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Sample records for alkaline salt solutions

  1. 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.

  2. Electrochemical Recovery of Sodium Hydroxide from Alkaline Salt Solution

    SciTech Connect

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

    1996-10-01

    A statistically designed set of tests determined the effects of current density, temperature, and the concentrations of nitrate/nitrite, hydroxide and aluminate on the recovery of sodium as sodium hydroxide (caustic) from solutions simulating those produced from the Savannah River Site (SRS) In-Tank Precipitation process. These tests included low nitrate and nitrite concentrations which would be produced by electrolytic nitrate/nitrite destruction. The tests used a two compartment electrochemical cell with a Nafion Type 324 ion-exchange membrane. Caustic was successfully recovered from the waste solutions. Evaluation of the testing results indicated that the transport of sodium across the membrane was not significantly affected by any of the varied parameters. The observed variance in the sodium flux is attributed to experimental errors and variations in the performance characteristics of individual pieces of the organic-based Nafion membrane.Additional testing is recommended to determine the maximum current density, to evaluate the chemical durability of the organic membrane as a function of current density and to compare the durability and performance characteristics of the organic-based Nafion membrane with that of other commercially available organic membranes and the inorganic class of membranes under development by Ceramatec and PNNL.

  3. 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

  4. [Salt-alkaline tolerance of sorghum germplasm at seedling stage].

    PubMed

    Gao, Jian-Ming; Xia, Bu-Xian; Yuan, Qing-Hua; Luo, Feng; Han, Yun; Gui, Zhi; Pei, Zhong-You; Sun, Shou-Jun

    2012-05-01

    A sand culture experiment with Hoagland solution plus NaCl and Na2CO3 was conducted to study the responses of sorghum seedlings to salt-alkaline stress. An assessment method for identifying the salt-alkaline tolerance of sorghum at seedling stage was established, and the salt-alkaline tolerance of 66 sorghum genotypes was evaluated. At the salt concentrations 8.0-12.5 g x L(-1), there was a great difference in the salt-alkaline tolerance between tolerant genotype 'TS-185' and susceptive 'Tx-622B', suggesting that this range of salt concentrations was an appropriate one to evaluate the salt-alkaline tolerance of sorghum at seedling stage. At the salt concentrations 10.0 and 12.5 g x L(-1), there existed significant differences in the relative livability, relative fresh mass, and relative height among the 66 genotypes, indicating a great difference in the salt-alkaline tolerance among these genotypes. The genotype 'Sanchisan' was highly tolerant, 16 genotypes such as 'MN-2735' were tolerant, 32 genotypes such as 'EARLY HONEY' were mild tolerant, 16 genotypes such as 'Tx-622B' were susceptive, and genotype 'MN-4588' was highly susceptive to salt-alkaline stress. Most of the sorghum genotypes belonging to Sudangrasses possessed a high salt-alkaline tolerance, while the sorghum genotypes belonging to maintainer lines were in adverse. PMID:22919841

  5. 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.

  6. 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.

  7. 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.

  8. Physiological and molecular features of Puccinellia tenuiflora tolerating salt and alkaline-salt stress.

    PubMed

    Zhang, Xia; Wei, Liqin; Wang, Zizhang; Wang, Tai

    2013-03-01

    Saline-alkali soil seriously threatens agriculture productivity; therefore, understanding the mechanism of plant tolerance to alkaline-salt stress has become a major challenge. Halophytic Puccinellia tenuiflora can tolerate salt and alkaline-salt stress, and is thus an ideal plant for studying this tolerance mechanism. In this study, we examined the salt and alkaline-salt stress tolerance of P. tenuiflora, and analyzed gene expression profiles under these stresses. Physiological experiments revealed that P. tenuiflora can grow normally with maximum stress under 600 mmol/L NaCl and 150 mmol/L Na2 CO3 (pH 11.0) for 6 d. We identified 4,982 unigenes closely homologous to rice and barley. Furthermore, 1,105 genes showed differentially expressed profiles under salt and alkaline-salt treatments. Differentially expressed genes were overrepresented in functions of photosynthesis, oxidation reduction, signal transduction, and transcription regulation. Almost all genes downregulated under salt and alkaline-salt stress were related to cell structure, photosynthesis, and protein synthesis. Comparing with salt stress, alkaline-salt stress triggered more differentially expressed genes and significantly upregulated genes related to H(+) transport and citric acid synthesis. These data indicate common and diverse features of salt and alkaline-salt stress tolerance, and give novel insights into the molecular and physiological mechanisms of plant salt and alkaline-salt tolerance.

  9. 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.

  10. Uptake of atmospheric mercury by deionized water and aqueous solutions of inorganic salts at acidic, neutral and alkaline pH.

    PubMed

    Waite, D T; Snihura, A D; Liu, Y; Huang, G H

    2002-10-01

    Mercury (Hg) is well known as a toxic environmental pollutant that is among the most highly bioconcentrated trace metals in the human food chain. The atmosphere is one of the most important media for the environmental cycling of mercury, since it not only receives mercury emitted from natural sources such as volcanoes and soil and water surfaces but also from anthropogenic sources such as fossil fuel combustion, mining and metal smelting. Although atmospheric mercury exists in different physical and chemical forms, as much as 90% can occur as elemental vapour Hg0, depending on the geographic location and time of year. Atmospheric mercury can be deposited to aquatic ecosystems through both wet (rain or snow) and dry (vapour adsorption and particulate deposition) processes. The purpose of the present study was to measure, under laboratory conditions, the rate of deposition of gaseous, elemental mercury (Hg0) to deionized water and to solutions of inorganic salt species of varying ionic strengths with a pH range of 2-12. In deionized water the highest deposition rates occurred at both low (pH 2) and high (pH 12). The addition of different species of salt of various concentrations for the most part had only slight effects on the absorption and retention of atmospheric Hg0. The low pH solutions of various salt concentrations and the high pH solutions of high salt concentrations tested in this study generally showed a greater tendency to absorb and retain atmospheric Hg0 than those at a pH closer to neutral.

  11. 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.

  12. Electrochromic Salts, Solutions, and Devices

    SciTech Connect

    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.

  13. Electrochromic salts, solutions, and devices

    SciTech Connect

    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

    SciTech Connect

    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. 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.

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  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. Protein aggregation in salt solutions.

    PubMed

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

    2015-05-26

    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.

  3. Contamination and purification of alkaline gas treating solutions

    SciTech Connect

    McCullough, J.G.; Nielsen, R.B.

    1996-08-01

    Alkanolamine and potassium carbonate solutions in gas treating units removing carbon dioxide, hydrogen sulfide, or both are contaminated by impurities in the feed gases and makeup water and by the products of the degradation and oxidation of amines occurring in the units themselves. Feed gas impurities include oxygen, carbonyl sulfide, carbon monoxide, hydrogen cyanide, ammonia, brine, solid particles, heavy hydrocarbons, sulfur dioxide, hydrochloric acid, organic acids, and pipeline corrosion inhibitors. Impure makeup water contains sulfate, chloride, alkali metal, and alkaline earth ions (hardness). Reactions causing contamination in the units include oxidation of hydrogen sulfide to sulfate and thiosulfate, oxidation of amines to formic acid and other products, and degradation of amines by carbon dioxide. The resulting heat-stable salts and polymers reduce the gas absorbing capacity of alkanolamine solutions and increase their corrosiveness. Similar problems occur in potassium carbonate solutions, except that degradation products of amine activators are too dilute to be harmful. Contaminants are removed by inlet gas separation, charcoal and mechanical filtration, neutralization of heat-stable salts, reclaiming at both atmospheric and reduced pressure, upstream washing of the feed gas, electrodialysis, use of antioxidants, ion exchange, and blowdown and dumping of the solution.

  4. Eco-physiological characteristics of alfalfa seedlings in response to various mixed salt-alkaline stresses.

    PubMed

    Peng, Yong-Lin; Gao, Zhan-Wu; Gao, Ying; Liu, Guo-Fang; Sheng, Lian-Xi; Wang, De-Li

    2008-01-01

    Soil salinization and alkalization frequently co-occur in nature, but little is known about the mixed effects of salt-alkaline stresses on plants. An experiment with mixed salts (NaCl, Na(2)SO(4), NaHCO(3) and Na(2)CO(3)) and 30 salt-alkaline combinations (salinity 24-120 mmol/L and pH 7.03-10.32) treating Medicago sativa seedlings was conducted. The results demonstrated that salinity and alkalinity significantly affected total biomass and biomass components of seedlings. There were interactive effects of salt composition and concentration on biomass (Palkalinity stresses led to changes in the root activity along the salinity gradient (Palkalinity on seedling survival rate were more significant than those of salinity, and the seedlings demonstrated some physiological responses (leaf electrolyte leakage rate and proline content) in order to adapt to mixed salt-alkaline stresses. It was concluded that the mixed salt-alkaline stresses, which differ from either salt or alkali stress, emphasize the significant interaction between salt concentration (salinity) and salt component (alkalinity). Further, the effects of the interaction between high alkalinity and salinity are more severe than those of either salt or alkali stress, and such a cooperative interaction results in more sensitive responses of ecological and physiological characteristics in plants. PMID:18666949

  5. 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...

  6. The effects of alkaline and alkaline earth metal salts on the performance of a polymer actuator based on single-wal led carbon nanotube-ionic liquid gel

    NASA Astrophysics Data System (ADS)

    Terasawa, Naohiro; Takeuchi, Ichiroh; Mukai, Ken; Asaka, Kinji

    We investigated an effect for alkaline metal salts or an alkaline earth metal salt on electrochemical and electromechanical properties of an actuator using a single-walled carbon nanotube (SWCNT)-ionic liquid (IL) gel electrode, and much better performance of the actuator containing the metal salt/IL. The actuator containing the alkaline metal salt /IL or alkaline earth metal salt/IL performed much better than that containing only the IL. It is considered that the higher ionic conductivity of the gel electrolyte layer containing the alkaline metal salt /IL or alkaline earth metal salt/IL produces the quick response actuator, and that the large capacitance gives the large generated strain.

  7. 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)

  8. Redox reactions of actinides in carbonate and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Shilov, Vladimir P.; Yusov, Aleksander B.

    2002-06-01

    Data on redox reactions involving uranium, neptunium, plutonium and americium ions in carbonate and alkaline solutions are generalised. The results of kinetic studies of these reactions are analysed and their mechanisms are discussed. The bibliography includes 169 references.

  9. 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.

  10. 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.

  11. 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.

  12. 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%).

  13. Alkaline solution/binder ratio as a determining factor in the alkaline activation of aluminosilicates

    SciTech Connect

    Ruiz-Santaquiteria, C.; Fernandez-Jimenez, A.; Palomo, A.

    2012-09-15

    This study investigates the effect of the alkaline solution/binder (S/B) ratio on the composition and nanostructure of the reaction products generated in the alkaline activation of aluminosilicates. The experiments used two mixtures of fly ash and dehydroxylated white clay and for each of these, varying proportions of the solution components. The alkali activator was an 8 M NaOH solution (with and without sodium silicate) used at three S/B ratios: 0.50, 0.75 and 1.25. The {sup 29}Si, {sup 27}Al MAS NMR and XRD characterisation of the reaction products reveal that for ratios nearest the value delivering suitable paste workability, the reaction-product composition and structure depend primarily on the nature and composition of the starting materials and the alkaline activator used. However, when an excess alkaline activator is present in the system, the reaction products tend to exhibit SiO{sub 2}/Al{sub 2}O{sub 3} ratios of approximately 1, irrespective of the composition of the starting binder or the alkaline activator.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Salting-in and salting-out of water-soluble polymers in aqueous salt solutions.

    PubMed

    Sadeghi, Rahmat; Jahani, Farahnaz

    2012-05-01

    To obtain further experimental evidence for the mechanisms of the salting effect produced by the addition of salting-out or sating-in inducing electrolytes to aqueous solutions of water-soluble polymers, systematic studies on the vapor-liquid equilibria and liquid-liquid equilibria of aqueous solutions of several polymers are performed in the presence of a large series of electrolytes. Polymers are polyethylene glycol 400 (PEG400), polyethylene glycol dimethyl ether 250 (PEGDME250), polyethylene glycol dimethyl ether 2000 (PEGDME2000), and polypropylene glycol 400 (PPG400), and the investigated electrolytes are KCl, NH(4)Cl, MgCl(2), (CH(3))(4)NCl, NaCl, NaNO(3), Na(2)CO(3), Na(2)SO(4), and Na(3)Cit (tri-sodium citrate). Aqueous solutions of PPG400 form aqueous two-phase systems with all the investigated salts; however, other investigated polymers form aqueous two-phase systems only with Na(2)CO(3), Na(2)SO(4), and Na(3)Cit. A relation was found between the salting-out or sating-in effects of electrolyte on the polymer aqueous solutions and the slopes of the constant water activity lines of ternary polymer-salt aqueous solutions, so that, in the case of the salting-out effect, the constant water activity lines had a concave slope, but in the case of the salting-in effects, the constant water activity lines had a convex slope. The effect of temperature, anion of electrolyte, cation of electrolyte, and type and molar mass of polymers were studied and the results interpreted in terms of the solute-water and solute-solute interactions. The salting-out effect results from the formation of ion (specially anion)-water hydration complexes, which, in turn, decreases hydration, and hence, the solubility of the polymer and the salting-in effect results from a direct binding of the cations to the ether oxygens of the polymers.

  19. 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…

  20. 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

  1. Electrochemical-metallothermic reduction of zirconium in molten salt solutions

    SciTech Connect

    McLaughlin, D.F.; Talko, F.

    1990-05-08

    This patent describes a method for separating hafnium from zirconium of the type wherein a feed containing zirconium and hafnium chlorides is prepared from zirconium-hafnium chloride and the feed is introduced into a distillation column, which distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and wherein a hafnium chloride enriched stream is taken from the top of the column and a zirconium enriched chloride stream is taken from the bottom of the column. It comprises: reducing the zirconium enriched chloride stream taken from the distillation column to metal by electrochemically reducing an alkaline earth metal in a molten salt bath with the molten salt in the molten salt bath consisting essentially of a mixture of at least one alkali metal chloride and at least one alkaline earth metal chloride and zirconium chloride, with the reduced alkaline earth metal reacting with the zirconium chloride to produce zirconium metal and alkaline earth metal chloride.

  2. 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.

  3. Chlorate salts and solutions on Mars

    NASA Astrophysics Data System (ADS)

    Hanley, Jennifer; Chevrier, Vincent F.; Berget, Deanna J.; Adams, Robert D.

    2012-04-01

    Chlorate (ClO3-) is an intermediate oxidation species between chloride (Cl-) and perchlorate (ClO4-), both of which were found at the landing site by the Wet Chemistry Lab (WCL). The chlorate ion is almost as stable as perchlorate, and appears to be associated with perchlorate in most terrestrial reservoirs (e.g. Atacama and Antarctica). It is possible that chlorate contributed to the ion sensor response on the WCL, yet was masked by the strong perchlorate signal. However, very little is known about chlorate salts and their effect on the stability of water. We performed evaporation rate experiments in our Mars simulation chamber, which enabled us to determine the activity of water for various concentrations. From this we constructed solubility diagrams for NaClO3, KClO3, Mg(ClO3)2 and Ca(ClO3)2, and determined the Pitzer parameters for each salt. Chlorate salt eutectic temperatures range from 270 K (KClO3) to 204 K (Mg(ClO3)2). Modeling the addition of chlorate to the initial WCL solutions shows that it precipitates in concentrations comparable to other common salts, such as gypsum and epsomite, and implies that chlorates may play an important role in the wet chemistry on Mars.

  4. THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

    PubMed

    Brdicka, R

    1936-07-20

    1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.

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

    PubMed

    Li, Weifeng; Mu, Yuguang

    2011-10-01

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

  6. Organic ionic salt draw solutions for osmotic membrane bioreactors.

    PubMed

    Bowden, Katie S; Achilli, Andrea; Childress, Amy E

    2012-10-01

    This investigation evaluates the use of organic ionic salt solutions as draw solutions for specific use in osmotic membrane bioreactors. Also, this investigation presents a simple method for determining the diffusion coefficient of ionic salt solutions using only a characterized membrane. A selection of organic ionic draw solutions underwent a desktop screening process before being tested in the laboratory and evaluated for performance using specific salt flux (reverse salt flux per unit water flux), biodegradation potential, and replenishment cost. Two of the salts were found to have specific salt fluxes three to six times lower than two commonly used inorganic draw solutions, NaCl and MgCl(2). All of the salts tested have organic anions with the potential to degrade in the bioreactor as a carbon source and aid in nutrient removal. Results demonstrate the potential benefits of organic ionic salt draw solutions over currently implemented inorganics in osmotic membrane bioreactor systems. PMID:22771022

  7. 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.

  8. Phase behavior of polyelectrolyte solutions with salt.

    PubMed

    Lee, Chi-Lun; Muthukumar, Murugappan

    2009-01-14

    We have computed the phase diagrams of solutions of flexible polyelectrolyte chains with added simple electrolytes. The calculations are based on our recent theory [M. Muthukumar, Macromolecules 35, 9142 (2002)], which accounts for conformational fluctuations of chains, charge density correlations arising from dissolved ions, hydrophobic interaction between polymer backbone and solvent, and translational entropy of all species in the system. The theory is at the mean field level and recovers the results of the restricted primitive model with the Debye-Huckel description for solutions of simple electrolytes without any polymer chains and those of the Flory-Huggins and scaling theories for uncharged polymers in the absence of charges or electrolytes. In constructing the phase diagrams, the chemical potential of each of the species is maintained to be the same in the coexisting phases and at the same time each phase being electrically neutral (Donnan equilibrium). Comparisons are made with a more constrained situation where the chemical potentials of the independent components are maintained to be the same in the coexisting phases. Our calculations predict several rich phenomena. Even for the salt-free solutions, two critical phenomena (corresponding to the Flory-Huggins-type and the restricted-primitive-model-type critical points) are predicted. The coupling between these two leads to two critical end points and triple points. In the presence of salt, the valency of electrolyte ions is found to influence drastically the phase diagrams. Specifically, the predicted liquid-liquid phase transitions in certain temperature ranges is reminiscent of the re-entrant-precipitation phenomenon observed experimentally for polyelectrolytes condensed with trivalent salts.

  9. Phase behavior of polyelectrolyte solutions with salt

    NASA Astrophysics Data System (ADS)

    Lee, Chi-Lun; Muthukumar, Murugappan

    2009-01-01

    We have computed the phase diagrams of solutions of flexible polyelectrolyte chains with added simple electrolytes. The calculations are based on our recent theory [M. Muthukumar, Macromolecules 35, 9142 (2002)], which accounts for conformational fluctuations of chains, charge density correlations arising from dissolved ions, hydrophobic interaction between polymer backbone and solvent, and translational entropy of all species in the system. The theory is at the mean field level and recovers the results of the restricted primitive model with the Debye-Hückel description for solutions of simple electrolytes without any polymer chains and those of the Flory-Huggins and scaling theories for uncharged polymers in the absence of charges or electrolytes. In constructing the phase diagrams, the chemical potential of each of the species is maintained to be the same in the coexisting phases and at the same time each phase being electrically neutral (Donnan equilibrium). Comparisons are made with a more constrained situation where the chemical potentials of the independent components are maintained to be the same in the coexisting phases. Our calculations predict several rich phenomena. Even for the salt-free solutions, two critical phenomena (corresponding to the Flory-Huggins-type and the restricted-primitive-model-type critical points) are predicted. The coupling between these two leads to two critical end points and triple points. In the presence of salt, the valency of electrolyte ions is found to influence drastically the phase diagrams. Specifically, the predicted liquid-liquid phase transitions in certain temperature ranges is reminiscent of the re-entrant-precipitation phenomenon observed experimentally for polyelectrolytes condensed with trivalent salts.

  10. 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.

  11. 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.

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

    SciTech Connect

    Griswold, G. B.

    1981-02-01

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

  13. 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.

  14. Identification of a major QTL allele from wild soybean (Glycine soja Sieb. & Zucc.) for increasing alkaline salt tolerance in soybean.

    PubMed

    Tuyen, D D; Lal, S K; Xu, D H

    2010-07-01

    Salt-affected soils are generally classified into two main categories, sodic (alkaline) and saline. Our previous studies showed that the wild soybean accession JWS156-1 (Glycine soja) from the Kinki area of Japan was tolerant to NaCl salt, and the quantitative trait locus (QTL) for NaCl salt tolerance was located on soybean linkage group N (chromosome 3). Further investigation revealed that the wild soybean accession JWS156-1 also had a higher tolerance to alkaline salt stress. In the present study, an F(6) recombinant inbred line mapping population (n = 112) and an F(2) population (n = 149) derived from crosses between a cultivated soybean cultivar Jackson and JWS156-1 were used to identify QTL for alkaline salt tolerance in soybean. Evaluation of soybean alkaline salt tolerance was carried out based on salt tolerance rating (STR) and leaf chlorophyll content (SPAD value) after treatment with 180 mM NaHCO(3) for about 3 weeks under greenhouse conditions. In both populations, a significant QTL for alkaline salt tolerance was detected on the molecular linkage group D2 (chromosome 17), which accounted for 50.2 and 13.0% of the total variation for STR in the F(6) and the F(2) populations, respectively. The wild soybean contributed to the tolerance allele in the progenies. Our results suggest that QTL for alkaline salt tolerance is different from the QTL for NaCl salt tolerance found previously in this wild soybean genotype. The DNA markers closely associated with the QTLs might be useful for marker-assisted selection to pyramid tolerance genes in soybean for both alkaline and saline stresses.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Theoretical investigation of the structures, stabilities, and NLO responses of calcium-doped pyridazine: alkaline-earth-based alkaline salt electrides.

    PubMed

    Wang, Yin-Feng; Huang, Jiangen; Jia, Li; Zhou, Guangpei

    2014-02-01

    Currently, whether alkaline-earth-doped compounds with electride characteristics are novel candidates for high-performance nonlinear optical (NLO) materials is unknown. In this paper, using quantum chemical computations, we show that: when doping calcium atoms into a family of alkaline-substituted pyridazines, alkaline-earth-based alkaline salt electrides M-H₃C₄N₂⋯Ca (M=H, Li, and K) with distended excess electron clouds are formed. Interestingly, from the triplet to the singlet state, the chemical valence of calcium atom changes from +1 to 0, and the dipole moment direction (μ₀) of the molecule reverses for each M-H₃C₄N₂⋯Ca. Changing pyridazine from without (H₄C₄N₂⋯Ca) to with one alkaline substituent (M-H₃C₄N₂⋯Ca, M=Li and K), the ground state changes from the triplet to the singlet state. The alkaline earth metal doping effect (electride effect) and alkaline salt effect on the static first hyperpolarizabilities (β₀) demonstrates that (1) the β₀ value is increased approximately 1371-fold from 2 (pyridazine, H₄C₄N₂) to 2745au (Ca-doped pyridazine, H₄C₄N₂⋯Ca), (2) the β₀ value is increased approximately 1146-fold from 2 in pyridazine (H₄C₄N₂) to 2294au in an Li-substituted pyridazine (Li-H₃C₄N₂), and (3) the β₀ value is increased 324-(M=Li) and 106-(M=K) fold from 826 (MLi) and 2294au (MK) to 268,679 (M=Li) and 245,878au (M=K), respectively, from the alkalized pyridazine (M-H₃C₄N₂) to the Ca-doped pyridazine (M-H₃C₄N₂⋯Ca). These results may provide a new means for designing high-performance NLO materials.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  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. 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.

  7. 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.

  8. 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.

  9. Dissolution rate of griseofulvin in bile salt solutions.

    PubMed

    de Smidt, J H; Offringa, J C; Crommelin, D J

    1991-04-01

    Bile salts increase the apparent solubility of lipophilic poorly water-soluble drugs like griseofulvin. In this study, the dissolution kinetics of griseofulvin in solutions of bile salts (sodium taurocholate and sodium cholate) were investigated. A rotating disk apparatus was chosen to monitor dissolution kinetics; it well-defined hydrodynamic conditions allowed for analysis of the behavior of bile salt micelles under different conditions. Griseofulvin solubility and dissolution rate increased with increasing bile salt concentration in the dissolution medium. The enhancement of the dissolution rate was not linearly related to the solubility increase, as diffusional transport of the solubilized drug proved to be less efficient than transport of the unsolubilized ("free") drug. The dissolution process proved to be controlled by convective diffusion. An analysis of the data with the phase separation model provided results for the micellar diffusion coefficient comparable with literature data obtained with different techniques. PMID:1865343

  10. [Determination of Chloride Salt Solution by NIR Spectroscopy].

    PubMed

    Zhang, Bin; Chen, Jian-hong; Jiao, Ming-xing

    2015-07-01

    Determination of chloride salt solution by near infrared spectrum plays a very important role in Biomedicine. The near infrared spectrum analysis of Sodium chloride, potassium chloride, calcium chloride aqueous solution shows that the concentration change of chloride salt can affect hydrogen bond, resulting in the variation of near infrared spectrum of water. The temperature influence on NIR spectrum has been decreased by choosing reasonable wavelength range and the wavelength where the temperature effects are zero (isosbestic point). Chlorine salt prediction model was established based on partial least squares method and used for predicting the concentration of the chlorine ion. The impact on near infrared spectrum of the cation ionic radius, the number of ionic charge, the complex effect of ionic in water has also discussed in this article and the reason of every factor are analysed. Experimental results show that the temperature and concentration will affect the near-infrared spectrum of the solution, It is found that the effect of temperature plays the dominant role at low concentrations of chlorine salt; rather, the ionic dominates at high concentration. Chloride complexes are formed in aqueous solution, It has an effect on hydrogen bond of water combining with the cations in chlorine salt solution, Comparing different chloride solutions at the same concentration, the destruction effects of chloride complexes and catnions on the hydrogen bond of water increases in the sequences: CaCl2 >NaCl>KC. The modeling result shows that the determination coefficients (R2) = 99.97%, the root mean square error of cross validation (RM- SECV) = 4.51, and the residual prediction deviation (RPD) = 62.7, it meets the daily requirements of biochemical detection accuracy.

  11. 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.

  12. 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.

  13. 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...

  14. 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?].

  15. 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.

  16. Fabrication of CPA Salt Pill with Circulating Solution Method

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  17. 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.

  18. Bioprecipitation of uranium from alkaline waste solutions using recombinant Deinococcus radiodurans.

    PubMed

    Kulkarni, Sayali; Ballal, Anand; Apte, Shree Kumar

    2013-11-15

    Bioremediation of uranium (U) from alkaline waste solutions remains inadequately explored. We engineered the phoK gene (encoding a novel alkaline phosphatase, PhoK) from Sphingomonas sp. for overexpression in the radioresistant bacterium Deinococcus radiodurans. The recombinant strain thus obtained (Deino-PhoK) exhibited remarkably high alkaline phosphatase activity as evidenced by zymographic and enzyme activity assays. Deino-PhoK cells could efficiently precipitate uranium over a wide range of input U concentrations. At low uranyl concentrations (1 mM), the strain precipitated >90% of uranium within 2h while a high loading capacity of around 10.7 g U/g of dry weight of cells was achieved at 10 mM U concentration. Uranium bioprecipitation by Deino-PhoK cells was not affected in the presence of Cs and Sr, commonly present in intermediate and low level liquid radioactive waste, or after exposure to very high doses of ionizing radiation. Transmission electron micrographs revealed the extracellular nature of bioprecipitated U, while X-ray diffraction and fluorescence analysis identified the precipitated uranyl phosphate species as chernikovite. When immobilized into calcium alginate beads, Deino-PhoK cells efficiently removed uranium, which remained trapped in beads, thus accomplishing physical separation of precipitated uranyl phosphate from solutions. The data demonstrate superior ability of Deino-PhoK, over earlier reported strains, in removal of uranium from alkaline solutions and its potential use in bioremediation of nuclear and other waste.

  19. Water dynamics in divalent and monovalent concentrated salt solutions.

    PubMed

    Giammanco, Chiara H; Wong, Daryl B; Fayer, Michael D

    2012-11-26

    Water hydrogen bond dynamics in concentrated salt solutions are studied using polarization-selective IR pump-probe spectroscopy and 2D IR vibrational echo spectroscopy performed on the OD hydroxyl stretching mode of dilute HOD in H(2)O/salt solutions. The OD stretch is studied to eliminate vibrational excitation transfer, which interferes with the dynamical measurements. Though previous research suggested that only the anion affected dynamics in solution, here it is shown that the cation plays a role as well. From FT-IR spectra of the OD stretch, it is seen that replacing either ion of the salt pair causes a shift in absorption frequency relative to that of the OD stretch absorption in bulk pure water. This shift becomes pronounced with larger, more polarizable anions or smaller, high charge-density cations. The vibrational lifetime of the OD hydroxyl stretch in these solutions is a local property and is primarily dependent on the nature of the anion and whether the OD is hydrogen bonded to the anion or to the oxygen of another water molecule. However, the cation still has a small effect. Time dependent anisotropy measurements show that reorientation dynamics in these concentrated solutions is a highly concerted process. While the lifetime, a local probe, displays an ion-associated and a bulk-like component in concentrated solutions, the orientational relaxation does not have two subensemble dynamics, as demonstrated by the lack of a wavelength dependence. The orientational relaxation of the single ensemble is dependent on the identity of both the cation and anion. The 2D IR vibrational echo experiments measure spectral diffusion that is caused by structural evolution of the system. The vibrational echo measurements yield the frequency-frequency correlation function (FFCF). The results also show that the structural dynamics are dependent on the cation as well as the anion. PMID:23113682

  20. 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

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. Simulation of hydrogen sulphide absorption in alkaline solution using a packed column.

