASA Astrophysics Data System (ADS)

    Skouras, Eugene D.; Jaho, Sofia; Pavlakou, Efstathia I.; Sygouni, Varvara; Petsi, Anastasia; Paraskeva, Christakis A.

    2015-04-01

    The deposition of salts in porous media is a major engineering phenomenon encountered in a plethora of industrial and environmental applications where in some cases is desirable and in other not (oil production, geothermal systems, soil stabilization etc). Systematic approach of these problems requires knowledge of the key mechanisms of precipitating salts within the porous structures, in order to develop new methods to control the process. In this work, the development and the solution of spatiotemporally variable mass balances during salt solution mixing along specific pores were performed. Both analytical models and finite differences CFD models were applied for the study of flow and transport with simultaneous homogeneous and heterogeneous nucleation (by crystal growth on the surface of the pores) in simple geometries, while unstructured finite elements and meshless methods were developed and implemented for spatial discretization, reconstruction, and solution of transport equations and homogeneous / heterogeneous reactions in more complex geometries. At initial stages of this work, critical problem parameters were identified, such as the characteristics of the porosity, the number of dissolved components, etc. The parameters were then used for solving problems which correspond to available experimental data. For each combination of ions and materials, specific data and process characteristics were included: (a) crystal kinetics (nucleation, growth rates or reaction surface rates of crystals, critical suspension concentrations), (b) physico-chemical properties (bulk density, dimensions of generated crystals, ion diffusion coefficients in the solution), (c) operating parameters (macroscopic velocity, flow, or pressure gradient of the solution, ion concentration) (d) microfluidic data (geometry, flow area), (e) porosity data in Darcy description (initial porosity, specific surface area, tortuosity). During the modeling of flow and transport in three

  19. Thermodynamics of binding water and solute to powdered long-chain salts of fatty acids.

    PubMed

    Mahapatra, P K; Chattoraj, D K

    1994-10-01

    Hydration of powdered fatty acids and their salts has been studied both in presence and absence of neutral salts, sucrose and urea using the isopiestic vapour pressure technique. Moles of water vapour adsorbed per mole or kg of soaps like sodium palmitate, sodium stearate, sodium myristate and sodium laurate have been measured in presence and absence of salts and compared with that of detergents (SDS, CTAB, DTAB and MTAB). For each case of positive excess adsorption of water vapour and negative excess adsorption of inorganic salts, urea and sucrose to different soaps, the standard free energy change (delta G degrees) per kg of substrate in bringing the bulk mole fraction from zero to unity have been calculated using an appropriate thermodynamic equation and the values so obtained have been compared critically. PMID:7851944

  20. Soft X-ray absorption spectra of aqueous salt solutions with highly charged cations in liquid microjets

    SciTech Connect

    Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.

    2010-03-11

    X-ray absorption spectra of 1M aqueous solutions of indium (III) chloride, yttrium (III) bromide, lanthanum (III) chloride, tin (IV) chloride and chromium (III) chloride have been measured at the oxygen K-edge. Relatively minor changes are observed in the spectra compared to that of pure water. SnCl{sub 4} and CrCl{sub 3} exhibit a new onset feature which is attributed to formation of hydroxide or other complex molecules in the solution. At higher energy, only relatively minor, but salt-specific changes in the spectra occur. The small magnitude of the observed spectral changes is ascribed to offsetting perturbations by the cations and anions.

  1. Rheological and kinetic study of the ultrasonic degradation of locust bean gum in aqueous saline and salt-free solutions.

    PubMed

    Li, Ruoshi; Feke, Donald L

    2015-11-01

    The ultrasonic degradation of locust bean gum (LBG) in aqueous solutions has been studied at 25°C for ultrasonication times up to 120 min. Although LBG is not a polyelectrolyte, the degradation extent and kinetics were found to be somewhat sensitive to the ionic conditions in solution, and this is attributed to changes in molecular conformation that can occur in different salt environments. Ultrasonic degradation was tracked by rheological measurements that lead to the determination of intrinsic viscosity for the LBG molecules. A kinetic model was also developed and successfully applied to characterize and predict the degradation results. PMID:26186852

  2. High-pressure densified solid solutions of alkaline earth hexaborides (Ca/Sr, Ca/Ba, Sr/Ba) and their high-temperature thermoelectric properties

    SciTech Connect

    Gürsoy, M.; Takeda, M.; Albert, B.

    2015-01-15

    Solid solutions of alkaline earth hexaborides were synthesized and densified by spark plasma sintering at 100 MPa. The high-temperature thermoelectric properties (Seebeck coefficients, electrical and thermal diffusivities, heat capacities) were measured between room temperature and 1073 K. CaB{sub 6}, SrB{sub 6}, BaB{sub 6} and the ternary hexaborides Ca{sub x}Sr{sub 1−x}B{sub 6}, Ca{sub x}Ba{sub 1−x}B{sub 6}, Sr{sub x}Ba{sub 1−x}B{sub 6} (x = 0.25, 0.5, 0.75) are n-type conducting compounds over the whole compositional and thermal ranges. The values of the figure of merit ZT for CaB{sub 6} (ca. 0.3 at 1073 K) were found to be significantly increased compared to earlier investigations which is attributed to the densification process. - Highlights: • Solid solutions of alkaline earth hexaborides were synthesized. • High-temperature thermoelectric properties of mixed calcium borides are excellent. • Spark plasma source densification results in high ZT values. • Borides are rare-earth free and refractory materials.

  3. Chloride-inducible transient apoplastic alkalinizations induce stomata closure by controlling abscisic acid distribution between leaf apoplast and guard cells in salt-stressed Vicia faba.

    PubMed

    Geilfus, Christoph-Martin; Mithöfer, Axel; Ludwig-Müller, Jutta; Zörb, Christian; Muehling, Karl H

    2015-11-01

    Chloride stress causes the leaf apoplast transiently to alkalize, an event that is presumed to contribute to the ability of plants to adapt to saline conditions. However, the initiation of coordinated processes downstream of the alkalinization is unknown. We hypothesize that chloride-inducible pH dynamics are a key chemical feature modulating the compartmental distribution of abscisic acid (ABA) and, as a consequence, affecting stomata aperture. Apoplastic pH and stomata aperture dynamics in intact Vicia faba leaves were monitored by microscopy-based ratio imaging and porometric measurements of stomatal conductance. ABA concentrations in leaf apoplast and guard cells were compared with pH dynamics by gas-chromatography-mass-spectrometry (GC-MS) and liquid-chromatography-tandem-mass spectrometry (LC-MS/MS). Results demonstrate that, upon chloride addition to roots, an alkalizing factor that initiates the pH dynamic propagates from root to leaf in a way similar to xylem-distributed water. In leaves, it induces a systemic transient apoplastic alkalinization that causes apoplastic ABA concentration to increase, followed by an elevation of endogenous guard cell ABA. We conclude that the transient alkalinization, which is a remote effect of chloride stress, modulates the compartmental distribution of ABA between the leaf apoplast and the guard cells and, in this way, is instrumental in inducing stomata closure during the beginning of salinity. PMID:26096890

  4. Estimation of free acid content in lanthanide salt solutions used for potentiometric determination of stability constant of lanthanide complexes with organic ligands

    SciTech Connect

    Zheltvai, T.I.; Tishchenko, M.A.

    1985-08-20

    This paper studies the possibility of alkalimetric titration of free acid after binding the metal ions by the disodium salt of ethylenediaminetetraacetic (complexone III). The proposed method of free acid determination in lanthanide salt solutions is very simple and helps to avoid gross methodical errors in works involving determination of stability constants of lanthanide complexes.

  5. Real-time monitoring of a salt solution mining cavern: view from microseismic and levelling monitoring

    NASA Astrophysics Data System (ADS)

    Contrucci, Isabelle; Cao, Ngoc-Tuyen; Klein, Emmanuelle; Daupley, Xavier; Bigarre, Pascal

    2010-05-01

    In 2004, in order to better understand processes involved in large-scale mine collapse, an instrumentation was settled in the surrounding of a salt cavern located at a depth of 180 m in NE France. The cavern was mined by solution mining until the large-scale ground failure occurred. A high resolution multi-parameter monitoring system was deployed in the framework of the GISOS (Scientific Interest Group on the Impact and Safety of Underground Structures formed by INERIS, BRGM, INPL and ENSG). Instrumentation, installed by INERIS, consisted of a microseismic network, coupled to automatic-measurement system for levelling (Tacheometer and RTK GPS). Quasi real time transmission of the data to INERIS, at Nancy, enabled rock mass activity of the site to be monitored on a few hours basis. Also, the various recorded observations, in the beginning of spring 2008, led the operator to cause the collapse in February 2009. This was done by intensive extraction of the brine contained in the cavern, which was considered to be at limit equilibrium. On the second day of pumping sudden increase in microseismic activity indicated the start of collapse, followed by manifestation of a surface crater about 35 hours later. All the data and information collected during this experiment are now being processed and back-analysed aimed at ensuring high quality of interpretation. In particular, the space-time distribution of the failures and the evolution of the waveforms enlighten the changing conditions in the geological overburden. When correlated with the measurements of the movement and the known geology, the microseismic data enable a precise description of the failure mechanism(s), and especially of the complex and major role of the overlying bedrock. Similarly, feedback from this experience should lead to practical recommendations concerning collapse phenomena monitoring in such a mining context. While the preliminary results already indicate the exceptional quality of this data set

  6. Insights to caving processes from localization of microseismic swarms induced by salt solution mining

    NASA Astrophysics Data System (ADS)

    Lennart Kinscher, Jannes; Bernard, Pascal; Contrucci, Isabelle; Mangeney, Anne; Piguet, Jack Pierre; Bigarre, Pascal

    2014-05-01

    In order to improve our understanding of hazardous ground failures, caving processes, and collapses of large natural or man-made underground cavities, we studied microseismicity induced by the development and collapse of a salt solution mining cavity with a diameter of ~ 200 m at Cerville-Buissoncourt in Lorraine, France. Microseismicity was recorded as part of a large geophysical, multi-parameter monitoring research project (GISOS) by a local, high resolution, triggered 40 Hz geophone monitoring system consisting of five one-component and four three-component borehole stations located around and in the center of the cavity. The recorded microseismic events are very numerous (~ 50.000 recorded event files) where the major portion (~ 80 %) appear in unusual swarming sequences constituted by complex clusters of superimposed microseismic events. Body wave phase based routine tools for microseismic event detection and localization face strong limitations in the treatment of these signals. To overcome these shortcomings, we developed two probabilistic methods being able to assess the spatio-temporal characteristics in a semi-automatic manner. The first localization approach uses simple signal amplitude estimates on different frequency bands, and an attenuation model to constrain hypocenter source location. The second approach was designed to identify significantly polarized P wave energies and the associated polarization angles. Both approaches and its probabilistic conjunction were applied to the data of a two months lasting microseismic crisis occurring one year before the final collapse that was related to caving processes leading to a maximal growth of ~ 50 m of the cavity roof. The obtained epicenter locations show systematic spatio-temporal migration trends observed for different time scales. During three phases of major swarming activity, epicenter migration trends appear in the order of several seconds to minutes, are spatially constrained, and show partially a

  7. Ultra fast cooling of hot steel plate by air atomized spray with salt solution

    NASA Astrophysics Data System (ADS)

    Mohapatra, Soumya S.; Ravikumar, Satya V.; Jha, Jay M.; Singh, Akhilendra K.; Bhattacharya, Chandrima; Pal, Surjya K.; Chakraborty, Sudipto

    2014-05-01

    In the present study, the applicability of air atomized spray with the salt added water has been studied for ultra fast cooling (UFC) of a 6 mm thick AISI-304 hot steel plate. The investigation includes the effect of salt (NaCl and MgSO4) concentration and spray mass flux on the cooling rate. The initial temperature of the steel plate before the commencement of cooling is kept at 900 °C or above, which is usually observed as the "finish rolling temperature" in the hot strip mill of a steel plant. The heat transfer analysis shows that air atomized spray with the MgSO4 salt produces 1.5 times higher cooling rate than atomized spray with the pure water, whereas air atomized spray with NaCl produces only 1.2 times higher cooling rate. In transition boiling regime, the salt deposition occurs which causes enhancement in heat transfer rate by conduction. Moreover, surface tension is the governing parameter behind the vapour film instability and this length scale increases with increase in surface tension of coolant. Overall, the achieved cooling rates produced by both types of salt added air atomized spray are found to be in the UFC regime.

  8. Plants increase arsenic in solution but decrease the non-specifically bound fraction in the rhizosphere of an alkaline, naturally rich soil.

    PubMed

    Obeidy, Carole; Bravin, Matthieu N; Bouchardon, Jean-Luc; Conord, Cyrille; Moutte, Jacques; Guy, Bernard; Faure, Olivier

    2016-04-01

    We aimed at determining the major physical-chemical processes that drive arsenic (As) dynamic in the rhizosphere of four species (Holcus lanatus, Dittrichia viscosa, Lotus corniculatus, Plantago lanceolata) tested for phytostabilization. Experiments were performed with an alkaline soil naturally rich in As. Composition of the soil solution of planted and unplanted pots was monitored every 15 days for 90 days, with a focus on the evolution of As concentrations in solution and in the non-specifically bound (i.e. easily exchangeable) fraction. The four species similarly increased As concentration in solution, but decreased As concentration in the non-specifically bound fraction. The major part (60%) of As desorbed from the non-specifically bound fraction in planted pots was likely redistributed on the less available fractions of As on the solid phase. A second part (35%) of desorbed As was taken up by plants. The minor part (5%) of desorbed As supplied As increase in solution. To conclude, plants induced a substantial redistribution of As on the less available fractions in the rhizosphere, as expected in phytostabilization strategies. Plants however concomitantly increased As concentration in the rhizosphere solution which may contribute to As transfer through plant uptake and leaching. PMID:26707185

  9. Salting the landscapes in Transbaikalia: natural and technogenic factors

    NASA Astrophysics Data System (ADS)

    Peryazeva, E. G.; Plyusnin, A. M.; Chinavlev, A. M.

    2010-05-01

    Salting the soils, surface and subsurface waters is widespread in Transbaikalia. Hearths of salting occur within intermountain depressions of the Mesozoic and Cenozoic age both in the steppe arid and forest humid landscapes. Total water mineralization reaches 80 g/dm3 in lakes and 4-5 g/dm3 in subsurface waters. The waters belong to hydrocarbonate sodium and sulfate sodium types by chemical composition. The soda type of waters is widely spread through the whole area. Sulfate waters are found in several hearths of salting. Deposition of salts takes place in some lakes. Mirabilite and soda depositions are most commonly observed in muds of salt lakes. Deposition of salts occurs both as a result of evaporative concentrating and during freezing out the solvent. In the winter period, efflorescences of salts, where decawater soda is main mineral, are observed on ice surface. Solonchaks are spread in areas of shallow ground waters (1-2m). Soil salting is most intense in the lower parts of depressions, where surface of ground waters is at depth 0.5-1.0m. In soil cover of solonchaks, salt horizon is of various thicknesses, and it has various morphological forms of occurrence, i.e. as thick deposits of salts on soil surface and salting the surficial horizons. The soil has low alkaline reaction of medium and is characterized by high content of exchangeable bases with significant content of exchangeable sodium in the absorbing complex. Total amount of salts varies from 0.7 to 1.3%. Their maximal quantity (3.1%) is confined to the surficial layer. Sulfate-sodium type of salting is noted in the solonchak upper horizons and sulfate-magnesium-calcium one in the lower ones (Ubugunov et al, 2009). Formation of salting hearths is associated with natural and technogenic conditions. The Mesozoic depressions of Transbaikalia are characterized by intense volcanism. Covers of alkaline and moderately alkaline basalts that are enriched in potassium, sodium, carbon dioxide, fluorine, chlorine

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

    PubMed

    Choi, Jun-Ho; Cho, Minhaeng

    2015-09-14

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

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

    NASA Astrophysics Data System (ADS)

    Choi, Jun-Ho; Cho, Minhaeng

    2015-09-01

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

  12. On the appearance of vorticity and gradient shear bands in wormlike micellar solutions of different CPCl/salt systems

    SciTech Connect

    Mütze, Annekathrin Heunemann, Peggy; Fischer, Peter

    2014-11-01

    Wormlike micellar salt/surfactant solutions (X-salicylate, cetylpyridinium chloride) are studied with respect to the applied shear stress, concentration, temperature, and composition of the counterions (X = lithium, sodium, potassium, magnesium, and calcium) of the salicylate salt solute to determine vorticity and gradient shear bands. A combination of rheological measurements, laser technique, video analysis, and rheo-small-angle neutron scattering allow for a detailed exploration of number and types of shear bands. Typical flow curves of the solutions show Newtonian, shear-thinning, and shear-thickening flow behavior. In the shear-thickening regime, the solutions show vorticity and gradient shear bands simultaneously, in which vorticity shear bands dominate the visual effect, while gradient shear bands always coexist and predominate the rheological response. It is shown that gradient shear bands change their phases (turbid, clear) with the same frequency as the shear rate oscillates, whereas vorticity shear bands change their phases with half the frequency of the shear rate. Furthermore, we show that with increasing molecular mass of the counterions the number of gradient shear bands increases, while the number of vorticity shear bands remains constant. The variation of temperature, shear stress, concentration, and counterions results in a predictable change in the rheological behavior and therefore allows adjustment of the number of vorticity shear bands in the shear band regime.

  13. Computer simulation studies of Aβ37-42 aggregation thermodynamics and kinetics in water and salt solution.

    PubMed

    Yang, Y Isaac; Gao, Yi Qin

    2015-01-22

    In vivo self-assembly of proteins into aggregates known as amyloids is related to many diseases. Although a large number of studies have been performed on the formation of amyloid, the molecular mechanism of polypeptide aggregation remains largely unclear. In this paper, we studied the aggregation of amyloid-forming peptide Aβ37-42 using all-atom molecular dynamics simulations. Using the integrated temperature sampling (ITS) simulation method, we observed the reversible formation of Aβ37-42 oligomers. The free-energy landscape for the polypeptide association was calculated, and aggregated states were then defined based on the landscape. To explore the kinetics and especially salt effects on the process of polypeptide aggregation, normal MD simulations were performed in pure water and NaCl solution, respectively. We then used the transition path theory (TPT) to analyze the transition network of polypeptide aggregation in solution. The dominant pathways of Aβ37-42 aggregation were found to differ significantly in pure water and the salt solution, indicating the change of molecular mechanism of polypeptide aggregation with the solution conditions. PMID:24861904

  14. Self-consistent field theory investigation of the behavior of hyaluronic acid chains in aqueous salt solutions

    NASA Astrophysics Data System (ADS)

    Nogovitsin, E. A.; Budkov, Yu. A.

    2012-04-01

    In this work we continue to develop a field-theoretic methodology, which combines the technique of Gaussian equivalent representation for the calculation of functional integrals with the continuous Gaussian thread model of flexible polymers for solving statistical-mechanical problems of polyelectrolyte solutions. We present new analytic expressions for the osmotic pressure, the potential of mean force, and the monomer-monomer pair distribution function, and employ them to investigate the structural and thermodynamic quantities of the polyelectrolyte system. We demonstrate the applicability of the method for systems of polyelectrolyte chains in which the monomers interact via a Yukawa-type pair potential. As a specific example, the present work focuses on aqueous solutions of hyaluronic acid with added salts NaCl and CaCl2. Hyaluronic acid is a high molecular weight linear polysaccharide, which has a multitude of roles in biological tissues. We conclude that the effect of sodium chloride and calcium chloride on the osmotic properties of hyaluronic acid solutions can be accounted for by their contributions to the ionic strength. Nevertheless, the effects of coiling and self-association can be stimulated in solution by added salt.

  15. Synthesis of size-selected Pt nanoparticles supported on sulfonated graphene with polyvinyl alcohol for methanol oxidation in alkaline solutions

    NASA Astrophysics Data System (ADS)

    Yang, Jen-Ming; Wang, Sheng-An; Sun, Chia-Liang; Ger, Ming-Der

    2014-05-01

    In this study, the size-selected platinum (Pt) nanoparticles are loaded on sulfonated graphene with polyvinyl alcohol (PVA) as the conductive polymer for fuel-cell applications. Methanol oxidation reactions and reliability of various catalysts based on carbon black, graphene, and sulfonated graphene catalyst supports are compared under alkaline conditions. When PVA is used as the conductive polymer in place of Nafion, both the electrochemical active surface area (ECSA) and the methanol oxidation property were superior, irrespective of the catalyst and support. On the other hand, the catalyst with Pt on sulfonated graphene (Pt/sG) outperforms those on other supports. For methanol oxidation, the catalyst decay occurs with a decay of only 9.06% for Pt/sG. It is suggested that the sulfonate functional group on graphene not only improves catalytic activity but can also enhance catalyst reliability.

  16. Bathing in a magnesium-rich Dead Sea salt solution improves skin barrier function, enhances skin hydration, and reduces inflammation in atopic dry skin.

    PubMed

    Proksch, Ehrhardt; Nissen, Hans-Peter; Bremgartner, Markus; Urquhart, Colin

    2005-02-01

    Magnesium salts, the prevalent minerals in Dead Sea water, are known to exhibit favorable effects in inflammatory diseases. We examined the efficacy of bathing atopic subjects in a salt rich in magnesium chloride from deep layers of the Dead Sea (Mavena(R) Dermaline Mg(46) Dead Sea salt, Mavena AG, Belp, Switzerland). Volunteers with atopic dry skin submerged one forearm for 15 min in a bath solution containing 5% Dead Sea salt. The second arm was submerged in tap water as control. Before the study and at weeks 1-6, transepidermal water loss (TEWL), skin hydration, skin roughness, and skin redness were determined. We found one subgroup with a normal and one subgroup with an elevated TEWL before the study. Bathing in the Dead Sea salt solution significantly improved skin barrier function compared with the tap water-treated control forearm in the subgroup with elevated basal TEWL. Skin hydration was enhanced on the forearm treated with the Dead Sea salt in each group, which means the treatment moisturized the skin. Skin roughness and redness of the skin as a marker for inflammation were significantly reduced after bathing in the salt solution. This demonstrates that bathing in the salt solution was well tolerated, improved skin barrier function, enhanced stratum corneum hydration, and reduced skin roughness and inflammation. We suggest that the favorable effects of bathing in the Dead Sea salt solution are most likely related to the high magnesium content. Magnesium salts are known to bind water, influence epidermal proliferation and differentiation, and enhance permeability barrier repair. PMID:15689218

  17. Sensitivity of red oak (Quercus rubra L.) and American beech (Fagus grandifolia Ehrh.) seedlings to sodium salts in solution culture.

