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Sample records for aqueous alkaline solution

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. Performed surfactant-optimized aqueous alkaline flood

    SciTech Connect

    Thigpen, D.R.; Lawson, J.B.; Nelson, R.C.

    1991-11-26

    This paper describes improvement in a process for recovering oil from an acidic oil reservoir by injecting an aqueous alkaline solution comprising water, sodium chloride, and alkaline material for reacting with the reservoir oil forming a petroleum acid soap to form an in-situ surfactant system. The improvement comprises: selecting a preformed cosurfactant which is soluble in both the aqueous solution and the reservoir oil and has a solubility ratio which is grater than the solubility ratio of the petroleum acid soap where the solubility ratio is the ratio of solubility in the aqueous alkaline solution to the solubility in the reservoir oil; combining with the alkaline solution an amount of the preformed cosurfactant which will result in the in-situ surfacant system having a salinity about equal to a salinity which results in minimal interfacial tension between the oil in the reservoir and the in-situ surfactant system at reservoir temperature, wherein the amount of the preformed cosurfactant is about 0.3 percent by weight in the aqueous alkaline solution; and injecting the cosurfactant-aqueous alkaline solution mixture into the reservoir to displace oil toward a fluid production location.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

    Estevez Mews, Jorge

    reactions. Each gas-phase potential energy profile obtained at a high level of theory was used as a post-correction of the corresponding reaction free energy profile in aqueous solution. A detailed picture of the actual mechanism driving the decomposition pathway of chloroform has emerged from these simulations.

  16. 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.

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

    DOE PAGES

    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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Reflectance of aqueous solutions

    NASA Technical Reports Server (NTRS)

    Querry, M. R.

    1972-01-01

    The optical properties and optical constants of water and aqueous solutions were studied to develop an accurate tabulation of graphical representations of the optical constants through a broad spectrum. Manuscripts of articles are presented concerning extinction coefficients, relative specular reflectance, and temperature effect on the water spectrum. Graphs of absolute reflectance, phase shifts, index of refraction, and extinction coefficients for water, heavy water and aqueous solutions are included.

  8. Cation exchange properties of zeolites in hyper alkaline aqueous media.

    PubMed

    Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric

    2015-02-01

    Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

  9. Technetium recovery from high alkaline solution

    DOEpatents

    Nash, Charles A.

    2016-07-12

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

  10. 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.

  11. 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.

  12. Synthesis, crystal structure and investigation of mononuclear copper(II) and zinc(II) complexes of a new carboxylate rich tripodal ligand and their interaction with carbohydrates in alkaline aqueous solution

    PubMed Central

    Stewart, Christopher D.; Pedraza, Mayra; Arman, Hadi; Fan, Hua-Jun; Schilling, Eduardo Luiz; Szpoganicz, Bruno; Musie, Ghezai T.

    2016-01-01

    A new carboxylate rich asymmetric tripodal ligand, N-[2-carboxybenzomethyl]-N-[carboxymethyl]-β-alanine (H3camb), and its di-copper(II), (NH4)2[1]2, and di-zinc(II), ((CH3)4 N)2[2]2, complexes have been synthesized as carbohydrate binding models in aqueous solutions. The ligand and complexes have been fully characterized using several techniques, including single crystal X-ray diffraction. The interactions of (NH4)2[1]2 and ((CH3)4 N)2[2]2 with D-glucose, D-mannose, D-xylose and xylitol in aqueous alkaline media were investigated using UV–Vis and 13C-NMR spectroscopic techniques, respectively. The molar conductance, NMR and ESI–MS studies indicate that the complexes dissociate in solution to produce the respective complex anions, 1− and 2−. Complexes 1− and 2− showed chelating ability towards the naturally abundant and biologically relevant sugars, D-glucose, D-mannose, D-xylose, and xylitol. The complex ions bind to one molar equivalent of the sugars, even in the presence of stoichiometric excess of the substrates, in solution. Experimentally obtained spectroscopic data and computational results suggest that the substrates bind to the metal center in a bidentate fashion. Apparent binding constant values, pKapp, between the complexes and the substrates were determined and a specific mode of substrate binding is proposed. The pKapp and relativistic density functional theory (DFT) calculated Gibbs free energy values indicate that D-mannose displayed the strongest interaction with the complexes. Syntheses, characterizations, detailed substrate binding studies using spectroscopic techniques, single crystal X-ray diffraction and geometry optimizations of the complex-substrates with DFT calculations are also reported. PMID:25969174

  13. 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

  14. 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.

  15. Materials compatibility issues associated with aqueous alkaline cleaners

    SciTech Connect

    Lopez, E.P.; Montoya, M.G.

    1996-04-01

    As part of the Environmentally Conscious Manufacturing (ECM) technology, and in support of various mechanical assembly applications, several aqueous alkaline cleaners were studied as potential candidates for cleaning mechanical piece parts. Historically, ozone depleting and hazardous chlorinated cleaners have been used to degrease mechanical assemblies. In an effort to replace these chemicals, several cleaning processes, including aqueous alkaline cleaners, were screened as potential candidates using a variety of criteria, including aqueous alkaline cleaners, were screened as potential candidates using a variety of criteria, including: cleaning efficiency, materials compatibility, etch rate, corrosion, immersion tests, temperature/humidity exposure, and an exposure to a simulated indoor industrial environment. Cleaning efficiency was determined using visual examination, Auger electron spectroscopy, X-ray photoelectron spectroscopy, MESERAN, and goniometer/contact angle measurements. Several cleaners were identified as potential alternatives based solely on the cleaning results. Some of the cleaners, however, left undesirable residues. This paper will focus on materials compatibility issues of these aqueous cleaners after immersion tests, an etch rate study, and exposures to temperature/humidity and a standard industrial environment.

  16. 2010 Water & Aqueous Solutions

    SciTech Connect

    Dor Ben-Amotz

    2010-08-13

    Water covers more than two thirds of the surface of the Earth and about the same fraction of water forms the total mass of a human body. Since the early days of our civilization water has also been in the focus of technological developments, starting from converting it to wine to more modern achievements. The meeting will focus on recent advances in experimental, theoretical, and computational understanding of the behavior of the most important and fascinating liquid in a variety of situations and applications. The emphasis will be less on water properties per se than on water as a medium in which fundamental dynamic and reactive processes take place. In the following sessions, speakers will discuss the latest breakthroughs in unraveling these processes at the molecular level: Water in Solutions; Water in Motion I and II; Water in Biology I and II; Water in the Environment I and II; Water in Confined Geometries and Water in Discussion (keynote lecture and poster winners presentations).

  17. CESIUM RECOVERY FROM AQUEOUS SOLUTIONS

    DOEpatents

    Goodall, C.A.

    1960-09-13

    A process is given for precipitating cesium on zinc ferricyanide (at least 0.0004 M) from aqueous solutions containing mineral acid in a concentration of from 0.2 N acidity to 0.61 N acid-deficiency and advantageously, but not necessarily, also aluminum nitrate in a concentration of from l to 2.5 M.

  18. Cesium recovery from aqueous solutions

    DOEpatents

    Goodhall, C. A.

    1960-09-13

    A process for recovering cesium from aqueous solutions is given in which precipitation on zinc ferricyanide is used. The precipitation is preferably carried out in solutions containing at least 0.0004M zinc ferricyanide, an acidity ranging from 0.2N mineral acid to 0.61N acid deficiency, and 1 to 2.5M aluminum nitrate. (D.L.C.)

  19. CESIUM RECOVERY FROM AQUEOUS SOLUTIONS

    DOEpatents

    Schneider, R.A.

    1961-06-20

    Cesium may be precipitated from an aqueous solution whose acidity ranges between a pH of 1.5 and a molarity of 5 on cobaltous, zinc, cadmium, nickel, or ferrous cobalticyanide. This precipitation brings about a separation from most fission products. Ruthenium which coprecipitates to a great degree can be removed by dissolving in sulfuric acid and boiling the solution in the presence of periodic acid for volatilization; other coprecipitated fission products can then be precipitated from the sulfuric acid solution with a ferric hydroxide carrier.

  20. Sucrose diffusion in aqueous solution.

    PubMed

    Price, Hannah C; Mattsson, Johan; Murray, Benjamin J

    2016-07-28

    The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes-Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle. PMID:27364512

  1. Sucrose diffusion in aqueous solution

    PubMed Central

    Murray, Benjamin J.

    2016-01-01

    The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes–Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle. PMID:27364512

  2. 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.

  3. Stabilized aqueous hydrogen peroxide solution

    SciTech Connect

    Malin, M.J.; Sciafani, L.D.

    1988-05-17

    This patent describes a stabilized aqueous hydrogen peroxide solution having a pH below 7 and an amount of Ferric ion up to about 2 ppm comprising hydrogen peroxide, acetanilide having a concentration which ranges between 0.74 M Mol/L and 2.22 mMol/L, and o-benzene disulfonic acid or salt thereof at a concentration between about 0.86 mMol/L to about 1.62 mMol/L.

  4. Determination of bisphenol A in thermal printing papers treated by alkaline aqueous solution using the combination of single-drop microextraction and HPLC.

    PubMed

    Gao, Leihong; Zou, Jing; Liu, Haihong; Zeng, Jingbin; Wang, Yiru; Chen, Xi

    2013-04-01

    A method for the quantitative determination of bisphenol A in thermal printing paper was developed and validated. Bisphenol A was extracted from the paper samples using 2% NaOH solution, then the extracted analyte was enriched using single-drop microextraction followed by HPLC analysis. Several parameters relating to the single-drop microextraction efficiency including extraction solvent, extraction temperature and time, stirring rate, and pH of donor phase were studied and optimized. Spiked recovery of bisphenol A at 20 and 5 mg/g was found to be 95.8 and 108%, and the method detection limit and method quantification limit was 0.03 and 0.01 mg/g, respectively. Under the optimized conditions, the proposed method was applied to the determination of bisphenol A in seven types of thermal printing paper samples, and the concentration of bisphenol A was found in the range of 0.53-20.9 mg/g. The considerably minimum usage of organic solvents (5 μL 1-octanol) and high enrichment factor (189-197) in the sample preparation are the two highlighted advantages in comparison with previously published works.

  5. 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.

  6. REMOVAL OF CHLORIDE FROM AQUEOUS SOLUTIONS

    DOEpatents

    Schulz, W.W.

    1959-08-01

    The removal of chlorides from aqueons solutions is described. The process involves contacting the aqueous chloride containing solution with a benzene solution about 0.005 M in phenyl mercuric acetate whereby the chloride anions are taken up by the organic phase and separating the organic phase from the aqueous solutions.

  7. 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.

  8. Modeling reactive geochemical transport of concentrated aqueous solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Guoxiang; Zheng, Zuoping; Wan, Jiamin

    2005-02-01

    Aqueous solutions with ionic strength larger than 1 M are usually considered concentrated aqueous solutions. These solutions can be found in some natural systems and are also industrially produced and released into accessible natural environments, and as such, they pose a big environmental problem. Concentrated aqueous solutions have unique thermodynamic and physical properties. They are usually strongly acidic or strongly alkaline, with the ionic strength possibly reaching 30 M or higher. Chemical components in such solutions are incompletely dissociated. The thermodynamic activities of both ionic and molecular species in these solutions are determined by the ionic interactions. In geological media the problem is further complicated by the interactions between the solutions and sediments and rocks. The chemical composition of concentrated aqueous solutions when migrating through the geological media may be drastically altered by these strong fluid-rock interactions. To effectively model reactive transport of concentrated aqueous solutions, we must take into account the ionic interactions. For this purpose we substantially extended an existing reactive transport code, BIO-CORE2D©, by incorporating a Pitzer ion interaction model to calculate the ionic activity. In the present paper, the model and two test cases of the model are briefly introduced. We also simulate a laboratory column experiment in which the leakage of highly alkaline waste fluid stored at Hanford (a U.S. Department of Energy site, located in Washington State) was studied. Our simulation captures the measured pH evolution and indicates that all the reactions controlling the pH evolution, including cation exchanges and mineral dissolution/precipitation, are coupled.

  9. Photochemistry of norharmane in aqueous solution.

    PubMed

    Gonzalez, M Micaela; Salum, M Laura; Gholipour, Yousef; Cabrerizo, Franco M; Erra-Balsells, Rosa

    2009-08-01

    The photochemistry of norharmane (9H-pyrido[3,4-b]indole) in acidic (pH 5.0+/-0.1) and alkaline (pH 10.0+/-0.1) aqueous solutions was studied. The photochemical reactions were monitored by TLC, UV/VIS absorption spectroscopy, high-performance liquid chromatography (HPLC), electronic ionization-mass spectrometry (EI-MS), UV-laser desorption/ionization-time of flight-mass spectrometry (UV-LDI-TOF-MS) and an enzymatic method for H2O2 determination. The neutral (nHoN) and the protonated (nHoH+) forms of norharmane irradiated under Ar atmosphere were photostable, but they suffered a photochemical transformation in the presence of O2, yielding as photoproducts norharmane dimers, trimers and tetramers. nHoN shown to be more photostable than nHoH+. The nHoH+ and nHoN consumption quantum yields were 1.82x10(-3) and 0.51x10(-3), respectively, and the mechanisms involved in its photochemistry are discussed. H2O2 and singlet oxygen (1O2) were also detected and quantified in irradiated solutions of norharmane, and their role in the photochemistry of norharmane is discussed.

  10. Stability of cefozopran hydrochloride in aqueous solutions.

    PubMed

    Zalewski, Przemysław; Skibiński, Robert; Paczkowska, Magdalena; Garbacki, Piotr; Talaczyńska, Alicja; Cielecka-Piontek, Judyta; Jelińska, Anna

    2016-01-01

    The influence of pH on the stability of cefozopran hydrochloride (CZH) was investigated in the pH range of 0.44-13.00. Six degradation products were identified with a hybrid ESI-Q-TOF mass spectrometer. The degradation of CZH as a result of hydrolysis was a pseudo-first-order reaction. As general acid-base hydrolysis of CZH was not occurred in the solutions of hydrochloric acid, sodium hydroxide, acetate, borate and phosphate buffers, kobs = kpH because specific acid-base catalysis was observed. Specific acid-base catalysis of CZH consisted of the following reactions: hydrolysis of CZH catalyzed by hydrogen ions (kH+), hydrolysis of dications (k1H2O), monocations (k2H2O) and zwitter ions (k3H2O) and hydrolysis of zwitter ions (k1OH-) and monoanions (k2OH-) of CZH catalyzed by hydroxide ions. The total rate of the reaction was equal to the sum of partial reactions: [Formula: see text]. CZH similarly like other fourth generation cephalosporin was most stable at slightly acidic and neutral pH and less stable in alkaline pH. The cleavage of the β-lactam ring resulting from a nucleophilic attack on the carbonyl carbon in the β-lactam moiety is the preferred degradation pathway of β-lactam antibiotics in aqueous solutions.

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

    DOEpatents

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

    2001-01-01

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

  12. 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.

  13. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

    SciTech Connect

    De Visscher, Alex; Vanderdeelen, Jan

    2012-06-15

    The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO{sub 3} types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO{sub 3}{center_dot} H{sub 2}O), the hexahydrate ikaite (CaCO{sub 3}{center_dot}6H{sub 2}O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

  14. ENGINEERING BULLETIN: AIR STRIPPING OF AQUEOUS SOLUTIONS

    EPA Science Inventory

    Air striding is a means to transfer contaminants from aqueous solutions to air. ontaminants are not destroyed by air stripping but are physically separated from the aqueous solutions. ontaminant vapors are transferred into the air stream and, if necessary, can be treated by incin...

  15. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Beederman, M.; Vogler, S.; Hyman, H.H.

    1959-07-14

    The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

  16. Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

    PubMed

    Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

    2014-10-01

    Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques. PMID:24735991

  17. Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

    PubMed

    Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

    2014-10-01

    Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques.

  18. RECOVERY OF TETRAVALENT CATIONS FROM AQUEOUS SOLUTIONS

    DOEpatents

    Moore, R.L.

    1958-05-01

    The recovery of plutonium, zirconium, and tetravalent cerium values from aqueous solutions is described. It consists of adding an alkyl phosphate to a nnineral acid aqueous solution containing the metal to be recovered, whereby a precipitate forms with the tetravalent values, and separating the precipitate from the solution. All alkyl phosphates, if water-soluble, are suitable for the process; however, monobutyl phosphate has been found best.

  19. 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)

  20. 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.

  1. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Callis, C.F.; Moore, R.L.

    1959-09-01

    >The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

  2. Separation of metal ions from aqueous solutions

    SciTech Connect

    Almon, A.

    1991-12-31

    This invention is comprised of a process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flowing cell containing flowing bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flowing cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flowing cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

  3. Separation of metal ions from aqueous solutions

    DOEpatents

    Almon, Amy C.

    1994-01-01

    A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

  4. 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.

  5. ADSORPTION OF CERIUM VALUES FROM AQUEOUS SOLUTIONS

    DOEpatents

    Roberts, F.P.

    1963-08-13

    Cerium can be removed from aqueous nitric acid (2 to 13 M) solutions by passing the latter over a PbO/sub 2/-containing anion exchange resin. The cerium is taken up by the resin, while any lanthanides, yttrium, and strontium present remain in the solution. (AEC)

  6. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    DOEpatents

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  7. Precipitation of neptunium dioxide from aqueous solution

    SciTech Connect

    Roberts, K E

    1999-12-01

    Tens of thousands of metric tons of highly radioactive, nuclear waste have been generated in the US. Currently, there is no treatment or disposal facility for these wastes. Of the radioactive elements in high-level nuclear waste, neptunium (Np) is of particular concern because it has a long half-life and may potentially be very mobile in groundwaters associated with a proposed underground disposal site at Yucca Mountain, Nevada. Aqueous Np concentrations observed in previous, short-term solubility experiments led to calculated potential doses exceeding proposed long-term regulatory limits. However, thermodynamic data for Np at 25 C showed that these observed aqueous Np concentrations were supersaturated with respect to crystalline NpO{sub 2}. It was hypothesized that NpO{sub 2} is the thermodynamically stable solid phase in aqueous solution, but it is slow to form in an aqueous solution of NpO{sub 2}{sup +} on the time scale of previous experiments. The precipitation of NpO{sub 2} would provide significantly lower aqueous Np concentrations leading to calculated doses below proposed regulatory limits. To test this hypothesis, solubility experiments were performed at elevated temperature to accelerate any slow precipitation kinetics. Ionic NpO{sub 2}{sup +} (aq) was introduced into very dilute aqueous solutions of NaCl with initial pH values ranging from 6 to 10. The reaction vessels were placed in an oven and allowed to react at 200 C until steady-state aqueous Np concentrations were observed. In all cases, aqueous Np concentrations decreased significantly from the initial value of 10{sup {minus}4} M. The solids that formed were analyzed by x-ray powder diffraction, x-ray absorption spectroscopy, and scanning electron microscopy. The solids were determined to be high-purity crystals of NpO{sub 2}. This is the first time that crystalline NpO{sub 2} has been observed to precipitate from NpO{sub 2}{sup +}(aq) in near-neutral aqueous solutions. The results obtained

  8. 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.

  9. Condensation of oligoglycines with trimeta- and tetrametaphosphate in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Yamanaka, Junpei; Inomata, Katsuhiko; Yamagata, Yukio

    1988-09-01

    The dehydration condensation of glycine with trimetaphosphate in aqueous solution has been reinvestigated. Although it has been reported that the condensation of glycine under the alkaline conditions was brought about through the formation of cyclic acylphosphoramidate and hence the condensation of polyglycines could not occur, we found that the condensation of oligoglycines with trimeta- and tetrametaphosphate in aqueous solution are possible through the formation of their acylphosphates under the neutral or weak acidic conditions. Aqueous solutions of 1.0 M glycylglycine and 1.0 M trimetaphosphate in the various pH from 4.0 to 9.0 were incubated at 38 °C. The solutions were analyzed by HPLC with ninhydrin reaction system. Tetraglycine and hexaglycine were detected and their maximum yields were given in the reaction carried out around pH 7. They are approximately 15% and 4% after 30 days, respectively. Analogous experiments were performed with tetrametaphosphate. The results showed a similar pH dependence for the condensation, but the yields were about one-tenth of those of corresponding experiments with trimetaphosphate. Relative rates of dimerization of glycine, diglycine and triglycine in the equimolar concentration were also investigated at pH 6.0 at 38 °C. The rates for digylcine and triglycine were approximately twice and four times as large as that for glycine. Relevance of the experiments to chemical evolution is discussed.

  10. RECOVERY OF PROTACTINIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Elson, R.E.

    1959-07-14

    The recovery of fluoride complexed protactinium from aqueous acidic solutions by solvent extraction is described. Generally the prccess of the invention com rises mixing an aqueous solution containing protactinium in a complexed form with an organic solvent which is specific for protactinium, such as diisopropyl carbinol, then decomposing the protactinium complex by adjusting the acidity of the aqueous solution to between 0-3 to 0-9 M in hydrogen ion concentration, and introducing a source of aluminum ions in sufficient quantity to establish a concentration of 0.5 to 1.2 M aluminum ion, whereupon decomposition of the protactinium fluoride complex takes place and the protactinium ion is taken up by the organic solvent phase.

  11. Hydrophobic Solvation: Aqueous Methane Solutions

    ERIC Educational Resources Information Center

    Konrod, Oliver; Lankau, Timm

    2007-01-01

    A basic introduction to concept of a solvation shell around an apolar solute as well as its detection is presented. The hydrophobic solvation of toluene is found to be a good teaching example which connects macroscopic, phenomenological thermodynamic results with an atomistic point of view.

  12. Removal of uranium from aqueous HF solutions

    DOEpatents

    Pulley, Howard; Seltzer, Steven F.

    1980-01-01

    This invention is a simple and effective method for removing uranium from aqueous HF solutions containing trace quantities of the same. The method comprises contacting the solution with particulate calcium fluoride to form uranium-bearing particulates, permitting the particulates to settle, and separting the solution from the settled particulates. The CaF.sub.2 is selected to have a nitrogen surface area in a selected range and is employed in an amount providing a calcium fluoride/uranium weight ratio in a selected range. As applied to dilute HF solutions containing 120 ppm uranium, the method removes at least 92% of the uranium, without introducing contaminants to the product solution.

  13. A new association state of solutes in nanoconfined aqueous solutions

    NASA Astrophysics Data System (ADS)

    Tu, YuSong; Zhao, Liang; Fang, HaiPing

    2016-11-01

    Recently, we have found a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, where solutes exhibit distinct behavior in a new association state from that in the dispersion and aggregation states observed usually in macroscopic systems. However, it remains unknown whether this new association state of solute molecules found in nanoconfined systems would vanish with the system size increasing and approaching the macroscopic scale. Here, we achieve the phase diagram of solute association states by making the analyses of Gibbs free energy of solutes in nanoconfined aqueous solutions in detail. In the phase diagram, we observe a closed regime with a finite system size of nanoconfined aqueous solutions and a solute concentration range, only in which there exists the new association state of solutes with the reversible transition between the aggregation and dispersion states, and there indeed exists an upper limit of the system size for the new association state, around several tens nanometers. These findings regarding the intimate connection between the system size and the solute association behavior provides the comprehensive understanding of the association dynamics of solutes in nanoconfined environment.

  14. Isothermal and nonisothermal decomposition of famotidine in aqueous solution.

    PubMed

    Junnarkar, G H; Stavchansky, S

    1995-04-01

    The kinetics of hydrolysis of famotidine in aqueous solution was studied by isothermal and nonisothermal method over the pH range of 1.71 to 10.0. Nonisothermal kinetics was studied with the purpose of determining its use in the establishment of the expiration date of pharmaceutical preparations, particularly drugs in solutions and for assessment of stability characteristics of pharmaceutical formulations during the development stage. A comparison of isothermal (55, 70 and 85 degrees C) and nonisothermal kinetics was performed. Aqueous solutions of famotidine were buffered at pH 1.71, 2.24, 2.66, 4.0, 8.5, 9.0 and 10.0 were used. In the nonisothermal studies, the temperature rate of the reaction was continuously varied throughout the experiment. The energies of activation were found to be in close agreement for isothermal and nonisothermal studies, indicating that nonisothermal studies may save considerable amount of time in the early stages of drug development and stability testing. Logk-pH profiles were constructed for 55, 70 and 85 degrees C from the first-order rate constants obtained from isothermal studies at pH values ranging from 1.71 to 10.00. The pH-rate profile indicated that famotidine undergoes specific acid catalysis in the acidic region and general base catalysis in the alkaline region. Hydrolysis in the acidic and alkaline media resulted in the formation of four and five degradation products, respectively. A possible degradation pathway for the acidic and alkaline hydrolysis was discussed. PMID:7596998

  15. Aqueous Solution Chemistry on Mars

    NASA Astrophysics Data System (ADS)

    Quinn, R.; Hecht, M.; Kounaves, S.; Young, S.; West, S.; Fisher, A.; Grunthaner, P.

    2007-12-01

    Currently en route to Mars, the Phoenix mission carries four wet chemistry cells designed to perform basic solution chemistry on martian soil. The measurement objectives are typical of those that would be performed on an unknown sample on Earth, including detection of common anions and cations, total conductivity, pH, redox potential, cyclic voltammetry (CV), etc. Both the challenge and the novelty arise from the necessity to perform these measurements with severely constrained resources in a harsh and (literally) alien environment. Sensors for all measurements are integrated into a common "beaker," with the ability to perform a two-point calibration of some sensors using a pair of low-concentration solutions. Sulfate measurement is performed with a crude titration. While most measurements use ion selective electrodes, halide interferences are resolved by independent chronopotentiometry (CP) measurements. No preconditioning of the soil-water mixture is possible, nor is any physical characterization of the introduced soil sample beyond coarse visual inspection. Among the idiosyncrasies of the measurement is the low external pressure, which requires that the analysis be performed close to the boiling point of water under an atmosphere consisting almost entirely of water vapor. Despite these liabilities, however, extensive laboratory characterization has validated the basic approach, and protocols for both CV and CP have been developed and tested. Enhancing the value of the measurement is the suite of coordinated observations, such as microscopy and evolved gas analysis, to be performed by other Phoenix instruments.

  16. RECOVERY OF PLUTONIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Reber, E.J.

    1959-09-01

    A process is described for recovering plutonium values from aqueous solutions by precipitation on bismuth phosphate. The plutonium is secured in its tetravalent state. bismuth salt is added to the solution, and ant excess of phosphoric acid anions is added to the solution in two approximately equal installments. The rate of addition of the first installment is about two to three times as high as the rate of addition of the second installment, whereby a precipitate of bismuth phosphate forms, the precipitate carrying the plutonium values. The precipitate is separated from the solution.

  17. PHOTOREACTION OF VALEROPHENONE IN AQUEOUS SOLUTION

    EPA Science Inventory

    Kinetics and products of the photoreaction of the phenyl ketone valerophenone were investigated as a function of temperature, pH, and wavelength in aqueous solution. Under these conditions (<10-4M), the photoreactions are pseudo-first-order with respect to valerophenone concentra...

  18. Water & Aqueous Solutions. Final Progress Report

    SciTech Connect

    2002-08-09

    The Gordon Research Conference (GRC) on Water & Aqueous Solutions was held at Holderness School, New Hampshire, 8/4/02 thru 8/9/02. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  19. SEPARATION OF SCANDIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Peppard, D.F.; Nachtman, E.S.

    1958-02-25

    This patent relates to a process for the separation of scandium from yttrium, thorium, and trivalent rare earths and with their separation from each other. It has been found that scandium and yttrium can be separated from trivalent rare earths in acidic solution, for example, a solution 6 M in HCl, by contacting with tributyl phosphate, whereupon the scandum is preferentially extracted into the organic phase, leaving the yttrium and trivalent rare earths in the aqueous phase.

  20. 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.

  1. Exclusion of Nitrate from Frozen Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Marrocco, H. A.; Michelsen, R. R.

    2013-12-01

    Reactions occurring at the surface of ice, sea ice, and snow in Earth's cryosphere have an impact on the composition of the overlying atmosphere. In order to elucidate reaction mechanisms and model their contributions to atmospheric processes, the morphology of frozen aqueous surfaces and amounts of reactants contained therein must be determined. To this end, the exclusion of nitrate ions to the surface of frozen aqueous solutions has been studied by attenuated total reflection infrared spectroscopy (ATR-IR). In this technique the near-surface region of the frozen films are interrogated to a depth of a few hundred nanometers from the film-crystal interface. Aqueous solutions (0.001 to 0.01 M) of sodium nitrate (NaNO3), magnesium nitrate (Mg(NO3)2), and nitric acid (HNO3) were quickly frozen on the germanium ATR crystal and observed at a constant temperature of about -18°C. In addition to ice and the solutes, liquid water in varying amounts was observed in the spectra. The amount of nitrate in the surface liquid is three to four orders of magnitude higher than in the unfrozen solution. While all the nitrate salts exhibit exclusion to the unfrozen surface, the dynamics are different for different counter-ions. Results are compared to freezing point depression data and the predictions of equilibrium thermodynamics.

  2. Air stripping of aqueous solutions. Engineering bulletin

    SciTech Connect

    Not Available

    1991-10-01

    Air stripping is a means to transfer contaminants from aqueous solutions to air. Contaminants are not destroyed by air stripping but are physically separated from the aqueous solutions. Contaminant vapors are transferred into the air stream and, if necessary, can be treated by incineration, adsorption, or oxidation. Most frequently, contaminants are collected in carbon adsorption systems and then treated or destroyed in this concentrated form. The concentrated contaminants may be recovered, incinerated for waste heat recovery, or destroyed by other treatment technologies. Generally, air stripping is used as one in a series of unit operations and can reduce the overall cost for managing a particular site. Air stripping is applicable to volatile and semivolatile organic compounds. It is not applicable for treating metals and inorganic compounds. The bulletin provides information on the technology applicability, the technology limitations, a description of the technology, the types of residuals produced, site requirements, the latest performance data, the status of the technology, and sources of further information.

  3. Aqueous solution dispersement of carbon nanotubes

    NASA Technical Reports Server (NTRS)

    Kim, Jae-Woo (Inventor); Park, Cheol (Inventor); Choi, Sang H. (Inventor); Lillehei, Peter T. (Inventor); Harrison, Joycelyn S. (Inventor)

    2011-01-01

    Carbon nanotubes (CNTs) are dispersed in an aqueous buffer solution consisting of at least 50 weight percent water and a remainder weight percent that includes a buffer material. The buffer material has a molecular structure defined by a first end, a second end, and a middle disposed between the first and second ends. The first end is a cyclic ring with nitrogen and oxygen heteroatomes, the middle is a hydrophobic alkyl chain, and the second end is a charged group.

  4. REMOVAL OF CHLORIDE FROM AQUEOUS SOLUTIONS

    DOEpatents

    Hyman, M.L.; Savolainen, J.E.

    1960-01-01

    A method is given for dissolving reactor fuel elements in which the uranium is associated with a relatively inert chromium-containing alloy such as stainless steel. An aqueous mixture of acids comprising 2 to 2.5 molar hydrochloric acid and 4 to 8 molar nitric acid is employed in dissolving the fuel element. In order io reduce corrosion in subsequent processing of the resulting solution, chloride values are removed from the solution by contacting it with concentrated nitric acid at an elevated temperature.

  5. Radiation chemistry of aqueous solutions of actinides

    NASA Astrophysics Data System (ADS)

    Pikaev, Alexei K.; Shilov, Vladimir P.; Gogolev, Andrei V.

    1997-09-01

    The data on radiolytic transformations of ions of uranium, neptunium, plutonium, americium, curium and transcurium elements in aqueous solutions are generalised. The results of studies on the kinetics of fast reactions of these ions with primary products of water radiolysis (hydrated electron e-aq, H, OH, and O- radicals and H2O2), many inorganic (Cl2-, NO3, SO4-, CO3-, O3- etc.) and organic free radicals are analysed. The mechanism of γ- and α-radiolysis of solutions of actinide ions is discussed. The bibliography includes 183 references.

  6. Density of aqueous solutions of CO2

    SciTech Connect

    Garcia, Julio E.

    2001-10-10

    In this report, we present a numerical representation for the partial molar volume of CO2 in water and the calculation of the corresponding aqueous solution density. The motivation behind this work is related to the importance of having accurate representations for aqueous phase properties in the numerical simulation of carbon dioxide disposal into aquifers as well as in geothermal applications. According to reported experimental data the density of aqueous solutions of CO2 can be as much as 2-3% higher than pure water density. This density variation might produce an influence on the groundwater flow regime. For instance, in geologic sequestration of CO2, convective transport mixing might occur when, several years after injection of carbon dioxide has stopped, the CO2-rich gas phase is concentrated at the top of the formation, just below an overlaying caprock. In this particular case the heavier CO2 saturated water will flow downward and will be replaced by water with a lesser CO2 content.

  7. Aqueous Solution Vessel Thermal Model Development II

    SciTech Connect

    Buechler, Cynthia Eileen

    2015-10-28

    The work presented in this report is a continuation of the work described in the May 2015 report, “Aqueous Solution Vessel Thermal Model Development”. This computational fluid dynamics (CFD) model aims to predict the temperature and bubble volume fraction in an aqueous solution of uranium. These values affect the reactivity of the fissile solution, so it is important to be able to calculate them and determine their effects on the reaction. Part A of this report describes some of the parameter comparisons performed on the CFD model using Fluent. Part B describes the coupling of the Fluent model with a Monte-Carlo N-Particle (MCNP) neutron transport model. The fuel tank geometry is the same as it was in the May 2015 report, annular with a thickness-to-height ratio of 0.16. An accelerator-driven neutron source provides the excitation for the reaction, and internal and external water cooling channels remove the heat. The model used in this work incorporates the Eulerian multiphase model with lift, wall lubrication, turbulent dispersion and turbulence interaction. The buoyancy-driven flow is modeled using the Boussinesq approximation, and the flow turbulence is determined using the k-ω Shear-Stress-Transport (SST) model. The dispersed turbulence multiphase model is employed to capture the multiphase turbulence effects.

  8. Formation of electroactive colloids via in situ coprecipitation under electric field: erbium chloride alkaline aqueous pseudocapacitor.

    PubMed

    Chen, Kunfeng; Xue, Dongfeng

    2014-09-15

    For the first time, a new ErCl3 alkaline aqueous pseudocapacitor system was demonstrated by designing commercial ErCl3 salt electrode in alkaline aqueous electrolyte, where the materials synthesis and subsequently integrating into practical electrode structures occur at the same spatial and temporal scale. Highly electroactive ErOOH colloids were in-situ crystallized via electric field assisted chemical coprecipitation of ErCl3 in KOH aqueous electrolyte. These electroactive ErOOH colloids absorbed by carbon black and PVDF matrix were highly redox-reactive with higher cation utilization ratio of 86 % and specific capacitance values of 1811F/g, exceeding the one-electron redox theoretical capacitance (Er(3+)↔Er(2+)). We believe that additional two-electron (Er(2+)↔Er) or three-electron (Er(3+)↔Er) reactions can occur in our designed ErCl3 alkaline aqueous pseudocapacitor system. The specific electrode configuration with ErOOH colloids grown among the carbon black/PVDF matrix can create short ion diffusion and electron transfer length to enable the fast and reversible Faradaic reactions. This work shows promising for finding high-performance electrical energy storage systems via designing the colloidal state of electroactive cations with the utilization of in-situ crystallization route.

  9. 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.

  10. Ultraviolet emission from porous silicon photosynthesized in aqueous alkali fluoride solutions

    SciTech Connect

    Uchida, Kaoru; Tomioka, Katsuhiro; Adachi, Sadao

    2006-07-01

    Stable ultraviolet (UV) photoluminescence (PL) has been observed at room temperature in porous silicon (PSi) fabricated by photoetching in aqueous alkali fluoride solutions. The aqueous solutions used are 1 M NaF and 1 M KF. They give an alkaline reaction caused by partial hydrolysis. The PL peaks at {approx}3.3 eV have a full width at half maximum of {approx}0.1 eV, which is much smaller than those reported previously ({>=}0.5 eV). Spectral analyses suggest that both quantum confinement and surface passivation effects enable the observation of UV emission in NaF- and KF-prepared PSi samples.

  11. Pulse Radiolysis of Aqueous Thiocyanate Solution

    SciTech Connect

    Milosavljevic, Bratoljub H.; LaVerne, Jay A.

    2005-01-13

    The pulse radiolysis of N2O saturated aqueous solutions of KSCN was studied under neutral pH conditions. The observed optical absorption spectrum of the SCN• radical in solution is more complex than previously reported, but it is in good agreement with that measured in the gas phase. Kinetic traces at 330 nm and 472 nm corresponding to SCN• and (SCN)2•¯, respectively, were fit using a Monte Carlo simulation kinetic model. The rate coefficient for the oxidation of SCN¯ ions by OH radicals, an important reaction used in competition kinetics measurements, was found to be 1.4 ± 0.1 x 1010 M-1 s-1, about 30 % higher than the normally accepted value. A detailed discussion of the reaction mechanism is presented.

  12. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments.

  13. Aqueous Solutions of Ionic Liquids: Microscopic Assembly.

    PubMed

    Vicent-Luna, Jose Manuel; Dubbeldam, David; Gómez-Álvarez, Paula; Calero, Sofia

    2016-02-01

    Aqueous solutions of ionic liquids are of special interest, due to the distinctive properties of ionic liquids, in particular, their amphiphilic character. A better understanding of the structure-property relationships of such systems is hence desirable. One of the crucial molecular-level interactions that influences the macroscopic behavior is hydrogen bonding. In this work, we conduct molecular dynamics simulations to investigate the effects of ionic liquids on the hydrogen-bond network of water in dilute aqueous solutions of ionic liquids with various combinations of cations and anions. Calculations are performed for imidazolium-based cations with alkyl chains of different lengths and for a variety of anions, namely, [Br](-), [NO3](-), [SCN](-) [BF4](-), [PF6](-), and [Tf2N](-). The structure of water and the water-ionic liquid interactions involved in the formation of a heterogeneous network are analyzed by using radial distribution functions and hydrogen-bond statistics. To this end, we employ the geometric criterion of the hydrogen-bond definition and it is shown that the structure of water is sensitive to the amount of ionic liquid and to the anion type. In particular, [SCN](-) and [Tf2N](-) were found to be the most hydrophilic and hydrophobic anions, respectively. Conversely, the cation chain length did not influence the results.

  14. Models of globular proteins in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Wentzel, Nathaniel James

    Protein crystallization is a continuing area of research. Currently, there is no universal theory for the conditions required to crystallize proteins. A better understanding of protein crystallization will be helpful in determining protein structure and preventing and treating certain diseases. In this thesis, we will extend the understanding of globular proteins in aqueous solutions by analyzing various models for protein interactions. Experiments have shown that the liquid-liquid phase separation curves for lysozyme in solution with salt depend on salt type and salt concentration. We analyze a simple square well model for this system whose well depth depends on salt type and salt concentration, to determine the phase coexistence surfaces from experimental data. The surfaces, calculated from a single Monte Carlo simulation and a simple scaling argument, are shown as a function of temperature, salt concentration and protein concentration for two typical salts. Urate Oxidase from Asperigillus flavus is a protein used for studying the effects of polymers on the crystallization of large proteins. Experiments have determined some aspects of the phase diagram. We use Monte Carlo techniques and perturbation theory to predict the phase diagram for a model of urate oxidase in solution with PEG. The model used includes an electrostatic interaction, van der Waals attraction, and a polymerinduced depletion interaction. The results agree quantitatively with experiments. Anisotropy plays a role in globular protein interactions, including the formation of hemoglobin fibers in sickle cell disease. Also, the solvent conditions have been shown to play a strong role in the phase behavior of some aqueous protein solutions. Each has previously been treated separately in theoretical studies. Here we propose and analyze a simple, combined model that treats both anisotropy and solvent effects. We find that this model qualitatively explains some phase behavior, including the existence of

  15. Terahertz absorption of dilute aqueous solutions

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  16. Terahertz absorption of dilute aqueous solutions.

    PubMed

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

    2012-12-21

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

  17. 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.

  18. Pathways of aqueous Cr(VI) attenuation in a slightly alkaline oxic subsurface

    SciTech Connect

    Qafoku, Nikolla; Dresel, P. Evan; McKinley, James P.; Liu, Chongxuan; Heald, Steve M.; Ainsworth, Calvin C.; Phillips, Jerry L.; Fruchter, Jonathan S.

    2009-01-21

    Column experiments combined with geochemical modeling, microscopic inspections and spectroscopic interrogations were conducted with four freshly or naturally aged contaminated sediments with concentrated Cr(VI) waste fluids. The objective was to determine sediment-dependent Cr(VI) desorption extent and rates, Cr(VI) physical location and soil mineral associations, and mechanism(s) of Cr(VI) attenuation under mild alkaline conditions. Results showed that majority of Cr(VI) mass was easily removed from all sediments. Equilibrium site Kd varied from 0 to 0.33 ml g-1 and equilibrium site fraction was greater than 95 %. In addition, long tailings of time-dependent Cr(VI) concentrations above Environmental Protection Agency maximum concentration limit (MCL) of 1.9 µmol L-1, were also observed (kinetic site Kd and desorption reaction half-life varied from 0 to 45 ml g-1, and 76.1 to 126 h, respectively). Aqueous phase pH, particle size distribution and pore water composition contributed to the variability observed among sediments. Microscopic and spectroscopic studies confirmed that Cr was concentrated within fine-grained coatings in small areas rich in phyllosilicates that contained mixed valence [Cr(III)/Cr(VI)]. However, Cr(VI) reduction was neither significant nor complete. The kinetically controlled Cr(VI) desorption may have resulted from the transport (diffusion) of Cr(VI) out of these areas. In summary, at least four pools of Cr(VI) with different leaching behavior might be present in sediments exposed to concentrated waste fluids: i.) The pool of highly mobile and easily removed Cr(VI) (over 95% of total Cr); ii.) The pool of Cr(VI) held in remote sites that provided a long-term continuing source of contaminant Cr; iii.) The pool of reduced immobile Cr(III) which was formed, most likely, by redox reactions of aqueous Cr(VI) and aqueous, sorbed, or structural Fe(II); vi.) The pool of sparingly soluble Cr(VI) phases (e.g., BaCrO4) or solid solutions which did not

  19. Aqueous solubility and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20).

    PubMed

    Karakaya, Pelin; Sidhoum, Mohammed; Christodoulatos, Christos; Nicolich, Steve; Balas, Wendy

    2005-04-11

    The recently developed polycyclic nitramine CL-20 is considered as a possible replacement for the monocyclic nitramines RDX and HMX. The present study reports aqueous solubility data for CL-20, as well as the kinetic parameters for its alkaline hydrolysis with sodium hydroxide below and above its solubility limits. Aqueous solubility of CL-20 was measured in the temperature range of 4-69 degrees C and the data were fitted to a generalized solubility model. Alkaline hydrolysis experiments were conducted at 15, 20, 30 and 40 degrees C, with hydroxide concentrations ranging from 0.25 to 300 mM. Like RDX and HMX, alkaline hydrolysis of CL-20 follows second-order kinetics. CL-20 alkaline hydrolysis was found to proceed at a significantly faster rate than RDX. The temperature dependency of the second-order rate constants was evaluated using the Arrhenius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX.

  20. Aqueous solubility and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20).

    PubMed

    Karakaya, Pelin; Sidhoum, Mohammed; Christodoulatos, Christos; Nicolich, Steve; Balas, Wendy

    2005-04-11

    The recently developed polycyclic nitramine CL-20 is considered as a possible replacement for the monocyclic nitramines RDX and HMX. The present study reports aqueous solubility data for CL-20, as well as the kinetic parameters for its alkaline hydrolysis with sodium hydroxide below and above its solubility limits. Aqueous solubility of CL-20 was measured in the temperature range of 4-69 degrees C and the data were fitted to a generalized solubility model. Alkaline hydrolysis experiments were conducted at 15, 20, 30 and 40 degrees C, with hydroxide concentrations ranging from 0.25 to 300 mM. Like RDX and HMX, alkaline hydrolysis of CL-20 follows second-order kinetics. CL-20 alkaline hydrolysis was found to proceed at a significantly faster rate than RDX. The temperature dependency of the second-order rate constants was evaluated using the Arrhenius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX. PMID:15811680

  1. 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.

  2. Stability of ricobendazole in aqueous solutions.

    PubMed

    Wu, Zimei; Tucker, Ian G; Razzak, Majid; Medlicott, Natalie J

    2009-07-12

    The chemical stability of ricobendazole (RBZ) was investigated using a stability-indicating high performance liquid chromatographic (HPLC) assay with ultraviolet detection. The degradation kinetics of RBZ in aqueous solution was evaluated as a function of pH, buffer strength and temperature. The oxidation reaction in hydrogen peroxide solution was also studied. Degradation products were analyzed by mass spectroscopy and degradation pathways are proposed. Degradation of RBZ followed pseudo first-order kinetics and Arrhenius behavior over the temperature range 24-55 degrees C. A V-shaped pH-rate profile over the pH range 2-12 was observed with maximum stability at pH 4.8. The shape of the pH-rate profile was rationalized by catalytic effects of various components in the solution on each RBZ species. At pH 11 the activation energy for hydrolysis was 79.5 kJ/mol, and phosphate catalysis was not observed. Oxidation occurred in hydrogen peroxide solutions and was catalyzed by the presence of copper (Cu(2+)) ions. Ricobendazole amine and albendazole sulfone were identified by MS assay to be the degradation products of hydrolysis and oxidation respectively. PMID:19342190

  3. Phase behavior of DODAB aqueous solution

    SciTech Connect

    Voronov, V. P.; Kuryakov, V. N.; Muratov, A. R.