    PubMed

    Azizi, Mohamed; Biard, Pierre-François; Couvert, Annabelle; Ben Amor, Mohamed

    2014-01-01

    In this work, a simulation tool was developed for hydrogen sulphide (H₂S) removal in an alkaline solution in packed columns working at countercurrent. Modelling takes into account the mass-transfer enhancement due to the reversible reactions between H₂S and the alkaline species (CO(²⁻)(3), HCO⁻(3), and HO⁻) in the liquid film. Many parameters can be controlled by the user such as the gas and liquid inlet H₂S concentrations, the gas and liquid flow rates, the scrubbing liquid pH, the desired H₂S removal efficiency, the temperature, the alkalinity, etc. Since the influence of the hydrodynamic and mass-transfer performances in a packed column is well known, the numerical resolutions performed were dedicated to the study of the influence of the chemical conditions (through the pH and the alkalinity), the temperature and the liquid-to-gas mass flow rate ratio (L/G). A packed column of 3 m equipped with a given random packing material working at countercurrent and steady state has been modelled. The results show that the H₂S removal efficiency increases with the L/G, the pH, the alkalinity and more surprisingly with the temperature. Alkalinity has a very significant effect on the removal efficiency through the mass-transfer enhancement and buffering effect, which limits pH decreasing due to H₂S absorption. This numerical resolution provides a tool for designers and researchers involved in H₂S treatment to understand deeper the process and optimize their processes.

  6. Anodically Electrodeposited Iridium Oxide Films (AEIROF) from Alkaline Solutions for Electrochromic Display Devices

    NASA Astrophysics Data System (ADS)

    Yamanaka, Kazusuke

    1989-04-01

    Anodically electrodeposited iridium oxide films from alkaline solutions were investigated for application to electrochromic devices. Micro-crystalline (diameter: 15Å) films obtained by the electrolysis of aqueous alkaline solutions containing iridium chloride, oxalic acid and potassium carbonate showed good electrochromic reaction reversibility. The coloration efficiency of the films was about one third that of typical evaporated tungsten oxide films, and the response rate measured by the amount of injected charge was about double. The cycle lives of the cells, composed of electrodeposited films, 1M H3PO4-NaOH (pH{=}3˜ 5), and an activated carbon cloth, were more than 8× 106 with a 0.6 V, 1 Hz continuous square wave.

  7. 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.

  8. Redox reactions of neptunium and plutonium in alkaline aqueous solutions upon gamma radiolysis

    NASA Astrophysics Data System (ADS)

    Pikaev, A. K.; Gogolev, A. V.; Shilov, V. P.

    1999-10-01

    The paper is a brief review of data obtained by the authors from the study on redox reactions of neptunium and plutonium ions upon γ-radiolysis of their aerated alkaline aqueous solutions. It includes the information on radiolytic reduction of Np(V), Np(VI), and Pu(VI) ions under various experimental conditions. It was found that the values of Np(VI) and Pu(VI) reduction yields do not depend on alkali concentration. The values considerably increase in the presence of some organic compounds (EDTA and formate were investigated). The formation of the Np(V) peroxo complex was observed in the γ-radiolysis of alkaline aqueous solutions of Np(VI) and Np(V) in the presence of nitrate. The mechanism of radiolytic redox reactions of the ions is discussed in some detail.

  9. 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.

  10. Occurrence of salt, pH, and temperature-tolerant, phosphate-solubilizing bacteria in alkaline soils

    PubMed

    Johri; Surange; Nautiyal

    1999-08-01

    An ecological survey was conducted to characterize 4800 bacterial strains isolated from the root-free soil, rhizosphere, and rhizoplane of Prosopis juliflora growing in alkaline soils. Of the 4800 bacteria, 857 strains were able to solubilize phosphate on plates. The incidence of phosphate-solubilizing bacteria (PSB) in the rhizoplane was highest, followed by rhizosphere and root-free soil. Eighteen bacterial strains out of 857 PSB were able to produce halo at 30 degrees C in a plate assay in the presence of 5% salt (NaCl) and solubilize tricalcium phosphate in National Botanical Research Institute's phosphate growth medium (NBRIP) broth, in the presence of various salts, pHs, and temperatures. Among the various bacteria tested, NBRI4 and NBRI7 did not produced halo in a plate assay at 30 degrees C in the absence of salt. Contrary to indirect measurement of phosphate solubilization by plate assay, the direct measurement of phosphate solubilization in NBRIP broth assay always resulted in reliable results. The phosphate solubilization ability of NBRI4 was higher than in the control in the presence of salts (NaCl, CaCl2, and KCl) at 30 degrees C. Phosphate solubilization further increased in the presence of salts at 37 degrees C as compared with 30 degrees C. At 37 degrees C, CaCl2 reduced phosphate solubilization ability of NBRI4 compared with the control. The results indicated the role of calcium salt in the phosphate solubilization ability of NBRI4.http://link.springer-ny. com/link/service/journals/00284/bibs/39n2p89.html PMID:10398833

  11. Study on Mixing Field of Salt Tolerant Polymer Solution

    NASA Astrophysics Data System (ADS)

    Zhang, L. H.; Zhang, M. G.; Li, X. G.; Zhang, D.; Jiang, B.

    The salt tolerant polymer (PAM) solution is a kind of viscoelastic fluid. The polymer. whose molecular weight is more than 2.5x107g/mol, is apt to form ultra-molecular structures in solution with pretty high viscoelasticity. These characteristics considerably affect the flow patterns and the mixing process. It is far more difficult to mix viscoelastic fluid homogeneously than Newtonian fluid. Because the molecular diffusion rate of viscoelastic fluid in mixing process is very low, improving the circulating performance of the agitator is the main path to increase the mixing velocity of the viscoelastic fluid. In this study, structure and operation parameters of new type agitator—double helical ribbon screw agitator designed for the salt tolerant polymer are optimized via laboratory experiment. The experiment results show that, compared with the screw propeller, the new type agitator improves circulation of fluid field effectively and increases the homogenized rate. It reduces the mixing time from 4h to 2h. And the viscosity of the polymer solution increases by 10%. However, the energy consumption does not increase.

  12. 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)

  13. 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.

  14. 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.

  15. Alkaline unfolding and salt-induced folding of yeast alcohol dehydrogenase under high pH conditions.

    PubMed

    Le, W P; Yan, S X; Li, S; Zhong, H N; Zhou, H M

    1996-06-01

    The conformational changes of yeast alcohol dehydrogenase during unfolding at alkaline pH have been followed by fluorescence emission and circular dichroism spectra. A result of comparison of inactivation and conformational changes shows that much lower values of alkaline pH are required to bring about inactivation than significant conformational change of the enzyme molecule. At pH 9.5, although the enzyme has been completely inactivated, no marked conformational changes can be observed. Even at pH 12, the apparently fully unfolded enzyme retains some ordered secondary structure. After removal of Zn2+ from the enzyme molecule, the conformational stability decreased. At pH 12 by adding the salt, the relatively unfolded state of denatured enzyme changes into a compact conformational state by hydrophobic collapsing. Folded states induced by salt bound ANS strongly, indicating the existence of increased hydrophobic surface. More extensive studies showed that although apo-YADH and holo-YADH exhibited similar behavior, the folding cooperative ability of apo-enzyme was lower than that of holo-enzyme. The above results suggest that the zinc ion plays an important role in helping the folding of YADH and in stabilizing its native conformation.

  16. Inhibitive effects of palm kernel oil on carbon steel corrosion by alkaline solution

    NASA Astrophysics Data System (ADS)

    Zulkafli, M. Y.; Othman, N. K.; Lazim, A. M.; Jalar, A.

    2013-11-01

    The behavior of carbon steel SAE 1045 in 1 M NaOH solution containing different concentrations of palm kernel oil (PKO) has been studied by weight loss and polarization measurement. Results showed that the corrosion of carbon steel in NaOH solution was considerably reduced in presence of such inhibitors. The inhibition efficiency increases when concentration of inhibitor increase. Maximum inhibition efficiency (≈ 96.67%) is obtained at PKO concentration 8 v/v %. This result revealed that palm kernel oil can act as a corrosion inhibitor in an alkaline medium. Corrosion rates of carbon steel decrease as the concentration of inhibitor is increased.

  17. Optical Sensor for Characterizing the Phase Transition in Salted Solutions

    PubMed Central

    Claverie, Rémy; Fontana, Marc D.; Duričković, Ivana; Bourson, Patrice; Marchetti, Mario; Chassot, Jean-Marie

    2010-01-01

    We propose a new optical sensor to characterize the solid-liquid phase transition in salted solutions. The probe mainly consists of a Raman spectrometer that extracts the vibrational properties from the light scattered by the salty medium. The spectrum of the O – H stretching band was shown to be strongly affected by the introduction of NaCl and the temperature change as well. A parameter SD defined as the ratio of the integrated intensities of two parts of this band allows to study the temperature and concentration dependences of the phase transition. Then, an easy and efficient signal processing and the exploitation of a modified Boltzmann equation give information on the phase transition. Validations were done on solutions with varying concentration of NaCl. PMID:22319327

  18. 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

  19. Adsorption of tungsten onto zeolite fly ash produced by hydrothermally treating fly ash in alkaline solution.

    PubMed

    Ogata, Fumihiko; Iwata, Yuka; Kawasaki, Naohito

    2014-01-01

    Fly ash (FA) was hydrothermally treated in an alkaline solution to produce zeolite fly ash (Z-FA). The properties of the FA and Z-FA were investigated. The amounts of tungsten (W) adsorbed onto the FA and Z-FA surfaces were evaluated. Z-FA was produced by hydrothermally treating FA in an alkaline solution. The specific surface area and pore volume of the Z-FA were greater than those of the FA. More W was adsorbed onto the Z-FA surface than onto the FA surface. The adsorption isotherms for W were fitted using both the Freundlich and Langmuir equations. The equilibrium concentrations of W adsorbed onto the FA and Z-FA surfaces were subsequently reached within 20 h. The pseudo-second-order model more accurately described the data than did the pseudo-first-order model. Sodium hydroxide solutions (1-50 mmol/L) were used to easily recover W from Z-FA, indicating that Z-FA was useful for recovering W from aqueous solutions.

  20. 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.

  1. Kinetics of CO2 Absorption into Aqueous Basic Amino Acid Salt: Potassium Salt of Lysine Solution.

    PubMed

    Shen, Shufeng; Yang, Ya-nan; Bian, Yangyang; Zhao, Yue

    2016-02-16

    Aqueous amino acid salts are considered as an attractive alternative to alkanolamine solvents (e.g., MEA) for carbon dioxide (CO2) absorption. The kinetics of CO2 into unloaded aqueous solutions of potassium lysinate (LysK) was studied using a wetted wall column at concentrations ranging from 0.25 to 2.0 M and temperatures from 298 to 333 K. Physicochemical properties of aqueous LysK solutions such as density, viscosity, and physical solubility of CO2 were measured to evaluate the reaction rate constants. The reaction pathway is described using zwitterion mechanism taking into account the effect of ionic strength on the reaction rate. Under the fast pseudo-first-order regime, the reaction rate parameters were obtained and correlated in a power-law reaction rate expression. LysK shows higher chemical reactivity toward CO2 than the industrial standard MEA and most of amino acid salts. Its reaction rate constants increase considerably with concentration and temperature. The reaction order is found to be an average value of 1.58 with respect to LysK. The forward second-order kinetic rate constant, k2 0 , are obtained as 31615 and 84822 m3 kmol−1 s−1 at 298 and 313 K, respectively with activation energy of 51.0 kJ mol−1. The contribution of water to the zwitterion deprotonation seems to be more significant than that of LysK for the above-mentioned kinetic conditions PMID:26751093

  2. Cyclohexanone solvent extraction of /sup 99/TcO/sub 4/ from alkaline nuclear waste solutions

    SciTech Connect

    Schulz, W.W.

    1980-01-01

    Although the /sup 99/Tc cyclohexanone solvent extraction process is still in the bench-scale development stage, the process appears well suited for engineering-scale removal of /sup 99/Tc from alkaline Hanford waste solutions. The most pressing process development need is to resolve the phase disengaging problems encountered during water stripping operations. Stripping tests in pulse columns and/or centrifugal contactors are particularly needed to determine the magnitude of the phase disengaging problem in engineering-scale equipment and to find suitable remedies. 5 figures, 7 tables.

  3. 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

  4. Cloning and overexpression of alkaline phosphatase PhoK from Sphingomonas sp. strain BSAR-1 for bioprecipitation of uranium from alkaline solutions.

    PubMed

    Nilgiriwala, Kayzad S; Alahari, Anuradha; Rao, Amara Sambasiva; Apte, Shree Kumar

    2008-09-01

    Cells of Sphingomonas sp. strain BSAR-1 constitutively expressed an alkaline phosphatase, which was also secreted in the extracellular medium. A null mutant lacking this alkaline phosphatase activity was isolated by Tn5 random mutagenesis. The corresponding gene, designated phoK, was cloned and overexpressed in Escherichia coli strain BL21(DE3). The resultant E. coli strain EK4 overexpressed cellular activity 55 times higher and secreted extracellular PhoK activity 13 times higher than did BSAR-1. The recombinant strain very rapidly precipitated >90% of input uranium in less than 2 h from alkaline solutions (pH, 9 +/- 0.2) containing 0.5 to 5 mM of uranyl carbonate, compared to BSAR-1, which precipitated uranium in >7 h. In both strains BSAR-1 and EK4, precipitated uranium remained cell bound. The EK4 cells exhibited a much higher loading capacity of 3.8 g U/g dry weight in <2 h compared to only 1.5 g U/g dry weight in >7 h in BSAR-1. The data demonstrate the potential utility of genetically engineering PhoK for the bioprecipitation of uranium from alkaline solutions.

  5. 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...

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. 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

  12. 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

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

    NASA Astrophysics Data System (ADS)

    Muñoz-Santiburcio, Daniel; Marx, Dominik

    2016-08-01

    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.

  14. Reaction of montmorillonite in alkaline solution at 60 C, 90 C, 120 C and 180 C

    SciTech Connect

    Amaya, Takayuki; Shimojo, Mikio; Fujihara, Hiroshi; Yokoyama, Katsuhiko

    1999-07-01

    The reaction of montmorillonite was investigated. Three kinds of bentonites with different montmorillonite composition were mixed with 0.3M NaOH solution and 0.3M Ca(OH){sub 2} slurry. They were immersed at 60 C, 90 C, 120 C, and 180 C for one month, three months and six months. The concentrations of the soluble ions were measured and the bentonites were analyzed quantitatively after the immersion. 50% of the montmorillonite was reacted within two weeks at greater than 90 C. Montmorillonite reacts less when mixed with Si-minerals. It extensively reacted in 0.3M Ca(OH){sub 2} slurry. These results suggest that the reaction mechanism of the montmorillonite in alkaline solution was dominantly Si dissolution, and would decrease by controlling the concentration of Si ion. The cement/bentonite system under Si saturated conditions is discussed.

  15. Recycling of Ni(II)-citrate complexes using precipitation in alkaline solutions.

    PubMed

    Gyliene, O; Aikaite, J; Nivinskiene, O

    2004-06-18

    When the excess of Ni(II) ions as compared to citrate concentration is used both Ni(II) ions and citrate can be precipitated in alkaline solutions. The ratio between Ni(II) and citrate in the precipitate and completeness of citrate precipitation depends on the ratio between the Ni(II) and citrate concentrations in the initial solution and its pH. The data of chemical analysis, potentiometric titration, FT-IR as well as visible spectrophotometric investigations suggest that Ni(II) in the insoluble compound is bound with three -COO- groups and -OH group of the citrate. The insoluble compound also contains SO4(2-) and hydroxides. The treatment of this precipitate with H2SO4 enables to recover a soluble Ni(II)-citrate complex, which can be reused in practice, and to remove the excess of Ni(II) in the form of insoluble Ni(OH)2. PMID:15177751

  16. 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.

  17. 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.

  18. 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.

  19. Geotechnical factors and guidelines for storage of compressed air in solution-mined salt cavities

    SciTech Connect

    Allen, R.D.; Doherty, T.J.; Thoms, R.L.

    1982-05-01

    The state of knowledge about utilization of solution-mined salt cavities for CAES including laboratory experiments, numerical modeling, field characterization, solution mining experience, and operating parameters is outlined in this report. Topics evaluated in recent studies include: cavern geometry and size; long-term creep and creep rupture of rock salt; effects of pressure and temperature loading rates; low frequency fatigue; progressive deterioration of salt fabric with possible air penetration; cavern monitoring methods; and salt properties at nonambient conditions. Currently, the only CAES operational facility in the world is located at Huntorf, West Germany. This CAES facility uses two solution-mined salt caverns for air storage and has been operating successfully for more than 2 years. Stability criteria for solution-mined salt caverns from the Huntorf facility and recent field and laboratory studies are included in this report.

  20. Methylene blue adsorption from aqueous solution by activated carbon: effect of acidic and alkaline solution treatments.

    PubMed

    Ijagbemi, Christianah O; Chun, Ji I; Han, Da H; Cho, Hye Y; O, Se J; Kim, Dong S

    2010-01-01

    The removal of Methylene Blue (MB) from aqueous solution using activated carbon (AC) has been investigated. Adsorption experiments were conducted and the maximum adsorption capacity was determined. The effect of experimental parameters such as pH, dye concentration and temperature were studied on the adsorption process. Equilibrium data were mathematically modeled using the Langmuir and Freundlich adsorption models to describe the equilibrium isotherms at different dye concentrations and temperature. Parameters of best-fit model were calculated and discussed. To understand the mechanism of adsorption, kinetic models were employed to follow the adsorption processes; the pseudo-first-order best described the adsorption of MB onto AC. It was found that pH plays a major role in the adsorption process; adsorption capacity was influenced by the physical and surface chemical properties of carbon and the pH of the solution. 99.0% MB removal was achieved at equilibrium.

  1. Distribution coefficients of vitamin B2 in hydrophilic organic solvent-aqueous salt solution systems

    NASA Astrophysics Data System (ADS)

    Korenman, Ya. I.; Mokshina, N. Ya.; Zykov, A. V.

    2010-03-01

    Distribution coefficients of vitamin B2 in hydrophilic solvent ( n-butanol, isopropanol, acetone, ethyl acetate, and their mixtures)-aqueous salt (potassium chloride, sodium fluoride, and ammonium sulfate salting-out agents) solution systems were calculated. The synergic effect and optimum proportions of components in the solvent mixture for efficient extraction of vitamin B2 from aqueous solutions were established.

  2. 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.

  3. 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

  4. Thermal Characteristics of Chemical Refrigerating Apparatus using Silica-Gel/ Inorganic-Salt-Solution Pair

    NASA Astrophysics Data System (ADS)

    Yanadori, Michio; Watabe, Yoshihito

    This report deals with chemical refrigerating apparatus using silica-gel / inorganic-salt-solution pair. Experiments are conducted by changing concentration of inorganic-salt solution and adsorbent / refrigerant pair. The following results are obtained. (1) The temperature of refrigerant in evaporator is lowered as decrease of inorganic-salt-solution concentration. (2) The available salt-concentration range as refrigerant are gained by supercooling in restricted temperature range lower than solidification temperature of solution. (3)Difference of minimum temperature among cooled refrigerants are little in low concentration region. (4)In concentration lower than about10wt%, refrigerants supercool and solidify suddenly. Accordingly these salt-solutions are not available in these region as refrigerants.

  5. Complexation of Al(III) with gluconate in alkaline to hyperalkaline solutions: formation, stability and structure.

    PubMed

    Pallagi, Attila; Tasi, Ágost Gyula; Peintler, Gábor; Forgo, Péter; Pálinkó, István; Sipos, Pál

    2013-10-01

    Contrary to suggestions in the literature, it has been proven that Al(III) forms a 1 : 1 complex with gluconate (hereafter Gluc(-)) in strongly alkaline (pH > 12) aqueous solutions. The complex formation was proven via(27)Al and (1)H NMR, freezing-point depression, polarimetric measurements as well as potentiometric and conductometric titrations. This complexation is a pH independent process, i.e., a condensation reaction takes place. The stability constant of the complex formed was derived from (1)H NMR and polarimetric measurements, and was found to be log K = 2.4 ± 0.4. In the complex formed, Al(III) has a tetrahedral geometry, and the Al(OH)4(-) is most probably statistically distributed between the alcoholate groups of the Gluc(-). PMID:23897548

  6. Salting-out effects in aqueous ionic liquid solutions: cloud-point temperature shifts.

    PubMed

    Trindade, Joana R; Visak, Zoran P; Blesic, Marijana; Marrucho, Isabel M; Coutinho, João A P; Lopes, José N Canongia; Rebelo, Luis P N

    2007-05-10

    The effects of the addition of three inorganic salts, namely, NaCl, Na(2)SO(4), and Na(3)PO(4), on the liquid-liquid (L-L) phase diagram of aqueous solutions containing the model ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF(4)], were investigated. All three inorganic salts trigger salting-out effects, leading to significant upward shifts of the L-L demixing temperatures of the systems. The magnitude of the shifts depends on both the water-structuring nature of the salt and its concentration; that is, the effects are correlated with the ionic strength of the solution and the Gibbs free energy of hydration of the inorganic salt. The pH effect and the occurrence of salt precipitation in concentrated solutions are also discussed.

  7. 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.

  8. A novel method to suppress the dispersal of Japanese cedar pollen by inducing morphologic changes with weak alkaline solutions.

    PubMed

    Ishii, K; Hamamoto, H; Sekimizu, K

    2007-10-01

    Inhalation of airborne pollen causes irritative symptoms in humans, known as pollinosis. The changing global climate and increased pollution contribute to enhance the release of pollen, thereby increasing the number of people suffering from allergies. We examined the effect of spraying weak alkaline solutions onto cedar trees, the main allergenic culprit in Japan, on pollen release. Weak alkaline solutions were sprayed onto Japanese cedar blossoms to disrupt the external walls of the pollen, and to induce swelling of the cytosolic components containing the nucleus. This morphologic change of the pollen grains depended on the pH of the suspending solution, with a threshold pH of near 7.5. As the breakdown of the external walls and swelling of the cytosolic components are inhibited by high osmolarity, the influx of water triggered the morphologic changes. Weak alkaline solutions sprayed onto cedar blossoms decreased the amount of pollen released from the anthers in a pH dependent manner. The addition of detergent to the sodium bicarbonate solution facilitated this effect on cedar pollen release. We suggest that spraying cedar and cypress forests with a weak alkaline solution might prevent the scattering of pollen that causes allergies in humans.

  9. 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

  10. Extraction of cesium from an alkaline leaching solution of spent catalysts using an ion-exchange column

    SciTech Connect

    Dumont, N.; Favre-Reguillon, A.; Dunjic, B.; Lemaire, M.

    1996-04-01

    The selective extraction of cesium from an alkaline leaching solution of spent catalysts using phenolic resins was studied. The resins were synthesized by alkaline polycondensation of formaldehyde by phenol, resorcinol, catechol, and phloroglucinol. Their ionoselectivities for five alkali metals were evaluated with a solid-liquid extraction, and their ion-exchange capacities were compared. The resin with the best selectivity for cesium was tested with a real solution at different pH values. An on-column extraction is proposed to obtain cesium with high purity.

  11. 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

  12. 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

  13. 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}.

  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. 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.

  16. 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

  17. 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.

  18. 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.

  19. Sulfur species leached from pyrite during oxidative desulfurization of coal in alkaline solutions

    SciTech Connect

    Stephenson, M.D.; Wheelock, T.D.; Markuszewski, R.

    1983-01-01

    The results indicate that thiosulfate, sulfite, and sulfate are the principal soluble sulfur species produced when coal-derived pyrite leached with a hot alkaline solution containing dissolved oxygen. The distribution of soluble sulfur species in the leachate was found to depend on leaching temperature, oxygen partial pressure, leachant composition, and time of contact. At lower temperatures and oxygen partial pressures and with a short time of contact between the leaching solution and pyrite, the leachate sulfur species were dominated by thiosulfate. However, the leachate also contained significant amounts of sulfite and sulfate. When the temperature, oxygen partial pressure, or time of contact were increased, the proportions of thiosulfate and sulfite decreased and the proportion of sulfate increased. It was observed also that reacted pyrite particles catalyzed the oxidation of thiosulfate to sulfite and sulfate. Consequently when pyrite was oxidized in a stirred reactor for 1 h at elevated temperature and oxygen partial pressure, most of the dissolved sulfur appeared as sulfate and very little as thiosulfate or sulfite. 10 references, 4 figures, 1 table.

  20. Modeling experimental results of diffusion of alkaline solutions through a compacted bentonite barrier

    SciTech Connect

    Fernandez, Raul; Cuevas, Jaime; Maeder, Urs K.

    2010-08-15

    The interaction between concrete/cement and swelling clay (bentonite) has been modeled in the context of engineered barrier systems for deep geological disposal of high-level radioactive waste. The geochemical transformations observed in laboratory diffusion experiments at 60 and 90 {sup o}C between bentonite and different high-pH solutions (K-Na-OH and Ca(OH){sub 2}-saturated) were reconciled with the reactive transport code CrunchFlow. For K-Na-OH solutions (pH = 13.5 at 25 {sup o}C) partial dissolution of montmorillonite and precipitation of Mg-silicates (talc-like), hydrotalcite and brucite at the interface are predicted at 60 {sup o}C, while at 90 {sup o}C the alteration is wider. Alkaline cations diffused beyond the mineralogical alteration zone by means of exchange with Mg{sup 2+} in the interlayer region of montmorillonite. Very slow reactivity and minor alteration of the clay are predicted in the Ca(OH){sub 2}-bentonite system. The model is a reasonable description of the experiments but also demonstrates the difficulties in modeling processes operating at a small scale under a diffusive regime.

  1. Inverse temperature dependence of electrical conductivity of solutions of lithium salts in aprotic media

    SciTech Connect

    Plakhotnik, V.N.; Tovmash, N.F.; Kovtum, Yu.V.

    1987-08-01

    Solutions of lithium salts in aprotic dipolar solvents are studied in this paper for their use as electrolytes in lithium batteries. The temperature dependence and isotherms of the electric conductivity of molten salts of lithium fluorides with arsenic and boron are assessed against a range of solvents including tetrahydrofuran, propylene carbonate, 1,3-dioxolane, gamma-butyrolactone, water, hydrogen, and dimethoxyethane. Ionization potentials are given and molar ratios for the salts and solvents are tabulated.

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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)

  9. 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.

  10. 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%.

  11. 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.

  12. 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.

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

    PubMed

    Bajnóczi, Eva G; Czeglédi, Eszter; Kuzmann, Ernő; Homonnay, Zoltán; Bálint, Szabolcs; Dombi, György; Forgo, Péter; Berkesi, Ottó; Pálinkó, István; Peintler, Gábor; Sipos, Pál; Persson, Ingmar

    2014-12-28

    The identity of the predominating tin(ii)-hydroxide complex formed in hyper-alkaline aqueous solutions (0.2 ≤CNaOH≤ 12 mol dm(-3)) is determined by potentiometric titrations, Raman, Mössbauer and XANES spectroscopy, supplemented by quantum chemical calculations. Thermodynamic studies using a H2/Pt electrode up to free hydroxide concentrations of 1 mol dm(-3) showed the presence of a single monomeric complex with a tin(II) : hydroxide ratio of 1 : 3. This observation together with Raman and Mössbauer spectroscopic measurements supplemented by quantum mechanical calculations proved that the predominating complex is [Sn(OH)3](-), and that the presence of the other possible complex, [SnO(OH)](-), could not be proven with either experiments or simulations. The structure of the trihydroxidostannate(II) complex, [Sn(OH)3](-), was determined by EXAFS and was found to be independent of the applied hydroxide and tin(II) concentrations. The mean Sn-O bond distance is short, 2.078 Å, and in very good agreement with the only structure reported in the solid state. It is also shown that at pH values above 13 the speciation of the predominant trihydroxidostannate(II) complex is not affected by the presence of high concentrations of chloride ions.