    PubMed

    Thorton, F C; Schaedle, M; Raynal, D J

    1988-06-01

    Sodium salt sensitivity of red oak (Quercus rubra L.) and American beech (Fagus grandifolia Ehrh.) was evaluated in solution culture. Both species showed symptoms of salt injury when grown in the presence of less than 10 mM Na. In red oak, leaf symptoms first appeared at a sodium concentration of 6.0 mM and leaf weight was significantly reduced at 7.5 mM Na. Leaf, stem and root dry weights of American beech were significantly reduced in the presence of 4.0 mM sodium. In both species, browning of leaf margins and necrosis were evident in the Na-treated plants. The observed symptoms were associated with high concentrations of sodium in the tissues. Neither species appears to have control over sodium uptake and translocation. PMID:14972826

  18. Dissipation behavior of organophosphorus pesticides during the cabbage pickling process: residue changes with salt and vinegar content of pickling solution.

    PubMed

    Lu, Yuele; Yang, Zhonghua; Shen, Luyao; Liu, Zhenmin; Zhou, Zhiqiang; Diao, Jinling

    2013-03-01

    In this experiment, the behavior of 10 pesticides in three different cabbage pickling treatments has been studied. The brine used for pickling was made up with different salt and vinegar contents to determine the influence of different pickling solutions on pesticide dissipation and distribution. A modified QuECHERS and SPE method was established for the analysis of the pesticides in the cabbage and brine. It was found that different pesticides showed different dissipation patterns and finally represented dissimilar residue levels in the cabbage and brine. Statistical analysis was performed to compare the distinctions of these pesticides between each treatment and proved that salt content and pH value had certain influence on the dissipation and distribution of these pesticides during the pickling process. The data from this experiment would help to control pesticide residues in pickled cabbage and prevent potential risk to human health and environmental safety. PMID:23402557

  19. Molecular-scale hydrophilicity induced by solute: molecular-thick charged pancakes of aqueous salt solution on hydrophobic carbon-based surfaces.

    PubMed

    Shi, Guosheng; Shen, Yue; Liu, Jian; Wang, Chunlei; Wang, Ying; Song, Bo; Hu, Jun; Fang, Haiping

    2014-01-01

    We directly observed molecular-thick aqueous salt-solution pancakes on a hydrophobic graphite surface under ambient conditions employing atomic force microscopy. This observation indicates the unexpected molecular-scale hydrophilicity of the salt solution on graphite surfaces, which is different from the macroscopic wetting property of a droplet standing on the graphite surface. Interestingly, the pancakes spontaneously displayed strong positively charged behavior. Theoretical studies showed that the formation of such positively charged pancakes is attributed to cation-π interactions between Na(+) ions in the aqueous solution and aromatic rings on the graphite surface, promoting the adsorption of water molecules together with cations onto the graphite surface; i.e., Na(+) ions as a medium adsorbed to the graphite surface through cation-π interactions on one side while at the same time bonding to water molecules through hydration interaction on the other side at a molecular scale. These findings suggest that actual interactions regarding carbon-based graphitic surfaces including those of graphene, carbon nanotubes, and biochar may be significantly different from existing theory and they provide new insight into the control of surface wettability, interactions and related physical, chemical and biological processes. PMID:25348642

  20. Molecular-scale Hydrophilicity Induced by Solute: Molecular-thick Charged Pancakes of Aqueous Salt Solution on Hydrophobic Carbon-based Surfaces

    PubMed Central

    Shi, Guosheng; Shen, Yue; Liu, Jian; Wang, Chunlei; Wang, Ying; Song, Bo; Hu, Jun; Fang, Haiping

    2014-01-01

    We directly observed molecular-thick aqueous salt-solution pancakes on a hydrophobic graphite surface under ambient conditions employing atomic force microscopy. This observation indicates the unexpected molecular-scale hydrophilicity of the salt solution on graphite surfaces, which is different from the macroscopic wetting property of a droplet standing on the graphite surface. Interestingly, the pancakes spontaneously displayed strong positively charged behavior. Theoretical studies showed that the formation of such positively charged pancakes is attributed to cation–π interactions between Na+ ions in the aqueous solution and aromatic rings on the graphite surface, promoting the adsorption of water molecules together with cations onto the graphite surface; i.e., Na+ ions as a medium adsorbed to the graphite surface through cation–π interactions on one side while at the same time bonding to water molecules through hydration interaction on the other side at a molecular scale. These findings suggest that actual interactions regarding carbon-based graphitic surfaces including those of graphene, carbon nanotubes, and biochar may be significantly different from existing theory and they provide new insight into the control of surface wettability, interactions and related physical, chemical and biological processes. PMID:25348642

  1. RESULTS OF ROUTINE STRIP EFFLUENT HOLD TANK AND DECONTAMINATED SALT SOLUTION HOLD TANK SAMPLES FROM MODULAR CAUSTIC-SIDE SOLVENT EXTRACTION UNIT DURING MACROBATCH 3 OPERATIONS

    SciTech Connect

    Peters, T.; Fink, S.

    2011-06-10

    Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the 'microbatches' of Integrated Salt Disposition Project (ISDP) Salt Batch ('Macrobatch') 3 have been analyzed for {sup 238}Pu, {sup 90}Sr, {sup 137}Cs, and by Inductively Coupled Plasma Emission Spectroscopy (ICPES). The results indicate good decontamination performance within process design expectations. While the data set is sparse, the results of this set and the previous set of results for Macrobatch 3 samples indicate consistent operations. However, the Decontamination Factors for plutonium and strontium removal have declined in Macrobatch 3, compared to Macrobatch 2. This may be due to the differences in the Pu concentration or the bulk chemical concentrations in the feed material. SRNL is considering the possible reasons for this decline. The DSSHT samples show continued presence of titanium, likely from leaching of the monosodium titanate in ARP. During operation of the ISDP, quantities of salt waste are processed through the Actinide Removal Process (ARP) and MCU in batches of {approx}3800 gallons. Monosodium titanate (MST) is used in ARP to adsorb actinides and strontium from the salt waste and the waste slurry is then filtered prior to sending the clarified salt solution to MCU. The MCU uses solvent extraction technology to extract cesium from salt waste and concentrate cesium in an acidic aqueous stream (Strip Effluent - SE), leaving a decontaminated caustic salt aqueous stream (Decontaminated Salt Solution - DSS). Sampling occurs in the Decontaminated Salt Solution Hold Tank (DSSHT) and Strip Effluent Hold Tank (SEHT) in the MCU process. The MCU sample plan requires that batches be sampled and analyzed for plutonium and strontium content by Savannah River National Lab (SRNL) to determine MST effectiveness. The cesium measurement is used to monitor cesium removal effectiveness and the inductively coupled plasma emission spectroscopy (ICPES) is

  2. An elastic rod model to evaluate effects of ionic concentration on equilibrium configuration of DNA in salt solution.

    PubMed

    Xiao, Ye; Huang, Zaixing; Wang, Shengnan

    2014-03-01

    As a coarse-gained model, a super-thin elastic rod subjected to interfacial interactions is used to investigate the condensation of DNA in a multivalent salt solution. The interfacial traction between the rod and the solution environment is determined in terms of the Young-Laplace equation. Kirchhoff's theory of elastic rod is used to analyze the equilibrium configuration of a DNA chain under the action of the interfacial traction. Two models are established to characterize the change of the interfacial traction and elastic modulus of DNA with the ionic concentration of the salt solution, respectively. The influences of the ionic concentration on the equilibrium configuration of DNA are discussed. The results show that the condensation of DNA is mainly determined by competition between the interfacial energy and elastic strain energy of the DNA itself, and the interfacial traction is one of forces that drive DNA condensation. With the change of concentration, the DNA segments will undergo a series of alteration from the original configuration to the condensed configuration, and the spiral-shape appearing in the condensed configuration of DNA is independent of the original configuration. PMID:24691983

  3. Preparation of porous monolayer film by immersing the stearic acid Langmuir-Blodgett monolayer on mica in salt solution

    NASA Astrophysics Data System (ADS)

    Wang, S.; Li, Y. L.; Zhao, H. L.; Liang, H.; Liu, B.; Pan, S.

    2012-11-01

    Porous materials have drawn attention from scientists in many fields such as life sciences, catalysis and photonics since they can be used to induce some materials growth as expected. Especially, porous Langmuir-Blodgett (LB) film is an ideal material with controlled thickness and flat surface. In this paper, stearic acid (SA), which has been extensively explored in LB film technique, is chosen as the template material with known parameters to prepare the LB film, and then the porous SA monolayer film is obtained by means of etching in salt solution. The main etching mechanism is suggested that the cations in the solution block the electrostatic interaction between the polar carboxyl group of SA and the electronegative mica surface. The influencing factors (such as concentration of salt solution, valence of cation and surface pressure) of the porous SA film are systematically studied in this work. The novel method proposed in this paper makes it convenient to prepare porous monolayer film for designed material growth or cell culture.

  4. History and future of human cadaver preservation for surgical training: from formalin to saturated salt solution method.

    PubMed

    Hayashi, Shogo; Naito, Munekazu; Kawata, Shinichi; Qu, Ning; Hatayama, Naoyuki; Hirai, Shuichi; Itoh, Masahiro

    2016-01-01

    Traditionally, surgical training meant on-the-job training with live patients in an operating room. However, due to advancing surgical techniques, such as minimally invasive surgery, and increasing safety demands during procedures, human cadavers have been used for surgical training. When considering the use of human cadavers for surgical training, one of the most important factors is their preservation. In this review, we summarize four preservation methods: fresh-frozen cadaver, formalin, Thiel's, and saturated salt solution methods. Fresh-frozen cadaver is currently the model that is closest to reality, but it also presents myriad problems, including the requirement of freezers for storage, limited work time because of rapid putrefaction, and risk of infection. Formalin is still used ubiquitously due to its low cost and wide availability, but it is not ideal because formaldehyde has an adverse health effect and formalin-embalmed cadavers do not exhibit many of the qualities of living organs. Thiel's method results in soft and flexible cadavers with almost natural colors, and Thiel-embalmed cadavers have been appraised widely in various medical disciplines. However, Thiel's method is relatively expensive and technically complicated. In addition, Thiel-embalmed cadavers have a limited dissection time. The saturated salt solution method is simple, carries a low risk of infection, and is relatively low cost. Although more research is needed, this method seems to be sufficiently useful for surgical training and has noteworthy features that expand the capability of clinical training. The saturated salt solution method will contribute to a wider use of cadavers for surgical training. PMID:26670696

  5. Alkaline oxide conversion coatings for aluminum alloys

    SciTech Connect

    Buchheit, R.G.

    1996-02-01

    Three related conversion coating methods are described that are based on film formation which occurs when aluminum alloys are exposed to alkaline Li salt solutions. Representative examples of the processing methods, resulting coating structure, composition and morphology are presented. The corrosion resistance of these coatings to aerated 0.5 M NaCl solution has been evaluated as a function of total processing time using electrochemical impedance spectroscopy (EIS). This evaluation shows that excellent corrosion resistance can be uniformly achieved using no more than 20 minutes of process time for 6061-T6. Using current methods a minimum of 80 minutes of process time is required to get marginally acceptable corrosion resistance for 2024-T3. Longer processing times are required to achieve uniformly good corrosion resistance.

  6. RECLAMATION OF ALKALINE ASH PILES

    EPA Science Inventory

    The objective of the study was to develop methods for reclaiming ash disposal piles for the ultimate use as agricultural or forest lands. The ashes studied were strongly alkaline and contained considerable amounts of salts and toxic boron. The ashes were produced from burning bit...

  7. Spiropyran salts and their neutral precursors: synthesis, crystal structure, photochromic transformations in solutions and solid state

    NASA Astrophysics Data System (ADS)

    Yurieva, E. A.; Aldoshin, S. M.

    2015-06-01

    This review covers investigations of spiropyran iodides with N-substituted indoline fragment, and with the pyran cycle being annelated to N-methylated pyridine ring. The schemes of synthesis of iodides and their neutral precursors, as well as results of X-ray analysis and photochemical study of the crystals of the obtained compounds are presented. Based on our and literature data, the relationship between the structure and photochromic properties has been discussed for a series of salts and neutral pyridospiropyrans.

  8. Viscosity Behavior of α-Amino Acids in Acetate Salt Solutions at Temperatures (303.15 to 323.15) K

    NASA Astrophysics Data System (ADS)

    Siddique, Jamal Akhter; Naqvi, Saeeda

    2012-01-01

    Viscosities of l-lysine monohydrochloride, l-histidine, and l-arginine in 1 m (mol · kg-1) aqueous solutions of sodium acetate, potassium acetate, and calcium acetate salts has been determined at (303.15, 308.15, 313.15, 318.15, and 323.15) K. The Falkenhagen coefficient, A, and Jones-Dole coefficient, B, relative viscosity, and specific viscosity of the solutions have also been determined using the measured viscosities. The results are interpreted in terms of solute-solute and solute-solvent interactions occurring in the system under investigation and also discussed in terms of the structure-making/breaking ability of the solute in these salt solutions. The structure making/breaking abilities of the solutes in the studied systems are strongly influenced by temperature.

  9. Enhanced removal of trace Cr(VI) from neutral and alkaline aqueous solution by FeCo bimetallic nanoparticles.

    PubMed

    Qin, Nannan; Zhang, Ya; Zhou, Hongjian; Geng, Zhigang; Liu, Gang; Zhang, Yunxia; Zhao, Huijun; Wang, Guozhong

    2016-06-15

    The reactivity of zero valent iron (Fe(0)) for removing Cr(VI) is self-inhibiting under neutral and alkaline conditions, due to the precipitation of ferrous hydroxide on the surface of Fe(0). To overcome this difficulty, we incorporated a second metal (Co) into Fe(0) to form FeCo bimetallic nanoparticles (FeCo BNPs), which can achieve higher activity and significant improvement in the reaction kinetics for the removal of Cr(VI) compared with Fe(0). The FeCo BNPs were synthesized by a hydrothermal reduction method without using any templates. The characterization analysis indicated that the products were highly uniform in large scale with 120-140 nm size in diameter. The obtained FeCo BNPs exhibited a remarkable removal ability for Cr(VI) in the pH range of 5.3-10.0. Especially, FeCo BNPs were able to reduce trace Cr(VI) (1.0 mg L(-1), pH=7.5) down to about 0.025 mg L(-1) within 1h. XPS analysis confirmed that Cr(VI) was reduced to Cr(III) by FeCo BNPs, while Fe and Co was oxidized, implying a chemical reduction process. The enhanced removal of trace Cr(VI) could be originated from the introduction of Co, which not only served as a protecting agent against surface corrosion by galvanic cell effect, but also enhanced the efficient flow of electron transfer between iron and Cr(VI). All the results primarily imply that FeCo BNPs can be employed as high efficient material for wastewater treatment. PMID:26998785

  10. Dielectric relaxation and underlying dynamics of electrolyte solutions and solvent-molten salt mixtures using terahertz time-domain transmission spectroscopy

    NASA Astrophysics Data System (ADS)

    Asaki, Melanie Lynette Thongs

    Terahertz (THz) transmission spectroscopy is used to obtain the frequency dependent complex dielectric constants of water, methanol, and propylene carbonate, and solutions of lithium salts in these solvents, as well as mixtures of acetonitrile and a room-temperature molten salt. The behavior of the pure solvents is modeled with either two (water and acetonitrile) or three (methanol and propylene carbonate) Debye relaxations. For solutions of lithium salts, the effects of ionic solvation on the relaxation behavior of the solvents is discussed in terms of modifications to the values of the Debye parameters of the pure solvents. In this way we obtain estimates for numbers of irrotationally bound solvent molecules, the numbers of bonds broken or formed, and the effects of ions on the higher frequency relaxations. The same information was obtained for molten salt-acetonitrile systems. In addition, it was determined that at low molten salt concentrations, the mixtures behave like electrolyte solutions of a crystalline salt dissolved in a solvent. At higher molten salt concentrations, the behavior is that of a mixture of two liquids.

  11. The solution structure of the four-way DNA junction at low-salt conditions: a fluorescence resonance energy transfer analysis.

    PubMed Central

    Clegg, R M; Murchie, A I; Lilley, D M

    1994-01-01

    The four-way DNA (Holliday) junction is an important postulated intermediate in the process of genetic recombination. Earlier studies have suggested that the junction exists in two alternative conformations, depending upon the salt concentration present. At high salt concentrations the junction folds into a stacked X structure, while at low salt concentrations the data indicate an extended unstacked conformation. The stereochemical conformation of the four-way DNA junction at low salt (low alkali ion concentration and no alkaline earth ions) was established by comparing the efficiency of fluorescence resonance energy transfer (FRET) between donor and acceptor molecules attached pairwise in three permutations to the 5' termini of the duplex arms. A new variation of FRET was implemented based upon a systematic variation of the fraction of donor labeled single strands. The FRET results indicate that the structure of the four-way DNA junction at low salt exists as an unstacked, extended, square arrangement of the four duplex arms. The donor titration measurements made in the presence of magnesium ions clearly show the folding of the junction into the X stacked structure. In addition, the FRET efficiency can be measured. The fluorescence anisotropy of the acceptor in the presence of Mg2+ during donor titrations was also measured; the FRET efficiency can be calculated from the anisotropy data and the results are consistent with the folded, stacked X structure. PMID:8130350

  12. Limitations of amorphous content quantification by isothermal calorimetry using saturated salt solutions to control relative humidity: alternative methods.

    PubMed

    Khalef, Nawel; Pinal, Rodolfo; Bakri, Aziz

    2010-04-01

    Despite the high sensitivity of isothermal calorimetry (IC), reported measurements of amorphous content by this technique show significant variability even for the same compound. An investigation into the reasons behind such variability is presented using amorphous lactose and salbutamol sulfate as model compounds. An analysis was carried out on the heat evolved as a result of the exchange of water vapor between the solid sample during crystallization and the saline solution reservoir. The use of saturated salt solutions as means of control of the vapor pressure of water within sealed ampoules bears inherent limitations that lead in turn to the variability associated with the IC technique. We present an alternative IC method, based on an open cell configuration that effectively addresses the limitations encountered with the sealed ampoule system. The proposed approach yields an integral whose value is proportional to the amorphous content in the sample, thus enabling reliable and consistent quantifications. PMID:19774655

  13. Solution-based approaches for making high-density sodalite waste forms to immobilize spent electrochemical salts

    NASA Astrophysics Data System (ADS)

    Lepry, William C.; Riley, Brian J.; Crum, Jarrod V.; Rodriguez, Carmen P.; Pierce, David A.

    2013-11-01

    Three different solution-based approaches were taken to make sodalite minerals as a host for a mixed salt simulating the waste in the electrochemical separations process of nuclear fuel reprocessing. The methods used an aqueous solution of mixed chlorides (simulated waste) but the other reactants varied: (1) Al(OH)3 + NaOH + CS, (2) NaAlO2 + CS, and (3) Al2Si2O7 + NaOH, (CS = colloidal silica). The products were dried, ground, pressed into pellets, and fired at 650-950 °C. In some cases, either 5 or 10 mass% of a Si-Na-B oxide glass sintering aid was introduced at different stages in the process. Method (2) proved the most successful at producing high sodalite fractions (up to 100%) with minimal sintering aid additions and showed high consolidation potential (up to 91.4% of theoretical density) at reduced firing temperatures.

  14. Inclusion of two push-pull N-methylpyridinium salts in anionic surfactant solutions: a comprehensive photophysical investigation.

    PubMed

    Cesaretti, Alessio; Carlotti, Benedetta; Consiglio, Giuseppe; Del Giacco, Tiziana; Spalletti, Anna; Elisei, Fausto

    2015-06-01

    Two N-methylpyridinium salts with push-pull properties have been investigated in the aqueous solution of anionic micelles of sodium dodecyl sulfate (SDS) and potassium p-(octyloxy)benzenesulfonate (pOoBSK) surfactants. These molecules are known to be extremely sensitive to the local environment, with their absorption spectrum being subjected to a net negative solvatochromism. These compounds are also characterized by an excited state deactivation strictly dependent on the physical properties of the chemical surrounding, with the formation of intramolecular charge-transfer (ICT) states accordingly stabilized. Thanks to steady-state and femtosecond resolved spectroscopic techniques, the photophysical properties of these molecules in the presence of anionic micelles have been fully characterized and an efficient permeation within the micellar aggregates can thus be inferred. The extent of the changes in the photophysical properties of these molecules (with respect to what is observed in water) is an indicator of the medium experienced in the nanoheterogeneous solutions: enhanced fluorescence emissions, reduced Stokes shifts and slowed-down excited state decays strongly confirm the confinement within a scarcely polar and restraining environment. The slightly different behavior shown in the two types of micelles can be ascribed to a peculiar interaction between the aromatic moiety of the surfactant and that of the cations. Additionally, the inclusion promotes the solubilization of these poorly water-soluble salts, which is alluring in their promising use as DNA binders for antitumor purposes. Thus, the anionic micelles allowed the solubilization of the pyridinium salts under investigation, which in turn allowed the characterization of the nonhomogeneous medium established by the micellar aggregates. PMID:25945687

  15. Water Uptake By Mars Salt Analogs: An Investigation Of Stable Aqueous Solutions On Mars Using Raman Microscopy

    NASA Astrophysics Data System (ADS)

    Nuding, D.; Gough, R. V.; Jorgensen, S. K.; Tolbert, M. A.

    2013-12-01

    To understand the formation of briny aqueous solutions on Mars, a salt analog was developed to closely match the individual cation and anion concentrations as reported by the Wet Chemistry Laboratory aboard the Phoenix Lander. ';Instant Mars' is a salt analog developed to fully encompass the correct concentrations of magnesium, calcium, potassium, sodium, perchlorate, chloride, and sulfate ions. Using environmental Raman microscopy, we have studied the water uptake by the Instant Mars analog as a function of temperature and relative humidity. Water uptake was monitored using Raman spectroscopy in combination with optical microscopy. A MicroJet droplet generator was used to generate 30 μm diameter particles that were deposited onto a quartz disc. The particles undergo visual transformations as the relative humidity (RH) is increased and the presence of water uptake is confirmed by Raman spectroscopy. At -30° C, water uptake begins at ~ 35% RH as humidity is increased. The water uptake is marked by the growth of a sulfate peak at 990 cm-1, an indicator that sulfate has undergone a phase transition into an aqueous state. As the RH continues to increase, the peak in the O-H region (~3500 cm-1) broadens as more liquid water accumulates in the particles. The Instant Mars particles achieve complete deliquescence at 68% RH, indicated both visually and with Raman spectroscopy. The gradual water uptake observed suggests that deliquescence of the Instant Mars particles is not an immediate process, but that it occurs in steps marked by the deliquescence of the individual salts. Perhaps of even more significance is the tendency for the Instant Mars particles to remain aqueous at low humidity as RH is decreased. Raman spectra indicate that liquid water is present as low as 2% RH at -30° C. Ongoing work will examine the phase of Instant Mars particles under simulated Martian surface and subsurface conditions to gain insight into the possibility for aqueous solutions on Mars

  16. Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions.

    PubMed

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-12-15

    Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na2SO4 as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO2-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV-visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature. PMID:19647934

  17. Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds.