    2012-12-15

    Phase behavior of DODAB aqueous solution, prepared without sonication, was studied by adiabatic scanning calorimetry. Measurements revealed four phase transitions with the temperatures 35.2, 39.6, 44.6, and 52.4 Degree-Sign C at heating and one transition at the temperature 40.4 Degree-Sign C at cooling. The first three transitions at heating occur in unilamellar vesicles. The first and third transitions correspond to the subgel-gel and gelliquid phase transitions, corresponding enthalpy jumps are equal to 33 and 49 kJ/mol. The second transition appears after some aging and is similar to gel-ripple phase transition in a DPPC solution, with the enthalpy jump under the transition exceeding 7.4 kJ/mol. The transition occurs in unilamellar vesicles. The transition at the temperature 52.4 Degree-Sign C occurs in another subsystem of the solution, which we believe to be multilamellar vesicles. The enthalpy jump at this transition is equal to 97 kJ/mol, and data analysis suggests that this is a subgel-liquid transition. The phase transition at cooling is the liquid-gel transition in unilamellar vesicles. During the measurements, a slow evolution of the solution occurs, consisting in a change of concentrations of unilamellar and multilamellar vesicles. This transformation mainly occurs at low temperatures.

  4. Heterogeneous nucleation of aspartame from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Kubota, Noriaki; Kinno, Hiroaki; Shimizu, Kenji

    1990-03-01

    Waiting times, the time from the instant of quenching needed for a first nucleus to appear, were measured at constant supercoolings for primary nucleation of aspartame (α-L-aspartyl-L-phenylalanine methylester) from aqueous solutions, which were sealed into glass ampoules (solution volume = 3.16 cm 3). Since the waiting time became shorter by filtering the solution prior to quenching, the nucleation was concluded to be heterogeneously induced. The measured waiting time consisted of two parts: time needed for the nucleus to grow to a detactable size (growth time) and stochastic time needed for nucleation (true waiting time). The distribution of the true waiting time, is well explained by a stochastic model, in which nucleation is regarded to occur heterogeneously and in a stochastic manner by two kinds of active sites. The active sites are estimated to be located on foreign particles in which such elements as Si, Al and Mg were contained. The amount of each element is very small in the order of magnitude of ppb (mass basis) of the whole solution. The growth time was correlated with the degree of supercooling.

  5. 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

  6. 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.

  7. Mg isotope fractionation between inorganic aragonite and aqueous solution

    NASA Astrophysics Data System (ADS)

    Wang, Z.; Zhang, S.; Hu, P.

    2012-12-01

    Recent studies showed δ26Mg values of some species of Scleractinian corals, and aragonitic sponges and Scaphopod are inconsistent with the Mg isotope fractionation calibrated previously between inorganic aragonite and seawater. In this study, we explored Mg isotope fractionation between aragonite and aqueous solution under various experimental conditions, including salinity (mostly in fresh water), Mg/Ca ratio (3-5 in molar), Ca concentration (400-1500 ppm), temperature (25-55oC) and duration of experiments (3-21 days). Precipitation experiments were conducted using 'free-drift' method. The starting solution was made by mixing an appropriate amount of reagent-grade NaHCO3, CaCl2 and MgCl2 in deionized water, flushed with CO2 gas. The mixed solution was filtered after these reagents completely dissolved before any experiment, and then passively-degassed in a water bath kept at a constant temperature. Over the course of the experiments, pH and alkalinity of the aqueous solution were closely monitored. At the end of the experiment, the precipitates were cleaned, characterized by SEM and checked by XRD. The solution and precipitates were treated by acid. The supernatant was passed through two chromatographic columns to extract pure Mg, and measured for their δ26Mg values. In each case, a leaching procedure is employed to clean aragonite before their isotopic compositions were measured. Our preliminary results show that the Mg isotope fractionation between aragonite and solution varies with Ca concentration at a given Mg/Ca ratio, i.e., aragonite are strongly depleted in 26Mg in solution with high and low Ca concentration (e.g., Ca = 400ppm and 2000 ppm), but less depleted in solutions with intermediate Ca concentration (e.g., Ca= 1000 ppm). At a given Ca and Mg/Ca, the fractionation factor is temperature-dependent, defining linear relationship with 1/T (T is temperature in Kelvin) with temperature sensitivity of ~ 0.01‰/oC. These results seem to suggest a kinetic

  8. Functionalized polymers for binding to solutes in aqueous solutions

    DOEpatents

    Smith, Barbara F.; Robison, Thomas W.

    2006-11-21

    A functionalized polymer for binding a dissolved molecule in an aqueous solution is presented. The polymer has a backbone polymer to which one or more functional groups are covalently linked. The backbone polymer can be such polymers as polyethylenimine, polyvinylamine, polyallylamine, and polypropylamine. These polymers are generally water-soluble, but can be insoluble when cross-linked. The functional group can be for example diol derivatives, polyol derivatives, thiol and dithiol derivatives, guest-host groups, affinity groups, beta-diphosphonic acids, and beta-diamides

  9. Photodegradation of acetone in dilute aqueous solution

    SciTech Connect

    Stefan, M.I.; Bolton, J.R.

    1995-12-31

    Photochemical methods for destroying organic pollutants found in industrial wastewaters and groundwaters are being used successfully in environment treatment systems. This study focuses on acetone photodegradation in aqueous solution by UV irradiation (1 kW medium pressure Hg lamp) in the presence and absence of H{sub 2}O{sub 2}. Intermediates such as acetic and formic acids were detected. The kinetic data were evaluated and the reaction mechanisms were postulated considering the influence of oxygen concentration and pH. The generation of {sm_bullet}OH radicals from the photolysis of H{sub 2}O{sub 2} induces a faster decomposition of acetone (depending on H{sub 2}O{sub 2} concentration) than does direct photolysis.

  10. Process for decomposing nitrates in aqueous solution

    DOEpatents

    Haas, Paul A.

    1980-01-01

    This invention is a process for decomposing ammonium nitrate and/or selected metal nitrates in an aqueous solution at an elevated temperature and pressure. Where the compound to be decomposed is a metal nitrate (e.g., a nuclear-fuel metal nitrate), a hydroxylated organic reducing agent therefor is provided in the solution. In accordance with the invention, an effective proportion of both nitromethane and nitric acid is incorporated in the solution to accelerate decomposition of the ammonium nitrate and/or selected metal nitrate. As a result, decomposition can be effected at significantly lower temperatures and pressures, permitting the use of system components composed of off-the-shelf materials, such as stainless steel, rather than more costly materials of construction. Preferably, the process is conducted on a continuous basis. Fluid can be automatically vented from the reaction zone as required to maintain the operating temperature at a moderate value--e.g., at a value in the range of from about 130.degree.-200.degree. C.

  11. 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.

  12. [Radiolysis of aqueous solution of thiocyanate by gamma-rays].

    PubMed

    Feng, Hai-bing; Yang, Ming-de; Hu, Hu-sheng; Huang, Hui-ping

    2008-06-01

    Radiolysis of aqueous solution of thiocyanate by 60Co gamma-rays was studied. In condition of pH = 1 and pH = 3,25 mg/L SCN- was decomposed under the dose of 6 kGy, with decomposition rate of 98.11% (pH = 1) and 95.97% (pH = 3) respectively. 25 mg/L SCN- (pH = 7) was decomposed under the dose of 9 kGy and the decomposition rate is 99.33%. In the alkaline condition, pH = 10 and pH = 12, the dose of 18 kGy was need, and the decomposition rate is 99.64% and 99.93% respectively. High SCN- concentration means that more radiation dose is need. From the comparison of before radiolysis and after radiolysis's TOC (total organic carbon) and TN (total nitrogen) of SCN- solution, little TOC and TN was removed. The determination of SO4(2-) and NO3- concentration indicated that sulfur element was removed and converted to SO4(2-), and nitrogen element rarely converted to NO3-, but converted to other forms of nitrogen.

  13. Biosorption of metal ions from aqueous solutions

    SciTech Connect

    Chen, Jiaping; Yiacoumi, Sotira

    1997-01-01

    Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role in the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.

  14. Formation of hydroxyapatite in various aqueous solutions

    NASA Astrophysics Data System (ADS)

    Sturgeon, Jacqueline Lee

    Hydroxyapatite (HAp), Ca10(PO4)6(OH) 2, is important in the field of biomaterials as it is the mineral component of bones and teeth. Biological apatites do not maintain an exact composition and are usually calcium-deficient, represented as Ca(10- x)(HPO 4)x(PO4)(6-x)(OH)(2-x), where x ranges from 0 to 1, with various ion substitutions. Formation of calcium-deficient hydroxyapatites (CDHAp) from solid calcium phosphate precursor materials was performed at physiologic temperature (37°C) in a variety of aqueous solutions. Two cement systems were utilized in these experiments: tetralcium phosphate (TetCP) with dicalcium phosphate anhydrous (DCPA) and beta-tricalcium phosphate (beta-TCP). The kinetics, solution chemistry, phase evolution, and microstructure of the developed apatites were analyzed as appropriate. Reaction of beta-TCP in ammonium fluoride solutions formed HAp substituted with fluoride and calculated to be deficient in calcium. A new ratio of TetCP to DCPA was used with solutions of sodium bicarbonate to form a calcium-deficient carbonate hydroxyapatite. The capacity for sodium dihydrogen phosphate to buffer pH increases and enhance reaction kinetics in this system was also explored. Formation of a highly crystalline CDHAp was achieved by hydrolyzing beta-TCP in water for extended time periods. Lattice parameters were among the features characterized for this apatite. The hydrolysis of beta-TCP in phosphate buffered saline (PBS) and simulated body fluids (SBF) was also investigated; use of SBF was found to completely inhibit formation of HAp in this system while reaction in PBS was slow in comparison to water. The effects of filler materials on the mechanical properties of a calcium phosphate cement were examined using the TetCP/DCPA system. Dense aggregates were not found to decrease compressive strength in comparison to the cement alone. The use of aggregates was found to improve the compressive strength of cement formed using NaHCO3 solution as a

  15. REDISTRIBUTION OF ALKALINE ELEMENTS IN ASSOCIATION WITH AQUEOUS ACTIVITY IN THE EARLY SOLAR SYSTEM

    SciTech Connect

    Hidaka, Hiroshi; Higuchi, Takuya; Yoneda, Shigekazu E-mail: s-yoneda@kahaku.go.jp

    2015-12-10

    It is known that the Sayama meteorite (CM2) shows an extensive signature for aqueous alteration on the meteorite parent body, and that most of the primary minerals in the chondrules are replaced with phyllosilicates as the result of the aqueous alteration. In this paper, it is confirmed from the observation of two-dimensional Raman spectra that a part of olivine in a chondrule collected from the Sayama chondrite is serperntinized. Ion microprobe analysis of the chondrule showed that alkaline elements such as Rb and Cs are heterogeneously redistributed in the chondrule. The result of higher Rb and Cs contents in serpentinized phases in the chondrule rather than in other parts suggested the selective adsorption of alkaline elements into the serpentine in association with early aqueous activity on the meteorite parent body. Furthermore Ba isotopic analysis provided variations of {sup 135}Ba/{sup 138}Ba and {sup 137}Ba/{sup 138}Ba in the chondrule. This result was consistent with our previous isotopic data suggesting isotopic evidence for the existence of the presently extinct nuclide {sup 135}Cs in the Sayama meteorite, but the abundance of {sup 135}Cs in the solar system remains unclear because of large analytical uncertainties.

  16. 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

  17. Structure of aqueous sodium perchlorate solutions.

    PubMed

    General, Ignacio J; Asciutto, Eliana K; Madura, Jeffry D

    2008-12-01

    Salt solutions have been the object of study of many scientists through history, but one of the most important findings came along when the Hofmeister series were discovered. Their importance arises from the fact that they influence the relative solubility of proteins, and solubility is directly related to one of today's holy grails: protein folding. In this work we characterize one of the more-destabilizing salts in the series, sodium perchlorate, by studying it as an aqueous solution at various concentrations ranging from 0.08 to 1.60 mol/L. Molecular dynamics simulations at room temperature permitted a detailed study of the organization of solvent and cosolvent, in terms of its radial distribution functions, along with the study of the structure of hydrogen bonds in the ions' solvation shells. We found that the distribution functions have some variations in their shape as concentration changes, but the position of their peaks is mostly unaffected. Regarding water, the most salient fact is the noticeable (although small) change in the second hydration shell and even beyond, especially for g(O(w)***O(w)), showing that the locality of salt effects should not be restricted to considerations of only the first solvation shell. The perturbation of the second shell also appears in the study of the HB network, where the difference between the number of HBs around a water molecule and around the Na(+) cation gets much smaller as one goes from the first to the second solvation shell, yet the difference is not negligible. Nevertheless, the effect of the ions past their first hydration shell is not enough to make a noticeable change in the global HB network. The Kirkwood-Buff theory of liquids was applied to our system, in order to calculate the activity derivative of the cosolvent. This coefficient, along with a previously calculated preferential binding, allowed us to establish that if a folded AP peptide is immersed in the studied solution, becoming the solute, then

  18. Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

    PubMed

    Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

    2016-06-13

    The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. PMID:27151516

  19. Direct Solar Charging of an Organic–Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode

    PubMed Central

    Wedege, Kristina; Azevedo, João; Khataee, Amirreza

    2016-01-01

    Abstract The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone‐2,7‐disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide‐hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron–hole recombination. PMID:27151516

  20. Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

    PubMed

    Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

    2016-06-13

    The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination.

  1. Primary radical yields in pulse irradiated alkaline aqueous solution

    NASA Technical Reports Server (NTRS)

    Fielden, E. M.; Hart, E. J.

    1969-01-01

    Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.

  2. Component dynamics in polyvinylpyrrolidone concentrated aqueous solutions.

    PubMed

    Busselez, Rémi; Arbe, Arantxa; Cerveny, Silvina; Capponi, Sara; Colmenero, Juan; Frick, Bernhard

    2012-08-28

    (2)H-nuclear magnetic resonance (NMR) and neutron scattering (NS) on isotopically labelled samples have been combined to investigate the structure and dynamics of polyvinylpyrrolidone (PVP) aqueous solutions (4 water molecules/monomeric unit). Neutron diffraction evidences the nanosegregation of polymer main-chains and water molecules leading to the presence of water clusters. NMR reveals the same characteristic times and spectral shape as those of the slower process observed by broadband dielectric spectroscopy in this system [S. Cerveny et al., J. Chem. Phys. 128, 044901 (2008)]. The temperature dependence of such relaxation time crosses over from a cooperative-like behavior at high temperatures to an Arrhenius behavior at lower temperatures. Below the crossover, NMR features the spectral shape as due to a symmetric distribution of relaxation times and the underlying motions as isotropic. NS results on the structural relaxation of both components-isolated via H/D labeling-show (i) anomalously stretched and non-Gaussian functional forms of the intermediate scattering functions and (ii) a strong dynamic asymmetry between the components that increases with decreasing temperature. Strong heterogeneities associated to the nanosegregated structure and the dynamic asymmetry are invoked to explain the observed anomalies. On the other hand, at short times the atomic displacements are strongly coupled for PVP and water, presumably due to H-bond formation and densification of the sample upon hydration.

  3. Spontaneous unilamellar polymer vesicles in aqueous solution.

    PubMed

    Kim, Tae-Hwan; Song, Chaeyeon; Han, Young-Soo; Jang, Jong-Dae; Choi, Myung Chul

    2014-01-21

    A unilamellar polymeric vesicle is a self-assembled structure of a block copolymer that forms a spherical single bilayer structure with a hydrophobic interlayer and a hydrophilic surface. Due to their enhanced colloidal stability and mechanical property, controllable surface functionality, or tunable membrane thickness, polymeric vesicles are useful in nano and bio-science, providing potential applications as nanosized carriers for catalysts, drugs, and enzymes. For fabrication of a unilamellar vesicle, however, preparative procedures with a few steps are inherently required. Herein, without complicated preparative procedures, we report spontaneous unilamellar polymeric vesicles with nanometer sizes (<100 nm), which are prepared by simply mixing a triblock copolymer, Pluronic P85 (PEO26PPO40PEO26), and an organic derivative, 5-methyl salicylic acid (5mS), in aqueous solution. Depending on the 5mS concentration and the temperature, the P85-5mS mixtures presented various self-assembled nanostructures such as spherical and cylindrical micelles or vesicles, which were characterized by small angle neutron scattering and cryo-TEM, resulting in a phase diagram drawn as a function of temperature and the 5mS concentration. Interestingly the critical temperature for the micelle-to-vesicle phase transition was easily controlled by varying the 5mS concentration, i.e. it was decreased with increasing the 5mS concentration. PMID:24652418

  4. Simulating Monovalent and Divalent Ions in Aqueous Solution Using a Drude Polarizable Force Field

    PubMed Central

    Yu, Haibo; Whitfield, Troy W.; Harder, Edward; Lamoureux, Guillaume; Vorobyov, Igor; Anisimov, Victor M.; MacKerell, Alexander D.; Roux, Benoît

    2010-01-01

    An accurate representation of ion solvation in aqueous solution is critical for meaningful computer simulations of a broad range of physical and biological processes. Polarizable models based on classical Drude oscillators are introduced and parametrized for a large set of monoatomic ions including cations of the alkali metals (Li+, Na+, K+, Rb+ and Cs+) and alkaline earth elements (Mg2+, Ca2+, Sr2+ and Ba2+) along with Zn2+ and halide anions (F−, Cl−, Br− and I−). The models are parameterized, in conjunction with the polarizable SWM4-NDP water model [Lamoureux et al., Chem. Phys. Lett. 418, 245 (2006)], to be consistent with a wide assortment of experimentally measured aqueous bulk thermodynamic properties and the energetics of small ion-water clusters. Structural and dynamic properties of the resulting ion models in aqueous solutions at infinite dilution are presented. PMID:20300554

  5. Photochemistry of dihydrobiopterin in aqueous solution.

    PubMed

    Vignoni, Mariana; Cabrerizo, Franco M; Lorente, Carolina; Claparols, Catherine; Oliveros, Esther; Thomas, Andrés H

    2010-02-21

    Dihydrobiopterin (H(2)Bip) and its oxidized analogue, biopterin (Bip), accumulate in the skin of patients suffering from vitiligo, a chronic depigmentation disorder in which the protection against UV radiation fails. The photochemistry of H(2)Bip was studied in neutral aqueous solutions upon UV-A irradiation (320-400 nm) at room temperature. The photochemical reactions were followed by UV/vis spectrophotometry, HPLC and enzymatic methods for hydrogen peroxide (H(2)O(2)) determination. Photoproducts were analyzed by means of electrospray ionization mass spectrometry. Under anaerobic conditions, excitation of H(2)Bip leads to the formation of at least two isomeric dimers with molecular masses equal to exactly twice the molecular mass of the reactant. This reaction takes place from the singlet excited state of the reactant. To the best of our knowledge, this is the first time that the photodimerization of a dihydropterin is reported. In the presence of air, the dimers are again the main photoproducts at the beginning of the reaction, but a small proportion of the reactant is converted into Bip. As the reaction proceeds and enough Bip accumulates in the solution, a photosensitized process starts, where Bip photoinduces the oxidation of H(2)Bip to Bip, and H(2)O(2) is formed. As a consequence, the rates of H(2)Bip consumption and Bip formation increase as a function of irradiation time, resulting in an autocatalytic photochemical process. In this process, Bip in its triplet excited state reacts with the ground state of H(2)Bip. The mechanisms involved are analyzed and the biological implications of the results are discussed.

  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. Ozone photolysis of paracetamol in aqueous solution.

    PubMed

    Neamţu, Mariana; Bobu, Maria; Kettrup, Antonius; Siminiceanu, Ilie

    2013-01-01

    The degradation of a paracetamol (N-acetil-para-aminofenol) aqueous solution (C (0) P = 5 mmol L(-1)) is studied in a bench-scale setup by means of simple ozonation (O3) and ozonation catalyzed with UV light (O3/UV) in order to quantify the influence of UV light on the degradation process. The results have shown that under the adopted experimental conditions (25°C, applied ozone dose = 9.8 mg L(-1) and gas flow rate of 20 L h(-1)) both oxidative systems are capable of removing the substrate with mineralization degrees up to 51% for ozonation and 53% for O3/UV. HPICE chromatography allowed the detection of nitrate ions and maleic and oxalic acids as ultimate carboxylic acids. The experimental data have been interpreted through 5 indicators: the conversion of paracetamol (XP ), the conversion degree of TOC (XTOC ), the apparent rate constant (kap ), the Hatta number (Ha) and the enhancement factor (E). The main advantage of photo-ozonation compared to simple ozonation was a more advanced conversion (79% vs. 92% after 90 min). The paracetamol decay follows a pseudo-first-order reaction with a superior rate constant (higher by 54%) for the UV catalyzed system in comparison with direct ozonation. Mineralization is slightly accelerated (+4%) in the O3/UV system, due to the additional production of hydroxyl radicals induced by the UV light and a higher Hatta number (+24%). Nevertheless, the process was still in the slow reaction kinetic regime (Ha < 0.3), and the enhancement factor was not significantly increased. The results are useful for the design and scale-up of the gas-liquid processes.

  11. Stability in alkaline aqueous electrolyte of air electrode protected with fluorinated interpenetrating polymer network membrane

    NASA Astrophysics Data System (ADS)

    Bertolotti, Bruno; Messaoudi, Houssam; Chikh, Linda; Vancaeyzeele, Cédric; Alfonsi, Séverine; Fichet, Odile

    2015-01-01

    We developed original anion exchange membranes to protect air electrodes operating in aqueous lithium-air battery configuration, i.e. supplied with atmospheric air and in concentrated aqueous lithium hydroxide. These protective membranes have an interpenetrating polymer network (IPN) architecture combining a hydrogenated cationic polyelectrolyte network based on poly(epichlorohydrin) (PECH) and a fluorinated neutral network based on perfluoropolyether (Fluorolink® MD700). Two phases, each one rich in one of the polymer, are co-continuous in the materials. This morphology allows combining their properties according to the weight proportions of each polymer. Thus, PECH/Fluorolink IPNs show ionic conductivity varying from 1 to 2 mS cm-1, water uptake from 30 to 90 wt.% and anionic transport number from 0.65 to 0.80 when the PECH proportion varies from 40 to 90 wt.%. These membranes have been systematically assembled on air electrodes. Air electrode protected with PECH/Fluorolink 70/30 IPN shows outstanding stability higher than 1000 h, i.e. a 20-fold increase in the lifetime of the non-modified electrode. This efficient membrane/air electrode assembly is promising for development of alkaline electrolyte based storage or production energy systems, such as metal air batteries or alkaline fuel cells.

  12. SEPARATION OF PLUTONIUM FROM AQUEOUS SOLUTIONS BY ION-EXCHANGE

    DOEpatents

    Schubert, J.

    1958-06-01

    A process is described for the separation of plutonium from an aqueous solution of a plutonium salt, which comprises adding to the solution an acid of the group consisting of sulfuric acid, phosphoric acid, and oxalic acid, and mixtures thereof to provide an acid concentration between 0.0001 and 1 M, contacting the resultant solution with a synthetic organic anion exchange resin, and separating the aqueous phase and the resin which contains the plutonium.

  13. ELECTROCHEMICAL DECHLORINATIONOF 2-CHLOROBIPHENYL IN AQUEOUS SOLUTION

    EPA Science Inventory

    This paper presents electrochemical dechlorination of 2-chlorobiphenyl (2-CI BP) in aqueous environment using palladium modified granular graphite electrodes. 2-CI BP, the PCB congener that requires the highest reduction potential, was effectively dechlorinated in electrochemical...

  14. Reaction mechanism of 3-chlorophenol with OH, H in aqueous solution.

    PubMed

    Zhu, Jie; Chen, Ye-Fei; Dong, Wen-Bo; Pan, Xun-Xi; Hou, Hui-Qi

    2003-01-01

    The reaction mechanism of 3-chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3-chlorophenol aqueous solutions have been saturated with air or N2 previously. Under alkaline condition, the reaction of OH radical with 3-chlorophenol produces 3-chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3-chlorophenol produces OH-adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3-chlorophenol produces H-adduct with the maximal absorption at about 320 nm. 3-chlorophenol is compared with 4-and 2-chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.

  15. Acoustic and thermodynamic investigations of aqueous solutions of some carbohydrates

    NASA Astrophysics Data System (ADS)

    Gepert, M.; Moskaluk, A.

    2006-11-01

    Acoustic and thermodynamic properties of aqueous solutions of three carbohydrates: D-glucose, D-fructose and D-saccharose are discussed. D-glucose and D-fructose have different molecular structures; thus they interact in different ways with the surrounding water molecules. Based on our experimental results, we found that the thermodynamic properties of the aqueous solutions of the two monosaccharides are similar, except the limiting apparent molar compressibilities. As anticipated, the thermodynamic properties of an aqueous solution of D-saccharose are mostly the resultant of the properties of both monosaccharides. Any modifications of these properties are probably caused by the specific linkage between two monosaccharide rings.

  16. 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

  17. Natural hydrophobic flocculation of fine coal particles in aqueous solution

    SciTech Connect

    Song, S.; Lu, S.; Trass, O.; Wang, G.; Wang, Z.

    1994-12-31

    The hydrophobic flocculation of fine coal particles with natural hydrophobicity in aqueous solution, which is called natural hydrophobic flocculation, has been studied in this paper. It features no surfactant addition but only high intensity mechanical agitation. The experimental results showed that this flocculation occurred even in the case of {minus}58 mV jet potential of coal particles, that is contrary to the classical DLVO (Derjaguin-LandauVerwey-Overbeek) theory. Wettability of coal particle surface dominates the stability o fine coal particles in aqueous solution. The bigger the contact angle, the more intensive the flocculation of the coal particle suspension. The quantitative theory of natural hydrophobic flocculation is presented in this paper. Using this theory, the authors have calculated the total potential energy of interaction between coal particles in aqueous solution. The results demonstrate that the hydrophobic interaction plays a dominant role in the interaction between coal particles in aqueous solution.

  18. Singlet Oxygen in Aqueous Solution: A Lecture Demonstration

    ERIC Educational Resources Information Center

    Shakhashiri, Bassam Z.; Williams, Lloyd G.

    1976-01-01

    Describes a demonstration that illustrates the red chemiluminescence due to singlet molecular oxygen that can be observed when aqueous solutions of hypochlorite ion and hydrogen peroxide are mixed. (MLH)

  19. "Switchable water": aqueous solutions of switchable ionic strength.

    PubMed

    Mercer, Sean M; Jessop, Philip G

    2010-04-26

    "Salting out" is a standard method for separating water-soluble organic compounds from water. In this method, adding a large amount of salt to the aqueous solution forces the organic compound out of the aqueous phase. However, the method can not be considered sustainable because it creates highly salty water. A greener alternative would be a method that allows reversible salting out. Herein, we describe aqueous solutions of switchable ionic strength. Aqueous solutions of a diamine in water have essentially zero ionic strength but are converted by CO(2) into solutions of high ionic strength. The change is reversible. Application to the reversible salting out of THF from water is described. PMID:20186910

  20. Evolution of hydrogen from acidic aqueous and aqueous-alcoholic solutions by reduced forms of isopolytungstates

    SciTech Connect

    Saidkhanov, S.S.; Parmon, V.N.; Savinov, E.N.

    1986-02-10

    The authors determine the specific nature of the hydrogen-releasing polytungstate (PT) species and investigate the features of H/sub 2/ evolution by this species. In aqueous and aqueous-alcohol solutions, reoxidation of the doubly reduced form of hexatungstate proceeds spontaneously, accompanied by hydrogen evolution; in contrast, the reduced form of the PT is stable with respect to reoxidation.

  1. Remote photoacoustic measurements in aqueous solutions using an optical fiber

    SciTech Connect

    Russo, R.E. ); Rojas, D. ); Robouch, P.; Silva, R.J. )

    1990-12-01

    A photoacoustic spectrometer was developed for remote optical absorption measurements in aqueous solutions using an 85-m optical fiber to deliver pulsed tunable dye laser radiation to a sample cuvette located in a glove box. The spectrometer was tested using aqueous solutions of praseodymium ions. Beer's law was verified down to a concentration of 8{times}10{sup {minus}6}M for an equivalent absorptance of 3.2{times}10{sup {minus}5} cm{sup {minus}1}.

  2. Amphipols: Polymers that Keep Membrane Proteins Soluble in Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Tribet, Christophe; Audebert, Roland; Popot, Jean-Luc

    1996-12-01

    Amphipols are a new class of surfactants that make it possible to handle membrane proteins in detergent-free aqueous solution as though they were soluble proteins. The strongly hydrophilic backbone of these polymers is grafted with hydrophobic chains, making them amphiphilic. Amphipols are able to stabilize in aqueous solution under their native state four well-characterized integral membrane proteins: (i) bacteriorhodopsin, (ii) a bacterial photosynthetic reaction center, (iii) cytochrome b6f, and (iv) matrix porin.

  3. Extracting alcohols from aqueous solutions. [USDOE patent application

    DOEpatents

    Compere, A.L.; Googin, J.M.; Griffith, W.L.

    1981-12-02

    The objective is to provide an efficient process for extracting alcohols in aqueous solutions into hydrocarbon fuel mixtures, such as gasoline, diesel fuel and fuel oil. This is done by contacting an aqueous fermentation liquor with a hydrocarbon or hydrocarbon mixture containing carbon compounds having 5-18 carbon atoms, which may include gasoline, diesel fuel or fuel oil. The hydrocarbon-aqueous alcohol solution is then mixed with one or more of a group of polyoxyalkylene polymers to extract the alcohol into the hydrocarbon fuel-polyoxyalkylene polymer mixture.

  4. Fabrication of ZnO:Mn nanoparticles with organic shell in a highly alkaline aqueous environment

    NASA Astrophysics Data System (ADS)

    Chawla, Santa; Sharda; Jayanthi, K.

    2011-01-01

    Synthesis of undoped and Mn doped ZnO nanoparticles by an inclusive co precipitation method and in situ capping with heteromultifunctional organic stabilizer mercaptosuccinic acid (MSA) in a core shell structure, in highly alkaline aqueous matrix have been accomplished. Near room temperature synthesis resulted in high quality monophasic wurtzite hexagonal structure of rod shaped nanoparticles of bare ZnO:Mn with no signature of dopant as separate phase. MSA capping resulted in nanoball like formation. Thermo gravimetric analysis (TGA) and FTIR confirmed MSA capping. ZnO: Mn particles emit in orange and red when excited by UV and blue light. Surface modification makes the nanoparticles hydrophilic with active organic surface easy for bioconjugation with any ligand and can have applications in drug delivery or as nanoscale fluorescent probe in a biological system.

  5. Solubility of vanadium from manganese vanadates in aqueous solutions of soda ash

    NASA Astrophysics Data System (ADS)

    Khalezov, B. D.; Krasheninin, A. G.; Vatolin, N. A.; Ovchinnikova, L. A.

    2016-05-01

    It is shown that, in the course of developing the technology of pure vanadium pentoxide preparation from manganic vanadium-containing metallurgical slags, their oxidative roasting and cinder formation without alkaline additives are accompanied by the decomposition of spinelides with the formation of manganese meta- and pyrovanadates. Concentrated aqueous solutions of soda ash with an Na2CO3 concentration of 120-150 g/dm3 are accepted as a selective leaching reagent for vanadium from a cinder. Manganese metaand pyrovanadates are synthesized, and the procedure of their preparation is presented. The solubility of vanadium from manganese vanadates in aqueous solutions of soda ash at C_{Na_2 CO_3 } = 150 g/dm^3 is studied at 20-95°C for pyrovanadate and at 85-95°C for metavanadate. It is shown that vanadium should be leached from converter manganic slags roasted without alkaline metal additives at a leaching solution temperature higher than 95°C. There is a possibility to increase the vanadium content in a leaching solution to 60-80 g/dm3. The results obtained are used in the development of the technology of vanadium leaching.

  6. 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}.

  7. Jarosite in a Pleistocene East African saline-alkaline paleolacustrine deposit: Implications for Mars aqueous geochemistry

    NASA Astrophysics Data System (ADS)

    McHenry, Lindsay J.; Chevrier, Vincent; Schröder, Christian

    2011-04-01

    Jarosite occurs within altered tephra from the saline-alkaline paleolake deposits of Pliocene-Pleistocene Olduvai Gorge, Tanzania. Zeolites (mainly phillipsite), authigenic K-feldspar, and Mg/Fe-smectites dominate the mineral assemblage, indicating saline-alkaline diagenetic conditions (pH > 9). As jarosite is ordinarily an indicator of acidic conditions on Earth and Mars, its association with such undisputed high-pH indicators is unexpected. Of 55 altered tephra samples collected from the paleolake basin and margin deposits, eleven contained jarosite detectable by X-ray Diffraction (XRD) (>0.15%). Mössbauer spectroscopy, Fourier Transform Infrared Reflectance (FTIR), Electron Probe Microanalysis (EPMA), X-ray Fluorescence (XRF), and Scanning Electron Microscopy (SEM) analyses confirm the presence and nature of the jarosite. This paper documents this occurrence and presents mechanisms that could produce this unusual and contradictory mineral assemblage. We favor a mechanism by which jarosite formed recently, perhaps as modern ground and meteoric water interacted with and oxidized paleolacustrine pyrite, providing local and temporary acidic conditions. However, local groundwater (at modern springs) has a pH > 9. In recent studies of Mars, the presence of jarosite or other Fe or Mg sulfates is often used to indicate dominantly acidic conditions. Regardless, the current study shows that jarosite can form in sediments dominated by alkaline minerals and solutions. Its coexistence with Mg/Fe smectites in particular makes it relevant to recent observations of Martian paleolakes.

  8. Aqueous Rechargeable Alkaline CoxNi2-xS2/TiO2 Battery.

    PubMed

    Liu, Jilei; Wang, Jin; Ku, Zhiliang; Wang, Huanhuan; Chen, Shi; Zhang, Lili; Lin, Jianyi; Shen, Ze Xiang

    2016-01-26

    An electrochemical energy storage system with high energy density, stringent safety, and reliability is highly desirable for next-generation energy storage devices. Here an aqueous rechargeable alkaline CoxNi2-xS2 // TiO2 battery system is designed by integrating two reversible electrode processes associated with OH(-) insertion/extraction in the cathode part and Li ion insertion/extraction in the anode part, respectively. The prototype CoxNi2-xS2 // TiO2 battery is able to deliver high energy/power densities of 83.7 Wh/kg at 609 W/kg (based on the total mass of active materials) and good cycling stabilities (capacity retention 75.2% after 1000 charge/discharge cycles). A maximum volumetric energy density of 21 Wh/l (based on the whole packaged cell) has been achieved, which is comparable to that of a thin-film battery and better than that of typical commercial supercapacitors, benefiting from the unique battery and hierarchical electrode design. This hybrid system would enrich the existing aqueous rechargeable LIB chemistry and be a promising battery technology for large-scale energy storage.

  9. Mechanism of glycine oxidation catalyzed by pyrroloquinoline quinone in aqueous solution

    NASA Astrophysics Data System (ADS)

    Uchida, Waka; Wakabayashi, Masamitsu; Ikemoto, Kazuto; Nakano, Masahiko; Ohtani, Hiroyuki; Nakamura, Shinichiro

    2015-01-01

    The mechanism of glycine oxidation reaction by PQQ in aqueous solution was investigated. A new crystal structure of PQQ under alkaline conditions was referred to calculate on a quantum chemical basis. Two mechanisms are investigated by this calculation: a 'stepwise' mechanism, namely, a nucleophilic attack on C5 or C4 by the nitrogen atom of glycine, and proton and electron transfer to PQQ. The second mechanism is a 'concerted' mechanism, namely, simultaneous reaction, which does not include the nucleophilic attack and include proton and electron transfer to PQQ.

  10. Kinetics of de-N-acetylation of the chitin disaccharide in aqueous sodium hydroxide solution.

    PubMed

    Khong, Thang Trung; Aachmann, Finn L; Vårum, Kjell M

    2012-05-01

    Chitosan is prepared from chitin, a process which is carried out at highly alkaline conditions, and that can be performed either on chitin in solution (homogeneous deacetylation) or heterogeneously with the chitin as a solid throughout the reaction. We report here a study of the de-N-acetylation reaction of the chitin dimer (GlcNAc-GlcNAc) in solution. The reaction was followed by (1)H NMR spectroscopy in deuterated aqueous sodium hydroxide solution as a function of time, sodium-hydroxide concentration and temperature. The (1)H NMR spectrum of GlcNAc-GlcNAc in 2.77 M deuterated aqueous sodium hydroxide solution was assigned. The interpretation of the (1)H NMR spectra allowed us to determine the rates of de-N-acetylation of the reducing and non-reducing ends, showing that the reaction rate at the reducing end is twice the rate at the non-reducing end. The total deacetylation reaction rate was determined as a function of the hydroxide ion concentration, showing for the first time that this de-N-acetylation reaction is second order with respect to hydroxide ion concentration. No significant difference in the deacetylation rates in deuterated water compared to water was observed. The activation energy for the reaction (26-54 °C) was determined to 114.4 and 98.6 kJ/mol at 2.77 and 5.5 M in deuterated aqueous sodium hydroxide solution, respectively.

  11. 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.

  12. SOLVENT EXTRACTION OF THORIUM VALUES FROM AQUEOUS SOLUTIONS

    DOEpatents

    Warf, J.C.

    1959-04-21

    The separation of thorium values from rare earth metals contained ln aqueous solutions by means of extraction with a water immiscible alkyl phosphate diluted with a hydrocarbon such as hexane is described. While the extraction according to this invention may be carried out from any aqueous salt solution, it is preferred to use solutions containing free mineral acid. Hydrochloric acid and in particular nitric acid are sultable in a concentration ranging from 0.1 to 7 normal. The higher acid concentration results in higher extraction values.

  13. Interactions of Cl- and OH radical in aqueous solution.

    PubMed

    Valiev, Marat; D'Auria, Raffaella; Tobias, Douglas J; Garrett, Bruce C

    2009-08-01

    There is a considerable controversy surrounding the nature of the Cl-/OH complex in aqueous solution, which appears as a byproduct of the irradiation of salt solutions in nuclear reactor operation, radioactive waste storage, medicine, and environmental problems. In this work, we report results of combined quantum mechanical molecular mechanics calculations of ground-state free-energy surfaces and absorption spectrum through the CCSDT level of theory that are consistent with the experimental data and suggest that hemibonded HOCl- species may indeed exist in bulk aqueous solution. PMID:19591498

  14. REMOVAL OF CESIUM BY SORPTION FROM AQUEOUS SOLUTIONS

    DOEpatents

    Ames, L.L.

    1962-01-16

    ABS>A process is given for selectively removing cesium from acid aqueous solutions containing cesium in microquantities and other cations in macroquantities by absorption on clinoptilolite. The cesium can be eluted from the clinoptilolite with a solution of ammonia, potassium hydroxide, or rubidium hydroxide. (AEC)

  15. SEPARATION OF TECHNETIUM FROM AQUEOUS SOLUTIONS BY COPRECIPITATION WITH MAGNETITE

    DOEpatents

    Rimshaw, S.J.

    1961-10-24

    A method of separating technetium in the 4+ oxidation state from an aqueous basic solution containing products of uranium fission is described. The method consists of contacting the solution with finely divided magnetite and recovering a technetium-bearing precipitate. (AEC)

  16. Acidities of Water and Methanol in Aqueous Solution and DMSO

    ERIC Educational Resources Information Center

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  17. Antiscalant properties of Spergularia rubra and Parietaria officinalis aqueous solutions

    NASA Astrophysics Data System (ADS)

    Cheap-Charpentier, Hélène; Gelus, Dominique; Pécoul, Nathalie; Perrot, Hubert; Lédion, Jean; Horner, Olivier; Sadoun, Jonathan; Cachet, Xavier; Litaudon, Marc; Roussi, Fanny

    2016-06-01

    The formation of calcium carbonate in water has important implications in industry. Chemical antiscalant is usually used to control scale depositions. Plant extracts have been recently used as new green antiscalant agents, as they can be easily prepared and are environmentally friendly. In this study, stock aqueous solutions of Spergularia rubra and Parietaria officinalis, two plants used in traditional medicine to treat or prevent urolithiasis, were obtained by infusion. The antiscaling properties of these extracts towards CaCO3 formation were tested by using chronoamperometry and Fast Controlled Precipitation methods. The aqueous solution of S. rubra was further fractionated to isolate compounds of lower polarity. Their efficiency towards CaCO3 precipitation was characterized by Fast Controlled Precipitation method. The inhibiting efficiency of this fractionated solution was greater than that of the stock aqueous solution.

  18. EMERGING TECHNOLOGY BULLETIN: REMOVAL OF PHENOL FROM AQUEOUS SOLUTIONS USING HIGH ENERGY ELECTRON BEAM IRRADIATION

    EPA Science Inventory

    Irradiation of aqueous solutions with high-energy electrons results in the formation of the aqueous electron, hydrogen radical, H-, and the hydroxyl radical, OH-. These reactive transient species initiate chemical reactions capable of destroying organic compounds in aqueous solut...

  19. The anomaly of oxygen diffusion in aqueous xanthan solutions.

    PubMed

    Ho, C S; Ju, L K; Baddour, R F

    1988-06-20

    A membrane-covered polarographic oxygen electrode was used to measure oxygen diffusion coefficients in aqueous polyelectrolyte solutions of xanthan gum, sodium alginate, and sodium carboxymethylcellulose (CMC). In sodium alginate solutions, dilute xanthan solutions, and solutions containing more than 0.3 wt % CMC, oxygen diffusion coefficients decrease with increasing polymer concentrations. Interestingly, in dilute CMC solutions and concentrate xanthan solutions containing more than 0.5 wt % xanthan gum, oxygen diffusion coefficients increase with increasing polymer concentrations, and values exceeding that in pure water are generally observed.

  20. Electrochemical Removal Of Selenate From Aqueous Solutions

    PubMed Central

    Baek, Kitae; Kasem, Naji; Ciblak, Ali; Vesper, Dorothy; Padilla, Ingrid; Alshawabkeh, Akram N.

    2013-01-01

    Removal of selenate from solution is investigated in batch electrochemical systems using reactive iron anodes and copper plate cathode in a bicarbonate medium. Iron anodes produce ferrous hydroxide, which is a major factor in the removal of selenate from solution. Iron anodes also generate a significant decrease in the oxidation-reduction potential (ORP) of the solution because it prevents generation of oxygen gas at the anode by electrolysis. The removal rates varied from 45.1 to 97.4%, depending on current density and selenate concentration. The transformation of selenate by the process is modeled based on a heterogeneous reaction coupled with electrochemical generation of ferrous and hydroxide. The rates are optimized at lower initial concentrations, higher electrical currents, and the presence of anions. Presence of dissolved oxygen does not cause any significant effects the removal of selenate. PMID:23378820

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

    DOEpatents

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

    1991-01-01

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

  2. Degradation kinetics of indocyanine green in aqueous solution.

    PubMed

    Saxena, Vishal; Sadoqi, Mostafa; Shao, Jun

    2003-10-01

    The degradation kinetics of a near-infrared fluorescent, diagnostic, and photodynamic agent, indocyanine green (ICG), was investigated in aqueous solution by steady-state fluorescence technique. The influence of ICG concentration on its fluorescence spectrum was determined. The degradation kinetics of ICG in aqueous solution was studied as a function of light exposure, type of light exposed, temperature, and ICG concentration. The degradation of ICG was found to follow first-order kinetics. Exposure to light and high temperatures caused acceleration in the degradation. The type and intensity of exposed light also affected degradation. ICG aqueous solutions were found to be more stable in dark, at low temperatures, and at higher ICG concentrations.

  3. Reorientation and Allied Dynamics in Water and Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Laage, Damien; Stirnemann, Guillaume; Sterpone, Fabio; Rey, Rossend; Hynes, James T.

    2011-05-01

    The reorientation of a water molecule is important for a host of phenomena, ranging over—in an only partial listing—the key dynamic hydrogen-bond network restructuring of water itself, aqueous solution chemical reaction mechanisms and rates, ion transport in aqueous solution and membranes, protein folding, and enzymatic activity. This review focuses on water reorientation and related dynamics in pure water, and for aqueous solutes with hydrophobic, hydrophilic, and amphiphilic character, ranging from tetra-methylurea to halide ions and amino acids. Attention is given to the application of theory, simulation, and experiment in the probing of these dynamics, in usefully describing them, and in assessing the description. Special emphasis is placed on a novel sudden, large-amplitude jump mechanism for water reorientation, which contrasts with the commonly assumed Debye rotational diffusion mechanism, characterized by small-amplitude angular motion. Some open questions and directions for further research are also discussed.

  4. 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.

  5. [Extraction of alpha-cypermethrin from aqueous methanol solutions].

    PubMed

    Shormanov, V K; Chigareva, E N; Belousova, O V

    2010-01-01

    Alpha cypermethrin was extracted from aqueous methanol solutions using hydrophobic organic solvents. The efficiency of extraction was shown to depend on the chemical nature of the solvent, the water to methanol ratio, and saturation of the aqueous methanol layer with an electrolyte. Optimal extraction of alpha-cypermethrin was achieved using toluene as the solvent under desalinization conditions. The extraction factor for the removal of the sought amount of alpha-cypermethrin from the water-methanol solution (4:1) using various solvents was calculated.

  6. Degradation Kinetics of Benzyl Nicotinate in Aqueous Solution

    PubMed Central

    Mbah, C. J.