  14. Effect of Freeze Concentration of Various Salt Solutions on the Denaturation of Carp Myofibrils

    NASA Astrophysics Data System (ADS)

    Takahashi, Katsuaki; Inoue, Norio; Shinano, Haruo

    The apparent rate constants of freeze inactivation (KF) at different storage temperatures for various salts were calculated. Comparisons were then made among salts with relation to storage temperature and ionic strength of unfrozen salt solutions. For three kinds of sulfates with high eutectic points,hardly any change occured in relation to the storage temperature and ionic strength. The reason was thought to be the weaker action of sulfates to protein denaturation. The KF values of six kinds of salts (namely NH4Cl, NaNO3, Mg(NO3)3, BaCl2, CaCl2 and MgCl2 ) were highest in the temperature range of - 6~-14 °C. The extent of denaturation in the KF value differed for each salt,although,no relationship was found between maximum KF value and eutectic point. A possible explanation for the above results relates to the amount and ionic strength of unfrozen salt solution. The log KF increased with an increase in ionic strength,and reached a maximum at about 0.9 due to the effect of salt concentration. However,above an ionic strength of 0.9, the log KF decreased with an increase in ionic strength due to the decrease of unfrozen salt solution.

  15. Apatite formation on alkaline-treated dense TiO2 coatings deposited using the solution precursor plasma spray process.

    PubMed

    Chen, Dianying; Jordan, Eric H; Gell, Maurice; Wei, Mei

    2008-05-01

    A dense titania (TiO2) coating was deposited from an ethanol-based solution containing titanium isopropoxide using the solution precursor plasma spray (SPPS) process. XRD and Raman spectrum analyses confirmed that the coating is exclusively composed of rutile TiO2. SEM micrographs show the as-sprayed coating is dense with a uniform thickness and there are no coarse splat boundaries. The as-sprayed coating was chemically treated in 5M NaOH solution at 80 degrees C for 48 h. The bioactivity of as-sprayed and alkaline-treated coatings was investigated by immersing the coatings in simulated body fluid (SBF) for 14-28 days, respectively. After 28 days immersion, there is a complete layer of carbonate-containing apatite formed on the alkaline-treated TiO2 coating surface, but none formed on the as-sprayed coating.

  16. 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

  17. 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.

  18. 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.

  19. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

    DOE PAGESBeta

    Liu, Shizhong; White, Michael G.; Liu, Ping

    2016-06-30

    Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e– or 4e– transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H2O)-mediated mechanism including 4e– transfers is identified, where the reduction stepsmore » via *H2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH–(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O2 binding is strong enough to enable the ORR via the 4e– transfer mechanism.« less

  20. First-principles molecular dynamics modeling of the molten fluoride salt with Cr solute

    NASA Astrophysics Data System (ADS)

    Nam, H. O.; Bengtson, A.; Vörtler, K.; Saha, S.; Sakidja, R.; Morgan, D.

    2014-06-01

    Fluoride salts and their interactions with metals are of wide interest for the nuclear community. In this work, first-principles molecular dynamics (FPMD) was employed to study both pure molten fluoride salt and fluoride salt with dissolved solute Cr ions (a common corrosion product) at high temperature (823-1423 K). Two types of molten fluoride salts, namely flibe (LiF-BeF2) and flinak (LiF-NaF-KF), with the Cr0, Cr2+ and Cr3+ ions were chosen as a target system for the FPMD modeling. The prediction of thermo-kinetic properties of pure fluoride salt, such as the equilibrium volume, density, bulk modulus, coefficient of thermal expansion, and self-diffusion coefficient, provide useful extensions of existing data and verify the accuracy of the FPMD simulation in modeling of fluoride salts. The FPMD modeling of solute Cr in fluoride salt shows the effect of Cr valence on diffusivity and local structure in the salt.

  1. Zinc(II) oxide stability in alkaline sodium phosphate solutions at elevated temperatures

    SciTech Connect

    Ziemniak, S.E.; Opalka, E.P.

    1993-04-01

    Zinc oxide (ZnO) is shown to transform into either of two phosphate-containing compounds in relatively dilute alkaline sodium phosphate solutions at elevated temperatures via ZnO(s) + Na{sup +} + H{sub 2}PO{sub 4}{sup {minus}} {r_reversible} NaZnPO{sub 4}(s) + H{sub 2}O or 2 ZnO(s) + H{sub 3}PO{sub 4}(aq) {r_reversible} Zn{sub 2}(OH)PO{sub 4}(s) + H{sub 2}O. X-ray diffraction analyses indicate that NaZnPO{sub 4} possesses an orthorhombic unit cell having lattice parameters a = 8.710 {+-} 0.013, b = 15.175 {+-} 0.010, and c = 8.027 {+-} 0.004 {angstrom}. The thermodynamic equilibria for these reactions were defined in the system ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O for Na/P molar ratios between 2.1 and 3. Based on observed reaction threshold values for sodium phosphate concentration and temperature, the standard entropy (S{degrees}) and free energy of formation ({Delta}G{sub f}{degrees}) for NaZnPO{sub 4} were calculated to be 169.0 J/mol-K and {minus}1510.6 kJ/mol, respectively; similar values for Zn{sub 2}(OH)PO{sub 4} (tarbuttite) were 235.9 J/mol-K and {minus}1604.6 kJ/mol. Additions of sodium sulfite and sulfate did not alter the above reactions.

  2. Zinc(II) oxide stability in alkaline sodium phosphate solutions at elevated temperatures

    SciTech Connect

    Ziemniak, S.E.; Opalka, E.P. )

    1994-04-01

    Zinc oxide (ZnO) is shown to transform into either of two phosphate-containing compounds in relatively dilute alkaline sodium phosphate solutions at elevated temperatures via ZnO(s) + Na[sup +] + H[sub 2]PO[sub 4]- [l reversible] NaZnPO[sub 4](s) + H[sub 2]O or 2ZnO(s) + H[sub 3]PO[sub 4](aq) [l reversible] Zn[sub 2](OH)PO[sub 4](s) + H[sub 2]O. X-ray diffraction analyses indicate that NaZnPO[sub 4] possesses an orthorhombic unit cell having lattice parameters a = 8.710 [+-] 0.013, b = 15.175 [+-] 0.010, c = 8.027 [+-] 0.004 [angstrom]. The thermodynamic equilibria for these reactions were defined in the system ZnO-Na[sub 2]O-P[sub 2]O[sub 5]-H[sub 2]O for Na/P molar ratios between 2.1 and 3. On the basis of observed reaction threshold values for sodium phosphate concentration and temperature, the standard entropy (S[degrees]) and free energy of formation ([delta]G[sub f][degrees]) for NaZnPO[sub 4] were calculated to be 169.0 J/(mol K) and -1510.6 kJ/mol, respectively; similar values for Zn[sub 2](OH)PO[sub 4] (tarbuttite) were 235.9 J/(mol K) and -1604.6 kJ/mol. Additions of sodium sulfite and sulfate did not alter the above reactions. 26 refs., 5 figs., 7 tabs.

  3. [A Contrastive Study on Salt-alkaline Resistance and Removal Efficiency of Nitrogen and Phosphorus by Phragmites australis and Typha angustifolia in Coastal Estuary Area].

    PubMed

    Chen, You-yuan; Sun, Ping; Chen, Guang-lin; Wang, Ning-ning

    2015-04-01

    The salt and alkali contents were so high that the ecological landscape was depressed in water body of a coastal estuary area. Screening some plants which could not only tolerate saline-alkaline but also effectively remove nitrogen and phosphorus was therefore in urgent need. The tolerance range and removal rate of nitrogen and phosphorus by Phragmites australis and Typha angustifolia under salt and pH stress were investigated by hydroponic experiments. The results showed that Phragmites australis could tolerate at least 10 per thousand salinity and pH 8.5, while Typha angustifolia tolerated 7.5 per thousand salinity and pH 8.0. Combined with the change of the growth and physiological indexes (relative conductivity, proline, chlorophyll and root activity), the salt resistance of Phragmites australis was stronger than that of Typha angustifolia. Under salt stress, the removal rate of ammonia nitrogen of Phragmites australis was higher. The removal rates of nitrate nitrogen and phosphorus of Typha angustifolia were 2.5% and 7.3% higher than those of Phragmites australis in average, respectively, because of the high biomass of Typha angustifolias. The total nitrogen removal rate was equivalent. Under pH stress, the removal rate of ammonia nitrogen and total phosphorus of Phragmites australis was a little higher than that of Typha angustifolia. However, Typha angustifolia had a higher removal rate of total nitrogen, which was 8.2% higher than that of Phragmites australis. All the analysis showed that both Phragmites australis and Typha angustifolia could be used as alternative plants to grow and remove nitrogen and phosphorus in the high salt-alkaline water body in coastal estuary area.

  4. 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.

  5. Correlation of second virial coefficient with solubility for proteins in salt solutions.

    PubMed

    Mehta, Chirag M; White, Edward T; Litster, James D

    2012-01-01

    In this work, osmotic second virial coefficients (B(22)) were determined and correlated with the measured solubilities for the proteins, α-amylase, ovalbumin, and lysozyme. The B(22) values and solubilities were determined in similar solution conditions using two salts, sodium chloride and ammonium sulfate in an acidic pH range. An overall decrease in the solubility of the proteins (salting out) was observed at high concentrations of ammonium sulfate and sodium chloride solutions. However, for α-amylase, salting-in behavior was also observed in low concentration sodium chloride solutions. In ammonium sulfate solutions, the B(22) are small and close to zero below 2.4 M. As the ammonium sulfate concentrations were further increased, B(22) values decreased for all systems studied. The effect of sodium chloride on B(22) varies with concentration, solution pH, and the type of protein studied. Theoretical models show a reasonable fit to the experimental derived data of B(22) and solubility. B(22) is also directly proportional to the logarithm of the solubility values for individual proteins in salt solutions, so the log-linear empirical models developed in this work can also be used to rapidly predict solubility and B(22) values for given protein-salt systems.

  6. Effect of water structure on adsorption of thermosensitive polymer hydrogel in salt solutions

    SciTech Connect

    Nakano, Yoshio; Seida, Yoshimi

    1996-12-31

    Effects of temperature and additive salt on an adsorption property of thermosensitive polymer hydrogel were studied in terms of (1) phase transition temperature of the gel, (2) hydration structure of network of the gel in the various salt solutions, and (3) structure of water in the solutions. The adsorption properties of the gel were correlated fairly well with the phase transition temperature of the gel and the structure of water both on the network of the gel and in the bulk solution. 2 refs., 5 figs.

  7. 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.

  8. Lanthanide salts solutions: representation of osmotic coefficients within the binding mean spherical approximation.

    PubMed

    Ruas, Alexandre; Moisy, Philippe; Simonin, Jean-Pierre; Bernard, Olivier; Dufrêche, Jean-François; Turq, Pierre

    2005-03-24

    Osmotic coefficients of aqueous solutions of lanthanide salts are described using the binding mean spherical approximation (BIMSA) model based on the Wertheim formalism for association. The lanthanide(III) cation and the co-ion are allowed to form a 1-1 ion pair. Hydration is taken into account by introducing concentration-dependent cation size and solution permittivity. An expression for the osmotic coefficient, derived within the BIMSA, is used to fit data for a wide variety of lanthanide pure salt aqueous solutions at 25 degrees C. A total of 38 lanthanide salts have been treated, including perchlorates, nitrates, and chlorides. For most solutions, good fits could be obtained up to high ionic strengths. The relevance of the fitted parameters has been discussed, and a comparison with literature values has been made (especially the association constants) when available.

  9. 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.

  10. 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.

  11. Unusual catalytic effects of iron salts on phenol degradation by glow discharge plasma in aqueous solution.

    PubMed

    Wang, Lei; Jiang, Xuanzhen

    2009-01-30

    Catalytic effects of iron salts on phenol degradation induced by glow discharge plasma (GDP) were examined. It was found that ferric ions showed much better catalytic effect than that of ferrous ions. The reason was that GDP could produce hydroxyl radicals and hydrogen peroxide simultaneously; the hydroxyl radicals reacted with phenol to produce dihydroxycyclohexadienyl radicals which reduced the ferric ions to ferrous ions and the newly formed ferrous ions catalyzed the hydrogen peroxide to produce more hydroxyl radicals. Without iron salts, TOC of the solution gradually decreased with treatment time while COD of the solution increased due to the accumulation of the hydrogen peroxide. Without iron salts, catechol, hydroquinone, and hydroxylhydroquinone were major by-products. However, large amounts of catechol, hydroquinone and benzoquinone yielded in the presence of iron salts. The present study presents some new information related to Fenton's reaction. PMID:18501506

  12. 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

  13. 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.

  14. 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.

  15. Electrolyte salts for power sources

    DOEpatents

    Doddapaneni, Narayan; Ingersoll, David

    1995-01-01

    Electrolyte salts 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Kinetics of oxidation of odorous sulfur compounds in aqueous alkaline solution with H2O2.

    PubMed

    Feliers, C; Patria, L; Morvan, J; Laplanche, A

    2001-10-01

    Sulfur species oxidation is a crucial issue wastewater treatment. The production of sulfur compounds like H2S,CH3SH, C2H5SH, disulfides and dimethyle sulfide generates odorous nuisances for the neighborhood. The oxidation of these species by H2O2 in alkaline solution has been investigated. The results showed that thiols CH3SH and C2H5SH react with H202 only in their dissociated form RS- with rate constants respectively k = 8.81 +/- 0.48 M-1s-1 and 8.37 +/- 0.63 M-1.s-1. Mercaptans oxidation produces 100 % of dimethyldisulfide or diethyldisulfide. The oxidation of disulfides shows a difference of reactivity between H2O2 and HO2- towards sulfur species. Increasing the pH accelerates significantly the reactions in the case of CH3SSCH3. The oxidation rate can be described as: r = k[RSSR][H2O2][RSSR][H2O2] + k[RSSR][HO2-] [RSSR][HO2-] with k[RSSR][H2O2] = 1.2 x 10(-4) +/- 0.2 x 10(-4) M-1s-1 and k[RSSR][HO2-] = 3.4 x 10(-4) +/- 0.6 x 10(-4) M-1.s-1 for CH3SSCH3. Dimethyl sulfide presents a reactivity different from disulfides. The oxidation rate can also be described as: r = k[CH3SCH3][H2O21][CH3SCH3][H2O2] + k[CH3SCH3][HO-] [CH3SCH3][HO2-], however, oxidation rate decreases with pH increase. k[CH3SCH3][H2O2] = 12.8 x 10(-3) +/- 0.96 x 10(-3) M-1.s-1 and k[CH3SCH3][HO2-] = 4 x 10(-3) +/- 0.3 x 10(-3) M-1.s-1.

  1. Evaluation of home-made salt-sugar oral rehydration solution in a rural Nigerian population.

    PubMed

    Nwoye, L O; Uwagboe, P E; Madubuko, G U

    1988-02-01

    Standardized local measures for preparing oral rehydration solution (ORS) in Nigeria were re-evaluated under laboratory conditions. Our results confirm those of the standardization team in respect of granulated and cube sugar. However, our mean weight of one salt measure (2.8155 +/- 0.292 g) is about 20% greater than their value. Consequently, correct use of the measures in our study gave solutions of 211-297 mmol-1 total concentration and 60-80 mmol-1, Na+ as against their values of 173-251 mmol 1-1 and 45-70 mmol-1, respectively. This discrepancy is most likely due to differences in salt type. Analysis of home-made solutions prepared by 40 illiterate mothers showed that 60% of them made accurately composed solutions. All the rest made hypertonic solutions. Salt type, spoon size and levelling technique are all possible causes of their error. The tendency to err only on the side of greater rather than lower salt concentration may be culture based or simply due to natural maternal instinct. To combat this trend, health education programmes in Nigeria should emphasize the danger in feeding a hypernatremic solution to a dehydrated child.

  2. Effect of magnesium cation on the interfacial properties of aqueous salt solutions.

    PubMed

    Callahan, Karen M; Casillas-Ituarte, Nadia N; Xu, Man; Roeselová, Martina; Allen, Heather C; Tobias, Douglas J

    2010-08-19

    Sodium chloride solutions have been used extensively as a model of seawater in both theoretical and experimental studies of the chemistry of sea salt aerosol. Many groups have found that chloride anions are present at the air-solution interface. This observation has been important for the development of a mechanism for the heterogeneous production of molecular chlorine from chloride in sea salt aerosol. However, while sodium chloride is a major constituent of seawater, it is by no means the only salt present. Seawater contains one Mg(2+) for every eight Na(+). Mg(2+) is naturally occurring in ocean waters from mineral deposits in the Earth's crust and biological sources. Mg(2+) forms a hexahydrate structure, rather than contact ion pairs with chloride anion, and this impacts the ordering of water in solution. In this study, we use molecular dynamics simulations, ab initio calculations, and vibrational sum frequency generation (SFG) spectroscopy to explore the effect of the Mg(2+) cation and its tightly bound solvation shell on the surface propensity of chloride, ion-ion interactions, and water structure of the air-solution interface of concentrated chloride salt solutions. In addition, we provide molecular level details that may be relevant to the heterogeneous reactions of chloride in deliquesced sea salt aerosols. In particular, we show that the presence of the divalent Mg(2+) cation does not modify the surface propensity of chloride compared to Na(+) and hence, its availability to interfacial reaction, although some differences in the behavior of chloride may occur due to specific ion interactions. In this work, we also discuss the SFG free OH band at the surface of salt solutions and conclude that it is often not straightforward to interpret.

  3. 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.

  4. Salting-out effect in aqueous NaCl solutions: trends with size and polarity of solute molecules.

    PubMed

    Endo, Satoshi; Pfennigsdorff, Andrea; Goss, Kai-Uwe

    2012-02-01

    Salting-out in aqueous NaCl solutions is relevant for the environmental behavior of organic contaminants. In this study, Setschenow (or salting-out) coefficients (K(s) [M(-1)]) for 43 diverse neutral compounds in NaCl solutions were measured using a shared headspace passive dosing method and a negligible depletion solid phase microextraction technique. The results were used to calibrate and evaluate estimation models for K(s). The molar volume of the solute correlated only moderately with K(s) (R(2) = 0.49, SD = 0.052). The polyparameter linear free energy relationship (pp-LFER) model that uses five compound descriptors resulted in a more accurate fit to our data (R(2) = 0.83, SD = 0.031). The pp-LFER analysis revealed that Na(+) and Cl(-) in aqueous solutions increase the cavity formation energy cost and the polar interaction energies toward neutral organic solutes. Accordingly, the salting-out effect increases with the size and decreases with the polarity of the solute molecule. COSMO-RS, a quantum mechanics-based fully predictive model, generally overpredicted the experimental K(s), but the predicted values were moderately correlated with the experimental values (R(2) = 0.66, SD = 0.042). Literature data (n = 93) were predicted by the calibrated pp-LFER and COSMO-RS models with root mean squared errors of 0.047 and 0.050, respectively. This study offers prediction models to estimate K(s), allowing implementation of the salting-out effect in contaminant fate models, linkage of various partition coefficients (such as air-water, sediment-water, and extraction phase-water partition coefficients) measured for fresh water and seawater, and estimation of enhancement of extraction efficiency in analytical procedures.

  5. Dynamics of single polyelectrolyte chains in salt-free dilute solutions investigated by analytical ultracentrifugation.

    PubMed

    Cao, Zhonglin; Wu, Sha; Zhang, Guangzhao

    2015-06-28

    The dynamics of polyelectrolytes in salt-free solution is an unsolved problem. We have investigated the sedimentation and diffusion of xanthan and poly(N-methyl 4-vinyl pyridine iodide) (P4VPI) in salt-free dilute solutions by analytical ultracentrifugation (AUC) using sedimentation velocity (SV) as a function of polyelectrolyte concentration (Cp). Our study reveals two concentration regimes distinguished in either polyanion (xanthan) or polycation (P4VPI) dilute aqueous solution. When Cp is below the Debye concentration (Cd) at which the chain separation (d) is close to the debye length (lD), the interchain electrostatic repulsion is negligible, and the reciprocal apparent sedimentation coefficient (1/s), apparent diffusion coefficient (D) or reciprocal apparent molecular weight (1/Mw) is linearly related to Cp. In the range Cp > Cd with d < lD, the interchain electrostatic repulsion is present, and the dynamics of polyelectrolytes becomes complex. The real sedimentation coefficient (s0), the diffusion coefficient (D0) and the molecular weight (Mw,0) of the single polyelectrolyte chain in salt-free dilute solution can be obtained by extrapolating the concentration to zero. The present study reveals that the complex dynamics of polyelectrolytes in salt-free dilute solutions arises due to the interchain electrostatic repulsion.

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

    PubMed

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

    2014-03-01

    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 salt of acemetacin exhibits superior

  7. 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

  8. 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.

  9. 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

  10. 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.

  11. Role of chain stiffness on the conformation of single polyelectrolytes in salt solutions

    NASA Astrophysics Data System (ADS)

    Wei, Yu-Fu; Hsiao, Pai-Yi

    2007-08-01

    Conformation of single polyelectrolytes in tetravalent salt solutions is investigated under the framework of a coarse-grained model, using Langevin dynamics simulations. The chain size, studied by the radius of gyration, shows three different variational behaviors with salt concentration, depending on the chain stiffness. According to the size variations, polyelectrolytes of fixed chain length are classified into three categories: (1) flexible chain, for which the variation shows a curve similar to a tilted L, (2) semiflexible chain, whose curve resembles U, and (3) rigid chain, for which the curve is a straight line. The wormlike chain model with persistence length predicted by the Odijk-Skolnick-Fixman theory is found to be able to qualitatively describe the end-to-end distance at low salt concentration not only for semiflexible and rigid chains but also for flexible chain. In a low salt region, a flexible polyelectrolyte extends more significantly than a semiflexible chain, in reference of the size of their uncharged counterparts, and in a high salt region, regardless of chain stiffness, a chain attains a dimension comparable to that of its neutral polymer. The chain stiffness influences both the local and the global chain structures. A flexible chain exhibits a zigzagged local structure in the presence of salt ions, and the condensed structure is a disordered, random globule. A semiflexible chain is locally smooth, and the condensed structure is orderly packed, taking a form such as hairpin or toroid. Moreover, the chain stiffness can also affect the nature of the coil-globule transition. The transition occurred in a discrete manner for semiflexible chain, whereas it occurred in a continuous way for flexible chain. This discrete feature happened not only at low salt concentration when a semiflexible chain collapsed but also at high salt concentration when the collapsed chain is reexpanded. At the end, the effects of chain stiffness and salt concentration on the

  12. Effects of treating wheat straw with pH-regulated solutions of alkaline hydrogen peroxide on nutrient digestion by sheep.

    PubMed

    Kerley, M S; Fahey, G C; Berger, L L; Merchen, N R; Gould, J M

    1987-10-01

    An experiment using a 4 X 4 Latin square design was to determine effects of treating wheat straw with pH-regulated (pH = 11.5) solutions of hydrogen peroxide on site and extent of nutrient digestion in multiple-fistulated sheep. Regulating reaction pH at 11.5 prevented solubilization of some cell wall hemicelluloses, resulting in improved retention of DM. Diets fed to sheep contained 33 or 70% wheat straw either untreated or treated with alkaline hydrogen peroxide. Sheep fed diets of treated wheat straw digested more DM, NDF, ADF, and cellulose anterior to the duodenum and in the total tract than when fed diets of untreated wheat straw. Apparent CP digestion before the duodenum was highest when sheep were fed the treated 33% wheat straw diet and untreated 70% wheat straw diet. Treatments did not affect apparent nutrient digestibilities in the large intestine. Ruminal pH was lower when sheep were fed the alkaline hydrogen peroxide-treated or diets containing 33% wheat straw. Ruminal ammonia concentrations were highest when sheep were fed the untreated 70% wheat straw diet. Molar proportions of ruminal acetic and propionic acids were unaffected by diet. Alkaline hydrogen peroxide treatment substantially increased susceptibility of structural carbohydrates of wheat straw to microbial degradation in the gastrointestinal tract of sheep.

  13. 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.

  14. 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

    2016-01-14

    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.

  15. Theoretical analysis of XANES for aqueous aluminum salt solutions

    NASA Astrophysics Data System (ADS)

    Matsuo, Shuji; Shirozu, Kaori; Tateishi, Yuichi; Wakita, Hisanobu; Yokoyama, Takushi

    In order to understand the coordination behavior of Al(III) ions in hydrosphere, discrete variational X[alpha] molecular orbital calculations were performed to analyze Al K-edge XANES spectra for the aqueous solutions of Al(NO3)3·9H2O and Al-EDTA (EDTA = ethylenediaminetetraacetate) complex. As to Al(NO3)3·9H2O, the hydrate structure was presumed to be rather an asymmetric hexahydrated structure than an high-symmetric structure. As to Al-EDTA, the 5-fold coordinated Al-EDTA was concluded to be the coexistence of the pyramidal and trigonal bipyramidal structures in proportion of 4 to 6.

  16. Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

    USGS Publications Warehouse

    Truesdell, A.H.

    1974-01-01

    Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275??C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (103 ln ??) between 1 molal solutions and pure water at 25, 100, and 275??C are: NaCl 0.0, -1.5, +1.0; KCl 0.0, -1.0, +2.0; LiCl -1.0, -0.6, -0.5; CaCl2 -0.4, -1.8, +0.8; MgCl2 -1.1, -0.7, -0.3; MgSO4 -1.1, +0.1, -; NaF (0.8 m) 0.0, -1.5, -0.3; and NH4Cl (0.55 m) 0.0, -1.2, -1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required. ?? 1974.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Electrodialysis for recovering salts from a urine solution containing micropollutants.

    PubMed

    Pronk, Wouter; Biebow, Martin; Boller, Markus

    2006-04-01

    Electrodialysis was investigated for the separation of micropollutants from nutrients in anthropogenic urine. In a continuously operated process, the nutrients were concentrated up to a factor of 3.2. The concentration factor was limited by water transport across the membrane. Water transport was caused by osmosis and electroosmosis, and a model was developed to describe these phenomena. The removal of several spiked micropollutants was investigated in continuous electrodialysis experiments. Ethinylestradiol was removed completely during the whole operating period. Diclofenac and carbamazepine were initially retained, but limited permeation (5-10%) occurred after longer operating times (90 days). Retentions of propranolol and ibuprofen were also high initially, but substantial breakthroughs occurred during extended operation. Considerable adsorption on the membranes was observed for all compounds. The permeation mechanism of several compounds appears to depend on the adsorbed amount on the membrane, which indicates that partitioning and diffusion mechanisms play an important role in the permeation transport. Partial desorption occurred in leaching experiments with polarity reversal, and almost quantitative desorption was observed after incubation of the membranes with Filter Count Gel Solution. Because environmental concentrations are much lower than the concentrations spiked here, it can be anticipated that operation without significant permeation is possible in practice during extended periods of time.

  2. 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.

  3. 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.

  4. 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

  5. Recent progress in electrochemical oxidation of saccharides at gold and copper electrodes in alkaline solutions.

    PubMed

    Torto, Nelson

    2009-09-01

    This article reviews the progress made in the past 10 years, on electrochemical oxidation of saccharides in alkaline media for gold and copper electrodes. The mechanism and processes associated with the electrochemical oxidation of saccharides at native and surface coated electrodes continues to be of great interest. Despite the effort and various mechanisms proposed, still the need for an electrochemically active material that understands the complexity associated with saccharides continues to increase as their detection poses a challenge for bioanalytical chemistry and liquid chromatography.

  6. 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

  7. 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.

  8. 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

  9. [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.

  10. 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

  11. 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.

  12. 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.

  13. Ordered mesoporous boron-doped carbons as metal-free electrocatalysts for the oxygen reduction reaction in alkaline solution.

    PubMed

    Bo, Xiangjie; Guo, Liping

    2013-02-21

    Ordered mesoporous boron-doped carbons (BOMCs) were prepared by co-impregnation and carbonization of sucrose and 4-hydroxyphenylboronic acid into SBA-15 silica template. Nitrogen sorption, small angle X-ray diffraction (XRD), and transmission electron microscopy (TEM) reveals that BOMCs possess highly ordered mesoporous structure, uniform pore size distribution, and high surface area. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that B atoms can be successfully doped into the framework of OMCs. Due to the desirable characteristics of BOMCs, BOMCs are highly active, cheap, and selective metal-free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline solution. Although B content is a key factor in determining ORR activity, the ORR activity of BOMCs is also dependent on the surface area. The high surface area of BOMCs facilitates the exposure of the active sites for ORR. BOMCs may be further exploited as potentially efficient and inexpensive metal-free ORR catalysts with good long-term stability in alkaline solution. PMID:23318553

  14. 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.

  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. 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.

  17. 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.