    PubMed

    Klotz, S; Komatsu, K; Pietrucci, F; Kagi, H; Ludl, A-A; Machida, S; Hattori, T; Sano-Furukawa, A; Bove, L E

    2016-01-01

    It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty » high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl∙RH2O and LiBr∙RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random. PMID:27562476

  18. Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds

    PubMed Central

    Klotz, S.; Komatsu, K.; Pietrucci, F.; Kagi, H.; Ludl, A.-A.; Machida, S.; Hattori, T.; Sano-Furukawa, A.; Bove, L. E.

    2016-01-01

    It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty » high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl∙RH2O and LiBr∙RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random. PMID:27562476

  19. Aggregation and antigenicity of virus like particle in salt solution--A case study with hepatitis B surface antigen.

    PubMed

    Chen, Yi; Zhang, Yan; Quan, Can; Luo, Jian; Yang, Yanli; Yu, Mengran; Kong, Yingjun; Ma, Guanghui; Su, Zhiguo

    2015-08-20

    The phenomenon of aggregation of virus-like particles (VLPs) in salt solution and the corresponding effect upon antigenicity was reported. Asymmetrical flow field-flow fractionation (AF4) combined with multi-angle laser light scattering (MALLS) was used to characterize the size and the aggregation behavior of hepatitis B surface antigen (HBsAg). The average diameter of HBsAg VLP was 22.8±0.4 nm and it tended to aggregate in salt solution to form large particles and the antigenicity changed accordingly. In 0-4 M NaCl solution, part of HBsAg molecules aggregated rapidly into oligomeric particles (OP), whose diameter distributed from 25 to 40 nm, and the antigenicity slightly decreased about 10%. The aggregation reaction is reversible. After removing NaCl, both size and antigenicity could recover to normal level (92-96%). By contrast, the aggregation process is more complicated in (NH4)2SO4 solution. Most of HBsAg particles aggregated into OP and further aggregated into polymeric particles (PP). The diameter of the PP could reach 40 to 140 nm. The concentration of (NH4)2SO4 had remarkable influence upon the rate of aggregation. When concentration of (NH4)2SO4 was below 1 M, most of HBsAg aggregated only into OP in 1 h. While with concentration of (NH4)2SO4 above 1 M, most of particles formed PP within 1 h. The aggregation process to PP was irreversible. After removing (NH4)2SO4, the large aggregates could not recover to normal particles and the remaining antigenicity was below 30%. PMID:25862298

  20. Production and characterization of a halo-, solvent-, thermo-tolerant alkaline lipase by Staphylococcus arlettae JPBW-1, isolated from rock salt mine.

    PubMed

    Chauhan, Mamta; Garlapati, Vijay Kumar

    2013-11-01

    Studies on lipase production and characterization were carried out with a bacterial strain Staphylococcus arlettae JPBW-1 isolated from rock salt mine, Darang, HP, India. Higher lipase activity has been obtained using 10 % inoculum with 5 % of soybean oil as carbon source utilizing a pH 8.0 in 3 h at 35 °C and 100 rpm through submerged fermentation. Partially purified S. arlettae lipase has been found to be active over a broad range of temperature (30-90 °C), pH (7.0-12.0) and NaCl concentration (0-20 %). It has shown extreme stability with solvents such as benzene, xylene, n-hexane, methanol, ethanol and toluene up to 30 % (v/v). The lipase activity has been found to be inhibited by metal ions of K(+), Co(2+) and Fe (2+) and stimulated by Mn(2+), Ca(2+) and Hg(2+). Lipase activity has been diminished with denaturants, but enhanced effect has been observed with surfactants, such as Tween 80, Tween 40 and chelator EDTA. The K m and V max values were found to be 7.05 mM and 2.67 mmol/min, respectively. Thus, the lipase from S. arlettae may have considerable potential for industrial application from the perspectives of its tolerance towards industrial extreme conditions of pH, temperature, salt and solvent. PMID:23955348

  1. Salting-out in the aqueous single-protein solution: the effect of shape factor.

    PubMed

    Chang, Bong Ho; Bae, Young Chan

    2003-06-01

    A molecular-thermodynamic model is developed to describe salt-induced protein precipitation. The protein-protein interaction goes through the potential of mean force. An equation of state is derived based on the generalized van der Waals partition function. The attractive term including the potential of mean force is perturbed by the statistical mechanical perturbation theory. The precipitation behaviors are studied by calculating the partition coefficient with various conditions such as the ionic strength and the shape of protein. Our results show that the protein shape plays a significant role in the protein precipitation behavior. PMID:12878319

  2. Poly(amidoamine) salt form: effect on pH-dependent membrane activity and polymer conformation in solution.

    PubMed

    Wan, Ka-Wai; Malgesini, Beatrice; Verpilio, Ilario; Ferruti, Paolo; Griffiths, Peter C; Paul, Alison; Hann, Anthony C; Duncan, Ruth

    2004-01-01

    On exposure to an acidic pH, linear poly(amidoamine)s (PAAs) cause membrane perturbation and consequently have potential as endosomolytic polymers for the intracellular delivery of genes and toxins. Previous studies used PAAs in the hydrochloride form only. The aim of this study was to investigate systematically the effect of the PAA counterion on pH-dependent membrane activity, general cytotoxicity, and PAA solution properties to help guide optimization of PAA structure for further development of PAA-protein conjugates. PAAs (ISA 1, 4, 22, and 23; M(w) 10000-50000 g/mol) were synthesized to provide a library of PAAs having different counterions including the acetate, citrate, hydrochloride, lactate, phosphate, and sulfate salts. pH-Dependent membrane activity was assessed using a rat red blood cell haemolysis assay (conducted at a starting pH of 7.4, 6.5, or 5.5; 1 mg/mL; 1 h), and general cytotoxicity was investigated using a murine melanoma cell line (B16F10) and a human bladder endothelial-like cell line (ECV-304). Whereas poly(ethyleneimine) was haemolytic at the starting pH of 7.4 at 1 h [ approximately 50% haemoglobin (Hb) release], none of the PAA salts were haemolytic at a starting pH of 7.4 or 6.5. Although PAA acetate, citrate, and lactate were also non-haemolytic at the starting pH of 5.5, the sulfate and hydrochloride forms caused significant haemolysis (up to 80% Hb release) and ISA 22 and 23 phosphate were also markedly haemolytic ( approximately 70% Hb release). These counterion-specific differences were also clearly visible using scanning electron microscopy, which was used to visualize the red blood cell morphology. All PAAs were relatively nontoxic (IC(50) >or= 300-5000 microg/mL) compared to poly-l-lysine (IC(50) = 2-10 microg/mL), the PAA hydrochloride salts produced the greatest cytotoxicity, and the B16F10 cells were more sensitive than the ECV-304 cells. Small-angle neutron scattering suggested that ISA 23 hydrochloride had a larger

  3. Water dynamics in aqueous solutions of tetra-n-alkylammonium salts: hydrophobic and Coulomb interactions disentangled.

    PubMed

    van der Post, Sietse T; Scheidelaar, Stefan; Bakker, Huib J

    2013-12-01

    We studied the effects of tetra-n-alkylammonium bromide (N(C(n)H(2n+1))(4)(+)Br(-)) salts on the dynamics of water using polarization-resolved femtosecond infrared spectroscopy. With this technique, we are capable of distinguishing the response of water solvating the hydrophobic cations from that of water solvating the bromide anion. We observe that both types of ions slow down the orientational dynamics of the water molecules in their solvation shells. However, the nature of this slowdown is different for both ions. For the hydrophobic cation, we find an increasing number of retarded water molecules, scaling with the alkyl chain length. Water in the bromide solvation shell experiences a partial decay of its orientation by a fast wobbling motion, after which the remaining anisotropy decays much slower. The dynamics of the wobbling motion are observed to be dependent on the nature of the cation. For Me(4)NBr, the slow reorientation time is not concentration-dependent, and no aggregation is observed. This is in contrast to the tetra-n-alkylammonium salts with longer alkyl chains, for which the slow reorientation time of bromide-bound water molecules increases dramatically with concentration, and clusters of cations and anions appear to be formed. PMID:24228939

  4. Synthesis and characterization of vinylimidazolium salts: Solution state study to realize the influence of different anions

    NASA Astrophysics Data System (ADS)

    Suresh, Paladugu; Samanta, Arpan; Sathyanarayana, Arruri; Prabusankar, Ganesan

    2012-09-01

    New vinylimidazolium salts, [9,10-bis{(N-vinylimidazolium)methyl}anthracene] bistetrafluoroborate (2) and [9,10-bis{(N-vinylimidazolium)methyl}anthracene] bishexafluorophosphate (3) have been prepared by the N alkylation of 9,10-bis(chloromethyl)anthracene with 1-vinylimidazole in 1,4-dioxane at 70 °C followed by the anion exchange reaction between [9,10-bis{(N-vinylimidazolium)methyl}anthracene] dichloride (1) and ammonium salt of tetrafluoroborate (for 2) or hexafluorophosphate (for 3). The interaction of tribromide anion with 1-3 has been studied with the help of 1H NMR and fluorescence spectra. Notably, the tribromide anion exhibits very strong fluorescent quenching effects towards 2 than 1 and 3. Similarly, 2 shows very strong fluorescent quenching effect in the presence of tribromide anion compare to bromide anion. Moreover the proton of imidazolium cation, Nsbnd CHsbnd N in 2 undergoes considerable downfield shift in the presence of tribromide anion, while the vinyl group depicts strong upfield shift due to the possible interaction of tribromide with vinylimidazolium unit.

  5. Uranium mobility during interaction of rhyolitic obsidian, perlite and felsite with alkaline carbonate solution: T = 120° C, P = 210 kg/cm2

    USGS Publications Warehouse

    Zielinski, Robert A.

    1979-01-01

    Well-characterized samples of rhyolitic obsidian, perlite and felsite from a single lava flow are leached of U by alkaline oxidizing solutions under open-system conditions. Pressure, temperature, flow rate and solution composition are held constant in order to evaluate the relative importance of differences in surface area and crystallinity. Under the experimental conditions U removal from crushed glassy samples proceeds by a mechanism of glass dissolution in which U and silica are dissolved in approximately equal weight fractions. The rate of U removal from crushed glassy samples increases with decreasing average grain size (surface area). Initial rapid loss of a small component (≈ 2.5%) of the total U from crushed felsite. followed by much slower U loss, reflects variable rates of attack of numerous uranium sites. The fractions of U removed during the experiment ranged from 3.2% (felsite) to 27% (perlite). An empirical method for evaluating the relative rate of U loss from contemporaneous volcanic rocks is presented which incorporates leaching results and rock permeability data.

  6. Recycling of waste printed circuit boards with simultaneous enrichment of special metals by using alkaline melts: A green and strategically advantageous solution.

    PubMed

    Stuhlpfarrer, Philipp; Luidold, Stefan; Antrekowitsch, Helmut

    2016-04-15

    The increasing consumption of electric and electronic equipment has led to a rise in toxic waste. To recover the metal fraction, a separation of the organic components is necessary because harmful substances such as chlorine, fluorine and bromine cause ecological damage, for example in the form of dioxins and furans at temperature above 400°C. Hence, an alternative, environmentally friendly approach was investigated exploiting that a mixture of caustic soda and potassium hydroxide in eutectic composition melts below 200°C, enabling a fast cracking of the long hydrocarbon chains. The trials demonstrate the removal of organic compounds without a loss of copper and precious metals, as well as a suppressed formation of hazardous off-gases. In order to avoid an input of alkaline elements into the furnace and ensuing problems with refractory materials, a washing step generates a sodium and potassium hydroxide solution, in which special metals like indium, gallium and germanium are enriched. Their concentrations facilitate the recovery of these elements, because otherwise they become lost in the typical recycling processes. The aim of this work was to find an environmental solution for the separation of plastics and metals as well as a strategically important answer for the recycling of printed circuit boards and mobile phones. PMID:26775099

  7. Novel one-step synthesis of wool-ball-like Ni-carbon nanotubes composite cathodes with favorable electrocatalytic activity for hydrogen evolution reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Chen, Zhouhao; Ma, Zhipeng; Song, Jianjun; Wang, Lixin; Shao, Guangjie

    2016-08-01

    In this work, supergravity fields are performed to prepare Ni-CNTs composite cathodes with wool-ball-like morphology from the Watts bath containing well-distributed functionalized CNTs. The prepared Ni-CNTs composite cathodes are used as noble metal-free electrocatalyst with favorable electrocatalytic activity for hydrogen evolution reaction (HER) in alkaline solutions. The crystal structure and morphology of the composite cathodes are characterized by XRD and SEM measurements. The electrochemical activities of the cathodes are characterized through Tafel polarization measurement, electrochemical impedance spectroscopy and cyclic voltammetric study in 1.0 M NaOH solution. The results indicate that catalytic activities of the Ni-CNTs cathodes prepared under supergravity fields are enhanced significantly, and the sample prepared at rotating speed 3000 rpm from the bath containing 1 g dm-3 CNTs exhibits the highest HER activity with smallest Tafel slope and largest exchange current density of 823.9 μA cm-2. Furthermore, the effects of both the CNTs concentrations and the intensities of supergravity fields on the properties of the Ni-CNTs cathodes are investigated.

  8. Non-monotonic course of protein solubility in aqueous polymer-salt solutions can be modeled using the sol-mxDLVO model.

    PubMed

    Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele

    2016-02-01

    Protein purification is often performed using cost-intensive chromatographic steps. To discover economic alternatives (e.g., crystallization), knowledge on protein solubility as a function of temperature, pH, and additives in solution as well as their concentration is required. State-of-the-art models for predicting protein solubility almost exclusively consider aqueous salt systems, whereas "salting-in" and "salting-out" effects induced by the presence of an additional polymer are not considered. Thus, we developed the sol-mxDLVO model. Using this newly developed model, protein solubility in the presence of one salt and one polymer, especially the non-monotonic course of protein solubility, could be predicted. Systems considered included salts (NaCl, Na-p-Ts, (NH(4))(2) SO(4)) and the polymer polyethylene glycol (MW: 2000 g/mol, 12000 g/mol) and proteins lysozyme from chicken egg white (pH 4 to 5.5) and D-xylose ketol-isomerase (pH 7) at 298.15 K. The results show that by using the sol-mxDLVO model, protein solubility in polymer-salt solutions can be modeled in good agreement with the experimental data for both proteins considered. The sol-mxDLVO model can describe the non-monotonic course of protein solubility as a function of polymer concentration and salt concentration, previously not covered by state-of-the-art models. PMID:26579880

  9. Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

    NASA Astrophysics Data System (ADS)

    Xiang-Hong, He; Zhao-Lian, Ye; Ming-Yun, Guan; Ning, Lian; Jian-Hua, Sun

    2016-02-01

    Pr3+-activated barium tungsto-molybdate solid solution phosphor Ba(Mo1-zWz)O4:Pr3+ is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr3+-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO4] for [MoO4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo1-zWz)O4:Pr3+ owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity, well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white light-emitting diodes (LEDs). Project supported by the Construction Fund for Science and Technology Innovation Group from Jiangsu University of Technology, China, the Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, China (Grant No. KHK1409), the Priority Academic Program Development of Jiangsu Higher Education Institutions, China, and the National Natural Science Foundation of China (Grant No. 21373103).

  10. Chemical Corrosion of Liquid-Phase Sintered SiC in Acidic/Alkaline Solutions Part 1. Corrosion in HNO3 Solution

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zhang, Ming; He, Xinnong; Tang, Wenming

    2016-03-01

    The corrosion behavior of the liquid-phase sintered SiC (LPS-SiC) was studied by dipping in 3.53 mol/L HNO3 aqueous solution at room temperature and 70 °C, respectively. The weight loss, strength reduction and morphology evolution of the SiC specimens during corroding were revealed and also the chemical corrosion process and mechanism of the SiC specimens in the acidic solution were clarified. The results show that the corrosion of the LPS-SiC specimens in the HNO3 solution is selective. The SiC particles are almost free from corrosion, but the secondary phases of BaAl2Si2O8 (BAS) and Y2Si2O7 are corroded via an acid-alkali neutralization reaction. BAS has a higher corrosion rate than Y2Si2O7, resulting in the formation of the bamboo-leaf-like corrosion pits. As the SiC specimens etched in the HNO3 solution at room temperature for 75 days, about 80 μm thickness corrosion layer forms. The weight loss and bending strength reduction of the etched SiC specimens are 2.6 mg/cm2 and 52%, respectively. The corrosion of the SiC specimens is accelerated in the 70 °C HNO3 solution with a rate about five times bigger than that in the same corrosion medium at room temperature.

  11. Results Of Routine Strip Effluent Hold Tank And Decontaminated Salt Solution Hold Tank Samples From Modular Caustic-Side Solvent Extraction Unit During Macrobatch 5 Operations

    SciTech Connect

    Peters, T. B.; Fondeur, F. F.

    2013-04-30

    Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the ''microbatches'' of Integrated Salt Disposition Project (ISDP) Salt Batch (''Macrobatch'') 5 have been analyzed for {sup 238}Pu, {sup 90}Sr, {sup 137}Cs, and by Inductively Coupled Plasma Emission Spectroscopy (ICPES). The results indicate good decontamination performance within process design expectations. While the data set is sparse, the results of this set and the previous set of results for Macrobatch 4 samples indicate generally consistent operations. The DSSHT samples show continued presence of titanium, likely from leaching of the monosodium titanate in the Actinide Removal process (ARP).

  12. Conformational Preferences of N,N-Dimethylsuccinamate as a Function of Alkali and Alkaline Earth Metal Salts: Experimental Studies in DMSO and Water As Determined by 1H NMR Spectroscopy

    PubMed Central

    2015-01-01

    The fraction of gauche conformers of N,N-dimethylsuccinamic acid (1) and its Li+, Na+, K+, Mg2+, Ca2+, and N(Bu)4+ salts were estimated in DMSO and D2O solution by comparing the experimental vicinal proton–proton couplings determined by 1H NMR spectroscopy with those calculated using the Haasnoot, de Leeuw, and Altona (HLA) equation. In DMSO, the gauche preferences were found to increase with decreasing Ahrens ionic radius of the metal counterion. The same trend was not seen in D2O, where the gauche fraction for all of the metallic salts were estimated to be approximately statistical or less. This highlights the importance of metal chelation on the conformation of organic molecules in polar aprotic media, which has implications for protein folding. PMID:24506581

  13. Conformation dynamics and polarization effect of α,α-trehalose in a vacuum and in aqueous and salt solutions.

    PubMed

    Kan, Zigui; Yan, Xiufen; Ma, Jing

    2015-03-01

    Conformational changes of α,α-trehalose in a vacuum, water, and 0-20 wt % NaCl solutions were investigated by means of molecular dynamics (MD) simulations at different levels of density function theory (DFT) and with fixed-charge nonpolarizable and variable-charge force fields (FFs), respectively. The relative thermodynamic stability of trehalose is enhanced by the formation of intercycle and/or intracycle hydrogen bonds, but some thermodynamically unfavorable structures can be sampled in the DFT-based ab initio MD simulation. The polarization effects of polar trehalose molecule in aqueous and NaCl solutions were studied by a series of MD simulations with both the conventional nonpolarizable and polarizable force field models. In the polarizable model, the partial charges of trehalose were updated every 2 ps using DFT calculations and fused with the other FF parameters for the energy calculation and MD simulation. Around the trehalose, water molecules located in an asymmetry model and trehalose have a stronger tendency to bind with water molecules than Na(+) and Cl(-) ions. When the trehalose concentration is increased from 3.26 to 6.31 wt % in salt aqueous solution, the two trehalose molecules periodically approach each other in a nearly anhydrate state and leave a way to keep the favorable hydration structure with the mean trehalose-trehalose distance of 8.6 Å. The similarity between the solvated dimer packing styles (shoulder-by-shoulder or head-to-head) and crystal stacking can be used to make an extrapolation to higher sugar concentrations and to rationalize the bioprotection function of trehalose in high salt concentration. PMID:25506668

  14. On the hydrophilicity of polyzwitterion poly (N,N-dimethyl-N-(3-(methacrylamido)propyl)ammoniopropane sulfonate) in water, deuterated water, and aqueous salt solutions.

    PubMed

    Hildebrand, Viet; Laschewsky, André; Zehm, Daniel

    2014-01-01

    A series of zwitterionic model polymers with defined molar masses up to 150,000 Da and defined end groups are prepared from sulfobetaine monomer N,N-dimethyl-N-(3-(methacrylamido)propyl)ammoniopropanesulfonate (SPP). Polymers are synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT) using a functional chain transfer agent labeled with a fluorescent probe. Their upper critical solution temperature-type coil-to-globule phase transition in water, deuterated water, and various salt solutions is studied by turbidimetry. Cloud points increase with polyzwitterion concentration and molar mass, being considerably higher in D2O than in H2O. Moreover, cloud points are strongly affected by the amount and nature of added salts. Typically, they increase with increasing salt concentration up to a maximum value, whereas further addition of salt lowers the cloud points again, mostly down to below freezing point. The different salting-in and salting-out effects of the studied anions can be correlated with the Hofmeister series. In physiological sodium chloride solution and in phosphate buffered saline (PBS), the cloud point is suppressed even for high molar mass samples. Accordingly, SPP-polymers behave strongly hydrophilic under most conditions encountered in biomedical applications. However, the direct transfer of results from model studies in D2O, using, e.g. (1)H NMR or neutron scattering techniques, to 'normal' systems in H2O is not obvious. PMID:25058808

  15. Frictional properties of the end-grafted polymer layer in presence of salt solution

    NASA Astrophysics Data System (ADS)

    Raftari, Maryam; Zhang, Zhenyu; Leggett, Graham J.; Geoghegan, Mark

    2012-02-01

    We have studied the frictional behaviour of grafted poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) films using friction force microscopy (FFM). The films were prepared on native oxide-terminated silicon substrates using the technique of atom transfer radical polymerization (ATRP). These brushes had constant grafting density (1.18 nm2), and of a thickness of ˜66 nm, as measured by ellipsometry. We show that single asperity contact mechanics (Johnson-Kendall-Roberts (JKR) and Derjaguin-M"uller-Toporov (DMT) models) as well as a linear (Amontons) relation between applied load and frictional load all apply to these systems depending on the concentration of salt and the nature of the FFM probe. Measurements were made using gold-coating and polymer functionalized silicon nitride triangular probes. Polymer functionalized probe included growth the PDMAEMA with same method on tips. The frictional behaviour are investigated between PDMAEMA and gold coated and PDMAEMA tips immersed in different concentrations of KCl, KBr and KI.

  16. Electrophoretic mobilities of neutral analytes and electroosmotic flow markers in aqueous solutions of Hofmeister salts.

    PubMed

    Křížek, Tomáš; Kubíčková, Anna; Hladílková, Jana; Coufal, Pavel; Heyda, Jan; Jungwirth, Pavel

    2014-03-01

    Small neutral organic compounds have traditionally the role of EOF markers in electrophoresis, as they are expected to have zero electrophoretic mobility in external electric fields. The BGE contains, however, ions that have unequal affinities to the neutral molecules, which in turn results in their mobilization. In this study we focused on two EOF markers-thiourea and DMSO, as well as on N-methyl acetamide (NMA) as a model of the peptide bond. By means of CE and all atom molecular dynamics simulations we explored mobilization of these neutral compounds in large set of Hofmeister salts. Employing a statistical mechanics approach, we were able to reproduce by simulations the experimental electrophoretic mobility coefficients. We also established the role of the chemical composition of marker and the BGE on the measured electrophoretic mobility coefficient. For NMA, we interpreted the results in terms of the relative affinities of cations versus anions to the peptide bond. PMID:24338984

  17. Detergent-, solvent- and salt-compatible thermoactive alkaline serine protease from halotolerant alkaliphilic Bacillus sp. NPST-AK15: purification and characterization.