    2010-01-01

    The degradation of benzyl nicotinate in aqueous solution over a pH range of 2.0-10.0 at 50±0.2° was studied. The degradation was determined by high performance liquid chromatography. The degradation was observed to follow apparent first-order rate kinetics and the rate constant for the decomposition at 25° was estimated by extrapolation. The reaction was shown to be hydroxide ion catalyzed and the Arrhenius plots showed the temperature dependence of benzyl nicotinate degradation. A significant increase in the stability of benzyl nicotinate was observed when glycerol or polyethylene glycol 400 was incorporated into the aqueous solution. PMID:20582189

  7. Removal of phosphate from aqueous solutions by electro-coagulation.

    PubMed

    Bektaş, Nihal; Akbulut, Hilal; Inan, Hatice; Dimoglo, Anatoly

    2004-01-30

    The aim of this paper was to investigate the feasibility of the removal of phosphate from aqueous solution by electro-coagulation (EC). The current density (CD) between 2.5 and 10 mA cm(-2) and duration in the limits of 5-20 min were tried for different concentrations. In order to determine optimal operating conditions, the EC process used for the phosphate removal was examined in dependence with the CD, initial concentrations and time. The results of the experimental batch processing showed high effectiveness of the EC method in removing phosphate from aqueous solutions. PMID:15177098

  8. Photodegradation of triazine herbicides in aqueous solutions and natural waters.

    PubMed

    Evgenidou, E; Fytianos, K

    2002-10-23

    The photodegradation of three triazines, atrazine, simazine, and prometryn, in aqueous solutions and natural waters using UV radiation (lambda > 290 nm) has been studied. Experimental results showed that the dark reactions were negligible. The rate of photodecomposition in aqueous solutions depends on the nature of the triazines and follows first-order kinetics. In the case of the use of hydrogen peroxide and UV radiation, a synergistic effect was observed. The number of photodegradation products detected, using FIA/MS and FIA/MS/MS techniques, suggests the existence of various degradation routes resulting in complex and interconnected pathways. PMID:12381128

  9. Method for removing organic liquids from aqueous solutions and mixtures

    DOEpatents

    Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.

    2004-03-23

    A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.

  10. [Extraction of alpha-cypermethrin from aqueous methanol solutions].

    PubMed

    Shormanov, V K; Chigareva, E N; Belousova, O V

    2010-01-01

    Alpha cypermethrin was extracted from aqueous methanol solutions using hydrophobic organic solvents. The efficiency of extraction was shown to depend on the chemical nature of the solvent, the water to methanol ratio, and saturation of the aqueous methanol layer with an electrolyte. Optimal extraction of alpha-cypermethrin was achieved using toluene as the solvent under desalinization conditions. The extraction factor for the removal of the sought amount of alpha-cypermethrin from the water-methanol solution (4:1) using various solvents was calculated. PMID:20734789

  11. Removal of phosphate from aqueous solutions by electro-coagulation.

    PubMed

    Bektaş, Nihal; Akbulut, Hilal; Inan, Hatice; Dimoglo, Anatoly

    2004-01-30

    The aim of this paper was to investigate the feasibility of the removal of phosphate from aqueous solution by electro-coagulation (EC). The current density (CD) between 2.5 and 10 mA cm(-2) and duration in the limits of 5-20 min were tried for different concentrations. In order to determine optimal operating conditions, the EC process used for the phosphate removal was examined in dependence with the CD, initial concentrations and time. The results of the experimental batch processing showed high effectiveness of the EC method in removing phosphate from aqueous solutions.

  12. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E.

    2016-05-01

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  13. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy.

    PubMed

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E

    2016-05-27

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  14. Phosphate Sorption and Desorption on Pyrite in Primitive Aqueous Scenarios: Relevance of acidic → Alkaline Transitions

    NASA Astrophysics Data System (ADS)

    de Souza-Barros, Fernando; Braz-Levigard, Raphael; Ching-San, Yonder; Monte, Marisa M. B.; Bonapace, José A. P.; Montezano, Viviane; Vieyra, Adalberto

    2007-02-01

    Phosphate (P i) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P i sorption whereas mild alkaline media as well as those simulating sulfur oxidation to SO2- 4 revert this capture process. Several mechanisms relevant to P i availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg2+ bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO2- 4 trapping by the mineral interface would provoke the release of sorbed P i due to charge polarization. Moreover it is shown that P i self-modulates its sorption, a mechanism that depends on the abundance of SO2- 4 in the interface. The relevance of the proposed mechanisms of P i capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since similarly to contemporary aqueous media inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P i could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.

  15. Phosphate sorption and desorption on pyrite in primitive aqueous scenarios: relevance of acidic --> alkaline transitions.

    PubMed

    de Souza-Barros, Fernando; Braz-Levigard, Raphael; Ching-San, Yonder; Monte, Marisa M B; Bonapace, José A P; Montezano, Viviane; Vieyra, Adalberto

    2007-02-01

    Phosphate (P(i)) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P(i) sorption whereas mild alkaline media--as well as those simulating sulfur oxidation to SO(2-) (4)--revert this capture process. Several mechanisms relevant to P(i) availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg(2+) bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO(2-) (4) trapping by the mineral interface would provoke the release of sorbed P(i) due to charge polarization. Moreover it is shown that P(i) self-modulates its sorption, a mechanism that depends on the abundance of SO(2-) (4) in the interface. The relevance of the proposed mechanisms of P(i) capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since--similarly to contemporary aqueous media--inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P(i) could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.

  16. Glasslike behavior in aqueous electrolyte solutions.

    PubMed

    Turton, David A; Hunger, Johannes; Hefter, Glenn; Buchner, Richard; Wynne, Klaas

    2008-04-28

    When salts are added to water, generally the viscosity increases, suggesting that the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules, implying no enhancement or breakdown of the hydrogen-bond network. Here, we report optical Kerr effect and dielectric relaxation spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture.

  17. Dissolution of lead paint in aqueous solutions

    SciTech Connect

    Barnes, G.L.; Davis, A.P.

    1996-07-01

    An analysis of the rate and extent of lead leaching from a lead-based paint was completed. At low-solution pH, dissolution was rapid and approached 80% of the total lead. Residual lead can be estimated based on the predicted solubility of lead carbonate and basic lead carbonate. Release of lead from the paint was slower than that from pure basic lead carbonate due to inhibition by the paint matrix. Although the dissolved concentration of lead in solution at neutral/high pH was low, the paint binder was apparently destroyed at these pH values, releasing colloidal lead pigment particles. The presence of ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) enhanced both the rate and degree of lead dissolution, while benzoic acid had a minimal effect.

  18. Binding sites of chlorpheniramine on 1:1 layered kaolinite from aqueous solution.

    PubMed

    Lv, Guocheng; Wu, Limei; Li, Zhaohui; Liao, Libing; Liu, Meitang

    2014-06-15

    Interactions between chlorpheniramine (CP), an antihistamine drug used to treat allergy, and kaolinite in aqueous solution were investigated under batch studies and molecular simulations. The CP adsorption was relatively fast with a large rate constant. The CP adsorption capacity on kaolinite was 25 mmol/kg, about the same magnitude of the cation exchange capacity of kaolinite. Molecular dynamic simulation showed that the edges of kaolinite were responsible for the uptake of CP, while a net repulsive interaction between the basal plane and CP molecules was obtained. As the broken bond effect of kaolinite was strongly affected by solution pH via protonation-deprotonation of kaolinite edges, a higher CP adsorption was achieved under neutral to weak alkaline solution. It was the charge density, rather than the surface area, that ultimately controlled the amount of CP adsorption on kaolinite.

  19. Automated iodine monitor system. [for aqueous solutions

    NASA Technical Reports Server (NTRS)

    1973-01-01

    The feasibility of a direct spectrophotometric measurement of iodine in water was established. An iodine colorimeter, was built to demonstrate the practicality of this technique. The specificity of this method was verified when applied to an on-line system where a reference solution cannot be used, and a preliminary design is presented for an automated iodine measuring and controlling system meeting the desired specifications. An Automated iodine monitor/controller system based on this preliminary design was built, tested, and delivered to the Johnson Space Center.

  20. Phosphorylation of glyceric acid in aqueous solution using trimetaphosphate.

    PubMed

    Kolb, V; Orgel, L E

    1996-02-01

    The phosphorylation of glyceric acid is an interesting prebiotic reaction because it converts a simple, potentially prebiotic organic molecule into phosphate derivatives that are central to carbohydrate metabolism. We find that 0.05 M glyceric acid in the presence of 0.5 M trimetaphosphate in alkaline solution gives a mixture of 2- and 3-phosphoglyceric acids in combined yields of up to 40%. PMID:11536746

  1. Phosphorylation of Glyceric Acid in Aqueous Solution Using Trimetaphosphate

    NASA Technical Reports Server (NTRS)

    Kolb, Vera; Orgel, Leslie E.

    1996-01-01

    The phosphorylation of glyceric acid is an interesting prebiotic reaction because it converts a simple, potentially prebiotic organic molecule into phosphate derivatives that are central to carbohydrate metabolism. We find that 0.05 M glyceric acid in the presence of 0.5 M trimetaphosphate in alkaline solution gives a mixture of 2- and 3-phosphoglyceric acids in combined yields of up to 40%.

  2. Photocatalytic degradation of molinate in aqueous solutions.

    PubMed

    Bizani, E; Lambropoulou, D; Fytianos, K; Poulios, I

    2014-11-01

    In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO2 as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H2O2 and K2S2O8) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron's and electron scavenger's concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.

  3. Optical properties of DNA in aqueous solution.

    PubMed

    Umazano, J P; Bertolotto, J A

    2008-04-01

    In the study of DNA electric birefringence, it is usual to use theories that consider that molecules in solution are small in relation to the light wavelength. In this work, we study the DNA electric birefringence using a broken-rod macroion (BRM) model composed of two cylindrical arms which does not restrict the size of the molecules. To achieve this, we include the inhomogeneity effect of the light electric field through the molecule and the interaction between its different parts. To analyze the interaction between a molecule and the incident beam of light, we apply the discrete dipole approximation (DDA), according to which each molecule is described as a finite array of electronic coupled oscillators. The electric birefringence is calculated from the oscillator polarizability. This is obtained from experimental data of electric birefringence saturation and from the increment of the solution refraction index in relation to that of the solvent. Furthermore, the oscillator polarizability is also estimated from DNA absorption spectrum using the Kronig-Kramers relations. This allows us to analyze the contributions of the different absorption bands of DNA to the electric birefringence. We analyze the influence of the inhomogeneity of the light electric field and of the intramolecular interactions in the characterization of DNA optical properties using electric birefringence measurements.

  4. Radiolysis of paracetamol in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  5. Permeability in a state of partial solidification of aqueous solution

    NASA Astrophysics Data System (ADS)

    Okada, Masashi; Kang, Chaedong; Okiyama, Haruhiko

    A mushy region was formed by solidifying NaCl aqueous solution in a circular tube or a rectangular tube. The measurements of permeability were performed by changing volume fraction of liquid region in the mushy region. The dendritic ice in the solidification process was observed with a CCD microscope. The following results were obtained. The permeability increases with the volume fraction of liquid phase, and decreases with increasing the super-cooling degree of the solution or increasing the initial concentration of the solution, and is constant after the mushy region was formed. The arm space of dendrite becomes narrower as the super-cooling degree of the solution increases.

  6. RECOVERY OF URANIUM FROM AQUEOUS PHOSPHATE-CONTAINING SOLUTIONS

    DOEpatents

    Igelsrud, I.; Stephen, E.F.

    1959-08-11

    ABS>A method is presented for recovering hexavalent uranium from an acidic phosphaie solution. A high molecular weight amine, such as a mixture of cccoanut oil amines, is added to the solution in such amount as to give a ratio of about 2000 parts by weight of amine to 1 part by weight of uranium. The uranium is precipitated with the amines and the whole filtered from the solution. The uranium is leached from the amine mass by washing with aqueous sodium carbonate solution; and the amine mixture is available for reuse.

  7. Hydrogen generation by electrolysis of aqueous organic solutions

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

    2006-01-01

    A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

  8. REMOVAL OF CESIUM FROM AQUEOUS SOLUTIONS BY ADSORPTION

    DOEpatents

    Knoll, K.C.

    1963-07-16

    A process of removing microquantities of cesium from aqueous solutions also containing macroquantities of other ions by adsorption on clinoptilolite is described. The invention resides in the pretreatment of the clinoptilolite by heating at 400 deg C and cooling prior to use. (AEC)

  9. Diagnostics of Apparent Wall Slip in Aqueous Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Wein, Ondřej; Tovčigrečko, Valentin V.; Sobolík, Václav; Večeř, Marek

    2009-07-01

    Two experimental methods, apparent-wall-slip (AWS) rotational viscometry with "Morse-taper" sensors and electrodiffusion (ED) flow diagnostics with auto-calibrated friction probes, are used to study velocity profiles in aqueous solutions of high-molecular polysaccharides. By comparing the velocity data from the both methods, estimates are obtained of depleted layer thickness in dependence on wall shear stress.

  10. Hydrogen generation by electrolysis of aqueous organic solutions

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

    2002-01-01

    A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

  11. RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION

    DOEpatents

    Moore, R.L.

    1959-09-01

    An organic solvent mixure is described for extracting actinides from aqueous solutions; the solvent mixture consists of from 10 to 25% by volume of tributyl phosphate and the remainder a chlorine-fluorine-substituted saturated hydrocarbon having two carbon atoms in the molecule.

  12. The precipitation of potassium aluminium sulphate from aqueous solution

    NASA Astrophysics Data System (ADS)

    Mullin, J. W.; Žáček, S.

    1981-06-01

    A precipitation study has been made with potassium aluminium sulphate (potash alum) produced by mixing aqueous solutions of its constituent salts. Rates of nucleation, as indicated by the induction period, were measured for both agitated and non-agitated solutions over the temperature range 15-35°C. Nucleation rates increase with increases in agitation, temperature and supersaturation, but the latter has the dominant effect, as predicted by classical nucleation theory. The temperature-dependence of the interfacial tension is evaluated.

  13. Non-aqueous solution preparation of doped and undoped lixmnyoz

    DOEpatents

    Boyle, Timothy J.; Voigt, James A.

    1997-01-01

    A method for generation of phase-pure doped and undoped Li.sub.x Mn.sub.y O.sub.z precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder.

  14. Formation of bioorganic compounds in aqueous solution induced by plasma.

    PubMed

    Harada, K; Takasaki, M; Naraoka, H; Nomoto, S

    1984-01-01

    When plasma jet of Ar-arc plasma was blown into an aqueous solution containing organic compounds, oxidation reactions were induced in the solution. The plasma-induced reaction was a powerful oxidation which could convert a methyl to a carboxyl group and cleave a carbon-carbon bond without using any oxidizing reagent. This reaction could be regarded as a model for the solar plasma-induced reaction in the primitive hydrosphere.

  15. Photocatalytical oxidation of de-icing agents in aqueous solutions and aqueous extract of jet fuel.

    PubMed

    Krichevskaya, M; Malygina, T; Preis, S; Kallas, J

    2001-01-01

    Improper handling of jet fuel at abandoned military bases has resulted in heavy pollution of the soil and groundwater. Experimental research of photocatalytical oxidation (PCO) of jet fuel aqueous extract and aqueous solutions of de-icing agents was undertaken. The influence of different parameters - pH, concentration of substances to be oxidised, presence of inorganic admixtures, effect of OH. radical generators--on the PCO of solutions of de-icing agents and jet fuel aqueous extract was determined. The role of OH. radicals was found to be less important in determining the PCO rate. The PCO of organic pollutants was also investigated using a catalyst immobilised onto the surface of buoyant hollow glass microspheres. Attached titanium dioxide (TiO2) showed lower photocatalytical activity than when suspended in slurry, although it allows waters to be treated in simple shallow ponds without intensive stirring. The biodegradability of aqueous solutions of de-icing agents and jet fuel aqueous extract increased as PCO proceeded. PMID:11695445

  16. Does Nitric Acid Dissociate at the Aqueous Solution Surface?

    SciTech Connect

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-11-03

    Nitric acid is a prevalent component of atmospheric aerosols, and the extent of nitric acid dissociation at aqueous interfaces is relevant to its role in heterogeneous atmospheric chemistry. Several experimental and theoretical studies have suggested that the extent of dissociation of nitric acid near aqueous interfaces is less than in bulk solution. Here, dissociation of HNO3 at the surface of aqueous nitric acid is quantified using X-ray photoelectron spectroscopy of the nitrogen local electronic structure. The relative amounts of undissociated HNO3(aq) and dissociated NO3-(aq) are identified by the distinguishable N1s core-level photoelectron spectra of the two species, and we determine the degree of dissociation, αint, in the interface (the first ~3 layers of solution) as a function of HNO3 concentration. Our measurements show that dissociation is decreased by approximately 20% near the solution interface compared with bulk, and furthermore that dissociation occurs even in the top-most solution layer. The experimental results are supported by first-principles MD simulations, which show that hydrogen-bonds between HNO3 and water molecules at the solution surface stabilize the molecular form at low concentration, in analogy to the stabilization of molecular HNO3 that occurs in bulk solution at high concentration. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  17. Untangling Element Fluxes From The Subducting Slabs: Aqueous Solutions Through The Electrostatic Lense

    NASA Astrophysics Data System (ADS)

    Galvez, M.; Connolly, J. A.; Manning, C. E.

    2015-12-01

    Understanding the deep cycling of elements hinges on characterizing the chemistry of fluids in subduction zones. Aqueous solutions dielectric properties determine their characteristics as solvents for rocks. Predicting the composition and speciation of fluid solutions at equilibrium with complex mineral assemblages has been a long lasting challenge. We have developed a model to explore the composition and speciation of metamorphic aqueous solutions to upper mantle pressure and temperature. Our model combines Gibbs free energy minimization of rock and molecular fluids with an electrostatic approach to describe solute-solute and solute-solvent interactions in the fluid phase. Using an extension of the Debye-Onsager-Kirkwood model to characterize the dielectric properties of COH solutions, we derive aqueous fluid speciation by solving the mass action and charge balance of the system. This framework is applied to various slab lithologies. We find, e.g., that the pH of carbonated basalts and pelites is alkaline, i.e. ~2-2.5 pH units above neutrality, in C and Cl-free fluids and shows an isothermal decrease above the albite-jadeite-quartz equilibrium, at P ~ 2 GPa. C and Chlorine (1M) decrease the alkalinity by a combined ~ 1.5 pH unit, with variations tied to the thermal structure and mineral assemblages along typical P-T paths. The results produced are compared with experimental solubility measurements on identical systems. Significant discrepancies reveal that the process of solute polymerization at elevated T and P is more general than previously recognized. Unaccounted species contain, in addition to Na, Si and Al, an important fraction of the total dissolved load of the elements K, Ca and Mg (>50% at T= 600 °C and P = 2 Ga). Finally, we show that knowledge of the acid-base properties of metamorphic fluid solutions affect the (de)coupling between C and alkali-earth mobility, and magnitude of low-T C transfers associated to carbonate dissolution through time. This

  18. Critical droplet theory explains the glass formability of aqueous solutions.

    PubMed

    Warkentin, Matthew; Sethna, James P; Thorne, Robert E

    2013-01-01

    When pure water is cooled at ~10(6) K / s, it forms an amorphous solid (glass) instead of the more familiar crystalline phase. The presence of solutes can reduce this required (or "critical") cooling rate by orders of magnitude. Here, we present critical cooling rates for a variety of solutes as a function of concentration and a theoretical framework for understanding these rates. For all solutes tested, the critical cooling rate is an exponential function of concentration. The exponential's characteristic concentration for each solute correlates with the solute's Stokes radius. A modification of critical droplet theory relates the characteristic concentration to the solute radius and the critical nucleation radius of ice in pure water. This simple theory of ice nucleation and glass formability in aqueous solutions has consequences for general glass-forming systems, and in cryobiology, cloud physics, and climate modeling. PMID:23383808

  19. Accurate description of calcium solvation in concentrated aqueous solutions.

    PubMed

    Kohagen, Miriam; Mason, Philip E; Jungwirth, Pavel

    2014-07-17

    Calcium is one of the biologically most important ions; however, its accurate description by classical molecular dynamics simulations is complicated by strong electrostatic and polarization interactions with surroundings due to its divalent nature. Here, we explore the recently suggested approach for effectively accounting for polarization effects via ionic charge rescaling and develop a new and accurate parametrization of the calcium dication. Comparison to neutron scattering and viscosity measurements demonstrates that our model allows for an accurate description of concentrated aqueous calcium chloride solutions. The present model should find broad use in efficient and accurate modeling of calcium in aqueous environments, such as those encountered in biological and technological applications.

  20. Raman spectra of amino acids and their aqueous solutions

    NASA Astrophysics Data System (ADS)

    Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

    2011-03-01

    Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids ( L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.

  1. Solubility of nitrous oxide in alkanolamine aqueous solutions

    SciTech Connect

    Tsai, T.C.; Ko, J.J.; Wang, H.M.; Lin, C.Y.; Li, M.H.

    2000-04-01

    The solubility of nitrous oxide (N{sub 2}O) in alkanolamine aqueous solutions has been measured at (30, 35, and 40) C. The systems studied are monoethanolamine, diethanolamine, diisopropanolamine, triethanolamine, and 2-amino-2-methyl-1-propanol aqueous solutions. The concentration of amine for monoethanolamine ranges from (1 to 6) kmol/m{sup 3} and for other amines from (0.5 to 3) kmol/m{sup 3}. The accuracy of the measurement is estimated to be {+-}2%. A semiempirical model of the excess Henry's constant proposed by Wang et al. (1992) was used to correlate the solubility of N{sub 2}O in amine solutions. The parameters of the correlation were determined from the measured solubility data and the available data in the open literature. For a wide temperature range from (15 to 75) C, the obtained correlation has been shown to represent reasonably the solubility of N{sub 2}O in six amine aqueous solutions: MEA, DEA, DIPA, TEA, MDEA, and AMP. For the purpose of process design, the obtained correlations are, in general, satisfactory for estimating the solubility of N{sub 2}O in amine solutions, which in turn can be used to estimate the correct free-gas solubility of CO{sub 2} in amines.

  2. Solid-like mechanical behaviors of ovalbumin aqueous solutions.

    PubMed

    Ikeda, S; Nishinari, K

    2001-04-12

    Flow and dynamic mechanical properties of ovalbumin (OVA) aqueous solutions were investigated. OVA solutions exhibited relatively large zero-shear viscosity values under steady shear flow and solid-like mechanical responses against oscillating small shear strains, that is, the storage modulus was always larger than the loss modulus in the examined frequency range (0.1--100 rad s(-1)). These results suggest that dispersed OVA molecules arranged into a colloidal crystal like array stabilized by large interparticle repulsive forces. However, marked solid-like mechanical behaviors were detected even when electrostatic repulsive forces among protein molecules were virtually absent, which could not be explained solely on the basis of conventional Derjaguin--Landau--Verwey--Overbeek (DLVO) theory. Large non-DLVO repulsive forces seem to stabilize native OVA aqueous solutions.

  3. Polytungstate-photosensitized formation of hydrogen from aqueous organic solutions

    SciTech Connect

    Muradov, N.Z.; Rustamov, M.I.; Guseinova, A.D.; Ismailov, E.G.; Bazhutin, Yu.V.

    1988-01-01

    When acidic aqueous organic solutions of polytungstates are irradiated by light of wavelength lambda < 400 nm in the photocatalytic evolution of hydrogen takes place, which is accelerated in the presence of colloidal platinum. The dependence of the rate of photoreduction of polytungstates and the photo-induced formation of hydrogen on the reactant concentrations, the amount of Pt, the pH of the solution, temperature, etc., have been determined for aqueous ethanol solutions. Aliphatic alcohols, aldehydes, organic acids, etc., were used as the organic reactants. The photoreduction of the polytungstates was studied by spectrophotometry and by EPR and a conclusion is draw on the mechanism for the photo-induced formation of hydrogen.

  4. Sorption of organics from aqueous solution onto polymeric resins

    SciTech Connect

    Gusler, G.M.; Browne, T.E.; Cohen, Y. . Dept. of Chemical Engineering)

    1993-11-01

    The uptake of phenol, toluene, chlorobenzene, and benzoic acid by several polymeric resins and activated carbon was investigated experimentally. Presentation of the sorption data in terms of the number of sorbed monolayers and fractional pore volume filled indicated that, for the polymeric resins, solute uptake cannot be viewed as only a surface adsorption phenomenon. It is suggested that the aqueous phase uptake of phenol, toluene, chlorobenzene, and benzoic acid by the polymeric resins is attributable, in part, to solute absorption. The present study also suggests that solute uptake is affected by the swelling of some of the polymeric resins in water.

  5. Spontaneous Oligomerization of Nucleotide Alternatives in Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Smith, Karen E.; House, Christopher H.; Dworkin, Jason P.; Callahan, Michael P.

    2016-03-01

    On early Earth, a primitive polymer that could spontaneously form from likely available precursors may have preceded both RNA and DNA as the first genetic material. Here, we report that heated aqueous solutions containing 5-hydroxymethyluracil (HMU) result in oligomers of uracil, heated solutions containing 5-hydroxymethylcytosine (HMC) result in oligomers of cytosine, and heated solutions containing both HMU and HMC result in mixed oligomers of uracil and cytosine. Oligomerization of hydroxymethylated pyrimidines, which may have been abundant on the primitive Earth, might have been important in the development of simple informational polymers.

  6. Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics, transformation products, and toxicity evolvement.

    PubMed

    Dong, Bizhang; Hu, Jiye

    2016-10-01

    The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 (-)), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 (-), Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L(-1) Fe (III) and 500 mg L(-1) TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.

  7. Photolysis kinetics and influencing factors of bisphenol S in aqueous solutions.

    PubMed

    Cao, Guiping; Lu, Jilai; Wang, Gongying

    2012-01-01

    The photodegradation of bisphenol S (BPS) in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics: the rate was gamma = 0.0161C(BPS) under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.

  8. Process of concentrating ethanol from dilute aqueous solutions thereof

    DOEpatents

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

    1981-07-07

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

  9. Process of concentrating ethanol from dilute aqueous solutions thereof

    DOEpatents

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

    1981-07-07

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

  10. Dephosphorization of Steelmaking Slag by Leaching with Acidic Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Qiao, Yong; Diao, Jiang; Liu, Xuan; Li, Xiaosa; Zhang, Tao; Xie, Bing

    2015-12-01

    In the present paper, dephosphorization of steelmaking slag by leaching with acidic aqueous solution composed of citric acid, sodium hydroxide, hydrochloric acid and ion-exchanged water was investigated. The buffer solution of C6H8O7-NaOH-HCl system prevented changes in the pH values. Kinetic parameters including leaching temperature, slag particle size and pH values of the solution were optimized. The results showed that temperature has no obvious effect on the dissolution ratio of phosphorus. However, it has a significant effect on the dissolution ratio of iron. The dephosphorization rate increases with the decrease of slag particle size and the pH value of the solution. Over 90% of the phosphorus can be dissolved in the solution while the corresponding leaching ratio of iron was only 30% below the optimal condition. Leaching kinetics of dephosphorization follow the unreacted shrinking core model with a rate controlled step by the solid diffusion layer, the corresponding apparent activation energy being 1.233 kJ mol-1. A semiempirical kinetic equation was established. After leaching, most of the nC2S-C3P solid solution in the steelmaking slag was selectively dissolved in the aqueous solution and the iron content in the solid residue was correspondingly enriched.

  11. Dephosphorization of Steelmaking Slag by Leaching with Acidic Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Qiao, Yong; Diao, Jiang; Liu, Xuan; Li, Xiaosa; Zhang, Tao; Xie, Bing

    2016-09-01

    In the present paper, dephosphorization of steelmaking slag by leaching with acidic aqueous solution composed of citric acid, sodium hydroxide, hydrochloric acid and ion-exchanged water was investigated. The buffer solution of C6H8O7-NaOH-HCl system prevented changes in the pH values. Kinetic parameters including leaching temperature, slag particle size and pH values of the solution were optimized. The results showed that temperature has no obvious effect on the dissolution ratio of phosphorus. However, it has a significant effect on the dissolution ratio of iron. The dephosphorization rate increases with the decrease of slag particle size and the pH value of the solution. Over 90% of the phosphorus can be dissolved in the solution while the corresponding leaching ratio of iron was only 30% below the optimal condition. Leaching kinetics of dephosphorization follow the unreacted shrinking core model with a rate controlled step by the solid diffusion layer, the corresponding apparent activation energy being 1.233 kJ mol-1. A semiempirical kinetic equation was established. After leaching, most of the nC2S-C3P solid solution in the steelmaking slag was selectively dissolved in the aqueous solution and the iron content in the solid residue was correspondingly enriched.

  12. Thermal Conductivity of Aqueous Sugar Solutions under High Pressure

    NASA Astrophysics Data System (ADS)

    Werner, M.; Baars, A.; Werner, F.; Eder, C.; Delgado, A.

    2007-08-01

    Molecular energy transport in aqueous sucrose and glucose solutions of different mass fractions and temperatures is investigated up to 400 MPa, using the transient hot-wire method. The results reveal an increasing thermal conductivity with increasing pressure and decreasing mass fraction of sugar. No significant differences between sucrose and glucose solutions were observed. Different empirical and semi-empirical relations from the literature are discussed to describe and elucidate the behavior of the solutions with pressure. The pressure-induced change of the thermal conductivity of sugar solutions is mainly caused by an increase of the thermal conductivity and the decrease of molar volume of the water fraction. A simple pressure adapted mass fraction model permits an estimation of the thermal conductivity of the investigated solutions within an uncertainty of about 3%.

  13. Sonoluminescence quenching in aqueous solutions of aliphatic diols and glycerol.

    PubMed

    Sunartio, Devi; Grieser, Franz; Ashokkumar, Muthupandian

    2009-01-01

    The multibubble sonoluminescence (MBSL) signals that were generated using 358 kHz ultrasound in aqueous solutions of ethylene glycol, 1,3-propanediol, 1,4-butanediol and glycerol, over a range of concentrations, have been studied. It was found that the intensity of the MBSL was either reduced or enhanced, relative to the signal in water, depending on the concentration of the solute. It was concluded that the reduction in the MBSL intensity was dependent on the strength of the intermolecular forces, in particular hydrogen bonding, between the solute molecules and water. The enhancement in the MBSL signal was ascribed to presence of the solute molecules at the bubble/solution interface that hinder the coalescence of the bubbles in the multibubble clouds produced at the antinodes in the system.

  14. Diketopiperazine-mediated peptide formation in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nagayama, M.; Takaoka, O.; Inomata, K.; Yamagata, Y.

    1990-05-01

    Though diketopiperazines (DKP) are formed in most experiments concerning the prebiotic peptide formation, the molecules have not been paid attention in the studies of chemical evolution. We have found that triglycine, tetraglycine or pentaglycine are formed in aqueous solution of glycine anhydride (DKP) and glycine, diglycine or triglycine, respectively. A reaction of alanine with DKP resulted in the formation of glycylglycylalanine under the same conditions. These results indicate that the formation of the peptide bonds proceeds through the nucleophilic attack of an amino group of the amino acids or the oligoglycines on the DKP accompanied by the ring-opening. The formation of glycine anhydride, di-, tri- and tetraglycine was also observed in a mixed aqueous solution of urea and glycine in an open system to allow the evaporation of ammonia. A probable pathway is proposed for prebiotic peptide formation through diketopiperazine on the primitive Earth.

  15. Laser purification of ultradispersed diamond in aqueous solution

    SciTech Connect

    Dolgaev, Sergei I; Kirichenko, N A; Lubnin, Evgenii N; Simakin, Aleksandr V; Shafeev, Georgii A; Kulevskii, L A

    2004-09-30

    The effect of pulsed radiation from a 2.92-{mu}m, 130-ns Cr{sup 3+}:Yb{sup 3+}:Ho{sup 3+}:YSGG holmium laser and a 510-nm, 20-ns copper vapour laser on an aqueous suspension of ultradispersed diamond is studied. X-ray photoelectron spectroscopy and electron energy loss spectroscopy revealed that exposure of the suspension to holmium laser radiation reduces the concentration of nondiamond carbon impurity in it. This is due to the dissolution of carbon impurity in supercritical aqueous solution, caused by radiation absorption. Dissolution of the nondiamond fraction may serve as an indicator of the solution being in the supercritical state as a result of laser irradiation of liquids. This process can be used for efficient purification of ultradispersed diamonds. (laser applications and other topics in quantum electronics)

  16. Polyamide nanofiltration membranes to remove aniline in aqueous solutions.

    PubMed

    Hidalgo, A M; León, G; Gómez, M; Murcia, M D; Bernal, M D; Ortega, S

    2014-01-01

    Aniline is commonly used in a number of industrial processes. It is known to be a harmful and persistent pollutant and its presence in wastewater requires treatment before disposal. In this paper, the effectiveness of nanofiltration (NF) to remove aniline from aqueous solutions is studied in a flat membrane test module using two thin-layer composite membranes of polyamide (NF97 and NF99HF). The influence of different operational variables (applied pressure, feed concentration and pH) on the removal of aniline from synthetic aqueous solutions was analysed. The experimental NF results are compared with results previously obtained by reverse osmosis. Based on this comparative study, the effective order for aniline rejection is: HR98PP > NF97 > DESAL3B > SEPA-MS05 > NF99HF.

  17. A lithium ion battery using an aqueous electrolyte solution

    NASA Astrophysics Data System (ADS)

    Chang, Zheng; Li, Chunyang; Wang, Yanfang; Chen, Bingwei; Fu, Lijun; Zhu, Yusong; Zhang, Lixin; Wu, Yuping; Huang, Wei

    2016-06-01

    Energy and environmental pollution have become the two major problems in today’s society. The development of green energy storage devices with good safety, high reliability, high energy density and low cost are urgently demanded. Here we report on a lithium ion battery using an aqueous electrolyte solution. It is built up by using graphite coated with gel polymer membrane and LISICON as the negative electrode, and LiFePO4 in aqueous solution as the positive electrode. Its average discharge voltage is up to 3.1 V and energy density based on the two electrode materials is 258 Wh kg‑1. It will be a promising energy storage system with good safety and efficient cooling effects.

  18. Electro-active paper made with aqueous cellulose solution

    NASA Astrophysics Data System (ADS)

    Wang, Niangui; Chen, Yi; Lee, Sunkon; Kim, Jaehwan

    2006-03-01

    Electro-Active Paper (EAPap) is attractive for EAP actuator due to its merits in terms of lightweight, dry condition, large displacement output, low actuation voltage and low power consumption. EAPap actuator has been made with cellulose material. Cellulose fibers are dissolved into a solution and cast in a sheet form, and a thin gold electrode is made on it. The cellulose solution has been made according to the viscous process that uses aqueous solvent NaOH/Urea. The use of strong alkali aqueous solvent results in decreasing hydrogen-bond of cellulose molecules. It makes EAPap material possessing ionic behavior. This paper presents the fabrication process and the performance evaluation of EAPap in terms of free displacement with respect to frequency and activation voltage.

  19. Polyamide nanofiltration membranes to remove aniline in aqueous solutions.

    PubMed

    Hidalgo, A M; León, G; Gómez, M; Murcia, M D; Bernal, M D; Ortega, S

    2014-01-01

    Aniline is commonly used in a number of industrial processes. It is known to be a harmful and persistent pollutant and its presence in wastewater requires treatment before disposal. In this paper, the effectiveness of nanofiltration (NF) to remove aniline from aqueous solutions is studied in a flat membrane test module using two thin-layer composite membranes of polyamide (NF97 and NF99HF). The influence of different operational variables (applied pressure, feed concentration and pH) on the removal of aniline from synthetic aqueous solutions was analysed. The experimental NF results are compared with results previously obtained by reverse osmosis. Based on this comparative study, the effective order for aniline rejection is: HR98PP > NF97 > DESAL3B > SEPA-MS05 > NF99HF. PMID:24701913

  20. Interaction between pirenoxine and bovine serum albumin in aqueous solution

    NASA Astrophysics Data System (ADS)

    Liao, Zhixi; Yu, Xianyong; Yao, Qing; Yi, Pinggui

    2014-08-01

    This work concerns the interaction of prenoxine sodium (PRX) and bovine serum albumin (BSA), which was conducted by spectroscopic means: fluorescence spectra, ultraviolet-visible spectra (UV-vis) and circular dichroism spectra (CD spectra) in physiological conditions. The results revealed the PRX can quench the fluorescence of BSA remarkably in aqueous solution. The quench mechanism has been obtained after corrected the fluorescence intensities for inner filter effects. The binding constants (Ka) were calculated according to the relevant fluorescence data at different temperatures. Moreover, from a series of analyses, we have obtained the binding sites, the binding distance and binding force. The effect of PRX on the conformation of BSA has been analyzed using synchronous fluorescence under experimental conditions. In addition, the CD spectra proved that the secondary structure of BSA changed in the presence of PRX in aqueous solution.

  1. A lithium ion battery using an aqueous electrolyte solution.

    PubMed

    Chang, Zheng; Li, Chunyang; Wang, Yanfang; Chen, Bingwei; Fu, Lijun; Zhu, Yusong; Zhang, Lixin; Wu, Yuping; Huang, Wei

    2016-06-22

    Energy and environmental pollution have become the two major problems in today's society. The development of green energy storage devices with good safety, high reliability, high energy density and low cost are urgently demanded. Here we report on a lithium ion battery using an aqueous electrolyte solution. It is built up by using graphite coated with gel polymer membrane and LISICON as the negative electrode, and LiFePO4 in aqueous solution as the positive electrode. Its average discharge voltage is up to 3.1 V and energy density based on the two electrode materials is 258 Wh kg(-1). It will be a promising energy storage system with good safety and efficient cooling effects.

  2. A lithium ion battery using an aqueous electrolyte solution

    PubMed Central

    Chang, Zheng; Li, Chunyang; Wang, Yanfang; Chen, Bingwei; Fu, Lijun; Zhu, Yusong; Zhang, Lixin; Wu, Yuping; Huang, Wei

    2016-01-01

    Energy and environmental pollution have become the two major problems in today’s society. The development of green energy storage devices with good safety, high reliability, high energy density and low cost are urgently demanded. Here we report on a lithium ion battery using an aqueous electrolyte solution. It is built up by using graphite coated with gel polymer membrane and LISICON as the negative electrode, and LiFePO4 in aqueous solution as the positive electrode. Its average discharge voltage is up to 3.1 V and energy density based on the two electrode materials is 258 Wh kg−1. It will be a promising energy storage system with good safety and efficient cooling effects. PMID:27328707

  3. Adsorption of cadmium from aqueous solutions by perlite.

    PubMed

    Mathialagan, T; Viraraghavan, T

    2002-10-14

    The present study examined the use of perlite for the removal of cadmium from aqueous solutions. The effects of pH and contact time on the adsorption process were examined. The optimum pH for adsorption was found to be 6.0. Residual cadmium concentration reached equilibrium in 6h and the rate of cadmium adsorption by perlite was rapid in the first hour of the reaction time. Ho's pseudo-second-order model best described the kinetics of the reaction. Batch adsorption experiments conducted at room temperature (22+/-1 degrees C) showed that the adsorption pattern followed the Freundlich isotherm model. The maximum removal of cadmium obtained from batch studies was 55%. Thomas model was used to describe the adsorption data from column studies. The results generally showed that perlite could be considered as a potential adsorbent for cadmium removal from aqueous solutions.

  4. Removal of methyl violet from aqueous solution by perlite.

    PubMed

    Doğan, Mehmet; Alkan, Mahir

    2003-11-01

    The use of perlite for the removal of methyl violet from aqueous solutions at different concentration, pH, and temperature has been investigated. Adsorption equilibrium is reached within 1 h. The capacity of perlite samples for the adsorption of methyl violet was found to increase with increasing pH and temperature and decrease with expansion and increasing acid-activation. The adsorption isotherms are described by means of the Langmuir and Freundlich isotherms. The adsorption isotherm was measured experimentally at different conditions and the experimental data were correlated reasonably well by the adsorption isotherm of Langmuir. The order of heat of adsorption corresponds to a physical reaction. It is concluded that the methyl violet is physically adsorbed onto the perlite. The removal efficiency (P) and dimensionless separation factor (R) have shown that perlite can be used for removal of methyl violet from aqueous solutions, but unexpanded perlite is more effective.

  5. Zinc chloride aqueous solution as a solvent for starch.

    PubMed

    Lin, Meiying; Shang, Xiaoqin; Liu, Peng; Xie, Fengwei; Chen, Xiaodong; Sun, Yongyi; Wan, Junyan

    2016-01-20

    It is important to obtain starch-based homogeneous systems for starch modification. Regarding this, an important key point is to find cheap, low-cost and low-toxicity solvents to allow complete dissolution of starch and its easy regeneration. This study reveals that a ZnCl2 aqueous solution is a good non-derivatizing solvent for starch at 50 °C, and can completely dissolve starch granules. The possible formation of a "zinc-starch complex" might account for the dissolution; and the degradation of starch, which was caused by the H(+) inZnCl2 aqueous solution, could not contribute to full dissolution. From polarized light microscopic observation combined with the solution turbidity results, it was found that the lowest ZnCl2 concentration for full dissolution was 29.6 wt.% at 50 °C, with the dissolving time being 4h. Using Fourier-transform infrared (FTIR), solid state (13)C nuclear magnetic resonance (NMR), and X-ray diffraction (XRD), it was revealed that ZnCl2 solution had no chemical reaction with starch glucosides, but only weakened starch hydrogen bonding and converted the crystalline regions to amorphous regions. In addition, as shown by intrinsic viscosity and thermogravimetric analysis (TGA), ZnCl2 solution caused degradation of starch macromolecules, which was more serious with a higher concentration of ZnCl2 solution.

  6. Adsorption analysis of ammonia in an aqueous solution

    SciTech Connect

    Arman, B.; Panchal, C.B.

    1993-08-01

    An analysis is carried out to determine the effects of the diffusional resistance on the rate of the adsorption of ammonia in an aqueous solution. A performance prediction model is developed to calculate the local rate of heat and mass transfer, including physical and thermodynamic property calculations of the mixture. An algorithm is developed for calculating the interfacial conditions. The local heat- and mass-transfer calculation is then incorporated into the performance prediction method for adsorption for a given geometry.

  7. 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.

  8. 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...

  9. 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?].

  10. [Adsorption of Congo red from aqueous solution on hydroxyapatite].

    PubMed

    Zhan, Yan-Hui; Lin, Jian-Wei

    2013-08-01

    The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

  11. [Adsorption of Congo red from aqueous solution on hydroxyapatite].

    PubMed

    Zhan, Yan-Hui; Lin, Jian-Wei

    2013-08-01

    The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution. PMID:24191561

  12. Hydrogen production via photolytic oxidation of aqueous sodium sulfite solutions.

    PubMed

    Huang, Cunping; Linkous, Clovis A; Adebiyi, Olawale; T-Raissi, Ali

    2010-07-01

    Sulfur dioxide (SO(2)) emission from coal-burning power plants and refinery operations has been implicated as a cause of acid rain and other air pollution related problems. The conventional treatment of SO(2)-contaminated air consists of two steps: SO(2) absorption using an aqueous sodium hydroxide solution, forming aqueous sodium sulfite (Na(2)SO(3)), and Na(2)SO(3) oxidation via air purging to produce sodium sulfate (Na(2)SO(4)). In this process, the potential energy of SO(2) is lost. This paper presents a novel ultraviolet (UV) photolytic process for production of hydrogen from aqueous Na(2)SO(3) solutions. The results show that the quantum efficiency of hydrogen production can reach 14.4% under illumination from a low pressure mercury lamp. The mechanism occurs via two competing reaction pathways that involve oxidation of SO(3)(2-) to SO(4)(2-) directly and through the dithionate (S(2)O(6)(2-)) ion intermediate. The first route becomes dominant once a photostationary state for S(2)O(6)(2-) is established. The initial pH of Na(2)SO(3) solution plays an important role in determining both the hydrogen production rate and the final products of the photolytic oxidation. At initial solution pH of 9.80 Na(2)SO(3) photo-oxidation generates Na(2)SO(4) as the final reaction product, while Na(2)S(2)O(6) is merely a reaction intermediate. The highest hydrogen production rate occurs when the initial solution pH is 7.55. Reduction in the initial solution pH to 5.93 results in disproportionation of HSO(3)(-) to elemental sulfur and SO(4)(2-) but no hydrogen production.

  13. Photodegradation kinetics of the new antibacterial fluoroquinolone derivative, orbifloxacin, in aqueous solution.

    PubMed

    Morimura, T; Ohno, T; Matsukura, H; Nobuhara, Y

    1995-06-01

    The photodegradation kinetics of orbifloxacin (1-cyclopropyl-5,6,8-trifluoro-1,4-dihydro-7-(cis-3,5-dimethyl-1-pipe raz inyl)-4-oxoquinoline-3-carboxylic acid) was investigated in aqueous solution at various pH values (1.2-12.5) and at an ionic strength of 0.5. The photodegradation experiments were performed using a fluorescent or a chemical lamp as a light source and the cumulative number of photons during exposure was determined by a ferrioxalate actinometer. It was found that the photodegradation of orbifloxacin followed apparent first-order kinetics under both types of artificial light. The photodegradation rates of orbifloxacin in a neutral medium were higher than those in acidic and alkaline media. Orbifloxacin was most unstable in solution at pH 7.4, and its degradation half-life was 0.9 h. Also, the log k-pH profile indicated that the photodegradation rate of orbifloxacin was related to the dissociation of the carboxylic and dimethylpiperazinyl groups and the main photo-labile species was the zwitterionic form. In addition, the photodegradation kinetics of the decarboxylated derivative of orbifloxacin in aqueous solution was investigated to determine the effect of the functional groups on the photodegradation of orbifloxacin.

  14. Preparation of thin ceramic films via an aqueous solution route

    DOEpatents

    Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

    1989-01-01

    A new chemical method of forming thin ceramic films has been developed. An aqueous solution of metal nitrates or other soluble metal salts and a low molecular weight amino acid is coated onto a substrate and pyrolyzed. The amino acid serves to prevent precipitation of individual solution components, forming a very viscous, glass-like material as excess water is evaporated. Using metal nitrates and glycine, the method has been demonstrated for zirconia with various levels of yttria stabilization, for lanthanum-strontium chromites, and for yttrium-barium-copper oxide superconductors on various substrates.