  18. Creep Behaviour of Alpine Salt Rock and the Influence of Insoluble Residues in Solution Mining

    NASA Astrophysics Data System (ADS)

    Pittino, Gerhard; Golser, Johann

    In Austrian salt mining, brine is won by way of solution mining with the borehole well method. The Alpine salt rock (Haselgebirge) consists of a high share of insolubles, and therefore leached caverns are filled with clay residues, as so-called Laist, a natural backfill, according to the salt content. The creep deformations of the Haselgebirge mainly correspond with a rupture-free flow and are calculated by means of an elasto-viscous model (power-law). These deformations mobilize the passive fill-pressure in clay residue that is described as elastoplastic with isotropic hardening by means of a modified Cam-clay model. The long-term laboratory tests are supported through calculations of the creep parameter via measured convergences of drifts at various depths. The long-term behaviour of the caverns is evaluated based on numerical calculations by the volume convergence and the degree of utilization of pillar.

  19. 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.

  20. Molecular thermodynamics for swelling of a mesoscopic ionomer gel in 1 : 1 salt solutions.

    PubMed

    Victorov, A; Radke, C; Prausnitz, J

    2006-01-14

    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. A geometry-dependent generalized analytical solution for the linearized Poisson-Boltzmann equation is obtained. This generalized solution not only reduces to those known previously for planar, cylindrical and spherical geometries, but is also applicable to saddle-like structures. 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 the 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. PMID:16482269

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

  2. Intrinsic viscosity and conformational parameters of xanthan in aqueous solutions: salt addition effect.

    PubMed

    Brunchi, Cristina-Eliza; Morariu, Simona; Bercea, Maria

    2014-10-01

    The intrinsic viscosity and conformational parameters of xanthan in aqueous solutions were investigated at 25°C as a function of salt nature (NaCl and KCl) and concentration (up to 3×10(-1)mol/L). The viscometric parameters were evaluated by applying semi-empirical equations proposed by Rao and Wolf. The results show that the new model proposed by Wolf provides accurate intrinsic viscosity values comparable with those obtained by using traditional methods. The experimental data were modeled with Boltzmann sigmoidal equation. The stiffness parameter, hydrodynamic volume and viscometric expansion factor were determined and discussed. With increasing salt concentration, the hydrodynamic volume and the viscometric expansion factor decrease and the critical overlap concentration increases, reaching limiting values above a given salt concentration. The high Huggins constant values suggest the existence of aggregates for salt concentrations above 5×10(-2) and 3×10(-3)mol/L for NaCl and KCl, respectively. Stiffness parameter was determined by Smidsrød and Haug method as being 5.45×10(-3), indicating a rigid conformation for xanthan macromolecules in solution.

  3. Effect of chloride concentration on the pitting and repassivation potentials of reinforcing steel in alkaline solutions

    SciTech Connect

    Li, L.

    1999-11-01

    Reinforcing steel bars ({approximately}12mm diameter and 150mm long) were used in cyclic polarization tests in saturated Ca(OH){sub 2} solution and simulated concrete pore solution (SPS) with various levels of sodium chloride addition. Below a limiting chloride level ({approximately}O.004M [Cl{sup {minus}}] in Ca(OH){sub 2} solution and {approximately}0.4M [Cl{sup {minus}}] in SPS solution), steel was not found to undergo pitting corrosion even if it was polarized to the oxygen evolution potential ({approximately}O.6V/SCE). At higher NaCl addition, pitting corrosion could often be initiated but the pitting potential was non-deterministic to a great extent. In Ca(OH){sub 2} solution the average pitting potential was found to be strongly dependent on chloride concentration when [Cl{sup {minus}}]{ge}0.008M. In SPS solution, the average pitting potential was almost independent of the chloride concentration when [Cl{sup {minus}}]{ge}0.8M. The repassivation potential was found to be a strong function of the severity of corrosion attack that has occurred on the steel surface before repassivation, rather than a function of the chloride content of the bulk solution. The pitting tendency in chloride-containing SPS and Ca(OH){sub 2} solutions was interpreted on a statistical basis. The threshold thus determined good agreement with other values reported in the literature.

  4. 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.

  5. 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.

  6. 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.

  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 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.

  8. 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.

  9. 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.

  10. 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

  11. Detection and identification of salts and frozen salt solutions combining laser-induced breakdown spectroscopy and multivariate analysis methods: A study for future martian exploration

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    For the geochemical investigation of extraterrestrial surfaces laser-induced breakdown spectroscopy (LIBS) has been suggested as a powerful analytical tool, and is part of the payload on NASA’s rover Curiosity, which reached Mars in August 2012. Apart from soil in general, LIBS is capable of analyzing ice and salts within the soil. This study demonstrates the feasibility of LIBS for investigating and differentiating between different salts by applying three multivariate analysis (MVA) techniques. The focus was on the capability of the MVA techniques for LIBS data to discriminate between sulfates and chlorides with cations of the same kind as pure pressed pellets and in frozen salt solutions. Two data sets of LIBS spectra of eight different salts (CaCl2, CaSO4, KCl, K2SO4, MgCl2, MgSO4, NaCl, Na2SO4), pure and as frozen salt solutions, were acquired in a dedicated simulation chamber under martian atmospheric conditions. With principal components analysis (PCA) both data sets were analyzed with the aim of dividing the spectra of the ices into groups and revealing the most important lines in the spectra for discrimination and identification of the type of salt. PCA performance is improved by selecting the most relevant lines with emphasis on the sulfur and chlorine lines and additionally averaging the spectra before analysis. Moreover, a subsequent PCA with a subset of data can improve the discrimination ability for a sulfate and a chloride with the same type of cation. Soft independent modeling of class analogy (SIMCA) and partial least squares discriminant analysis (PLS-DA) were performed for both data sets. While SIMCA worked well for the pressed salt samples, its application to the spectra of the frozen salt solutions was not successful. A local PLS-DA of the LIBS spectra of salts with the same cation is capable of distinguishing sulfate and chloride.

  12. 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.

  13. External application of hypertonic salt solution for treatment of posttraumatic oedema.

    PubMed

    Atalar, Hakan; Yavuz, Osman Y; Uras, Ismail; Selek, Hakan; Erakar, Aziz; Sayli, Ugur

    2005-08-01

    In 20 New Zealand rabbits (two groups of 10 rabbits each), hind limb circumference and anterior compartment pressure were measured following ketamin anaesthesia (time zero). During the same anaesthesia, closed transverse proximal tibial shaft fractures were created in both groups. Twenty-four hours after the fractures, during a second anaesthesia, limb circumference and compartment pressure were measured as before, and fractured limbs were fixed to the rabbits' bodies. At the same time, treatment was started: one group received external application of saturated salt solution and the other group received intermittent ice application. During 48 hours of treatment (from 24 to 72 hours) in the saturated salt solution group, the mean limb circumference decreased from 125.70 +/- 9.93 mm to 115.70 +/- 8.78 mm (p = 0.005) and the mean compartment pressure decreased from 18.30 +/- 1.70 mmHg to 12.40 +/- 1.77 mmHg (p = 0.005). In the control group, the mean limb circumference decreased from 127.85 +/- 7.47 mm to 122.00 +/- 6.83 mm (not significant) and the mean compartment pressure decreased from 19.57 +/- 1.27 mmHg to 17.85 +/- 2.67 mmHg (not significant). In short, differences in compartment pressure and limb circumference before and after treatment were statistically significant in the saturated salt solution group (p = 0.005) but not in the control group.

  14. Investigation of the salting out of methane from aqueous electrolyte solutions using computer simulations.

    PubMed

    Docherty, H; Galindo, A; Sanz, E; Vega, C

    2007-08-01

    We calculate the excess chemical potential of methane in aqueous electrolyte solutions of NaCl using Monte Carlo computer simulations. In a recent work [Docherty et al. J. Chem. Phys. 2006, 125, 074510], we presented a new potential model for methane in water which is capable of describing accurately the excess chemical potential of methane in pure water over a range of temperatures, a quantity that can be related to the solubility and which is commonly used to study the hydrophobic effect. Here, we use the same potential model for the water-methane interactions and investigate the effect of added salt on the chemical potential of methane in the solution. The methane molecules are modeled as single Lennard-Jones (LJ) interaction sites, and the water molecules are modeled with the TIP4P/2005 model. A correcting factor of chi = 1.07 for the energetic Berthelot (geometric) combining rule of the methane-water interaction is also used, which mimics the polarization of methane in water. We consider NaCl as the salt and treat the ions with the Smith and Dang model (i.e., as charged LJ interaction sites). Ion-water, ion-ion, and ion-methane interactions are treated using Lorentz-Berthelot combining rules. In addition, the Coulombic potential is used to model charge-charge interactions which are calculated using the Ewald sum. We have carried out isobaric-isothermal (NpT) simulations to determine the equilibrium densities of the solutions. The simulation data is in excellent agreement with experimental densities of aqueous NaCl solutions of different concentration. Hydration numbers are also obtained and found to be in agreement with reported data. Canonical (NVT) simulations at the averaged densities are then performed using the Widom test-particle insertion method to obtain the excess chemical potential of methane in the saline solutions. An increase in the chemical potential of methane, corresponding to a salting out effect, is observed when salt is added to the solution

  15. Investigation of the salting out of methane from aqueous electrolyte solutions using computer simulations.

    PubMed

    Docherty, H; Galindo, A; Sanz, E; Vega, C

    2007-08-01

    We calculate the excess chemical potential of methane in aqueous electrolyte solutions of NaCl using Monte Carlo computer simulations. In a recent work [Docherty et al. J. Chem. Phys. 2006, 125, 074510], we presented a new potential model for methane in water which is capable of describing accurately the excess chemical potential of methane in pure water over a range of temperatures, a quantity that can be related to the solubility and which is commonly used to study the hydrophobic effect. Here, we use the same potential model for the water-methane interactions and investigate the effect of added salt on the chemical potential of methane in the solution. The methane molecules are modeled as single Lennard-Jones (LJ) interaction sites, and the water molecules are modeled with the TIP4P/2005 model. A correcting factor of chi = 1.07 for the energetic Berthelot (geometric) combining rule of the methane-water interaction is also used, which mimics the polarization of methane in water. We consider NaCl as the salt and treat the ions with the Smith and Dang model (i.e., as charged LJ interaction sites). Ion-water, ion-ion, and ion-methane interactions are treated using Lorentz-Berthelot combining rules. In addition, the Coulombic potential is used to model charge-charge interactions which are calculated using the Ewald sum. We have carried out isobaric-isothermal (NpT) simulations to determine the equilibrium densities of the solutions. The simulation data is in excellent agreement with experimental densities of aqueous NaCl solutions of different concentration. Hydration numbers are also obtained and found to be in agreement with reported data. Canonical (NVT) simulations at the averaged densities are then performed using the Widom test-particle insertion method to obtain the excess chemical potential of methane in the saline solutions. An increase in the chemical potential of methane, corresponding to a salting out effect, is observed when salt is added to the solution

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. Stoichiometric C6-oxidation of hyaluronic acid by oxoammonium salt TEMPO⁺Cl⁻ in an aqueous alkaline medium.

    PubMed

    Ponedel'kina, Irina Yu; Khaibrakhmanova, Elvira A; Tyumkina, Tatyana V; Romadova, Irina V; Odinokov, Victor N

    2015-10-01

    This paper reports the selective oxidation of hyaluronic acid (HA) by stoichiometric quantity of 2,2,6,6-tetramethylpiperidine-1-oxoammonium chloride (TEMPO(+)) in aqueous alkaline medium. High efficiency of the HA oxidation and quantitative yield of carboxy-HA per starting TEMPO(+), as well as unusual behavior of the oxidation system generating an oxygen upon alkali-induced oxoammonium chloride decomposition are demonstrated. The scheme for HA oxidation involving both TEMPO(+) and oxygen produced upon the TEMPO(+)Cl(-) decomposition and/or air oxygen is proposed. For comparison, the data on stoichiometric oxidation of such substrates as dermatan sulfate, water-soluble potato starch, methyl 2-acetamido-2-deoxy-β-d-glucopyranoside and ethanol are presented.

  3. 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

  4. 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

  5. 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.

  6. A parallel-plate electrochemical reactor model for the destruction of nitrate and nitrite in alkaline waste solutions

    SciTech Connect

    Coleman, D.H.; White, R.E.; Hobbs, D.T.

    1995-04-01

    The electrochemical treatment of nuclear waste is the subject of much current interest. After radioactive decontamination, the liquid waste from nuclear fuel processing still contains many hazardous substances, among them nitrate and nitrite. A parallel-plate electrochemical reactor model with multiple reactions at both electrodes and anolyte and catholyte recirculation tanks was modeled for the electrochemical destruction of nitrate and nitrite species in an alkaline solution. The model can be used to predict electrochemical reaction current efficiencies and outlet concentrations of species from the reactor, given inlet feed conditions and cell operating conditions. Also, predictions are made for off-gas composition and liquid-phase composition in the recirculation tanks. The results of case studies at different applied potentials are shown here. At lower applied potentials, the model predictions show that the destruction process is more energy efficient, but the time required to destroy a given amount of waste is increased.

  7. 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.

  8. Unified molecular picture of the surfaces of aqueous acid, base, and salt solutions.

    PubMed

    Mucha, Martin; Frigato, Tomaso; Levering, Lori M; Allen, Heather C; Tobias, Douglas J; Dang, Liem X; Jungwirth, Pavel

    2005-04-28

    The molecular structure of the interfacial regions of aqueous electrolytes is poorly understood, despite its crucial importance in many biological, technological, and atmospheric processes. A long-term controversy pertains between the standard picture of an ion-free surface layer and the strongly ion specific behavior indicating in many cases significant propensities of simple inorganic ions for the interface. Here, we present a unified and consistent view of the structure of the air/solution interface of aqueous electrolytes containing monovalent inorganic ions. Molecular dynamics calculations show that in salt solutions and bases the positively charged ions, such as alkali cations, are repelled from the interface, whereas the anions, such as halides or hydroxide, exhibit a varying surface propensity, correlated primarily with the ion polarizability and size. The behavior of acids is different due to a significant propensity of hydronium cations for the air/solution interface. Therefore, both cations and anions exhibit enhanced concentrations at the surface and, consequently, these acids (unlike bases and salts) reduce the surface tension of water. The results of the simulations are supported by surface selective nonlinear vibrational spectroscopy, which reveals among other things that the hydronium cations are present at the air/solution interface. The ion specific propensities for the air/solution interface have important implications for a whole range of heterogeneous physical and chemical processes, including atmospheric chemistry of aerosols, corrosion processes, and bubble coalescence.

  9. Rheological properties and thickening mechanism of aqueous diutan gum solution: Effects of temperature and salts.

    PubMed

    Xu, Long; Gong, Houjian; Dong, Mingzhe; Li, Yajun

    2015-11-01

    Rheological properties of a new microbial polysaccharide, diutan gum in aqueous solution have been systematically investigated. It is found that molecular aggregates of diutan gum can be formed at a very low concentration (0.12 g/L), and the mechanism of thickening by diutan gum is proposed. The viscosity retention rate of diutan gum changes little when increasing the temperature from 298 K to 348 K or in a high salinity solution (55.5 g L(-1)). Gel structure can be formed in the diutan gum solution, owing to the finding that the dynamic modulus has an exponential relationship with the concentration. The gel properties of diutan gum are not sensitive to temperature, and are virtually independent of cationic environment (Na(+) and Ca(2+)). The temperature/salt tolerance of the diutan gum solution is mainly attributed to its perfect double helix molecular conformation, the location of the side chains of its molecules, and its water retention capacity.

  10. Conformational transitions of flexible hydrophobic polyelectrolytes in solutions of monovalent and multivalent salts and their mixtures.

    PubMed

    Trotsenko, Oleksandr; Roiter, Yuri; Minko, Sergiy

    2012-04-10

    Conformations of cationic polyelectrolytes (PEs), a weak poly(2-vinylpyridine) (P2VP) and a strong poly(N-methyl-2-vinylpyridinium iodide) (qP2VP), adsorbed on mica from saline solutions in the presence of counterions of different valences are studied using in situ atomic force microscopy (AFM). Quantitative characteristics of chain conformations are analyzed using AFM images of the adsorbed molecules. The results of the statistical analysis of the chain contour reveal collapse of the PE coils when ionic strength is in a range from tens to hundreds of millimoles per kilogram and re-expansion of the coils with a further increase of ionic strength up to a region of the saturated saline solutions. The competition between monovalent and multivalent counterions simultaneously present in solutions strongly affects conformations of PE chains even at a very small fraction of multivalent counterions. Shrinkage of PE coils is steeper for multivalent counterions than for monovalent counterions. However, the re-expansion is only incremental in the presence of multivalent counterions. Extended adsorbed coils at low salt concentrations and at very high concentrations of monovalent salt exhibit conformation corresponding to a 2D coil with 0.95 fraction of bound segments (segments in "trains") in the regime of diluted surface concentration of the PE. Shrunken coils in the intermediate range of ionic strength resemble 3D-globules with 0.8 fraction of trains. The incrementally re-expanded PE coils at a high ionic strength remain unchanged at higher multivalent salt concentrations up to the solubility limit of the salt. The formation of a strong PE complex with multivalent counterions at high ionic strength is not well understood yet. A speculative explanation of the observed experimental result is based on possible stabilization of the complex due to hydrophobic interactions of the backbone.

  11. A unified molecular picture of the surfaces of aqueous acid, base, and salt solutions

    SciTech Connect

    Mucha, M.; Frigato, Tomaso; Levering, Lori; Allen, Heather C.; Tobias, Douglas J.; Dang, Liem X.; Jungwirth, Pavel

    2005-04-28

    A unified view of the structure of the air/solution interface of simple aqueous electrolytes containing monovalent inorganic ions is developed using molecular dynamics simulations and vibrational sum frequency generation spectroscopy. In salt solutions and bases the positively charged ions, such as alkali cations, are repelled from the air/solution interface, while the anions, such as halides or hydroxide, exhibit a varying propensity for the surface, correlated primarily with the polarizability of the ion. As a result, there is a net depletion of ions from the interfacial layer as a whole, which is connected via the Gibbs adsorption equation to an increase in surface tension with respect to neat water. The behavior of acids, such as aqueous HCl or HBr, is different due to a significant propensity of hydronium cations for the air/solution interface. Therefore, both cations and anions exhibit enhanced concentrations at the surface and, consequently, these acids reduce the surface tension of water. The key to the qualitatively different surface behavior of aqueous salt solutions and bases on one side and acids on the other thus lies in the appreciable adsorption of hydronium cations at the air/solution interface with their “hydrophobic” oxygen side oriented towards the gas phase. The results of the molecular dynamics calculations are supported by surface selective non-linear vibrational spectroscopy, which reveals among other things that the hydronium cations are present at the air/solution interface. The propensity of inorganic ions for the air/solution interface has important implications for heterogeneous chemical processes, in particular for atmospheric chemistry.

  12. Absorption and desorption of SO2 in aqueous solutions of diamine-based molten salts.

    PubMed

    Lim, Seung Rok; Hwang, Junhyeok; Kim, Chang Soo; Park, Ho Seok; Cheong, Minserk; Kim, Hoon Sik; Lee, Hyunjoo

    2015-05-30

    SO2 absorption and desorption behaviors were investigated in aqueous solutions of diamine-derived molten salts with a tertiary amine group on the cation and a chloride anion, including butyl-(2-dimethylaminoethyl)-dimethylammonium chloride ([BTMEDA]Cl, pKb=8.2), 1-butyl-1,4-dimethylpiperazinium chloride ([BDMP]Cl, pKb=9.8), and 1-butyl-4-aza-1-azoniabicyclo[2,2,2]octane chloride ([BDABCO]Cl, pKb=11.1). The SO2 absorption and desorption performance of the molten salt were greatly affected by the basicity of the molten salt. Spectroscopic, X-ray crystallographic, and computational results for the interactions of SO2 with molten salts suggest that two types of SO2-containg species could be generated depending on the basicity of the unquaternized amino group: a dicationic species comprising two different anions, HSO3(-) and Cl(-), and a monocationic species bearing Cl(-) interacting with neutral H2SO3.

  13. Coloring Rate of Phenolphthalein by Reaction with Alkaline Solution Observed by Liquid-Droplet Collision.

    PubMed

    Takano, Yuuka; Kikkawa, Shigenori; Suzuki, Tomoko; Kohno, Jun-ya

    2015-06-11

    Many important chemical reactions are induced by mixing two solutions. This paper presents a new way to measure rates of rapid chemical reactions induced by mixing two reactant solutions using a liquid-droplet collision. The coloring reaction of phenolphthalein (H2PP) by a reaction with NaOH is investigated kinetically. Liquid droplets of H2PP/ethanol and NaOH/H2O solutions are made to collide, which induces a reaction that transforms H2PP into a deprotonated form (PP(2-)). The concentration of PP(2-) is evaluated from the RGB values of pixels in the colored droplet images, and is measured as a function of the elapsed time from the collision. The obtained rate constant is (2.2 ± 0.7) × 10(3) M(-1) s(-1), which is the rate constant for the rate-determining step of the coloring reaction of H2PP. This method was shown to be applicable to determine rate constants of rapid chemical reactions between two solutions.

  14. 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...

  15. 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.

  16. Enhanced copper surface protection in aqueous solutions containing short-chain alkanoic acid potassium salts.

    PubMed

    Abelev, Esta; Starosvetsky, David; Ein-Eli, Yair

    2007-10-23

    The ability of dissolved potassium monocarboxylate salts to produce surface passivation and to inhibit aqueous corrosion of copper was studied. The electrochemical measurements indicate that the inhibiting efficiency of these compounds, with a general formula Cn-1H2n-1COOK or CnK (n=3...12), is dependent on the hydrocarbon chain length. The inhibiting efficiency was higher for a longer hydrocarbon chain of n-alkanoic acid. The degree of copper protection was found to increase with an increase in n-alkanoic acid potassium salt concentration; the optimum concentration of potassium dodecanoate (C12K) in sulfate solutions was found to be 0.07 M. The protective layers formed at the copper surface subsequent to exposure in various n-alkanoic acid potassium salt solutions were characterized by contact angle measurements, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared reflection spectroscopy. Pronounced copper protection was attributed to the growth of a protective film on the copper surface, containing both copper oxides and copper carboxylate compounds. It is suggested that the organic molecules enhance copper protection by covering copper oxides with a thin and dense organic layer, which prevents water molecules or aggressive anions from interacting with the copper surface.

  17. 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.

  18. Effects of detergent β-octylglucoside and phosphate salt solutions on phase behavior of monoolein mesophases.

    PubMed

    Khvostichenko, Daria S; Ng, Johnathan J D; Perry, Sarah L; Menon, Monisha; Kenis, Paul J A

    2013-10-15

    Using small-angle x-ray scattering (SAXS), we investigated the phase behavior of mesophases of monoolein (MO) mixed with additives commonly used for the crystallization of membrane proteins from lipidic mesophases. In particular, we examined the effect of sodium and potassium phosphate salts and the detergent β-octylglucoside (βOG) over a wide range of compositions relevant for the crystallization of membrane proteins in lipidic mesophases. We studied two types of systems: 1), ternary mixtures of MO with salt solutions above the hydration boundary; and 2), quaternary mixtures of MO with βOG and salt solutions over a wide range of hydration conditions. All quaternary mixtures showed highly regular lyotropic phase behavior with the same sequence of phases (Lα, Ia3d, and Pn3m) as MO/water mixtures at similar temperatures. The effects of additives in quaternary systems agreed qualitatively with those found in ternary mixtures in which only one additive is present. However, quantitative differences in the effects of additives on the lattice parameters of fully hydrated mesophases were found between ternary and quaternary mixtures. We discuss the implications of these findings for mechanistic investigations of membrane protein crystallization in lipidic mesophases and for studies of the suitability of precipitants for mesophase-based crystallization methods.

  19. 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

  20. 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.

  1. Volume change effect on the salt-finger stability of directionally solidifying ammonium chloride solution

    NASA Astrophysics Data System (ADS)

    Lee, Y. C.; Chen, Falin

    1995-09-01

    The effect of the volume change due to phase transformation on the stability of salt-finger convection of directionally solidifying NH 4Cl aqueous solution cooling from below is investigated. The basic flow, induced by the volume change, not only changes the morphology and the depth of the dendritic mushy layer, but also influences the stability of salt-finger convection. A new mathematical model is proposed, which differs from the previous one mainly on the dynamical condition at the melt/mush interface. This difference not only leads to a less stable state, but can also be crucial to the dynamical behavior of the oscillatory instability mode since the convection cells of this mode are coupled viscously through the interface. In the discussion, special emphasis is placed on the volume change effect on the instability mode competition, which may be influential to the stability characteristics of the subsequent plume convection.

  2. 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.

  3. Interaction of adenylic acid with alkaline earth metal ions in the crystalline solid and aqueous solution. Evidence for the sugar C'2-endo/anti, C'3-endo/anti and C'4-exon/anti conformational changes.

    PubMed

    Tajmir-Riahi, H A

    1990-09-10

    The reaction of adenosine 5'-monophosphoric acid (H2-AMP) with the alkaline earth metal ions has been investigated in aqueous solution at neutral pH. The solid salts of Mg-AMP.5H2O, Ca-AMP.6H2O, Sr-AMP.7H2O and Ba-AMP.7H2O were isolated and characterized by Fourier transform infrared, 1H-NMR spectroscopy and X-ray powder diffraction measurements. Spectroscopic and other evidence showed that the Sr-AMP.7H2O and Ba-AMP.7H2O are isomorphous, whereas the Mg-AMP.5H2O and Ca-AMP.6H2O are not similar. The Mg2+ binding is through the N-7 (inner-sphere) and the phosphate group (outer-sphere via H2O), while the Ca2+ binds to the phosphate group (inner-sphere) and to the base N-7 site (outer-sphere through H2O). The Sr2+ and Ba2+ bind to H2O molecules, H-bonding to the N-7, N-1 and the phosphate group (outer-sphere). In aqueous solution, an equilibrium between the inner- and outer-sphere metal ion bindings can be established. The sugar moiety exhibited C'2-endo/anti conformation, in the free H2-AMP acid and the magnesium salt, C'3-endo/anti in the calcium salt and unusual C'4-exo/anti, in the strontium and barium salts.

  4. 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.

  5. 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

  6. 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.

  7. 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

    2015-01-22

    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.

  8. 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

  9. Spectroscopic study of Mg(II) ion influence on the autoxidation of gallic acid in weakly alkaline aqueous solutions

    NASA Astrophysics Data System (ADS)

    Nikolić, G. M.; Veselinović, A. M.; Nikolić, R. S.; Mitić, S. S.

    2011-12-01

    Gallic acid autoxidation in weakly alkaline aqueous solutions was studied by UV-Vis spectrophotometry and ESR spectroscopy under various conditions. Lowering the pH value from 10 to 8.5 probably changes the mechanism of the autoxidation reaction as evidenced by the different time variations of UV-Vis spectra of solutions. The presence of Mg(II) ions greatly influences the autoxidation reaction at pH 8.5. Although the UV-Vis spectral changes with time follow the similar pattern during the gallic acid autoxidation at pH 10 and at pH 8.5 in the presence of Mg(II) ions, some small differences indicate that Mg(II) ions not only affect the electron density of absorbing species but also influence the overall mechanism of the autoxidation reaction. ESR spectra of free radials formed during the initial stage of gallic acid autoxidation at pH 8.5 in the presence of Mg(II) ions were recorded. Computer simulation of ESR spectra allows partial characterization of these free radicals.

  10. 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.

  11. Comprehensive study of the chemical reactions resulting from the decomposition of chloroform in alkaline aqueous solution

    NASA Astrophysics Data System (ADS)

    Estevez Mews, Jorge

    Chloroform (CHCl3) is a volatile liquid, which has a rather slow rate of decomposition in ground water. It is a known carcinogen and one of the most common contaminants found at toxic waste sites. The dominant degradation process for chloroform in both the atmosphere and the groundwater is the reaction with the hydroxyl radical or hydroxide ion. This process triggers a sequence of reactions which ultimately yield carbon monoxide, hydrogen chloride, and formic acid. The rate of chloroform degradation is considerably larger in solution than that in the gas phase and it increases dramatically with increasing pH. However, only one of the viable reactions had been studied previously at a high level of theory in solution. It is of great interest to gain a deeper understanding of the decomposition reaction mechanism. Quantum mechanical methods are well suited for studying the mechanism of organic reactions. However, a full quantum mechanical treatment of the entire fluid system is not computationally feasible. In this work, combined quantum mechanical and molecular mechanical (QM/MM) methods are used for studying chemical reactions in condensed phases. In these calculations, the solute molecules are treated quantum mechanically (QM), whereas the solvent molecules are approximated by empirical (MM) potential energy functions. The use of quantum mechanics and statistical sampling simulation is necessary to determine the reaction free energy profile. In the present study, the ab initio Hartree-Fock theory along with the 3-21G basis set was used in the quantum mechanical calculations to elucidate the reaction pathways of chloroform decomposition, with a focus on basic reaction conditions. Statistical mechanical Monte Carlo approach was then applied in molecular mechanical simulations, employing the empirical TIP3P model for water. We employed state-of-the-art electronic structure methods to determine the gas-phase inter-nuclear potential energy profile for all the relevant

  12. 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

  13. Solubility of uranium (IV) oxide in alkaline aqueous solutions to 300/sup 0/C

    SciTech Connect

    Tremaine, P.R.; Chen, J.D.; Wallace, G.J.; Boivin, W.A.