    PubMed

    Ibrahim, Abdelnasser S S; Al-Salamah, Ali A; El-Badawi, Yahya B; El-Tayeb, Mohamed A; Antranikian, Garabed

    2015-09-01

    Alkaline protease produced by the halotolerant alkaliphilic Bacillus sp. strain NPST-AK15 was purified to homogeneity by the combination of ammonium sulfate precipitation, anion-exchange and gel permeation chromatography. The purified enzyme was a monomeric protein with an estimated molecular weight of 32 kDa. NPST-AK15 protease was highly active and stable over a wide pH range, with a maximal activity at pH 10.5. The enzyme showed optimum activity at 60 °C and was stable at 30-50 °C for at least 1 h. Thermal stability of the purified protease was substantially improved by CaCl2 (1.1- to 6.6-fold). The K m, V max and k cat values for the enzyme were 2.5 mg ml(-1), 42.5 µM min(-1) mg(-1), and 392.46 × 10(3) min(-1), respectively. NPST-AK15 protease activity was strongly inhibited by PMSF, suggesting that the enzyme is a serine protease. The enzyme was highly stable in NaCl up to 20 % (w/v). Moreover, the purified enzyme was stable in several organic solvents such as diethyl ether, benzene, toluene, and chloroform. In addition, it showed high stability and compatibility with a wide range of surfactants and commercial detergents and was slightly activated by hydrogen peroxide. These features of NPST-AK15 protease make this enzyme a promising candidate for application in the laundry and pharmaceutical industries. PMID:26159877

  18. Use of alkali metal salts to prepare high purity single-walled carbon nanotube solutions and thin films

    NASA Astrophysics Data System (ADS)

    Ashour, Rakan F.

    Single-walled carbon nanotubes (SWCNTs) display interesting electronic and optical properties desired for many advanced thin film applications, such as transparent conductive electrodes or thin-film transistors. Large-scale production of SWCNTs generally results in polydispersed mixtures of nanotube structures. Since SWCNT electronic character (conducting or semiconducting nature) depends on the nanotube structure, application performance is being held back by this inability to discretely control SWCNT synthesis. Although a number of post-production techniques are able to separate SWCNTs based on electronic character, diameter, or chirality, most still suffer from the disadvantage of high costs of materials, equipment, or labor intensity to be relevant for large-scale production. On the other hand, chromatographic separation has emerged as a method that is compatible with large scale separation of metallic and semiconducting SWCNTs. In this work, SWCNTs, in an aqueous surfactant suspension of sodium dodecyl sulfate (SDS), are separated by their electronic character using a gel chromatography process. Metallic SWCNTs (m-SWCNTs) are collected as initial fractions since they show minimum interaction with the gel medium, whereas, semiconducting SWCNTs (sc- SWCNTs) remain adsorbed to the gel. The process of sc-SWCNT retention in the gel is found to be driven by the packing density of SDS around the SWCNTs. Through a series of separation experiments, it is shown that sc-SWCNTs can be eluted from the gel simply by disturbing the configuration of the SDS/SWCNT micellar structure. This is achieved by either introducing a solution containing a co-surfactant, such as sodium cholate (SC), or solutions of alkali metal ionic salts. Analysis of SWCNT suspensions by optical absorption provides insights into the effect of changing the metal ion (M+ = Li+, Na+, and K+) in the eluting solution. Salts with smaller metal ions (e.g. Li+) require higher concentrations to achieve

  19. Bottom-up synthesis of high-performance nitrogen-enriched transition metal/graphene oxygen reduction electrocatalysts both in alkaline and acidic solution

    NASA Astrophysics Data System (ADS)

    Lai, Qingxue; Gao, Qingwen; Su, Qi; Liang, Yanyu; Wang, Yuxi; Yang, Zhi

    2015-08-01

    Oxygen reduction electrocatalysts with low cost and excellent performance are urgently required for large-scale application in fuel cells and metal-air batteries. Though nitrogen-enriched transition metal/graphene hybrids (N-TM/G, TM = Fe, Co, and Ni and related compounds) have been developed as novel substitutes for precious metal catalysts (PMCs) towards oxygen reduction reaction (ORR), a significant challenge still remains for simple and efficient synthesis of N-TM/G catalysts with satisfactory electrocatalytic behavior. Herein, we demonstrate a universal bottom-up strategy for efficient fabrication of strongly-coupled N-TM/G catalysts. This strategy is implemented via direct polymerization of transition metal phthalocyanine (TMPc) in the two-dimensional confined space of in situ generated g-C3N4 and a subsequent pyrolysis. Such a space-confined bottom-up synthesis route successfully constructs a strongly-coupled triple junction of transition metal-graphitic carbon-nitrogen-doped graphene (TM-GC-NG) with extensive controllability over the specific surface area, nitrogen content/types as well as the states of metal. As a result, the optimized N-Fe/G materials have promising potential as high-performance NPMCs towards ORR both in alkaline and acidic solution.Oxygen reduction electrocatalysts with low cost and excellent performance are urgently required for large-scale application in fuel cells and metal-air batteries. Though nitrogen-enriched transition metal/graphene hybrids (N-TM/G, TM = Fe, Co, and Ni and related compounds) have been developed as novel substitutes for precious metal catalysts (PMCs) towards oxygen reduction reaction (ORR), a significant challenge still remains for simple and efficient synthesis of N-TM/G catalysts with satisfactory electrocatalytic behavior. Herein, we demonstrate a universal bottom-up strategy for efficient fabrication of strongly-coupled N-TM/G catalysts. This strategy is implemented via direct polymerization of transition

  20. Effects of temperature and salt concentration on the structural and dynamical features in aqueous solutions of charged triblock copolymers.

    PubMed

    Kjøniksen, Anna-Lena; Zhu, Kaizheng; Behrens, Manja A; Pedersen, Jan Skov; Nyström, Bo

    2011-03-17

    Effects of temperature and salt addition on the association behavior in aqueous solutions of a series of charged thermosensitive methoxypoly(ethylene glycol)-block-poly(N-isopropylacrylamide)-block-poly(4-styrenesulfonic acid sodium) triblock copolymers (MPEG(45)-b-P(NIPAAM)(n)-b-P(SSS)(22)) with different lengths of the PNIPAAM block (n=17, 48, and 66) have been studied with the aid of turbidity, small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS). Increasing temperature and salinity as well as longer PNIPAAM blocks are all factors that promote the formation of association structures. The SAXS data show that, for the copolymers with n=48 and n=66, increasing temperature and salt concentration induce interchain associations and higher values of the aggregation number, whereas no aggregation was observed for the copolymer with the shortest PNIPAAM chain. However, DLS measurements reveal the presence of larger association clusters. The cloud point is found to decrease with raising salinity and longer PNIPAAM block. The general picture that emerges is the delicate interplay between repulsive electrostatic forces and hydrophobic interactions and that this balance can be tuned by changing the temperature, salinity, and the length of the PNIPAAM block. PMID:21338148

  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. Water purification using organic salts

    DOEpatents

    Currier, Robert P.

    2004-11-23

    Water purification using organic salts. Feed water is mixed with at least one organic salt at a temperature sufficiently low to form organic salt hydrate crystals and brine. The crystals are separated from the brine, rinsed, and melted to form an aqueous solution of organic salt. Some of the water is removed from the aqueous organic salt solution. The purified water is collected, and the remaining more concentrated aqueous organic salt solution is reused.

  3. Effect of laser irradiation of nanoparticles in aqueous uranium salt solutions on nuclide activity

    SciTech Connect

    Simakin, Aleksandr V; Shafeev, Georgii A

    2011-07-31

    This paper presents an experimental study of the effect of laser irradiation of aqueous uranyl chloride solutions containing gold nanoparticles on the activity of the uranium series radionuclides {sup 234}Th, {sup 234m}Pa, and {sup 235}U. The solutions were exposed to femtosecond Ti:sapphire laser pulses and to the second or third harmonic of a Nd:YAG laser (150-ps pulses) at a peak intensity in the medium of {approx}10{sup 12} W cm{sup -2}. The activities of the radionuclides in the irradiated solutions were shown to differ markedly from their equilibrium values. The sign of the deviation depends on the laser wavelength. The measured activity deviations can be interpreted as evidence that laser exposure of nanoparticles accelerates the alpha and beta decays of the radionuclides. The observed effects are accounted for in terms of a mechanism that involves resonant enhancement of optical waves by metallic nanoparticles. (interaction of laser radiation with matter)

  4. Experimental study of evaporation of horizontal films of water-salt solutions

    NASA Astrophysics Data System (ADS)

    Elistratov, S. L.; Morozov, V. S.

    2015-01-01

    The present studies were carried out for the horizontal films (thin layers) of water and water solutions of NaCl, CaCl2, LiCl, and LiBr with different solubility characteristics, as well as with specific features of formation and decay of water hydrates. Required volume of solution Vo of given weight concentration ξo, preliminary heated to the working surface temperature, was put in one step on the horizontal bottom of the bowl, heated to working temperature tCT, by means of volume batchers Thermo Scientific. After evaporation completion, the final mass of solution and form of their residue were registered. At the final stage of evaporation formation of NaCl crystals and water hydrates of CaCl2 · 2H2O, LiCl · H2O, and LiBr · 2H2O occurred.

  5. Effect of salt identity on the phase diagram for a globularprotein in aqueous electrolyte solution

    SciTech Connect

    Bostrom, Mathias; Tavares, Frederico W.; Ninham, Barry W.; Prausnitz, John M.

    2006-02-22

    Monte Carlo simulations are used to establish the potential of mean force between two globular proteins in an aqueous electrolyte solution. This potential includes nonelectrostatic contributions arising from dispersion forces first, between the globular proteins, and second, between ions in solution and between each ion and the globular protein. These latter contributions are missing from standard models. The potential of mean force, obtained from simulation, is fitted to an analytic equation. Using our analytic potential of mean force and Barker-Henderson perturbation theory, we obtain phase diagrams for lysozyme solutions that include stable and metastable fluid-fluid and solid-fluid phases when the electrolyte is 0.2 M NaSCN or NaI or NaCl. The nature of the electrolyte has a significant effect on the phase diagram.

  6. Alkaline Waterflooding Demonstration Project, Ranger Zone, Long Beach Unit, Wilmington Field, California. Fourth annual report, June 1979-May 1980. Volume 1. Body of report

    SciTech Connect

    Carmichael, J.D.

    1981-03-01

    Comparative core flood testing of preserved Ranger Zone core rock samples was completed; the past year's results were discouraging. In contrast, Ranger sand pack alkaline flood tests gave encouraging results. New insights were gained on in-situ alkaline consumption. Dehydration of sodium orthosilicate water-produced water-crude oil systems does not appear to create any operational problems. The alkaline injection facilities were completed and placed in operation on March 27, 1980. The preflush injection, which was composed of 11.5 million barrels of softened fresh water with an average 0.96% of salt, was completed at that time. The total preflush amounted to approximately 10 pore volume percent. The 0.4% sodium orthosilicate-1.0% salt-soft fresh water injection started at the end of the preflush. A loss of injectivity began at the same time as alkaline injection, which is attributed to divalent ions in the salt brine. Salt was removed temporarily from the system on May 30, 1980. No injection wells were redrilled during the year. Other than plug back of one injector and one producer because of bad liners and repair of one injection well with an inner liner, well work was routine and minor in nature. Dual injection strings were transferred from one well to another. One of the injection wells whose injectivity was damaged by the alkaline-salt injection was successfully stimulated. The pilot was self certified under the tertiary incentive program and cost recoupments obtained. Preparations are underway for making the alkaline flood simulator performance prediction for the pilot. Laboratory testing is actively underway in an attempt to quickly find a remedy for the floc formation that occurs on mixing the salt brine and dilute alkaline solution. Volume 1 describes the activities for this period. Volumes 2 and 3 contain appendices.

  7. Long-living nanobubbles of dissolved gas in aqueous solutions of salts and erythrocyte suspensions.

    PubMed

    Bunkin, Nikolai F; Ninham, Barry W; Ignatiev, Pavel S; Kozlov, Valery A; Shkirin, Alexey V; Starosvetskij, Artem V

    2011-03-01

    Results of experiments combining laser modulation interference microscopy and Mueller matrix scatterometry show that macroscopic scatterers of light are present in liquids free of external solid impurities. Experimental data on distilled water and aqueous NaCl solutions of various concentrations as well as physiological saline solution are reported. The experimental data can be interpreted by using a model of micron-scale clusters composed of polydisperse air nanobubbles having effective radii of 70-100 nm. Their concentration increases with the growth of ionic content. We hypothesize that under certain conditions those clusters of nanobubbles can affect the erythrocyte structure. PMID:21287687

  8. Report on variation of electrical conductivity during steam injection in unconsolidated sand saturated with a salt solution

    SciTech Connect

    Vaughan, P.; Udell, K.S.; Wilt, M.

    1992-04-01

    Geophysical electrical methods are useful in evaluating the performance of certain classes of enhanced oil recovery (EOR) operations and also remediation operations for contaminant spills. Electrical resistivity is sensitive to the concentration of ionic species in solution in fluids present in the subsurface zone. Such fluids are displaced during oil recovery operations and contaminant remediation. If the resistivity of the displacing fluid differs from the in situ fluid, then a geophysical method for detecting resistivity variations may be capable of tracking the advance of the displacing fluid. This report presents the results of experiments designed to determine the variations in resistivity that occur when steam is injected into a homogeneous, fully-saturated sand. These experiments were simple, one-dimensional laboratory steam injection experiments. They were performed using a glass tube filled with a tightly-packed sand and fitted with an injection port at one end and an exit port at the other In each experiment, the sand pack was initially saturated with a brine and then steam was introduced at one end of the tube. Analytic solutions for the steam front velocity, steam temperature, steam distribution, salt concentration profile, and liquid saturation are presented and are used with appropriate correlations of electrical conductivity to describe the observed behavior. The results of these experiments should provide experimental justification for the electrical conductivity variations that are calculated from the analytic solutions. In addition, the experiments may yield new information regarding features of the data that may not result from the analytical modelling.

  9. Economic feasibility and performance study of a solar-powered absorption cycle using some aqueous salt solutions

    SciTech Connect

    Malik, I.H.; Siddiqui, M.A.

    1997-02-01

    Economic analyses of solar collectors, for optimizing generator temperatures in the absorption cycle using aqueous solutions of LiBr, LiBr-ZnBr{sub 2}, LiBr-ZnBr{sub 2}-LiCl, and LiBr-ZnCl{sub 2}-CaBr{sub 2} salts, have been carried out for a wide range of the operating conditions. Ordinary collectors with two glass covers and evacuated-tubular collectors have been selected as the sources of energy for providing hot liquid in the generator of the absorption cycle. Of the four solutions, as the working fluids in the absorption cycles, those having better coefficients of performance are the LiBr/H{sub 2}O at the low evaporator temperatures, and the (LiBr-ZnBr{sub 2}-LiCl)/H{sub 2}O as well as the (LiBr-ZnCl{sub 2}-CaBr{sub 2})/H{sub 2}O at the high evaporator temperatures. Similarly, costs of the solar collectors are low, at low evaporation temperatures for the LiBr/H{sub 2}O and at high temperatures for the other two solutions: the (LiBr-ZnBr{sub 2})/H{sub 2}O, on the other hand, have relatively low COP and high operating costs.

  10. Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

    NASA Astrophysics Data System (ADS)

    Bajdik, János; Fehér, Máté; Pintye-Hódi, Klára

    2007-06-01

    Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit ® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.

  11. Effects of solution conditions and surface chemistry on the adsorption of three recombinant botulinum neurotoxin antigens to aluminum salt adjuvants.

    PubMed

    Vessely, Christina; Estey, Tia; Randolph, Theodore W; Henderson, Ian; Nayar, Rajiv; Carpenter, John F

    2007-09-01

    Botulinum neurotoxin (BoNT) is a biological warfare threat. Protein antigens have been developed against the seven major BoNT serotypes for the development of a recombinant protein vaccine. This study is an evaluation of adsorption profiles for three of the recombinant protein antigens to aluminum salt adjuvants in the development of a trivalent vaccine against BoNT. Adsorption profiles were obtained over a range of protein concentrations. The results document that charge-charge interactions dominate the adsorption of antigen to adjuvant. Optimal conditions for adsorption were determined. However, potency studies and solution stability studies indicated the necessity of using aluminum hydroxide adjuvant at low pH. To improve the adsorption profiles to AlOH adjuvant, phosphate ions were introduced into the adsorption buffers. The resulting change in the adjuvant chemistry led to an improvement of adsorption of the BoNT antigens to aluminum hydroxide adjuvant while maintaining potency. Competitive adsorption profiles were also determined, and showed changes in maximum adsorption from mixed solutions compared to adsorption from individual protein solutions. The adsorption profiles for each protein varied due to differences in adsorption mechanism and affinity for the adjuvant surface. These results emphasize the importance of evaluating competitive adsorption in the development of multivalent vaccine products. PMID:17518359

  12. Application of nano-sized nanoporous zinc 2-methylimidazole metal-organic framework for electrocatalytic oxidation of methanol in alkaline solution

    NASA Astrophysics Data System (ADS)

    Samadi-Maybodi, Abdolraouf; Ghasemi, Shahram; Ghaffari-Rad, Hamid

    2016-01-01

    In this work, a novel non-platinum group metals (non-PGM) catalyst based on modified zinc 2-methylimidazole metal-organic framework (ZIF-8) is proposed and used for electrooxidation of methanol. Nano-sized particles of nonporous ZIF-8 are synthesized at room temperature using a simple template-free method. The synthesized ZIF-8 nanoparticles are characterized by X-ray diffraction, scanning electronic microscopy and nitrogen adsorption-desorption techniques. In order to decrease the overvoltage of methanol oxidation on carbon paste electrode (CPE), nickel species doped ZIF-8 modified carbon paste electrode (Ni/ZIF-8CPE) is fabricated as a modified electrode. Electrochemical techniques such as cyclic voltammetry and chronoamperometry are used to investigate the electrocatalytic activity of Ni/ZIF-8CPE toward methanol oxidation in alkaline solution. Cyclic voltammetry results show that oxidation current is considerably increased using Ni/ZIF-8CPE in comparison with unmodified CPE. Catalytic rate constant of methanol oxidation on Ni/ZIF-8CPE is obtained using chronoamperometric studies. Besides the good catalytic activity of the modified electrode toward methanol oxidation, it has other advantages such as simple preparation, ease of operation, good stability and low cost, which can be promising in the field of preparation of non-PGM electrocatalysts for application in fuel cells.

  13. Bottom-up synthesis of high-performance nitrogen-enriched transition metal/graphene oxygen reduction electrocatalysts both in alkaline and acidic solution.

    PubMed

    Lai, Qingxue; Gao, Qingwen; Su, Qi; Liang, Yanyu; Wang, Yuxi; Yang, Zhi

    2015-09-21

    Oxygen reduction electrocatalysts with low cost and excellent performance are urgently required for large-scale application in fuel cells and metal-air batteries. Though nitrogen-enriched transition metal/graphene hybrids (N-TM/G, TM = Fe, Co, and Ni and related compounds) have been developed as novel substitutes for precious metal catalysts (PMCs) towards oxygen reduction reaction (ORR), a significant challenge still remains for simple and efficient synthesis of N-TM/G catalysts with satisfactory electrocatalytic behavior. Herein, we demonstrate a universal bottom-up strategy for efficient fabrication of strongly-coupled N-TM/G catalysts. This strategy is implemented via direct polymerization of transition metal phthalocyanine (TMPc) in the two-dimensional confined space of in situ generated g-C3N4 and a subsequent pyrolysis. Such a space-confined bottom-up synthesis route successfully constructs a strongly-coupled triple junction of transition metal-graphitic carbon-nitrogen-doped graphene (TM-GC-NG) with extensive controllability over the specific surface area, nitrogen content/types as well as the states of metal. As a result, the optimized N-Fe/G materials have promising potential as high-performance NPMCs towards ORR both in alkaline and acidic solution. PMID:26282404

  14. FTIR study of the photocatalytic degradation of gaseous benzene over UV-irradiated TiO{sub 2} nanoballs synthesized by hydrothermal treatment in alkaline solution

    SciTech Connect

    Zhu, Zhengru; Li, Xinyong; Zhao, Qidong; Qu, Zhenping; Hou, Yang; Zhao, Ling; Liu, Shaomin; Chen, Guohua

    2010-12-15

    In this study, photocatalysts of TiO{sub 2} nanoballs were obtained via a hydrothermal treating of commercial P25 in alkaline solution, and then characterized with SEM, XRD, BET and surface photovoltage spectroscopy techniques. The UV-assisted photodegradation of gaseous benzene over P25 and the prepared TiO{sub 2} nanoballs was monitored by an in situ infrared technique. The results demonstrated that the prepared TiO{sub 2} nanoballs in anatase form were more active than commercial P25 in photocatalytic oxidation of gaseous benzene. The promoted activity of the hydrothermal-treated TiO{sub 2} is attributed to the increasing specific surface area and larger band gap induced by the reduced crystallite size. The spectra of FTIR indicated that weakly adsorbed phenol was formed as the reaction progress. Hydroxyl groups on the surface of TiO{sub 2} nanoballs are able to react with photo-produced phenol, which is then retained on the catalyst surface leading to the progressive deactivation of the catalyst in the gas-solid system.

  15. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    PubMed Central

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-01-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm−2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm−2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms. PMID:25765731

  16. Growth of lithium triborate single crystals from molten salt solution under various temperature gradients

    NASA Astrophysics Data System (ADS)

    Guretskii, S. A.; Ges, A. P.; Zhigunov, D. I.; Ignatenko, A. A.; Kalanda, N. A.; Kurnevich, L. A.; Luginets, A. M.; Milovanov, A. S.; Molchan, P. V.

    1995-12-01

    Single crystals of lithium triborate LiB 3O 5 (LBO) have been grown by the top-seeded solution growth method with B 2O 3 as a solvent using different temperature gradients in the zone of crystallization. Optical and nonlinear optical properties of LBO single crystals have been investigated. The influence of post-growth thermal treatment in oxygen atmosphere on the optical properties has been studied.

  17. 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.

  18. Tank Waste Transport Stability: Summaries of Hanford Slurry and Salt-Solution Studies in FY 2000

    SciTech Connect

    Welch, T.D.