  15. Radiolysis of berberine or palmatine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Marszalek, Milena; Wolszczak, Marian

    2011-01-01

    The reactions of hydrated electron (eaq-), hydrogen atom (H rad ) (reducing species) and Cl2•-, Br2•-, N,O•H radicals (oxidizing species) with berberine or palmatine in aqueous solution have been studied by steady-state and pulse radiolysis. The spectra of transient intermediates, leading to the final products, are presented. The rate constants of the reaction of eaq- and rad OH radical with both alkaloids in the homogenous solution and in the presence of DNA are reported. It is demonstrated that the primary products of the reaction of berberine and palmatine with eaq- and radicals generated during radiolysis are unstable and undergo further reactions.

  16. [Extraction of lambda-cyhalothrin from aqueous dioxan solutions].

    PubMed

    Shormanov, V K; Chigareva, E N; Belousova, O V

    2011-01-01

    The results of extraction of lambda-cigalotrin from dioxan aqueous solutions by hydrophobic organic solvents are presented. It is shown that the degree of extraction depends on the nature of the extractant, the water to dioxan ratio, and saturation of the water-dioxan layer with the electrolyte. The highest efficiency of lambda-cigalotrin extraction was achieved using chlorophorm as a solvent under desalination conditions. The extraction factor was calculated necessary to obtain the desired amount of lambda-cigalotrin from the water-dioxan solution (4:1) with the help of the extractants being used.

  17. Oxidation of ammonium sulfite in aqueous solutions using ozone technology

    NASA Astrophysics Data System (ADS)

    Li, Yue; Shang, Kefeng; Lu, Na; Li, Jie; Wu, Yan

    2013-03-01

    How to deal with unstable ammonium sulfite, the byproduct of flue gas desulfuration by ammonia absorption methods, has been a difficult problem in recent years. Oxidation of ammonium sulfite in aqueous solutions using ozone produced by a surface discharge system was investigated in the paper. The oxidation efficiency of ammonium sulfite by ozone and traditional air aeration were compared, and the factors including ozone concentration, gas flow rate, initial concentration of ammonium sulfite solution and reaction temperature were discussed. The results show that the oxidation efficiency of ammonium sulfite by ozone technology reached nearly 100% under the optimum conditions, which had a significant increase compared with that by air aeration.

  18. Decomposition of aniline in aqueous solution by UV/TiO2 process with applying bias potential.

    PubMed

    Ku, Young; Chiu, Ping-Chin; Chou, Yiang-Chen

    2010-11-15

    Application of bias potential to the photocatalytic decomposition of aniline in aqueous solution was studied under various solution pH, bias potentials and concentrations of potassium chloride. The decomposition of aniline by UV/TiO(2) process was found to be enhanced with the application of bias potential of lower voltages; however, the electrolysis of aniline became more dominant as the applying bias potential exceeding 1.0 V. Based on the experimental results and calculated synergetic factors, the application of bias potential improved the decomposition of aniline more noticeably in acidic solutions than that in alkaline solutions. Decomposition of aniline by UV/bias/TiO(2) process in alkaline solutions was increased to certain extent with the concentration of potassium chloride present in aqueous solution. Experimental results also indicated that the energy consumed by applying bias potential for aniline decomposition by UV/bias/TiO(2) process might be much lower than that consumed for increasing light intensity for photocatalysis.

  19. Association of riboflavin, caffeine, and sodium salicylate in aqueous solution

    NASA Astrophysics Data System (ADS)

    Baranovskii, S. F.; Bolotin, P. A.

    2007-03-01

    We have used UV and visible spectrophotometry to study self-association of aromatic riboflavin molecules (RFN, vitamin B2, 7,8-dimethyl-10-N-(1'-D-ribityl)isoalloxazine) in aqueous solution (pH 6.86) at T = 298 K, using a dimer model. We have determined the equilibrium dimerization constant for riboflavin, KdB = 125 ± 40 M-1. We have studied heteroassociation in the system of molecules of 7,8-dimethyl-10-ribitylisoalloxazine with 1,3,7-trimethylxanthine (caffeine) and sodium salicylate (NAS) in aqueous solution (pH 6.86; T = 298 K). We have determined the heteroassociation constants for RFN-NAS and RFN-caffeine molecules in the absence and in the presence of urea in solutions using a modified Benesi-Hildebrand equation: 25 ± 4, 17 ± 3, and 74 ± 11, 53 ± 7 M-1 respectively. We have determined the dimerization constants for NAS (2.7 ± 0.5 M-1) and caffeine (17.0 ± 1.5 M-1). We conclude that heteroassociation of the aromatic molecules leads to a lower effective riboflavin concentration in solution, and the presence of urea in mixed solutions leads to an decrease in the complexation constants for the RFN-NAS and RFN-caffeine systems.

  20. Initiation of sugars synthesis from formaldehyde in the aqueous solution with ultraviolet radiation

    NASA Astrophysics Data System (ADS)

    Pestunova, O.; Simonov, A.; Stojanovskii, V.; Snytnikov, V.; Parmon, V.

    Many scientists consider autocatalytic sugars synthesis from formaldehyde in alkaline aqueous solutions via so-called formose reaction as a probable way of sugars formation at the prebiotic stage of the Earth evolution [1, 2]. However, the authors of paper [3] shown, that in the pure aqueous solution of formaldehyde, which does not contain even seeds of monosaccharides, the formose reaction of formaldehyde polymerisation does not occur. In this work we demonstrate that in the above mentioned solution the formose reaction can be initiated by ultraviolet radiation. A quartz cuvette (l = 10 mm) with an aqueous solution of formaldehyde (2 or 0.5 mol/l) and a magnetic stirrer was exposed to an ArF excimer laser radiation (wavelength 193 nm, 15 ns, 150 mJ, beam area 24 mm2). The location of the absorption maximum of carbonyl group of formaldehyde is 190 nm. In the course of the light-initiated reaction, in the UV spectra of solutions two absorption bands at 205 and 270 nm appear. Apparently, these bands are belonging to formic acid and glycolaldehyde, respectively. The increase of the optical density of the solution during such transformation decrease the transparency of the solution for the laser beam, this resulted in a gradual reducing of the reaction rate and the further stop of reaction. The conversion of formaldehyde at the photoreaction stopping was 7 % for the 2 mol/l solution and 16 % for the 0.5 mol/l one. The analysis of exposed solutions with a HPLC method has shown, that one of the products of the reaction is glycol aldehyde (C2O2H4), which formally is a primary C2-sugar. The yield of glycol aldehyde was 0.5 and 0.4 mol % respectively. It is well-known, that glycol aldehyde initiates the autocatalytic formose reaction, being a better initiator than other monosaccharides [4]. In our case, the addition of the UV-exposed solution to a formaldehyde and calcium hydroxide containing solution stimulated the formose reaction with a sharp reduction of the induction

  1. Stimuli-responsive supramolecular polymers in aqueous solution.

    PubMed

    Ma, Xiang; Tian, He

    2014-07-15

    CONSPECTUS: Aiming to construct various novel supramolecular polymeric structures in aqueous solution beyond small supramolecular self-assembly molecules and develop functional supramolecular polymeric materials, research interest on functional supramolecular polymers has been prevailing in recent years. Supramolecular polymers are formed by bridging monomers or components together via highly directional noncovalent interactions such as hydrogen bonding, hydrophobic interaction, π-π interaction, metal-ligand coordination, electrostatic interaction, and so forth. They can be easily functionalized by employing diverse building components with specific functions besides the traditional polymeric properties, a number of which are responsive to such external stimuli as pH variance, photoirradiation, chemically or electrochemically redox with the controllable conformation or construction switching, polymerization building and rebuilding, and function adjustment reversibly owing to the reversibility of noncovalent interactions. Supramolecular polymers are "soft matters" and can be functionalized with specific properties such as morphology adjustment, controllable luminescence, shape memory, self-healing, and so forth. Supramolecular polymers constructed based on macrocycle recognition and interlocked structures represent one typical branch of the supramolecular polymer family. Cyclodextrin (CD), cucurbituril (CB), and hydrophilic calixarene derivatives are usually employed to construct hydrophilic supramolecular polymers in aqueous solution. Stimuli-responsive hydrophilic supramolecular polymers, constructed in aqueous solution particularly, can be promising candidates for mimicking biocompatible or vital functional materials. This Account mainly focuses on the recent stimuli-responsive supramolecular polymers based on the host-guest interaction in aqueous solution. We describe the hydrophilic supramolecular polymers constructed via hydrophobic effects, electrostatic

  2. Protein Conformation and Supercharging with DMSO from Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Sterling, Harry J.; Prell, James S.; Cassou, Catherine A.; Williams, Evan R.

    2011-07-01

    The efficacy of dimethyl sulfoxide (DMSO) as a supercharging reagent for protein ions formed by electrospray ionization from aqueous solution and the mechanism for supercharging were investigated. Addition of small amounts of DMSO to aqueous solutions containing hen egg white lysozyme or equine myoglobin results in a lowering of charge, whereas a significant increase in charge occurs at higher concentrations. Results from both near-UV circular dichroism spectroscopy and solution-phase hydrogen/deuterium exchange mass spectrometry indicate that DMSO causes a compaction of the native structure of these proteins at low concentration, but significant unfolding occurs at ~63% and ~43% DMSO for lysozyme and myoglobin, respectively. The DMSO concentrations required to denature these two proteins in bulk solution are ~3-5 times higher than the concentrations required for the onset of supercharging, consistent with a significantly increased concentration of this high boiling point supercharging reagent in the ESI droplet as preferential evaporation of water occurs. DMSO is slightly more basic than m-nitrobenzyl alcohol and sulfolane, two other supercharging reagents, based on calculated proton affinity and gas-phase basicity values both at the B3LYP and MP2 levels of theory, and all three of these supercharging reagents are significantly more basic than water. These results provide additional evidence that the origin of supercharging from aqueous solution is the result of chemical and/or thermal denaturation that occurs in the ESI droplet as the concentration of these supercharging reagents increases, and that proton transfer reactivity does not play a significant role in the charge enhancement observed.

  3. Method of solidifying waste materials, such as radioactive or toxic materials, contained in aqueous solutions

    SciTech Connect

    Knieper, J.; May, K.; Printz, H.

    1984-07-24

    A method is disclosed of solidifying waste materials, such as radioactive or toxic materials, which are contained in aqueous solutions. To accomplish this solidification, an inorganic, non-metallic binding agent such as gypsum is intermixed with the aqueous solution and a substance such as pumice or ceramic tile which promotes the intermixing of the binding agent and the aqueous solution.

  4. 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.

  5. Sorption behavior of fluoride ions from aqueous solutions by hydroxyapatite.

    PubMed

    Jiménez-Reyes, M; Solache-Ríos, M

    2010-08-15

    The effects of pH, contact time, fluoride-ion concentration, and the dose of sorbent on the sorption of fluoride ions by hydroxyapatite were studied. Equilibrium was reached in 16 h of contact time and the maximum sorption of fluoride ions was in the pH(eq) range between 5 and 7.3. The highest efficiency in the sorption system was determined by using 0.01 g of hydroxyapatite and 25 mL of solution. The pseudo-second order model described the kinetic sorption processes, and the Freundlich model, the sorption isotherm process. These results indicated that the mechanism was chemisorption on a heterogeneous material. Fluoride ions were partially desorbed using an alkaline solution.

  6. Inclusion complexation of novocaine by beta-cyclodextrin in aqueous solutions.

    PubMed

    Iglesias, Emilia

    2006-06-01

    The formation of inclusion complexes between beta-cyclodextrin (beta-CD) and the local anesthetic 2-(diethylamino)ethyl-p-amino-benzoate (novocaine) in aqueous solutions under different acidity conditions, using steady-state fluorescence or UV-vis spectroscopies, electrical conductivity, or the kinetic study of both the nitrosation reaction of the primary amine group in a mild acid medium and the hydrolysis of the ester function under an alkaline medium, has been studied. The inclusion complex formation between neutral or protonated novocaine and beta-CD of 1:1 stoichiometry was observed; however, the magnitude of the binding constants depends on the nature of both the guest and the host, and the higher-affinity guest-host was found under conditions when both the novocaine and the beta-CD were neutral molecules.

  7. Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

  8. Opto-electrochemical spectroscopy of metals in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Habib, K.

    2016-03-01

    In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the electrical resistance of aluminium samples during the initial stage of anodisation processes in aqueous solution. In fact, because the resistance values in this investigation were obtained by holographic interferometry, electromagnetic method rather than electronic method, the abrupt rate change of the resistance was called electrical resistance-emission spectroscopy. The anodisation process of the aluminium samples was carried out by electrochemical impedance spectroscopy (EIS) in different sulphuric acid concentrations (1.0%-2.5% H2SO4) at room temperature. In the meantime, the real time holographic interferometry was used to determine the difference between the electrical resistance of two subsequent values, dR, as a function of the elapsed time of the EIS experiment for the aluminium samples in 1.0%, 1.5%, 2.0%, and 2.5% H2SO4 solutions. The electrical resistance-emission spectra of the present investigation represent a detailed picture of not only the rate change of the electrical resistance throughout the anodisation processes but also the spectra represent the rate change of the growth of the oxide films on the aluminium samples in different solutions. As a result, a new spectrometer was developed based on the combination of the holographic interferometry and electrochemical impedance spectroscopy for studying in situ the electrochemical behavior of metals in aqueous solutions.

  9. Wash Solution Bath Life Extension for the Space Shuttle Rocket Motor Aqueous Cleaning System

    NASA Technical Reports Server (NTRS)

    Saunders, Chad; Evans, Kurt; Sagers, Neil

    1999-01-01

    A spray-in-air aqueous cleaning system, which replaced 1,1,1 trichloroethane (TCA) vapor degreasing, is used for critical cleaning of Space Shuttle Redesigned Solid Rocket Motor (RSRM) metal parts. Small-scale testing demonstrated that the alkaline-based wash solution possesses adequate soil loading and cleaning properties. However, full-scale testing exhibited unexpected depletion of some primary components of the wash solution. Specifically, there was a significant decrease in the concentration of sodium metasilicate which forced change-out of the wash solution after eight days. Extension of wash solution bath life was necessary to ease the burden of frequent change-out on manufacturing. A laboratory study supports a depletion mechanism that is initiated by the hydrolysis of sodium tripolyphosphate (STPP) lowering the pH of the solution. The decrease in pH causes polymerization and subsequent precipitation of sodium metasilicate (SM). Further investigation showed that maintaining the pH was the key to preventing the precipitation of the sodium metasilicate. Implementation to the full scale operation demonstrated that periodic additions of potassium hydroxide (KOH) extended the useful bath life to more than four months.

  10. Adsorption of chromium from aqueous solution on treated sawdust.

    PubMed

    Garg, V K; Gupta, Renuka; Kumar, Rakesh; Gupta, R K

    2004-03-01

    The adsorption of Cr(VI) from aqueous solutions on formaldehyde treated sawdust (SD) and sulphuric acid treated sawdust carbon (SDC) of Indian Rosewood, a timber industry waste, was studied at varying Cr(VI) concentrations, adsorbent dose, pH and agitation time. Similar experiments were conducted with commercially available coconut based activated carbon to compare the results. The Cr(VI) adsorption efficiency on SDC was higher than SD. The adsorption followed first order rate expression and Lagergren equation. An initial pH of 3.0 was most favorable for Cr(VI) removal by both the adsorbents. Maximum Cr(VI) was sequestered from the solution within 60 min after the beginning for every experiment. It is proposed that SDC and SD can be potential adsorbents for Cr(VI) removal from dilute solutions. PMID:14643989

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

    USGS Publications Warehouse

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

    2001-01-01

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

  12. Direct contact membrane distillation of sugar aqueous solutions

    SciTech Connect

    Izquierdo-Gil, M.A.; Garcia-Payo, M.C.; Fernandez-Pineda, C.

    1999-06-01

    Results are given from direct contact membrane distillation, using tangential flows to the membrane, with sugar aqueous solutions. Several effects on the distillation process are examined: flow rate through the cell, nature of the feed solutions, initial concentrations of the feed solutions, average temperature, and temperature difference. On the basis of enthalpy flux conservation in the different regions, various systems of equations are proposed for the estimation of the interfacial temperatures. Based on the known temperatures of the liquid-vapor interfaces, the experimental distillate fluxes for several sets are fitted to the gas stagnant film diffusion model to obtain the effective diffusion coefficients of the water vapor-air mixture, D{sub ef}, and the results are analyzed.

  13. Process for disposal of aqueous solutions containing radioactive isotopes

    DOEpatents

    Colombo, Peter; Neilson, Jr., Robert M.; Becker, Walter W.

    1979-01-01

    A process for disposing of radioactive aqueous waste solutions whereby the waste solution is utilized as the water of hydration to hydrate densified powdered portland cement in a leakproof container; said waste solution being dispersed without mechanical inter-mixing in situ in said bulk cement, thereafter the hydrated cement body is impregnated with a mixture of a monomer and polymerization catalyst to form polymer throughout the cement body. The entire process being carried out while maintaining the temperature of the components during the process at a temperature below 99.degree. C. The container containing the solid polymer-impregnated body is thereafter stored at a radioactive waste storage dump such as an underground storage dump.

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

    SciTech Connect

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

    2010-01-01

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

  15. Diffusion of Trehalose and Sucrose in Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Feick, E.; von Meerwall, E.; Ekdawi, N.; de Pablo, J.

    2000-10-01

    Trehalose is emerging as superior substitute for sucrose in solution as a cryoprotectant, e. g., to preserve organs destined for transplantation. We have used the proton NMR pulsed-gradient spin-echo method between T = 30 and 85 deg. C to study the self-diffusion of solvent and solute in aqueous solutions of these molecules as function of their concentration, c. We find that both solute molecules diffuse substantially more slowly than water at corresponding c and T; that addition of water accelerates solute diffusion more rapidly than that of water; and that while at a given c and T water diffusion is insensitive to solute identity, trehalose diffusion is slower than sucrose diffusion. The latter effect increases with c, approaching a factor of two at the highest c. In these respects our results correspond closely to those of our extensive numerical simulations of these systems. Free-volume theory is employed to explore the cooperative kinetic interactions between solvent and solutes, and to account tentatively for part of the superiority of trehalose to sucrose as preservation agent. Differences in crystallization behavior also seem to be involved.

  16. 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.

  17. Boron removal from aqueous solution by direct contact membrane distillation.

    PubMed

    Hou, Deyin; Wang, Jun; Sun, Xiangcheng; Luan, Zhaokun; Zhao, Changwei; Ren, Xiaojing

    2010-05-15

    The removal of boron from aqueous solution by direct contact membrane distillation (DCMD) was studied with self-prepared polyvinylidene fluoride (PVDF) hollow fiber membranes in the present work. The effect of pH, boron concentration, temperature and salt concentration of the feed solution on the boron rejection was investigated. The experimental results indicated that boron rejection was less dependent on the feed pH and salt concentration. DCMD process had high boron removal efficiency (>99.8%) and the permeate boron was below the maximum permissible level even at feed concentration as high as 750 mg/L. Although the permeate flux was enhanced exponentially with the feed temperature increasing, the influence of feed temperature on the boron rejection could be neglected. Finally, the natural groundwater sample containing 12.7 mg/L of boron was treated by DCMD process. The permeate boron kept below 20 microg/L whether the feed was acidified or not, but pre-acidification was helpful to maintain the permeate flux stability. All the experimental results indicated that DCMD could be efficiently used for boron removal from aqueous solution.

  18. Nanoscale adhesive forces between silica surfaces in aqueous solutions.

    PubMed

    Troncoso, Paula; Saavedra, Jorge H; Acuña, Sergio M; Jeldres, Ricardo; Concha, Fernando; Toledo, Pedro G

    2014-06-15

    Nanoscale adhesive forces between a colloidal silica probe and a flat silica substrate were measured with an atomic force microscope (AFM) in a range of aqueous NaCl, CaCl2, and AlCl3 solutions, with concentrations ranging from 10(-)(6) to 10(-)(2) M at pH ∼5.1. Notably, the measured force curves reveal large pull-off forces in water which increase in electrolyte solutions, with jump-off-contact occurring as a gradual detachment of the probe from the flat substrate rather than as a sharp discontinuous jump. The measured force curves also show that the number and size of the steps increase with concentration and notably with electrolyte valence. For the higher concentration and valence the steps become jumps. We propose that these nanoscale adhesive forces between mineral surfaces in aqueous solutions may arise from newly born cavities or persistent subnanometer bubbles. Formation of cavities or nanobubbles cannot be observed directly in our experiments; however, we cannot disregard them as responsible for the discontinuities in the measured force data. A simple model based on several cavities bridging the two surfaces we show that is able to capture all the features in the measured force curves. The silica surfaces used are clean but not intentionally hydroxylated, as contact angle measurements show, and as such may be responsible for the cavities.

  19. Removing Phosphorus from Aqueous Solutions Using Lanthanum Modified Pine Needles

    PubMed Central

    Wang, Xianze; Liu, Zhongmou; Liu, Jiancong; Huo, Mingxin; Huo, Hongliang; Yang, Wu

    2015-01-01

    The renewable pine needles was used as an adsorbent to remove phosphorus from aqueous solutions. Using batch experiments, pine needles pretreated with alkali-isopropanol (AI) failed to effectively remove phosphorus, while pine needles modified with lanthanum hydroxide (LH) showed relatively high removal efficiency. LH pine needles were effective at a wide pH ranges, with the highest removal efficiency reaching approximately 85% at a pH of 3. The removal efficiency was kept above 65% using 10 mg/L phosphorus solutions at desired pH values. There was no apparent significant competitive behavior between co-existing anions of sulfate, nitrate, and chloride (SO42-, NO3- and Cl-); however, CO32- exhibited increased interfering behavior as concentrations increased. An intraparticle diffusion model showed that the adsorption process occurred in three phases, suggesting that a boundary layer adsorption phenomena slightly affected the adsorption process, and that intraparticle diffusion was dominant. The adsorption process was thermodynamically unfavorable and non-spontaneous; temperature increases improved phosphorus removal. Total organic carbon (TOC) assays indicated that chemical modification reduced the release of soluble organic compounds from 135.6 mg/L to 7.76 mg/L. This new information about adsorption performances provides valuable information, and can inform future technological applications designed to remove phosphorus from aqueous solutions. PMID:26630014

  20. Lubrication, adsorption, and rheology of aqueous polysaccharide solutions.

    PubMed

    Stokes, Jason R; Macakova, Lubica; Chojnicka-Paszun, Agnieszka; de Kruif, Cornelis G; de Jongh, Harmen H J

    2011-04-01

    Aqueous lubrication is currently at the forefront of tribological research due to the desire to learn and potentially mimic how nature lubricates biotribological contacts. We focus here on understanding the lubrication properties of naturally occurring polysaccharides in aqueous solution using a combination of tribology, adsorption, and rheology. The polysaccharides include pectin, xanthan gum, gellan, and locus bean gum that are all widely used in food and nonfood applications. They form rheologically complex fluids in aqueous solution that are both shear thinning and elastic, and their normal stress differences at high shear rates are found to be characteristic of semiflexible/rigid molecules. Lubrication is studied using a ball-on-disk tribometer with hydrophobic elastomer surfaces, mimicking biotribological contacts, and the friction coefficient is measured as a function of speed across the boundary, mixed, and hydrodynamic lubrication regimes. The hydrodynamic regime, where the friction coefficient increases with increasing lubricant entrainment speed, is found to depend on the viscosity of the polysaccharide solutions at shear rates of around 10(4) s(-1). The boundary regime, which occurs at the lowest entrainment speeds, depends on the adsorption of polymer to the substrate. In this regime, the friction coefficient for a rough substrate (400 nm rms roughness) is dependent on the dry mass of polymer adsorbed to the surface (obtained from surface plasmon resonance), while for a smooth substrate (10 nm rms roughness) the friction coefficient is strongly dependent on the hydrated wet mass of adsorbed polymer (obtained from quartz crystal microbalance, QCM-D). The mixed regime is dependent on both the adsorbed film properties and lubricant's viscosity at high shear rates. In addition, the entrainment speed where the friction coefficient is a minimum, which corresponds to the transition between the hydrodynamic and mixed regime, correlates linearly with the ratio

  1. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions

    NASA Astrophysics Data System (ADS)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2 ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0 ± 1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1ρ) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ∼104 s-1 at pH 7.4 and 37 °C, the activation energy, 50.2 kJ/mol and its pH dependence at 1.1 °C was fitted to: k (s-1) = 520 + 6.5 × 107[H+] + 3.0 × 109[OH-].

  2. Theoretical study of decomposition of methanediol in aqueous solution.

    PubMed

    Inaba, Satoshi

    2015-06-01

    Methanediol is a product of the hydration of formaldehyde and is more abundant than formaldehyde in aqueous solution. We carried out a number of quantum chemical simulations to study the decomposition of methanediol in aqueous solution. The decomposition of a methanediol proceeds by transferring a proton from a hydroxyl to an oxygen atom of the other hydroxyl in the methanediol. The decomposition of the methanediol completes after the cleavage of the bond between the formaldehyde and the water molecule. The probability of the proton transfer increases by the quantum mechanical tunneling at the low temperature because the width of the potential barrier for the decomposition becomes similar to the de Broglie wavelength of the proton. We consider the catalytic effect of water molecules in aqueous solution. The structure of the methanediol is not required to change significantly when undergoing decomposition due to the active role of water molecules to transfer a proton. We consider three types of arrangement for water molecules with respect to a methanediol: (1) a ring structure formed by a methanediol and water molecules; (2) a water cluster attracted to a methanediol by hydrogen bonds; and (3) a water cluster and additional water molecules, both of which are attracted to a methanediol by hydrogen bonds. The activation energy for the decomposition is reduced by a water cluster more efficiently than water molecules in a ring structure. However, the activation energy reduced by a water cluster is still larger than that obtained from laboratory experiments. We include water molecules that are attracted to a methanediol by hydrogen bonds during the water-cluster-catalyzed decomposition of a methanediol. The hydrogen bonds with the water molecules permit little change in the structure of the methanediol during the decomposition and play a significant role to reduce the activation energy for the decomposition. The rate constant obtained from the theoretical simulation

  3. Hydrate-based heavy metal separation from aqueous solution

    NASA Astrophysics Data System (ADS)

    Song, Yongchen; Dong, Hongsheng; Yang, Lei; Yang, Mingjun; Li, Yanghui; Ling, Zheng; Zhao, Jiafei

    2016-02-01

    A novel hydrate-based method is proposed for separating heavy metal ions from aqueous solution. We report the first batch of experiments and removal characteristics in this paper, the effectiveness and feasibility of which are verified by Raman spectroscopy analysis and cross-experiment. 88.01-90.82% of removal efficiencies for Cr3+, Cu2+, Ni2+, and Zn2+ were obtained. Further study showed that higher R141b-effluent volume ratio contributed to higher enrichment factor and yield of dissociated water, while lower R141b-effluent volume ratio resulted in higher removal efficiency. This study provides insights into low-energy, intensive treatment of wastewater.

  4. Degradation kinetics of butylmethoxydibenzoylmethane (avobenzone) in aqueous solution.

    PubMed

    Mbah, C J

    2007-10-01

    The degradation kinetics of avobenzone in aqueous solution was studied at 60 +/- 0.2 degrees C over a pH range of 2.0-10.0. The degradation rates were determined by high performance liquid chromatography. The reaction is found to follow first-order kinetics and the rate constant for the decomposition at 25 degrees C is estimated by extrapolation. The breakdown of avobenzone is shown to be hydroxide ion catalyzed and the Arrhenius plots showed the temperature dependence of avobenzone degradation. PMID:18236778

  5. Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals

    SciTech Connect

    Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; Lymar, Sergei V.; Merenyi, Gabor; Neta, Pedatsur; Ruscic, Branko; Stanbury, David M.; Steenken, Steen; Wardman, Peter

    2015-12-01

    Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pKa’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations

  6. Gas solubilities in aqueous solutions of organic substances

    SciTech Connect

    Rischbieter, E.; Schumpe, A.; Wunder, V.

    1996-07-01

    The solubilities of He, N{sub 2}, O{sub 2}, CH{sub 4}, and CO{sub 2} in aqueous solutions of glycerol, acetic acid, glucose, sucrose, and lactose were measured at 303.2 K. Additional data were generated for CO{sub 2} at 293.2 K and 323.2 K. The present results and literature data were analyzed to develop an empirical model. The parameter set allows predictions for 15 gases and 63 organic substances at temperatures between 273 K and 343 K.

  7. Adsorption of phosphate from aqueous solution by hydrous zirconium oxide.

    PubMed

    Rodrigues, Liana Alvares; Maschio, Leandro José; Coppio, Luciana de Simone Cividanes; Thim, Gilmar Patrocínio; da Silva, Maria Lúcia Caetano Pinto

    2012-06-01

    Synthetic ZrO2 x nH2O was used for phosphate removal from aqueous solution. The optimum adsorbent dose obtained for phosphate adsorption on to hydrous zirconium oxide was 0.1 g. The kinetic process was described very well by a pseudo-second-order rate model. The phosphate adsorption tended to increase with the decrease in pH. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. A phosphate desorption of approximately 74% was obtained using water at pH 12.

  8. Polymerization of beta-amino acids in aqueous solution

    NASA Technical Reports Server (NTRS)

    Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

  9. Formation of glycolaldehyde phosphate from glycolaldehyde in aqueous solution

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R.; Arrhenius, G.; Eschenmoser, A.; Bada, J. L. (Principal Investigator)

    1999-01-01

    Amidotriphosphate (0.1 M) in aqueous solution at near neutral pH in the presence of magnesium ions (0.25 M) converts glycolaldehyde (0.025 M) within days at room temperature into glycolaldehyde phosphate in (analytically) nearly quantitative yields (76% in isolated product). This robust phosphorylation process was observed to proceed at concentrations as low as 30 microM glycolaldehyde and 60 microM phosphorylation reagent under otherwise identical conditions. In sharp contrast, attempts to achieve a phosphorylation of glycolaldehyde with cyclotriphosphate ('trimetaphosphate') as phosphorylating reagent were unsuccessful. Mechanistically, the phosphorylation of glycolaldehyde with amidotriphosphate is an example of intramolecular delivery of the phosphate group.

  10. The effect of ultrasound on heme enzymes in aqueous solution.

    PubMed

    Gebicka, L; Gebicki, J L

    1997-06-01

    The effect of cavitating 22 kHz ultrasound on aqueous solutions of hydrogen peroxide-consuming enzymes, catalase and peroxidases, both plant (horseradish peroxidase) and animal (lactoperoxidase) was studied. Catalase did not undergo inactivation during sonication, whereas activity of peroxidases decreased with increased duration of sonication. It is suggested, basing on the absorption spectra, that some conformational changes occur in peroxidases upon sonolysis. It is concluded from the experiments with free radical scavengers that partial enzyme inactivation and modification has not a chemical but a mechanical basis. PMID:9247855

  11. Fluorescence of aqueous solutions of commercial humic products

    NASA Astrophysics Data System (ADS)

    Gosteva, O. Yu.; Izosimov, A. A.; Patsaeva, S. V.; Yuzhakov, V. I.; Yakimenko, O. S.

    2012-01-01

    We have studied the spectral luminescence characteristics of aqueous solutions of humic products obtained from different raw material sources, and their behavior as the excitation wavelength increases from 270 nm to 355 nm. We have identified differences in the spectral properties of industrial humic products from coalified materials, lignin-containing organic waste, and humic products from plant raw material (peat, sapropel, vermicompost). We have shown that humic products from plant raw material have spectral properties closer to those for humic substances in natural water or soil than humic products from coalified materials.

  12. Interfacial aqueous solutions dielectric constant measurements using atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Teschke, O.; Ceotto, G.; de Souza, E. F.

    2000-08-01

    The exchange of the volume of a region of the electric double layer of a mica surface immersed in aqueous solutions, with a dielectric constant ɛDL, by a nanosized radius tip, with a dielectric constant ɛTip, is responsible for the repulsion at large distances from the surface (starting at ˜100 nm, diffuse layer) and followed by an attraction when the tip is immersed in the inner layer (˜10 nm). The calculated dielectric constant as a function of the distance to the charged interface obtained by fitting the force versus distance curves, allows the mapping of the inner layer dielectric constant profiles with a nanometer resolution.

  13. Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV-vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved.

  14. Kinetics of synthesis of monomeric betaines in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Kazantsev, O. A.; Baruta, D. S.; Kamorin, D. M.; Shirshin, K. V.; Shirshin, K. K.; Kolosov, E. S.

    2016-05-01

    In the nucleophilic addition of N-(3-dimethylaminopropyl)methacrylamide to acrylic acid (1 : 1) in aqueous solutions, forming monomeric β-propiobetaine, the dependence of the initial rate on the starting reagent concentration was found to have a pronounced maximum (whose position does not depend on the temperature at 30-70°C). In the case of the addition of N, N-dimethylaminoethyl methacrylate, the dependence was exponential. The dependences of equilibrium conversions on the starting reagent concentrations were of the same type and had a maximum for both systems. The detected concentration effects are related to the peculiarities of the pre-reaction association of the reagents.

  15. Removal of synthetic food dyes in aqueous solution by Octolig.

    PubMed

    Martin, Dean F; Alessio, Rachael J; McCane, Cheryl H

    2013-01-01

    We studied six of the seven food dyes commonly used, e.g., FD&C Blue No. 1 and No. 2, Green No. 3, Red No. 3 and No. 40, Yellow No. 5 and No. 6. Quantitative removal was achieved by passage of dyes in aqueous solutions over chromatography columns packed with Octolig, a polyethylenediimine covalently attached to high-surface-area silica. A structural feature most of the dyes have in common are the presence of sulfonate groups attached to aromatic molecules. Prior studies and the current one indicated that the seventh food dye (Green No. 3) should also be quantitatively removed. Matrix effects were considered, but none were observed.

  16. Removal of phenols from aqueous solutions by emulsion liquid membranes.

    PubMed

    Reis, M Teresa A; Freitas, Ondina M F; Agarwal, Shiva; Ferreira, Licínio M; Ismael, M Rosinda C; Machado, Remígio; Carvalho, Jorge M R

    2011-09-15

    The present study deals with the extraction of phenols from aqueous solutions by using the emulsion liquid membranes technique. Besides phenol, two derivatives of phenol, i.e., tyrosol (2-(4-hydroxyphenyl)ethanol) and p-coumaric acid (4-hydroxycinnamic acid), which are typical components of the effluents produced in olive oil plants, were selected as the target solutes. The effect of the composition of the organic phase on the removal of solutes was examined. The influence of pH of feed phase on the extraction of tyrosol and p-coumaric was tested for the membrane with Cyanex 923 as an extractant. The use of 2% Cyanex 923 allowed obtaining a very high extraction of phenols (97-99%) in 5-6 min of contact time for either single solute solutions or for their mixtures. The removal efficiency of phenol and p-coumaric acid attained equivalent values by using the system with 2% isodecanol, but the removal rate of tyrosol was found greatly reduced. The extraction of tyrosol and p-coumaric acid from their binary mixture was also analysed for different operating conditions like the volume ratio of feed phase to stripping phase (sodium hydroxide), the temperature and the initial concentration of solute in the feed phase.

  17. Optical spectroscopy of simple aqueous solutions under extreme conditions

    NASA Astrophysics Data System (ADS)

    Vass, H.; Edington, D.; Crain, J.

    2003-06-01

    We report the results of an extensive series of Brillouin scattering experiments on simple aqueous solutions with a view to exploring their dynamical properties over a wide range of temperatures and pressures. For all solutes studied that inhibit freezing and allow access to temperatures far below the normal supercooling limit of water, we find clear spectroscopic evidence of GHz-range viscoelastic behavior below ≈-40 °C. This is manifested by a dramatic rise in the Brillouin mode frequencies accompanied by initial broadening and subsequent narrowing of the spectral linewidths on cooling. We find similar behavior in pure compressed (to between 2 and 4 kbar) supercooled water. This suggests that the low-temperature viscoelastic dynamics of these solutions is dominated by the behavior of the aqueous component which evidently exhibits a pronounced decrease in relaxation time though the temperature range over which it occurs is inaccessible unless freezing is suppressed either by pressure or the presence of solutes. No firm conclusion can be drawn concerning the proposed second critical point at these very low temperatures though it is not required for a consistent interpretation of the data. In the high-temperature regime, where the hydrogen bond structure is disrupted, we find considerable chemical sensitivity (even among the three chloride salts NaCl, CsCl, and CaCl2) in the dynamics especially in the vicinity of the liquid-gas critical point. This is in contrast to the low-temperature case where the cooperative dynamics of the water network dominates and appears to remain intact in the presence of a wide variety of solutes.

  18. 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.

  19. Removal of pesticides from aqueous solutions using liquid membrane emulsions

    SciTech Connect

    Norwood, V.M. III.

    1991-01-01

    Extractive liquid membrane technology is based on a water-in-oil emulsion as the vehicle to effect separation. An aqueous internal reagent phase is emulsified into an organic phase containing a surfactant and optional complexing agents. The emulsion, presenting a large membrane surface area, is then dispersed in an aqueous continuous phase containing the species to be removed. The desired species is transferred from the continuous, phase through the organic liquid membrane and concentrated in the internal reagent phase. Extraction and stripping occur simultaneously rather than sequentially as in conventional solvent extraction. Experiments were conducted to assess the feasibility of using liquid membranes to extract pesticides from rinsewaters typical of those generated by fertilizer/agrichemical dealers. A liquid membrane emulsion containing 10% NaOH as the internal reagent phase was used to extract herbicides from aqueous solution at a continuous phase:emulsion ratio of 5:1. Removals of 2,4-D, MCPA, Carbaryl, Diazinon, and Atrazine were investigated.

  20. Removal of pesticides from aqueous solutions using liquid membrane emulsions

    SciTech Connect

    Norwood, V.M. III

    1991-12-31

    Extractive liquid membrane technology is based on a water-in-oil emulsion as the vehicle to effect separation. An aqueous internal reagent phase is emulsified into an organic phase containing a surfactant and optional complexing agents. The emulsion, presenting a large membrane surface area, is then dispersed in an aqueous continuous phase containing the species to be removed. The desired species is transferred from the continuous, phase through the organic liquid membrane and concentrated in the internal reagent phase. Extraction and stripping occur simultaneously rather than sequentially as in conventional solvent extraction. Experiments were conducted to assess the feasibility of using liquid membranes to extract pesticides from rinsewaters typical of those generated by fertilizer/agrichemical dealers. A liquid membrane emulsion containing 10% NaOH as the internal reagent phase was used to extract herbicides from aqueous solution at a continuous phase:emulsion ratio of 5:1. Removals of 2,4-D, MCPA, Carbaryl, Diazinon, and Atrazine were investigated.

  1. 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.

  2. Regeneration of Aqueous Periodate Solutions by Ozone Treatment: A Sustainable Approach for Dialdehyde Cellulose Production.

    PubMed

    Koprivica, Slavica; Siller, Martin; Hosoya, Takashi; Roggenstein, Walter; Rosenau, Thomas; Potthast, Antje

    2016-04-21

    A method for easy and fast regeneration of aqueous periodate solutions from dialdehyde cellulose (DAC) production by ozone treatment is presented, along with a direct and reliable simultaneous quantification of iodate and periodate by reversed-phase HPLC. The influence of iodate and ozone concentration, solution pH, and reaction time on the regeneration efficiency was studied, as well as the reaction kinetics. Regeneration of spent periodate solutions by ozone was successfully performed in alkaline medium, which favors the formation of free (.) OH radicals, as supported by the addition of radical scavengers and quantum mechanical calculations. At pH 13 and an ozone concentration of approximately 150 mg L(-1) , periodate was completely regenerated from a 100 mm solution of iodate within 1 h at room temperature. A cyclic process of cellulose oxidation and subsequent regeneration of spent periodate with 90 % efficiency has been developed. So far, commercial applications of DAC have been hampered by difficulties in reusing the costly periodate. This work overcomes this hurdle and presents a highly efficient, clean, and low-cost protocol for the preparation of DAC with integrated periodate recycling, with the possibility of scaling the process up.

  3. Computer analysis of vibrational spectra of aqueous ethanol solutions

    NASA Astrophysics Data System (ADS)

    Burikov, S. A.; Dolenko, T. A.; Kurchatov, I. S.; Patsaeva, S. V.; Starokurov, Yu. V.

    2012-09-01

    Results of decomposition of vibrational spectra for aqueous ethanol solutions into components in the region of hydroxyl group stretching vibrations are presented. The infrared light absorption and Raman scattering spectra are investigated for alcohol concentrations in the solution changing from 0 to 90 mass %. Methods of higher derivatives and genetic algorithms together with the simplex method are used to investigate the OH stretching vibrational band contour. Independent methods of spectral structure resolution demonstrate good agreement in the number of the major spectral components as well as in the dependences of the peak wavenumbers, band widths, and amplitudes of spectral components on the ethanol concentration in water. The observed changes in the shape of the spectral contour for OH stretching vibration and, therefore, its components are explained in terms of the hydrogen bonding in non-electrolyte/water mixtures.

  4. Rheological properties of aqueous solutions of biopolymeric hyaluronan

    NASA Astrophysics Data System (ADS)

    Szwajczak, Elzbieta

    2004-09-01

    Aqueous solutions of hyaluronic acid (hyaluronan, HA) were studied. The HA compound is a natural polysaccharide, bipolymer. It plays an important role in numerous biological processes as a component of the extracellular matrix, connective tissues and, especially, human and animal synovial joints. Natural and artificial solutions of the HA have demonstrated the viscoelastic nature. These properties are shown to be related to the microstructure parameters (bulk concentration, molecular weight) and external parameters (temperature, stress, shear rate). We emphasize the role of the flow properties of polymeric systems. It is found a liquid crystalline "order" can be "induced" during the material flow. The dynamic properties, such as the elastic shear modulus and viscous shear modulus, are given. These results are discussed in relation to the postulated function of hyaluronic acid in synovial joint and with respect to possibilities o their application in medicine and pharmacology.

  5. Degradation of aqueous DEA solutions in heat transfer tubes

    SciTech Connect

    Meisen, A.; Chakma, A.

    1985-01-01

    Experiments were performed on the degradation of aqueous diethanolamine (DEA) solutions passing through a coiled heat transfer tube (2.0032 mm ID, 3.175 mm OD, 4.8 m long) immersed in a constant temperature bath. The operating conditions were: DEA flow rate 0.011 to 0.0172 L/s, DEA concentration 20 to 40 wt%, DEA temperature 60 to 200/sup 0/C, CO/sub 2/ partial pressure 1.38 to 4.18 MPa. The degradation rate was found to increase with temperature, DEA concentration and CO/sub 2/ partial pressure; it decreased with solution flow rate. The degradation was accompanied by the formation of a fouling deposit. A simple mathematical model is presented for predicting DEA degradation.

  6. Oxidation of aqueous polyselenide solutions. A mechanistic pulse radiolysis study

    SciTech Connect

    Goldbach, A.; Saboungi, M.L.; Johnson, J.A.; Cook, A.R.; Meisel, D.

    2000-05-04

    The oxidation of aqueous polyselenide solutions was studied by pulse radiolysis in the presence of N{sub 2}O at pH 12.3; the hydroxyl radical OH was the predominant oxidant, while hydrogen selenide anions HSe{sup {minus}} and triselenide dianions Se{sub 3}{sup 2{minus}} were the major selenide species in the starting solution. The progress of the oxidation was monitored by optical spectroscopy. Transient polyselenides appeared immediately after the electron pulse and rapidly proceeded to form adducts with HSe{sup {minus}}, i.e., HSe{sub 2}{sup 2{minus}} and H{sub 2}Se{sub 2}{sup {minus}}, and a fairly long-lived intermediate that was identified as the diselenide radical anion Se{sub 2}{sup {minus}}. These radicals recombine to give eventually the tetraselenide dianion, Se{sub 4}{sup 2{minus}}.

  7. Adsorption of thorium from aqueous solutions by perlite.

    PubMed

    Talip, Z; Eral, M; Hiçsönmez, U

    2009-02-01

    The use of expanded perlite for the adsorption of thorium from aqueous solution by batch technique is presented. The effects of particle size, pH of the solution, initial thorium concentration, shaking time, V/m ratio and temperature were determined. It was found that the adsorption capacity increases by the increase in the pH of the suspensions. The rate of thorium adsorption on expanded perlite was observed to be fast in the first hour of the reaction time. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models and the adsorption experiments conducted at 30 +/- 1 degrees C showed that the adsorption isotherms correlated well with the Langmuir model. From the adsorption data, thermodynamic parameters such as DeltaG(o), DeltaH(o) and DeltaS(o) were calculated as a function of temperature.

  8. Nitrate Concentration near the Surface of Frozen Aqueous Solutions.

    PubMed

    Marrocco, Harley A; Michelsen, Rebecca R H

    2014-12-26

    Photolysis of nitrate plays an important role in the emission of nitrogen oxides from snow and ice, which affects the composition of the overlying atmosphere. In order to quantify these reactions, it is necessary to know how much nitrate is available for photolysis near the surfaces of snow and ice. The concentration of nitrate excluded from frozen solutions of nitric acid, sodium nitrate, and magnesium nitrate was measured with attenuated total reflection infrared spectroscopy. Liquid water and nitrate were observed at and near the bottom surface of frozen aqueous solutions during annealing from -18 to -2 °C. At -2 °C, the nitrate concentration was determined to be ∼1.0 mol/L for frozen NaNO(3) and Mg(NO(3))(2) solutions and ∼0.8 mol/L for frozen HNO(3) solutions. At lower temperatures, nitrate concentration ranged from 1.6 to 3.7 mol/L. Ideal thermodynamics overestimates nitrate concentration at colder temperatures where the brine is highly concentrated for all solutions. The nitrate concentration at ice surfaces is well described by bulk freezing point depression data close to the melting point of ice and for nitric acid at colder temperatures. Effects of temperature and counterions and implications for modeling snow chemistry are discussed. PMID:25495473

  9. The stability of thiosulfate in the presence of pyrite in low-temperature aqueous solutions

    NASA Astrophysics Data System (ADS)

    Xu, Yong; Schoonen, Martin A. A.