    1981-03-01

    The solubility of carefully characterized UO/sub 2/ in pOH 1.5 and pOH 2.5 aqueous solutions has been determined from 25 to 300/sup 0/C using a flow apparatus. Data were analyzed in terms of reversible reaction, UO/sub 2/ + 2H/sub 2/O + OH/sup -/ ..-->.. U(OH)/sub 5//sup -/, where log K = -5.86 + 32/T. The extreme sensitivity of both the UO/sub 2/ surface and aqueous U(IV) to oxidation is discussed.

  14. Electrochemical Behavior of Nano-grained Pure Copper in Dilute Alkaline Solution with Chloride Ion Trace

    NASA Astrophysics Data System (ADS)

    Fattah-Alhosseini, Arash; Imantalab, Omid; Attarzadeh, Farid Reza

    2016-10-01

    Effect of nano-grained structure on the interface behavior of pure copper in 0.01M KOH solution with chloride ion trace is investigated by various electrochemical techniques. Nano-grained structure was achieved by accumulative roll bonding (ARB) technique. Before any electrochemical measurements, microstructure was evaluated by means of optical microscopy and transmission electron microscopy (TEM). TEM observations showed that nano-grains (with an average size of below 100 nm) appeared after eight passes of ARB. Polarization curves revealed that increasing chloride ion concentration leads to a decrease in the corrosion and pitting potentials of both annealed and nano-grained pure copper samples. Electrochemical impedance spectroscopy revealed that chloride ion trace lowers passive film resistance and charge-transfer resistance in both annealed and nano-grained samples. Mott-Schottky analysis showed that the surface films formed on annealed and nano-grained samples in KOH solution with and without NaCl addition are of p-type semiconducting behavior. Moreover, this analysis showed that the acceptor density increases by increasing chloride ion concentration.

  15. Electrochemical Behavior of Nano-grained Pure Copper in Dilute Alkaline Solution with Chloride Ion Trace

    NASA Astrophysics Data System (ADS)

    Fattah-Alhosseini, Arash; Imantalab, Omid; Attarzadeh, Farid Reza

    2016-08-01

    Effect of nano-grained structure on the interface behavior of pure copper in 0.01M KOH solution with chloride ion trace is investigated by various electrochemical techniques. Nano-grained structure was achieved by accumulative roll bonding (ARB) technique. Before any electrochemical measurements, microstructure was evaluated by means of optical microscopy and transmission electron microscopy (TEM). TEM observations showed that nano-grains (with an average size of below 100 nm) appeared after eight passes of ARB. Polarization curves revealed that increasing chloride ion concentration leads to a decrease in the corrosion and pitting potentials of both annealed and nano-grained pure copper samples. Electrochemical impedance spectroscopy revealed that chloride ion trace lowers passive film resistance and charge-transfer resistance in both annealed and nano-grained samples. Mott-Schottky analysis showed that the surface films formed on annealed and nano-grained samples in KOH solution with and without NaCl addition are of p-type semiconducting behavior. Moreover, this analysis showed that the acceptor density increases by increasing chloride ion concentration.

  16. 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.

  17. The effect of salt solutes on the relaxation dynamics of water from 65 to 720 GHz

    NASA Astrophysics Data System (ADS)

    Vinh, Nguyen; Sherwin, Mark; Allen, Jim; Plaxco, Kevin

    2012-02-01

    During the past decade, a variety of measurement techniques have provided evidence that ions and other solute molecules effect the structure and dynamics of the water molecules directly surrounding them. Most of these experiments have employed infrared spectroscopy which explores vibrational relaxation of the hydration shell by observing intramolecular vibrations. Terahertz spectroscopy, in contrast is sensitive to intermolecular dynamics. Here we use a vector network analyzer based terahertz dielectric relaxation spectrometer operating over the frequency range from 65 to 720 GHz. The literature on relaxation dynamics of water is extensive and variable. But these measurements clarify the situation and confirm that the dynamics of water over this regime are best described in terms of three Debye relaxation processes with the characteristic times of 8.56, 1.1 ps and 179 fs (at 25.0 C). Remarkably, while the relaxation times themselves are not sensitive to salt concentration, the relative strength of the relaxation modes depends in a systematic way on the solute molarity. We discuss these results by relating the salt concentration dependent strength of the three processes to the dynamics and structure of first three hydration shells. Our measurements shed light on the dynamics of hydration shells around solute molecules in a biologically relevant environment.

  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.

  20. 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

  1. Modeling pitting corrosion of iron exposed to alkaline solutions containing nitrate and nitrite

    NASA Astrophysics Data System (ADS)

    Chen, Lifeng

    2001-07-01

    Pitting corrosion could be extremely serious for dilute high-level radioactive waste stored or processed in carbon steel tanks at the Savannah River Site. In these solutions, nitrate is an aggressive ion with respect to pitting of carbon steel while nitrite can be used as an inhibitor. Excessive additions of nitrite increase the risk of generating unstable nitrogen compounds during waste processing, and insufficient additions of nitrite could increase the risk of corrosion-induced failure. Thus there are strong incentives to obtain a fundamental understanding of the role of nitrite in pitting corrosion prevention with these solution chemistries. In this dissertation, both a 1-D and a 2-D model are used to study the pitting mechanism as a function of nitrite/nitrate ratios. The 1-D model used BAND(J) to test a reaction mechanism for the passivation behavior by comparing the predicted Open Circuit Potential (OCP) with OCP data from experiments at different NO2-/NO3- ratio. The model predictions are compared with Cyclic Potentiodynamic Polarization (CPP) experiments. A 2-D model was developed for the propagation of a pit in iron by writing subroutines for finite element software of GAMBIT and FIDAP. Geometrically distributed anodic and cathodic reactions are assumed. The results show three partial explanations describing the inhibition influence of nitrite to iron corrosion: the competing reduction reaction of nitrate to nitrite, the formation of Fe(OH)+, and the function of the porous film. The current distributions and the effect of porosity of the film on pH are also explained. The calculation results also show that rate of pit growth decreases as the pit diameter increases until it reaches a constant value. The profile of the local current density on the pit wall is parabolic for small pits and it changes to a linear distribution for large pits. The model predicts that addition of nitrite will decrease the production of ferrous ions and those can prevent iron from

  2. Characterization of solid reaction products from wet oxidation of pyrite in coal using alkaline solutions

    SciTech Connect

    Greer, R.T.; Markuszewski, R.; Wheelock, T.D.

    1980-01-01

    Oxidation of pyrite alone and pyrite embedded in coal by leaching with hot solutions of sodium carbonate containing dissolved oxygen under pressure produces hematite, the major solid reaction product. The hematite is deposited as a concentric rim surrounding the core of unreacted pyrite. The thickness of the rim is greater for products obtained after longer leaching time or under conditions of higher oxygen partial pressure. The product is identified as hematite by X-ray diffraction analysis. Data from scanning electron microscopy, and energy-dispersive X-ray analysis show that under these conditions of desulfurization, phase transformations occur (from pyrite to hematite). In addition, great differences in porosity of the two zones (core and rim) are observed. The nature and extent of these transformations are discussed in terms of the desulfurization potential of pyrite in coal. (10 refs.)

  3. Investigation of the swelling behaviour of hydrogels in aqueous acid or alkaline solutions

    NASA Astrophysics Data System (ADS)

    Althans, Daniel; Enders, Sabine

    2014-09-01

    For development of tailor made drug delivery systems using poly(N-isopropylacrylamide) hydrogels, the influence of acids and bases added to the aqueous solution on the swelling behaviour as function of concentration, temperature and kind of acid or base were investigated experimentally. The selected acids are formic, acetic, propionic, lactic, succinic, α-ketoglutaric and citric acid. The applied bases are sodium and potassium hydroxide. The swelling behaviour was characterised by the degree of swelling and by the uptake of acids by the hydrogel in the swollen state. In the case of weak acids the properties of the swollen hydrogel as well as the phase transition temperature and phase transition acid concentration depends on the type of acids, whereas the properties of the shrunken state do not depend on the acid used. In the case of strong bases, the properties of the shrunken and swollen state depend on the ionic strength, but not on the base applied.

  4. Enzymatic methods for the determination of pollution in seawater using salt resistant alkaline phosphatase from eggs of the sea urchin Strongylocentrotus intermedius.

    PubMed

    Menzorova, Natalie I; Seitkalieva, Alexandra V; Rasskazov, Valerу A

    2014-02-15

    A new salt resistant alkaline phosphatase from eggs of the sea urchin Strongylocentrotus intermedius (StAP) has been shown to have a unique property to hydrolyze substrate in seawater without loss of enzymatic activity. The enzyme has pH optimum at 8.0-8.5. Model experiments showed various concentrations of copper, zinc, cadmium and lead added to seawater or a standard buffer mixture to inhibit completely the enzyme activity at the concentrations of 15-150 μg/l. StAP sensitivity to the presence in seawater of metals, pesticides, detergents and oil products appears to be considerably less. Samples of seawater taken from aquatic areas of the Troitsy Bay of the Peter the Great Bay, Japan Sea have been shown to inhibit the enzyme activity; the same was shown for the samples of fresh waters. The phosphatase inhibition assay developed proved to be highly sensitive, technically easy-to use allowing to test a great number of samples.

  5. Synthesis of the compatible solutes glucosylglycerol and trehalose by salt-stressed cells of Stenotrophomonas strains.

    PubMed

    Roder, Anja; Hoffmann, Eik; Hagemann, Martin; Berg, Gabriele

    2005-02-01

    In this study, physiological processes were analysed, which are involved in salt acclimation of two Stenotrophomonas species, Stenotrophomonas maltophilia strain DSM 50170 and Stenotrophomonas rhizophila strain DSM 14405. S. maltophilia accumulated trehalose as the only osmolyte, whereas S. rhizophila produced additionally to trehalose glucosylglycerol (GG). The different spectrum and amounts of compatible solutes in these two strains led to differences in terms of their salt tolerance. The human-associated S. maltophilia was able to grow in media containing up to 3% NaCl (w/v). In contrast, S. rhizophila propagated in salinities up to 5% NaCl (w/v). The strain was isolated from the rhizosphere, a microenvironment which is characterised by high and changing salinities. Light microscopic analysis of S. rhizophila cells showed a significant increase in cell length of salt-treated cells in comparison to control cells. Cells of S. rhizophila exposed to more than 2% NaCl excreted GG into the medium during the transition from exponential to stationary growth phase, while the internal trehalose pool remained constant. This feature offers a high potential for the biotechnological production of GG.

  6. 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.

  7. Glyme-lithium salt equimolar molten mixtures: concentrated solutions or solvate ionic liquids?

    PubMed

    Ueno, Kazuhide; Yoshida, Kazuki; Tsuchiya, Mizuho; Tachikawa, Naoki; Dokko, Kaoru; Watanabe, Masayoshi

    2012-09-13

    To demonstrate a new family of ionic liquids (ILs), i.e., "solvate" ionic liquids, the properties (thermal, transport, and electrochemical properties, Lewis basicity, and ionicity) of equimolar molten mixtures of glymes (triglyme (G3) and tetraglyme (G4)) and nine different lithium salts (LiX) were investigated. By exploring the anion-dependent properties and comparing them with the reported data on common aprotic ILs, two different classes of liquid regimes, i.e., ordinary concentrated solutions and "solvate" ILs, were found in the glyme-Li salt equimolar mixtures ([Li(glyme)]X) depending on the anionic structures. The class a given [Li(glyme)]X belonged to was governed by competitive interactions between the glymes and Li cations and between the counteranions (X) and Li cations. [Li(glyme)]X with weakly Lewis basic anions can form long-lived [Li(glyme)](+) complex cations. Thus, they behaved as typical ionic liquids. The lithium "solvate" ILs based on [Li(glyme)]X have many desirable properties for lithium-conducting electrolytes, including high ionicity, a high lithium transference number, high Li cation concentration, and high oxidative stability, in addition to the common properties of ionic liquids. The concept of "solvate" ionic liquids can be utilized in an unlimited number of combinations of other metal salts and ligands, and will thus open a new field of research on ionic liquids.

  8. Interconnection of Salt-induced Hydrophobic Compaction and Secondary Structure Formation Depends on Solution Conditions

    PubMed Central

    Haldar, Shubhasis; Chattopadhyay, Krishnananda

    2012-01-01

    What happens in the early stage of protein folding remains an interesting unsolved problem. Rapid kinetics measurements with cytochrome c using submillisecond continuous flow mixing devices suggest simultaneous formation of a compact collapsed state and secondary structure. These data seem to indicate that collapse formation is guided by specific short and long range interactions (heteropolymer collapse). A contrasting interpretation also has been proposed, which suggests that the collapse formation is rapid, nonspecific, and a trivial solvent related compaction, which could as well be observed by a homopolymer (homopolymer collapse). We address this controversy using fluorescence correlation spectroscopy (FCS), which enables us to monitor the salt-induced compaction accompanying collapse formation and the associated time constant directly at single molecule resolution. In addition, we follow the formation of secondary structure using far UV CD. The data presented here suggest that both these models (homopolymer and heteropolymer) could be applicable depending on the solution conditions. For example, the formation of secondary structure and compact state is not simultaneous in aqueous buffer. In aqueous buffer, formation of the compact state occurs through a two-state co-operative transition following heteropolymer formalism, whereas secondary structure formation takes place gradually. In contrast, in the presence of urea, a compaction of the protein radius occurs gradually over an extended range of salt concentration following homopolymer formalism. The salt-induced compaction and the formation of secondary structure take place simultaneously in the presence of urea. PMID:22303014

  9. 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).

  10. 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[degrees]C and geochemical implications

    SciTech Connect

    Horita, J.; Cole, D.R.; Wesolowski, D.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[sub 4]-H[sub 2]O was determined by means of a vapor-liquid water equilibration method over the temperature range of 50 to 100[degrees]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).

  11. Raman spectroscopic determination of the speciation of ore metals in hydrothermal solutions. I. Speciation of antimony in alkaline sulfide solutions at 25 degree C

    SciTech Connect

    Wood, S.A. )

    1989-02-01

    The Raman spectra of the thio-antimony species present in alkaline Na{sub 2}S solutions were obtained at 25{degree}C. The Na{sub 2}S concentration of the solutions was approximately 1.0 molal and the Sb concentrations ranged from 0.005 to 0.1 molal. The spectrum in 0.1 molal Sb solutions consists of a broad, weak band at 314 cm{sup {minus}1}, a more intense band at 369 cm{sup {minus}1}, and prominent shoulder at approximately 350 cm{sup {minus}1} and a suggestion of a shoulder near 380 cm{sup {minus}1}. All of these bands are polarized. An additional line is observed at 2,574 cm{sup {minus}1} due to the H-S stretch of HS{sup {minus}}. The observed Raman spectrum is consistent with either Sb{sub 2}S{sup 2{minus}}{sub 7}, but the former is preferred based on the small number of bands observed. The spectra of solutions at Sb concentrations of 0.06 or less consist of a polarized band at 369 cm{sup {minus}1} and a polarized shoulder at approximately 380 cm{sup {minus}1}. These spectra are consistent with either a bend SbS{sup {minus}}{sub 2} or a pyramidal SbS{sup 3{minus}}{sub 3} species. The present data suggest that the thioantimony species present in most geological fluids, which are generally at higher temperatures, lower pH and contain lower Sb contents than those employed in this study, will be monomeric rather than polymeric. Most previous experimental reports of polymeric species, based solely on solubility or potentiometric studies, and any thermodynamic data derived from these studies, are suspect.

  12. 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.

  13. Simple hydrated salts in methanolic and aqueous solutions - Acoustic and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    Burakowski, Andrzej; Gliński, Jacek; Wachał, Joanna; Guzik, Małgorzata

    2015-12-01

    Hydrated salts, MgCl2·6H2O, CuCl2·2H2O and EuCl3·6H2O when dissolved in methanol, conserve their original coordination numbers, probably dissociating two chloride anions (magnesium chloride), stepwise in equilibrium reactions (copper chloride) or probably only one Cl- (europium chloride). Water hydrating molecules are almost fully removed from the coordination shell only in the case of MgCl2·6H2O. The above conclusions were drawn from analyzing the acoustic and densimetric properties of the title systems and confirmed by conductivity tests. The results are also compared to those in aqueous solutions. The emission and excitation spectra obtained for europium chloride were applied as spectroscopic probes of solution structure, as well as of the number of existing species and their symmetries.

  14. [Rheological properties of salt-free solutions of H+- and Na+-DNA].

    PubMed

    Paponov, V D; Fabrichnaia, O B; Kuznetsov, I A

    1984-01-01

    Rheological properties of the water solutions of H+- and Na+-DNA were studied at shear rates in the range of 0.12-126 sec-1. It was found that the concentration dependences of reduced viscosity of these systems have the maxima which displaced to the left along abscissa after ultrasonic degradation or long keeping and to the right after the salt or urea addition. Na+-DNA solutions have the rheological curve of flow typical of pseudoplastical systems (RCF-1): the viscosity decreases with increasing shear rate. H+-DNA solutions undergo RCF-1 RCF-2 transition leading to reverse dependence of viscosity on shear rate after long keeping or sonicating (i. e. the systems become dilatant). At centrifugation and in shear fields RCF-2 RCF-1 transition occurs. Urea prevents both transitions. These discovered phenomena as well as weakening of the dilatant properties in concentrated H+-DNA solutions allow us to assume that in these systems exist circular structures consisting of single strands of DNA associated by means of ionic bonds between phosphates and protonated bases. Rheological behaviour of DNA obtained by the method of Georgiev and Struchkov was explained by the presence of circular double stranded DNA molecules in their preparations. The analysis of the non-equilibrium behavior of water solutions of DNA allows to determine the rate constants of H+- and Na+-DNA unwinding.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Determining the Enthalpy of Vaporization of Salt Solutions Using the Cooling Effect of a Bubble Column Evaporator

    ERIC Educational Resources Information Center

    Fan, Chao; Pashley, Richard M.

    2016-01-01

    The enthalpy of vaporization (?H[subscript vap]) of salt solutions is not easily measured, as a certain quantity of pure water has to be evaporated from a solution, at constant composition, and at a fixed temperature and pressure; then the corresponding heat input has to be measured. However, a simple bubble column evaporator (BCE) was used as a…

  4. 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.

  5. 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.

  6. 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

  7. Measuring and modeling the salting-out effect in ammonium sulfate solutions.

    PubMed

    Wang, Chen; Lei, Ying Duan; Endo, Satoshi; Wania, Frank

    2014-11-18

    The presence of inorganic salts significantly influences the partitioning behavior of organic compounds between environmentally relevant aqueous phases, such as seawater or aqueous aerosol, and other, nonaqueous phases (gas phase, organic phase, etc.). In this study, salting-out coefficients (or Setschenow constants) (KS [M(-1)]) for 38 diverse neutral compounds in ammonium sulfate ((NH4)2SO4) solutions were measured using a shared headspace passive dosing method and a negligible depletion solid phase microextraction technique. The measured KS were all positive, varied from 0.216 to 0.729, and had standard errors in the range of 0.006-0.060. Compared to KS for sodium chloride (NaCl) in the literature, KS values for (NH4)2SO4 are always higher for the same compound, suggesting a higher salting-out effect of (NH4)2SO4. A polyparameter linear free energy relationship (pp-LFER) for predicting KS in (NH4)2SO4 solutions was generated using the experimental data for calibration. pp-LFER predicted KS agreed well with measured KS reported in the literature. KS for (NH4)2SO4 was also predicted using the quantum-chemical COSMOtherm software and the thermodynamic model AIOMFAC. While COSMOtherm generally overpredicted the experimental KS, predicted and experimental values were correlated. Therefore, a fitting factor needs to be applied when using the current version of COSMOtherm to predict KS. AIOMFAC tends to underpredict the measured KS((NH4)2SO4) but always overpredicts KS(NaCl). The prediction error is generally larger for KS(NaCl) than for KS((NH4)2SO4). AIOMFAC also predicted a dependence of KS on the salt concentrations, which is not observed in the experimental data. In order to demonstrate that the models developed and calibrated in this study can be applied to estimate Setschenow coefficients for atmospherically relevant compounds involved in secondary organic aerosol formation based on chemical structure alone, we predicted and compared KS for selected

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Isolation and characterization of coagulant extracted from Moringa oleifera seed by salt solution.

    PubMed

    Okuda, T; Baes, A U; Nishijima, W; Okada, M

    2001-02-01

    It is known that M. oleifera contains a natural coagulant in the seeds. In our previous research, the method using salt water to extract the active coagulation component from M. oleifera seeds was developed and compared with the conventional method using water. In this research, the active coagulation component was purified from a NaCl solution crude extract of Moringa oleifera seeds. The active component was isolated and purified from the crude extract through a sequence of steps that included salting-out by dialysis, removal of lipids and carbohydrates by homogenization with acetone, and anion exchange. Specific coagulation activity of the active material increased up to 34 times more than the crude extract after the ion exchange. The active component was not the same as that of water extract. The molecular weight was about 3000 Da. The Lowry method and the phenol-sulfuric acid method indicated that the active component was neither protein nor polysaccharide. The optimum pH of the purified active component for coagulation of turbidity was pH 8 and above. Different from the conventional water extracts, the active component can be used for waters with low turbidity without increase in the dissolved organic carbon concentration.

  14. Release of alkaline phosphatase from membranes by a phosphatidylinositol-specific phospholipase C.

    PubMed

    Low, M G; Finean, J B

    1977-10-01

    Purified phosphatidylinositol-specific phospholipase C from Staphylococcus aureus released a substantial proportion of the total alkaline phosphatase activity from a wide range of tissues from several mammalian species. Co-purification of the phospholipase C and alkaline phosphatase-releasing activities and the inhibition of both these activities by iso-osmotic salt solutions suggested that the releasing effect was unlikely to be due to a contaminant.

  15. 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.

  16. 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.

  17. Solubility and reactivity of peroxyacetyl nitrate (PAN) in dilute aqueous salt solutions and in sulphuric acid

    NASA Astrophysics Data System (ADS)

    Frenzel, A.; Kutsuna, S.; Takeuchi, K.; Ibusuki, T.

    The loss rates of PAN in several dilute aqueous salt solutions (NaBr, Na 2SO 3, KI, NaNO 2, FeCl 3, and FeSO 4) and in sulphuric acid were measured at 279 K with a simple bubbler experiment. They are little different from that in pure water. For 5 M sulphuric acid hydrolysis and solubility were determined in the temperature range of 243-293 K. The hydrolysis rate kh=3.2×10 -4 s -1 at 293 K is close to that in water. The observed temperature dependence of the Henry's Law constant H=10- 6.6±0.6exp((4780±420)/T) M atm -1 leads to enthalpy and entropy of solvation Δ Hsolv=-39.7±3.5 kJ mol -1 and Δ Ssolv=-126±11 J mol -1 K -1, respectively.

  18. Computational studies of aqueous interfaces of SrCl2 salt solutions

    SciTech Connect

    Sun, Xiuquan; Wick, Collin D.; Dang, Liem X.

    2009-10-22

    The electron density profiles and the corresponding surface structures of an aqueous interface of SrCl2 salt solution were computed using molecular dynamics simulations. We used both polarizable and non-polarizable potential models to describe molecular interactions. The results demonstrate that the polarizable models captured the essential features of the x-ray reflectivity experimental data while the corresponding non-polarizable models could not. While there is qualitative agreement in the shape of the x-ray reflectivity curve, we find that quantitative agreement is still forthcoming. We suggest that improved agreement can be achieved if the contribution of Sr2+ ions to the total electron density profile is reduced, but not eliminated. This work was performed at Pacific Northwest National Laboratory under the auspices of the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). Pacific Northwest National Laboratory is operated by Battelle for the DOE.

  19. 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.

  20. Investigation of fundamental transport properties and thermodynamics in diglyme-salt solutions.

    PubMed

    Petrowsky, Matt; Frech, Roger; Suarez, Sophia N; Jayakody, J R P; Greenbaum, Steven

    2006-11-23

    Ionic mobility, the thermodynamics of ionic association, and the structure of associated species are studied in solutions of diglyme containing either lithium triflate or tetrabutylammonium triflate. Infrared spectroscopic, PFG NMR, thermodynamic, and crystallographic data suggest that the solute species existing in diglyme-lithium triflate are "free" ions, contact ion pairs, and dimers. Equilibrium constants, S(o), deltaH(o), and deltaG(o) are calculated for processes occurring between these species. In particular, the equilibrium constant, corrected for nonideality using a modified Debye-Hückel expression, is calculated for the dissociation of contact ion pairs into "free" cations and anions. A second equilibrium constant for the formation of dimers from contact ion pairs is also calculated; these constants do not significantly vary with salt concentration up to about 1.3 x 10(-3) mol cm(-3). The measured temperature dependence of equilibrium constants was used to calculate deltaH(o) and deltaS(o) for the two processes. The value of deltaS(o) = -102 J mol(-1) K(-1) for the dissociation of contact ion pairs shows that the large entropy decrease due to cation solvation outweighs the entropy increase due to dissociation of a contact ion pair. Ionic mobilities are calculated in lithium triflate-diglyme solutions using conductivity data in conjunction with information about the nature and concentrations of solute species obtained from IR spectroscopy. Mobilities in tetrabutlyammonium triflate-diglyme solutions are calculated directly from conductivity data. It was concluded that the concentration dependence of the molar conductivity is due in large part to the variation of the ion mobilities with concentration.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. An alkalinizing oral rehydration solution containing lecithin-coated citrus fiber is superior to a nonalkalinizing solution in treating 360 calves with naturally acquired diarrhea.

    PubMed

    Goodell, G M; Campbell, J; Hoejvang-Nielsen, L; Stansen, W; Constable, P D

    2012-11-01

    The aim of this field study was to compare the efficacy and cost of 2 commercially available oral rehydration therapy (ORT) solutions in treating dairy calves with naturally acquired diarrhea. A total of 1,349 newborn Holstein-Friesian calves were prospectively enrolled in the study. Calves were housed in individual hutches and fed a mixture of pasteurized hospital milk and an all-milk protein milk replacer twice per day. Calves were monitored twice each day from d 2 of life until 30 d of age for the presence or absence of diarrhea, and were assigned a fecal score and a hydration score at each examination. Calves that developed mild to severe diarrhea that did not need intravenous fluids and did not have clinical evidence of concurrent disease (n = 360) were assigned randomly to receive 1 of 2 commercial ORT solutions: a hypertonic alkalinizing ORT containing lecithin-coated citrus fibers (Diaque, group D, n = 180; Boehringer Ingelheim, Ingelheim, Germany), and an isotonic nonalkalinizing ORT (RE-SORB, group R, n = 180; Pfizer Animal Health, New York, NY) for 2 to 8d; the duration of treatment depended on whether diarrhea was still present. No significant differences were observed in mortality rates or treatment failure rates between the 2 treatment groups. Fecal consistency returned to normal more quickly in group D calves than in group R calves; consequently, group D calves were treated for 1d less than were group R calves. The increase in body weight after 4d of treatment was larger in group D than in group R. The average daily gain from birth to weaning in calves that did not develop concurrent disease (such as pneumonia) during the study period tended to be higher in group D calves (0.53±0.11 kg/d) than in group R calves (0.51±0.09 kg/d). The smaller number of treatments at a lower cost per treatment produced a cost advantage of $4.82 per treated calf in group D calves compared with group R calves. Our findings support the concept that milk should continue

  8. 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.

  9. 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

  10. Excellent dynamic stability under saturated salt solution for aqueous quantum dots capped by multi-branched ligands

    NASA Astrophysics Data System (ADS)

    Xu, Jingkun; Xu, Shuhong; Lv, Changgui; Wang, Chunlei; Cui, Yiping

    2016-09-01

    Preparing quantum dots (QDs) with strong stability against salts is extremely important in some environments with ultrahigh salts concentration, such as the oil exploitation, wastewater treatment and biological markers. In this paper, we reported a simple new method to prepared highly stable QDs by using multi-branched ligands. Our results suggested that multi-branched ligands-capped QDs have extremely good dynamic stability even in salt-saturated solution. Unlike to traditional dynamic stability theory, which considers the electrostatic repulsion of QDs dominant QD stability, the current work found a new determined factor: the steric hindrance of ligand structure. The high steric hindrance effect of multi-branched ligands can maintain the single dispersity of QDs even at extremely low electrostatic repulsion. As a result, QDs with ultrahigh stability against salts can be realized.

  11. 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.

  12. 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.

  13. A quantitative assessment of the Nigerian mothers' ability to prepare salt-sugar solution for the home management of diarrhoea.