    2002-07-08

    This report is a collection of summary articles on FY 2000 studies of slurry transport and salt-well pumping related to Hanford tank waste transfers. These studies are concerned with the stability (steady, uninterrupted flow) of tank waste transfers, a subset of the Department of Energy (DOE) Tanks Focus Area Tank (TFA) Waste Chemistry effort. This work is a collaborative effort of AEA Technology plc, the Diagnostic Instrumentation and Analysis Laboratory at Mississippi State University (DIAL-MSU), the Hemispheric Center for Environmental Technology at Florida International University (HCET-FIU), Numatec Hanford Corporation (NHC), and the Oak Ridge National Laboratory (ORNL). The purpose of this report is to provide, in a single document, an overview of these studies to help the reader identify contacts and resources for obtaining more detailed information and to help promote useful interchanges between researchers and users. Despite over 50 years of experience in transporting radioactive tank wastes to and from equipment and tanks at the Department of Energy's Hanford, Savannah River, and Oak Ridge sites, waste slurry transfer pipelines and process piping become plugged on occasion. At Hanford, several tank farm pipelines are no longer in service because of plugs. At Savannah River, solid deposits in the outlet line of the 2H evaporator have resulted in an unplanned extended downtime. Although waste transfer criteria and guidelines intended to prevent pipeline plugging are in place, they are not always adequate. To avoid pipeline plugging in the future, other factors that are not currently embodied in the transfer criteria may need to be considered. The work summarized here is being conducted to develop a better understanding of the chemical and waste flow dynamics during waste transfer. The goal is to eliminate pipeline plugs by improving analysis and engineering tools in the field that incorporate this understanding.

  19. Different sodium salts cause different solute accumulation in the halophyte Prosopis strombulifera.

    PubMed

    Llanes, A; Bertazza, G; Palacio, G; Luna, V

    2013-01-01

    The success of Prosopis strombulifera in growing under high NaCl concentrations involves a carefully controlled balance among different processes, including compartmentation of Cl(-) and Na(+) in leaf vacuoles, exclusion of Na(+) in roots, osmotic adjustment and low transpiration. In contrast, Na(2) SO(4) causes growth inhibition and toxicity. We propose that protection of the cytoplasm can be achieved through production of high endogenous levels of specific compatible solutes. To test our hypothesis, we examined endogenous levels of compatible solutes in roots and leaves of 29-, 40- and 48-day-old P. strombulifera plants grown in media containing various concentrations of NaCl, Na(2) SO(4) or in mixtures of both, with osmotic potentials of -1.0,-1.9 and -2.6 MPa, as correlated with changes in hydric parameters. At 24 h after the last pulse plants grown in high NaCl concentrations had higher relative water content and relatively higher osmotic potential than plants grown in Na(2) SO(4) (at 49 days). These plants also had increased synthesis of proline, pinitol and mannitol in the cytoplasm, accompanied by normal carbon metabolism. When the sulphate anion is present in the medium, the capacities for ion compartmentalisation and osmotic adjustment are reduced, resulting in water imbalance and symptoms of toxicity due to altered carbon metabolism, e.g. synthesis of sorbitol instead of mannitol, reduced sucrose production and protein content. This inhibition was partially mitigated when both anions were present together in the solution, demonstrating a detrimental effect of the sulphate ion on plant growth. PMID:22747518

  20. Comparative ion insertion study into a nanostructured vanadium oxide in aqueous salt solutions

    SciTech Connect

    Yuan, Q.; Ren, S. L.; Zukowski, J.; Pomeroy, M.; Soghomonian, V.

    2014-07-07

    We present a comparative study for the electrochemical insertion of different cations into a nanostructured vanadium oxide material. The oxide is hydrothemally synthesized and electrically characterized by variable temperature measurements. The electrochemical reactions are performed in aqueous chloride solutions of lithium, sodium, potassium, and ammonium, and the electrochemical behavior of various cycles are correlated with visual changes in the vanadium oxide nanosheets as observed by scanning electron microscopy. We note an increase in the specific charge per cycle in the cases of sodium and ammonium ions only, correlated with minimal physical changes to the nanosheets. The differing behavior of the various ions has implications for their use in electrical energy storage applications.

  1. Process for preparing chemically modified micas for removal of cesium salts from aqueous solution

    SciTech Connect

    Yates, Stephen Frederic; DeFilippi, Irene; Gaita, Romulus; Clearfield, Abraham; Bortun, Lyudmila; Bortun, Anatoly

    2000-09-05

    A chemically modified mica composite formed by heating a trioctahedral mica in an aqueous solution of sodium chloride having a concentration of at least 1 mole/liter at a temperature greater than 180 degrees Centigrade for at least 20 hours, thereby replacing exchangeable ions in the mica with sodium. Formation is accomplished at temperatures and pressures which are easily accessed by industrial equipment. The reagent employed is inexpensive and non-hazardous, and generates a precipitate which is readily separated from the modified mica.

  2. A Platinum-Dithiolene Monoanionic Salt Exhibiting Multiproperties, Including Room-Temperature Proton-Dependent Solution Luminescence.

    PubMed

    Attar, Salahuddin; Espa, Davide; Artizzu, Flavia; Mercuri, M Laura; Serpe, Angela; Sessini, Elisa; Concas, Giorgio; Congiu, Francesco; Marchiò, Luciano; Deplano, Paola

    2016-06-01

    The platinum salt C[PtL2], where C = [(R)-Ph(Me)HC*-NMe3](+) and [PtL2](-) = radical monoanion based on [4', 5': 5, 6][1, 4]dithiino[2,3-b]quinoxaline-1',3'dithiolato, shows a variety of properties both in solution and in the solid state thanks to the electronic and/or structural features of the ligand. The complex crystallizes in the chiral space group P1 due to the presence of the enantiopure cation (R)-Ph(Me)HC*-NMe3(+), and it shows paramagnetic behavior relatable to the [PtL2](-) radical monoanion. This anionic complex is redox active and shows a strong near-infrared absorbance peak at 1085 nm tunable with the oxidation state of the complex. This complex exhibits a proton-dependent emission at 572 nm in solution at room temperature. The excitation band corresponds to the HOMO-1 (π-orbitals of the S2C2S2 system) → LUMO (π-orbitals of the quinoxaline and benzene-like moieties) transition suggesting that emission is mainly ligand centered in character. The luminescent properties are highly unusual, since the emission falls well above the energy of the lowest energy absorption (anti-Kasha behavior). Joint experimental and density functional theory (DFT) and time-dependent DFT studies are discussed to provide a satisfactory structure/property relationship. PMID:27163727

  3. Partitioning of mobile ions between ion exchange polymers and aqueous salt solutions: importance of counter-ion condensation.

    PubMed

    Kamcev, Jovan; Galizia, Michele; Benedetti, Francesco M; Jang, Eui-Soung; Paul, Donald R; Freeman, Benny D; Manning, Gerald S

    2016-02-17

    Equilibrium partitioning of ions between a membrane and a contiguous external solution strongly influences transport properties of polymeric membranes used for water purification and energy generation applications. This study presents a theoretical framework to quantitatively predict ion sorption from aqueous electrolytes (e.g., NaCl, MgCl2) into charged (i.e., ion exchange) polymers. The model was compared with experimental NaCl, MgCl2, and CaCl2 sorption data in commercial cation and anion exchange membranes. Ion sorption in charged polymers was modeled using a thermodynamic approach based on Donnan theory coupled with Manning's counter-ion condensation theory to describe non-ideal behavior of ions in the membrane. Ion activity coefficients in solution were calculated using the Pitzer model. The resulting model, with no adjustable parameters, provides remarkably good agreement with experimental values of membrane mobile salt concentration. The generality of the model was further demonstrated using literature data for ion sorption of various electrolytes in charged polymers, including HCl sorption in Nafion. PMID:26840776

  4. Ion pairing in aqueous lithium salt solutions with monovalent and divalent counter-anions.

    PubMed

    Pluhařová, Eva; Mason, Philip E; Jungwirth, Pavel

    2013-11-21

    Molecular dynamics simulations of concentrated aqueous solutions of LiCl and Li2SO4 were conducted in order to provide molecular insight into recent neutron scattering data. The structures predicted from the molecular dynamics simulations using standard nonpolarizable force fields provided a very poor fit to the experiment; therefore, refinement was needed. The electronic polarizability of the medium was effectively accounted for by implementing the electronic continuum correction, which practically means rescaling the ionic charges. Consistent with previous studies, we found that this approach in each case provided a significantly improved fit to the experimental data, which was further enhanced by slightly adjusting the radius of the lithium ion. The polarization effect was particularly pronounced in the Li2SO4 solution where the ions in the nonpolarizable simulations tended to cluster unphysically. With the above alterations, the employed force field displayed an excellent fit to the neutron scattering data and provided a useful interpretative framework for the experimental measurements. At the same time, the present study underlines the importance of solvent polarization effects in hydration of ions with high charge density. PMID:23581250

  5. Photoemission spectra of aqueous solutions of salts from many-body perturbation theory

    NASA Astrophysics Data System (ADS)

    Gaiduk, Alex P.; Skone, Jonathan H.; Govoni, Marco; Galli, Giulia

    The computational design of electrode materials for energy conversion and storage processes requires an accurate description of the energy levels of the electrolyte and of electrolyte/electrode interfaces. Conventional density-functional approximations are in general not well suited for this task as they yield inaccurate orbital energies. Many-body perturbation theory (MBPT) predicts vertical ionization potentials and energy gaps in better agreement with experiments, providing the possibility for an accurate description of the electronic properties of electrolytes. We coupled ab initio molecular dynamics with MBPT calculations to investigate the photoemission spectra of a 1 M aqueous solution of NaCl. For the first time we were able to determine the absolute positions of the spectra peaks, with excellent agreement with experiments for both the solute and solvent peak positions. The best results were obtained using wavefunctions obtained from dielectric-dependent hybrid calculations as a starting point for MBPT. Work supported by DOE BES DE-SC0008938. Computer time provided by the Argonne Leadership Computing Facility through the INCITE program.

  6. Heat Transfer from Optically Excited Gold Nanostructures into Water, Sugar, and Salt Solutions

    NASA Astrophysics Data System (ADS)

    Green, Andrew J.

    coherence length associated with the liquid-liquid transition. The second topic will measure the change in heat dissipation with respect to solute adhesion onto the nanoheater. A small amount of aqueous solute molecules (1 solute molecule in 550 water molecules) dramatically increases the heat dissipation from a nanoparticle into the surrounding liquid. This result is consistent with a thermal conductance that is limited by an interface interaction where minority aqueous components significantly alter the surface properties and heat transport through the interface. The increase in heat dissipation can be used to make an extremely sensitive molecular detector that can be scaled to give single molecule detection without amplification or utilizing fluorescence labels.

  7. Investigation on the coprecipitation of transuranium elements from alkaline solutions by the method of appearing reagents. Study of the effects of waste components on decontamination from Np(IV) and Pu(IV)

    SciTech Connect

    Bessonov, A.A.; Budantseva, N.A.; Gelis, A.V.; Nikonov, M.V.; Shilov, V.P.

    1997-09-01

    The third stage of the study on the homogeneous coprecipitation of neptunium and plutonium from alkaline high-level radioactive waste solutions by the Method of Appearing Reagents has been completed. Alkaline radioactive wastes exist at the U.S. Department of Energy Hanford Site. The recent studies investigated the effects of neptunium chemical reductants, plutonium(IV) concentration, and the presence of bulk tank waste solution components on the decontamination from tetravalent neptunium and plutonium achieved by homogeneous coprecipitation. Data on neptunium reduction to its tetravalent state in alkaline solution of different NaOH concentrations are given. Eleven reductants were tested to find those most suited to remove neptunium, through chemical reduction, from alkaline solution by homogeneous coprecipitation. Hydrazine, VOSO{sub 4}, and Na{sub 2}S{sub 2}O{sub 4} were found to be the most effective reductants. The rates of reduction with these reductants were comparable with the kinetics of carrier formation. Solution decontamination factors of about 400 were attained for 10{sup -6}M neptunium. Coprecipitation of plutonium(IV) with carriers obtained as products of thermal hydrolysis, redox transformations, and catalytic decomposition of [Co(NH{sub 3}){sub 6}]{sup 3+}, [Fe(CN){sub 5}NO]{sup 2-}, Cr(NO{sub 3}){sub 3}, KMnO{sub 4}, and Li{sub 4}UO{sub 2}(O{sub 2}){sub 3} was studied and results are described. Under optimum conditions, a 100-fold decrease of plutonium concentration was possible with each of these reagents.

  8. Spectroscopic Investigation of the Formation of Radiolysis By-Products By 13/9 MeV Linear Accelerator of Electrons (LAE) in Salt Solutions

    SciTech Connect

    Paviet-Hartmann, P.; Dziewinski, J.; Hartmann, T.; Marczak, S.; Lu, N.; Walthall, M.; Rafalski, A.; Zagorski, Z. P.

    2002-02-26

    In the near-field chemistry of a salt repository, the radiolytically-induced redox reactions in concentrated saline solution are of particular importance because the radiolysis of saline solutions results in oxidizing chlorine-containing species, which may oxidize actinide species to higher oxidation states. If the brines are irradiated, the solutions containing radiolytic species such as hypochlorite, hypochlorous acid or hydrogen peroxide, their pH and Eh may be altered. The oxidation and complexation states of actinides, which might be present in the salt brine, will change thus influencing their speciation and consequently their mobility. Furthermore, radiolytically formed oxidizing species such as ClO- or H2O2 may enhance the corrosion of the canister material. Therefore, radiation effects on salt brines must be integrated into the database, which described the chemical processes near a disposal site. Investigations in that context usually focus on the radiation chemistry of solid NaCl however our focus is on the radiolytic products, which are formed when salt brines are irradiated by a 10 MeV linear accelerator of electrons (LAE). We attempt to quantify the irradiation-induced formation of typical radiolysis by-products such as the hypochlorite ion (OCl-) by using a 13/9 MeV LAE with doses between 120 KGy to 216 KGy while monitoring the pH of the brine solutions.

  9. Use of a liter-scale microbial desalination cell as a platform to study bioelectrochemical desalination with salt solution or artificial seawater.

    PubMed

    Jacobson, Kyle S; Drew, David M; He, Zhen

    2011-05-15

    Bioelectrochemical desalination is potentially advantageous because of bioenergy production and integrated wastewater treatment and desalination. In this work, the performance and energy benefits of a liter-scale upflow microbial desalination cell (UMDC) were evaluated. The UMDC desalinated both salt solution (NaCl) and artificial seawater, and the removal rate of total dissolved solid (TDS) increased with an increased hydraulic retention time, although TDS reduction in artificial seawater was lower than that in salt solution. Our analysis suggested that electricity generation was a predominant factor in removing TDS (more than 70%), and that other factors, like water osmosis and unknown processes, also contributed to TDS reduction. It was more favorable given the high energy efficiency, when treating salt solution, to operate the UMDC under the condition of high power output compared with that of high current generation because of the amount of energy production; while high current generation was more desired with seawater desalination because of lower salinity in the effluent. Under the condition of the high power output and the assumption of the UMDC as a predesalination in connection with a reversal osmosis (RO) system, the UMDC could produce electrical energy that might potentially account for 58.1% (salt solution) and 16.5% (artificial seawater) of the energy required by the downstream RO system. Our results demonstrated the great potential of bioelectrochemical desalination. PMID:21526816

  10. SPECTROSCOPIC INVESTIGATION OF THE FORMATION OF RADIOLYSIS BY-PRODUCTS BY 13/9 MEV LINEAR ACCELERATOR OF ELECTRONS (LAE) IN SALT SOLUTIONS.

    SciTech Connect

    Paviet-Hartmann, P.; Dziewinski, J. J.; Marczak, Stanislaw; Lu, N.; Walthall, M.

    2001-01-01

    In the near-field chemistry of a salt repository, the radiolytically-induced redox reactions in concentrated saline solution are of particular importance because the radiolysis of saline solutions results in oxidizing chlorine-containing species, which may oxidize actinide species to higher oxidation states. If the brines are irradiated, the solutions containing radiolytic species such as hypochlorite, hypochlorous acid or hydrogen peroxide, their pH and Eh may be altered. The oxidation and complexation states of actinides, which might be present in the salt brine, will change thus influencing their speciation and consequently their mobility. Furthermore, radiolytically formed oxidizing species such as ClO- or H2O2 may enhance the corrosion of the canister material. Therefore, radiation effects on salt brines must be integrated into the database, which described the chemical processes near a disposal site. Investigations in that context usually focus on the radiation chemistry of solid NaCl however our focus is on the radiolytic products, which are formed when salt brines are irradiated by a 10 MeV linear accelerator of electrons (LAE). We attempt to quantify the irradiation-induced formation of typical radiolysis by-products such as the hypochlorite ion (OCl-) by using a 13/9 MeV LAE with doses between 120 KGy to 216 KGy while monitoring the pH of the brine solutions

  11. Studies on Nylon-66 membrane using aqueous solutions of potassium and lead nitrate salts as permeants

    NASA Astrophysics Data System (ADS)

    Kumar, Manoj; Ram, Bali

    2015-03-01

    Measurements on hydrodynamic and electro-osmotic permeability of water and aqueous solutions of KNO3 and Pb(NO3)2 in the concentration (C) range of 10 -4 10^{-4} M to 10 -3 10^{-3} M are made across the Nylon-66 membrane. The data obtained are used to ascertain the form of transport equation using the theory of non-equilibrium thermodynamics. Conductance of membrane equilibrated with water and aqueous solutions are measured and the data are used to estimate phenomenological coefficients. These phenomenological coefficients are used to determine the average pore radius, the average number of pores and the membrane constant. Zeta potentials are evaluated using electro-osmotic permeability and membrane-permeant conductance data to understand the electrical nature of the membrane-permeant interface. It is observed that hydrodynamic permeability and electro-osmotic permeability depend linearly on the applied pressure difference and the potential difference, respectively.

  12. Orientation- and concentration-dependent surfactant adsorption on silicon in aqueous alkaline solutions: explaining the changes in the etch rate, roughness and undercutting for MEMS applications

    NASA Astrophysics Data System (ADS)

    Gosálvez, M. A.; Tang, B.; Pal, P.; Sato, K.; Kimura, Y.; Ishibashi, K.

    2009-12-01

    We combine spectroscopic ellipsometry (SE), Fourier transform infrared spectroscopy (FT-IR), kinetic Monte Carlo simulations (KMC) and convex corner undercutting analysis in order to characterize and explain the effect of the addition of small amounts of surfactant in alkaline aqueous solutions, such as Triton X-100 in tetra methyl ammonium hydroxide (TMAH). We propose that the surfactant is adsorbed at the silicon-etchant interface as a thin layer, acting as a filter that moderates the surface reactivity by reducing the amount of reactant molecules that reach the surface. According to the SE and FT-IR measurements, the thickness of the adsorbed layer is an orientation- and concentration-dependent quantity, mostly due to the orientation dependence of the surface density of H-terminations and the concentration dependence of the relative rates of the underlying oxidation and etching reactions, which have a direct impact on the number of OH terminations. For partial OH coverage of the surface, the hydration of the OH group effectively acts as an anchoring location for the hydration shell of a surfactant molecule, thus enabling the formation of hydration bridges that amplify the adsorption density of the surfactant. At high concentration, the model explains the large reduction in the etch rate of the exact and vicinal Si{1 1 0} surfaces, and the small changes in the etch rates for the exact and vicinal Si{1 0 0} surfaces. At low concentration, it explains how the etch rate for both families is significantly reduced. The orientation and concentration dependence of the surfactant adsorption explains the dramatic differences in the micron-scale wet-etched patterns obtained using TMAH and TMAH+Triton for microelectromechanical systems applications.

  13. Effect of hyperosmotic solutions on salt excretion and thirst in rats

    NASA Technical Reports Server (NTRS)

    Schoorlemmer, G. H.; Johnson, A. K.; Thunhorst, R. L.

    2000-01-01

    We investigated urinary changes and thirst induced by infusion of hyperosmotic solutions in freely moving rats. Intracarotid infusions of 0.3 M NaCl (4 ml/20 min, split between both internal carotid arteries) caused a larger increase in excretion of Na(+) and K(+) than intravenous infusions, indicating that cephalic sensors were involved in the response to intracarotid infusions. Intravenous and intracarotid infusions of hyperosmotic glycerol or urea (300 mM in 150 mM NaCl) had little or no effect, suggesting the sensors were outside the blood-brain barrier (BBB). Intracarotid infusion of hypertonic mannitol (300 mM in 150 mM NaCl) was more effective than intravenous infusion, suggesting that cell volume rather than Na(+) concentration of the blood was critical. Similarly, intracarotid infusion (2 ml/20 min, split between both sides), but not intravenous infusion of hypertonic NaCl or mannitol caused thirst. Hyperosmotic glycerol, infused intravenously or into the carotid arteries, did not cause thirst. We conclude that both thirst and electrolyte excretion depend on a cell volume sensor that is located in the head, but outside the BBB.

  14. Interfacial behavior of perchlorate versus chloride ions in saturated aqueous salt solutions

    SciTech Connect

    Ghosal, S; Kuo, I W; Baer, M D; Bluhm, H

    2009-04-14

    In recent years combination of theoretical and experimental work have presented a novel view of the aqueous interface wherein hard and/or multiply charged ions are excluded from the interface, but large polarizable anions show interfacial enhancement relative to the bulk. The observed trend in the propensity of anions to adsorb at the air/water interface appears to be reverse of the Hofmeister series for anions. This study focuses on experimental and theoretical examination of the partitioning behavior of perchlorate (ClO{sub 4}{sup -}) and chloride (Cl{sup -}) ions at the air/water interface. We have used ambient pressure X-ray photoelectron spectroscopy technique to directly probe the interfacial concentrations of ClO{sub 4}{sup -} and Cl{sup -} ions in sodium perchlorate and sodium chloride solutions, respectively. Experimental observations are compared with first principles molecular dynamics simulations. Both experimental and simulation results show enhancement of ClO{sub 4}{sup -} ion at the interface, compared with the absence of such enhancement in the case of Cl{sup -} ion. These observations are in agreement with the expected trend in the interfacial propensity of anions based on the Hofmeister series.

  15. Dissolution of nickel ferrite in aqueous solutions containing oxalic acid and ferrous salts

    SciTech Connect

    Figueroa, C.A.; Sileo, E.E.; Morando, P.J.; Blesa, M.A.

    2000-05-15

    The dissolution of nickel ferrite in oxalic acid and in ferrous oxalate-oxalic acid aqueous solution was studied. Nickel ferrite was synthesized by thermal decomposition of a mixed tartrate; the particles were shown to be coated with a thin ferric oxide layer. Dissolution takes place in two stages, the first one corresponding to the dissolution of the ferric oxide outer layer and the second one being the dissolution of Ni{sub 1.06}Fe{sub 1.96}O{sub 4}. The kinetics of dissolution during this first stage is typical of ferric oxides: in oxalic acid, both a ligand-assisted and a redox mechanism operates, whereas in the presence of ferrous ions, redox catalysis leads to a faster dissolution. The rate dependence on both oxalic acid and on ferrous ion is described by the Langmuir-Hinshelwood equation. In the second stage, Langmuir-Hinshelwood kinetics also describes the dissolution of iron and nickel from nickel ferrite. It may be concluded that oxalic acid operates to dissolve iron, and the ensuing disruption of the solid framework accelerates the release of nickel.