    1995-11-01

    The decomposition rate of thiosulfate (S 2O 32-) and the formation rates of its partial decomposition products, sulfite (SO 32-), sulfate (SO 42-), and tetrathionate (S 4O 62-), were measured in the absence and presence of pyrite in aqueous solution of pH 2.9-8.6 at 20°C. The pyrite-surface-catalyzed oxidation of S 2O 32- to S 40 62- by dissolved oxygen is the dominant S 2O 32- decomposition mechanism under the experimental conditions. The rate of tetrathionate formation is first order with respect to the pyrite surface concentration and has a fractional order (0 ≤ n ≤ 1) with respect to the S 20 32- concentration. This result is consistent with a surface-controlled heterogeneous mechanism and can be fitted with a Langmuir-Hinshelwood rate equation. The rate shows no pH dependence in the pH range between 2.9 and 6.6, but decreases in alkaline solution. The catalysis of pyrite in this reaction originates from its strong affinity for aqueous sulfur species and its semiconducting properties. Pyrite is thought to form an interfacial intermediate complex with the aqueous electron donor, S 2O 32-, on anodic sites, and the terminal electron acceptor, O 2, on cathodic sites. The electrons can transfer from the anodic site to the cathodic site via the conduction band of pyrite. In essence, the presence of pyrite eliminates a symmetry mismatch between the frontier orbitals of thiosulfate and oxygen. In the absence of pyrite, this symmetry overlap precludes the progress of this reaction and thiosulfate decomposes via disproportionation to yield sulfite and elemental sulfur.

  10. Removal of lead from aqueous solutions by activated phosphate.

    PubMed

    Mouflih, M; Aklil, A; Sebti, S

    2005-03-17

    The potential of using activated phosphate as a new adsorbent for the removal of Pb from aqueous solutions was investigated. The kinetic of lead adsorption and the adsorption process were compared for natural phosphate (NP) and activated phosphate (AP). The results indicate that equilibrium was established in about 1h for NP and 3 h for AP. The effect of the pH was examined in the range 2-6. The maximum removal obtained is between two and three for NP and between three and four for AP. The maximum adsorption capacities at 25 degrees C are 155.04 and 115.34 mg/g for AP and NP, respectively. The effect of temperature has been carried out at 25, 35 and 45 degrees C. The data obtained from adsorption isotherms of lead at different temperatures fit to linear form of Langmuir adsorption equation. The thermodynamic parameters such as enthalpy (DeltaH), free energy (DeltaG) and entropy (DeltaS) were calculated. They show that adsorption of lead on NP and AP is an endothermic process more effective at high temperatures. These results show that AP is a good adsorbent for heavy metals from aqueous solutions and could be used as a purifier for water and wastewater. PMID:15752864

  11. Photochemistry of Tetrabromobisphenol A in Frozen and Liquid Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Reich, J.; Grannas, A. M.; Dolak, E.

    2012-12-01

    Brominated flame retardants are an emerging environmental contaminant and are now globally distributed in the environment, including the Polar Regions. Because bioaccumulation presents serious concerns for human and wildlife health within the Arctic, it is important to assess the potential fate of these contaminants. Despite some established knowledge regarding photochemical processes in reactive frozen media, little published literature exists regarding the chemical transformations and fate of brominated flame retardants in the Arctic. Here, we consider the photochemical transformation of tetrabromobisphenol A (TBBPA). We have conducted field-based experiments in Barrow, Alaska to investigate the potential photochemical degradation of TBBPA in snow/ice samples and found that TBBPA was efficiently photodegraded in frozen aqueous samples under natural Barrow sunlight. The main pathway of degradation was direct photolysis and the addition of photosensitizers had no significant impact on TBBPA photodegradation. In aqueous solution the solubility and light absorption properties of TBBPA are pH dependent, indicating that the photodegradation of TBBPA in the environment will be highly pH dependent. Reactions than are pH dependent may be affected by the nature of the liquid-like layers in snow/ice as well as the presence of other solutes that may indirectly affect the local pH. Here we will discuss our field and laboratory-based results investigating the role that snow/ice composition may play on TBBPA photochemical reactivity.

  12. Removal of fluoride from aqueous solution by using alum sludge

    SciTech Connect

    Sujana, M.G.; Thakur, R.S.; Rao, S.B.

    1998-10-01

    The ability of treated alum sludge to remove fluoride from aqueous solution has been investigated. The studies were carried out as functions of contact time, concentration of adsorbent and adsorbate, temperature, pH, and effect of concentrations of other anions. The data indicate that treated alum sludge surface sites are heterogeneous in nature and that fits into a heterogeneous site binding model. The optimum pH for complete removal of fluoride from aqueous solution was found to be 6. The rate of adsorption was rapid during the initial 5 minutes, and equilibrium was attained within 240 minutes. The adsorption followed first-order rate kinetics. The present system followed the Langmuir adsorption isotherm model. The loading factor (i.e., the milligram of fluoride adsorbed per gram of alum sludge) increased with initial fluoride concentration, whereas a negative trend was observed with increasing temperature. The influence of addition of anions on fluoride removal depends on the relative affinity of the anions for the surface and the relative concentrations of the anions.

  13. Efficient removal of mercury from aqueous solutions and industrial effluent.

    PubMed

    Dos Santos, Maria B P; Leal, Katia Z; Oliveira, Fernando J S; Sella, Silvia M; Vieira, Méri D; Marques, Elisa M D; Gomes, Vanessa A C

    2015-01-01

    The objective of this study was to examine the ability of a solid waste produced during beneficiation of ornamental rocks to remove mercury (Hg) from an industrial effluent and aqueous solutions under various conditions. Batch studies have been carried out by observing the effects of pH, concentration of the adsorbate, contact time, and so on. Various sorption isotherm models such as Langmuir, Freundlich, and Tóth have been applied for the adsorbent. Film and intraparticle diffusion were both found to be rate-limiting steps. Adsorption was properly described by the Freundlich model (capacity constant of 0.3090 (mg g(-1))(mg L(-1))(-1/n) and adsorption intensity indicator of 2.2939), which indicated a favorable sorption and encouraged subsequent studies for treatment of Hg-containing industrial effluent. Industrial effluent treatment efficiency reached Hg removals greater than 90% by using ornamental rock solid waste (ORSW). Besides, desorption studies indicated that the maximum recovery of mercury was 100 ± 2% for 1 mol L(-1) HNO3 and 74 ± 8% for 0.1 mol L(-1) HNO3. The ORSW could be reused thrice without significant difference on the Hg removal rate from industrial effluent. These findings place ORSW as a promising efficient and low-cost adsorbent for the removal of Hg from aqueous solutions and industrial effluent. PMID:26301849

  14. Efficient removal of mercury from aqueous solutions and industrial effluent.

    PubMed

    Dos Santos, Maria B P; Leal, Katia Z; Oliveira, Fernando J S; Sella, Silvia M; Vieira, Méri D; Marques, Elisa M D; Gomes, Vanessa A C

    2015-01-01

    The objective of this study was to examine the ability of a solid waste produced during beneficiation of ornamental rocks to remove mercury (Hg) from an industrial effluent and aqueous solutions under various conditions. Batch studies have been carried out by observing the effects of pH, concentration of the adsorbate, contact time, and so on. Various sorption isotherm models such as Langmuir, Freundlich, and Tóth have been applied for the adsorbent. Film and intraparticle diffusion were both found to be rate-limiting steps. Adsorption was properly described by the Freundlich model (capacity constant of 0.3090 (mg g(-1))(mg L(-1))(-1/n) and adsorption intensity indicator of 2.2939), which indicated a favorable sorption and encouraged subsequent studies for treatment of Hg-containing industrial effluent. Industrial effluent treatment efficiency reached Hg removals greater than 90% by using ornamental rock solid waste (ORSW). Besides, desorption studies indicated that the maximum recovery of mercury was 100 ± 2% for 1 mol L(-1) HNO3 and 74 ± 8% for 0.1 mol L(-1) HNO3. The ORSW could be reused thrice without significant difference on the Hg removal rate from industrial effluent. These findings place ORSW as a promising efficient and low-cost adsorbent for the removal of Hg from aqueous solutions and industrial effluent.

  15. Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

  16. Gamma radiolytic degradation of naphthalene in aqueous solution

    NASA Astrophysics Data System (ADS)

    Chu, Libing; Yu, Shaoqing; Wang, Jianlong

    2016-06-01

    The decomposition of naphthalene in aqueous solution was studied using gamma irradiation combined with both H2O2 and TiO2 nanoparticles. Gamma irradiation led to a complete degradation of naphthalene and a partial mineralization. With initial concentration of 5-32 mg/L, more than 98% of naphthalene was removed and TOC reduction reached 28-31% at an absorbed dose of 3.0 kGy. The degradation of naphthalene was faster at neutral pH and the initial degradation rate increased with increasing the initial concentration of naphthalene. Addition of H2O2 and TiO2 nanoparticles all enhanced the degradation and mineralization of naphthalene. TOC removal efficiency increased from 28% (irradiation alone) to 35% with addition of H2O2 (40 mg/L), and to 48% with addition of TiO2 (0.8 g/L). The degradation of naphthalene in aqueous solution by gamma irradiation was mainly through the oxidation by ·OH radicals. The intermediate naphthol and carboxylic acids such as formic acid and oxalic acid were identified by LC-MS and IC.

  17. Radiation crosslinking of methylcellulose and hydroxyethylcellulose in concentrated aqueous solutions

    NASA Astrophysics Data System (ADS)

    Wach, Radoslaw A.; Mitomo, Hiroshi; Nagasawa, Naotsugu; Yoshii, Fumio

    2003-12-01

    The effects of ionizing radiation on aqueous solutions of cellulose ethers, methylcellulose (MC) and hydroxyethylcellulose (HEC) were investigated. The well-established knowledge states that cellulose and its derivatives belong to degrading type of polymers. However, in our study intermolecular crosslinking initiated by gamma rays or electron beam leaded to the formation of insoluble gel. This is an opposite effect of irradiation to the degradation. Paste-like form of the initial specimen, i.e. concentration 20-30%, when water plasticizes the bulk of polymer; and a high dose rate were favorable for hydrogel formation. Gel fraction up to 60% and 70% was obtained from solutions of HEC and MC, respectively. Produced hydrogels swell markedly in aqueous media by imbibing and holding the solvent. Radiation parameters of irradiation, such as yields of degradation and crosslinking and the gelation dose, were evaluated by sol-gel analysis on the basis of Charlesby-Rosiak equation. Despite of the crosslinked structure, obtained hydrogels can be included into the group of biodegradable materials. They undergo decomposition by the action of cellulase enzyme or microorganisms from compost.

  18. Preparation of metallic nanoparticles by irradiation in starch aqueous solution

    SciTech Connect

    Nemţanu, Monica R. Braşoveanu, Mirela Iacob, Nicuşor

    2014-11-24

    Colloidal silver nanoparticles (AgNPs) were synthesized in a single step by electron beam irradiation reduction of silver ions in aqueous solution containing starch. The nanoparticles were characterized by spectrophotocolorimetry and compared with those obtained by chemical (thermal) reduction method. The results showed that the smaller sizes of AgNPs were prepared with higher yields as the irradiation dose increased. The broadening of particle size distribution occurred by increasing of irradiation dose and dose rate. Chromatic parameters such as b* (yellow-blue coordinate), C* (chroma) and ΔE{sub ab} (total color difference) could characterize the nanoparticles with respect of their concentration. Hue angle h{sup o} was correlated to the particle size distribution. Experimental data of the irradiated samples were also subjected to factor analysis using principal component extraction and varimax rotation in order to reveal the relation between dependent variables and independent variables and to reduce their number. The radiation-based method provided silver nanoparticles with higher concentration and narrower size distribution than those produced by chemical reduction method. Therefore, the electron beam irradiation is effective for preparation of silver nanoparticles using starch aqueous solution as dispersion medium.

  19. New terahertz dielectric spectroscopy for the study of aqueous solutions

    SciTech Connect

    George, Deepu K.; Charkhesht, Ali; Vinh, N. Q.

    2015-12-15

    We present the development of a high precision, tunable far-infrared (terahertz) frequency-domain dielectric spectrometer for studying the dynamics of biomolecules in aqueous solutions in the gigahertz-to-terahertz frequency. As an important benchmark system, we report on the measurements of the absorption and refractive index for liquid water in the frequency range from 5 GHz to 1.12 THz (0.17–37.36 cm{sup −1} or 0.268–60 mm). The system provides a coherent radiation source with power up to 20 mW in the gigahertz-to-terahertz region. The dynamic range of our instrument reaches 10{sup 12} and the system achieves a spectral resolution of less than 100 Hz. The temperature of samples can be controlled precisely with error bars of ±0.02 °C from 0 °C to 90 °C. Given these attributes, our spectrometer provides unique capabilities for the accurate measurement of even very strongly absorbing materials such as aqueous solutions.

  20. Preparation of metallic nanoparticles by irradiation in starch aqueous solution

    NASA Astrophysics Data System (ADS)

    NemÅ£anu, Monica R.; Braşoveanu, Mirela; Iacob, Nicuşor

    2014-11-01

    Colloidal silver nanoparticles (AgNPs) were synthesized in a single step by electron beam irradiation reduction of silver ions in aqueous solution containing starch. The nanoparticles were characterized by spectrophotocolorimetry and compared with those obtained by chemical (thermal) reduction method. The results showed that the smaller sizes of AgNPs were prepared with higher yields as the irradiation dose increased. The broadening of particle size distribution occurred by increasing of irradiation dose and dose rate. Chromatic parameters such as b* (yellow-blue coordinate), C* (chroma) and ΔEab (total color difference) could characterize the nanoparticles with respect of their concentration. Hue angle ho was correlated to the particle size distribution. Experimental data of the irradiated samples were also subjected to factor analysis using principal component extraction and varimax rotation in order to reveal the relation between dependent variables and independent variables and to reduce their number. The radiation-based method provided silver nanoparticles with higher concentration and narrower size distribution than those produced by chemical reduction method. Therefore, the electron beam irradiation is effective for preparation of silver nanoparticles using starch aqueous solution as dispersion medium.

  1. New terahertz dielectric spectroscopy for the study of aqueous solutions.

    PubMed

    George, Deepu K; Charkhesht, Ali; Vinh, N Q

    2015-12-01

    We present the development of a high precision, tunable far-infrared (terahertz) frequency-domain dielectric spectrometer for studying the dynamics of biomolecules in aqueous solutions in the gigahertz-to-terahertz frequency. As an important benchmark system, we report on the measurements of the absorption and refractive index for liquid water in the frequency range from 5 GHz to 1.12 THz (0.17-37.36 cm(-1) or 0.268-60 mm). The system provides a coherent radiation source with power up to 20 mW in the gigahertz-to-terahertz region. The dynamic range of our instrument reaches 10(12) and the system achieves a spectral resolution of less than 100 Hz. The temperature of samples can be controlled precisely with error bars of ±0.02 °C from 0 °C to 90 °C. Given these attributes, our spectrometer provides unique capabilities for the accurate measurement of even very strongly absorbing materials such as aqueous solutions.

  2. Removal of Cr6+ from aqueous solution by some algae.

    PubMed

    Baran, Ayşe; Baysal, Senay Hamarat; Sukatar, Atakan

    2005-06-01

    Biosorption of Cr6+ from aqueous solution on dried (Halimeda tuna, Sargassum vulgare, Pterocladia capillacea, Hypnea musciformis, Laurencia papillosa) algae were studied with variation in the parameters of pH, initial metal ion concentration and agitation time. From the batch system studies the working sorption pH value was determined as 1.0 for Halimeda tuna and Sargassum vulgare, 2.0 for Pterocladia capillacea and Hypnea musciformis, 3.0 for Laurencia papillosa. The total adsorbed quantities, equilibrium uptakes and total removal percents of Cr6+ were determined by evaluating the breakthrough curves obtained at different inlet Cr6+ concentration for each sorbent. The maximum chromium biosorption occured at 120 min for Halimeda tuna, 180 min for Sargassum vulgare, Hypnea musciformis and Pterocladia capillacea, 60 min for Laurencia papillosa. The suitability of the Freundlich and Langmiur adsorption models were also investigated for each chromium-sorbent system. The results showed that Sargassum vulgare was found suitable for removing chromium from aqueous solution. The maximum sorption capacities of Halimeda tuna, Sargassum vulgare, Pterocladia capillacea, Hypnea musciformis, Laurencia papillosa were determined as 2.3, 33.0, 6.6, 4.7 and 5.3 mgg(-1). PMID:16334262

  3. Method of precipitating uranium from an aqueous solution and/or sediment

    SciTech Connect

    Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

    2013-08-20

    A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

  4. 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.

  5. Relationship between solution structure and phase behavior: a neutron scattering study of concentrated aqueous hexamethylenetetramine solutions.

    PubMed

    Burton, R C; Ferrari, E S; Davey, R J; Finney, J L; Bowron, D T

    2009-04-30

    The water-hexamethylenetetramine system displays features of significant interest in the context of phase equilibria in molecular materials. First, it is possible to crystallize two solid phases depending on temperature, both hexahydrate and anhydrous forms. Second, saturated aqueous solutions in equilibrium with these forms exhibit a negative dependence of solubility (retrograde) on temperature. In this contribution, neutron scattering experiments (with isotopic substitution) of concentrated aqueous hexamethylenetetramine solutions combined with empirical potential structure refinement (EPSR) were used to investigate the time-averaged atomistic details of this system. Through the derivation of radial distribution functions, quantitative details emerge of the solution coordination, its relationship to the nature of the solid phases, and of the underlying cause of the solubility behavior of this molecule.

  6. Adsorption of cesium on cement mortar from aqueous solutions.

    PubMed

    Volchek, Konstantin; Miah, Muhammed Yusuf; Kuang, Wenxing; DeMaleki, Zack; Tezel, F Handan

    2011-10-30

    The adsorption of cesium on cement mortar from aqueous solutions was studied in series of bench-scale tests. The effects of cesium concentration, temperature and contact time on process kinetics and equilibrium were evaluated. Experiments were carried out in a range of initial cesium concentrations from 0.0103 to 10.88 mg L(-1) and temperatures from 278 to 313 K using coupons of cement mortar immersed in the solutions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectroscopy. Depending on the initial cesium concentration, its equilibrium concentration in solution ranged from 0.0069 to 8.837 mg L(-1) while the respective surface concentration on coupons varied from 0.0395 to 22.34 μg cm(-2). Equilibrium test results correlated well with the Freundlich isotherm model for the entire test duration. Test results revealed that an increase in temperature resulted in an increase in adsorption rate and a decrease in equilibrium cesium surface concentration. Among several kinetic models considered, the pseudo-second order reaction model was found to be the best to describe the kinetic test results in the studied range of concentrations. The adsorption activation energy determined from Arrhenius equation was found to be approximately 55.9 kJ mol(-1) suggesting that chemisorption was the prevalent mechanism of interaction between cesium ions and cement mortar.

  7. Spectral reflectance of selected aqueous solutions for water quality applications

    NASA Technical Reports Server (NTRS)

    Querr, M. R.; Waring, R. C.; Holland, W. E.; Nijm, W.; Hale, G. M.

    1972-01-01

    The relative specular reflectances of individual aqueous solutions having a particular chemical salt content were measured in the 2 to 20 micrometers region of the infrared component or radiant flux. Distilled water was the reflectance standard. The angle of incidence was 70.03 deg plus or minus 0.23 deg. Absolute reflectances of the solutions for the same polarization and angle of incidence were computed by use of the measured relative reflectances, one of the Fresnel equations, and the optical constants of distilled water. Phase shift and phase difference spectra were obtained by respectively applying a Kramers-Kronig dispersion analysis to the absolute and relative reflectance spectra. The optical constants of the solutions were determined by algorithms commonly associated with the Kramers-Kronig analysis. Spectral signatures that qualitatively and quantitatively characterize the solute and that show structure of the infrared bands of water were noted in the phase difference spectra. The relative and absolute reflectances, the phase shift and phase difference spectra and the optical constants are presented in graphical form. Application of these results to remote sensing of the chemical quality of natural waters is discussed briefly.

  8. Peculiarity of aqueous solutions of 2,2,2-trifluoroethanol.

    PubMed

    Burakowski, Andrzej; Gliński, Jacek; Czarnik-Matusewicz, Bogusława; Kwoka, Paulina; Baranowski, Andrzej; Jerie, Kazimierz; Pfeiffer, Helge; Chatziathanasiou, Nikos

    2012-01-12

    Aqueous solutions of 2,2,2-trifluoroethanol appear to show a structural transition at alcohol mole fraction equal to x(TFE) = 0.05, which can be concluded from a discontinuity of the speed of sound. At the same concentration, a discontinuity was observed in the parameters of the long-living component of the positron annihilation spectrum. Moreover, the partial molar volumes of components show transition-like behavior in the range of low solute contents, which is significantly different from nonsubstituted ethanol. The peculiarities of the low concentration system correlate with minor infrared spectra changes assigned to a mode composed of the CH(2) bending and CF(3) stretching internal vibrations being sensitive to polarity of the hydration shell surrounding the solute. The majority of the spectral changes arise from a gradual shift of the equilibrium between trans ↔ gauche isomers when the composition of the solution is changing. A possible explanation for the peculiar behavior of the system is a thermodynamic equilibrium between hydrated monomers and dimers at that respective mole number. PMID:22142252

  9. Neptunium interaction with uranium dioxide in aqueous solution

    NASA Astrophysics Data System (ADS)

    Batuk, O. N.; Kalmykov, St. N.; Petrov, V. G.; Zakharova, E. V.; Teterin, Yu. A.; Teterin, A. Yu.; Shapovalov, V. I.; Haire, M. J.

    2007-05-01

    Neptunium, Np(V) and Np(IV), sorption onto uranium dioxide surface was studied at various values of pH. Sorption was studied in two sets of experiments with different redox conditions that correspond to either Np(V) (Set 1) or Np(IV) (Set 2) in solution. In Set 1 the reduction of Np(V) was established when low pH solution covered a UO2 surface. When the pH increased, the sorption of neptunium is decreased. At pH > 5.5 neptunium sequestration from solution is governed by Np(V) sorption onto UO2.25. In Set 2 (the more anoxic conditions) complete neptunium sorption is established at pH > 2: it is present in the tetravalent form over the whole pH range. The proposed mechanisms of neptunium sorption was suggested by using pH sorption edges of Th(IV) as an analog to Np(IV) onto UO2 and Np(V) onto ThO2. The UO2 surface was characterized by X-ray photoelectron spectroscopy (XPS) after equilibration with aqueous solutions at different pH values.

  10. Electrical conductivity of aqueous solutions of aluminum salts

    NASA Astrophysics Data System (ADS)

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

    2005-03-01

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

  11. Crystallization in solid solution-aqueous solution systems: Thermodynamic and kinetic approaches

    SciTech Connect

    Shtukenberg, A. G. Punin, Yu. O.; Azimov, P. Ya.

    2010-03-15

    A new phenomenological approach is proposed to describe the crystallization kinetics in solid solution-aqueous solution binary systems. The phase diagrams, equilibria, and quasie-quilibria are considered within this approach. The crystallization kinetics near the true equilibrium and the crystallization features at large deviations from equilibrium are discussed on this basis. Special attention is paid to possible interactions in a solution with a seed crystal placed in it. In particular, the interactions leading to the seed's crystal growth or dissolution and to a possible exchange or metasomatic reactions are considered. In addition, the effect of the generated mismatch stress on the crystal growth rate and composition is analyzed.

  12. The aqueous-polyelectrolyte dye solution as an active laser medium

    SciTech Connect

    Akimov, A I; Saletskii, A M

    2000-11-30

    The spectral, luminescent, and lasing properties of aqueous solutions of a cationic dye rhodamine 6G with additions of anion polyelectrolytes - polyacrylic and polymethacrylic acids - are studied. It is found that the energy and spectral properties of lasing of these solutions depend on the ratio of concentrations of polyelectrolyte and molecules. It is also found that the lasing parameters of aqueous-polyelectrolyte dye solutions can be controlled by changing the structure of the molecular system. The variation in the structure of aqueous-polyelectrolyte dye solutions of rhodamine 6G resulted in an almost five-fold increase in the lasing efficiency compared to that in aqueous dye solutions. (lasers, active media)

  13. Nanobuffering property of Fe3O4 magnetic nanoparticles in aqueous solution

    NASA Astrophysics Data System (ADS)

    Zapotoczny, B.; Dudek, M. R.; Kozioł, J. J.; Mleczko, J.

    2013-03-01

    In the present study, the buffering effect of magnetite nanoparticles (Fe3O4) dispersed in an aqueous solution on the local pH value is investigated. It manifests itself in the fact that when some amount of acid or base is added to the solution then the solution near the nanoparticles surface becomes, respectively, less acidic and less alkaline than it is expected. It is the result of both the local electrostatic field, which represents the electric double layer at the surface of magnetic nanoparticles and the magnetic field around the nanoparticles. The magnetite nanoparticles exhibit very low toxicity and they are becoming increasingly important for new biomedical applications related to their effects on chemical reactions in body tissues and cells. The question arises, how strong are these effects at the nanoscale? The strength of the buffering property of magnetite nanoparticles is investigated both theoretically and experimentally by the direct measurement of the local pH value of a magnetic nanoparticles suspension. The theoretical model is based on stochastic equations describing the ions diffusing in the neighborhood of the electric double layer of the magnetic material. The electric double layer is modeled with the help of the Poisson-Boltzmann model. It is directly shown that both the electrostatic field and the magnetic field are responsible for the observed local changes of the pH value with respect to the bulk pH value.

  14. Reduction of hexavalent chromium by ascorbic acid in aqueous solutions.

    PubMed

    Xu, Xiang-Rong; Li, Hua-Bin; Li, Xiao-Yan; Gu, Ji-Dong

    2004-11-01

    Hexavalent chromium is a priority pollutant in the USA and many other countries. Reduction of Cr(VI) to Cr(III) is environmentally favorable as the latter species is not toxic to most living organisms and also has a low mobility and bioavailability. Reduction of Cr(VI) by ascorbic acid (vitamin C) as a reductant was studied using potassium dichromate solution as the model pollutant. Effects of concentration of vitamin C, pH, temperature, irradiation and reaction time on the reduction of Cr(VI) were examined. Cr(VI) might be reduced by vitamin C not only in acidic conditions but also in weakly alkaline solutions. The reduction of Cr(VI) by vitamin C might occur not only under irradiation but also in the dark. Vitamin C is an important biological reductant in humans and animals, and not toxic. It is water-soluble and can easily permeate through various types of soils. The results indicate that vitamin C could be used in effective remediation of Cr(VI)-contaminated soils and groundwater in a wide range of pH, with or without sunlight. PMID:15488923

  15. Reduction of hexavalent chromium by ascorbic acid in aqueous solutions.

    PubMed

    Xu, Xiang-Rong; Li, Hua-Bin; Li, Xiao-Yan; Gu, Ji-Dong

    2004-11-01

    Hexavalent chromium is a priority pollutant in the USA and many other countries. Reduction of Cr(VI) to Cr(III) is environmentally favorable as the latter species is not toxic to most living organisms and also has a low mobility and bioavailability. Reduction of Cr(VI) by ascorbic acid (vitamin C) as a reductant was studied using potassium dichromate solution as the model pollutant. Effects of concentration of vitamin C, pH, temperature, irradiation and reaction time on the reduction of Cr(VI) were examined. Cr(VI) might be reduced by vitamin C not only in acidic conditions but also in weakly alkaline solutions. The reduction of Cr(VI) by vitamin C might occur not only under irradiation but also in the dark. Vitamin C is an important biological reductant in humans and animals, and not toxic. It is water-soluble and can easily permeate through various types of soils. The results indicate that vitamin C could be used in effective remediation of Cr(VI)-contaminated soils and groundwater in a wide range of pH, with or without sunlight.

  16. Aqueous solution synthesis of zinc oxide for application in optoelectronics

    NASA Astrophysics Data System (ADS)

    Joo, John Hwajong

    Recently, ZnO has garnered widespread attention in the semiconductor community for its large set of useful properties, which include a wide bandgap and its resulting optical transparency, a large exciton binding energy, a significant piezoelectric response, and good electrical conductivity. In many ways, it shares many properties with a widely used and technologically important semiconductor GaN, which is widely used for blue LEDs and lasers. However, ZnO cannot substitute for GaN in most optoelectronic applications, because it cannot be doped p-type. On the other hand, unlike many traditional, covalently bonded semiconductors like GaN, ZnO can be easily formed aqueous solutions at close to room temperature and pressure in the form of large crystals or a variety of nanostructures, making possible applications that are normally very difficult with traditional semiconductors. In this light, we aimed to take advantage of aqueous solution-based, ZnO growth techniques and incorporated ZnO structures novel optoelectronic and photonic structures. By controlling the morphology of ZnO, we studied the effects of nanowire-based ZnO/Cu2O solar cells. Carrier collection was increased using a nanowire-based device architecture. The main result, however, was the time evolution of the performance of these devices due to the movement of ionized defects in the material. The effects of geometry on the ageing characteristics were studied, which showed that the carrier collection could be increased further with aging in a nanowire Cu2O solar cell. The aging behavior was substantially different between nanowire and planar solar cells, which implies that future design of nanostructured solar cells must long term aging effects. In addition to solar cells, we explored the possibilities of using aqueous solution growth of ZnO to fabricated whispering gallery mode optical cavities and waveguides for enhancing extraction from a single photon source. In both applications, we used templated

  17. Hydration force between mica surfaces in aqueous KCl electrolyte solution.

    PubMed

    Leng, Yongsheng

    2012-03-27

    Liquid-vapor molecular dynamics simulations are performed to study the interaction forces between two mica surfaces in an aqueous KCl electrolyte solution. Strong repulsive hydration force is obtained within a distance of ~2 nm between the two mica surfaces, which cannot be explained by the continuum theory of double-layer repulsion. We find that this short-range repulsive hydration force is much stronger than the double-layer force between mica surfaces. Whereas the simulation system is much smaller than the surface force measurement system, fundamental mechanisms of repulsive hydration force are revealed. In particular, important features of the step-like force oscillatory behavior during normal compression and force hysteresis during retraction are observed. Detailed analysis of the ionic density distributions shows that the "forced adsorption" of diffusive K(+) ions onto mica surfaces during compression and the subsequent "slow desorption" of the absorbed K(+) ions from mica surfaces upon retraction are responsible for the hysteresis phenomenon. From a mechanics point of view, we attribute the load bearing capacity of the dense electrolyte to the very hard hydration shells of K(+) metal ions under confinement. We find that the hydrated K(+) ions and Cl(-) co-ions remain very diffusive in the aqueous film. Water molecules in the hydration layer are also very fluidic, in the sense that the diffusion constant of water molecules is less than its bulk value by at most 3 orders of magnitude under the extreme confinement. PMID:22369483

  18. DNA dynamics in aqueous solution: opening the double helix

    NASA Technical Reports Server (NTRS)

    Pohorille, A.; Ross, W. S.; Tinoco, I. Jr; MacElroy, R. D. (Principal Investigator)

    1990-01-01

    The opening of a DNA base pair is a simple reaction that is a prerequisite for replication, transcription, and other vital biological functions. Understanding the molecular mechanisms of biological reactions is crucial for predicting and, ultimately, controlling them. Realistic computer simulations of the reactions can provide the needed understanding. To model even the simplest reaction in aqueous solution requires hundreds of hours of supercomputing time. We have used molecular dynamics techniques to simulate fraying of the ends of a six base pair double strand of DNA, [TCGCGA]2, where the four bases of DNA are denoted by T (thymine), C (cytosine), G (guanine), and A (adenine), and to estimate the free energy barrier to this process. The calculations, in which the DNA was surrounded by 2,594 water molecules, required 50 hours of CRAY-2 CPU time for every simulated 100 picoseconds. A free energy barrier to fraying, which is mainly characterized by the movement of adenine away from thymine into aqueous environment, was estimated to be 4 kcal/mol. Another fraying pathway, which leads to stacking between terminal adenine and thymine, was also observed. These detailed pictures of the motions and energetics of DNA base pair opening in water are a first step toward understanding how DNA will interact with any molecule.

  19. Strong adhesion and cohesion of chitosan in aqueous solutions

    PubMed Central

    Lee, Dong Woog; Lim, Chanoong; Israelachvili, Jacob N.; Hwang, Dong Soo

    2014-01-01

    Chitosan, a load-bearing biomacromolecule found in the exoskeletons of crustaceans and insects, is a promising biopolymer for the replacement of synthetic plastic compounds. Here, surface interactions mediated by chitosan in aqueous solutions, including the effects of pH and contact time, were investigated using a surface forces apparatus (SFA). Chitosan films showed an adhesion to mica for all tested pH ranges (3.0–8.5), achieving a maximum value at pH 3.0 after a contact time of 1 hr (Wad ~6.4 mJ/m2). We also found weak or no cohesion between two opposing chitosan layers on mica in aqueous buffer until the critical contact time for maximum adhesion (chitosan-mica) was reached. Strong cohesion (Wco ~8.5 mJ/m2) between the films was measured with increasing contact times up to 1 hr at pH 3.0, which is equivalent to ~60% of the strongest, previously reported, mussel underwater adhesion. Such time-dependent adhesion properties are most likely related to molecular or molecular group reorientations and interdigitations. At high pH (8.5), the solubility of chitosan changes drastically, causing the chitosan-chitosan (cohesion) interaction to be repulsive at all separation distances and contact times. The strong contact time and pH-dependent chitosan-chitosan cohesion and adhesion properties provide new insight into the development of chitosan based load-bearing materials. PMID:24138057

  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. PMID:23592759

  1. 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.

  2. 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.

  3. Cellulose aerogels from aqueous alkali hydroxide-urea solution.

    PubMed

    Cai, Jie; Kimura, Satoshi; Wada, Masahisa; Kuga, Shigenori; Zhang, Lina

    2008-01-01

    Highly porous and strong cellulose aerogels were prepared by gelation of cellulose from aqueous alkali hydroxide/urea solution, followed by drying with supercritical CO2. Their morphology, pore structure, and physical properties were characterized by scanning and transmission electron microscopy, X-ray diffraction, nitrogen adsorption measurements, UV/Vis spectrometry, and tensile tests. The cellulose hydrogel was composed of interconnected about 20 nm wide. By using supercritical CO2 drying, the network structure in the hydrogel was well preserved in the aerogel. The results are preliminary but demonstrate the ability of this method to give cellulose aerogels of large surface areas (400-500 m2 g(-1)) which may be useful as adsorbents, heat/sound insulators, filters, catalyst supports, or carbon aerogel precursors. PMID:18605678

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  5. Hydrate-based heavy metal separation from aqueous solution

    PubMed Central

    Song, Yongchen; Dong, Hongsheng; Yang, Lei; Yang, Mingjun; Li, Yanghui; Ling, Zheng; Zhao, Jiafei

    2016-01-01

    A novel hydrate-based method is proposed for separating heavy metal ions from aqueous solution. We report the first batch of experiments and removal characteristics in this paper, the effectiveness and feasibility of which are verified by Raman spectroscopy analysis and cross-experiment. 88.01–90.82% of removal efficiencies for Cr3+, Cu2+, Ni2+, and Zn2+ were obtained. Further study showed that higher R141b–effluent volume ratio contributed to higher enrichment factor and yield of dissociated water, while lower R141b–effluent volume ratio resulted in higher removal efficiency. This study provides insights into low-energy, intensive treatment of wastewater. PMID:26887357

  6. Solvent selection for the extraction of ethanol from aqueous solutions

    SciTech Connect

    Koullas, D.P.; Umealu, O.S.; Koukios, E.G.

    1999-08-01

    Several organic solvents were examined as potential separating agents for ethanol recovery from aqueous solutions by liquid-liquid extraction. Phase composition determinations for five promising ethanol-water-solvent systems at 20 and 40 C and two solvent-to-feed ratios show that isoamyl acetate (IAA) and isooctyl alcohol (IOA) along with n-butyl acetate (BA) present a greater potential than dibutyl ether and dibutyl oxalate. Tie-line liquid-liquid equilibrium data at 25 C for the three promising solvents (IAA, IOA, and BA) were collected and analyzed. Both IAA and IOA were found to be very good separating agents, exhibiting ethanol distribution coefficients greater than 1, and separation factors in Bancroft coordinates of the order of 70 and 2,000, respectively.

  7. Experimental study on thermophoresis of colloids in aqueous surfactant solutions

    NASA Astrophysics Data System (ADS)

    Dong, Ruo-Yu; Zhou, Yi; Yang, Chun; Cao, Bing-Yang

    2015-12-01

    Thermophoresis refers to the motion of particles under a temperature gradient and it is one of the particle manipulation techniques. Regarding the thermophoresis of particles in liquid media, however, many open questions still remain, especially the role of the interfacial effect. This work reports on a systematic experimental investigation of surfactant effects, especially the induced interfacial effect, on the thermophoresis of colloids in aqueous solutions via a microfluidic approach. Two kinds of commonly used surfactants, sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB), are selected and the results show that from relatively large concentrations, the two surfactants can greatly enhance the thermophilic mobilities. Specifically, it is found that the colloid-water interfaces modified with more polar end groups can potentially lead to a stronger thermophilic tendency. Due to the complex effects of surfactants, further theoretical model development is needed to quantitatively describe the dependence of thermophoresis on the interface characteristics.

  8. Plasma-induced degradation of diphenylamine in aqueous solution.

    PubMed

    Gai, Ke

    2007-07-19

    The liquid-phase degradation induced by a gaseous plasma was investigated. The plasma was generated between an electrolytic solution and an anode tip by means of contact glow discharge electrolysis (CGDE). Aqueous diphenylamine was smoothly oxidized and eventually degradad to inorganic carbon. Results indicated that the degradation rate can be considerably raised by prolonging the discharge time and the optimum pH value was 6.0 for diphenylamine degradation. Fe2+ shows an evident accelerated effect on the diphenylamine elimination, meanwhile the presence of H2O2 benefited the degradation but the presence of n-butanol inhibited the degradation, demonstrating that the hydroxyl radicals were the most responsible oxidants in the diphenylamine degradation. The major intermediate products resulted from the degradation were identified by an HPLC analysis and a degradation path way was proposed. PMID:17296262

  9. The stability of oxymetazoline hydrochloride in aqueous solution.

    PubMed

    Stanisz, Beata

    2002-01-01

    The kinetics of the hydrolysis reaction of oxymetazoline hydrochloride in aqueous solution at three temperatures (343 K, 353 K, 363 K), over the pH-range 0.5-12.5 and ionic strength 0.5 has been investigated. The changes of concentration of oxymetazoline hydrochloride were followed by the HPLC method with UV detection. In the pH range from 0.45 to 12.50, the hydrolysis of oxymetazoline consists of hydrolysis of oxymetazoline molecules catalyzed by hydrogen ions, spontaneous hydrolysis of the dissociated and undissociated oxymetazoline molecules. A minimal rate of the hydrolysis oxymetazoline was observed to occur in the pH range from 2.0 to 5.0. Thermodynamic parameters of the reaction: energy, entropy and enthalpy of activation and the frequency factor for the specific rate constants were determined.

  10. Photo-degradation behaviour of roseoflavin in some aqueous solutions

    NASA Astrophysics Data System (ADS)

    Tyagi, A.; Penzkofer, A.; Mathes, T.; Hegemann, P.

    2010-03-01

    An absorption and emission spectroscopic characterization of roseoflavin (8-dimethylamino-8-demethyl-riboflavin, RoF) in aqueous solutions was carried out. The studies were concentrated on roseoflavin in pH 8 phosphate buffer. Absorption cross-section spectra, fluorescence excitation spectra, fluorescence quantum distributions, fluorescence quantum yields and fluorescence lifetimes were determined. The fluorescence of RoF is quenched by photo-induced intra-molecular charge-transfer at room temperature. The photo-degradation of RoF in un-buffered water, in Tris-HCl buffer, and in phosphate buffer was studied. Phosphate buffer and to a smaller extent Tris buffer catalyse the RoF photo-degradation. Photo-excitation of the primary photoproduct, 8-methylamino-riboflavin (8-MNH-RF), enhanced the RoF degradation by triplet 8-MNH-RF - singlet RoF excitation transfer with subsequent triplet-state RoF degradation.

  11. Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers.

    PubMed

    Sun, Yue; Li, Xiao-Tao; Xu, Chao; Chen, Jin-Long; Li, Ai-Min; Zhang, Quan-Xing

    2005-01-01

    Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

  12. γ-Irradiation of malic acid in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Negron-Mendoza, Alicia; Graff, Rebecca L.; Ponnamperuma, Cyril

    1980-12-01

    The γ-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the non-volatile products. Thin layer chromotography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the γ-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

  13. Electrokinetic Characteristics of Calcined Kaolinite in Aqueous Electrolytic Solutions

    NASA Astrophysics Data System (ADS)

    Chen, Tianxing; Zhao, Yunliang; Li, Hongliang; Liu, Jia; Song, Shaoxian

    2015-03-01

    In this work, the electrokinetic characteristics of calcined kaolinite in aqueous solutions has been studied in the presence of the electrolytes of NaCl, KCl, NH4Cl, NaNO3, MgCl2, CaCl2 and AlCl3, through electrophoretic measurement. The experimental results have shown that the zeta potential was closely dependent on the valence and concentration of the electrolytic cations, but not on the type of the cations. The higher the valence and the concentration were, the stronger the impact to the zeta potential was. Al3+ could reverse the potential sign from negative to positive. In addition, it was found that the monovalent anions of Cl- and NO3- made a big difference to the zeta potential at the same dosage.

  14. Multi-basin dynamics of a protein in aqueous solution

    SciTech Connect

    Garcia, A.E.

    1994-10-01

    A molecular dynamics simulation of crambin in aqueous solution shows that motions are characteristic of non-linear systems. The authors describe typical non-linear excitations, such as intermittency, for various representations of the protein dynamics and structure. The protein backbone dihedral angles show fast correlated transitions from one minimum well to another. Each transition is followed by small overdamped oscillations. Equal-time cross correlations of all ({phi},{psi}) angles show that correlations are extended along the backbone chain. An analysis based on a generalized least squares fitting of the protein fluctuations along vectors show that a small set of molecule optimal dynamic coordinates (MODC) describe most of the protein fluctuations. In addition, the MODC describe a trajectory where the protein conformation jumps from one minimum well to another. An extension of the MODC describing 2- and 3-dimensional cuts of the protein configurational space clearly shows a trajectory around multiple basins of attraction.

  15. Molar extinction coefficients of some carbohydrates in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Singh, K.; Sandhu, G. K.; Lark, B. S.; Sud, S. P.

    2002-03-01

    Molar extinction coefficients of some carbohydrates viz. L-arabinose (C5H10O5), D-glucose (C6H12O6), D-mannose (C6H12O6), D-galactose (C6H12O6), D(-) fructose (C6H12O6) and maltose (C12H24O12) in aqueous solutions have been determined at 81, 356, 511, 662, 1173 and 1332 keV by gamma ray transmission method in a narrow beam good geometry set-up. These coefficients have been found to depend upon the photon energy following a 4-parameter polynomial. These extinction coefficients for different sugars having the same molecular formula have same values varying within experimental uncertainty. Within concentration ranges studied, Beer--Lambert law is obeyed very well.

  16. Degradation of aqueous solutions of camphor by heterogeneous photocatalysis.

    PubMed

    Sirtori, Carla; Altvater, Priscila K; de Freitas, Adriane M; Peralta-Zamora, Patricio G

    2006-02-28

    In this study the photocatalytic degradation of aqueous solutions of camphor was investigated by using TiO2 and ZnO photocatalysts. In the presence of artificial UV-light the highly photosensitive camphor was almost totally degraded after reaction times of 60 min. However, under these conditions the mineralization degree was lower than 25%. In the presence of semiconductors the degradation was complete after a treatment time of about 30 min. Moreover, the mineralization was considerably greater, mainly with the use of TiO2 (> 80% at reaction time of 60 min). Heterogeneous photocatalytic processes applied in the presence of solar radiation show a promising degradation capability. TiO2-based processes afforded mineralization degrees of about 90% after a reaction time of 120 min, when the system was assisted by aeration.

  17. Removal of lead from aqueous solutions by Penicillium biomass

    SciTech Connect

    Hui Niu; Xue Shu Xu; Jian Hua Wang . Dept. of Chemical Engineering); Volesky, B. . Dept. of Chemical Engineering)

    1993-09-05

    The removal of lead ions from aqueous solutions by adsorption on nonliving Penicillium chrysogenum biomass was studied. Biosorption of the Pb[sup +2] ion was strongly affected by pH. Within a pH range of 4 to 5, the saturated sorption uptake of Pb[sup +2] was 116 mg/g dry biomass, higher than that of activated charcoal and some other microorganisms. At pH 4.5, P. chrysogenum biomass exhibited selectivity for Pb[sup +2] over other metal ions such as Cd[sup +2], Cu[sup +2], Zn [sup +2], and As[sub +3]. Sorption preference for metals decreased in the following order: Pb > Cd > Cu > Zn > As. The sorption uptake of Pb[sup +2] remained unchanged in the presence of Cu[sup +2] and As [sup +3], it decreased in the presence of Zn[sup +2], and increased in the presence of Cd[sup +2].