    PubMed

    Ekanem, E E; Akitoye, C O; Adedeji, O T; Salako, Q A

    1993-10-01

    This study aimed at assessing qualitatively and quantitatively the ability of Nigerian mothers to prepare salt-sugar solutions (SSS) (according to the Nigerian standard formula) under the usual home environment. Mothers were provided with the ingredients but not with measurement spoons nor containers. 274 mothers randomly selected from a peri-urban community participated in the study. Of the 192 (70.1%) who claimed knowledge on SSS preparation, only 47 (24.5%) gave a correct description of its constitution and 103 (54.2%) were willing to prepare the solution. Of the 103 who prepared the solution, 34 (33.0%) used the correct number of teaspoons of salt and of sugar. The composition of the solutions prepared by the mothers varied greatly with sodium levels ranging from 0-760 mmols/l (mean 225.8 +/- 155.3, median 177.3) and glucose, 0-262.6 mmols/l (mean 68.7 +/- 54.4, median 52.0). Only 7 mothers (6.8%) prepared solutions with acceptable sodium and glucose levels. It is concluded that salt-sugar solutions prepared by Nigerian mothers are not safe. There is a great need to review the oral rehydration therapy (ORT) promotion strategies and messages in order to avoid the dangers associated with improperly constituted solutions. PMID:8230075

  14. 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.

  15. 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)

  16. Comparison of the effect of hormones on the hormone synthesis of Tetrahymena in medium or salt solution.

    PubMed

    Csaba, G; Lajkó, Eszter; Pállinger, Eva

    2010-11-01

    Tetrahymena pyriformis was maintained in TYM (tryptone-yeast medium) as well as in Losina salt solution. One hour treatment of 10⁻¹⁵ M histamine, serotonin or insulin was given before the histamine, serotonin, triiodothyronine and adrenocorticotropin contents of the cells were measured by flow cytometry after immunocytochemical staining. Maintenance in salt solution increased the hormone level in the cells, and use of the treatment hormone treatments further increased the endogenous hormone content relative to that in medium. The cells in salt mimic better the natural conditions, which means that the effects of hormones under more natural conditions are expressed to a greater extent than the exogenously given hormones in TYM typically used under laboratory conditions. Intercellular hormonal communication between the cells of a Tetrahymena population might assist in the survival of the individual cells.

  17. 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.

  18. 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.

  19. On the feasibility of near infrared spectroscopy to detect contaminants in water using single salt solutions as model systems.

    PubMed

    Gowen, A A; Marini, F; Tsuchisaka, Y; De Luca, S; Bevilacqua, M; O'Donnell, C; Downey, G; Tsenkova, R

    2015-01-01

    This research work evaluates the feasibility of NIRS to detect contaminants in water using single salt solutions as model systems. Previous research has indicated the potential of near infrared spectroscopy (NIRS) for detecting solutes in water; however, a comprehensive investigation of the limit of detection of this technique has not been carried out. Near infrared transmittance spectra of aqueous salt solutions in the concentration range 0.002-0.1 mol L(-1) (equivalent to 117-13,334 ppm or 0.0001-0.01% mass/mass) were investigated. The first overtone region of the near infrared spectrum (1300-1600 nm) was found to be the most effective wavelength range for prediction of salt concentration in aqueous solutions. Calibration models built using this wavelength range and employing the extended multiplicative scatter spectral pre-treatment resulted in root mean squared error of prediction values ranging from 0.004 to 0.01 mol L(-1). The limit of detection (LOD) was estimated to be of the order of 0.1% (mass/mass) or 1000 ppm. Within the framework of Aquaphotomics, it was possible to examine the effect of different salts on the NIR spectra of water in the first overtone range. Our results were confirmed through test experiments at various geographical locations employing dispersive and Fourier transform type NIRS instruments.

  20. 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.

  1. 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

  2. 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.

  3. Molecular insights into shellac film coats from different aqueous shellac salt solutions and effect on disintegration of enteric-coated soft gelatin capsules.

    PubMed

    Al-Gousous, J; Penning, M; Langguth, P

    2015-04-30

    The purpose of this investigation was to study the effect of using different salts of shellac on the disintegration properties of shellac-based enteric coatings. In the last two decades, shellac has been increasingly used as an aqueous solution for enteric coating purposes, with the ammonium salt being the form typically used. Little investigation has been performed on using other salts, and therefore, this was the focus of our work. Enteric coatings, based on different shellac salts (ammonium, sodium, potassium and composite ammonium-sodium), were applied onto soft gelatin capsules. Disintegration testing of the coated soft gelatin capsules showed that alkali metal salts promote faster disintegration than ammonium salts. In order to determine the causes behind these differences, the solubility, thermal and spectroscopic properties of films cast from the different salts were investigated. The results show that films cast from ammonium-based salts of shellac are, unlike those cast from alkali metal-based salts, water-insoluble. Spectroscopic evidence suggests that this might be due to partial salt dissociation resulting in loss of ammonium as ammonia and reduced degree of shellac ionization during drying. In addition, oxidation of shellac aldehyde groups of the ammonium-based shellac salts could also play a role. And possible higher extent of shellac hydrolysis during the preparation of alkali metal salts might also be a factor. Therefore, the nature of the shellac salt used in the preparation of shellac-based aqueous coating solutions is a significant formulation factor affecting product performance. PMID:25578368

  4. 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.

  5. 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

  6. Diclofenac Salts, VIII. Effect of the Counterions on the Permeation through Porcine Membrane from Aqueous Saturated Solutions

    PubMed Central

    Fini, Adamo; Bassini, Glenda; Monastero, Annamaria; Cavallari, Cristina

    2012-01-01

    The following bases: monoethylamine (EtA), diethylamine (DEtA), triethylamine (TEtA), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), pyrrolidine (Py), piperidine (Pp), morpholine (M), piperazine (Pz) and their N-2-hydroxyethyl (HE) analogs were employed to prepare 14 diclofenac salts. The salts were re-crystallized from water in order to obtain forms that are stable in the presence of water. Vertical Franz-type cells with a diffusional surface area of 9.62 cm2 were used to study the permeation of these diclofenac salts from their saturated solutions through an internal pig ear membrane. The receptor compartments of the cells contained 100 mL of phosphate buffer (pH 7.4); a saturated solution (5 mL) of each salt was placed in the donor compartment, thermostated at 37 °C. Aliquots were withdrawn at predetermined time intervals over 8 h and then immediately analyzed by HPLC. Fluxes were determined by plotting the permeated amount, normalized for the membrane surface area versus time. Permeation coefficients were obtained dividing the flux values J by the concentration of the releasing phase—that is, water solubility of each salt. Experimental results show that fluxes could be measured when diclofenac salts with aliphatic amines are released from a saturated aqueous solution. Different chemical species (acid, anion, ion pairs) contribute to permeation of the anti-inflammatory agent even though ion-pairs could be hypothesized to operate to a greater extent. Permeation coefficients were found higher when the counterion contains a ring; while hydroxy groups alone do not appear to play an important role, the ring could sustain permeation, disrupting the organized domains of the membrane. PMID:24300300

  7. Survival of Bifidobacterium longum immobilized in calcium alginate beads in simulated gastric juices and bile salt solution.

    PubMed

    Lee, K Y; Heo, T R

    2000-02-01

    Bifidobacterium longum KCTC 3128 and HLC 3742 were independently immobilized (entrapped) in calcium alginate beads containing 2, 3, and 4% sodium alginate. When the bifidobacteria entrapped in calcium alginate beads were exposed to simulated gastric juices and a bile salt solution, the death rate of the cells in the beads decreased proportionally with an increase in both the alginate gel concentration and bead size. The initial cell numbers in the beads affected the numbers of survivors after exposure to these solutions; however, the death rates of the viable cells were not affected. Accordingly, a mathematical model was formulated which expressed the influences of several parameters (gel concentration, bead size, and initial cell numbers) on the survival of entrapped bifidobacteria after sequential exposure to simulated gastric juices followed by a bile salt solution. The model proposed in this paper may be useful for estimating the survival of bifidobacteria in beads and establishing optimal entrapment conditions.

  8. Water-Insoluble Surface Coatings of Polyion-Surfactant Ion Complex Salts Respond to Additives in a Surrounding Aqueous Solution.

    PubMed

    Gustavsson, Charlotte; Obiols-Rabasa, Marc; Piculell, Lennart

    2015-06-16

    Hydrated, but water-insoluble, "complex salts" (CS) composed of alkyltrimethylammonium surfactant ions with polyacrylate counterions are known to exhibit a rich phase behavior in bulk mixtures with water and have recently been shown to act as water-responsive surface coatings. Here it is shown, by SAXS measurements, that surface coatings of CS also respond to various added solutes in a surrounding aqueous solution, by altering their liquid crystalline structure. The obtained results provide new information on the phase behavior of CS in contact with water and aqueous solutions. Solutes such as acids, salts, excess ionic surfactant, or water-soluble polymers act on the CS by altering the polyion charge density, screening the electrostatic interaction, changing the curvature of the surfactant aggregate, or increasing the osmotic pressuring in the surrounding solution, all of which may result in a phase transition in the film. In water, all studied CS surface coatings had a micellar cubic structure, which could change to 2D hexagonal, HCP, or disordered micellar structure, depending on the identity of the CS and the identity and concentration of the added solute. For some systems, even dissolved CO2 from the ambient air was sufficient to induce a structural change in the film. Especially the films containing the long polyions remained intact even for large concentrations of solutes in the contacting solutions, and extensive washing in water resulted, in most cases, in films with the "original" structure found in water. PMID:26017683

  9. 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

  10. 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

  11. 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.

  12. Salting-Out of Methane in the Aqueous Solutions of Urea and Glycine-Betaine.

    PubMed

    Dixit, Mayank Kumar; Siddique, Asrar A; Tembe, B L

    2015-08-27

    We have studied the hydrophobic association and solvation of methane molecules in aqueous solutions of urea and glycine betaine (GB). We have calculated the potentials of mean force (PMFs) between methane molecules in water, aqueous GB, aqueous urea and aqueous urea-GB mixtures. The PMFs and equilibrium constants indicate that both urea and GB increase the hydrophobic association of methane. Calculation of thermodynamic parameters shows that the association of methane is stabilized by entropy whereas solvation is favored by enthalpy. In the case of the water-urea-GB mixture, both hydrophobic association and solvation are stabilized by entropy. From the investigation of radial distribution functions, running coordination numbers and excess coordination numbers, we infer that both urea and GB are preferentially excluded from methane surface in the mixtures of osmolytes and methane is preferentially solvated by water molecules in all the mixtures. The favorable exclusion of both urea and GB from the methane surface suggests that both urea and GB increase the interaction between methane molecules, i.e., salting-out of methane. We observe that addition of both urea and GB to water enhances local water structure. The calculated values of diffusion constants of water also suggest enhanced water-water interactions in the presence of urea and GB. The calculated free energies of methane in these mixtures show that methane is less soluble in the mixtures of urea and GB than in water. The data on solvation free energies support the observations obtained from the PMFs of methane molecules.

  13. 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.

  14. The structure and terahertz dynamics of water confined in nanoscale pools in salt solutions.

    PubMed

    Turton, David A; Corsaro, Carmelo; Candelaresi, Marco; Brownlie, Angela; Seddon, Ken R; Mallamace, Francesco; Wynne, Klaas

    2011-01-01

    The behaviour of liquid water below its melting point is of great interest as it may hold clues to the properties of normal liquid water and of water in and on the surfaces of biomolecules. A second critical point, giving rise to a polyamorphic transition between high and low density water, may be hidden in the supercooled region but cannot be observed directly. Here it is shown that water can be locked up in nano-pools or worm-like structures using aqueous LiCl salt solutions and can be studied with terahertz spectroscopies. Very high dynamic range ultrafast femtosecond optical Kerr effect (OKE) spectroscopy is used to study the temperature-dependent behaviour of water in these nano-pools on timescales from 10 fs to 4 ns. These experiments are complemented by temperature-dependent nuclear magnetic resonance (NMR) diffusion measurements, concentration-dependent Fourier-transform infrared (FTIR) measurements, and temperature-dependent rheology. It is found that liquid water in the nanoscale pools undergoes a fragile-to-strong transition at about 220 K associated with a sharp increase in the inhomogeneity of translational dynamics.

  15. 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.

  16. Simple theoretical model for ion cooperativity in aqueous solutions of simple inorganic salts and its effect on water surface tension.

    PubMed

    Gao, Yi Qin

    2011-11-01

    Careful analysis of experimental data showed that the salt aqueous solution/air surface tension depends on a rather complicated manner of salt composition and points to the importance of ion cooperativity. In this short article, we include the selective binding of anions over cations at interfaces (as revealed from molecular dynamics simulations, spectroscopic measurements, and Record's analysis of the surface tension data) and the anion-cation association (based on the observation of matching water affinity) in a simple theoretical model to understand salt effects on surface tension. The introduction of the surface effect and ion association provides a qualitative explanation of the experimental data, in particular, the strong anion dependence of the cations' rank according to their ability of increasing water surface tension. We hope that the physical insight provided by this study can be used to point to new directions for more detailed studies. PMID:21958050

  17. 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.

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

    Yanosky, Thomas M.; Kappel, William M.

    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.

  8. 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.

  9. A solution for cesium removal from high-salinity acidic or alkaline liquid waste: The crown calix[4]arenes

    SciTech Connect

    Dozol, J.F.; Simon, N.; Lamare, V.; Rouquette, H.; Eymard, S.; Tournois, B.; Marc, D. de; Macias, R.M.

    1999-04-01

    Calix[4]arenes monocrown or biscrown, blocked in 1,3 alternative cone conformation, display an exceptional efficiency for cesium extraction, even from very acid or alkaline media. Moreover, they possess an important selectivity for cesium over sodium that makes possible the extraction of cesium from media containing high sodium nitrate loadings. Another advantage, since the extraction of cesium is reversible, is that the stripping of cesium can be carried out in deionized water, a property which leads to very high concentration factors. 79 refs., 10 figs., 6 tabs.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Photochemical aerobic detoxification of aqueous phenol and chlorophenol solutions promoted by iron salts and iron, vanadium, and copper oxides

    SciTech Connect

    Nizova, G.V.; Bochkova, M.M.; Kozlova, N.B.; Shul`pin, G.B.

    1995-09-10

    Phenol, 2,4,5-trichlorophenol, and pentachlorophenol in air in the presence of soluble iron salts or insoluble V{sub 2}O{sub 5}, Fe{sub 2}O{sub 3}, and CuO decompose in aqueous solution when irradiated by a luminescent lamp. The degree and the rate of decomposition are strongly influenced by the nature of the substrate and metal-containing promoter. As a result of decomposition, toxicity of solutions containing 2,4,5-trichlorophenol with respect to two types of living organisms - Protozoa (Tetrahymena pyriformis) and bacteria (Beneckea harveyi) - decreases significantly.

  15. 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

  16. [Aqueous and salt solutions of quinine of low concentrations: self-organization, physicochemical properties and actions on the electrical characteristics of neurons].

    PubMed

    Murtazina, L I; Ryzhkina, I S; Mishina, O A; Andrianov, V V; Bogodvid, T Kh; Gaĭnutdinov, Kh L; Muranova, L N; Konovalov, A I

    2014-01-01

    Self-organization, the physicochemical properties of aqueous and salt solutions of quinine and the effects of salt quinine solutions in a wide range of concentrations (1 x 10(-22) - 1 x 10(-3) M) on the electrical characteristics of the edible snail's identified neurons were studied. Similar non-monotonic concentration dependencies of physicochemical properties of aqueous and salt quinine solutions at low concentrations are obtained. This allows of predicting the occurrence of biological effects at low concentrations of quinine solutions. Intrinsic (within 5% of the interval) changes in membrane potential, the amplitude and duration of the neuron action potential under the influence of quinine salt solutions at concentrations of quinine of 1 x 10(-20), 1 x 10(-18), 1 x 10(-10) M are found. For these concentrations the extreme values of specific conductivity and pH are shown.

  17. Glyoxal and Methylglyoxal Setschenow Salting Constants in Sulfate, Nitrate, and Chloride Solutions: Measurements and Gibbs Energies.

    PubMed

    Waxman, Eleanor M; Elm, Jonas; Kurtén, Theo; Mikkelsen, Kurt V; Ziemann, Paul J; Volkamer, Rainer

    2015-10-01

    Knowledge about Setschenow salting constants, KS, the exponential dependence of Henry's Law coefficients on salt concentration, is of particular importance to predict secondary organic aerosol (SOA) formation from soluble species in atmospheric waters with high salt concentrations, such as aerosols. We have measured KS of glyoxal and methylglyoxal for the atmospherically relevant salts (NH4)2SO4, NH4NO3, NaNO3, and NaCl and find that glyoxal consistently "salts-in" (KS of -0.16, -0.06, -0.065, -0.1 molality(-1), respectively) while methylglyoxal "salts-out" (KS of +0.16, +0.075, +0.02, +0.06 molality(-1)). We show that KS values for different salts are additive and present an equation for use in atmospheric models. Additionally, we have performed a series of quantum chemical calculations to determine the interactions between glyoxal/methylglyoxal monohydrate with Cl(-), NO3(-), SO4(2-), Na(+), and NH4(+) and find Gibbs free energies of water displacement of -10.9, -22.0, -22.9, 2.09, and 1.2 kJ/mol for glyoxal monohydrate and -3.1, -10.3, -7.91, 6.11, and 1.6 kJ/mol for methylglyoxal monohydrate with uncertainties of 8 kJ/mol. The quantum chemical calculations support that SO4(2-), NO3(-), and Cl(-) modify partitioning, while cations do not. Other factors such as ion charge or partitioning volume effects likely need to be considered to fully explain salting effects. PMID:26335375

  18. Glyoxal and Methylglyoxal Setschenow Salting Constants in Sulfate, Nitrate, and Chloride Solutions: Measurements and Gibbs Energies.

    PubMed

    Waxman, Eleanor M; Elm, Jonas; Kurtén, Theo; Mikkelsen, Kurt V; Ziemann, Paul J; Volkamer, Rainer

    2015-10-01

    Knowledge about Setschenow salting constants, KS, the exponential dependence of Henry's Law coefficients on salt concentration, is of particular importance to predict secondary organic aerosol (SOA) formation from soluble species in atmospheric waters with high salt concentrations, such as aerosols. We have measured KS of glyoxal and methylglyoxal for the atmospherically relevant salts (NH4)2SO4, NH4NO3, NaNO3, and NaCl and find that glyoxal consistently "salts-in" (KS of -0.16, -0.06, -0.065, -0.1 molality(-1), respectively) while methylglyoxal "salts-out" (KS of +0.16, +0.075, +0.02, +0.06 molality(-1)). We show that KS values for different salts are additive and present an equation for use in atmospheric models. Additionally, we have performed a series of quantum chemical calculations to determine the interactions between glyoxal/methylglyoxal monohydrate with Cl(-), NO3(-), SO4(2-), Na(+), and NH4(+) and find Gibbs free energies of water displacement of -10.9, -22.0, -22.9, 2.09, and 1.2 kJ/mol for glyoxal monohydrate and -3.1, -10.3, -7.91, 6.11, and 1.6 kJ/mol for methylglyoxal monohydrate with uncertainties of 8 kJ/mol. The quantum chemical calculations support that SO4(2-), NO3(-), and Cl(-) modify partitioning, while cations do not. Other factors such as ion charge or partitioning volume effects likely need to be considered to fully explain salting effects.

  19. A study on lithium/air secondary batteries-Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions

    NASA Astrophysics Data System (ADS)

    Shimonishi, Yuta; Zhang, Tao; Imanishi, Nobuyuki; Im, Dongmin; Lee, Dong Joon; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu; Sammes, Nigel

    The stability of the high lithium ion conducting glass ceramics, Li 1+ x+ yTi 2- xAl xSi yP 3- yO 12 (LTAP) in alkaline aqueous solutions with and without LiCl has been examined. A significant conductivity decrease of the LTAP plate immersed in 0.057 M LiOH aqueous solution at 50 °C for 3 weeks was observed. However, no conductivity change of the LTAP plate immersed in LiCl saturated LiOH aqueous solutions at 50 °C for 3 weeks was observed. The pH value of the LiCl-LiOH-H 2O solution with saturated LiCl was in a range of 7-9. The molarity of LiOH and LiCl in the LiOH and LiCl saturated aqueous solution were estimated to be 5.12 and 11.57 M, respectively, by analysis of Li + and OH -. The high concentration of LiOH and the low pH value of 8.14 in this solution suggested that the dissociation of LiOH into Li + and OH - is too low in the solution with a high concentration of Li +. These results suggest that the water stable LTAP could be used as a protect layer of the lithium metal anode in the lithium/air cell with LiCl saturated aqueous solution as the electrolyte, because the content of OH - ions in the LiCl saturated aqueous solution does not increase via the cell reaction of Li + 1/2O 2 + H 2O → 2LiOH, and LTAP is stable under a deep discharge state.

  20. Mixtures of lecithin and bile salt can form highly viscous wormlike micellar solutions in water.

    PubMed

    Cheng, Chih-Yang; Oh, Hyuntaek; Wang, Ting-Yu; Raghavan, Srinivasa R; Tung, Shih-Huang

    2014-09-01

    The self-assembly of biological surfactants in water is an important topic for study because of its relevance to physiological processes. Two common types of biosurfactants are lecithin (phosphatidylcholine) and bile salts, which are both present in bile and involved in digestion. Previous studies on lecithin-bile salt mixtures have reported the formation of short, rodlike micelles. Here, we show that lecithin-bile salt micelles can be further induced to grow into long, flexible wormlike structures. The formation of long worms and their resultant entanglement into transient networks is reflected in the rheology: the fluids become viscoelastic and exhibit Maxwellian behavior, and their zero-shear viscosity can be up to a 1000-fold higher than that of water. The presence of worms is further confirmed by data from small-angle neutron and X-ray scattering and from cryo-transmission electron microscopy (cryo-TEM). We find that micellar growth peaks at a specific molar ratio (near equimolar) of bile salt:lecithin, which suggests a strong binding interaction between the two species. In addition, micellar growth also requires a sufficient concentration of background electrolyte such as NaCl or sodium citrate that serves to screen the electrostatic repulsion of the amphiphiles and to "salt out" the amphiphiles. We postulate a mechanism based on changes in the molecular geometry caused by bile salts and electrolytes to explain the micellar growth.

  1. 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.

  2. 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

  3. Urothelial injury to the rabbit bladder from various alkaline and acidic solutions used to dissolve kidney stones.

    PubMed

    Reckler, J; Rodman, J S; Jacobs, D; Rotterdam, H; Marion, D; Vaughan, E D

    1986-07-01

    Different irrigating solutions are used clinically to dissolve uric acid, cystine and struvite stones. These studies were undertaken to assess the toxicity to the rabbit bladder epithelium of several commonly used formulations. Test solutions were infused antegrade through a left ureterotomy overnight. Bladders were removed and routine histological sections made. A pH 7.6 solution of NaHCO3 appeared harmless. The same solution with two per cent acetylcysteine produced slight injury. All pH 4 solutions caused significant damage to the urothelium. Hemiacidrin, which contains magnesium, produced less damage than did other pH 4 solutions without that cation. Our data tend to support Suby's conclusions that addition of magnesium reduces urothelial injury even though the presence of magnesium will slow dissolution of struvite.

  4. 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

  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. Thermoresponsive Poly(Ionic Liquid)s in Aqueous Salt Solutions: Salting-Out Effect on Their Phase Behavior and Water Absorption/Desorption Properties.

    PubMed

    Okafuji, Akiyoshi; Kohno, Yuki; Ohno, Hiroyuki

    2016-07-01

    Here, a thermoresponsive phase behavior of polymerized ionic liquids (PILs) composed of poly([tri-n-alkyl(vinylbenzyl)phosphonium]chloride) (poly([Pnnn VB ]Cl) is reported, where n (the number of carbon atoms of an alkyl chain) = 4, 5, or 6 after mixing with aqueous sodium chloride solutions. Both monomeric [P555VB ]Cl and the resulting poly([P555VB ]Cl) linear homopolymer show a lower critical solution temperature (LCST)-type phase behavior in aq. NaCl solutions. The phase transition temperature of the PIL shifts to lower value by increasing concentration of NaCl. Also the swelling degree of cross-linked poly([P555VB ]Cl) gel decreases by increasing NaCl concentration, clearly suggesting the "salting-out" effect of NaCl results in a significant dehydration of the poly([P555VB ]Cl) gel. The absorbed water in the PIL gel is desorbed by moderate heating via the LCST behavior, and the absolute absorption/desorption amount is improved by copolymerization of [P555VB ]Cl with more hydrophilic [P444VB ]Cl monomer.

  7. Thermoresponsive Poly(Ionic Liquid)s in Aqueous Salt Solutions: Salting-Out Effect on Their Phase Behavior and Water Absorption/Desorption Properties.

    PubMed

    Okafuji, Akiyoshi; Kohno, Yuki; Ohno, Hiroyuki

    2016-07-01

    Here, a thermoresponsive phase behavior of polymerized ionic liquids (PILs) composed of poly([tri-n-alkyl(vinylbenzyl)phosphonium]chloride) (poly([Pnnn VB ]Cl) is reported, where n (the number of carbon atoms of an alkyl chain) = 4, 5, or 6 after mixing with aqueous sodium chloride solutions. Both monomeric [P555VB ]Cl and the resulting poly([P555VB ]Cl) linear homopolymer show a lower critical solution temperature (LCST)-type phase behavior in aq. NaCl solutions. The phase transition temperature of the PIL shifts to lower value by increasing concentration of NaCl. Also the swelling degree of cross-linked poly([P555VB ]Cl) gel decreases by increasing NaCl concentration, clearly suggesting the "salting-out" effect of NaCl results in a significant dehydration of the poly([P555VB ]Cl) gel. The absorbed water in the PIL gel is desorbed by moderate heating via the LCST behavior, and the absolute absorption/desorption amount is improved by copolymerization of [P555VB ]Cl with more hydrophilic [P444VB ]Cl monomer. PMID:26987760

  8. 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.

  9. Modulating the structure and properties of poly(sodium 4-styrenesulfonate)/poly(diallyldimethylammonium chloride) multilayers with concentrated salt solutions.

    PubMed

    Han, Lulu; Mao, Zhengwei; Wuliyasu, He; Wu, Jindan; Gong, Xiao; Yang, Yuguang; Gao, Changyou

    2012-01-10

    Poly(sodium 4-styrenesulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) multilayers were treated with 1-5 M NaCl solutions, resulting in continuous changes in the physicochemical properties of the multilayers. Significant mass loss was observed when the salt concentration was higher than 2 M and reached as high as 72% in a 5 M NaCl solution. The disassembly occurred initially in the superficial layers and then developed in the bulk multilayers. For the multilayers with PDADMAC as the outmost layer, the molar ratio of PSS/PDADMAC was increased and the surface chemistry was changed from PDADMAC domination below 2 M NaCl to PSS domination above 3 M NaCl. Owing to the higher concentrations of uncompensated for polyelectrolytes at both lower and higher salt concentrations, the swelling ratio of the multilayers was decreased until reaching 3 M NaCl and then was increased significantly again. The salt-treated PSS/PDADMAC thin films are expected to show different behaviors in terms of the physical adsorption of various functional substances, cell adhesion and proliferation, and chemical reaction activity.

  10. 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

  11. 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

  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. 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.

  14. 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

  15. 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.

  16. Amino-functionalized alkaline clay with cationic star-shaped polymer as adsorbents for removal of Cr(VI) in aqueous solution

    NASA Astrophysics Data System (ADS)

    Pan, Yuanfeng; Cai, Pingxiong; Farmahini-Farahani, Madjid; Li, Yiduo; Hou, Xiaobang; Xiao, Huining

    2016-11-01

    Pentaerythritol (PER) was esterified with 2-bromoisobutyryl bromide to synthesize a four-arm initiator 4Br-PER for atom transfer radical polymerization (ATRP). Star-shaped copolymers (P(AM-co-DMAEMA)4, CSP) were prepared via ATRP using dimethyl aminoethyl methacrylate (DMAEMA) and acrylamide (AM) as comonomers, while Br-PER and CuBr/2,2‧-bipyridine (BPY) as the initiator and the catalyst, respectively. The resulting four-arm initiator and star-shaped polymer (CSP) were characterized with FT-IR, 1H NMR and Ubbelohde viscometry. Alkaline clay (AC) was immobilized with CSPs to yield amino groups, and the cationic star polymer-immobilized alkaline clay (CSP-AC) was applied to remove Cr(VI) from the aqueous solution in batch experiments. Various influencing factors, including pH, contact time and immobilization amount of CSP on adsorption capacity of CSP-AC for Cr(VI) were also investigated. The results demonstrated that Cr(VI) adsorption was highly pH dependent. The optimized pH value was 4.0. The adsorption isotherms of the adsorbent fit the Langmuir model well, with the maximum adsorption capacity of 137.9 mg/g at 30 °C. The material should be a promising adsorbent for Cr(VI) removal, with the advantages of high adsorption capacity.