  16. Alkaline galvanic cells

    SciTech Connect

    Eisenberg, M.

    1993-06-01

    A battery is described having an anode, a cathode and an electrolyte with the anode having zinc or a zinc alloy as an active anodic material, the cathode having a metal oxide or hydroxide as an active cathodic material, and the electrolyte comprising a solution of a first salt formed by the reaction of one or more acids selected from the group consisting of boric acid, phosphoric acid and arsenic acid with an alkali or earth alkali hydroxide present in an amount to produce a stoichiometric, excess of said hydroxide to said acid in the range of 2.5 to 11.0 equivalents per liter, and a solution of a second salt which is a soluble alkali or earth alkali fluoride in an amount corresponding to a concentration range of 0.01 to 1.0 equivalents per liter of total solution.

  17. Structure Formation in Salt-Free Solutions of Amphiphilic Sulfonated Polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Bockstaller, Michael; Koehler, Werner

    2000-03-01

    Self-assembled systems have long attracted attention due to their practical importance in many technical and biological fields. Dodecyl-substituted poly(para-phenylen)sulfonates (abbreviated PPPS) are highly charged polyelectrolytes which in the uncharged state have been investigated extensively and an intrinsic persistence length of 15 nm has been reported. Due to their hydrophobic side chains, PPPS are compatible with water only as micellar aggregates and tend to form supramolecular structures even at concentrations as low as 10-5mol_mon.units/l. Because of the rodlike conformation of PPPS, this self-assembly leads to aggregates of anisotropic shape. Therefore, depolarized light scattering was employed to yield complementary information about structure and dynamics of these complex fluids. Aqueous solutions of PPPS at room temperature undergo a structural transition at a critical concentration of c_crit.=0.016 g/l. This transition is characterized by a strong increase of scattered intensity in forward direction and dynamic depolarized scattering. Above c_crit. the cylindrical micelles (L=310 nm, d=3.1 nm, N_radial=12) self assembly into large ellipsoidal clusters of size in the μ m range. Due to the strong increase of depolarized scattered intensity there has to be a preferential orientation of the micelles inside those clusters, which thus represent a lyotropic mesophase. By combining static and dynamic light scattering for the low q-range as well as small angle x-ray scattering for the higher q-range it is possible to determine size and shape of each aggregation step. Decreasing the molecular weight of the PPPS has profound influence on the micellar length and hence on c_crit. which is close to the overlap concentration (c ~ 1/L^3) allowing for the observation of the polyelectrolyte effect.

  18. Ecology of mixed biofilms subjected daily to a chlorinated alkaline solution: spatial distribution of bacterial species suggests a protective effect of one species to another.

    PubMed

    Leriche, V; Briandet, R; Carpentier, B

    2003-01-01

    Three bacterial strains (Kocuria sp. C714.1, Brevibacterium linens B337.1 and Staphylococcus sciuri CCL101) were grown together on stainless steel and were subjected daily to a commercial alkaline chlorine solution (22 mg l-1 of free chlorine, pH 11) over a period of 4 weeks. After the daily chemical shock, culture madia [1:20 dilution of tryptic soy broth (TSB-YE/20) or diluted whey] was deposited on the biofilms. The chemical shocks led first to a drop in the culturable population, followed by an increase and finally stabilization at around 106-107 CFU cm-2 by day 11 of the experiment. These changes in the microbial population can be attributed to a decreasing susceptibility to the antimicrobial agent with biofilm age, and to the consumption of free chlorine by biofilm exoproteins. The microbial composition appeared to be linked to the free chlorine concentration that depended on exoprotein production. At the end of the experiment, exoprotein production was greater for biofilms grown in TSBYE/20 than in whey. As a consequence, biofilms grown in whey did not neutralize the chlorine and the dominant strain was the one having the highest resistance to chlorine: K. varians. When biofilm were grown in TSBYE/20, chlorine was neutralized and the dominant strain was the one having the highest growth rate: S. sciuri. The presence of chlorine may also explain the distribution of S. sciuri cells as a ring around Kocuria sp. microcolonies. When chlorine was totally consumed by the biofilm during the chemical shock, S. sciuri was no longer grouped around Kocuria sp. microcolonies but was evenly scattered over the substratum as single cells or in small clusters, as it was before any chemical treatment. These findings strongly suggest protection of S. sciuri by Kocuria sp. microcolonies against the chlorinated solution. This phenomenon, added to the low susceptibility phenotype of the biofilm cells, could at least partly explain the survival of microbial cells in an adverse

  19. Water dynamics in salt solutions studied with ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy.

    PubMed

    Fayer, Michael D; Moilanen, David E; Wong, Daryl; Rosenfeld, Daniel E; Fenn, Emily E; Park, Sungnam

    2009-09-15

    with another pulse, the local oscillator. Heterodyne detection provides phase and amplitude information, which are both necessary to perform the two Fourier transforms that take the data from the time domain to a two-dimensional frequency domain spectrum. The time dependence of a series of 2D IR vibrational echo spectra provides direct information on system dynamics. Here, we use two types of 2D IR vibrational echo experiments to examine the influence that charged species have on water hydrogen-bond dynamics. Solutions of NaBr and NaBF(4) are studied. The NaBr solutions are studied as a function of the concentration using vibrational echo measurements of spectral diffusion and polarization-selective IR pump-probe measurements of orientational relaxation. Both types of measurements show the slowing of hydrogen-bond network structural evolution with an increasing salt concentration. NaBF(4) is studied using vibrational echo chemical-exchange spectroscopy. In these experiments, it is possible to directly observe the chemical exchange of water molecules switching their hydrogen-bond partners between BF(4)(-) and other water molecules. The results demonstrate that water interacting with ions has slower hydrogen-bond dynamics than pure water, but the slowing is a factor of 3 or 4 rather than orders of magnitude. PMID:19378969

  20. Studies of Quaternary saline lakes - III. Mineral, chemical, and isotopic evidence of salt solution and crystallization processes in Owens Lake, California, 1969-1971

    NASA Astrophysics Data System (ADS)

    Smith, George I.; Friedman, Irving; McLaughlin, Robert J.

    1987-04-01

    deposition, some salts reacted in situ to form other minerals in less than one month, and all salts (except halite) decomposed or recrystallized at least once in response to seasons. (3) Warming in early 1971 caused solution of all the mirabilite and some of the natron deposited a few months earlier, a deepening of the lake (though the lake-surface lowered), and an increase in dissolved solids. (4) Phase and solubility-index data suggest that at the close of desiccation, Na 2CO 3·7H 2O, never reported as a mineral, could have been the next phase to crystallize.

  1. Studies of Quaternary saline lakes-III. Mineral, chemical, and isotopic evidence of salt solution and crystallization processes in Owens Lake, California, 1969-1971

    USGS Publications Warehouse

    Smith, G.I.; Friedman, I.; McLaughlin, R.J.

    1987-01-01

    deposition, some salts reacted in situ to form other minerals in less than one month, and all salts (except halite) decomposed or recrystallized at least once in response to seasons. (3) Warming in early 1971 caused solution of all the mirabilite and some of the natron deposited a few months earlier, a deepening of the lake (though the lake-surface lowered), and an increase in dissolved solids. (4) Phase and solubility-index data suggest that at the close of desiccation, Na2CO3??7H2O, never reported as a mineral, could have been the next phase to crystallize. ?? 1987.

  2. Corrosion performance of MAO coatings on AZ31 Mg alloy in simulated body fluid vs. Earle's Balance Salt Solution

    NASA Astrophysics Data System (ADS)

    Wilke, Benjamin M.; Zhang, Lei; Li, Weiping; Ning, Chengyun; Chen, Cheng-fu; Gu, Yanhong

    2016-02-01

    Earle's Balance Salt Solution (EBSS) provides an alternative to the conventional simulated body fluids (c-SBF) and has been shown to better simulate the corrosion conditions in vivo. In this work, a series of tests were conducted to explore the corrosion performance of MAO-coated AZ31 samples in EBSS vs. c-SBF. Samples were produced by varying MAO process parameters and then immersed up to 21 days in both EBSS and c-SBF. The corrosion rates were evaluated by the electrochemical impedance spectroscopy and potentiodynamic scanning. Scanning electron microscope (SEM) was used to compare the progression of microcracks across the surface of the coatings. The evaluation of cross-sectional thickness showed an increase in MAO coating thickness with the process voltage. MAO samples with a thicker coating generally have higher impedance and lower current density at the initial immersion time point of 0.5 h. Samples in EBSS showed higher initial impedance and lower current density values as compared to c-SBF counterparts for all process groups. Samples in EBSS demonstrated a much slower corrosion rate than c-SBF samples because of the decreased chloride content and CO2 buffering mechanism of the EBSS.

  3. Atomistic molecular dynamics simulations of the structure of symmetric Polyelectrolyte block copolymer micelle in salt-free aqueous solution

    NASA Astrophysics Data System (ADS)

    Chockalingam, Rajalakshmi; Natarajan, Upendra

    2014-03-01

    The structure of a symmetric polystyrene- b - poly(acrylic acid) (PS- b - PAA) micelle in salt-free aqueous solution as a function of degree-of-neutralization (or ionization, f) of the PAA is studied via explicit-atom-ion MD simulations, for the first time for a polyelectrolyte block copolymer in a polar solvent. Micelle size increases with fin agreement with experimental observations in literature, due to extension of PAA at higher ionization. Pair RDF's with respect to water oxygens show that corona-water interaction becomes stronger with f due to an increase in number density of carboxylate (COO-) groups on the chain. Water-PAA coordination (carboxylate O's) increases with ionization. H-bonding between PAA and water increases with f due to greater extent of corona-water affinity. With increase in f, atom and counter-ion ρ profiles confirm extension of corona blocks and micelle existing in the ``osmotic regime,'' and a decrease in scattering peak intensity, in agreement with neutron scattering experiments and mean-field theory in literature. Inter-chain distance in PS core is found to decrease with ionization. Macromolecular Simulation and Modeling Laboratory, Dept. of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036.

  4. Monte Carlo simulation for the potential of mean force between ionic colloids in solutions of asymmetric salts

    SciTech Connect

    Wu, J.Z.; Bratko, D.; Blanch, H.W.; Prausnitz, J.M. |

    1999-10-01

    A new technique for Monte Carlo sampling of the hard-sphere collision force has been applied to study the interaction between a pair of spherical macroions in primitive-model electrolyte solutions with valences 1:2, 2:1, and 2:2. Macroions of the same charge can attract each other in the presence of divalent counterions, in analogy with earlier observations for planar and cylindrical geometries. The attraction is most significant at intermediate counterion concentrations. In contrast to the entropic depletion force between neutral particles, attraction between macroions is of energetic origin. The entropic contribution to the potential of mean force is generally repulsive at conditions corresponding to aqueous colloids with or without salt. For systems with divalent counterions, the potentials of mean force predicted by mean-field approximations like the Derjaguin{endash}Landau{endash}Verwey{endash}Overbeek (DLVO) theory or the Sogami{endash}Ise (SI) theory are qualitatively different from those observed in the simulations. However, for systems with monovalent counterions, predictions of DLVO theory are in fair agreement with simulation results. {copyright} {ital 1999 American Institute of Physics.}

  5. Electrochemical Investigations of Polycaprolactone-Coated AZ31 Mg Alloy in Earle's Balance Salt Solution and Conventional Simulated Body Fluid

    NASA Astrophysics Data System (ADS)

    Wilke, Benjamin M.; Zhang, Lei

    2016-06-01

    Polycaprolactone (PCL) coating has been shown to increase the corrosion resistance of magnesium alloys when exposed to a simulated body fluid. A PCL dip coating was applied to AZ31 Mg alloy. Samples were immersed in both Earle's Balance Salt Solution (EBSS) and conventional simulated body fluids (c-SBF) up to 14 days. Microscopic morphology, electrochemical impedance spectroscopy, and potentiodynamic polarization tests were performed to evaluate the corrosion behavior changes of PCL coatings against immersion times in EBSS and c-SBF as compared to the uncoated AZ31 substrate. PCL-coated samples demonstrated improved corrosion resistance compared to bare AZ31 in both EBSS and c-SBF, indicating that the PCL coating exhibited good corrosion protection of AZ31 in simulated body fluid. Samples immersed in EBSS showed significantly higher electrochemical impedance values and slower corrosion progression as compared to the samples in c-SBF, because of the decreased chloride content and CO2 buffering mechanism of the EBSS.

  6. Salt-Induced Universal Slowing Down of the Short-Time Self-Diffusion of a Globular Protein in Aqueous Solution

    DOE PAGESBeta

    Grimaldo, Marco; Roosen-Runge, Felix; Hennig, Marcus; Zanini, Fabio; Zhang, Fajun; Zamponi, Michaela; Jalarvo, Niina; Schreiber, Frank; Seydel, Tilo

    2015-06-17

    The short-time self-diffusion D of the globular model protein bovine serum albumin in aqueous (D2O) solutions has been measured comprehensively as a function of the protein and trivalent salt (YCl3) concentration, noted cp and cs, respectively. We observe that D follows a universal master curve D(cs,cp) = D(cs = 0,cp) g(cs/cp), where D(cs= 0,cp) is the diffusion coefficient in the absence of salt and g(cs/cp) is a scalar function solely depending on the ratio of the salt and protein concentration. This observation is consistent with a universal scaling of the bonding probability in a picture of cluster formation of patchymore » particles. In conclusion, the finding corroborates the predictive power of the description of proteins as colloids with distinct attractive ion-activated surface patches.« less

  7. Electrical conductivity of polyelectrolyte solutions in the presence of added salt: The role of the solvent quality factor in light of a scaling approach

    NASA Astrophysics Data System (ADS)

    Bordi, F.; Cametti, C.; Gili, T.

    2003-07-01

    The effects of added salt on the electrical conductivity behavior of a polyelectrolyte solution are described in light of the scaling approach recently proposed by Dobrynin and Rubinstein [Macromolecules 28, 1859 (1995); 32, 915 (1999)], taking into account the influence of the solvent quality factor. The coupling between the conformation of the chain and the local charge distribution, giving rise to different conductometric behaviors, has been investigated under different conditions, in a wide concentration range of added salt. The polyion equivalent conductances λp have been evaluated in different concentration regimes for a hydrophilic polyion in good solvent condition and compared with the experimental values obtained from electrical conductivity measurements. The agreement is rather good in the wide range of concentration of the added salt investigated. In the case of poor solvent conditions, we find the appropriate expressions for the electrical conductivity when the polyion chain consists into collapsed beads alternating with stretched segments in the framework of the necklace globule model.

  8. Salt-Induced Universal Slowing Down of the Short-Time Self-Diffusion of a Globular Protein in Aqueous Solution.

    PubMed

    Grimaldo, Marco; Roosen-Runge, Felix; Hennig, Marcus; Zanini, Fabio; Zhang, Fajun; Zamponi, Michaela; Jalarvo, Niina; Schreiber, Frank; Seydel, Tilo

    2015-07-01

    The short-time self-diffusion D of the globular model protein bovine serum albumin in aqueous (D2O) solutions has been measured comprehensively as a function of the protein and trivalent salt (YCl3) concentration, noted cp and cs, respectively. We observe that D follows a universal master curve D(cs,cp) = D(cs = 0,cp) g(cs/cp), where D(cs = 0,cp) is the diffusion coefficient in the absence of salt and g(cs/cp) is a scalar function solely depending on the ratio of the salt and protein concentration. This observation is consistent with a universal scaling of the bonding probability in a picture of cluster formation of patchy particles. The finding corroborates the predictive power of the description of proteins as colloids with distinct attractive ion-activated surface patches. PMID:26266736

  9. A method for making an alkaline battery electrode plate

    NASA Technical Reports Server (NTRS)

    Chida, K.; Ezaki, T.

    1983-01-01

    A method is described for making an alkaline battery electrode plate where the desired active substances are filled into a nickel foam substrate. In this substrate an electrolytic oxidation reduction occurs in an alkaline solution containing lithium hydroxide.

  10. A balanced salt solution that prevents agglomeration of nano iron oxo-hydroxides in serum-free cellular assays

    NASA Astrophysics Data System (ADS)

    Pereira, Dora I. A.; Lederer, Bianca; Powell, Jonathan J.

    2015-01-01

    Nano iron oxo-hydroxides have numerous and increasing applications in biology and medicine. Assessment of their uptake and toxicity often requires cell culture but maintaining iron oxides uniformly nano-dispersed in such conditions can be challenging. We describe a balanced salt solution (BSS) compatible with cellular assays for use in such investigations. We determined hydrodynamic particle size and dispersibility of nano iron in BSS. The BSS, containing 130 mM NaCl, 10 mM KCl, 1 mM MgSO4, 5 mM glucose and 1.8 mM CaCl2 in 10 mM PIPES buffer (pH 7.4), was capable of maintaining nanoparticulate tartrate-modified Fe(III) oxo-hydroxide (i.e. nano Fe) mono-disperse (≥95% nanoparticulate) with a mean hydrodynamic particle diameter of 6.1 ± 0.3 nm. This size was similar to the native form of the nano Fe material (i.e. as synthesized) with a mean hydrodynamic particle diameter of 4.3 ± 0.1 nm in water. Furthermore, we show that BSS also adequately maintains nano Fe dispersion when supplemented with inhibitors of particle uptake or lysosomal acidification, namely chloropromazine and monensin, and when used at pHs 6.5 or 5.8. In conclusion, we provide a method for nanodispersion of iron oxo-hydroxides that is suitable for short term (1-3 h) cellular exposure investigations.

  11. De Novo Transcriptional Analysis of Alfalfa in Response to Saline-Alkaline Stress

    PubMed Central

    An, Yi-Min; Song, Li-Li; Liu, Ying-Rui; Shu, Yong-Jun; Guo, Chang-Hong

    2016-01-01

    Saline-alkaline stress, caused by high levels of harmful carbonate salts and high soil pH, is a major abiotic stress that affects crop productivity. Alfalfa is a widely cultivated perennial forage legume with some tolerance to biotic and abiotic stresses, especially to saline-alkaline stress. To elucidate the mechanism underlying plant saline-alkaline tolerance, we conducted transcriptome analysis of whole alfalfa seedlings treated with saline-alkaline solutions for 0 day (control), 1 day (short-term treatment), and 7 days (long-term treatment) using ion torrent sequencing technology. A transcriptome database dataset of 53,853 unigenes was generated, and 2,286 and 2,233 genes were differentially expressed in the short-term and long-term treatment, respectively. Gene ontology analysis revealed 14 highly enriched pathways and demonstrated the differential response of metabolic pathways between the short-term and long-term treatment. The expression levels of 109 and 96 transcription factors were significantly altered significantly after 1 day and 7 days of treatment, respectively. Specific responses of peroxidase, flavonoids, and the light pathway component indicated that the antioxidant capacity was one of the central mechanisms of saline-alkaline stress tolerance response in alfalfa. Among the 18 differentially expressed genes examined by real time PCR, the expression levels of eight genes, including inositol transporter, DNA binding protein, raffinose synthase, ferritin, aldo/keto reductase, glutathione S-transferase, xyloglucan endotrans glucosylase, and a NAC transcription factor, exhibited different patterns in response to saline and alkaline stress. The expression levels of the NAC transcription factor and glutathione S-transferase were altered significantly under saline stress and saline-alkaline stress; they were upregulated under saline-alkaline stress and downregulated under salt stress. Physiology assays showed an increased concentration of reactive oxygen

  12. De Novo Transcriptional Analysis of Alfalfa in Response to Saline-Alkaline Stress.

    PubMed

    An, Yi-Min; Song, Li-Li; Liu, Ying-Rui; Shu, Yong-Jun; Guo, Chang-Hong

    2016-01-01

    Saline-alkaline stress, caused by high levels of harmful carbonate salts and high soil pH, is a major abiotic stress that affects crop productivity. Alfalfa is a widely cultivated perennial forage legume with some tolerance to biotic and abiotic stresses, especially to saline-alkaline stress. To elucidate the mechanism underlying plant saline-alkaline tolerance, we conducted transcriptome analysis of whole alfalfa seedlings treated with saline-alkaline solutions for 0 day (control), 1 day (short-term treatment), and 7 days (long-term treatment) using ion torrent sequencing technology. A transcriptome database dataset of 53,853 unigenes was generated, and 2,286 and 2,233 genes were differentially expressed in the short-term and long-term treatment, respectively. Gene ontology analysis revealed 14 highly enriched pathways and demonstrated the differential response of metabolic pathways between the short-term and long-term treatment. The expression levels of 109 and 96 transcription factors were significantly altered significantly after 1 day and 7 days of treatment, respectively. Specific responses of peroxidase, flavonoids, and the light pathway component indicated that the antioxidant capacity was one of the central mechanisms of saline-alkaline stress tolerance response in alfalfa. Among the 18 differentially expressed genes examined by real time PCR, the expression levels of eight genes, including inositol transporter, DNA binding protein, raffinose synthase, ferritin, aldo/keto reductase, glutathione S-transferase, xyloglucan endotrans glucosylase, and a NAC transcription factor, exhibited different patterns in response to saline and alkaline stress. The expression levels of the NAC transcription factor and glutathione S-transferase were altered significantly under saline stress and saline-alkaline stress; they were upregulated under saline-alkaline stress and downregulated under salt stress. Physiology assays showed an increased concentration of reactive oxygen

  13. Laboratory studies of the low-temperature deliquescence of calcium chloride salts: Relevance to aqueous solutions on Mars and in the Antarctic Dry Valleys

    NASA Astrophysics Data System (ADS)

    Gough, R. V.; Chevrier, V.; Tolbert, M. A.

    2013-12-01

    There is significant interest in the possible existence of liquid water on current Mars. This water would likely exist as a brine in order to be stable on Mars today. It has been proposed that soil salts could form aqueous solutions through either the melting of ice by low-eutectic salts, or by the deliquescence of hygroscopic salts present in the Martian soil. The focus thus far has largely been on perchlorate species, which can melt ice at temperatures as low as 206 K and can deliquesce at relative humidity values as low as 38% RH. A Mars-relevant salt that has been neglected thus far is calcium chloride (CaCl2). Calcium has been reported to be an abundant cation at the Phoenix landing site and Mars Science Laboratory instruments have recently identified calcium as well. Simulations suggest subsurface CaCl2 is an ideal candidate to produce brines with seasonality consistent with observed recurring slope lineae (RSL) (Chevrier et al., 2012). Finally, the only terrestrial site where RSL-like features have been observed (near Don Juan Pond in the Antarctic Dry Valleys) contains abundant CaCl2. These seasonal slope streaks are thought to form when CaCl2 in the soil deliquesces due to contact with atmospheric water vapor (Dickson et al., 2013). It is important to understand how this CaCl2 interacts with water vapor at low temperatures relevant to Mars and the Martian analog sites. Here we use a Raman microscope and environmental cell to monitor the low-temperature (223 - 273 K) deliquescence (solid to aqueous phase transition) and efflorescence (aqueous to solid phase transition) of three hydration states of CaCl2 (dihydrate, tetrahydrate, hexahydrate). We have found that the deliquescence relative humidity (DRH) increases with increasing hydration state, which is an expected result. Average DRH values over the temperature range studied are 20.0 × 2.6% RH for the dihydrate, 31.8 × 6.3% RH for the tetrahydrate and 60.7 × 1.6% RH for the hexahydrate. Once the aqueous

  14. Molten salt technology

    SciTech Connect

    Lovering, D.G.