  18. Sonochemical degradation of ethylbenzene in aqueous solution: a product study.

    PubMed

    De Visscher, A; Van Langenhove, H; Van Eenoo, P

    1997-04-01

    The degradation of ethylbenzene in aqueous solution by 520 kHz ultrasound was investigated. The products formed were analysed using solid phase microextraction (SPME), a sampling technique that allows convenient GC-MS and GC-FID analysis in the micromolar range. A broad range of monosubstituted monocyclic and dicyclic aromatic hydrocarbons was found as well as some oxygenated products. The results clearly indicate that pyrolysis is an important pathway of ethylbenzene degradation. The side chain is dehydrogenated, forming styrene, or cleaved. The radicals formed upon cleavage are subsequently added to the double bond of the styrene side chain or recombined. This mechanism explains the formation of most of the products. Formation and breakdown of the reaction products follow first-order kinetics in spite of the fact that the selectivity of the reactions depends on the initial ethylbenzene concentration considerably. Changes in the temperature and the pressure of cavitation are expected to cause this dependence. PMID:11237033

  19. Reverse Stability of Oxyluciferin Isomers in Aqueous Solutions.

    PubMed

    Noguchi, Yoshifumi; Hiyama, Miyabi; Shiga, Motoyuki; Sugino, Osamu; Akiyama, Hidefumi

    2016-09-01

    We investigated the stability of oxyluciferin anions (keto, enol, and enolate isomers) in aqueous solution at room temperature by performing a nanosecond time scale first-principles molecular dynamics simulation. In contrast to all previous quantum chemistry calculations, which suggested the keto-type to be the most stable, we show that the enol-type is slightly more stable than the keto-type, in agreement with some recent experimental studies. The simulation highlights the remarkable hydrophobicity of the keto-type by the cavity formed at the oxyluciferin-water interface as well as a reduction in hydrophobicity with the number of hydrating water molecules. It is therefore predicted that the isomeric form in a hydrated cluster is size-dependent. PMID:27479583

  20. Hydrothermal Dehydration of Aqueous Fructose Solutions in a Closed System

    SciTech Connect

    Yao, Chunhua; Shin, Yongsoon; Wang, Li Q.; Windisch, Charles F.; Samuels, William D.; Arey, Bruce W.; Wang, Chong M.; Risen Jr., William M.; Exarhos, Gregory J.

    2007-10-25

    The synthesis of materials with targeted size and shape has attracted much attention. Specifically, colloidal spheres with targeted and uniform sizes have opened the door for a variety of applications associated with drug delivery, and manipulation of light (photonic band-gap crystals). Surface modification is a key to realizing many of these applications owing to the inherent inert surface.The remarkable transformation of carbohydrate molecules including sugars to homogeneous carbon spheres is found to readily occur by a dehydration mechanism and subsequent sequestering in aqueous solutions that are heated at 160-180oC in a pressurized vessel. Under such conditions, these molecules actually dehydrate even though they are dissolved in water. Size-tunable metal and metal oxides with uniform shells have also been prepared by using carbon spheres as templates.

  1. Acid gas absorption in aqueous solutions of mixed amines

    SciTech Connect

    Rinker, E.B.; Ashour, S.S.; Sandall, O.C.

    1996-12-31

    A mass transfer model has been developed to describe the rate of absorption (or desorption) of H{sub 2}S and CO{sub 2} in aqueous blends of a tertiary and a secondary or a primary amine. The model is based on penetration theory, and all significant chemical reactions are incorporated in the model. The reactions are taken to be reversible, with reactions involving only a proton transfer considered to be at equilibrium. The particular amines studied in this research were methyldiethanolamine (MDEA), a tertiary amine, and diethanolamine (DEA), a secondary amine. Key physicochemical data needed in the model, such as diffusion coefficients, kinetic rate constants, and gas solubilities, were measured. Experimental absorption rates of CO{sub 2} and H{sub 2}S were measured in a model gas-liquid contacting device and were compared with model predictions. Experiments were carried out for single amine solutions (both MDEA and DEA) and for amine blends.

  2. Adsorption of CTAB onto perlite samples from aqueous solutions.

    PubMed

    Alkan, Mahir; Karadaş, Mecit; Doğan, Mehmet; Demirbaş, Ozkan

    2005-11-15

    In this study, the adsorption properties of unexpanded and expanded perlite samples in aqueous cetyltrimethylammonium bromide (CTAB) solutions were investigated as a function of ionic strength, pH, and temperature. It was found that the amount of cetyltrimethylammonium bromide adsorbed onto unexpanded perlite was greater than that onto expanded perlite. For both perlite samples, the sorption capacity increased with increasing ionic strength and pH and decreasing temperature. Experimental data were analyzed by Langmuir and Freundlich isotherms and it was found that the experimental data were correlated reasonably well by the Freundlich adsorption isotherm. Furthermore, the isotherm parameters (KF and n) were also calculated. The adsorption enthalpy was determined from experimental data at different temperatures. Results have shown that the interaction between the perlite surface and CTAB is a physical interaction, and the adsorption process is an exothermic one.

  3. Pulse radiolysis study of diacrylate macromonomer in aqueous solution

    NASA Astrophysics Data System (ADS)

    Kozicki, Marek; Kujawa, Piotr; Rosiak, Janusz M.

    2002-09-01

    The early stages of the polymerization of difunctional acrylate macromonomer, poly(ethylene glycol) diacrylate of average molecular weight of 700 Da (PEGDA700), were studied in aqueous solution by pulse radiolysis. The rate constant of the reaction of this monomer with OH rad and hydrated electron was measured as 3.0×10 10 and 1.7×10 10 mol -1 dm 3 s -1, respectively. The absorption spectrum of the OH rad adduct to PEGDA700 appeared to have a maximum at 275 nm. Its decay depends on monomer concentration, which was assigned to the propagation reaction, and the fast crosslinking of the macromonomer. Similar features were observed in the case of the spectrum of the H rad adduct. The shape of the absorption spectrum of electron adduct to the PEGDA700 depends on the pH of the solution. Radical anion formed at low pH undergoes protonation at carbonyl oxygen atom, giving carbon-centred radical with a maximum of absorption below 260 nm. In basic solution, protonation takes place at the β-carbon atom, giving α-carboxyalkyl radical with a maximum of the absorption at 275 nm.

  4. Hydrophobicity and thermodynamic response for aqueous solutions of amphiphiles

    NASA Astrophysics Data System (ADS)

    Zemánková, Katerina; Troncoso, Jacobo; Cerdeiriña, Claudio A.; Romaní, Luis; Anisimov, Mikhail A.

    2016-06-01

    The anomalous behavior of aqueous solutions of amphiphiles in the water-rich region is analyzed via a phenomenological approach that utilizes the isobaric heat capacity Cp as an experimental probe. We report extensive data for solutions of 14 amphiphiles as a function of temperature at atmospheric pressure. Beyond that, Cp data but also isobaric thermal expansivities and isothermal compressibilities for three solutions of tert-butanol as a function of both temperature and pressure are presented. Results rule out the possibility that the observed phenomenology is associated with the anomalous thermodynamics of pure water. Indeed, our Cp data, quantitatively consistent with recent spectroscopic analyses, suggest that water-mediated interactions between the nonpolar parts of amphiphiles are at the origin of anomalies, with the effects of such "hydrophobic aggregation" being observed at mole fractions as small as 0.01. Physicochemical details like the size, the electronic charge distribution and the geometry of amphiphile molecules as well as third-order derivatives of the Gibbs energy and the associated Koga lines support the above claims while they further contribute to characterizing the role of hydrophobicity in these phenomena. Progress with a view to gain a deeper, more concrete understanding remains.

  5. Standard enthalpies of formation for glycyl-tyrosine and products of its dissociation in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Kochergina, L. A.; Badelin, V. G.; Krutova, O. N.; Volkov, A. V.; Damrina, K. V.

    2015-07-01

    The enthalpies of solution of crystalline glycyl-tyrosine in water and potassium hydroxide aqueous solutions are determined at 298.15 K by means of direct calorimetry. Standard enthalpies of formation for dipeptide and its products of dissociation in an aqueous solution are calculated.

  6. Supercharging Protein Complexes from Aqueous Solution Disrupts their Native Conformations

    NASA Astrophysics Data System (ADS)

    Sterling, Harry J.; Kintzer, Alexander F.; Feld, Geoffrey K.; Cassou, Catherine A.; Krantz, Bryan A.; Williams, Evan R.

    2012-02-01

    The effects of aqueous solution supercharging on the solution- and gas-phase structures of two protein complexes were investigated using traveling-wave ion mobility-mass spectrometry (TWIMS-MS). Low initial concentrations of m-nitrobenzyl alcohol ( m-NBA) in the electrospray ionization (ESI) solution can effectively increase the charge of concanavalin A dimers and tetramers, but at higher m-NBA concentrations, the increases in charge are accompanied by solution-phase dissociation of the dimers and up to a ~22% increase in the collision cross section (CCS) of the tetramers. With just 0.8% m-NBA added to the ESI solution of a ~630 kDa anthrax toxin octamer complex, the average charge is increased by only ~4% compared with the "native" complex, but it is sufficiently destabilized so that extensive gas-phase fragmentation occurs in the relatively high pressure regions of the TWIMS device. Anthrax toxin complexes exist in either a prechannel or a transmembrane channel state. With m-NBA, the prechannel state of the complex has the same CCS/charge ratio in the gas phase as the transmembrane channel state of the same complex formed without m-NBA, yet undergoes extensive dissociation, indicating that destabilization from supercharging occurs in the ESI droplet prior to ion formation and is not a result of Coulombic destabilization in the gas phase as a result of higher charging. These results demonstrate that the supercharging of large protein complexes is the result of conformational changes induced by the reagents in the ESI droplets, where enrichment of the supercharging reagent during droplet evaporation occurs.

  7. Removal characteristics of As(III) and As(V) from acidic aqueous solution by steel making slag.

    PubMed

    Oh, Chamteut; Rhee, Sungsu; Oh, Myounghak; Park, Junboum

    2012-04-30

    This study focused on the environmental risk of steel making slag itself, arsenic removal mechanism and re-leaching possibility of arsenic to aqueous state after the adsorption. The purpose of the study is to promote the use of steel making slag as a low-cost adsorbent for arsenic in aqueous system. Calcium was easily dissolved out from the slag and become the dominant substance in the leachate. Some of the calcium could form amorphous calcium carbonate in alkaline condition, and arsenic in the aqueous solution would be removed by being co-precipitated with or adsorbed onto the amorphous calcium carbonate. Most of the amorphous calcium carbonate containing arsenic would be bound to amorphous iron oxide of the slag. When the slag was used as an adsorbent for arsenic removal, a little amount of toxic chemicals were leached from the slag itself under pH 0.8 to 13.6. Also, 70-80% of arsenic laden on the slag was bound to amorphous iron oxide which would not easily desorb unless given a reducing and complexing condition. Showing 95-100% removal efficiency near initial pH 2, the slag, therefore, could be used as an appropriate adsorbent for eliminating arsenic in acidic aqueous solution.

  8. Cations bind only weakly to amides in aqueous solutions.

    PubMed

    Okur, Halil I; Kherb, Jaibir; Cremer, Paul S

    2013-04-01

    We investigated salt interactions with butyramide as a simple mimic of cation interactions with protein backbones. The experiments were performed in aqueous metal chloride solutions using two spectroscopic techniques. In the first, which provided information about contact pair formation, the response of the amide I band to the nature and concentration of salt was monitored in bulk aqueous solutions via attenuated total reflection Fourier transform infrared spectroscopy. It was found that molar concentrations of well-hydrated metal cations (Ca(2+), Mg(2+), Li(+)) led to the rise of a peak assigned to metal cation-bound amides (1645 cm(-1)) and a decrease in the peak associated with purely water-bound amides (1620 cm(-1)). In a complementary set of experiments, the effect of cation identity and concentration was investigated at the air/butyramide/water interface via vibrational sum frequency spectroscopy. In these studies, metal ion-amide binding led to the ordering of the adjacent water layer. Such experiments were sensitive to the interfacial partitioning of cations in either a contact pair with the amide or as a solvent separated pair. In both experiments, the ordering of the interactions of the cations was: Ca(2+) > Mg(2+) > Li(+) > Na(+) ≈ K(+). This is a direct cationic Hofmeister series. Even for Ca(2+), however, the apparent equilibrium dissociation constant of the cation with the amide carbonyl oxygen was no tighter than ∼8.5 M. For Na(+) and K(+), no evidence was found for any binding. As such, the interactions of metal cations with amides are far weaker than the analogous binding of weakly hydrated anions.

  9. Biosorption of arsenic from aqueous solution using dye waste.

    PubMed

    Nigam, Shubha; Vankar, Padma S; Gopal, Krishna

    2013-02-01

    The purpose of this study is to examine on removal of arsenic from water by biosorption through potential application of herbal dye wastes. Four different flower dye residues (after extraction of natural dye) viz. Hibiscus rosasinensis, Rosa rosa, Tagetes erecta, and Canna indica were utilized successfully for the removal of arsenic from aqueous solution. Batch studies were carried out for various parameters viz. pH, sorbent dose, contact time, initial metal ion concentration, and temperature. Data were utilized for isothermal, kinetic, and thermodynamic studies. Scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDAX), and Fourier transform infrared (FTIR) analyses of biomass were performed. The results showed that 1 g/100 ml for 5.0-5.5 h contact time at pH 6.0-7.5 with agitation rate 150 rpm provided 98, 96, 92, and 85 % maximum absorption of arsenic by R. rosa, H. rosasinensis, T. erecta, and C. indica, respectively, at initial concentration of 500 ppb. Data followed Langmuir isotherm showing sorption to be monolayer on heterogeneous surface of biosorbent. Negative values of ΔG° indicated spontaneous nature, whereas ΔH° indicates exothermic nature of system followed by pseudo-first-order adsorption kinetics. FTIR results showed apparent changes in functional group regions after metal chelation. SEM and EDAX analyses showed the changes in surface morphology of all test biosorbents. Herbal dye wastes, used as biosorbent, exhibited significant (85-98 %) removal of arsenic from aqueous solution. Hence, these biosorbents are cost-effective, easily available, eco-friendly, and comparatively more effective than other biosorbents already in use. These may be used to remove arsenic and other toxic metals from water.

  10. Understanding the Aldo-Enediolate Tautomerism of Glycolaldehyde in Basic Aqueous Solutions.

    PubMed

    Azofra, Luis Miguel; Quesada-Moreno, María Mar; Alkorta, Ibon; Avilés-Moreno, Juan Ramón; Elguero, José; López-González, Juan Jesús

    2015-07-20

    The biochemically important interconversion process between aldoses and ketoses is assumed to take place via 1,2-enediol or 1,2-enediolate intermediates, but such intermediates have never been isolated. The current work was undertaken in an attempt to detect the presence of the 1,2-enediol structure of glycolaldehyde in alkaline medium, actually a 1,2-enediolate, and to try to clarify the scarce data existing about both the formation of deprotonated enediol and the aldo-enediolate equilibrium. The Raman spectra of neutral and basic solutions were recorded as a function of time for eleven days. Several bands associated with the presence of the enediolate were observed in alkaline medium. Glycolaldehyde exists as three different structures in aqueous solution at neutral pH, that is, hydrated aldehydes, aldehydes and dimers, with a respective ratio of approximately 4:0.25:1. Additionally, the formation of Z-enediolate forms takes place at basic pH, together with an increase in the concentration of aldehyde species, such as 2-oxoethan-1-olate, and a decrease in the concentrations of the hydrated aldehyde and dimeric forms. The theoretical ratio of ≈1.5:1 for aldehyde:Z-enediolate reproduces the experimental Raman spectrum in basic medium, with an additional contribution of the previously mentioned ratio between the hydrated aldehyde and dimeric forms. Finally, Raman spectroscopy allowed us to monitor the enolization of this carbohydrate model and conclude that aldo-enediol tautomerism-formally aldo-enediolate-happens when a suitable amount of basic species is added.

  11. 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.

  12. Study of the decomposition pathway of 12-molybdophosphoric acid in aqueous solutions by micro Raman spectroscopy.

    PubMed

    Bajuk-Bogdanović, D; Uskoković-Marković, S; Hercigonja, R; Popa, A; Holclajtner-Antunović, I

    2016-01-15

    Micro Raman spectroscopy was applied to investigate the speciation of heteropoly and isopoly molybdates in 0.05 and 0.005 M aqueous solutions of 12-molybdophosphoric acid at pH values between 1 and 6. For comparative purposes, (31)P NMR spectroscopy was applied too. It is shown that stability of Keggin anion is influenced both by pH and concentration of solution. The Keggin structure is stable in acidic solutions (pH<1.6) while defective Keggin structures are formed with further alkalization (up to pH5.6). Monolacunary anion PMo11O(39)(7-) is the main component in the pH region from 1.6 to 3.4. Further removal of molybdenyl species causes the appearance of other vacant Keggin structures such as PMo9O31(OH)(3)(6-) and PMo6O(25)(9-) at about pH4. At pH5.0, anion PMo6O(25)(9-) is the main species. In solutions with pH greater than 5.0, heteropolymolybdates disappear completely and isopolymolybdates Mo7O(24)(6-) and MoO(4)(2-) are formed in higher amounts. In more diluted solution of 0.005 M, the decomposition scheme of 12-molybdophosphoric acid solution with increasing of pH takes place without observation of significant amounts of Mo7O(24)(6-) species. If alkalinization is performed with 0.5 M instead of 5 M NaOH, there are no significant changes in the Raman spectra of solutions. It is shown that the spectra of evaporated samples may be used for the identification of molecular species in corresponding concentrated solutions. However, Raman spectra of dry residues of more diluted solutions differ from spectra of corresponding solutions due to the reactions performed during the process of drying and cannot be used for unambiguous identification of species in solution. Acidification of 0.05 M solution of Na2MoO4 shows that at pH>5.6, molybdate anion MoO(4)(2-) dominates, while in the pH range between 5.6 and 1, heptamolybdate anion Mo7O(24)(6-) is preferentially formed.

  13. The self-aggregation of some 7H-indolo[1,2-a]quinolinium dyes in aqueous solution

    NASA Astrophysics Data System (ADS)

    Sawicka, Marta J.

    2015-10-01

    The aggregation of some 7H-indolo[1,2-a]quinolinium dyes in aqueous solution was investigated based on UV-vis spectroscopy. The influence of pH, dye concentration, ionic strength and the addition of organic solvents on the process was studied. The aggregation took place in alkaline solution and was strongly affected by ionic strength and the presence of organic solvents. The existence of aggregates in the solution was manifested in a new band appearance which exhibited bathochromic shift with respect to the monomer band. For all studied dyes the band was assigned to the dimer and the equilibrium constants for dimer formation were calculated. The dye tendency to aggregate was determined by its structure and was enhanced by the presence of naphthalene moiety in comparison to that of benzene ring as well as electron-rich substituents such as halogens.

  14. 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.

  15. 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.

  16. 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.

  17. Viscosities of cetylpyridinium bromide solutions (aqueous and aqueous KBr) in the presence of alcohols and amines

    SciTech Connect

    David, S.L.; Kumar, S.; Kabir-ud-Din

    1997-01-01

    Among the large number of additives, alcohols hold a special place, being by far the most common cosurfactants which are added to surfactant-oil combinations to generate microemulsions. Though the studies using amines as cosurfactant in microemulsions are few, it has been proved that they are also potential candidates for such formulations. The effect of organic additives (aliphatic/aromatic amines or alcohols) on the viscosities of aqueous and 0.1 M KBr solutions of 0.05 or 0.1 M cetylpyridinium bromide have been measured under Newtonian flow conditions. The viscosity changed dramatically in the presence of KBr. This is explained by the favorable conditions produced by the salt which assists the micellar growth by organic additives with a concomitant enhancement in viscosity. Reasons for the effectiveness of these additives are suggested. The causes of the viscosity decrease at higher concentrations of the additive are also explained.

  18. Free radical generation by ultrasound in aqueous and nonaqueous solutions.

    PubMed Central

    Riesz, P; Berdahl, D; Christman, C L

    1985-01-01

    The physical principles underlying the oscillatory behavior of minute gas bubbles in liquids exposed to ultrasound are reviewed. Results from mathematical analyses suggest that these oscillations sometimes become unstable leading to transient cavitation in which a bubble violently collapses during a single acoustic half-cycle producing high temperatures and pressures. The role that micronuclei, resonant bubble size, and rectified diffusion play in the initiation of transient cavitation is explained. Evidence to support these theoretical predictions is presented with particular emphasis on sonoluminescence which provides some non-chemical evidence for the formation of free radicals. Acoustic methods for conducting sonochemical investigations are discussed. In aqueous solutions transient cavitation initially generates hydrogen atoms and hydroxyl radicals which may recombine to form hydrogen and hydrogen peroxide or may react with solutes in the gas phase, at the gas-liquid boundary or in the bulk of the solution. The analogies and differences between sonochemistry and ionizing radiation chemistry are explored. The use of spin trapping and electron spin resonance to identify hydrogen atoms and hydroxyl radicals conclusively and to detect transient cavitation produced by continuous wave and by pulsed ultrasound is described in detail. The study of the chemical effects of cavitation in organic liquids is a relatively unexplored area which has recently become the subject of renewed interest. Examples of the decomposition of solvent and solute, of ultrasonically initiated free-radical polymerization and polymer degradation are presented. Spin trapping has been used to identify radicals in organic liquids, in polymer degradation and in the decomposition of organometallic compounds. PMID:3007091

  19. 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.

  20. Effect of Nicotinamide on the Photolysis of Riboflavin in Aqueous Solution.

    PubMed

    Ahmad, Iqbal; Ahmed, Sofia; Sheraz, Muhammad Ali; Anwar, Zubair; Qadeer, Kiran; Noor, Adnan; Evstigneev, Maxim P

    2016-01-01

    The photolysis of riboflavin (RF) in aqueous solution in the presence of nicotinamide (NA) by visible light has been studied in the pH range 1.0-12.0 and the various photoproducts have been identified as known compounds. RF has been determined in degraded solutions by a specific multicomponent spectrometric method in the presence of its photoproducts and NA. The second-order rate constants (k 2) for the bimolecular interaction of RF and NA range from 0.54 (pH 1.0) to 9.66 M(-1) min(-1) (pH 12.0). The log k 2-pH profile for the photolysis reaction follows a sigmoid curve showing a gradual increase in the rate of pH due to a change in the ionization behavior of the molecule. The lower rate in the acid region is probably due to protonation of the molecule since the cationic form of RF is less susceptible to photolysis than the neutral form. Similarly, a slowing of the rate in the alkaline region is due to anion formation of the molecule. NA is involved as an electron acceptor during the sequence of reactions and thus enhances the rate of photolysis of RF. Absorption and fluorescence measurements did not provide evidence for the complex formation between the two compounds under the present conditions. PMID:27222605

  1. Oxidation of L-phenylalanine by diperiodatoargentate(III) in aqueous alkaline medium. A Mechanistic approach

    NASA Astrophysics Data System (ADS)

    Lamani, S. D.; Veeresh, T. M.; Nandibewoor, S. T.

    2009-12-01

    The kinetics of oxidation of L-phenylalanine (L-Phe) by diperiodatoargentate(III) (DPA) in alkaline medium at a constant ionic strength of 0.25 mol/dm-3 has been studied spectrophotometrically. The reaction between DPA and L-phenylalanine in alkaline medium exhibits 1: 1 stoichiometry (L-phenylalanine: DPA). The reaction shows first order in [DPA] and has less than unit order dependence each in both [L-Phe] and [Alkali] and retarding effect of [IO{4/-}] under the reaction conditions. The active species of DPA is understood to be as monoperiodatoargentate(III) (MPA). The reaction is shown to proceed via a MPA-L-Phe complex, which decomposes in a rate-determining step to give intermediates followed by a fast step to give the products. The products were identified by spot and spectroscopic studies. The reaction constants involved in the different steps of the mechanisms were calculated. The activation parameters with respect to slow step of the mechanism were computed and discussed. The thermodynamic quantities were also determined for the reaction.

  2. Self-assembly and phase behavior of germanium oxide nanoparticles in basic aqueous solutions.

    PubMed

    Rimer, Jeffrey D; Roth, Daniel D; Vlachos, Dionisios G; Lobo, Raul F

    2007-02-27

    We show that germania nanoparticle self-assembly in basic aqueous solutions occurs at a critical aggregation concentration (CAC) corresponding to a 1:1 GeO2/OH- molar ratio. A combination of pH, conductivity, and small-angle X-ray scattering (SAXS) measurements was used to monitor the effect of incremental additions of germanium (IV) ethoxide to basic solutions of sodium hydroxide or tetraalkylammonium cations. Plots of pH versus total germania concentration at varying alkalinities generated a phase diagram with three distinct regions. The diagram was analyzed with a thermodynamic model based on the chemical equilibria of germania speciation and dissociation. The model, which uses the GeO-H dissociation constant (pK = 7.1) as the single fitting parameter, quantitatively captures trends in the CAC and pH. SAXS patterns reveal that the germania nanoparticles have either a cubic or a spherical geometry of dimension approximately 1 nm that is independent of solution pH and cation. On the basis of these and other literature findings, we propose that the germania nanoparticle structure is that of the cubic octamer (double four-membered ring, Ge8O12(OH)8), which is common among condensed GeO2 materials and building units in [Ge,Si]-zeolites. Comparisons between germania and silica solutions show distinct differences in their phase behavior and nanoparticle structure. The results presented here, in combination with previous studies of siliceous solutions, provide a framework for ongoing studies of combined germania-silica phase behavior, which is part of an overarching effort to understand the influence of heteroatoms in the growth and structure direction of zeolites.

  3. Rotational dynamics of thiocyanate ions in highly concentrated aqueous solutions.

    PubMed

    Kim, Heejae; Park, Sungnam; Cho, Minhaeng

    2012-05-14

    The thiocyanate (SCN(-)) anion is known as one of the best denaturants, which is also capable of breaking the hydrogen-bond network of water and destabilizing native structures of proteins. Despite prolonged efforts to understand the underlying mechanism of such Hofmeister effects, detailed dynamics of the ions in a highly concentrated solution have not been fully elucidated yet. Here, we used a dispersive IR pump-probe spectroscopic method to study the dependence of vibrational lifetimes and rotational relaxation times of thiocyanate ions on KSCN concentration in D(2)O. The nitrile stretch mode is used as a vibrational probe for dispersed IR pump-probe and FTIR measurements. To avoid possible self-attenuation of the IR pump-probe signal by highly concentrated SCN(-) ions, we added a small amount of (13)C-isotope-labeled thiocyanate ions (S(13)CN(-)) and focused on the excited-state absorption contribution to the IR pump-probe signal of the (13)C-isotope-labeled nitrile stretch mode. Quite unexpectedly, the vibrational lifetime of S(13)CN(-) ions is independent of the total KSCN concentration in the range from 0.46 m (molality) to 11.8 m while the rotational relaxation time of S(13)CN(-) ions is linearly dependent on the total KSCN concentration. By combining the present experimental findings with the fact that the dissolved ions of KSCN salt have a strong tendency to form a large ion cluster in a highly concentrated aqueous solution, we believe that the ion clusters consisting of potassium and thiocyanate ion pairs in D(2)O behave like ionic liquids and the ions inside ion clusters are weakly bound by electrostatic Coulombic interactions. The ability of SCN(-) ions to form ion clusters in aqueous protein solutions seems to be a key to understand the Hofmeister ion effect. We anticipate that the present experimental results provide a clue for further elucidating the underlying mechanism of the Hofmeister ion effects on protein stability in the future. PMID:22407336

  4. Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

    PubMed

    Byers, Joshua C; Paulose Nadappuram, Binoy; Perry, David; McKelvey, Kim; Colburn, Alex W; Unwin, Patrick R

    2015-10-20

    Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.

  5. Study of phosphate removal from aqueous solution by zinc oxide.

    PubMed

    Luo, Zhen; Zhu, Suiyi; Liu, Zhongmou; Liu, Jiancong; Huo, Mingxin; Yang, Wu

    2015-09-01

    Zinc oxide (ZnO) was synthesized and used to investigate the mechanism of phosphate removal from aqueous solution. ZnO particles were characterized by X-ray diffraction, scanning electron microscope and Fourier transform infrared spectroscopy before and after adsorption. Batch experiments were carried out to investigate the kinetics, isotherms, effects of initial pH and co-existing anions. The adsorption process was rapid and equilibrium was almost reached within 150 min. The adsorption kinetics were described well by a pseudo-second-order equation, and the maximum phosphate adsorption capacity was 163.4 mg/g at 298 K and pH ∼6.2±0.1. Thermodynamic analysis indicated the phosphate adsorption onto ZnO was endothermic and spontaneous. The point of zero charge of ZnO was around 8.4 according to the pH-drift method. Phosphate adsorption capacity reduced with the increasing initial solution pH values. The ligand exchange and Lewis acid-base interaction dominated the adsorption process in the lower and the higher pH range, respectively. Nitrate, sulfate and chloride ions had a negligible effect on phosphate removal, while carbonate displayed significant inhibition behavior.

  6. [Ammonium Adsorption Characteristics in Aqueous Solution by Dairy Manure Biochar].

    PubMed

    Ma, Feng-feng; Zhao, Bao-wei; Diao, Jing-ru; Zhong, Jin-kui; Li, An-bang

    2015-05-01

    The adsorption characteristics of ammonium from aqueous solution onto biochar derived from dairy manure were investigated as a function of parameters such as solution pH, particle size, adsorbent dosage, temperature and competitive cations. The results indicated that the effects of other cations on the adsorption of ammonium followed the order of preference Na > Ca2+ at identical mass concentrations. It was observed that pH played an important role in the ammonium adsorption and the optimal pH values ranged between 5 and 8. The kinetic data fitted the pseudo-second-order model (R2 = 0.967 3) but showed very poor fits for the pseudo-first-order model (R2 = 0.765 9) and the Elovich model (R2 = 0.724 9). The results from the Intra-particle model also showed that there were two separate stages in sorption process, which were external diffusion and the diffusion of inter-particle. Adsorption isotherms for dairy manure biochar were fitted the Freundlich model (R2 = 0.976 2) more effectively than other models. Thermodynamics parameters such as free energy (ΔGθ), enthalpy (ΔHθ), and entropy (ΔSθ) were also determined, which indicated that the adsorption was a spontaneous and endothermic process. PMID:26314116

  7. Metal ion removal from aqueous solution using physic seed hull.

    PubMed

    Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

    2010-07-15

    The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. PMID:20362390

  8. Study of phosphate removal from aqueous solution by zinc oxide.

    PubMed

    Luo, Zhen; Zhu, Suiyi; Liu, Zhongmou; Liu, Jiancong; Huo, Mingxin; Yang, Wu

    2015-09-01

    Zinc oxide (ZnO) was synthesized and used to investigate the mechanism of phosphate removal from aqueous solution. ZnO particles were characterized by X-ray diffraction, scanning electron microscope and Fourier transform infrared spectroscopy before and after adsorption. Batch experiments were carried out to investigate the kinetics, isotherms, effects of initial pH and co-existing anions. The adsorption process was rapid and equilibrium was almost reached within 150 min. The adsorption kinetics were described well by a pseudo-second-order equation, and the maximum phosphate adsorption capacity was 163.4 mg/g at 298 K and pH ∼6.2±0.1. Thermodynamic analysis indicated the phosphate adsorption onto ZnO was endothermic and spontaneous. The point of zero charge of ZnO was around 8.4 according to the pH-drift method. Phosphate adsorption capacity reduced with the increasing initial solution pH values. The ligand exchange and Lewis acid-base interaction dominated the adsorption process in the lower and the higher pH range, respectively. Nitrate, sulfate and chloride ions had a negligible effect on phosphate removal, while carbonate displayed significant inhibition behavior. PMID:26322756

  9. Characterization of Chitin and Chitosan Molecular Structure in Aqueous Solution

    SciTech Connect

    Franca, Eduardo D.; Lins, Roberto D.; Freitas, Luiz C.; Straatsma, t. P.

    2008-11-08

    Molecular dynamics simulations have been used to characterize the structure of chitin and chitosan fibers in aqueous solutions. Chitin fibers, whether isolated or in the form of a β-chitin nanoparticle, adopt the so-called 2-fold helix with Φ and φ values similar to its crystalline state. In solution, the intramolecular hydrogen bond HO3(n)•••O5(n+1) responsible for the 2-fold helical motif is stabilized by hydrogen bonds with water molecules in a well-defined orientation. On the other hand, chitosan can adopt five distinct helical motifs and its conformational equilibrium is highly dependent on pH. The hydrogen bond pattern and solvation around the O3 atom of insoluble chitosan (basic pH) are nearly identical to these quantities in chitin. Our findings suggest that the solubility and conformation of these polysaccharides are related to the stability of the intrachain HO3(n)•••O5(n+1) hydrogen bond, which is affect by the water exchange around the O3-HO3 hydroxyl group.

  10. Dielectric barrier discharge induced degradation of diclofenac in aqueous solution.

    PubMed

    Rong, Shaopeng; Sun, Yabing; Zhao, Zehua; Wang, Huiying

    2014-01-01

    A dielectric barrier discharge (DBD) reactor as one of the advanced oxidation processes was applied to the degradation of diclofenac in aqueous solution. The various parameters that affect the degradation of diclofenac and the proposed evolutionary process were investigated. The results indicated that the inner concentrations of 10 mg/L diclofenac can be all removed within 10 min under conditions of 50 W and pH value of 6.15. The existence of Fe(2+) in the liquid phase can promote the degradation of diclofenac. But it was rather ineffective in mineralization, because the intermediates containing the aromatic rings were recalcitrant to be degraded. Five intermediates were identified by liquid chromatography-mass spectrometry (LC-MS), the OH · radical and O(3) were the major reactive species, and played an important role in the degradation of diclofenac. The toxicity of diclofenac degraded by DBD was assessed and the results indicated the efficiency of the DBD in the detoxification of the diclofenac solution.

  11. Structure and phase behavior of aqueous methylcellulose solutions

    NASA Astrophysics Data System (ADS)

    McAllister, John; Schmidt, Peter; Lodge, Timothy; Bates, Frank

    2015-03-01

    Cellulose ethers (CE) constitute a multi-billion dollar industry, and have found end uses in a broad array of applications from construction materials, food products, personal care products, and pharmaceuticals for more than 80 years. Methylcellulose (MC, with the trade name METHOCEL™) is a CE in which there is a partial substitution of -OH groups with -OCH3 groups. This results in a polymer that is water-soluble at low temperatures, and aqueous solutions of MC display gelation and phase separation at higher temperatures. The nature of MC gelation has been debated for many years, and this project has made significant advances in the understanding of the solution properties of CEs. We have characterized a fibrillar structure of MC gels by cryogenic transmission electron microscopy (cryo-TEM) and small angle neutron scattering (SANS). Using light scattering, turbidity measurements, and dynamic mechanical spectroscopy (DMS) we report that MC microphase separates by nucleation and growth of fibril aggregates, and is a different process from LCST phase separation.

  12. 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.

  13. Lead(II) binding to the chelating agent D-penicillamine in aqueous solution.

    PubMed

    Sisombath, Natalie S; Jalilehvand, Farideh; Schell, Adam C; Wu, Qiao

    2014-12-01

    A spectroscopic investigation of the complexes formed between the Pb(II) ion and D-penicillamine (H2Pen), a chelating agent used in the treatment of lead poisoning, was carried out on two sets of alkaline aqueous solutions with CPb(II) ≈ 10 and 100 mM, varying the H2Pen/Pb(II) molar ratio (2.0, 3.0, 4.0, 10.0). Ultraviolet-visible (UV-vis) spectra of the 10 mM Pb(II) solutions consistently showed an absorption peak at 298 nm for S(-) → Pb(II) ligand-to-metal charge-transfer. The downfield (13)C NMR chemical shift for the penicillamine COO(-) group confirmed Pb(II) coordination. The (207)Pb NMR chemical shifts were confined to a narrow range between 1806 ppm and 1873 ppm for all Pb(II)-penicillamine solutions, indicating only small variations in the speciation, even in large penicillamine excess. Those chemical shifts are considerably deshielded, relative to the solid-state (207)Pb NMR isotropic chemical shift of 909 ppm obtained for crystalline penicillaminatolead(II) with Pb(S,N,O-Pen) coordination. The Pb LIII-edge extended X-ray absorption fine structure (EXAFS) spectra obtained for these solutions were well-modeled with two Pb-S and two Pb-(N/O) bonds with mean distances 2.64 ± 0.04 Å and 2.45 ± 0.04 Å, respectively. The combined spectroscopic results, reporting δ((207)Pb) ≈ 1870 ppm and λmax ≈ 298 nm for a Pb(II)S2NO site, are consistent with a dominating 1:2 lead(II):penicillamine complex with [Pb(S,N,O-Pen)(S-HnPen)](2-n) (n = 0-1) coordination in alkaline solutions, and provide useful structural information on how penicillamine can function as an antidote against lead toxicity in vivo. PMID:25385465

  14. Lead(II) Binding to the Chelating Agent d-Penicillamine in Aqueous Solution

    PubMed Central

    2015-01-01

    A spectroscopic investigation of the complexes formed between the Pb(II) ion and d-penicillamine (H2Pen), a chelating agent used in the treatment of lead poisoning, was carried out on two sets of alkaline aqueous solutions with CPb(II) ≈ 10 and 100 mM, varying the H2Pen/Pb(II) molar ratio (2.0, 3.0, 4.0, 10.0). Ultraviolet–visible (UV-vis) spectra of the 10 mM Pb(II) solutions consistently showed an absorption peak at 298 nm for S– → Pb(II) ligand-to-metal charge-transfer. The downfield 13C NMR chemical shift for the penicillamine COO– group confirmed Pb(II) coordination. The 207Pb NMR chemical shifts were confined to a narrow range between 1806 ppm and 1873 ppm for all Pb(II)-penicillamine solutions, indicating only small variations in the speciation, even in large penicillamine excess. Those chemical shifts are considerably deshielded, relative to the solid-state 207Pb NMR isotropic chemical shift of 909 ppm obtained for crystalline penicillaminatolead(II) with Pb(S,N,O-Pen) coordination. The Pb LIII-edge extended X-ray absorption fine structure (EXAFS) spectra obtained for these solutions were well-modeled with two Pb–S and two Pb-(N/O) bonds with mean distances 2.64 ± 0.04 Å and 2.45 ± 0.04 Å, respectively. The combined spectroscopic results, reporting δ(207Pb) ≈ 1870 ppm and λmax ≈ 298 nm for a PbIIS2NO site, are consistent with a dominating 1:2 lead(II):penicillamine complex with [Pb(S,N,O-Pen)(S-HnPen)]2–n (n = 0–1) coordination in alkaline solutions, and provide useful structural information on how penicillamine can function as an antidote against lead toxicity in vivo. PMID:25385465

  15. Process for separating and recovering an anionic dye from an aqueous solution

    DOEpatents

    Rogers, R.; Horwitz, E.P.; Bond, A.H.

    1998-01-13

    A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

  16. Process for separating and recovering an anionic dye from an aqueous solution

    DOEpatents

    Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

    1998-01-01

    A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

  17. Sorption of acid red 57 from aqueous solution onto sepiolite.

    PubMed

    Alkan, Mahir; Demirbaş, Ozkan; Celikçapa, Sermet; Doğan, Mehmet

    2004-12-10

    Sepiolite, a highly porous mineral, is becoming widely used as an alternative material in areas where sorptive, catalytic and rheological applications are required. High ion exchange capacity and high surface area and more importantly its relatively cheap price make it an attractive adsorbent. In this study, the adsorption of acid red 57 by natural mesoporous sepiolite has been examined in order to measure the ability of this mineral to remove coloured textile dyes from wastewater. For this purpose, a series of batch adsorption tests of acid red 57 from aqueous sepiolite solutions have been systematically investigated as a function of parameters such as pH, ionic strength and temperature. Adsorption equilibrium was reached within 1h. The removal of acid red 57 decreases with pH from 3 to 9 and temperature from 25 to 55 degrees C, whereas it increases with ionic strength from 0 to 0.5 mol L(-1). Adsorption isotherms of acid red on sepiolite were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. It was found that the Langmuir model appears to fit the isotherm data better than the Freundlich model. The physical properties of this adsorbent were consistent with the parameters obtained from the isotherm equations. Approximately, 21.49% weight loss was observed. The surface area value of sepiolite was 342 m2 g(-1) at 105 degrees C, and it increased to 357 m2 g(-1) at 200 degrees C. Further increase in temperature caused channel plugging and crystal structure deformation, as a result the surface area values showed a decrease with temperature. The data obtained from adsorption isotherms at different temperatures have been used to calculate some thermodynamic quantities such as the Gibbs energy, heat and entropy of adsorption. The thermodynamic data indicate that acid red 57 adsorption onto sepiolite is characterized by physical adsorption. The dimensionless separation factor (RL) have shown that sepiolite can be used for

  18. Inversion of 4-methoxybenzophenone triplet in aqueous solutions.

    PubMed

    Boscá, Francisco; Cosa, Gonzalo; Miranda, Miguel A; Scaiano, J C

    2002-09-01

    The triplet state of 4-methoxybenzophenone (4-MBP) has been investigated by laser flash photolysis and emission techniques in several solvents. In non-polar cyclohexane, 4-MBP triplet has an (n,pi*) configuration with the typical triplet-triplet absorption spectrum of benzophenone (lambda(max) ca. 525 nm). However, due to the proximity of the two lowest triplet states of different configuration, some unusual features are observed in polar solvents. Thus, 4-MBP shows in aqueous solutions a transient absorption spectrum with lambda(max) at 450 and 680 nm, which can be attributed to a T1 (pi,pi*) state. Further, transient absorption spectra due to T1 (n,pi*) and T2 (pi,pi*) being simultaneously populated are observed upon laser excitation of 4-MBP in polar solvents such as acetonitrile or methanol. The triplet state inversion (n,pi* to pi,pi*) is also detected by the measurement of triplet quenching rate constants by 1,4-cyclohexadiene (a good hydrogen donor) in acetonitrile and water (kH ca. 2 x 10(8) and 5 x 10(5) M(-1) s(-1), respectively) and by the determination of room-temperature phosphorescence (the emission quantum yield at room-temperature decreases from 0.004 in acetonitrile to less than 1 x 10(-6) in water). Further, the energy of the 4-MBP triplet state is ca. 288 kJ mol(-1) both in polar and non-polar organic solvents, while in water it drops to 275 kJ mol(-1). The photophysical properties of 4-MBP are compared with those of 4-aminobenzophenone (4-ABP), which also possesses an electron-donating group. In polar organic solvents such as acetonitrile, the transient absorption spectrum and the quenching rate constant of hydrogen abstraction for triplet 4-ABP are practically the same as those obtained for 4-MBP in aqueous solutions. On the other hand, a small T2 (pi,pi*) contribution is observed in the triplet-triplet absorption spectrum of 4-ABP in cyclohexane.

  19. 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.

  20. 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

  1. A thermodynamic model for aqueous solutions of liquid-like density

    SciTech Connect

    Pitzer, K.S.

    1987-06-01

    The paper describes a model for the prediction of the thermodynamic properties of multicomponent aqueous solutions and discusses its applications. The model was initially developed for solutions near room temperature, but has been found to be applicable to aqueous systems up to 300/sup 0/C or slightly higher. A liquid-like density and relatively small compressibility are assumed. A typical application is the prediction of the equilibrium between an aqueous phase (brine) and one or more solid phases (minerals). (ACR)

  2. Interactions of Aqueous U(VI) with Soil Minerals in Slightly Alkaline Natural Systems

    SciTech Connect

    Qafoku, Nik; Icenhower, Jonathan P.

    2008-12-01

    Uranium (U) is a common contaminant at numerous surface and subsurface sites around the world. This paper covers some important aspects of the aqueous hexavalent uranium [U(VI)] interactions with soil minerals that are present in contaminated soils and sediments. The retention of U via interactions with soil minerals has significant consequences for the prediction of its short – and long – term behavior in soils and geological systems. Studies of the nature and type of these interactions have provided the necessary evidence for assessing the geochemical behavior of U in natural systems under different physical, biogeochemical, hydrological, and reducing or oxidizing conditions. Over the last 20 years, aqueous U(VI):solid phase interactions have been studied by geochemists, soil chemists, soil mineralogists and soil microbiologists, and the progress in some areas is remarkable. Although a mechanistic description and understanding of the complex interactions involving U and soil minerals of natural systems is currently impossible, results from carefully designed and executed experiments with these materials have improved our understanding of the heterogeneous system’s behavior and U contaminant mobility and transport. There are, however, areas that need further exploration and study. Numerous research publications were reviewed in this paper to present important findings coming out of the research, to reveal the current level of the understanding of the U(VI) interactions with soil minerals, and to provide ideas for future needs and research directions.

  3. Tested Demonstrations. Color, Solubility, and Complex Ion Equilibria of Nickel (II) Species in Aqueous Solution.

    ERIC Educational Resources Information Center

    Gilbert, George L., Ed.; And Others

    1980-01-01

    Presents three different procedures in which reagents are added in a specified order to a large beaker containing an aqueous solution of nickel sulfate. Complex ions of nickel (II) are prepared by using aqueous solutions of ammonia, ethylenediamine, dimethylglyoxime, and cyanide ion. (CS)

  4. 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.

  5. Optical properties of chitosan in aqueous solution of L- and D-ascorbic acids

    NASA Astrophysics Data System (ADS)

    Malinkina, Olga N.; Shipovskaya, Anna B.; Kazmicheva, Olga F.