  17. On the vibrational behaviour of cyanide adsorbed at Pt(1 1 1) and Pt(1 0 0) surfaces in alkaline solutions

    NASA Astrophysics Data System (ADS)

    Huerta, F.; Montilla, F.; Morallón, E.; Vázquez, J. L.

    2006-03-01

    This communication deals with the vibrational behaviour of cyanide adlayers formed on Pt(1 1 1) and Pt(1 0 0) surfaces in the electrochemical environment. In situ FTIR spectroscopy can be employed to follow the potential dependence of the C-N stretching frequency in acidic electrolytes with quite a low uncertainty. Owing to the stability of the cyanide adlayer in alkaline solutions, experiments performed in NaOH medium are usually perturbed by the significant overlapping of the reference and the sample FTIR spectra. Deconvolution of the spectra was carried out assuming a Lorentz oscillator. The procedure allowed to confirm that two potential regions with different band centre frequency tuning coexist for Pt(1 1 1)-CN in perchloric acid medium. Conversely, in the alkaline electrolyte a single tuning rate for the band position was found for both surfaces studied. The lack of reorientation of the C-N molecular axis together with the occurrence of a certain screening effect of negatively charged hydroxyl anions on the electric field at the interface could be at the origin of the different behaviour displayed in both electrolytic media.

  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. Comparison of soymilk, powdered milk, Hank's balanced salt solution and tap water on periodontal ligament cell survival.

    PubMed

    Moazami, Fariborz; Mirhadi, Hosein; Geramizadeh, Bita; Sahebi, Safoura

    2012-04-01

    The purpose of this study was to evaluate the ability of soymilk, powdered milk, and Hank's balanced salt solution (HBSS) to maintain human periodontal ligament (PDL) cell viability in vitro. PDL cells were obtained from extracted healthy third molars and cultured in Dulbecco's modified Eagles medium (DMEM). The cultures were exposed for 1, 2, 4, and 8 h to experimental solutions (tap water served as negative control and DMEM as positive control) at 37°C. The viable cells were then counted using the trypan blue exclusion technique. Data were analyzed by using one-way anova, post hoc Scheffe and two-way anova test. Statistical analysis showed that HBSS, powdered baby formula, and soymilk maintain cell viability equally well in different periods of times. Tap water cannot keep cells viable as well as other solutions. Soymilk and powdered baby formula can be recommended as suitable storage media for avulsed teeth for up to 8 h.

  20. 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

  1. Prediction of the concentration dependence of the surface tension and density of salt solutions: atomistic simulations using Drude oscillator polarizable and nonpolarizable models.

    PubMed

    Neyt, Jean-Claude; Wender, Aurélie; Lachet, Véronique; Ghoufi, Aziz; Malfreyt, Patrice

    2013-07-28

    Molecular simulations using Drude oscillator polarizable and nonpolarizable models for water and ions are carried out to predict the dependence of the surface tension on salt concentration. The polarizable water and ion models are based only on the classical Drude oscillators. The temperature dependence of the surface tension of water is examined for different water models. The dependence of salt densities on salt concentration is investigated through the nonpolarizable and Drude oscillator polarizable models. Finally, the reproduction of the surface tension of salt solution over a large range of concentrations is analyzed through a number of combinations between ions and water force fields. The structure of the interface is then discussed as a function of polarization effects. We establish here the inability of the Drude oscillator polarizable force fields to reproduce the salt concentration dependence of surface tension of NaCl aqueous solutions.

  2. Synthesis and crystal structure solution of potassium dawsonite: An intermediate compound in the alkaline hydrolysis of calcium aluminate cements

    SciTech Connect

    Fernandez-Carrasco, L.; Puertas, F.; Blanco-Varela, M.T.; Vazquez, T.; Rius, J

    2005-04-01

    Potassium dawsonite is formed as an intermediate compound during the alkaline hydrolysis (AH) in calcium aluminate cements (CACs). A synthesis method of potassium dawsonite has been developed. The crystal structure of potassium dawsonite KAl(CO{sub 3})(OH){sub 2} has been solved by direct methods from X-ray powder diffraction data and refined with the Rietveld method. It crystallises in the orthorhombic Cmcm space group with unit cells parameters a=6.3021(3) A, b=11.9626(5) A, c=5.6456(3) A and Z=4. The structure consists of carboaluminate chains, formed by the basic unit [Al{sub 2}(OH){sub 4}(CO{sub 3}){sub 2}]{sup 2-} arranged along the c axis. The carbonate groups are placed in an alternate manner at both sides of the carboaluminate chains. The carboaluminate chains are also held together by the K{sup +} cations that are located in the middle of three such chains. Finally, the chemical reactions explaining the AH process in CACs are postulated.

  3. 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

  4. 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.

  5. Analysis of corrosion data for carbon steels in simulated salt repository brines and acid chloride solutions at high temperatures

    SciTech Connect

    Diercks, D.R.; Hull, A.B.; Kassner, T.F.

    1988-03-01

    Carbon steel is currently the leading candidate material for fabrication of a container for isolation of high level nuclear waste in a salt repository. Since brine entrapped in the bedded salt can migrate to the container by several transport processes, corrosion is an important consideration in the long-term performance of the waste package. A detailed literature search was performed to compile relevant corrosion data for carbon steels in anoxic acid chloride solutions, and simulated salt repository brines at temperatures between approx. 20 and 400/sup 0/C. The hydrolysis of Mg/sup 2 +/ ions in simulated repository brines containing high magnesium concentrations causes acidification at temperatures above 25/sup 0/C, which, in turn, influences the protective nature of the magnetite corrosion product layer on carbon steel. The corrosion data for the steels were analyzed, and an analytical model for general corrosion was developed to calculate the amount of penetration (i.e., wall thinning) as a function of time, temperature, and the pressure of corrosion product hydrogen than can build up during exposure in a closed system (e.g., a sealed capsule). Both the temperature and pressure dependence of the corrosion rate of steels in anoxic acid chloride solutions indicate that the rate-controlling partial reaction is the cathodic reduction of water to form hydrogen. Variations in the composition and microstructure of the steels or the concentration of the ionic species in the chloride solutions (provided that they do not change the pH significantly) do not appear to strongly influence the corrosion rate.

  6. 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.

  7. 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.

  8. 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.

  9. Selective colorimetric determination of TNT partitioned between an alkaline solution and a strongly basic Dowex 1-X8 anion exchanger.

    PubMed

    Uzer, Ayşem; Erçağ, Erol; Apak, Reşat

    2008-01-30

    The Meisenheimer anions formed from TNT in KOH solutions in alcohol or acetone were used in screening tests for TNT among possible nitro-explosives. The same reaction was used for the spectrophotometric assay of TNT in soil by CRREL (Cold Regions Research & Engineering Laboratory of the U.S. Army) method, also known as Jenkins' method, but the color stability was too dependent on the solution composition and the water tolerance was low, necessitating complete drying of soil samples (which may cause partial analyte decomposition) prior to analysis. This study reports the development of a colorimetric method based on the solid phase extraction (SPE) of the Meisenheimer anion formed from TNT and aqueous NaOH into a strongly basic anion exchange resin Dowex 1-X8 (OH(-) form). The orange-red color that developed both in the solid resin and solution phases was persistent for at least 1h. The resin was let to swell in alcohol, washed first with 1M aqueous NaOH, and then with H(2)O before use. To 5 mL of 4-400 ppm TNT solutions in 1:1 (v/v) acetone-water, 0.5 mL of 5% NaOH was added, diluted to 50 mL with 1:1 acetone-water, and the resulting solutions (containing the orange-red Meisenheimer anion of TNT) were agitated at room temperature with 0.9 g resin for < or =50 min. TNT exhibited a reasonably constant distribution coefficient between the resin and aqueous phases. The absorbance of the filtered solutions was measured against a reagent blank at 500nm. The TNT-loaded resins were regenerated with 1M HCl containing sodium sulfite. The calibration line of filtrate absorbance versus analytical concentration was linear over two orders of magnitude between 0.4 and 40 ppm TNT in final solution. Unlike Jenkins' method, the method was tolerant to 100-fold (by mass) of common soil anions like sulfate, nitrate, and chloride. The basic advantages of the developed colorimetric method over the similar CRREL/Jenkins' method may be summarized as color stability, water and common ion

  10. Selective colorimetric determination of TNT partitioned between an alkaline solution and a strongly basic Dowex 1-X8 anion exchanger.

    PubMed

    Uzer, Ayşem; Erçağ, Erol; Apak, Reşat

    2008-01-30

    The Meisenheimer anions formed from TNT in KOH solutions in alcohol or acetone were used in screening tests for TNT among possible nitro-explosives. The same reaction was used for the spectrophotometric assay of TNT in soil by CRREL (Cold Regions Research & Engineering Laboratory of the U.S. Army) method, also known as Jenkins' method, but the color stability was too dependent on the solution composition and the water tolerance was low, necessitating complete drying of soil samples (which may cause partial analyte decomposition) prior to analysis. This study reports the development of a colorimetric method based on the solid phase extraction (SPE) of the Meisenheimer anion formed from TNT and aqueous NaOH into a strongly basic anion exchange resin Dowex 1-X8 (OH(-) form). The orange-red color that developed both in the solid resin and solution phases was persistent for at least 1h. The resin was let to swell in alcohol, washed first with 1M aqueous NaOH, and then with H(2)O before use. To 5 mL of 4-400 ppm TNT solutions in 1:1 (v/v) acetone-water, 0.5 mL of 5% NaOH was added, diluted to 50 mL with 1:1 acetone-water, and the resulting solutions (containing the orange-red Meisenheimer anion of TNT) were agitated at room temperature with 0.9 g resin for < or =50 min. TNT exhibited a reasonably constant distribution coefficient between the resin and aqueous phases. The absorbance of the filtered solutions was measured against a reagent blank at 500nm. The TNT-loaded resins were regenerated with 1M HCl containing sodium sulfite. The calibration line of filtrate absorbance versus analytical concentration was linear over two orders of magnitude between 0.4 and 40 ppm TNT in final solution. Unlike Jenkins' method, the method was tolerant to 100-fold (by mass) of common soil anions like sulfate, nitrate, and chloride. The basic advantages of the developed colorimetric method over the similar CRREL/Jenkins' method may be summarized as color stability, water and common ion

  11. Salting effects on protein components in aqueous NaCl and urea solutions: toward understanding of urea-induced protein denaturation.

    PubMed

    Li, Weifeng; Zhou, Ruhong; Mu, Yuguang

    2012-02-01

    The mechanism of urea-induced protein denaturation is explored through studying the salting effect of urea on 14 amino acid side chain analogues, and N-methylacetamide (NMA) which mimics the protein backbone. The solvation free energies of the 15 molecules were calculated in pure water, aqueous urea, and NaCl solutions. Our results show that NaCl displays strong capability to salt out all 15 molecules, while urea facilitates the solvation (salting-in) of all the 15 molecules on the other hand. The salting effect is found to be largely enthalpy-driven for both NaCl and urea. Our observations can explain the higher stability of protein's secondary and tertiary structures in typical salt solutions than that in pure water. Meanwhile, urea's capability to better solvate protein backbone and side-chain components can be extrapolated to explain protein's denaturation in aqueous urea solution. Urea salts in molecules through direct binding to solute surface, and the strength is linearly dependent on the number of heavy atoms of solute molecules. The van der Waals interactions are found to be the dominant force, which challenges a hydrogen-bonding-driven mechanism proposed previously.

  12. 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.

  13. Electrokinetic charging and evidence for charge evaporation in liquid microjets of aqueous salt solution.

    PubMed

    Preissler, Natalie; Buchner, Franziska; Schultz, Thomas; Lübcke, Andrea

    2013-02-28

    Electrokinetic charging of aqueous microjets was characterized by measuring streaming currents as a function of sodium iodide salt concentration. Measured streaming currents at high salt concentrations (up to 0.5 M) varied nonmonotonically with the jet velocity and can be explained by a multipolar charge distribution at the nozzle-water interface. In the case of potassium fluoride no multipolar charge distribution is observed. Electrokinetic potentials were estimated from the streaming currents, under the assumption that all excess charges are confined within the liquid jet. Measured photoelectron spectra indicate much smaller streaming potentials. To resolve the apparent discrepancy, we propose that a significant fraction of excess charges evaporates in the form of ion-water clusters. PMID:23330711

  14. 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.

  15. 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.

  16. Effect of salts and organic additives on the solubility of proteins in aqueous solutions.

    PubMed

    Ruckenstein, Eli; Shulgin, Ivan L

    2006-11-16

    The goal of this review is to examine the effect of salts and organic additives on the solubility of proteins in aqueous mixed solvents. The focus is on the correlation between the aqueous protein solubility and the osmotic second virial coefficient or the preferential binding parameter. First, several approaches which connect the solubility and the osmotic second virial coefficient are presented. Most of the experimental and theoretical results correlate the solubility and the osmotic second virial coefficient in the presence of salts. The correlation of the aqueous protein solubility with the osmotic second virial coefficient when the cosolvent is an organic component requires additional research. Second, the aqueous protein solubility is correlated with the preferential binding parameter on the basis of a theory developed by the authors of the present review. This theory can predict (i) the salting-in or -out effect of a cosolvent and (ii) the initial slope of the solubility curve. Good agreement was obtained between theoretical predictions and experimental results.

  17. Bupivacaine salts of diflunisal and other aromatic hydroxycarboxylic acids: aqueous solubility and release characteristics from solutions and suspensions using a rotating dialysis cell model.

    PubMed

    Østergaard, Jesper; Larsen, Susan W; Parshad, Henrik; Larsen, Claus

    2005-11-01

    In the search for poorly soluble bupivacaine salts potentially enabling prolonged postoperative pain relief after local joint administration in the form of suspensions the solubility of bupivacaine salts of diflunisal and other aromatic hydroxycarboxylic acids were investigated together with the release characteristics of selected 1:1 salts from solutions and suspensions using a rotating dialysis cell model. The poorest soluble bupivacaine salts were obtained from the aromatic ortho-hydroxycarboxylic acids diflunisal, 5-iodosalicylic acid, and salicylic acid (aqueous solubilities: 0.6-1.9 mM at 37 degrees C). Diffusant appearance rates in the acceptor phase upon instillation of solutions of various salts in the donor cell applied to first-order kinetics. Calculated permeability coefficients for bupivacaine and the counterions diflunisal, 5-iodosalicylic acid, and mandelic acid were found to be correlated with the molecular size of the diffusants. Release experiments at physiological pH involving suspensions of the bupivacaine-diflunisal salt revealed that at each sampling point the diflunisal concentration exceeded that of bupivacaine in the acceptor phase. However, after an initial lag period, a steady state situation was attained resulting in equal and constant fluxes of the two diffusants controlled by the permeability coefficients in combination with the solubility product of the salt. Due to the fact that the saturation solubility of the bupivacaine-salicylic acid salt in water exceeded that of bupivacaine at pH 7.4, suspensions of the latter salt were unable to provide simultaneous release of the cationic and anionic species at pH 7.4. The release profiles were characterised by a rapid release of salicylate accompanied by a much slower appearance of bupivacaine in the acceptor phase caused by precipitation of bupivacaine base from the solution upon dissolution of the salt in the donor cell.

  18. 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

  19. Computer modeling of the local structure, mixing properties, and stability of solid solutions of alkaline-earth metal oxides

    SciTech Connect

    Urusov, V. S. Petrova, T. G. Eremin, N. N.

    2008-11-15

    A technique for the computer modeling of disordered binary oxide solid solutions MO-M'O in a wide composition range has been developed. The method of atomistic pair potentials was used for 4 x 4 x 4 supercells. The parameters of the potentials are optimized using the structural and elastic properties of pure components MgO, CaO, SrO, and BaO. The temperature dependences of the heat capacity and entropy are calculated for pure components. The excess mixing properties (enthalpy, volume, bulk modulus, vibrational entropy) are found for different compositions of Mg{sub x}Ca{sub (1-x)}O, Ca{sub x}Sr{sub (1-x)}O, and Sr{sub x}Ba{sub (1-x)}O solid solutions. Temperature and composition dependences of the excess Gibbs energy were constructed, which made it possible to approximately estimate the critical decomposition temperatures and limits of component miscibility. Statistical analysis of lattice distortions in the first and second coordination spheres reveals a detailed picture of the solid-solution local structure.

  20. Computer modeling of the local structure, mixing properties, and stability of solid solutions of alkaline-earth metal oxides

    NASA Astrophysics Data System (ADS)

    Urusov, V. S.; Petrova, T. G.; Eremin, N. N.

    2008-11-01

    A technique for the computer modeling of disordered binary oxide solid solutions MO- M'O in a wide composition range has been developed. The method of atomistic pair potentials was used for 4 × 4 × 4 supercells. The parameters of the potentials are optimized using the structural and elastic properties of pure components MgO, CaO, SrO, and BaO. The temperature dependences of the heat capacity and entropy are calculated for pure components. The excess mixing properties (enthalpy, volume, bulk modulus, vibrational entropy) are found for different compositions of Mg x Ca(1 - x)O, Ca x Sr(1 - x)O, and Sr x Ba(1 - x)O solid solutions. Temperature and composition dependences of the excess Gibbs energy were constructed, which made it possible to approximately estimate the critical decomposition temperatures and limits of component miscibility. Statistical analysis of lattice distortions in the first and second coordination spheres reveals a detailed picture of the solid-solution local structure.

  1. 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

  2. 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

  3. Effect of ammonium-salt solutions on the surface properties of carbon fibers in electrochemical anodic oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Xin; Wang, Xuefei; Ouyang, Qin; Chen, Yousi; Yan, Qing

    2012-10-01

    The surfaces of polyacrylonitrile-based carbon fibers were treated by an electrochemical anodic method. Three different kinds of ammonium-salt solutions namely NH4HCO3, (NH4)2CO3 and (NH4)3PO4 were respectively chosen as the electrolytes. The effect of these electrolytes on the surface structure was studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results showed that longitudinal grooves on the fiber surface became more well-defined and much deeper after surface treatment, and the root mean square roughness (RMS) of carbon fiber surface increased from 4.6 nm for untreated fibers to 13.5 nm for treated fibers in (NH4)3PO4 electrolytes. The concentration of oxygen and nitrogen atomic on the fiber surface increased after surface treatment. The tensile strength of oxidized fibers had an obvious decrease, whereas the interlaminar shear strength (ILSS) value of corresponding carbon fiber reinforced polymers (CFRPs) increased in a large extent. The intensity of oxidative reaction varied with the change of ammonium-salt solutions and electrochemical oxidation in (NH4)3PO4 electrolyte was of the most violence. The corresponding mechanism was also discussed and the result showed that the higher the concentration of OH- ions in the electrolytes, the violent the oxidative reaction happened.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  5. 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

  6. Copper(II) directs formation of toxic amorphous aggregates resulting in inhibition of hen egg white lysozyme fibrillation under alkaline salt-mediated conditions.

    PubMed

    Ghosh, Sudeshna; Pandey, Nitin K; Banerjee, Priyanka; Chaudhury, Koel; Nagy, Nóra Veronika; Dasgupta, Swagata

    2015-01-01

    Hen egg white lysozyme (HEWL) adopts a molten globule-like state at high pH (~12.75) and is found to form amyloid fibrils at alkaline pH. Here, we report that Cu(II) inhibits self-association of HEWL at pH 12.75 both at 37 and 65 °C. A significant reduction in Thioflavin T fluorescence intensity, attenuation in β-sheet content and reduction in hydrophobic exposure were observed with increasing Cu(II) stoichiometry. Electron paramagnetic resonance spectroscopy suggests a 4N type of coordination pattern around Cu(II) during fibrillation. Cu(II) is also capable of altering the cytotoxicity of the proteinaceous aggregates. Fibrillar species of diverse morphology were found in the absence of Cu(II) with the generation of amorphous aggregates in the presence of Cu(II), which are more toxic compared to the fibrils alone.

  7. 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.

  8. Solid-phase extraction of gallium(III) with hydrophobic 8-quinolinol derivatives-impregnated resin from aqueous acidic and alkaline solutions.

    PubMed

    Hatori, Nahoko; Imura, Hisanori; Ohashi, Akira; Ohashi, Kousaburo

    2008-12-01

    Solid-phase extraction (SPE) of gallium(III) with hydrophobic 8-quinolinol derivatives (HQs)-impregnated resin from aqueous acidic and alkaline solutions has been investigated. The HQs used were 7-(4-ethyl-1-methyloctyl)-8-quinolinol (HEMOQ), 5-octyloxymethyl-8-quinolinol (HO(8)Q), 2-methyl-5-octyloxymethyl-8-quinolinol (HMO(8)Q), 5-dioctylaminomethyl-8-quinolinol (HN(8)Q), 7-bromo-5-octyloxymethyl-8-quinolinol (HBrO(8)Q), and 5-(2-ethylhexyloxymethyl)-8-quinolinol (HOEHQ). Various factors affecting the SPE, such as the substituents of the HQs, HCl and NaOH concentrations in the aqueous phase, the HQ concentration in the resin, and the equilibration time were clarified. The extractability for gallium(III) from the aqueous solution became higher in the following order: HBrO(8)Q < HEMOQ < HO(8)Q < HN(8)Q < HMO(8)Q at 3 mol l(-1) HCl; HMO(8)Q < HO(8)Q < HOEHQ < HEMOQ < HN(8)Q < HBrO(8)Q at pH 0.4; HMO(8)Q < HO(8)Q asymptotically equal to HOEHQ < HN(8)Q < HEMOQ at 3 mol l(-1) NaOH.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Polymer-induced fractal patterns of [60]fullerene containing poly(methacrylic acid) in salt solutions.

    PubMed

    Tan, Chung How; Ravi, Palaniswamy; Dai, Sheng; Tam, Kam Chiu

    2004-11-01

    Well-defined water-soluble pH-responsive [60]fullerene (C60) containing poly(methacrylic acid) (PMAA-b-C60) was synthesized using the atom transfer radical polymerization technique. By varying pH and salt concentration, different types of fractal patterns at nano- to microscopic dimensions were observed for negatively charged PMAA-b-C60, while such structure was not observed for positively charged poly(2-dimethylaminoethyl methacrylate)-b-C60. We demonstrated that negatively charged fullerene containing polymeric systems can serve as excellent nanotemplates for the controlled growth of inorganic crystals at the nano- to micrometer length scale, and the possible mechanism was proposed.

  14. Acute salt poisoning due to different oral rehydration solution (ORS) packet sizes.

    PubMed

    Quereshi, Umar A; Bhat, Javeed I; Ali, Syed W; Mir, Abid A; Kambay, Altaf H; Bhat, Imtiyaz N

    2010-06-01

    The packing and composition of ORS has undergone a change since its introduction. In India, some companies are manufacturing smaller pouches (4.2 g) to be dissolved in 200 ml of water. Therefore, out of confusion some prescribers routinely advise the patients to dissolve the standard formulation ORS pouch (21 g) in a glass (200 ml) of water. Two cases are discussed. First patient developed salt poisoning due to improper dilution and recovered after rapid correction. In the second patient improper reconstitution led to hypernatremia and death.

  15. Notable effects of the metal salts on the formation and decay reactions of α-tocopheroxyl radical in acetonitrile solution. The complex formation between α-tocopheroxyl and metal cations.

    PubMed

    Kohno, Yutaro; Fujii, Miyabi; Matsuoka, Chihiro; Hashimoto, Haruka; Ouchi, Aya; Nagaoka, Shin-ichi; Mukai, Kazuo

    2011-08-18

    The measurement of the UV-vis absorption spectrum of α-tocopheroxyl (α-Toc(•)) radical was performed by reacting aroxyl (ArO(•)) radical with α-tocopherol (α-TocH) in acetonitrile solution including four kinds of alkali and alkaline earth metal salts (MX or MX(2)) (LiClO(4), LiI, NaClO(4), and Mg(ClO(4))(2)), using stopped-flow spectrophotometry. The maximum wavelength (λ(max)) of the absorption spectrum of the α-Toc(•) at 425.0 nm increased with increasing concentration of metal salts (0-0.500 M) in acetonitrile, and it approached constant values, suggesting an [α-Toc(•)-M(+) (or M(2+))] complex formation. The stability constants (K) were determined to be 9.2, 2.8, and 45 M(-1) for LiClO(4), NaClO(4), and Mg(ClO(4))(2), respectively. By reacting ArO(•) with α-TocH in acetonitrile, the absorption of ArO(•) disappeared rapidly, while that of α-Toc(•) appeared and then decreased gradually as a result of the bimolecular self-reaction of α-Toc(•) after passing through the maximum. The second-order rate constants (k(s)) obtained for the reaction of α-TocH with ArO(•) increased linearly with an increasing concentration of metal salts. The results indicate that the hydrogen transfer reaction of α-TocH proceeds via an electron transfer intermediate from α-TocH to ArO(•) radicals followed by proton transfer. Both the coordination of metal cations to the one-electron reduced anions of ArO(•) (ArO:(-)) and the coordination of counteranions to the one-electron oxidized cations of α-TocH (α-TocH(•)(+)) may stabilize the intermediate, resulting in the acceleration of electron transfer. A remarkable effect of metal salts on the rate of bimolecular self-reaction (2k(d)) of the α-Toc(•) radical was also observed. The rate constant (2k(d)) decreased rapidly with increasing concentrations of the metal salts. The 2k(d) value decreased at the same concentration of the metal salts in the following order: no metal salt > NaClO(4) > LiClO(4) > Mg

  16. Meso/macroporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers as an efficient and robust catalyst for the oxygen reduction reaction in both acidic and alkaline solutions.

    PubMed

    Xiao, Meiling; Zhu, Jianbing; Feng, Ligang; Liu, Changpeng; Xing, Wei

    2015-04-17

    Meso-/macroporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers are fabricated by a facile approach. This efficient and robust material exhibits superior catalytic performance toward the oxygen reduction reaction in both acidic and alkaline solutions and is the most promising alternative to a Pt catalyst for use in electrochemical energy devices.

  17. 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.

  18. 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

  19. 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

  20. Fracture phenomena in an isotonic salt solution during freezing and their elimination using glycerol.

    PubMed

    Gao, D Y; Lin, S; Watson, P F; Critser, J K

    1995-06-01

    Thermal stress and consequent fracture in frozen organs or cell suspensions have been proposed to be two causes of cell cryoinjury. A specific device was developed to study the thermal stress and the fracture phenomena during a slow cooling process of isotonic NaCl solutions with different concentrations of glycerol (cryoprotectant) in a cylindrical tube. It was shown from the experimental results that glycerol significantly influenced the solidification process of the ternary solutions and reduced the thermal stress. The higher the initial glycerol concentration, the lower the thermal stress in the frozen solutions. Glycerol concentrations over 0.3 M were sufficient to eliminate the fracture of the frozen solutions under the present experimental conditions. To explain the action of glycerol in reducing the thermal stress and preventing the ice fracture, a further study on ice crystal formation and growth of ice in these solutions was undertaken using cryomicroscopy. It is known from previous studies that an increase of initial glycerol concentration reduced frozen fraction of water in the solution at any given low temperature due to colligative properties of solution, which reduced the total ice volume expansion during water solidification. The present cryomicroscopic investigation showed that under a fixed cooling condition the different initial glycerol concentrations induced the different microstructures of the frozen solutions at not only a given low temperature but also a given frozen fraction of water. It has been known that ice volume expansion during solidification is a major factor causing the thermal stress and the interior microstructure is critical for the mechanical strength of a solid. Therefore, functions of glycerol in reducing the total ice volume expansion during water solidification and in influencing interior microstructure of the ice may contribute to reduce the thermal stress and prevent the fracture in the frozen solutions.

  1. Solubilities and Glass Formation in Aqueous Solutions of the Sodium Salts of Malonic Acid With and Without Ammonium Sulfate.

    PubMed

    Kissinger, Jared A; Buttke, Lukas G; Vinokur, Anastasiya I; Guzei, Ilia A; Beyer, Keith D

    2016-06-01

    The solubility of sodium hydrogen malonate and sodium malonate in water both with and without ammonium sulfate present has been studied using differential scanning calorimetry and infrared spectroscopy. The crystals that form from sodium hydrogen malonate/water solutions were determined to be sodium hydrogen malonate monohydrate by single-crystal X-ray diffractometry. The crystals formed in sodium malonate/water solutions were determined to be sodium malonate monohydrate, a compound whose structure had not been previously known. When ammonium sulfate is added to these respective aqueous systems, the precipitation solids contain sodium sulfate decahydrate under low to moderate ammonium concentrations and lecontite (NaNH4SO4·2H2O) under high ammonium concentrations, which can be found under dry atmospheric conditions. Thus, it appears the presence of malonate and hydrogen malonate ions does not significantly affect the precipitation of inorganic salts in these systems. The glass transition temperatures of all solutions were also determined, and it was observed that the addition of ammonium sulfate slightly lowers the glass transition temperature in these solutions.