    1982-01-01

    In this volume, the historical background, scope, problems, economics, and future applications of molten salt technologies are discussed. Topics presented include molten salts in primary production of aluminum, general principles and handling and safety of the alkali metals, first-row transition metals, group VIII metals and B-group elements, solution electrochemistry, transport phenomena, corrosion in different molten salts, cells with molten salt electrolytes and reactants, fuel cell design, hydrocracking and liquefaction, heat storage in phase change materials, and nuclear technologies.

  15. Anditalea andensis ANESC-ST--An Alkaliphilic Halotolerant Bacterium Capable of Electricity Generation under Alkaline-Saline Conditions.

    PubMed

    Shi, Wei; Wang, Victor Bochuan; Zhao, Cui-E; Zhang, Qichun; Loo, Say Chye Joachim; Yang, Liang; Xu, Chenjie

    2015-01-01

    A great challenge in wastewater bioremediation is the sustained activity of viable microorganisms, which can contribute to the breakdown of waste contaminants, especially in alkaline pH conditions. Identification of extremophiles with bioremediation capability can improve the efficiency of wastewater treatment. Here, we report the discovery of an electrochemically active alkaliphilic halotolerant bacterium, Anditalea andensis ANESC-ST (=CICC10485T=NCCB 100412T), which is capable of generating bioelectricity in alkaline-saline conditions. A. andensis ANESC-ST was shown to grow in alkaline conditions between pH 7.0-11.0 and also under high salt condition (up to 4 wt% NaCl). Electrical output was further demonstrated in microbial fuel cells (MFCs) with an average current density of ~0.5 µA/cm2, even under the harsh condition of 4 wt% NaCl and pH 9.0. Subsequent introduction of secreted extracellular metabolites into MFCs inoculated with Escherichia coli or Pseudomonas aeruginosa yielded enhanced electrical output. The ability of A. andensis ANESC-ST to generate energy under alkaline-saline conditions points towards a solution for bioelectricity recovery from alkaline-saline wastewater. This is the first report of A.andensis ANESC-ST producing bioelectricity at high salt concentration and pH. PMID:26171779

  16. Specificity of the chemical and mineralogical composition of salts in solonchak playas and lakes of the Kulunda steppe

    NASA Astrophysics Data System (ADS)

    Lebedeva (Verba), M. P.; Lopukhina, O. V.; Kalinina, N. V.

    2008-04-01

    The chemical composition of water in 44 lakes of the Kulunda steppe has been studied. It is shown that solute concentrations in different lakes vary from 1 to 390 g/l. Four chemical types of the water salinity—chloride, sulfate, chloride-sulfate with the presence of sodium bicarbonate, and sodic waters—are distinguished. The nature of the water alkalinity has been studied in 12 lakes. In the lakes with neutral chloride and sulfate salts, the total alkalinity does not exceed 16.56 meq/l. In the lakes with the presence of soda, it reaches 189 meq/l. In sodic waters, the total alkalinity varies from 600 to 1504.6 meq/l. In the latter case, the water alkalinity is conditioned by the presence of soda and borate salts. Salt minerals in the bottom sediments and in the salt crusts of solonchakous playas around the lakes are represented by halite, calcite, dolomite, and thenardite. In two salt crusts, the presence of soda and trona has been diagnosed.

  17. 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.

  18. Alloy 22 Localized Corrosion Susceptibility In Aqueous Solutions Of Chloride And Nitrate Salts Of Sodium And Potassium At 110 - 150?C

    SciTech Connect

    Felker, S; Hailey, P D; Lian, T; Staggs, K J; Gdowski, G E

    2006-01-17

    Alloy 22 (a nickel-chromium-molybdenum-tungsten alloy) is being investigated for use as the outer barrier of waste containers for a high-level nuclear waste repository in the thick unsaturated zone at Yucca Mountain, Nevada. Experiments were conducted to assess crevice corrosion of Alloy 22 in de-aerated aqueous solutions of chloride and nitrate salts of potassium and sodium in the temperature range 110-150 C (some limited testing was also conducted at 90 C). Electrochemical tests were run in neutral salt solutions without acid addition and others were run in salt solutions with an initial hydrogen ion concentration of 10{sup -4} molal. The Alloy 22 specimens were weld prism specimens and de-aeration was performed with nitrogen gas. No evidence of crevice corrosion was observed in the range 125-150 C. In the 120 to 160 C temperature range, the anionic concentration of stable aqueous solutions is dominated by nitrate relative to chloride. At nominally 120 C, the minimum nitrate to chloride ratio is about 4.5, and it increases to about 22 at nominally 155 C. The absence of localized corrosion susceptibility in these solutions is attributed to the known inhibiting effect of the nitrate anion. At 110 C, aqueous solutions can have dissolved chloride in excess of nitrate. Localized corrosion was observed at nitrate to chloride ratios up to 1.0, the highest ratio tested. The extent of localized corrosion was confined to the crevice region of the samples, and was limited for nitrate to chloride ratios greater than or equal to 0.3. Aqueous solution chemistry studies indicate that nitrate to chloride ratios of less than 0.5 are possible for temperatures up to nominally 116 C. However, the exact upper temperature limit is unknown and no electrochemical testing was done at these temperatures. Limited comparison between 8 m Cl aqueous solutions of Na + K on the one hand and Ca on the other indicated similar electrochemical E{sub crit} values and similar morphology of attack

  19. Cumulates, Dykes and Pressure Solution in the Ice-Salt Mantle of Europa: Geological Consequences of Pressure Dependent Liquid Compositions and Volume Changes During Ice-Salt Melting Reactions.

    NASA Astrophysics Data System (ADS)

    Day, S.; Asphaug, E.; Bruesch, L.

    2002-12-01

    Water-salt analogue experiments used to investigate cumulate processes in silicate magmas, along with observations of sea ice and ice shelf behaviour, indicate that crystal-melt separation in water-salt systems is a rapid and efficient process even on scales of millimetres and minutes. Squeezing-out of residual melts by matrix compaction is also predicted to be rapid on geological timescales. We predict that the ice-salt mantle of Europa is likely to be strongly stratified, with a layered structure predictable from density and phase relationships between ice polymorphs, aqueous saline solutions and crystalline salts such as hydrated magnesium sulphates (determined experimentally by, inter alia, Hogenboom et al). A surface layer of water ice flotation cumulate will be separated from denser salt cumulates by a cotectic horizon. This cotectic horizon will be both the site of subsequent lowest-temperature melting and a level of neutral buoyancy for the saline melts produced. Initial melting will be in a narrow depth range owing to increasing melting temperature with decreasing pressure: the phase relations argue against direct melt-though to the surface unless vesiculation occurs. Overpressuring of dense melts due to volume expansion on cotectic melting is predicted to lead to lateral dyke emplacement and extension above the dyke tips. Once the liquid leaves the cotectic, melting of water ice will involve negative volume change. Impact-generated melts will drain downwards through the fractured zones beneath crater floors. A feature in the complex crater Mannan'an, with elliptical ring fractures around a conical depression with a central pit, bears a close resemblance to Icelandic glacier collapse cauldrons produced by subglacial eruptions. Other structures resembling Icelandic cauldrons occur along Europan banded structures, while resurgence of ice rubble within collapse structures may produce certain types of chaos region. More general contraction of the ice mantle

  20. Influence of Proton and Salt Concentration on the Chromonic Liquid Crystal Phase Diagram of Disodium Cromoglycate Solutions: Prospects and Limitations of a Host for DNA Nanostructures.

    PubMed

    Zhang, Bingru; Kitzerow, Heinz-S

    2016-03-31

    Lyotropic chromonic liquid crystals have recently been suggested for use as a self-organized host for dispersing and aligning self-organized DNA origami nanostructures. However, an appropriate pH value and a suitable cation concentration are necessary to stabilize such nanostructures and to avoid unfolding of the DNA. The present study shows that the nematic and columnar liquid crystal phases appearing in aqueous solutions of disodium cromoglycate are robust against the replacement of deionized water by a neutral or alkaline buffer solution. However, disodium cromoglycate precipitates when an acidic buffer is used or when the concentration of magnesium cations exceeds a critical concentration of about 0.6-0.7 mmol/L. PMID:26964003

  1. Experimental Microbiology of Saturated Salt Solutions and Other Harsh Environments. III. Growth of Salt-Tolerant Penicillium notatum in Boron-Rich Media 1

    PubMed Central

    Roberts, Karen; Siegel, S. M.

    1967-01-01

    A stress-tolerant strain of Penicillium notatum, isolated by passage through a nutrient solution saturated with calcium acetate, was found to have a tolerance to boron in several states of oxidation. Growth in the presence of elementary boron, saturating amounts of boric acid, and with various concentrations of sodium borohydride was observed and mycelial mats were spectrographically analyzed for boron accumulation. PMID:6076112

  2. Efficacy of a solution-based approach for making sodalite waste forms for an oxide reduction salt utilized in the reprocessing of used uranium oxide fuel

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Pierce, David A.; Frank, Steven M.; Matyáš, Josef; Burns, Carolyne A.

    2015-04-01

    This paper describes the various approaches evaluated for making solution-derived sodalite with a LiCl-Li2O oxide reduction salt selected to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (∼92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt but that the incorporation of Li into the sodalite is low.

  3. Degradation of the herbicide 2, 4-dichlorophenoxyacetic acid (2,4-D) dimethylamine salt by gamma radiation from cobalt-60 in aqueous solution containing humic acid

    NASA Astrophysics Data System (ADS)

    Campos, Sandro X.; Vieira, Eny M.; Cordeiro, Paulo J. M.; Rodrigues-Fo, Edson; Murgu, Michael

    2003-12-01

    In this study, gamma radiation from cobalt-60 was used to degrade the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) dimethylamine salt in water in the presence of humic acid. The 2,4-D dimethylamine salt 1.13×10 -4 mol dm -3 solution was irradiated with different doses. HPLC was used as an analytical technique to determine the degradation rate of herbicide studied. The results showed that the herbicide was completely degraded at an absorbed dose of 3 kGy. Degradation decreased when humic acid was added to all the doses. ESI/MS and MS/MS were used to identify the radiolytic degradation products. A fragmentation path for production of 4.6-dichlororesorcinol, is suggested. The radiolytic yields ( G) were calculated.

  4. FINAL REPORT. ACTINIDE-ALUMINATE SPECIATION IN ALKALINE RADIOACTIVE WASTE

    EPA Science Inventory

    Investigation of behavior of actinides in alkaline media containing Al(III) showed that no aluminate complexes of actinides in oxidation states (III-VII) were formed in alkaline solutions. At alkaline precipitation (pH 10-14) of actinides in presence of Al(III) formation of alumi...

  5. Performed surfactant-optimized aqueous alkaline flood

    SciTech Connect

    Thigpen, D.R.; Lawson, J.B.; Nelson, R.C.

    1991-11-26

    This paper describes improvement in a process for recovering oil from an acidic oil reservoir by injecting an aqueous alkaline solution comprising water, sodium chloride, and alkaline material for reacting with the reservoir oil forming a petroleum acid soap to form an in-situ surfactant system. The improvement comprises: selecting a preformed cosurfactant which is soluble in both the aqueous solution and the reservoir oil and has a solubility ratio which is grater than the solubility ratio of the petroleum acid soap where the solubility ratio is the ratio of solubility in the aqueous alkaline solution to the solubility in the reservoir oil; combining with the alkaline solution an amount of the preformed cosurfactant which will result in the in-situ surfacant system having a salinity about equal to a salinity which results in minimal interfacial tension between the oil in the reservoir and the in-situ surfactant system at reservoir temperature, wherein the amount of the preformed cosurfactant is about 0.3 percent by weight in the aqueous alkaline solution; and injecting the cosurfactant-aqueous alkaline solution mixture into the reservoir to displace oil toward a fluid production location.

  6. A Hypermedia Environment To Explore and Negotiate Students' Conceptions: Animation of the Solution Process of Table Salt.

    ERIC Educational Resources Information Center

    Ebenezer, Jazlin V.

    2001-01-01

    Describes the characteristics and values of hypermedia for learning chemistry. Reports on how a hypermedia environment was used to explore a group of 11th grade chemistry students' conceptions of table salt dissolving in water. Indicates that a hypermedia environment can be used to explore, negotiate, and assess students' conceptions of…

  7. Lorentz Force on Sodium and Chlorine Ions in a Salt Water Solution Flow under a Transverse Magnetic Field

    ERIC Educational Resources Information Center

    De Luca, R.

    2009-01-01

    It is shown that, by applying elementary concepts in electromagnetism and electrochemistry to a system consisting of salt water flowing in a thin rectangular pipe at an average velocity v[subscript A] under the influence of a transverse magnetic field B[subscript 0], an electromotive force generator can be conceived. In fact, the Lorentz force…

  8. Basic trends and chief products in the electrolysis of methanolic solutions of monomethyl adipate and its alkali salts

    SciTech Connect

    Shul'zhenko, G.I.; Freidlin, G.N.; Kovsman, E.P.; Vasil'ev, Yu. B.

    1986-08-01

    Preparative electrolysis under galvanostatic conditions was used to study the effect of the principal adjustable process parameters, such as temperature, the water content of the original electrolyte, current density, electrolysis time, and the concentration of monoester salt, on the formation of methyl valerate and methyl allylacetate. The character of the influence of these parameters was established.

  9. ALP (Alkaline Phosphatase) Test

    MedlinePlus

    ... known as: ALK PHOS; Alkp Formal name: Alkaline Phosphatase Related tests: AST ; ALT ; GGT ; Bilirubin ; Liver Panel ; Bone Markers ; Alkaline Phosphatase Isoenzymes; Bone Specific ALP All content on Lab ...

  10. Efficacy of a solution-based approach for making sodalite waste forms for an oxide reduction salt utilized in the reprocessing of used uranium oxide fuel

    SciTech Connect

    Riley, Brian J.; Pierce, David A.; Frank, Steven M.; Matyáš, Josef; Burns, Carolyne A.

    2015-04-01

    This paper describes the various approaches attempted to make solution-derived sodalite with a LiCl-Li2O oxide reduction salt used to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solutionbased synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3- SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt but that the incorporation of Li into the sodalite is low.

  11. Efficacy of a solution-based approach for making sodalite waste forms for an oxide reduction salt utilized in the reprocessing of used uranium oxide fuel

    DOE PAGESBeta

    Riley, Brian J.; Pierce, David A.; Frank, Steven M.; Matyáš, Josef; Burns, Carolyne A.

    2015-04-01

    This paper describes the various approaches attempted to make solution-derived sodalite with a LiCl-Li2O oxide reduction salt used to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solutionbased synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3- SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2Omore » and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt but that the incorporation of Li into the sodalite is low.« less

  12. Efficacy of a Solution-Based Approach for Making Sodalite Waste Forms for an Oxide Reduction Salt Utilized in the Reprocessing of Used Uranium Oxide Fuel

    SciTech Connect

    Riley, Brian J.; Pierce, David A.; Frank, Steven M.; Matyas, Josef; Burns, Carolyn A.

    2015-04-01

    This paper describes various approaches for making sodalite with a LiCl-Li2O oxide reduction salt used to recover uranium from used oxide fuel. The approaches include sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt.

  13. Swelling and Surface Interactions of End-Grafted Poly(2-vinylpyridine) Layers in Acidic Solution: Influence of Grafting Density and Salt Concentration.

    PubMed

    Elmahdy, Mahdy M; Drechsler, Astrid; Uhlmann, Petra; Stamm, Manfred

    2016-06-01

    In previous studies, the authors found that end-grafted layers of the weak polybase poly(2-vinylpyridine) (P2VP) in aqueous solutions do not only swell and collapse if the pH value and salt concentration are varied but also exhibit a pH- and salinity-dependent adhesion to microsized silica spheres. For a better understanding of these effects, in situ force measurements using the AFM colloidal probe technique were applied to end-grafted P2VP layers of different grafting densities in NaCl solutions at pH 2.5. Although a mushroom-to-brush transition could be seen in the dry state, the layers were in the brush regime in aqueous solutions at all NaCl concentrations and grafting densities. We observed an increase of the brush height with increasing grafting density and a salinity-dependent collapse and reswelling of the brushes. The adhesion between the P2VP layer and a silica sphere depended on both grafting density and salinity. At low salt concentrations, the adhesion reached its highest value at the intermediate grafting density and disappeared with denser brushes. Maximum adhesion was obtained for high NaCl concentrations and the lowest grafting density. From a detailed analysis of the experiments, we gained insight into chain stretching and density profiles under complex ionic conditions and into the mechanism of adhesion of polyelectrolytes to solid surfaces. PMID:27172173

  14. Interfacial activity in alkaline flooding enhanced oil recovery

    SciTech Connect

    Chan, M.K.

    1981-01-01

    The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical species in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.

  15. Data on energy-band-gap characteristics of composite nanoparticles obtained by modification of the amorphous potassium polytitanate in aqueous solutions of transition metal salts.

    PubMed

    Zimnyakov, D A; Sevrugin, A V; Yuvchenko, S A; Fedorov, F S; Tretyachenko, E V; Vikulova, M A; Kovaleva, D S; Krugova, E Y; Gorokhovsky, A V

    2016-06-01

    Here we present the data on the energy-band-gap characteristics of composite nanoparticles produced by modification of the amorphous potassium polytitanate in aqueous solutions of different transition metal salts. Band gap characteristics are investigated using diffuse reflection spectra of the obtained powders. Calculated logarithmic derivative quantity of the Kubelka-Munk function reveals a presence of local maxima in the regions 0.5-1.5 eV and 1.6-3.0 eV which correspond to band gap values of the investigated materials. The values might be related to the constituents of the composite nanoparticles and intermediate products of their chemical interaction. PMID:27158654

  16. Pressure-tuning spectroscopy of charge-transfer salts. X-ray crystallography and comparative studies in solution and in the solid state

    SciTech Connect

    Bockman, T.M.; Kochi, J.K. ); Chang, H.R.; Drickamer, H.G. )

    1990-11-01

    The highly colored pyridinium (P{sup +}) and cobaltocenium (C{sup +}) iodides are charge-transfer salts by virtue of the new electronic absorption bands that follow Mulliken theory. X-ray crystallography establishes the relevant interionic separation and steric orientation of the cation/anion pairs P{sup +}I{sup {minus}} and C{sup +}I{sup {minus}} constrained for optimum charge-transfer interaction in the crystal lattice. Spectral comparisons of the charge-transfer (CT) transitions by absorption (solution) and by diffuse reflectance (solid-state) measurements reveals the commonality of contact ion pairs (CIP) in aprotic nonpolar solvents (dichloromethane) with those extant in crystalline charge-transfer salts. As such, the compression of the charge-transfer salts P{sup +}I{sup {minus}} in the solid state by the application of pressures up to 140 kbar leads to unusual red shifts of the CT bands indicative of the dominance of destabilizing charge-transfer interactions.

  17. Salt-Induced Universal Slowing Down of the Short-Time Self-Diffusion of a Globular Protein in Aqueous Solution

    SciTech Connect

    Grimaldo, Marco; Roosen-Runge, Felix; Hennig, Marcus; Zanini, Fabio; Zhang, Fajun; Zamponi, Michaela; Jalarvo, Niina; Schreiber, Frank; Seydel, Tilo

    2015-06-17

    The short-time self-diffusion D of the globular model protein bovine serum albumin in aqueous (D2O) solutions has been measured comprehensively as a function of the protein and trivalent salt (YCl3) concentration, noted cp and cs, respectively. We observe that D follows a universal master curve D(cs,cp) = D(cs = 0,cp) g(cs/cp), where D(cs= 0,cp) is the diffusion coefficient in the absence of salt and g(cs/cp) is a scalar function solely depending on the ratio of the salt and protein concentration. This observation is consistent with a universal scaling of the bonding probability in a picture of cluster formation of patchy particles. In conclusion, the finding corroborates the predictive power of the description of proteins as colloids with distinct attractive ion-activated surface patches.

  18. Hunting liquid micro-pockets in snow and ice: Phase transition in salt solutions at the bulk and interface with X-ray photoelectron spectroscopy.

    NASA Astrophysics Data System (ADS)

    Bartels-Rausch, Thorsten; Orlando, Fabrizio; Kong, Xiangrui; Waldner, Astrid; Artiglia, Luca; Ammann, Markus; Huthwelker, Thomas

    2016-04-01

    Sea salt, and in particular chloride, is an important reactant in the atmosphere. Chloride in air-borne sea salt aerosol is - once chemically converted to a molecular halogen (Cl2, BrCl) and released to the atmosphere - well known as important atmospheric reactant, driving large-scale changes to the atmospheric composition and in particular to ozone levels in remote areas, but also in coastal mega cities. Similar chemistry has been proposed for sea salt deposits in polar snow covers. A crucial factor determining the overall reactivity is the local physical environment of the chloride ion. For example, the reactivity of liquid aerosols decreases significantly upon crystallization. Surprisingly, the phases of NaCl-containing systems are still under debate, partially due to the limited availability of in situ measurements directly probing the local environment at the surface of frozen NaCl-water binary systems. Using core electron spectroscopy of the oxygen atoms in water, we previously showed that these systems follow the phase rules at the air-ice interface. This finding contrasts some earlier observations, where the presence of liquid below the eutectic point of bulk solutions was postulated. In the present study, we present new electron yield near-edge X-ray absorption fine structure spectroscopy (NEXAFS) data obtained at near-ambient pressures up to 20 mbar of NaCl frozen solutions. The method is sensitive to small changes in the local environment of the chlorine atom. The measurements were performed at the PHOENIX beamline at SLS. The study indicates frapant differences in the phases of NaCl - water mixtures at temperatures blow the freezing point for the surface of the ice vs. the bulk. This has significant impact on modelling chemical reactions in snow or ice and it's environmental consequences.

  19. Long-term cement corrosion in chloride-rich solutions relevant to radioactive waste disposal in rock salt - Leaching experiments and thermodynamic simulations

    NASA Astrophysics Data System (ADS)

    Bube, C.; Metz, V.; Bohnert, E.; Garbev, K.; Schild, D.; Kienzler, B.