    2016-04-01

    The optical properties of aqueous chitosan solutions in L- and D-ascorbic acids were studied by optical rotatory dispersion and spectrophotometry. The specific optical rotation [α] of all chitosan solutions tested was positive, in contrast to aqueous solutions of the ascorbic acid enantiomers, which exhibit an inverse relationship of [α] values. Significant differences in the absolute values of [α] of the chitosan solutions at polymer-acid ratios exceeding the equimolar one were found.

  6. Electrochemical degradation of amaranth aqueous solution on ACF.

    PubMed

    Fan, Li; Zhou, Yanwei; Yang, Weishen; Chen, Guohua; Yang, Fenglin

    2006-09-21

    The degradation of Amaranth, a kind of azo dye, has been studied under galvanostatic model with activated carbon fiber (ACF) electrode in aqueous solution with electrochemical method. The ACF was used as anode and cathode, respectively for the decolorization process. The onset oxidation potential and reduction potential for Amaranth on ACF were respectively ascertained at 0.6 and -0.4 V. During the range of -1.1 to 0.50 mA cm(-2), the decolorization was clarified into three processes as electroreduction, adsorption and electrooxidation. There were little contributions to the color and COD removals for the process of adsorption. The color removal can be up to 99% when the current density was 0.50 mA cm(-2). The maximum COD removal was 52% for the process of electrooxidation. Hundred percent color removal was obtained when the current density of -1.0 mA cm(-2) was applied. The maximum COD removal was 62% for the electroreduction. The COD removal results from the adsorption of products for the decolorization process of electrooxidation or electroreduction.

  7. Removal of lead from aqueous solutions with sodium caprate

    SciTech Connect

    Husein, M.M.; Vera, J.H.; Weber, M.E.

    1998-09-01

    Lead was removed from aqueous solutions by precipitation using sodium caprate [CH{sub 3}(CH{sub 2}){sub 8}COONa]. For a feed concentration of 7 mM (1,450 ppm) lead and a mole ratio of caprate to lead of 2, the percentage removal of lead and the percentage loss of caprate were 99.5 {+-} 0.2 and 0.8 {+-} 0.3, respectively. The effects of pH and the concentrations of lead, calcium, chloride, and nitrate in the feed on the removal step were determined. At a mole ratio of caprate to lead of 2.0, the equilibrium concentrations of lead and caprate were independent of the feed concentration of lead. Decreasing the pH of the feed decreased the removal of lead but did not affect the loss of caprate. The presence of calcium, chloride, or nitrate in the feed did not affect the removal of lead. Sodium caprate was regenerated by adding HNO{sub 3} to the lead caprate precipitate to form capric acid from which sodium caprate was recovered by adding NaOH. Based on the amount of caprate used in the lead removal step, a percentage recovery of 98.9 {+-} 0.3 was achieved.

  8. Products of hexachlorocyclopentadiene (C-56) in aqueous solution

    USGS Publications Warehouse

    Chou, S.-F.J.; Griffin, R.A.; Chou, I.-Ming; Larson, R.A.

    1987-01-01

    The photodegradation and degradation products of hexachlorocyclopentadiene (C-56) in aqueous solutions were studied in the laboratory. In each case, the half-life of C-56 was less than 4 min when exposed to sunlight. At least eight degradation products were positively or tentatively identified: 2,3,4,4,5-Pentachloro-2-cyclopentenone, hexachloro-2-cyclopentenone and hexachloro-3-cyclopentenone were the primary photodegradation products, and pentachlorocis-2,4-pentadienoic acid, Z- and E-pentachlorobutadiene and tetrachlorobutyne were the secondary degradation products. Dissociation of the primary photolysis products may proceed through corresponding pentadienoic acids to form smaller molecular weight compounds such as pentachlorobutadiene isomers and tetrachlorobutyne. In addition, dimerization of 2,3,4,4,5-pentachloro-2-cyclopentenone to form higher molecular weight compounds such as hexachloroindenone may present a minor route of degradation. The results also indicate that C-56 is highly photoreactive and suggest a possible pathway for the compound's transformation in the environment when exposed to sunlight. ?? 1987.

  9. Defluoridation from aqueous solutions by granular ferric hydroxide (GFH).

    PubMed

    Kumar, Eva; Bhatnagar, Amit; Ji, Minkyu; Jung, Woosik; Lee, Sang-Hun; Kim, Sun-Joon; Lee, Giehyeon; Song, Hocheol; Choi, Jae-Young; Yang, Jung-Seok; Jeon, Byong-Hun

    2009-02-01

    This research was undertaken to evaluate the feasibility of granular ferric hydroxide (GFH) for fluoride removal from aqueous solutions. Batch experiments were performed to study the influence of various experimental parameters such as contact time (1 min-24h), initial fluoride concentration (1-100 mgL(-1)), temperature (10 and 25 degrees C), pH (3-12) and the presence of competing anions on the adsorption of fluoride on GFH. Kinetic data revealed that the uptake rate of fluoride was rapid in the beginning and 95% adsorption was completed within 10 min and equilibrium was achieved within 60 min. The sorption process was well explained with pseudo-first-order and pore diffusion models. The maximum adsorption capacity of GFH for fluoride removal was 7.0 mgg(-1). The adsorption was found to be an endothermic process and data conform to Langmuir model. The optimum fluoride removal was observed between pH ranges of 4-8. The fluoride adsorption was decreased in the presence of phosphate followed by carbonate and sulphate. Results from this study demonstrated potential utility of GFH that could be developed into a viable technology for fluoride removal from drinking water.

  10. Analysis of oxyluciferin photoluminescence pathways in aqueous solutions.

    PubMed

    Hiyama, Miyabi; Mochizuki, Toshimitsu; Akiyama, Hidefumi; Koga, Nobuaki

    2015-01-01

    We evaluated the pK(a) values of oxyluciferin and its conjugate acids and bases theoretically with the help of experimental correction values, from which free energies for the first excited and the ground states of all the species were estimated. On the basis of these results, we calculated pH-dependent absorption spectra, where the relative absorption intensities of various species strongly depend on photoexcitation energy, and we further analyzed the photoluminescence pathways of oxyluciferin in aqueous solutions with various pH. In the case of 350 nm photoexcitation, in particular, experiments have shown that dominant emission color is green and it attenuates with pH decreasing, while blue (3 < pH < 8) and red (pH < 3) emissions appear. Our present results clarify the pathways of these photoluminescence depending on the pH values and thus should be useful in further analyses of photoluminescence pathways for other photoexcitation wavelength in comparison with experiments. PMID:25334091

  11. Direct Photolysis of Chlorophenols In Aqueous Solution By Ultraviolet Excilamps

    NASA Astrophysics Data System (ADS)

    Matafonova, Galina; Philippova, Natalya; Batoev, Valeriy

    2011-08-01

    The direct photolysis of 2-chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) in model aqueous solution was studied using UV XeBr (282 nm) and KrCl (222 nm) excilamps. The highest pseudo-first order rate constants and quantum yields were found for molecular form of 4-CP (at pH 2 and 5.7) and anionic forms of 2-CP and 2,4-DCP (at pH 11) when irradiated by XeBr excilamp. The maximum removal efficiency of molecular form of 2-CP and 2,4-DCP with the lowest UV dose of absorbed energy was observed using KrCl excilamp. On the contrary, the XeBr excilamp required the lowest dose (˜2 Jṡcm-2) for complete degradation of molecular 4-CP and anionic 2-CP. The highest removal efficiency of anionic form of 4-CP (65%) was achieved when using KrCl excilamp.

  12. A modified homogeneous freezing rate parameterization for aqueous solution droplets

    NASA Astrophysics Data System (ADS)

    Moehler, O.; Benz, S.; Hoehler, K.; Wagner, R.

    2012-12-01

    It is still a matter of debate wether cirrus cloud formation is dominated by heterogeneous ice nucleation, leading to low ice crystal number concentrations, or is also influenced by homogeneous freezing of solution aerosols leading to higher ice crystal number concentrations. Part of the discussion is due to the fact that current models seem to overestimate ice crystal numbers from homogeneous freezing compared to measurements, though the formation rate of cirrus ice crystals by homogeneous freezing of aqueous particles is believed to be well understood and formulated in terms of e.g. the concept of effective freezing temperatures or the water activity dependent ice nucleation rates. Series of recent cirrus cloud simulation experiments at the cloud chamber facility AIDA at the Karlsruhe Institute of Technology at temperatures between -40°C and -80°C together with process modeling studies demonstrated, that the freezing formulations tend to show a low bias in the humidity onset thresholds for homogeneous ice formation at temperatures below about 210 K, and furthermore overestimate the ice formation rate by at least a factor of 2. The experimental results will be summarized and a new empirical fit to the experimental data will be suggested for use in atmospheric models.

  13. Conformation of poly(γ-glutamic acid) in aqueous solution.

    PubMed

    Muroga, Yoshio; Nakaya, Asami; Inoue, Atsuki; Itoh, Daiki; Abiru, Masaya; Wada, Kaori; Takada, Masako; Ikake, Hiroki; Shimizu, Shigeru

    2016-04-01

    Local conformation and overall conformation of poly(γ-DL-glutamic acid) (PγDLGA) and poly(γ-L-glutamic acid) (PγLGA) in aqueous solution was studied as a function of degree of ionization ε by (1) H-NMR, circular dichroism, and potentiometric titration. It was clarified that their local conformation is represented by random coil over an entire ε range and their overall conformation is represented by expanded random-coil in a range of ε > ε(*) , where ε(*) is about 0.3, 0.35, 0.45, and 0.5 for added-salt concentration of 0.02M, 0.05M, 0.1M, and 0.2M, respectively. In a range of ε < ε(*) , however, ε dependence of their overall conformation is significantly differentiated from each other. PγDLGA tends to aggregate intramolecularly and/or intermolecularly with decreasing ε, but PγLGA still behaves as expanded random-coil. It is speculated that spatial arrangement of adjacent carboxyl groups along the backbone chain essentially affects the overall conformation of PγGA in acidic media.

  14. New photoacoustic cell design for studying aqueous solutions and gels.

    PubMed

    Kottmann, J; Rey, J M; Sigrist, M W

    2011-08-01

    A new photoacoustic (PA) cell design, which is particularly suitable for investigations of liquids, gels, and outgassing samples is presented. The setup is based on a PA cell of only 78.5 mm(3) volume, which is sealed on the sample side with either a 163 μm thick chemical vapor deposition diamond window or a 3.91 μm thin diamond membrane. This design offers great advantages compared to traditionally used open-ended PA cells especially when investigating volatile compounds. The new PA cell design is particularly interesting in the studies of biological samples characterized by a high water content. The performance was demonstrated with mid-infrared PA measurements of glucose in aqueous solutions using a tunable quantum-cascade laser as a light source. A detection limit of 100 mg/dl (SNR = 3) has been achieved. Furthermore, the spectral changes of glucose dissolved in water caused by mutorotation have been monitored time-resolved.

  15. Racemization kinetics of meluadrine tartrate in aqueous solution.

    PubMed

    Matsuo, K; Yamamoto, Y; Kado, N; Yamazaki, M; Nagata, O; Kato, H; Tsuji, A

    2001-01-01

    The kinetics of racemization of meluadrine tartrate in aqueous solution was investigated by HPLC, over the pH range of 1.2 to 12 at 40, 60 and 80 degrees C. The racemization was followed by measuring both the residual (R)-enantiomer and formed (S)-enantiomer of meluadrine. The pH-racemization rate profile of meluadrine showed a minimum racemization rate constant between pH 4 and 6, and the rate constant increased rapidly with decreasing pH below pH 3. In the basic region, the racemization rate constant showed a maximum at around pH 9. Four pathways of racemization of meluadrine are proposed, depending on the dissociation state of the phenolic and amino groups. The calculated racemization rate-pH profile agreed well with the observations. The values of activation energy (95-115 kJ/mol) suggest that a similar quinoid intermediate is involved throughout the pH range examined. The objective of this study is to clarify the racemization mechanism of benzylalcohol derivative with phenoric group. This study offers fundamental knowledge for the other benzylalcohol derivatives, which have similar moiety structure.

  16. CW laser compaction of aqueous solution deposited metal oxide films

    SciTech Connect

    Exarhos, G.J.; Dennis, T.

    1997-12-01

    Zirconium dioxide films were spin cast onto silica or silicon substrates from an aqueous solution comprised of the precursor metal nitrate and an organic complexant such as glycine. The hydrated films so derived consist of an amorphous organic phase in which the metal cations and nitrate anions are homogeneously dispersed. Heating to temperatures above 200 {degrees}C leads to film dehydration followed by an auto-catalyzed oxidation reaction whereby the bound nitrate oxidizes the organic matrix leaving behind an intact stoichiometric and crystalline metal oxide film. Films are characterized using AFM, XRD, and optical methods. Transformation processes in these films have been studied in detail by means of spectroscopic ellipsometry and laser induced fluorescence from films doped with a suitable rare earth probe ion such as SM{sup +3}. In the latter case, the measured fluorescence emission spectra are used to identify the hydrated, dehydrated, amorphous and crystalline metal oxide phases which evolve during processing. These transformations also have been induced upon visible CW laser irradiation at fluences in excess of 1 MW/cm{sup 2}. Under these conditions, the film dehydrates and compacts within the footprint of the incident laser beam rendering this region of the film water insoluble. Post irradiation washing of the film with water removes all vestiges of the film outside of the beam footprint suggesting a possible use of this technique for lithography applications. Films subjected to laser irradiation and post irradiation heating have been characterized with respect to thickness, phase composition, crystallite size and optical constants.

  17. Removal of hexavalent chromium from aqueous solution by iron nanoparticles*

    PubMed Central

    Niu, Shao-feng; Liu, Yong; Xu, Xin-hua; Lou, Zhang-hua

    2005-01-01

    Groundwater remediation by nanoparticles has received increasing interest in recent years. This report presents a thorough evaluation of hexavalent chromium removal in aqueous solutions using iron (Fe0) nanoparticles. Cr(VI) is a major pollutant of groundwater. Zero-valent iron, an important natural reductant of Cr(VI), is an option in the remediation of contaminated sites, transforming Cr(VI) to essentially nontoxic Cr(III). At a dose of 0.4 g/L, 100% of Cr(VI) (20 mg/L) was degraded. The Cr(VI) removal efficiency decreased significantly with increasing initial pH. Different Fe0 type was compared in the same conditions. The reactivity was in the order starch-stabilized Fe0 nanoparticles>Fe0 nanoparticles>Fe0 powder>Fe0 filings. Electrochemical analysis of the reaction process led to the conclusion that Cr(OH)3 should be the final product of Cr(VI). Iron nanoparticles are good choice for the remediation of heavy metals in groundwater. PMID:16187417

  18. Direct Photolysis of Chlorophenols In Aqueous Solution By Ultraviolet Excilamps

    SciTech Connect

    Matafonova, Galina; Philippova, Natalya; Batoev, Valeriy

    2011-08-25

    The direct photolysis of 2-chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) in model aqueous solution was studied using UV XeBr (282 nm) and KrCl (222 nm) excilamps. The highest pseudo-first order rate constants and quantum yields were found for molecular form of 4-CP (at pH 2 and 5.7) and anionic forms of 2-CP and 2,4-DCP (at pH 11) when irradiated by XeBr excilamp. The maximum removal efficiency of molecular form of 2-CP and 2,4-DCP with the lowest UV dose of absorbed energy was observed using KrCl excilamp. On the contrary, the XeBr excilamp required the lowest dose ({approx}2 J{center_dot}cm{sup -2}) for complete degradation of molecular 4-CP and anionic 2-CP. The highest removal efficiency of anionic form of 4-CP (65%) was achieved when using KrCl excilamp.

  19. Interactions of vanadates with carbohydrates in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Ribeiro, Ana C. F.; Valente, Artur J. M.; Lobo, Victor M. M.; Azevedo, Eduarda F. G.; Amado, Ana M.; da Costa, A. M. Amorim; Ramos, M. Luísa; Burrows, H. D.

    2004-10-01

    The interaction between the vanadate ion (VO 3-, i.e. vanadium (V)) and the carbohydrates sucrose, glucose and fructose has been studied in aqueous solutions (pH ≈6, 298.15 K) using measurements of diffusion coefficients, electrical conductivity, Raman and multinuclear NMR spectroscopy. With sucrose and glucose, indications of hydrolysis of the anion in the absence of the sugars came from a decrease in the diffusion coefficient with increasing concentration. Significant effects on the diffusion coefficients were observed in the presence of sucrose and glucose, suggesting interactions between the carbohydrates and vanadate ion. Support for this came from electrical conductivity measurements, where there were indications of formation of oligomeric species. These were found to depend on the carbohydrate used: confirmation of oligomer formation came from Raman spectroscopy, where it was possible to identify these species, and see their dependence on the particular carbohydrate used. Information on the interactions between the carbohydrates glucose or sucrose and vanadate came from 51V and 1H NMR spectroscopy, where the dominant species appeared to be a 2:2 complex with glucose, possessing trigonal bipyramidal centres, whereas with sucrose it is suggested that octahedral species are formed. Studies with fructose were complicated by competing oxidation of this carbohydrate and reduction of vanadium (V).

  20. A vibrational spectroscopy study on anserine and its aqueous solutions.

    PubMed

    Akkaya, Y; Balci, K; Goren, Y; Akyuz, S; Stricker, M C; Stover, D D; Ritzhaupt, G; Collier, W B

    2015-01-01

    In this study based on vibrational spectroscopic measurements and Density Functional Theory (DFT), we aimed for a reliable interpretation of the IR and Raman spectra recorded for anserine in the solid phase and water (H2O) and heavy water (D2O) solutions. Initial DFT calculations at the B3LYP/6-31G(d) searched possible conformers of the anserine zwitterion using a systematic conformational search. The corresponding equilibrium geometrical parameters and vibrational spectral data were determined for each of the stable conformers (in water) by the geometry optimization and hessian calculations performed at the same level of theory using the polarized continuum model (PCM). The same calculations were repeated to determine the most energetically preferred dimer structure for the molecule and the associated geometry, force field and vibrational spectral data. The harmonic force constants obtained from these calculations were scaled by the Scaled Quantum Mechanical Force Field (SQM) method and then used in the calculation of the refined wavenumbers, potential energy distributions, IR and Raman intensities. These refined theoretical data, which confirm the zwitterion structure for anserine in the solid phase or aqueous solvents, revealed the remarkable effects of intermolecular hydrogen bonding on the structural properties and observed IR and Raman spectra of this molecule. PMID:25997178

  1. Sonochemical degradation of organophosphorus pesticide in dilute aqueous solutions.

    PubMed

    Farooq, Robina; Lin, Feng-Kai; Shaukat, S F; Huang, Jian-Jun

    2003-09-01

    Ultrasonic irradiation was found to accelerate the rate of hydrolysis of omethoate in aqueous solution over the pH range of 2-12. Process parameters studied include pH, steady-state temperature, concentration, and the type of gases. Greater than 96% hydrolysis was observed in 30 minutes through this process and the rate of destruction increased with the help of more soluble and low thermal inert gas. So with Krypton, omethoate was found to undergo rapid destruction as compared with Argon. In the presence of ultrasound, the observed first-order rate of hydrolysis of omethoate is found to be independent of pH. The formation of transient supercritical water (SCW) appears to be an important factor in the acceleration of chemical reactions in the presence of ultrasound. A detailed chemical reaction mechanism for omethoate destruction in water was formulated. Experimental results and theoretical kinetic mechanism demonstrated that the most of the omethoate undergo destruction inside the cavitating holes. A very less effect of temperature on the degradation of omethoate within a temperature range of 20-70 degrees C proves that a small quantity of omethoate undergoes secondary destruction in the bulk liquid.

  2. The evaporation behavior of sessile droplets from aqueous saline solutions.

    PubMed

    Soulié, Virginie; Karpitschka, Stefan; Lequien, Florence; Prené, Philippe; Zemb, Thomas; Moehwald, Helmuth; Riegler, Hans

    2015-09-14

    Quantitative experiments on the evaporation from sessile droplets of aqueous saline (NaCl) solutions show a strong dependence on salt concentration and droplet shape. The experiments were performed with seven decades of initial NaCl concentrations, with various droplet sizes and with different contact angles. The evaporation rate is significantly lower for high salt concentrations and small contact angles than what is expected from the well-accepted diffusion-controlled evaporation scenario for sessile droplets, even if the change of the vapor pressure due to the salt is taken into account. Particle tracking velocimetry reveals that this modification of the evaporation behavior is caused by marangoni flows that are induced by surface tension gradients originating from the local evaporative peripheral salt enrichment. In addition it is found that already very low salt concentrations lead to a pinning of the three phase contact line. Whereas droplets with concentration ≥10(-6) M NaCl are pinned as soon as evaporation starts, droplets with lower salt concentration do evaporate in a constant contact angle mode. Aside from new, fundamental insights the findings are also relevant for a better understanding of the widespread phenomenon of corrosion initiated by sessile droplets.

  3. Removal of hexavalent chromium from aqueous solution by iron nanoparticles.

    PubMed

    Niu, Shao-Feng; Liu, Yong; Xu, Xin-Hua; Lou, Zhang-Hua

    2005-10-01

    Groundwater remediation by nanoparticles has received increasing interest in recent years. This report presents a thorough evaluation of hexavalent chromium removal in aqueous solutions using iron (Fe(0)) nanoparticles. Cr(VI) is a major pollutant of groundwater. Zero-valent iron, an important natural reductant of Cr(VI), is an option in the remediation of contaminated sites, transforming Cr(VI) to essentially nontoxic Cr(III). At a dose of 0.4 g/L, 100% of Cr(VI) (20 mg/L) was degraded. The Cr(VI) removal efficiency decreased significantly with increasing initial pH. Different Fe(0) type was compared in the same conditions. The reactivity was in the order starch-stabilized Fe(0) nanoparticles>Fe(0) nanoparticles>Fe(0) powder>Fe(0) filings. Electrochemical analysis of the reaction process led to the conclusion that Cr(OH)(3) should be the final product of Cr(VI). Iron nanoparticles are good choice for the remediation of heavy metals in groundwater.

  4. Glycine phases formed from frozen aqueous solutions: Revisited

    SciTech Connect

    Surovtsev, N. V.; Adichtchev, S. V.; Malinovsky, V. K.; Ogienko, A. G.; Manakov, A. Yu.; Drebushchak, V. A.; Ancharov, A. I.; Boldyreva, E. V.; Yunoshev, A. S.

    2012-08-14

    Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice I{sub h} was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into {beta}-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice I{sub h} and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine 'X-phase') at 209-216 K, which at 218-226 K transformed into {beta}-polymorph of glycine. The 'X-phase' was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a= 6.648 A, b= 25.867 A, c= 5.610 A, {beta}= 113.12 Masculine-Ordinal-Indicator ); the formation of 'X-phase' from the glycine glassy phase and its transformation into {beta}-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

  5. Amp Synthesis in Aqueous Solution of Adenosine and Phosphorus Pentoxide

    NASA Astrophysics Data System (ADS)

    Yamagata, Y.; Kojima, H.; Ejiri, K.; Inomata, K.

    1982-12-01

    Possible formation of a P4O10 molecule in magma, the stability of the molecule in hydrous volcanic gas at high temperatures and a possible prebiotic phosphate cycle were discussed in relation to chemical evolution. To demonstrate the utility of phosphorus pentoxide as a phosphorylating agent, aqueous solutions of adenosine (0.02M) and phosphorus pentoxide (0.2M) were incubated at 37°C for 5 months. The pH of the solutions was adjusted every day or every few days to each fixed value (9.0, 10.5, 11.5, 12.5) with 10 N NaOH. The HPLC analysis showed the formation of 2'-AMP, 3'-AMP, 5'-AMP, cyclic (2' 3')-AMP and cyclic (3' 5')-AMP. The main components of the products were 2'- and 3'-AMP, though cyclic (2' 3')-AMP was the main component in the early period of the incubation at pH 9.0. The yields (conversion rate of adenosine to AMPs) were increased almost linearly with the incubation time for 5 months in the case of pH 9.0. The final yields were about 3% (pH 9.0), 6% (pH 9.0, 1 M NaCl), 5% (pH 9.0, 0.01 M CaCl2, 0.01 M MgCl2), 7% (pH 9.0, 0.5 M NaCl, 0.01 M CaCl2, 0.01 M MgCl2), 9% (pH 9.0, 1 M NaCl, 0.01 M CaCl2, 0.01 M MgCl2), 32% (pH 10.5), 43% (pH 11.5), 35% (pH 12.5).

  6. Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

    NASA Astrophysics Data System (ADS)

    González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

    2016-04-01

    Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and

  7. Phase transfer catalyzed extraction of phenolic substances from aqueous alkaline stream

    SciTech Connect

    Dutta, N.N.; Borthakur, S.; Patil, G.S. )

    1992-09-01

    Experimental investigations are presented on the extraction/removal of such phenolic compounds as phenol, m-cresol, and resorcinol from alkaline medium via reaction with benzoyl chloride dissolved in toluene as the solvent under two-phase conditions using hexadecyltributyl phosphonium bromide as a phase transfer catalyst. Two types of experiments were performed in order to assess the utility of the reaction scheme for treatment of industrial wastewater. The results of stirred cell experiments revealed that the reactions of phenolics conform to a diffusion-limited fast pseudo-first-order regime. The rate enhancement of the reaction was found to be reasonably low as compared to that reported when Aliquat 336 was used as the catalyst. The specific rate of extraction decreases for the phenolics in the order phenol > m-cresol > resorcinol. Batch experiments conducted in a baffled agitated reactor with individual phenolic compounds as well as mixtures of all components, representing compositions typical of industrial wastewater, revealed that the volumetric rate of extraction is dependent on the stirring speed under otherwise identical conditions. Conversion of phenolics in a batch agitated reactor was found to be more than 99.5% under suitable conditions of stirring speed and reaction time, and the products of reaction, essentially esters, are completely partitioned to the organic phase. Some aspects of product recovery, solvent, and catalyst recycle are discussed.

  8. Pseudohydroxide Extraction from Aqueous Sodium Hydroxide Solutions with 3,5-di-tert-Butylphenol in Isopar® L Modified with 1-Octanol

    SciTech Connect

    Lumetta, Gregg J.; Levitskaia, Tatiana G.

    2006-06-01

    Pseudohydroxide extraction (PHE) was investigated for recovery of sodium hydroxide (NaOH) from alkaline process solutions. PHE relies on the deprotonation of a lipophilic weak acid by hydroxide ion with concomitant transfer of sodium ion into an organic phase. Contact of the sodium-loaded organic phase with water results in the reconstitution of the extractant in the organic phase and NaOH in the aqueous phase, thus leading to a process in which NaOH equivalents are transferred from an alkaline feed solution to an aqueous stripping solution. In this work, we researched PHE using a process-friendly diluent—Isopar® L. The lipophilic cation exchanger 3,5-di-tert-butylphenol (35-DTBP) was used as the extractant. The Isopar® L diluent was modified with 1-octanol to improve its solvation properties and the solubility of 35-DTBP so that practical Na+ concentrations could be achieved in the process solvent. The PHE mechanism at process-relevant conditions was explored by Raman and FTIR spectroscopic measurements. Electrospray mass spectroscopic results indicated extensive aggregation of the sodium phenolate at high Na+ loading. An equilibrium computer modeling suggested that the Na+ extraction behavior can be largely explained by the formation of 1:1 and 1:2 Na/35-DTBP species in the organic phase. Extraction isotherms obtained using caustic leaching simulant solutions indicate the potential utility of this approach for recycling NaOH from complex alkaline mixtures.

  9. Inhibition of growth in solid solution-aqueous solution systems by non-incorporating impurities

    NASA Astrophysics Data System (ADS)

    Pina, Carlos M.

    2011-03-01

    Crystal growth inhibition by non-incorporating impurities has been described and quantified since 1958 by the so-called step pinning model by Cabrera and Vermilyea [1]. In the original model, as well as in its recent improvements by Weaver et al. in 2006 and 2007 [2,3], only the inhibition by the adsorption of impurities on crystal surfaces with fixed compositions is considered. However, most of the crystals found in nature are solid solutions with more or less wide chemical variability. Therefore, in order to provide more realistic models of crystal growth inhibition in natural systems, it is fundamental to study in detail the inhibition of surfaces of solid solutions by non-incorporating impurities. In this paper, the Cabrera-Vermilyea model has been generalised for the case of growth inhibition in solid solution-aqueous solution (SS-AS) systems. This generalisation was made by considering that supersaturation and the physicochemical properties of the solid solutions are functions of the solid composition. The main implication of the model is that a progressive inhibition of growth of a solid solution by increasing the concentration of an adsorbed impurity results in compositional changes on the growing surfaces.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Mineralization of paracetamol in aqueous solution with advanced oxidation processes.

    PubMed

    Torun, Murat; Gültekin, Özge; Şolpan, Dilek; Güven, Olgun

    2015-01-01

    Paracetamol is a common analgesic drug widely used in all regions of the world more than hundred tonnes per year and it poses a great problem for the aquatic environment. Its phenolic intermediates are classified as persistent organic pollutants and toxic for the environment as well as human beings. In the present study, the irradiation of aqueous solutions of paracetamol with 60Co gamma-rays was examined on a laboratory scale and its degradation path was suggested with detected radiolysis products. The synergic effect of ozone on gamma-irradiation was investigated by preliminary ozonation before irradiation which reduced the irradiation dose from 5 to 3 kGy to completely remove paracetamol and its toxic intermediate hydroquinone from 6 to 4 kGy as well as increasing the radiation chemical yield (Gi values 1.36 and 1.66 in the absence and presence of ozone, respectively). The observed amount of formed hydroquinone was also decreased in the presence of ozone. There is a decrease in pH from 6.4 to 5.2 and dissolved oxygen consumed, which is up to 0.8 mg l(-1), to form some peroxyl radicals used for oxidation. Analytical measurements were carried out with gas chromatography/mass spectrometry and ion chromatography (IC) both qualitatively and quantitatively. Amounts of paracetamol and hydroquinone were measured with gas chromatography after trimethylsilane derivatization. Small aliphatic acids, such as acetic acid, formic acid and oxalic acid, were measured quantitatively with IC as well as inorganic ions (nitrite and nitrate) in which their yields increase with irradiation.

  15. Mineralization of paracetamol in aqueous solution with advanced oxidation processes.

    PubMed

    Torun, Murat; Gültekin, Özge; Şolpan, Dilek; Güven, Olgun

    2015-01-01

    Paracetamol is a common analgesic drug widely used in all regions of the world more than hundred tonnes per year and it poses a great problem for the aquatic environment. Its phenolic intermediates are classified as persistent organic pollutants and toxic for the environment as well as human beings. In the present study, the irradiation of aqueous solutions of paracetamol with 60Co gamma-rays was examined on a laboratory scale and its degradation path was suggested with detected radiolysis products. The synergic effect of ozone on gamma-irradiation was investigated by preliminary ozonation before irradiation which reduced the irradiation dose from 5 to 3 kGy to completely remove paracetamol and its toxic intermediate hydroquinone from 6 to 4 kGy as well as increasing the radiation chemical yield (Gi values 1.36 and 1.66 in the absence and presence of ozone, respectively). The observed amount of formed hydroquinone was also decreased in the presence of ozone. There is a decrease in pH from 6.4 to 5.2 and dissolved oxygen consumed, which is up to 0.8 mg l(-1), to form some peroxyl radicals used for oxidation. Analytical measurements were carried out with gas chromatography/mass spectrometry and ion chromatography (IC) both qualitatively and quantitatively. Amounts of paracetamol and hydroquinone were measured with gas chromatography after trimethylsilane derivatization. Small aliphatic acids, such as acetic acid, formic acid and oxalic acid, were measured quantitatively with IC as well as inorganic ions (nitrite and nitrate) in which their yields increase with irradiation. PMID:25263253

  16. Complexation of heterocyclic ligands with DNA in aqueous solution

    NASA Astrophysics Data System (ADS)

    Baranovskii, S. F.; Bolotin, P. A.; Evstigneev, M. P.; Chernyshev, D. N.

    2008-03-01

    We have used spectrophotometry to study self-association and complexation with DNA by organic heterocyclic compounds in the acridine and phenothiazine series: proflavin, thionine, and methylene blue. Based on the experimental concentration dependences of the molar absorption coefficient of the molecules in an aqueous buffer solution (0.01 M NaCl, 0.01 M Na2EDTA, 0.01 M Tris, pH 7.4, T = 298 K), we have determined the equilibrium dimerization constants for the dyes and the DNA complexation parameters using the Scatchard and McGhee-von Hippel models. The observed increase in the cooperativity parameters as the dimerization constants of the ligands increase allowed us to hypothesize that the same interactions occur between dye molecules adsorbed on DNA as in their self-association. The equilibrium DNA-binding constants for the ligands, obtained using the McGhee-von Hippel cooperative model, are (20.9 ± 2.7)·103 M-1 for proflavin and (33.8 ± 4.1)·103 M-1 for thionine. Using the Scatchard model, taking into account intercalation and “external” binding of ligands with DNA, we determined the DNA complexation constants for methylene blue: (26.4 ± 4.6)·103 and (96 ± 17)·103 M-1 respectively. Based on analysis of the data obtained, we hypothesized that the predominant type of binding with DNA is intercalation binding in the case of proflavin and thionine, and “external” binding with the DNA surface in the case of methylene blue.

  17. 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

  18. Assemblies of protective anion exchange membrane on air electrode for its efficient operation in aqueous alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Bertolotti, Bruno; Chikh, Linda; Vancaeyzeele, Cédric; Alfonsi, Séverine; Fichet, Odile

    2015-01-01

    Aqueous alkaline metal-air batteries represent promising energy storage devices when supplied with atmospheric air. However, under this condition, the air electrode shows a very short life time (i.e. 50 h of operation in 5 M LiOH at -10 mA cm-2), mainly due to the precipitation of carbonates inside the electrode porosity. The air electrode can then be protected by an anion exchange membrane on the electrolyte side. In this paper, we demonstrate that the efficiency of this protective membrane depends on the assembly method on the electrode. When a modified poly(epichlorohydrin) (PECH) network is synthesized directly on the electrode, the polymer seeps inside the electrode porosity, and a suitable interface inducing negligible additional polarization in comparison with classical pressure-assembled membranes is obtained. This protected electrode shows improved stability of up to 160 h of operation in 5 M LiOH. This performance is improved to 350 h by adjusting the conductivity and the ionic exchange capacity. Finally, the interest of interpenetrating polymer network (IPN) architecture compared to a single network is confirmed. Indeed, an electrode protected with a PECH/poly(2-hydroxyethyl methacrylate) (PHEMA) IPN is stable for 650 h in 5 M LiOH. In addition, degradation process becomes reversible since the assembly can be regenerated, which is not possible for the bare electrode.

  19. ELVIS: Multi-Electrolyte Aqueous Activity Model for Geothermal Solutions

    NASA Astrophysics Data System (ADS)

    Hingerl, F. F.; Wagner, T.; Driesner, T.; Kulik, D. A.; Kosakowski, G.

    2011-12-01

    High temperature, pressure, and fluid salinities render geochemical modeling of fluid-rock interactions in Enhanced Geothermal Systems a demanding task. Accurate prediction of fluid-mineral equilibria strongly depends on the availability of thermodynamic data and activity models. Typically, the Pitzer activity model is applied for geothermal fluids. A drawback of this model is the large number of parameters required to account for temperature and pressure dependencies, which significantly reduces computational efficiency of reactive transport simulations. In addition, most available parameterizations are valid only at vapor-saturated conditions. As an alternative we implemented the EUNIQUAC local composition model [2] that needs substantially fewer fitting parameters. However, the current EUNIQUAC model design does not include provision for high temperature (>150°C) applications and lacks a formulation for pressure dependence. Therefore, its application to geothermal conditions requires a re-formulation and re-fitting of the model. We developed a new tool termed GEMSFIT that allows generic fitting of activity models (for aqueous electrolyte and non-electrolyte solutions) and equations of state implemented in our geochemical equilibrium solver GEM-Selektor (http://gems.web.psi.ch). GEMSFIT combines a PostgreSQL database for storing and managing the datasets of experimental measurements and interaction parameters, the parallelized genetic algorithm toolbox of MATLAB° for the parameter fitting, and an interface to the numerical kernel of GEM-Selektor to access activity models and perform chemical equilibrium calculations. Benchmarking of the partly re-parameterized EUNIQUAC model against Pitzer revealed that the former is less accurate, which can result in incorrect predictions of mineral precipitation/dissolution. Consequently, we modified the EUNIQUAC model and concurrently introduced a pressure dependence to be able to fit experimental data over wide ranges of

  20. Method for Non-Invasive Determination of Chemical Properties of Aqueous Solutions

    NASA Technical Reports Server (NTRS)

    Todd, Paul W. (Inventor); Jones, Alan (Inventor); Thomas, Nathan A. (Inventor)

    2016-01-01

    A method for non-invasively determining a chemical property of an aqueous solution is provided. The method provides the steps of providing a colored solute having a light absorbance spectrum and transmitting light through the colored solute at two different wavelengths. The method further provides the steps of measuring light absorbance of the colored solute at the two different transmitted light wavelengths, and comparing the light absorbance of the colored solute at the two different wavelengths to determine a chemical property of an aqueous solution.

  1. 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.

  2. 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.

  3. Ion Association, Solubilities, and Reduction Potentials in Aqueous Solution.

    ERIC Educational Resources Information Center

    Russo, Steven O.; Hanania, George I. H.

    1989-01-01

    Incorporates the combined effects of ionic strength and ion association to show how calculations involving ionic equilibria are carried out. Examines the variability of reduction potential data for two aqueous redox systems. Provides several examples. (MVL)

  4. ELECTROCHEMICAL DECHLORINATION OF 2-CHLOROBIPHENYL IN AQUEOUS SOLUTION

    EPA Science Inventory

    This paper presents electrochemical dechlorination of 2-chlorobiphenyl (2-Cl BP) in aqueous environment using palladium modified granular graphite electrodes. 2-Cl BP, the PCB congener that requires the highest reduction potential, was effectively dechlorinated in electrochemical...

  5. Behaviors of acrylamide/itaconic acid hydrogels in uptake of uranyl ions from aqueous solutions

    SciTech Connect

    Karadag, E.; Saraydin, D.; Gueven, O.

    1995-12-01

    In this study, adsorptions of uranyl ions from two different aqueous uranyl solutions by acrylamide-itaconic acid hydrogels were investigated by a spectroscopic method. The hydrogels were prepared by irradiating with {gamma}-radiation. In the experiment of uranyl ions adsorption, Type II adsorption was found. One gram of acrylamide-itaconic acid hydrogels sorbed 178-219 mg uranyl ions from the solutions of uranyl acetate, 42-76 mg uranyl ions from the aqueous solutions of uranyl nitrate, while acrylamide hydrogel did not sorb any uranyl ion. For the hydrogel containing 40 mg of itaconic acid and irradiated to 3.73 kGy, swelling of the hydrogels was observed in water (1660%), in the aqueous solution of uranyl acetate (730%), and in the aqueous solution of uranyl nitrate (580%). Diffusions of water onto hydrogels were a non-Fickian type of diffusion, whereas diffusions of uranyl ions were a Fickian type of diffusion.

  6. Supercooling and vitrification of aqueous glycerol solutions at normal and high pressures.

    PubMed

    Miyata, K; Hayakawa, S; Kajiwara, K; Kanno, H

    2012-10-01

    The supercooling and vitrification of aqueous glycerol solutions was studied at high pressures. Homogeneous ice nucleation temperatures (T(H)) were obtained for aqueous glycerol solutions of R=50, 30, 20, 12, and 10 (R: moles of water/moles of glycerol) up to 300MPa. The R=20 glycerol solution formed a glass above 200MPa at a cooling rate of 200°C/min, indicating that pressure enhances glass-formation of aqueous glycerol solutions. The (dT(g)/dP) values were obtained for vitrified aqueous glycerol solutions of R=3, 5, 10, and 20. These data can be used for the development of cryo-preservation liquids for living cells at high pressures.

  7. Adsorption of methylene blue dye from aqueous solutions using Eichhornia crassipes.

    PubMed

    Wanyonyi, Wycliffe Chisutia; Onyari, John Mmari; Shiundu, Paul Mwanza

    2013-09-01

    Adsorption of methylene blue (MB) from aqueous solution using dried roots, stems, and leaves of Eichhornia crassipes biomass obtained from Lake Victoria was studied. Batch experimental results revealed that the adsorption process was highly dependent on adsorbent dosage, initial MB concentration, E. crassipes particle size and aqueous solution temperature. The isotherm data fitted Freundlich mathematical models with maximum dye adsorption of 35.37 mg g(-1). Roots adsorbed over 99 % of the MB in <5 min. Sorption kinetics followed a pseudo-second-order model. Results provide evidence that E. crassipes is an effective and inexpensive biomaterial for dye removal from aqueous dye solutions and industrial effluents.

  8. Formation and disappearance of superoxide radicals in aqueous solutions. [79 references

    SciTech Connect

    Allen, A O; Bielski, B H.J.

    1980-01-01

    A literature review of superoxide radicals in aqueous solutions is presented covering the following: history; methods of formation of aqueous HO/sub 2//HO/sub 2//sup -/ by radiolysis and photolysis, electrolysis, mixing nonaqueous solutions into water, chemical reactions, enzymatic generation of O/sub 2//sup -/, and photosensitization; and properties of HO/sub 2//O/sub 2//sup -/ in aqueous solution, which cover spontaneous dismutation rates, pk and absorption spectra, catalyzed dismutation, thermodynamics and the so-called Haber-Weiss Reaction.

  9. Process for recovering chaotropic anions from an aqueous solution also containing other ions

    DOEpatents

    Rogers, R.; Horwitz, E.P.; Bond, A.H.

    1999-03-30

    A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

  10. Process for recovering chaotropic anions from an aqueous solution also containing other ions

    DOEpatents

    Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

    1999-01-01

    A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

  11. New porous titanium–niobium oxide for photocatalytic degradation of bromocresol green dye in aqueous solution

    SciTech Connect

    Chaleshtori, Maryam Zarei; Hosseini, Mahsa; Edalatpour, Roya; Masud, S.M. Sarif; Chianelli, Russell R.

    2013-10-15

    Graphical abstract: The photocatalytic activity of different porous titanium–niobium oxides was evaluated toward degradation of bromocresol green (BG) under UV light. A better catalytic activity was observed for all samples at lower pH. Catalysts have a stronger ability for degradation of BG in acid media than in alkaline media. - Highlights: • Different highly structured titanium–niobium oxides have been prepared using improved methods of synthesis. • Photo-degradation of bromocresol green dye (BG) with nanostructure titanium–niobium oxide catalysts was carried out under UV light. • The photo-catalytic activity of all catalysts was higher in lower pH. • Titanium–niobium oxide catalysts are considerably stable and reusable. - Abstract: In this study, high surface area semiconductors, non porous and porous titanium–niobium oxides derived from KTiNbO{sub 5} were synthesized, characterized and developed for their utility as photocatalysts for decontamination with sunlight. These materials were then used in the photocatalytic degradation of bromocresol green dye (BG) in aqueous solution using UV light and their catalytic activities were evaluated at various pHs. For all catalysts, the photocatalytic degradation of BG was most efficient in acidic solutions. Results show that the new porous oxides have large porous and high surface areas and high catalytic activity. A topotactic dehydration treatment greatly improves catalyst performance at various pHs. Stability and long term activity of porous materials (topo and non-topo) in photocatalysis reactions was also tested. These results suggest that the new materials can be used to efficiently purify contaminated water.

  12. Metallocoenzyme-mediated reductive transformation of carbon tetrachloride in titanium (III) citrate aqueous solution

    SciTech Connect

    Chiu, P.C.; Reinhard, M.

    1995-03-01

    Transformation pathways for carbon tetrachloride (CCl{sub 4}) catalyzed by hematin or vitamin B{sub 12} in aqueous titanium(III) citrate solution are proposed. The reaction of CCl{sub 4} with B{sub 12} was zero order in CCl{sub 4} and first order in B{sub 12}, and the rate constant was measured from pH 7.3 to pH 10.3. The proposed rate-limiting step is the reduction of the stable trichloromethylcobalamin (CCl{sub 3}-Cbl) intermediate by titanium(III) citrate at alkaline pH and the sterically induced CCl{sub 3}-Cbl decomposition at neutral pH. The reaction kinetics can be described by a modified Michaelis-Menten model in the saturated regime. With hematin, only the pseudo-first-order rate constant was determined due to the significant deactivation of the coenzyme. The turnover number of hematin (molecules of CCl{sub 4} transformed/molecule of hematin deactivated) was 27 at pH 8.0 and 42 at pH 9.9. Vitamin B{sub 12} was a more stable and more effective catalyst (on a molar basis) than hematin with respect to CCl{sub 4}. Chloroform (CHCl{sub 3}) was the primary product in titanium(III) citrate solution, and the yield was a function of pH, Ti(III) concentration, and organic content regardless of whether a coenzyme was present or which coenzyme was used. Although B{sub 12} and hematin can both enhance the CCl{sub 4} transformation rate, they have little effect on the CHCl{sub 3} yield. Titanium(III) citrate, on the other hand, controls not only the transformation rate but also CHCl{sub 3} formation. 77 refs., 10 figs.

  13. 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

  14. Conformational properties of branched RNA fragments in aqueous solution

    SciTech Connect

    Damha, M.J.; Ogilvie, K.K.