  2. 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).

  3. Potential Dependent Adlayer Structures of a Sulfur-Covered Au(111) Electrode in Alkaline Solution: An in Situ STM Study

    SciTech Connect

    Schlaup, C.; Friebel, D.; Broekmann, P.; Wandelt, K.; /Bonn U. /SLAC, SSRL

    2009-05-11

    A sulfur-covered Au(1 1 1) electrode ({Theta}{sub S} = 0.33 ML) subjected to potential increases in an S-free NaOH solution, i.e., at a fixed S coverage, leads to the reversible formation of a rhombic phase at anodic potentials. The local S coverage increase which is required for the formation of the rhombic phase results from a coverage decrease within the ({radical}3 x {radical}3)R30{sup o} regions, where single-S-atom-defects and, in later stages, S vacancy islands are formed. Due to the high potential induced S-Au bond strength, it was possible for the first time to retain islands of this incomplete ({radical}3 x {radical}3)R30{sup o} S layer in the 2D solid state. Furthermore, a Au mass transport was observed during the growth of the rhombic phase. This clearly calls for a reinterpretation of its chemical nature.

  4. 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.

  5. 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).

  6. 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

  7. 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

  8. 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.

  9. Capillary electrophoresis analysis of hydrolysis, isomerization and enantiomerization of aspartyl model tripeptides in acidic and alkaline solution.

    PubMed

    De Boni, Silvia; Scriba, Gerhard K E

    2007-01-01

    In order to investigate the degradation of two aspartyl tripeptides, Gly-Asp-PheNH2 and Phe-Asp-GlyNH2 in solution capillary, electrophoresis methods were developed and validated. Separation of most degradation products including those arising from isomerization and enantiomerization of the Asp residues was achieved in a 50 mM sodium phosphate buffer, pH 3.0. Resolution of comigrating compounds could be achieved by addition of cyclodextrins to the background electrolyte. For tripeptide derivatives the assays were linear in the range of 0.015-3.0 mmol/l. Some dipeptides and amino acids exhibited a narrower linear range due to low UV absorbance. The limits of detection were in the range of 0.005-0.1 mmol/l. Incubation of the model peptides was carried out at pH 2 and 10. At pH 2, degradation of the peptides proceeded via C-terminal deamidation and peptide backbone hydrolysis. In contrast, isomerization and enantiomerization were observed in combination with deamidation at pH 10. Generally, degradation of Phe-Asp-GlyNH2 proceeded faster compared to Gly-Asp-PheNH2 due to steric hindrance by the phenyl side chain.

  10. 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

  11. 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.

  12. Salt-induced vesicle formation from single anionic surfactant SDBS and its mixture with LSB in aqueous solution.

    PubMed

    Zhai, Limin; Zhao, Mei; Sun, Dejun; Hao, Jingcheng; Zhang, Lungjun

    2005-03-31

    Vesicles can be formed spontaneously in aqueous solution of a single anionic surfactant sodium dodecyl benzenesulfonate (SDBS) just under the inducement of salt, which makes the formation of vesicle much easier and simpler. The existence of vesicles was demonstrated by TEM image using the negative-staining method. The mechanism of the formation may be attributed to the compression of salt on the electric bilayer of the surfactant headgroups, which alters the packing parameter of the surfactant. The addition of the zwitterionic surfactant lauryl sulfonate betaine (LSB) makes the vesicles more stable, expands the range of formation and vesicle size, and reduces the polydispersity of the vesicles. The vesicle region was presented in a pseudoternary diagram of SDBS/LSB/brine. The variations of vesicle size with the salinity and mixing ratios, as well as the surfactant concentration, were determined using the dynamic light scattering method. It is found that the vesicle size is independent of the surfactant concentration but subject to the salinity and the mixing ratio of the two surfactants.

  13. Salt-free catanionic surface active ionic liquids 1-alkyl-3-methylimidazolium alkylsulfate: aggregation behavior in aqueous solution.

    PubMed

    Jiao, Jingjing; Han, Bing; Lin, Meijia; Cheng, Ni; Yu, Li; Liu, Min

    2013-12-15

    A series of salt-free catanionic surface active ionic liquids (SAILs), 1-alkyl-3-methylimidazolim alkyl sulfates (denoted as [Cnmim][CmSO4], n=6, 8, 10; m=12 and n=4; m=10, 14) were synthesized by an ion exchange reaction and their surface properties in aqueous solution were examined systematically by surface tension, fluorescence and electrical conductivity measurements. As catanionic surfactants, these SAILs exhibit notably higher surface activity, compared to the cationic or anionic analogues. Increment in both cationic and anionic alkyl chain lengths for [Cnmim][CmSO4] can both improve the amphiphilic character remarkably. This can be ascribed to cooperative interactions as formation of catanionic pairs between alkyl-substituted imidazolium cations and alkyl sulfate anions. The negative micellization Gibbs free energy values prove that the micellization of all the 1-alkyl-3-methylimidazolim alkyl sulfates investigated is a spontaneous process. Any additional CH2 group makes the micellization process easier regardless if it is on a cation or an anion. When keeping the total carbon atom number constant, we find that the [Cnmim][CmSO4] molecules with greater asymmetric alkyl chains display superior surface activity. This work indicates that the self-assembly of these imidazolium-based salt-free catanionic SAILs can be tailored by adjusting the mismatch of alkyl chains. These SAILs are expected to have potential applications in the fields of colloidal and interface and nanomaterial synthesis.

  14. The effect of solution electrolytes on the uptake of photosensitizers by liposomal membranes: a salting-out effect.

    PubMed

    Minnes, Refael; Ytzhak, Shany; Weitman, Hana; Ehrenberg, Benjamin

    2008-09-01

    In this study we investigated, spectroscopically, the effect of electrolytes on the partitioning of hematoporphyrin IX (HP) and hypericin (Hy) into non-charged lipid vesicles. Our aim was to assess the salting-out effect of electrolytes on membrane-partitioning. We titrated aqueous solutions of HP and Hy with lecithin liposomes, at different concentrations of several monovalent and divalent electrolytes in the suspension. The partitioning constant of HP to lecithin liposomes increased from 3.3 (mL/mg) in water containing only 5mM buffer to 8.7 (mL/mg) at 0.36M KCl. KF had a similar effect. NaCl caused a 3-fold increase in the partitioning of Hy to liposomes. MgSO(4) and MgCl(2) also increased the partitioning of HP, by a factor of more than 4 and this occurred already at 0.03M concentration. We analyze the comparative effects of the electrolytes in relation to the Hofmeister series. The salting-out effect could be utilized to enhance the uptake of HP and Hy, and possibly other photosensitizers as well, by artificial and natural membranes.

  15. 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)

  16. 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.

  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.

  18. 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.

  19. 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

  20. 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.

  1. Analysis of the corrosion of carbon steels in simulated salt repository brines and acid chloride solutions at high temperatures

    SciTech Connect

    Diercks, D.R.; Kassner, T.F.

    1988-04-01

    An analysis of literature data on the corrosion of carbon steels in anoxic brines and acid chloride solutions was performed, and the results were used to assess the expected life of high-level nuclear waste package containers in a salt repository environment. The corrosion rate of carbon steels in moderately acidic aqueous chloride environments obeys an Arrhenius dependence on temperature and a (pH{sub 2}){sup {minus}1/2} dependence on hydrogen partial pressure. The cathodic reduction of water to produce hydrogen is the rate-controlling step in the corrosion process. An expression for the corrosion rate incorporating these two dependencies was used to estimate the corrosion life of several proposed waste package configurations. 42 refs., 11 figs., 2 tabs.

  2. Effect of salt solutions applied during wheat conditioning on lipase activity and lipid stability of whole wheat flour.

    PubMed

    Doblado-Maldonado, Andrés F; Arndt, Elizabeth A; Rose, Devin J

    2013-09-01

    Lipolytic activity in whole wheat flour (WWF) is largely responsible for the loss in baking quality during storage. Metal ions affect the activity of seed lipases; however, no previous studies have applied this information to WWF in a way that reduces lipase activity, is practical for commercial manufacture, and uses common food ingredients. NaCl, KCl, Ca-propionate, or FeNa-ethylenediaminetetraacetic acid (FeNa-EDTA) were applied to hard red winter (HRW) and hard white spring (HWS) wheats during conditioning as aqueous solutions at concentrations that would be acceptable in baked goods. Salts affected lipase activity to different degrees depending on the type of wheat used. Inhibition was greater in HRW compared with HWS WWF, probably due to higher lipase activity in HRW wheat. In HRW WWF, 1% NaCl (flour weight) reduced hydrolytic and oxidative rancidity and resulted in higher loaf volume and lower firmness than untreated WWF after 24 weeks of storage.

  3. Novel dual-salts electrolyte solution for dendrite-free lithium-metal based rechargeable batteries with high cycle reversibility

    NASA Astrophysics Data System (ADS)

    Miao, Rongrong; Yang, Jun; Feng, Xuejiao; Jia, Hao; Wang, Jiulin; Nuli, Yanna

    2014-12-01

    Metallic lithium is the most promising negative electrode for high energy rechargeable batteries due to its extremely high specific capacity and the lowest redox potential. However, the low cycle efficiency and lithium dendrite formation during charge/discharge processes consistently hinder its practical application. Here a new dual-salts electrolyte composed of Li[N(SO2F)2] and Li[N(SO2CF3)2] has been explored to simultaneously cope with these two problems. Under the unique protection of solid electrolyte interphase (SEI) film formed in this electrolyte solution and the improvement in Li crystal growth pattern, high cycle efficiency of ca. 99% and dendrite-free Li deposit have been achieved. Moreover, the excellent cycling performance and favorable lithium morphology can be retained even at high current density of 10 mA cm-2. This study will greatly promote the development of Li-metal rechargeable batteries with high power and high energy density.

  4. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-03-01

    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.

  5. Graphene oxide electrocatalyst on MnO₂ air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution.

    PubMed

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-03-13

    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.

  6. 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

  7. Mechanochemical synthesis, structure, and properties of solid solutions of alkaline earth metal fluorides: Ma1-xMbxF2 (M: Ca, Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

    2016-10-01

    The capability of mechanochemical synthesis for the formation of solid solutions of alkaline earth metal fluorides Ma1-xMbxF2 (M: Ca, Sr, Ba) was tested by fluorination of metal acetates and metal hydroxides with ammonium fluoride directly at milling. Evidence was found for a mutual substitution of cations on their lattice positions in Ca1-xSrxF2 and Ba1-xSrxF2 samples. For the Ba/Ca-system this synthesis route is only partially successful. X-ray diffraction and 19F MAS NMR spectroscopy were used to characterize all samples concerning their crystal structure and local fluorine coordination. Calculations of 19F chemical shifts with the superposition model along with probability calculations for the intensity of the individual 19F lines, performed in dependence on the molar composition of the samples, perfectly agree with the experimental findings. The fluoride ion conductivity of as-prepared samples, determined by temperature dependent DC conductivity measurements, is significantly higher than those of crystalline binary fluorides. Moreover, a higher F- ion conductivity is observed for samples with higher mixing grade in the Ca/Sr-and the Ba/Sr-systems.

  8. 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

  9. Influence of arbuscular mycorrhiza on organic solutes in maize leaves under salt stress.

    PubMed

    Sheng, Min; Tang, Ming; Zhang, Fengfeng; Huang, Yanhui

    2011-07-01

    A pot experiment was conducted to examine the effect of the arbuscular mycorrhizal (AM) fungus, Glomus mosseae, on plant biomass and organic solute accumulation in maize leaves. Maize plants were grown in sand and soil mixture with three NaCl levels (0, 0.5, and 1.0 g kg(-1) dry substrate) for 55 days, after 15 days of establishment under non-saline conditions. At all salinity levels, mycorrhizal plants had higher biomass and higher accumulation of organic solutes in leaves, which were dominated by soluble sugars, reducing sugars, soluble protein, and organic acids in both mycorrhizal and non-mycorrhizal plants. The relative abundance of free amino acids and proline in total organic solutes was lower in mycorrhizal than in non-mycorrhizal plants, while that of reducing sugars was higher. In addition, the AM symbiosis raised the concentrations of soluble sugars, reducing sugars, soluble protein, total organic acids, oxalic acid, fumaric acid, acetic acid, malic acid, and citric acid and decreased the concentrations of total free amino acids, proline, formic acid, and succinic acid in maize leaves. In mycorrhizal plants, the dominant organic acid was oxalic acid, while in non-mycorrhizal plants, the dominant organic acid was succinic acid. All the results presented here indicate that the accumulation of organic solutes in leaves is a specific physiological response of maize plants to the AM symbiosis, which could mitigate the negative impact of soil salinity on plant productivity.

  10. 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.

  11. 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.

  12. Occlusion and ion exchange in the molten (lithium chloride + potassium chloride + alkaline earth chloride) salt + zeolite 4A system with alkaline earth chlorides of calcium and strontium, and in the molten (lithium chloride + potassium chloride + actinide chloride) salt + zeolite 4A system with the actinide chloride of uranium.

    SciTech Connect

    Lexa, D.; Chemical Engineering

    2003-04-01

    The interaction between molten salts of the type LiCl-KCl-MeCl n (Me=Ca, Sr, U; x{sub MeCLn} $$ = to 0.45; and x {sub KCl}/x LiCl=0.69) and zeolite 4A have been studied at 823 K. The main interactions between these salts and zeolite are molten salt occlusion to form salt-loaded zeolite and ion exchange between the molten salt and salt-loaded zeolite. An irreversible chemical reaction has been observed in the LiCl-KCl-UCl{sup 3+}zeolite system. The extent of occlusion is a function of the concentration of MeCl n in the zeolite and is equal to 10{+-}1 Cl- per zeolite unit cell, (AlSiO{sub 4}){sub 12}, at infinite MeCl n dilution. The ion-exchange mole-fraction equilibrium constants (separation factors) with respect to Li are decreasing functions of the concentration of SrCl{sub 2} and UCl{sub 3}, but an increasing function of the concentration of CaCl{sub 2} in the zeolite. At infinite MeCl n dilution, they are equal to 0.9, 11.9, and 13 for CaCl{sub 2}, SrCl{sub 2}, and UCl{sub 3}, respectively. The standard ion-exchange chemical potentials are equal to -50.0, -84, and -101.1 kJ x mol-1 for Ca{sup 2+}, Sr{sup 2+}, and U{sup 3+}, respectively.

  13. 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.

  14. OSMOTIC COEFFICIENTS, SOLUBILITIES, AND DELIQUESCENCE RELATIONS IN MIXED AQUEOUS SALT SOLUTIONS AT ELEVATED TEMPERATURE

    SciTech Connect

    M.S. Gruszkiewicz; D.A. Palmer

    2006-02-22

    While thermodynamic properties of pure aqueous electrolytes are relatively well known at ambient temperature, there are far fewer data for binary systems extending to elevated temperatures and high concentrations. There is no general theoretically sound basis for prediction of the temperature dependence of ionic activities, and consequently temperature extrapolations based on ambient temperature data and empirical equations are uncertain and require empirical verification. Thermodynamic properties of mixed brines in a wide range of concentrations would enhance the understanding and precise modeling of the effects of deliquescence of initially dry solids in humid air in geological environments and in modeling the composition of waters during heating, cooling, evaporation or condensation processes. These conditions are of interest in the analysis of waters on metal surfaces at the proposed radioactive waste repository at Yucca Mountain, Nevada. The results obtained in this project will be useful for modeling the long-term evolution of the chemical environment, and this in turn is useful for the analysis of the corrosion of waste packages. In particular, there are few reliable experimental data available on the relationship between relative humidity and composition that reveals the eutonic points of the mixtures and the mixture deliquescence RH. The deliquescence RH for multicomponent mixtures is lower than that of pure component or binary solutions, but is not easy to predict quantitatively since the solutions are highly nonideal. In this work we used the ORNL low-temperature and high-temperature isopiestic facilities, capable of precise measurements of vapor pressure between ambient temperature and 250 C for determination of not only osmotic coefficients, but also solubilities and deliquescence points of aqueous mixed solutions in a range of temperatures. In addition to standard solutions of CaCl{sub 2}, LiCl, and NaCl used as references, precise direct

  15. Scale-up of osmotic membrane bioreactors by modeling salt accumulation and draw solution dilution using hollow-fiber membrane characteristics and operation conditions.

    PubMed

    Kim, Suhan

    2014-08-01

    A full-scale osmotic membrane bioreactor (OMBR) model was developed to simulate salt accumulation, draw solution (DS) dilution, and water flux over the hollow-fiber membrane length. The model uses the OMBR design parameters, DS properties, and forward osmosis (FO) membrane characteristics obtained from lab-scale tests. The modeling results revealed a tremendous water flux decline (10→0.82LMH) and short solids retention time (SRT: 5days) due to salt accumulation and DS dilution when OMBR is scaled up using commercially available DS and FO membrane. Simulated water flux is a result of interplay among reverse salt flux, internal and external concentration polarization (ICP and ECP). ECP adversely impacts water flux considerably in full-scale OMBR although it is often ignored in previous works. The OMBR model makes it possible to select better DS properties (higher flow rate and salt concentration) and FO membranes with higher water flux propensity in full-scale operation.

  16. Scale-up of osmotic membrane bioreactors by modeling salt accumulation and draw solution dilution using hollow-fiber membrane characteristics and operation conditions.

    PubMed

    Kim, Suhan

    2014-08-01

    A full-scale osmotic membrane bioreactor (OMBR) model was developed to simulate salt accumulation, draw solution (DS) dilution, and water flux over the hollow-fiber membrane length. The model uses the OMBR design parameters, DS properties, and forward osmosis (FO) membrane characteristics obtained from lab-scale tests. The modeling results revealed a tremendous water flux decline (10→0.82LMH) and short solids retention time (SRT: 5days) due to salt accumulation and DS dilution when OMBR is scaled up using commercially available DS and FO membrane. Simulated water flux is a result of interplay among reverse salt flux, internal and external concentration polarization (ICP and ECP). ECP adversely impacts water flux considerably in full-scale OMBR although it is often ignored in previous works. The OMBR model makes it possible to select better DS properties (higher flow rate and salt concentration) and FO membranes with higher water flux propensity in full-scale operation. PMID:24746768

  17. 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

  18. 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.

  19. Process for preparing chemically modified micas for removal of cesium salts from aqueous solution

    DOEpatents

    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.

  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. Note: Evidence against 2D-Ising criticality in aqueous solutions with added salt

    NASA Astrophysics Data System (ADS)

    Troncoso, Jacobo; Cerdeiriña, Claudio A.

    2013-11-01

    Coexistence-curve data in the refractive index-temperature plane for solutions of 3-methyl-pyridine in heavy water with a small amount of added sodium tetraphenylborate have been determined. The analysis of such data indicates that this system belongs to the universality class of the three-dimensional Ising model (3D-Ising). This finding contrasts with previous work by Sadakane et al. [Soft Matter 7, 1334 (2011)] in which 2D-Ising criticality is invoked, but agrees with the recent assessment by Leys et al. [Soft Matter 9, 9326 (2013)].

  2. 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.

  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. Effects of tectonic structures, salt solution mining, and density-driven groundwater hydraulics on evaporite dissolution (Switzerland)

    NASA Astrophysics Data System (ADS)

    Zechner, Eric; Konz, Markus; Younes, Anis; Huggenberger, Peter

    2011-11-01

    Subsurface dissolution (subrosion) of evaporites such as halite and gypsum can lead to extensive land subsidence. Recent land subsidences have been surveyed at six separate locations in northwestern Switzerland. The diameters of the affected surface areas range from 100 to 1,500 m, and corresponding subsidence rates reached more than 100 mm/year. Based on a geometrical model, three sites could be outlined where land subsidence can likely be attributed to salt solution mining. The effects of increased hydrostatic gradient due to both groundwater withdrawal and fluid density contrasts were evaluated in more detail for the remaining sites with a series of 2D density-coupled solute-transport simulations along an approximately 1,000-m-long and 150-m-deep 2D cross section. Simulation results indicate that the upconing process of saline groundwater into the main aquifer occurs under different distributions of subsurface parameters and hydraulic boundary conditions. For the presented setup, the simulations also revealed that the most sensitive factor for the dissolution rate is the structure or dip of the halite formation, which leads to an increase of dissolution rate with increasing dip. Due to the increased density of the brine, an intrinsic flow dynamic develops which follows the direction of the dip.

  5. Study of quantitative interactions of potato and corn starch granules with ions in diluted solutions of heavy metal salts.

    PubMed

    Szymońska, Joanna; Molenda, Marcin; Wieczorek, Jerzy

    2015-12-10

    Interactions of potato and corn starch granules with ions in diluted solutions of silver, lead, copper or iron salts were investigated. It was shown experimentally that granules accumulated the cations in amounts depending on the granule structure and water content as well as a type of both metal and counter-ions present in solution. Potato starch retained almost three times more cations compared to corn starch what was proportional to the total phosphorous content in these starches. Quantity of milligrams of cations bound by 1g of starch was inversely correlated with the cation hydration. Ag(+), Pb(2+) and Cu(2+) were connected in stoichiometric amounts of moles to semicrystalline and amorphous parts of the granules. Fe(3+) ions were accumulated in higher than stoichiometric quantities mainly in granule amorphous regions. Metal ions penetrated into granules together with anions except nitrates which remained on surface of potato starch granules. Cations facilitated the starch thermal decomposition in accordance with values of their standard redox potentials. Nitrates supported this process only in the presence of base metal cations.

  6. Unusual Salt and pH Induced Changes in Polyethylenimine Solutions

    PubMed Central

    Millard, Paul; Basu, Saswati; Horkay, Ferenc; Chandran, Preethi L

    2016-01-01

    Linear PEI is a cationic polymer commonly used for complexing DNA into nanoparticles for cell-transfection and gene-therapy applications. The polymer has closely-spaced amines with weak-base protonation capacity, and a hydrophobic backbone that is kept unaggregated by intra-chain repulsion. As a result, in solution PEI exhibits multiple buffering mechanisms, and polyelectrolyte states that shift between aggregated and free forms. We studied the interplay between the aggregation and protonation behavior of 2.5 kDa linear PEI by pH probing, vapor pressure osmometry, dynamic light scattering, and ninhydrin assay. Our results indicate that: At neutral pH, the PEI chains are associated and the addition of NaCl initially reduces and then increases the extent of association. The aggregate form is uncollapsed and co-exists with the free chains. PEI buffering occurs due to continuous or discontinuous charging between stalled states. Ninhydrin assay tracks the number of unprotonated amines in PEI. The size of PEI-DNA complexes is not significantly affected by the free vs. aggregated state of the PEI polymer. Despite its simple chemical structure, linear PEI displays intricate solution dynamics, which can be harnessed for environment-sensitive biomaterials and for overcoming current challenges with DNA delivery. PMID:27685846

  7. 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.

  8. 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.

  9. 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.

  10. 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

  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. Effect of pH and succinic acid on the morphology of α-calcium sulfate hemihydrate synthesized by a salt solution method

    NASA Astrophysics Data System (ADS)

    Li, Fan; Liu, Jianli; Yang, Guangyong; Pan, Zongyou; Ni, Xiao; Xu, Huazi; Huang, Qing

    2013-07-01

    Well-crystallized α-calcium sulfate hemihydrate (α-CSH) powders useful for bone defect filling were synthesized using a salt solution method and their morphologies were effectively modified by adjusting the pH of the reaction solutions or by adding succinic acid. The effect and its mechanism of the pH and the succinic acid on the phase composition and the morphology of the crystals were discussed in detail.

  13. 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.

  14. 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.

  15. 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.

  16. Viscosity-Lowering Effect of Amino Acids and Salts on Highly Concentrated Solutions of Two IgG1 Monoclonal Antibodies.

    PubMed

    Wang, Shujing; Zhang, Ning; Hu, Tao; Dai, Weiguo; Feng, Xiuying; Zhang, Xinyi; Qian, Feng

    2015-12-01

    Monoclonal antibodies display complicated solution properties in highly concentrated (>100 mg/mL) formulations, such as high viscosity, high aggregation propensity, and low stability, among others, originating from protein-protein interactions within the colloidal protein solution. These properties severely hinder the successful development of high-concentration mAb solution for subcutaneous injection. We hereby investigated the effects of several small-molecule excipients with diverse biophysical-chemical properties on the viscosity, aggregation propensity, and stability on two model IgG1 (JM1 and JM2) mAb formulations. These excipients include nine amino acids or their salt forms (Ala, Pro, Val, Gly, Ser, HisHCl, LysHCl, ArgHCl, and NaGlu), four representative salts (NaCl, NaAc, Na2SO4, and NH4Cl), and two chaotropic reagents (urea and GdnHCl). With only salts or amino acids in their salt-forms, significant decrease in viscosity was observed for JM1 (by up to 30-40%) and JM2 (by up to 50-80%) formulations, suggesting charge-charge interaction between the mAbs dictates the high viscosity of these mAbs formulations. Most of these viscosity-lowering excipients did not induce substantial protein aggregation or changes in the secondary structure of the mAbs, as evidenced by HPLC-SEC, DSC, and FT-IR analysis, even in the absence of common protein stabilizers such as sugars and surfactants. Therefore, amino acids in their salt-forms and several common salts, such as ArgHCl, HisHCl, LysHCl, NaCl, Na2SO4, and NaAc, could potentially serve as viscosity-lowering excipients during high-concentration mAb formulation development.

  17. Amorphous silica solubilities—III. Activity coefficient relations and predictions of solubility behavior in salt solutions, 0-350°C

    NASA Astrophysics Data System (ADS)

    Marshall, William L.

    1980-07-01

    Activity coefficients of amorphous silica in added salt solutions, obtained from solubility measurements, were calculated on the basis of concentration (molarity) and composition (molality). The logarithm of the activity coefficients based on concentration when plotted against molarity of added salt, as previous observations would dictate, yielded straight line relations even to 6 M. The use of composition units produced instead curves at the highest molalities and caused divergences in behavior from the single straight lines for 1-1 salts of a common cation. Introduction of the activity of water also caused divergences in behavior. Thus, it might appear that amorphous silica is fully hydrated at 25°C as a solid in equilibrium with solution. Lack of densities of aqueous sodium nitrate necessitated using units of molality in interpretations at high temperatures. Nevertheless, approximately straight line behavior of log activity coefficient vs m was still observed to reasonably high molalities, and allowed a simple equation to describe activity coefficient behavior as a function of both molality of sodium nitrate and temperature. The simplicity of the relation, with some assumptions, might be used to predict solubility of amorphous silica at high temperatures in other added aqueous salt solutions.

  18. 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.

  19. Inclusion of mPRISM potential for polymer-induced protein interactions enables modeling of second osmotic virial coefficients in aqueous polymer-salt solutions.

    PubMed

    Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele

    2016-01-01

    The downstream processing of therapeutic proteins is a challenging task. Key information needed to estimate applicable workup strategies (e.g. crystallization) are the interactions of the proteins with other components in solution. This information can be deduced from the second osmotic virial coefficient B22 , measurable by static light scattering. Thermodynamic models are very valuable for predicting B22 data for different process conditions and thus decrease the experimental effort. Available B22 models consider aqueous salt solutions but fail for the prediction of B22 if an additional polymer is present in solution. This is due to the fact that depending on the polymer concentration protein-protein interactions are not rectified as assumed within these models. In this work, we developed an extension of the xDLVO model to predict B22 data of proteins in aqueous polymer-salt solutions. To show the broad applicability of the model, lysozyme, γ-globulin and D-xylose ketol isomerase in aqueous salt solution containing polyethylene glycol were considered. For all proteins considered, the modified xDLVO model was able to predict the experimentally observed non-monotonical course in B22 data with high accuracy. When used in an early stage in process development, the model will contribute to an efficient and cost effective downstream processing development.

  20. Electrochemical behavior of Al in a non-aqueous alkyl carbonate solution containing LiBOB salt

    NASA Astrophysics Data System (ADS)

    Myung, Seung-Taek; Natsui, Hiroshi; Sun, Yang-Kook; Yashiro, Hitoshi

    Aluminum was studied as a current collector for rechargeable lithium batteries to understand electrochemical and passivation behavior. Electrochemical polarization tests, in situ scratch polarization tests and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) analysis in lithium bis-oxalato borate (LiBOB)-containing alkyl carbonate solution were conducted. The Al foil did not follow the alloy and de-alloy process with the LiBOB salt in electrolyte at 0 V vs. Li/Li + in the cathodic sweep. During the anodic scan to the noble direction, the absence of an oxidation peak up to 3 V vs. Li/Li + indicated that the air-formed oxide layer of Al was not reduced to metal. Oxide-free Al surfaces made by the in situ scratch test during the electrochemical polarization resulted in abrupt alloy formation with Li at 0 V vs. Li/Li +, but the newly formed surface formed passive films at higher potential with oxygen, namely, Al-O compound, as confirmed by ToF-SIMS.