    Low- and intermediate-level radioactive wastes are frequently solidified in a cement matrix. In a potential repository for nuclear wastes, the cementitious matrix is altered upon contact with solution and the resulting secondary phases may provide for significant retention of the radionuclides incorporated in the wastes. In order to assess the secondary phases formed upon corrosion in chloride-rich solutions, which are relevant for nuclear waste disposal in rock salt, leaching experiments were performed. Conventional laboratory batch experiments using powdered hardened cement paste in MgCl2-rich solutions were left to equilibrate for up to three years and full-scale cemented waste products were exposed to NaCl-rich and MgCl2-rich solutions for more than twenty years, respectively. Solid phase analyses revealed that corrosion of hardened cement in MgCl2-rich solutions advanced faster than in NaCl-rich solutions due to the extensive exchange of Mg from solution against Ca from the cementitious solid. Thermodynamic equilibrium simulations compared well to results at the final stages of the respective experiments indicating that close to equilibrium conditions were reached. At high cement product to brine ratios (>0.65 g mL-1), the solution composition in the laboratory-scale experiments was close to that of the full-scale experiments (cement to brine ratio of 2.5 g mL-1) in the MgCl2 systems. The present study demonstrates the applicability of thermodynamic methods used in this approach to adequately describe full-scale long-term experiments with cemented waste simulates.

  20. Effect of the oxygen content in a salt solution on the characteristics of sodium-reduced tantalum powders

    NASA Astrophysics Data System (ADS)

    Kolosov, V. N.; Orlov, V. M.; Miroshnichenko, M. N.; Prokhorova, T. Yu.; Masloboeva, S. M.; Belyaevskii, A. T.

    2009-02-01

    The characteristics of the tantalum powders produced by sodium thermal reduction from salt melts based on K2TaF7 and NaCl with various amounts of added oxycompounds K3TaOF6 and K2Ta2O3F6 are studied. At a molar ratio of oxygen to tantalum of 1.25 in the initial melt, capacitor tantalum powders with a specific surface area more than 3 m2/g are produced. The specific capacitance of the anodes made from these powders reaches 58 mC/g.

  1. Metals removal from spent salts

    DOEpatents

    Hsu, Peter C.; Von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Brummond, William A.; Adamson, Martyn G.

    2002-01-01

    A method and apparatus for removing metal contaminants from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents may be added to precipitate the metal oxide and/or the metal as either metal oxide, metal hydroxide, or as a salt. The precipitated materials are filtered, dried and packaged for disposal as waste or can be immobilized as ceramic pellets. More than about 90% of the metals and mineral residues (ashes) present are removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be spray-dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 1.0 ppm of contaminants.

  2. Actinide removal from spent salts

    DOEpatents

    Hsu, Peter C.; von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Adamson, Martyn G.

    2002-01-01

    A method for removing actinide contaminants (uranium and thorium) from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents are added to precipitate the thorium as thorium oxide and/or the uranium as either uranium oxide or as a diuranate salt. The precipitated materials are filtered, dried and packaged for disposal as radioactive waste. About 90% of the thorium and/or uranium present is removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 0.1 ppm of thorium or uranium.

  3. Combined capillary electrophoresis and high performance liquid chromatography studies on the kinetics and mechanism of the hydrogen peroxide-thiocyanate reaction in a weakly alkaline solution.

    PubMed

    Hu, Ying; Song, Yanan; Horváth, Attila K; Cui, Yin; Ji, Chen; Zhao, Yuemin; Gao, Qingyu

    2014-03-01

    The hydrogen peroxide-thiocyanate reaction has been reinvestigated by means of capillary electrophoresis and high performance liquid chromatography under weakly alkaline conditions at 25.0±0.1 °C. Concentration-time series of thiocyanate, sulfate and cyanate have been followed by capillary electrophoresis as well as that of thiocyanate and hydrogen peroxide by HPLC. It has been clearly demonstrated that OxSCN(-) (where x=1, 2 and 3) cannot be accumulated in detectable amount in contrast to the results of Christy and Egeberg, hence these species can only be regarded as short-lived intermediates. It has been shown that the overall rate law is first-order with respect to both reactants, but no pH-dependence was observed within the pH range of 8.86-10.08. A simple kinetic model has been proposed to fit all the concentration-time curves simultaneously at five different pHs demonstrating the powerful combination of the experimental techniques CE and HPLC with simultaneous evaluation of kinetic curves. It is also enlightened that the quality of the buffer strongly affects the rate of the overall reaction that increases in the order of application of ammonia, phosphate, carbonate and borate, respectively at a constant ionic strength and pH. PMID:24468335

  4. Structural stability of beta-globulin, the low molecular weight protein fraction from sesame seed (Sesamum indicum L.) in alkaline solution.

    PubMed

    Rajendran, S; Prakash, V

    1993-02-01

    Beta-globulin, a single polypeptide chain of molecular weight 15,000 +/- 1,000, undergoes denaturation in alkaline pH (7.0-13.0), thereby affecting the hydrodynamic properties of the protein, viz. a decrease in sedimentation coefficient from a value of 2.0s to 1.4s at pH 11.3, an increase in reduced viscosity from 0.042 dl/g to 0.158 dl/g at pH 12.6 and a decrease in partial specific volume resulting in a volume change of 6.3 +/- 1.0 ml/mole residue at pH 11.7. The perturbation of tryptophanyl residues and ionization of tyrosyl residues are preceded by alteration in conformational status of the protein. The fluorescence emission measurements indicate initial unfolding of the protein molecule which exposes the tryptophan and tyrosyl residues to the solvent. The tyrosyl phenolic group ionization is anomalous having a pKint value of 11.2. The reduced viscosity value reaches a plateau region at pH 12.5. PMID:8509122

  5. Solubility of hydrogen sulfide in aqueous solutions of the single salts sodium sulfate, ammonium sulfate, sodium chloride, and ammonium chloride at temperatures from 313 to 393 K and total pressures up to 10 MPa

    SciTech Connect

    Xia, J.; Kamps, A.P.S.; Rumpf, B.; Maurer, G.

    2000-04-01

    New experimental results for the solubility of hydrogen sulfide in aqueous solutions of the single salts sodium sulfate, ammonium sulfate, sodium chloride, and ammonium chloride at temperatures from 313 to 393 K and total pressures up to 10 MPa are reported. As in the salt-free system, a second-hydrogen sulfide-rich--liquid phase is observed at high hydrogen sulfide concentrations. A model to describe the phase equilibrium is presented. Calculations are compared to the new experimental data.

  6. Association constants in solutions of lithium salts in butyrolactone and a mixture of propylene carbonate with 1,2-dimethoxyethane (1 : 1), according to conductometric data

    NASA Astrophysics Data System (ADS)

    Chernozhuk, T. V.; Sherstyuk, Yu. S.; Novikov, D. O.; Kalugin, O. N.

    2016-02-01

    A conductometric study is performed with solutions of lithium bis(oxalato)borate (LiBOB) in γ-butyrolactone (γ-BL) at 278.15-388.15 K and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), LiBOB, and lithium tetrafluoroborate (LiBF4) in mixtures of propylene carbonate and 1,2-dimethoxyethane (PC + 1,2-DME) (1 : 1) at 278.15-348.15 K. Limiting molar electrical conductivities (LMECs) and association constants ( K a) in the studied solutions of electrolytes are determined using the Lee-Wheaton equation. The effect temperature, the nature of the solvent, and the properties of the anion have on the conductivity and interparticle interactions in solutions of lithium salts in γ-BL and PC + 1,2-DME (1 : 1) is established. It was concluded that the studied solutions are characterized by low values of their association constants. It was found that the BOB;- anion destroys the structure of the solvent.The thickness of the dynamic solvation shell of ions (Δ R) remains constant for both solvents over the studied range of temperatures, and Δ R is significantly greater for Li+ than for other ions.

  7. Alkaline injection for enhanced oil recovery: a status report

    SciTech Connect

    Mayer, E.H.; Berg, R.L.; Carmichael, J.D.; Weinbrandt, R.M.

    1983-01-01

    In the past several years, there has been renewed interest in enhanced oil recovery (EOR) by alkaline injection. Alkaline solutions also are being used as preflushes in micellar/polymer projects. Several major field tests of alkaline flooding are planned, are in progress, or recently have been completed. Considerable basic research on alkaline injection has been published recently, and more is in progress. This paper summarizes known field tests and, where available, the amount of alkali injected and the performance results. Recent laboratory work, much sponsored by the U.S. DOE, and the findings are described. Alkaline flood field test plans for new projects are summarized.

  8. Effects of Cations on Corrosion of Inconel 625 in Molten Chloride Salts

    NASA Astrophysics Data System (ADS)

    Zhu, Ming; Ma, Hongfang; Wang, Mingjing; Wang, Zhihua; Sharif, Adel

    2016-04-01

    Hot corrosion of Inconel 625 in sodium chloride, potassium chloride, magnesium chloride, calcium chloride and their mixtures with different compositions is conducted at 900°C to investigate the effects of cations in chloride salts on corrosion behavior of the alloy. XRD, SEM/EDS were used to analyze the compositions, phases, and morphologies of the corrosion products. The results showed that Inconel 625 suffers more severe corrosion in alkaline earth metal chloride molten salts than alkaline metal chloride molten salts. For corrosion in mixture salts, the corrosion rate increased with increasing alkaline earth metal chloride salt content in the mixture. Cations in the chloride molten salts mainly affect the thermal and chemical properties of the salts such as vapor pressure and hydroscopicities, which can affect the basicity of the molten salt. Corrosion of Inconel 625 in alkaline earth metal chloride salts is accelerated with increasing basicity.

  9. QM/MM analysis suggests that Alkaline Phosphatase (AP) and Nucleotide pyrophosphatase/phosphodiesterase slightly tighten the transition state for phosphate diester hydrolysis relative to solution: implication for catalytic promiscuity in the AP superfamily

    PubMed Central

    Hou, Guanhua

    2011-01-01

    Several members of the Alkaline Phosphatase (AP) superfamily exhibit a high level of catalytic proficiency and promiscuity in structurally similar active sites. A thorough characterization of the nature of transition state for different substrates in these enzymes is crucial for understanding the molecular mechanisms that govern those remarkable catalytic properties. In this work, we study the hydrolysis of a phosphate diester, MpNPP−, in solution, two experimentally well-characterized variants of AP (R166S AP, R166S/E322Y AP) and wild type Nucleotide pyrophosphatase/phosphodiesterase (NPP) by QM/MM calculations in which the QM method is an approximate density functional theory previously parameterized for phosphate hydrolysis (SCC-DFTBPR). The general agreements found between these calculations and available experimental data for both solution and enzymes support the use of SCC-DFTBPR/MM for a semi-quantitative analysis of the catalytic mechanism and nature of transition state in AP and NPP. Although phosphate diesters are cognate substrates for NPP but promiscuous substrates for AP, the calculations suggest that their hydrolysis reactions catalyzed by AP and NPP feature similar synchronous transition states that are slightly tighter in nature compared to that in solution, due in part to the geometry of the bimetallic zinc motif. Therefore, this study provides the first direct computational support to the hypothesis that enzymes in the AP superfamily catalyze cognate and promiscuous substrates via similar transition states to those in solution. Our calculations do not support the finding of recent QM/MM studies by López-Canut and coworkers, who suggested that the same diester substrate goes through a much looser transition state in NPP/AP than in solution, a result likely biased by the large structural distortion of the bimetallic zinc site in their simulations. Finally, our calculations for different phosphate diester orientations and phosphorothioate diesters

  10. The effects of steam injection on the electrical conductivity of an unconsolidated sand saturated with a salt solution

    SciTech Connect

    Vaughan, P.J.; Udell, K.S. ); Wilt, M.J. )

    1993-01-10

    The spatial and temporal variation of electrical conductivity in saturated sands during steam injection has been measured and modeled. Experiments consisted of introducing steam into one end of a tube filled with sand saturated with a slightly saline solution. A steam condensation front formed, separating the mixed-phase steam zone from the liquid zone. Measurements of electrical conductivity were made at 10 locations along the tube using a four-electrode technique. Results show that conductivity starts at a constant value, decreases before the steam front arrives and then, immediately prior to the steam front arrival, goes through a maximum before dropping by a factor of about 25. These variations can be explained by first, a dilution of the interstitial solution causing the initial drop in conductivity; second, an increase in temperature of the solution immediately prior to the arrival of the steam front causing the conductivity maximum; and finally, the large drop in conductivity due to the combined effects of a decrease in saturation and dilution of the residual liquid in the two-phase zone. Mathematical solutions of a set of differential equations that take into consideration all of these effects are presented. These solutions reproduce the significant features of the conductivity data. This study suggests that the measurement of changes in the subsurface conductivity field during steam injection operations may indicate the location of ionic concentration, temperature, and steam saturation fields. 28 refs., 7 figs., 1 tab.

  11. Photochemistry of triarylsulfonium salts

    SciTech Connect

    Dektar, J.L.; Hacker, N.P. )

    1990-08-01

    The photolysis of triphenylsulfonium, tris(4-methylphenyl)sulfonium, tris(4-chlorophenyl)sulfonium, several monosubstituted (4-F, 4-Cl, 4-Me, 4-MeO, 4-PhS, and 4-PhCO), and disubstituted (4,4{prime}-Me{sub 2} and 4,4{prime}-(MeO){sub 2}) triphenylsulfonium salts was examined in solution. It was found that direct irradiation of triphenylsulfonium salts produced new rearrangement products, phenylthiobiphenyls, along with diphenyl sulfide, which had been previously reported. Similarly, the triarylsulfonium salts, with the exception of the (4-(phenylthio)phenyl)diphenylsulfonium salts produced new rearrangement products, phenylthiobiphenyls, along with diphenyl sulfide, which had been previously reported. Similarly, the triarylsulfonium salts, with the exception of the (4-(phenylthio)phenyl)diphenylsulfonium salts, gave the new rearrangement products. The mechanism for direct photolysis is proposed to occur from the singlet excited states to give a predominant heterolytic cleavage along with some homolytic cleavage.

  12. Effects of Amendment of Biochar and Pyroligneous Solution from wheat straw pyrolysis on Yield and soil and crop salinity in a Salt stressed cropland from Central China Great Plain

    NASA Astrophysics Data System (ADS)

    Li, L.; Liu, Y.; Pan, W.; Pan, G.; Zheng, J.; Zheng, J.; Zhang, X.

    2012-04-01

    Crop production has been subject to salt stress in large areas of world croplands. Organic and/or bio-fertilizers have been applied as soil amendments for alleviating salt stress and enhancing crop productivity in these salt-stressed croplands. While biochar production systems using pyrolysis of crop straw materials have been well developed in the world, there would be a potential measure to use materials from crop straw pyrolysis as organic amendments in depressing salt stress in agriculture. In this paper, a field experiment was conducted on the effect of biochar and pyroligneous solution from cropstraw pyrolysis on soil and crop salinity, and wheat yield in a moderately salt stressed Entisol from the Central Great Plain of North China. Results indicated that: biochar and pyroligneous solution increased soil SOC, total nitrogen, available potassium and phosphorous by 43.77%, 6.50%, 45.54% and 108.01%, respectively. While Soil bulk density was decreased from 1.30 to 1.21g cm-3; soil pH (H2O) was decreased from 8.23 to 7.94 with a decrease in soluble salt content by 38.87%. Wheat yield was doubled over the control without amendment. In addition, sodium content was sharply declined by 78.80% in grains, and by 70.20% and 67.00% in shoot and root, respectively. Meanwhile, contents of potassium and phosphorus in plant tissue were seen also increased despite of no change in N content. Therefore, the combined amendment of biochar with pyroligneous solution would offer an effective measure to alleviate the salt stress and improving crop productivity in world croplands. Keywords: biochar, salt affected soils, wheat, crop productivity, salinity

  13. Precipitation of jarosite-type double salts from spent acid solutions from a chemical coal cleaning process

    SciTech Connect

    Norton, G.

    1990-09-21

    The precipitation of jarosite compounds to remove Na, K, Fe, and SO{sub 4}{sup 2{minus}} impurities from spent acid solutions from a chemical coal cleaning process was studied. Simple heating of model solutions containing Fe{sub 2}(SO{sub 4}){sub 3}, Na{sub 2}SO{sub 4}, and K{sub 2}SO{sub 4} caused jarosite (KFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}) to form preferentially to natrojarosite (NaFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}). Virtually all of the K, about 90% of the Fe, and about 30% of the SO{sub 4}{sup 2{minus}} could be precipitated from those solutions at 95{degree}C, while little or no Na was removed. However, simple heating of model solutions containing only Fe{sub 2}(SO{sub 4}){sub 3} and Na{sub 2}SO{sub 4} up to 95{degree}C for {le}12 hours produced low yields of jarosite compounds, and the Fe concentration in the solution had to be increased to avoid the formation of undesirable Fe compounds. Precipitate yields could be increased dramatically in model solutions of Na{sub 2}SO{sub 4}/Fe{sub 2}(SO{sub 4}){sub 3} containing excess Fe by using either CaCO{sub 3}, Ca(OH){sub 2}, or ZnO to neutralize H{sub 2}SO{sub 4} released during hydrolysis of the Fe{sub 2}(SO{sub 4}){sub 3} and during the precipitation reactions. Results obtained from the studies with model solutions were applied to spent acids produced during laboratory countercurrent washing of coal which had been leached with a molten NaOH/KOH mixture. Results indicated that jarosite compounds can be precipitated effectively from spent acid solutions by heating for 6 hours at 80{degree}C while maintaining a pH of about 1.5 using CaCO{sub 3}.

  14. Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

    NASA Astrophysics Data System (ADS)

    Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

    2016-02-01

    The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

  15. Microstructure and corrosion behavior of die-cast AM60B magnesium alloys in a complex salt solution. A slow positron beam study

    SciTech Connect

    Liu, Y. F.; Yang, W.; Qin, Q. L.; Wen, W.; Zhai, T.; Yu, B.; Liu, D. Y.; Luo, A.; Song, GuangLing

    2013-12-15

    The microstructure and corrosion behavior of high pressure die-cast (HPDC) and super vacuum die-cast (SVDC) AM60B magnesium alloys were investigated in a complex salt solution using slow positron beam technique and potentiodynamic polarization tests. The experiments revealed that a CaCO3 film was formed on the surface of the alloys and that the rate of CaCO3 formation for the SVDC alloy with immersion time was slower than that of the HPDC alloy. The larger volume fraction of b-phase in the skin layer of the SVDC alloy than that of the HPDC alloy was responsible for the better corrosion resistance.

  16. Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System.

    PubMed

    Lavrynenko, O M; Pavlenko, O Yu; Shchukin, Yu S

    2016-12-01

    The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations. PMID:26847693

  17. Behavior of Zn2+, Cd2+, Ba2+ and Pb2+ cations in ferromanganese crusts from the Marcus Wake seamount (Pacific Ocean) in aqueous solutions of metal salts

    NASA Astrophysics Data System (ADS)

    Novikov, G. V.; Bogdanova, O. Yu.; Melnikov, M. E.; Lobus, N. V.; Drozdova, A. N.; Shulga, N. A.

    2016-01-01

    The behavior of heavy-metal cations in ore minerals of cobalt-rich ferromanganese crusts from the Marcus Wake seamount in aqueous solutions of metal salts was studied in experiments. The Zn2+ and Cd2+ cations showed high reactivity and Ba2+ and Pb2+ showed low reactivity. It was found that Zn2+ and Cd2+ cations within the ore mineral composition are mainly absorbed (up to 66%) whereas Pb2+ and Ba2+ are chemically bound (up to 70%). Ore minerals in the crusts are characterized by sorption properties and high ionexchange capacity by these cations (1.94-2.62 mg-equiv/g). The capacity values by heavy-metal cations for ore minerals of the crusts from different areas of the Marcus Wake seamount are close to each other.

  18. Data on energy-band-gap characteristics of composite nanoparticles obtained by modification of the amorphous potassium polytitanate in aqueous solutions of transition metal salts

    PubMed Central

    Zimnyakov, D.A.; Sevrugin, A.V.; Yuvchenko, S.A.; Fedorov, F.S.; Tretyachenko, E.V.; Vikulova, M.A.; Kovaleva, D.S.; Krugova, E.Y.; Gorokhovsky, A.V.

    2016-01-01

    Here we present the data on the energy-band-gap characteristics of composite nanoparticles produced by modification of the amorphous potassium polytitanate in aqueous solutions of different transition metal salts. Band gap characteristics are investigated using diffuse reflection spectra of the obtained powders. Calculated logarithmic derivative quantity of the Kubelka–Munk function reveals a presence of local maxima in the regions 0.5–1.5 eV and 1.6–3.0 eV which correspond to band gap values of the investigated materials. The values might be related to the constituents of the composite nanoparticles and intermediate products of their chemical interaction. PMID:27158654

  19. A New Attempt at Alkaline Texturization of Monocrystaline Silicon with Anionic Surfactant as the Additive

    NASA Astrophysics Data System (ADS)

    Li, Hailing; Wang, Wenjing; Zhao, Lei; Zhou, Chunlan; Diao, Hongwei

    2012-10-01

    Owing to the volatilization of isopropanol (IPA), instability in the alkaline texturization of monocrystalline silicon has been a big problem for a long time. Many additives were adapted to replace IPA, such as high boiling point alcohols. In this experiment, as a new attempt, sodium lauryl sulfate (SDS), a type of anionic surfactant, was used as the additive in NaOH solution. The etching properties of silicon in 2 wt % NaOH/15-30 mg/L SDS solution were analyzed. To improve the wettability of silicon, two types of metal salt, NaCl and Na2CO3 with concentration from 2 to 15 wt %, were applied to the 2 wt % NaOH/15 mg/L SDS solution. The results showed that the effect of NaCl was better than that of Na2CO3. Finally, the role of the additive was discussed.

  20. Summary technical report on the electrochemical treatment of alkaline nuclear wastes

    SciTech Connect

    Hobbs, D.T.

    1994-07-30

    This report summarizes the laboratory studies investigating the electrolytic treatment of alkaline solutions carried out under the direction of the Savannah River Technology Center from 1985-1992. Electrolytic treatment has been demonstrated at the laboratory scale to be feasible for the destruction of nitrate and nitrite and the removal of radioactive species such as {sup 99}Tc and {sup 106}Ru from Savannah River Site (SRS) decontaminated salt solution and other alkaline wastes. The reaction rate and current efficiency for the removal of these species are dependent on cell configuration, electrode material, nature of electrode surface, waste composition, current density, and temperature. Nitrogen, ammonia, and nitrous oxide have been identified as the nitrogen-containing reaction products from the electrochemical reduction of nitrate and nitrite under alkaline conditions. The reaction mechanism for the reduction is very complex. Voltammetric studies indicated that the electrode reactions involve surface phenomena and are not necessarily mass transfer controlled. In an undivided cell, results suggest an electrocatalytic role for oxygen via the generation of the superoxide anion. In general, more efficient reduction of nitrite and nitrate occurs at cathode materials with higher overpotentials for hydrogen evolution. Nitrate and nitrite destruction has also been demonstrated in engineering-scale flow reactors. In flow reactors, the nitrate/nitrite destruction efficiency is improved with an increase in the current density, temperature, and when the cell is operated in a divided cell configuration. Nafion{reg_sign} cation exchange membranes have exhibited good stability and consistent performance as separators in the divided-cell tests. The membranes were also shown to be unaffected by radiation at doses approximating four years of cell operation in treating decontaminated salt solution.