    1988-08-23

    The conformational properties of branched trinucleoside diphosphates A/sub C//sup C/, A/sub G//sup C/, A/sub C//sup G/, A/sub G//sup G/, A/sub U//sup U/, A/sub U//sup G/, A/sub G//sup U/, A/sub T//sup T/, G/sub U//sup U/, and aA/sub U/sup U/ (X/sub Z//sup Y/ = X(2'p5'Y)3'p5'Z) have been studied in aqueous solution by nuclear magnetic resonance (/sup 1/H, /sup 13/C), ultraviolet absorption, and circular dichroism. It is concluded from these studies that the purine ring of the central residue (X; e.g., adenosine) forms a base-base stack exclusively with the purine or pyrimidine ring of the 2'-nucleotidyl unit (Y; 2'-residue). The residue attached to the central nucleoside via the 3'-5'-linkage (Z; 3'-residue) is free from the influence of the other two heterocyclic rings. The ribose rings of the central nucleoside and the 2'- and 3'-residues exist as equilibrium mixtures of C2'-endo (/sup 2/E)-C3'-endo (/sup 3/E) conformers. The furanose ring of the central nucleoside (e.g., A) when linked to a pyrimidine nucleoside via the 2'-5'-linkage shows a higher preference for the /sup 2/E pucker conformation than those linked to a guanosine nucleoside through the same type of bond. This indicates some correlation between nucleotide sequence and ribose conformational equilibrium. Conformational properties were quantitatively evaluated for most of the bonds in the branched trinucleotides A/sub U//sup U/ and A/sub G//sup G/ by analysis of /sup 1/H-/sup 1/H, /sup 1/H-/sup 31/P, and /sup 13/C-/sup 31/P coupling constants. The conformational features of A/sub U//sup U/ and A/sub G//sup G/ were compared to those of their constitutive dimers A3'p5'G, A2'p5'G, A3'p5'U, and A2'p5'U and monomers 5'pG and 5'pU.

  15. Microevaporators with accumulators for the screening of phase diagrams of aqueous solutions

    NASA Astrophysics Data System (ADS)

    Moreau, P.; Dehmoune, J.; Salmon, J.-B.; Leng, J.

    2009-07-01

    We design near-autonomous microfluidic devices for concentrating aqueous solutions steadily over days in a very controlled manner. We combine suction pumps that drive the solution and concentrate it steadily, with a nanoliter-sized storage pool where the solute accumulates. The fine balance between advection and diffusion in the pump and diffusion alone in the accumulation pool yields several filling regimes. One of them is universal as being steady and independent of the solute itself. It results a specific equivalence between time and concentration, which we use to build the phase quantitative diagram of a ternary aqueous solution on nanoliter scale.

  16. Investigation of the colloidal Cr2O3 removal possibilities from aqueous solution using the ionic polyamino acid block copolymers.

    PubMed

    Ostolska, Iwona; Wiśniewska, Małgorzata

    2015-06-15

    Disposal of the environmentally dangerous metal oxide suspensions from the waste water is an essential problem. The polymers adsorption can be one of the most effective and suitable methods. In the presented paper the ionic diblock copolymers impact on the Cr2O3 suspensions was investigated. The copolymer adsorption layers structure was determined on the basis of the adsorption and electrokinetic (surface charge density and zeta potential) tests. The polymers adsorption amount was measured using the static method from aqueous solutions. Additionally, the application of the turbidimetric method enabled determination of the interactions between the system constituents. Analysis of this data allows the estimation of the most probable stabilization (or destabilization) mechanism of the Cr2O3 suspensions in the presence of the studied macromolecular compounds. Hence, the Cr2O3 suspensions are unstable in the presence of the anionic copolymer at pH 3 and the cationic one in the alkaline medium. PMID:25746566

  17. 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.

  18. 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.

  19. Paul trapping of charged particles in aqueous solution

    PubMed Central

    Guan, Weihua; Joseph, Sony; Park, Jae Hyun; Krstić, Predrag S.; Reed, Mark A.

    2011-01-01

    We experimentally demonstrate the feasibility of an aqueous Paul trap using a proof-of-principle planar device. Radio frequency voltages are used to generate an alternating focusing/defocusing potential well in two orthogonal directions. Individual charged particles are dynamically confined into nanometer scale in space. Compared with conventional Paul traps working in frictionless vacuum, the aqueous environment associated with damping forces and thermally induced fluctuations (Brownian noise) exerts a fundamental influence on the underlying physics. We investigate the impact of these two effects on the confining dynamics, with the aim to reduce the rms value of the positional fluctuations. We find that the rms fluctuations can be modulated by adjusting the voltages and frequencies. This technique provides an alternative for the localization and control of charged particles in an aqueous environment. PMID:21606331

  20. Paul trapping of charged particles in aqueous solution.

    PubMed

    Guan, Weihua; Joseph, Sony; Park, Jae Hyun; Krstic, Predrag S; Reed, Mark A

    2011-06-01

    We experimentally demonstrate the feasibility of an aqueous Paul trap using a proof-of-principle planar device. Radio frequency voltages are used to generate an alternating focusing/defocusing potential well in two orthogonal directions. Individual charged particles are dynamically confined into nanometer scale in space. Compared with conventional Paul traps working in frictionless vacuum, the aqueous environment associated with damping forces and thermally induced fluctuations (Brownian noise) exerts a fundamental influence on the underlying physics. We investigate the impact of these two effects on the confining dynamics, with the aim to reduce the rms value of the positional fluctuations. We find that the rms fluctuations can be modulated by adjusting the voltages and frequencies. This technique provides an alternative for the localization and control of charged particles in an aqueous environment.

  1. Surface Charge and Hydrophobicity of Endospores of Bacillus anthracis and Related Species in Aqueous Solution

    EPA Science Inventory

    The surface properties of microorganisms play an important role in attachment and detachment in the environment. The change in surface charge can effect coagulation, disinfection, adhesion to surfaces, uptake of chemicals, and environmental transport. In aqueous solution, cell s...

  2. Infrared and Raman spectroscopical studies of salicylic and salicylate derivatives in aqueous solution

    NASA Astrophysics Data System (ADS)

    Humbert, B.; Alnot, M.; Quilès, F.

    1998-03-01

    The assignment of vibrations of salicylic acid, salicylate monoanion and salicylate bianion in aqueous solution are discussed with the help of Raman spectroscopy, of attenuated total reflection infrared spectroscopy and of the computational density functional theory (DFT) approach.

  3. Thermodynamics of the complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mudarisova, R. Kh.; Badykova, L. A.

    2016-03-01

    The thermodynamics of complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions is studied by means spectroscopy. The standard thermodynamic characteristics (Δ H°; Δ G°; Δ S°) of complexation are calculated.

  4. Removal of polychlorinated biphenyls from aqueous solutions using beta-cyclodextrin grafted multiwalled carbon nanotubes.

    PubMed

    Shao, Dadong; Sheng, Guodong; Chen, Changlun; Wang, Xiangke; Nagatsu, Masaaki

    2010-04-01

    Cyclodextrins have excellent ability in the preconcentration of organic pollutants from aqueous solutions by forming inclusion complexes. Multiwalled carbon nanotubes (MWCNTs) possess high adsorption capacity in the removal of organic pollutants through the formation of conjugated complexes. In this paper, beta-cyclodextrin (beta-CD) was grafted on the surfaces of MWCNTs by using plasma technique. The beta-CD grafted MWCNTs (MWCNT-g-CD) were characterized by using Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermo gravimetric analysis-differential thermal analysis, and scanning electron microscopy in detail. The prepared MWCNT-g-CD were used to remove polychlorinated biphenyls (PCBs) from aqueous solutions under ambient conditions. The results suggest that MWCNT-g-CD have much higher adsorption capacity than MWCNTs in the removal of PCBs from aqueous solutions. MWCNT-g-CD are suitable materials in the preconcentration and immobilization of PCBs from large volumes of aqueous solutions in environmental pollution cleanup.

  5. Method and apparatus for measuring volatile compounds in an aqueous solution

    DOEpatents

    Gilmore, Tyler J [Pasco, WA; Cantrell, Kirk J [West Richland, WA

    2002-07-16

    The present invention is an improvement to the method and apparatus for measuring volatile compounds in an aqueous solution. The apparatus is a chamber with sides and two ends, where the first end is closed. The chamber contains a solution volume of the aqueous solution and a gas that is trapped within the first end of the chamber above the solution volume. The gas defines a head space within the chamber above the solution volume. The chamber may also be a cup with the second end. open and facing down and submerged in the aqueous solution so that the gas defines the head space within the cup above the solution volume. The cup can also be entirely submerged in the aqueous solution. The second end of the. chamber may be closed such that the chamber can be used while resting on a flat surface such as a bench. The improvement is a sparger for mixing the gas with the solution volume. The sparger can be a rotating element such as a propeller on a shaft or a cavitating impeller. The sparger can also be a pump and nozzle where the pump is a liquid pump and the nozzle is a liquid spray nozzle open, to the head space for spraying the solution volume into the head space of gas. The pump could also be a gas pump and the nozzle a gas nozzle submerged in the solution volume for spraying the head space gas into the solution volume.

  6. Theoretical prediction of phase relations among aqueous solutions and minerals: Salton Sea geothermal system

    NASA Astrophysics Data System (ADS)

    Bird, Dennis K.; Norton, Denis L.

    1981-09-01

    Thermodynamic calculations of compositional relations among aqueous solutions and minerals in the system Na2O-K2O-CaO-MgO-Fe2O3 Al2O3-SiO2-H2O-CO2 HCl at pressures and temperatures corresponding to liquid-vapor equilibrium of H2O permit quantitative description and interpretation of phase relations among rock forming minerals and aqueous solutions in magma-hydrothermal systems. The extensive data base on the Salton Sea geothermal system provides an exemplary case for predicting the chemical characteristics of geothermal fluids associated with metasomatic mineral zones observed in deep drillhole samples. Near the Elmore No. 1 well aqueous species activity ratios of {aNa+}/{aH+} and {aK+}/{aH+} vary several tenths of a log unit with increasing depth and temperature from ∼ 0.6 km and ∼250°C to ∼ 2.2 km and ∼350°C, whereas {aCa2+}/{a2H+} decreases ∼ 2 orders of magnitude for a comparable range in depth and temperature. The fugacity of CO2 gas is ∼1.5-6 bars at ≲ 310°C. Calculated values of aSio2(aq), {aNa+}/{aK+}, {aCa2+}/{aMg2+} and fCO2(g), in the fluid phase coexisting with observed mineralogic phase relations are in remarkably close agreement with measured solute concentrations in geothermal fluids produced from deep drillholes near the Salton Sea. Hydrolysis reactions representing observed phase relations and written with alkali and alkaline earth cations as products have negative standard molal enthalpies (ΔH0P,T,r) and volumes (ΔV0P,T,r) of reactions; consequently, {aNa+}/{aH+}, {aK+}/{aH+}, {aCa2+}/{a2H+}, and {aMg2+}/{a2H+} decrease with increasing temperature at constant pressure, but increase with increasing pressure at constant temperature. An approximate linear relationship exists among these activity ratios and the reciprocal of absolute temperatures because ΔH0P,T,r varies only slightly with increasing temperature at ≲ 250 to 300°C. However, at ≳300°C, ΔH0P,T,r and ΔV0P,T,R decrease dramatically as a consequence of extrema in

  7. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

    NASA Astrophysics Data System (ADS)

    Kanno, H.; Kajiwara, K.; Miyata, K.

    2010-05-01

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  8. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

    PubMed

    Kanno, H; Kajiwara, K; Miyata, K

    2010-05-21

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (Rsolutions of R=10 and 12 indicates that the two phase-separated components in the DMSO solution of R=10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  9. Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Eckert, S.; Miedema, P. S.; Quevedo, W.; O'Cinneide, B.; Fondell, M.; Beye, M.; Pietzsch, A.; Ross, M.; Khalil, M.; Föhlisch, A.

    2016-03-01

    The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms.

  10. Sugar interaction with metals in aqueous solution: indirect determination from infrared and direct determination from nuclear magnetic resonance spectroscopy.

    PubMed

    Rondeau, Philippe; Sers, Sandrine; Jhurry, Dhanjay; Cadet, Frederic

    2003-04-01

    In this article, mid-infrared Fourier transform (Mid-FT-IR) and carbon thirteen nuclear magnetic resonance (13C NMR) spectroscopy have been used to determine possible interactions between sucrose and various alkali or alkaline earth metals in aqueous solution. In the presence of these metals, significant shifts in the absorption bands of sucrose were noted by mid-FT-IR coupled with principal component analysis (PCA). These shifts were explained on the basis of weakening of the H-bond network between sucrose and water and possible interactions between sucrose and the metal ion. Factorial maps were established and the spectral patterns obtained show that these interactions vary according to the nature of the metal ion. 13C NMR analysis showed that the carbon atoms of sucrose undergo shielding or deshielding in the presence of metal ions in aqueous solutions. Two factors were invoked to account for the variation of chemical shifts: the rupture of hydrogen bonds due to hydration of the metal ion and the possible coordination of the metal ion to the oxygen atoms of sucrose. PMID:14658645

  11. The solubility of Ag sub 2 S in near-neutral aqueous sulfide solutions at 25 to 300 degree C

    SciTech Connect

    Gammons, C.H.; Barnes, H.L. )

    1989-02-01

    The solubility of Ag{sub 2}S (acanthite/argentite) was measured in vapor-saturated aqueous sulfide solutions at 25-300{degree}C, total sulfide = 0.2-1.4 m, and pH{sub 25{degree}} = 5.8-7.3. Although Seward (1976) has shown that considerable silver can be dissolved as chloride complexes, the authors data indicate that Ag(HS){sup {minus}}{sub 2} is the dominant silver species in hydrothermal fluids with near-neutral to alkaline pH, relatively low oxidation state, high total sulfide, and T < 300{degree}C (e.g., Broadlands, N.Z.; Brown, 1986). Silver transported as Ag(HS){sup {minus}}{sub 2} is precipitated in response to a decrease in aqueous sulfide concentration, a change in pH away from the pK{sub 1} for H{sub 2}S or, in the native silver field, a decrease in oxidation state. Cooling is a less important depositional mechanism, particularly for solutions whose pH is buffered by feldspar alteration reactions.

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

    USGS Publications Warehouse

    Zielinski, Robert A.

    1977-01-01

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

  13. 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.

  14. Interaction between bacteriophage and pyrophyllite clay in aqueous solution

    NASA Astrophysics Data System (ADS)

    Park, Jeong-Ann; Kim, Jae-Hyun; Kang, Jin-Kyu; Son, Jeong-Woo; Yi, In-Geol; Kim, Song-Bae

    2014-05-01

    Viral contamination results in a degradation in drinking water quality and a threat to public health. Toprovide safe drinking water, water treatment alternatives using various adsorbents and filter media such as activated carbon, bituminous coal, quartz sand and clay have been considered. Pyrophyllite is a 2:1 clay mineral having dioctahedral layer structure with octahedrally coordinated Al ion sheets between two sheets of SiO4 tetrahedra. It is a hydrous aluminosilicate clay with the chemical composition AlSi2O5(OH). Pyrophyllite has recently been investigated as a potential low-cost and environmental friendly adsorbent for removing various contaminants. The aim of this study was to investigate the removal of the bacteriophage MS2 from aqueous solution using pyrophyllite. Batch experiments were conducted to examine the MS2 sorption to pyrophyllite. The influence of fluoride, a groundwater contaminant, on the removal of MS2 was also observed. Batch results demonstrated that pyrophyllite was effective in MS2 removal. The percent removal increased from 5.26% to 99.99% (= 4.0 log removal) as the pyrophyllite concentrations increased from 0.2 to 20 g/L. More than 99% of MS2 could be removed with a pyrophyllite concentration of ≥ 4 g/L. The sorption of MS2 to pyrophyllite was rapid. Within 15 min, approximately 99.98% (= 3.7 log removal) of MS2 was attained. More than 4.0 log removal was achieved after 180 min. The experimental data were analyzed with the pseudo first-order and pseudo second-order kinetic models. The correlation coefficient showed that pseudo second-order model was better than pseudo first-order model at describing the kinetic data. The amount of MS2 removed at equilibrium was determined to be 1.43 × 108 pfu/g from the pseudo second-order model. The experimental data were also analyzed with the Freundlich and Langmuir isotherm models. The correlation coefficients showed that the Langmuir model was more suitable than the Freundlich model for MS2

  15. Determination of the stability of dopamine in aqueous solutions by high performance liquid chromatography

    SciTech Connect

    Shen, Y. . Dept. of Veterinary Physiology and Pharmacology); Ye, M.Y. . Dept. of Biology and Chemistry ManTech Environmental Technology, Inc., Ada, OK )

    1994-01-01

    Methods for the analysis of dopamine and its degradation products in aqueous solutions are described. The technique of reverse phase chromatography with electrochemical detection is used to investigate the stability of dopamine in various aqueous solutions. In neutral and basic solutions, dopamine is rapidly oxidized by dissolved oxygen to form degradation products. The results demonstrate that dopamine is stable in 0.1 N HCl solution, pH < 1. The study indicates that EDTA can slow down the oxidation process. The detection limit for the analysis of dopamine is 0.1 [mu]M with 100 [mu]l injection.

  16. Reusable nanocomposite of CoFe2O4/chitosan-graft-poly(acrylic acid) for removal of Ni(II) from aqueous solution

    NASA Astrophysics Data System (ADS)

    Nguyen, Van Cuong; Huynh, Thi Kim Ngoc

    2014-06-01

    In this paper, CoFe2O4/chitosan-graft-poly(acrylic acid) (CoFe2O4/CS-graft-PAA) nanocomposites were prepared successfully by coprecipitation of the compounds in alkaline solution and were used for removal of nickel (II) ions from aqueous solution. The sorption rate was affected significantly by the initial concentration of the solution, sorbent amount, and pH value of the solution. Batch experiments were conducted to investigate the adsorption capacity under different initial concentration (ranging from 25 to 150 mg L-1), solution pH (4.1, 5.3, 6.4 and 7.6), and contact time. These nanocomposites can be recycled conveniently from water with the assistance of an external magnet because of their exceptional properties. The prepared nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), x-ray powder diffraction (XRD), and thermogravimetric analysis (TGA).

  17. 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

  18. Aspheric Solute Ions Modulate Gold Nanoparticle Interactions in an Aqueous Solution: An Optimal Way To Reversibly Concentrate Functionalized Nanoparticles.

    PubMed

    Villarreal, Oscar D; Chen, Liao Y; Whetten, Robert L; Demeler, Borries

    2015-12-17

    Nanometer-sized gold particles (AuNPs) are of peculiar interest because their behaviors in an aqueous solution are sensitive to changes in environmental factors including the size and shape of the solute ions. In order to determine these important characteristics, we performed all-atom molecular dynamics simulations on the icosahedral Au144 nanoparticles each coated with a homogeneous set of 60 thiolates (4-mercaptobenzoate, pMBA) in eight aqueous solutions having ions of varying sizes and shapes (Na(+), K(+), tetramethylamonium cation TMA(+), tris-ammonium cation TRS(+), Cl(-), and OH(-)). For each solution, we computed the reversible work (potential of mean of force) to bring two nanoparticles together as a function of their separation distance. We found that the behavior of pMBA protected Au144 nanoparticles can be readily modulated by tuning their aqueous environmental factors (pH and solute ion combinations). We examined the atomistic details on how the sizes and shapes of solute ions quantitatively factor in the definitive characteristics of nanoparticle-environment and nanoparticle-nanoparticle interactions. We predict that tuning the concentrations of nonspherical composite ions such as TRS(+) in an aqueous solution of AuNPs be an effective means to modulate the aggregation propensity desired in biomedical and other applications of small charged nanoparticles.

  19. Modeling reactive geochemical transport of concentrated aqueous solutions in variably saturated media

    SciTech Connect

    Zhang, Guoxiang; Zheng, Zuoping; Wan, Jiamin

    2004-01-28

    Concentrated aqueous solutions (CAS) have unique thermodynamic and physical properties. Chemical components in CAS are incompletely dissociated, especially those containing divalent or polyvalent ions. The problem is further complicated by the interaction between CAS flow processes and the naturally heterogeneous sediments. As the CAS migrates through the porous media, the composition may be altered subject to fluid-rock interactions. To effectively model reactive transport of CAS, we must take into account ion-interaction. A combination of the Pitzer ion-interaction and the ion-association model would be an appropriate way to deal with multiple-component systems if the Pitzer' parameters and thermodynamic data of dissolved components and the related minerals are available. To quantify the complicated coupling of CAS flow and transport, as well as the involved chemical reactions in natural and engineered systems, we have substantially extended an existing reactive biogeochemical transport code, BIO-CORE{sup 2D}{copyright}, by incorporating a comprehensive Pitzer ion-interaction model. In the present paper, the model, and two test cases against measured data were briefly introduced. Finally we present an application to simulate a laboratory column experiment studying the leakage of the high alkaline waste fluid stored in Hanford (a site of the U.S. Department of Energy, located in Washington State, USA). With the Pitzer ion-interaction ionic activity model, our simulation captures measured pH evolution. The simulation indicates that all the reactions controlling the pH evolution, including cation exchanges, mineral precipitation and dissolution, are coupled.

  20. Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

    SciTech Connect

    Glynn, P.D.; Plummer, L.N.; Busenberg, E. ); Reardon, E.J. )

    1990-02-01

    Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO{sub 4} and (Sr, Ca)CO{sub 3orth.} solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO{sub 3orth.} solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallization experiments in the highly soluble KCl-KBr-H{sub 2}O system demonstrate equilibrium. The phase diagram reveals an alyotropic maximum located at {chi}{sub KBr} = 0.676 and at a total solubility product, {Sigma}II = (K{sup +})((Cl{sup {minus}}) + (Br{sup {minus}})) = 15.35.

  1. Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

    2016-09-01

    Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

  2. Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration.

    PubMed

    Luna, Airton J; Chiavone-Filho, Osvaldo; Machulek, Amilcar; de Moraes, José Ermírio F; Nascimento, Cláudio A O

    2012-11-30

    A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe(2+) ([Fe(2+)](0)) from 1.0 up to 2.5 mM, the rate in mmol of H(2)O(2) fed into the system (FH(2)O(2);in) from 3.67 up to 7.33 mmol of H(2)O(2)/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes.

  3. 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%.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Method for gettering organic, inorganic and elemental iodine in aqueous solutions

    DOEpatents

    Beahm, Edward C.; Shockley, William E.

    1990-07-03

    A process for the removal of iodine from aqueous solutions, particularly the trapping of radioactive iodine to mitigate damage resulting from accidents or spills associated with nuclear reactors, by exposing the solution to well dispersed silver carbonate which reacts with the iodine and iodides, thereby gettering iodine and iodine compounds from solution. The iodine is not only removed from solution but also from the contiguous vapor.

  9. Method for gettering organic, inorganic and elemental iodine in aqueous solutions

    DOEpatents

    Beahm, Edward C.; Shockley, William E.

    1990-01-01

    A process for the removal of iodine from aqueous solutions, particularly the trapping of radioactive iodine to mitigate damage resulting from accidents or spills associated with nuclear reactors, by exposing the solution to well dispersed silver carbonate which reacts with the iodine and iodides, thereby gettering iodine and iodine compounds from solution. The iodine is not only removed from solution but also from the contiguous vapor.

  10. Rapid hydrolysis of model phosphate diesters by alkaline-earth cations in aqueous DMSO: speciation and kinetics.

    PubMed

    Taran, Olga; Medrano, Felipe; Yatsimirsky, Anatoly K

    2008-12-14

    Kinetics of the cleavage of two phosphate diesters, bis(4-nitrophenyl) phosphate and 2-hydroxypropyl 4-nitrophenyl phosphate and a triester, 4-nitrophenyl diphenyl phosphate, in the presence of Mg(II), Ca(II) and Sr(II) were studied in 90% vol. DMSO at 37 degrees C. The alkaline hydrolysis of the triester was inhibited by all cations, but with both phosphodiesters strong catalytic effects were observed. Potentiometric titrations of metal perchlorates by Bu4N(OH) revealed formation of M2(OH)3+, M(OH)+, M(OH)2 and M2(OH)5- species. Rate constants for phosphodiester cleavage by individual species were obtained from analysis of rate-concentration profiles. Observed first-order rate constants in the presence of 1-2 mM Mg(II) or Ca(II) in neutral and weakly basic solutions were 10(8)-10(11) times higher than those for background hydrolysis at the same pH while in water additions of up to 50 mM metal produced <100-fold accelerations. Possible structures of DMSO solvated catalyst-substrate complexes were modeled by DFT calculations with Mg(II). The increased catalytic activity in 90% DMSO is attributed to stronger association of hydroxide ions and anionic phosphodiesters with metal ions and to preferable solvation of cations by DMSO, which creates favorable for reaction anhydrous microenvironment in the coordination sphere of the catalyst.

  11. Alkaline electrochemical cells and method of making

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1970-01-01

    Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

  12. RECOVERY OF URANIUM AND THORIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Calkins, G.D.

    1958-06-10

    >A process is described for the recovery of uranium and thorium from monazite sand, which is frequently processed by treating it with a hot sodium hydroxide solution whereby a precipitate forms consisting mainly of oxides or hydroxides of the rare earths, thorium and uranium. The precipitate is dissolved in mineral acid, and the acid solution is then neutralized to a pH value of between 5.2 and 6.2 whereby both the uranium and thorium precipitate as the hydroxides, while substantially all the rare earth metal values present remain in the solution. The uranium and thoriunn can then be separated by dissolving the precipitate in a solution containing a mixture of alkali carbonate and alkali bicarbonate: and contacting the carbonate solution with a strong-base anion exchange resin whereby the uranium values are adsorbed on the resin while the thorium remains in solution.

  13. Densities of Sodium Tetrafluoroborate Aqueous Solutions at 20 Degrees C

    SciTech Connect

    Crooks, W.J. III

    2002-07-09

    Analytical data and plant solution compositions are often reported in molarity units. Densities of salt solutions are needed to convert the concentrations to molal basis in order to utilize physical property data that have been established on a molal basis, for example, solution reaction equilibrium constants or activity coefficients. We report here the densities at 20.0 Degrees C of sodium tetrafluoroborate (NaBF4) solutions from 0.05 molal to 9.0 molal, near saturation of 9.2 molal.

  14. Experimental determination of the temperature dependence of water activities for a selection of aqueous organic solutions

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Stratmann, G.; Peter, T.

    2014-09-01

    This work presents experimental data of the temperature dependence of water activity in aqueous organic solutions relevant for tropospheric conditions (200-273 K). Water activity (aw) at low temperatures (T) is a crucial parameter for predicting homogeneous ice nucleation. We investigated temperature-dependent water activities, ice freezing and melting temperatures of solutions, and vapour pressures of a selection of atmospherically relevant aqueous organic systems. To measure aw over a wide composition range and with a focus on low temperatures, we use various aw measurement techniques and instruments: a dew point water activity meter, an electrodynamic balance (EDB), differential scanning calorimetry (DSC), and a setup to measure the total gas phase pressure at equilibrium over aqueous solutions. Water activity measurements were performed for aqueous multicomponent and multifunctional organic mixtures containing the functional groups typically found in atmospheric organic aerosols, such as hydroxyl, carboxyl, ketone, ether, ester, and aromatic groups. The aqueous organic systems studied at several fixed compositions over a considerable temperature range differ significantly in their temperature dependence. Aqueous organic systems of 1,4-butanediol and methoxyacetic acid show a moderate decrease in aw with decreasing temperature. The aqueous M5 system (a multicomponent system containing five different dicarboxylic acids) and aqueous 2-(2-ethoxyethoxy)ethanol solutions both show a strong increase of water activity with decreasing temperature at high solute concentrations for T < 270 K and T < 260 K, respectively. These measurements show that the temperature trend of aw can be reversed at low temperatures and that linear extrapolations of high-temperature data may lead to erroneous predictions. To avoid this, experimentally determined aw at low temperature are needed to improve thermodynamic models towards lower temperatures and for improved predictions of the ice

  15. Experimental determination of the temperature dependence of water activities for a selection of aqueous organic solutions

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Stratmann, G.; Peter, T.

    2014-05-01

    This work presents experimental data of the temperature dependence of water activity in aqueous organic solutions relevant for tropospheric conditions (200-273 K). Water activity (aw) at low temperatures (T) is a crucial parameter for predicting homogeneous ice nucleation. We investigated temperature dependent water activities, ice freezing and melting temperatures of solutions, and vapour pressures of a selection of atmospherically relevant aqueous organic systems. To measure aw over a wide composition range and with a focus on low temperatures, we use various aw measurement techniques and instruments: a dew point water activity meter, an electrodynamic balance (EDB), differential scanning calorimetry (DSC), and a setup to measure the total gas phase pressure at equilibrium over aqueous solutions. Water activity measurements were performed for aqueous multicomponent and multifunctional organic mixtures containing the functional groups typically found in atmospheric organic aerosols, such as hydroxyl, carboxyl, ketone, ether, ester, and aromatic groups. The aqueous organic systems studied at several fixed compositions over a considerable temperature range differ significantly in their temperature dependence. Aqueous organic systems of 1,4-butanediol and methoxyacetic acid show a moderate decrease in aw with decreasing temperature. The aqueous M5 system (a multicomponent system containing five different dicarboxylic acids) and aqueous 2-(2-ethoxyethoxy)ethanol solutions both show a strong increase of water activity with decreasing temperature at high solute concentrations for T<270 K and T<260 K, respectively. These measurements show that the temperature trend of aw can be reversed at low temperatures and that linear extrapolations of high temperature data may lead to erroneous predictions. To avoid this, experimentally determined aw at low temperature are needed to improve thermodynamic models towards lower temperatures and for improved predictions of the ice

  16. Purification of aqueous plutonium chloride solutions via precipitation and washing.

    SciTech Connect

    Stroud, M. A.; Salazar, R. R.; Abney, Kent David; Bluhm, E. A.; Danis, J. A.

    2003-01-01

    Pyrochemical operations at Los Alamos Plutonium Facility (TA-55) use high temperature melt s of calcium chloride for the reduction of plutonium oxide to plutonium metal and hi gh temperature combined melts of sodium chloride and potassium chloride mixtures for the electrorefining purification of plutonium metal . The remaining plutonium and americium are recovered from thes e salts by dissolution in concentrated hydrochloric acid followed by either solvent extraction or io n exchange for isolation and ultimately converted to oxide after precipitation with oxalic acid . Figur e 1 illustrates the current aqueous chloride flow sheet used for plutonium processing at TA-55 .

  17. SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

    DOEpatents

    Van Winkle, Q.; Kraus, K.A.

    1959-10-27

    A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

  18. Stable aqueous colloidal solutions of intact surfactant-free graphene nanoribbons and related graphitic nanostructures.

    PubMed

    Dimiev, Ayrat M; Gizzatov, Ayrat; Wilson, Lon J; Tour, James M

    2013-04-01

    Here we demonstrate a simple, nondestructive method for the preparation of stable aqueous colloidal solutions of graphene nanoribbons and carbon nanotubes. The method includes sonication of carbon nanomaterials in hypophosphorous acid, filtration accompanied by washing the solids with water and dispersion of the solids in a fresh portion of water to form colloidal solutions.

  19. MODELING SMALL-SCALE SPILLS OF AQUEOUS SOLUTIONS IN THE INDOOR ENVIRONMENT

    EPA Science Inventory

    A mass transfer model is proposed to estimate the rates of chemical emissions from aqueous solutions spilled on hard surfaces inside buildings. The model is presented in two forms: a set of four ordinary differential equations and a simplified exact solution. The latter can be ...

  20. Stable aqueous colloidal solutions of intact surfactant-free graphene nanoribbons and related graphitic nanostructures.

    PubMed

    Dimiev, Ayrat M; Gizzatov, Ayrat; Wilson, Lon J; Tour, James M

    2013-04-01

    Here we demonstrate a simple, nondestructive method for the preparation of stable aqueous colloidal solutions of graphene nanoribbons and carbon nanotubes. The method includes sonication of carbon nanomaterials in hypophosphorous acid, filtration accompanied by washing the solids with water and dispersion of the solids in a fresh portion of water to form colloidal solutions. PMID:23435853

  1. A computer simulation study of the separation of aqueous solutions using thin zeolite membranes

    NASA Astrophysics Data System (ADS)

    Lin, J.; Murad, S.

    2001-07-01

    A recently developed molecular simulation scheme for studying solutions undergoing osmosis and reverse osmosis was used to study the separation of aqueous solutions using thin zeolite membranes. This method allows for the preservation of the atomic roughness of the membranes, while the molecules that constitute the membranes are also allowed to vibrate. In the simulations, two thin membranes cut from a cubic cell of ZK-4 zeolite were used as the semi-permeable membranes to separate water from aqueous NaCl solutions. Both osmosis and reverse-osmosis phenomena were observed. The study showed that ZK-4 zeolite membranes show promise for use in membrane-based separation of aqueous electrolyte solutions, as well as other similar systems.

  2. Morphological modifications of selenium by recrystallization of its aqueous complex solutions.

    PubMed

    Batabyal, Sudip K; Basu, C; Das, A R; Sanyal, G S

    2006-07-01

    Recrystallization of elemental selenium (Se) from aqueous solution in presence of sodium sulphite (Na2SO3) and sodium sulphide (Na2S) acting as complexing agents has resulted in the formation of nano and microstructures of Se having five different morphological modifications. (1) An aqueous solution of sodium selenosulphate (Na2SO3Se) obtained by dissolving Se in Na2SO3 under refluxing condition yields hemispherical microcrystals. (2) The filtrate of the above reaction mixture on aging produces hexagonal prismatic microrods of Se. Addition of Na2SO3Se solution to formalin (HCHO) at room temperature and refluxing conditions generates (3) Se nanorods, and (4) spherical microcrystals, respectively. (5) Recrystallization of Se from aqueous solution of Na2S develops flower shaped microcrystals.

  3. Comparison of cytotoxicity in vitro and irritation in vivo for aqueous and oily solutions of surfactants.

    PubMed

    Czajkowska-Kośnik, Anna; Wolska, Eliza; Chorążewicz, Juliusz; Sznitowska, Małgorzata

    2015-01-01

    The in vivo model on rabbit eyes and the in vitro cytotoxicity on fibroblasts were used to compare irritation effect of aqueous and oily (Miglyol 812) solutions of surfactants. Tween 20, Tween 80 and Cremophor EL were tested in different concentrations (0.1, 1 or 5%) and the in vitro test demonstrated that surfactants in oil are less cytotoxic than in aqueous solutions. In the in vivo study, the aqueous solutions of surfactants were characterized as non-irritant while small changes in conjunctiva were observed after application the oily solutions of surfactants and the preparations were classified as slightly irritant, however this effect was similar when Miglyol was applied alone. In conclusion, it is reported that the MTT assay does not correlate well with the Draize scores.

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

    DOE PAGES

    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

  5. Near infrared photochemistry of pyruvic acid in aqueous solution.

    PubMed

    Larsen, Molly C; Vaida, Veronica

    2012-06-21

    Recent experimental and theoretical results have suggested that organic acids such as pyruvic acid, can be photolyzed in the ground electronic state by the excitation of the OH stretch vibrational overtone. These overtones absorb in the near-infrared and visible regions of the spectrum where the solar photons are plentiful and could provide a reaction pathway for the organic acids and alcohols that are abundant in the earth's atmosphere. In this paper the overtone initiated photochemistry of aqueous pyruvic acid is investigated by monitoring the evolution of carbon dioxide. In these experiments CO(2) is being produced by excitation in the near-infrared, between 850 nm and ∼1150 nm (11,765-8696 cm(-1)), where the second OH vibrational overtone (Δν = 3) of pyruvic acid is expected to absorb. These findings show not only that the overtone initiated photochemical decarboxylation reaction occurs but also that in the aqueous phase it occurs at a lower energy than was predicted for the overtone initiated reaction of pyruvic acid in the gas phase (13,380 cm(-1)). A quantum yield of (3.5 ± 1.0) × 10(-4) is estimated, suggesting that although this process does occur, it does so with a very low efficiency.

  6. 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

  7. Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

    USGS Publications Warehouse

    Glynn, P.D.; Reardon, E.J.; Plummer, L.N.; Busenberg, E.

    1990-01-01

    Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

  8. 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.

  9. 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.

  10. 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.

  11. Removal of aqueous rinsable flux residues in a batch spray dishwater

    SciTech Connect

    Slanina, J.T.

    1992-02-01

    An alkaline detergent solution used in an industrial dishwasher was evaluated to remove aqueous rinsable flux residues on printed wiring boards (PWBs) after hot air solder leveling and hot oil solder dip and leveling. The dishwasher, a batch cleaning process, was compared to an existing conveyorized aqueous cleaning process. The aqueous soluble flux residues from both soldering processes were removed with a solution of a mild alkaline detergent dissolved in hot deionized (DI) water.

  12. 21 CFR 524.1200b - Kanamycin ophthalmic aqueous solution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... solution including suitable and harmless preservatives and buffer substances, contains 10 milligrams of..., removal of foreign bodies, and intraocular surgery. Instill a few drops into the affected eye every...

  13. 21 CFR 524.1200b - Kanamycin ophthalmic aqueous solution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... solution including suitable and harmless preservatives and buffer substances, contains 10 milligrams of..., removal of foreign bodies, and intraocular surgery. Instill a few drops into the affected eye every...

  14. Radiation induced degradation of ketoprofen in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  15. Kinetic and mechanistic study of reaction between sulfide and sulfite in aqueous solution

    SciTech Connect

    Siu, T.; Jia, C.Q.

    1999-10-01

    The reaction between sulfide and sulfite in neutral to weak alkaline aqueous solutions was studied by following thiosulfate and sulfite concentrations using ion chromatography. The thiosulfate formation rate from the reaction 2HS{sup {minus}} + 4HSO{sub 3}{sup {minus}} {yields} 3S{sub 2}O{sub 3}{sup 2{minus}} + 3H{sub 2}O at pH 8 to 9 was found to be d[S{sub 2}O{sub 3}{sup 2{minus}}]/dt = k{sub A}[HS{sup {minus}}][HSO{sub 3}{sup {minus}}]{sup 2}, where k{sub A} = 1.1 x 10{sup 12} exp({minus}48000/RT) M{sup {minus}2} s{sup {minus}1}. A mechanism for this reaction has been proposed with disulfite (S{sub 2}O{sub 5}{sup 2{minus}}) and HSO{sub 2}{sup {minus}} intermediates. The measured rate of sulfite disappearance was higher than that calculated from the stoichiometry of the above reaction. This phenomenon is attributed to other reactions, that consume sulfite and form other sulfur compounds such as polythionates, polysulfides, and elemental sulfur. These reactions were treated as a single reaction, whose rate was found to be ({minus}d[HSO{sub 3}{sup {minus}}]/dt){sub B} = k{sub B}[H{sup +}]{sup {minus}0.6}[HS{sup {minus}}]{sup 0.7}[HSO{sub 3}{sup {minus}}]{sup 1.5}, where k{sub B} = 5 x 10{sup {minus}5} M{sup {minus}0.6} s{sup {minus}1} at 20 C. A kinetic model was established on the basis of the kinetic data obtained in this and a previous work. The experimental data at pH 7 agreed with the model prediction in a satisfactory manner. The biphasic behavior of thiosulfate is considered to be critical in developing a new sulfur-producing flue gas desulfurization (SP-FGD) process based on sulfur dioxide absorption using sodium sulfide solution.

  16. Lead(II) Complex Formation with L-cysteine in Aqueous Solution

    PubMed Central

    Jalilehvand, Farideh; Sisombath, Natalie S.; Schell, Adam C.; Facey, Glenn A.

    2015-01-01

    The lead(II) complexes formed with the multidentate chelator L-cysteine (H2Cys) in alkaline aqueous solution were studied using 207Pb, 13C and 1H NMR, Pb LIII-edge X-ray absorption and UV-vis. spectroscopic techniques, complemented by electro-spray ion mass spectrometry (ESI-MS). The H2Cys/Pb(II) mole ratios were varied from 2.1 to 10.0 for two sets of solutions with CPb(II) = 0.01 and 0.1 M, respectively, prepared at pH values (9.1 – 10.4) for which precipitates of Pb(II)-cysteine dissolved. At low H2Cys/Pb(II) mole ratios (2.1 – 3.0) a mixture of the dithiolate [Pb(S,N-Cys)2]2− and [Pb(S,N,O-Cys)(S-HCys)]− complexes with the average Pb-(N/O) and Pb-S distances 2.42 ± 0.04 Å and 2.64 ± 0.04 Å, respectively, was found to dominate. At high concentration of free cysteinate (> 0.7 M) a significant amount converts to the trithiolate [Pb(S,N-Cys)(S-HCys)2]2−, including a minor amount of a PbS3 coordinated [Pb(S-HCys)3]− complex. The coordination mode was evaluated by fitting linear combinations of EXAFS oscillations to the experimental spectra, and by the 207Pb NMR signals in the chemical shift range δPb = 2006 – 2507 ppm, which became increasingly deshielded with increasing free cysteinate concentration. One-pulse magic angle spinning (MAS) 207Pb NMR spectra of crystalline Pb(aet)2 (Haet = 2-aminoethanethiol or cysteamine) with PbS2N2 coordination were measured for comparison (δiso = 2105 ppm). The UV-vis. spectra displayed absorption maxima at 298 – 300 nm (S− → PbII charge transfer) for the dithiolate PbS2N(N/O) species; with increasing ligand excess a shoulder appeared at ∼ 330 nm for the trithiolate PbS3N and PbS3 (minor) complexes. The results provide spectroscopic fingerprints for structural models for Pb(II) coordination modes to proteins and enzymes. PMID:25695880

  17. Chemical and photochemical properties of chloroharmine derivatives in aqueous solutions.

    PubMed

    Rasse-Suriani, Federico A O; Denofrio, M Paula; Yañuk, Juan G; Gonzalez, M Micaela; Wolcan, Ezequiel; Seifermann, Marco; Erra-Balsells, Rosa; Cabrerizo, Franco M

    2016-01-14

    Thermal and photochemical stability (Φ(R)), room temperature UV-vis absorption and fluorescence spectra, fluorescence quantum yields (Φ(F)) and lifetimes (τ(F)), quantum yields of hydrogen peroxide (Φ(H2O2)) and singlet oxygen (Φ(Δ)) production, and triplet lifetimes (τ(T)) have been obtained for the neutral and protonated forms of 6-chloroharmine, 8-chloroharmine and 6,8-dichloroharmine, in aqueous media. When it was possible, the effect of pH and oxygen concentration was evaluated. The nature of electronic transitions of protonated and neutral species of the three investigated chloroharmines was established using Time-Dependent Density Functional Theory (TD-DFT) calculations. The impact of all the foregoing observations on the biological role of the studied compounds is discussed.

  18. Stability of peptides in high-temperature aqueous solutions

    NASA Astrophysics Data System (ADS)

    Shock, Everett L.

    1992-09-01

    Estimated standard molal thermodynamic properties of aqueous dipeptides and their constituent amino acids indicate that temperature increases correspond to increased stability of peptide bonds relative to hydrolysis reactions. Pressure increases cause slight decreases in peptide bond stability, which are generally offset by greater stability caused by temperature increases along geothermal gradients. These calculations suggest that peptides, polypeptides, and proteins may survive hydrothermal alteration of organic matter depending on the rates of the hydrolysis reactions. Extremely thermophilic organisms may be able to take advantage of the decreased energy required to form peptide bonds in order to maintain structural proteins and enzymes at elevated temperatures and pressures. As the rates of hydrolysis reactions increase with increasing temperature, formation of peptide bonds may become a facile process in hydrothermal systems and deep in sedimentary basins.

  19. Enthalpic parameters of interaction between diglycylglycine and polyatomic alcohols in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mezhevoi, I. N.; Badelin, V. G.

    2015-12-01

    Integral enthalpies of solution Δsol H m of diglycylglycine in aqueous solutions of glycerol, ethylene glycol, and 1,2-propylene glycol are measured via solution calorimetry. The experimental data are used to calculate the standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of the tripeptide from water to aqueous solutions of polyatomic alcohols. The enthalpic pairwise coefficients h xy of interactions between the tripeptide and polyatomic alcohol molecules are calculated using the McMillan-Mayer solution theory and are found to have positive values. The findings are discussed using the theory of estimating various types of interactions in ternary systems and the effect the structural features of interacting biomolecules have on the thermochemical parameters of diglycylglycine dissolution.

  20. Self-assembly in aqueous solutions of a non-ionic hydrotrope

    NASA Astrophysics Data System (ADS)

    Subramanian, Deepa

    Hydrotropes are amphiphilic molecules, too small to cause spontaneous self-assembly towards equilibrium mesoscale structures in aqueous solutions, but they form dynamic, noncovalent assemblies, which may create microscopic regions of lowered polarity. This enhances the solubilization of hydrophobic compounds, also known as solubilizates, in aqueous solutions and may cause further aggregation to larger structures. In this work, unusual mesoscopic properties of aqueous solutions of a non-ionic hydrotrope, namely tertiary butyl alcohol (TBA) have been investigated by light scattering, microscopy, and chromatography. Aqueous TBA solutions show anomalous thermodynamic and structural properties in the range of concentrations 3-8 mol % TBA and temperatures 0-25 °C. These anomalies appear to be associated with short-lived, short-ranged micelle-like structural fluctuations, distinctly different from usual concentration fluctuations in non-ideal solutions. Molecular dynamics simulations and neutron-scattering experiments show clustering of TBA molecules on a nanometer scale, interacting through hydrogen bonds with a shell of water molecules. In this concentration range, TBA aqueous solutions, although macroscopically homogeneous, occasionally show the presence of "mysterious" inhomogeneities on a 100 nm scale. We have found that the emergence of such inhomogeneities strongly correlates with impurities present in commercial TBA samples. Experiments with controlled addition of a third component, such as propylene oxide, isobutyl alcohol, or cyclohexane, reveal the mechanism of formation of these inhomogeneities through stabilization of micelle-like fluctuations by a solubilizate. These structures are long-lived, i.e., stable from a few days up to many months. We have confirmed that mesoscale structures in aqueous solutions can be generated from self-assembly of small molecules, without involvement of surfactants or polymers. This kind of self-assembly may potentially result