Using the Binary Phase-Field Crystal Model to Describe Non-Classical Nucleation Pathways in Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Smith, Nathan; Provatas, Nikolas

Recent experimental work has shown that gold nanoparticles can precipitate from an aqueous solution through a non-classical, multi-step nucleation process. This multi-step process begins with spinodal decomposition into solute-rich and solute-poor liquid domains followed by nucleation from within the solute-rich domains. We present a binary phase-field crystal theory that shows the same phenomology and examine various cross-over regimes in the growth and coarsening of liquid and solid domains. We'd like to the thank Canada Research Chairs (CRC) program for funding this work.

Adsorption of arsenic from aqueous solution using magnetic graphene oxide

NASA Astrophysics Data System (ADS)

Sherlala, A. I. A.; Raman, A. A.; Bello, M. M.

2017-06-01

A binary of graphene oxide (GO) and iron oxide (IO) was prepared and used for the removal of arsenic from aqueous solution. The synthesized compound was characterized using XRD analysis. The prepared composite was used for the adsorption of arsenic from aqueous solution. Central Composite Design was used to design the adsorption experiments and to investigate the effects of operational parameters (initial concentration of arsenic, adsorbent dosage, pH and time) on the adsorption capacity and efficiency. The adsorbent shows a high adsorption capacity for the arsenic. The adsorption efficiency ranges between 33.2 % and 99.95 %. The most significant factors affecting the adsorption capacity were found to be the initial concentration of arsenic and the adsorbent dosage. The initial pH of the solution slightly affects the adsorption capacity, with the maximum adsorption capacity occurring around pH 6 - 7. Thus, the developed adsorbent has a potential for effective removal of arsenic from aqueous solution.

Interactions of S-peptide analogue in aqueous urea and trimethylamine-N-oxide solutions: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Sarma, Rahul; Paul, Sandip

2013-07-01

The ability of the osmolyte, trimethylamine-N-oxide (TMAO), to protect proteins from deleterious effect of urea, another commonly available osmolyte, is well-established. However, the molecular mechanism of this counteraction is not understood yet. To provide a molecular level understanding of how TMAO protects proteins in highly concentrated urea solution, we report here molecular dynamics simulation results of a 15-residue model peptide in two different conformations: helix and extended. For both conformations, simulations are carried out in pure water as well as in binary and ternary aqueous solutions of urea and TMAO. Analysis of solvation characteristics reveals direct interactions of urea and TMAO with peptide residues. However, the number of TMAO molecules that enter in the first solvation shell of the peptide is significantly lower than that of urea, and, unlike water and urea, TMAO shows its inability to form hydrogen bond with backbone oxygen and negatively charged sidechains. Preferential accumulation of urea near the peptide surface and preferential exclusion of TMAO from the peptide surface are observed. Inclusion of osmolytes in the peptide solvation shell leads to dehydration of the peptide in binary and ternary solutions of urea and TMAO. Solvation of peptide residues are investigated more closely by calculating the number of hydrogen bonds between the peptide and solution species. It is found that number of hydrogen bonds formed by the peptide with solution species increases in binary urea solution (relative to pure water) and this relative enhancement in hydrogen bond number reduces upon addition of TMAO. Our simulation results also suggest that, in the ternary solution, the peptide solvation layer is better mixed in terms of water and urea as compared to binary urea solution. Implications of the results for counteraction mechanism of TMAO are discussed.

Coefficients of interphase distribution and Gibbs energy of the transfer of nicotinic acid from water into aqueous solutions of ethanol and dimethylsulfoxide

NASA Astrophysics Data System (ADS)

Grazhdan, K. V.; Gamov, G. A.; Dushina, S. V.; Sharnin, V. A.

2012-11-01

Coefficients of the interphase distribution of nicotinic acid are determined in aqueous solution systems of ethanol-hexane and DMSO-hexane at 25.0 ± 0.1°C. They are used to calculate the Gibbs energy of the transfer of nicotinic acid from water into aqueous solutions of ethanol and dimethylsulfoxide. The Gibbs energy values for the transfer of the molecular and zwitterionic forms of nicotinic acid are obtained by means of UV spectroscopy. The diametrically opposite effect of the composition of binary solvents on the transfer of the molecular and zwitterionic forms of nicotinic acid is noted.

Single-solute and bisolute sorption of phenol and trichloroethylene from aqueous solution onto modified montmorillonite and application of sorption models.

PubMed

Wu, C D; Wang, L; Hu, C X; He, M H

2013-01-01

The single-solute and bisolute sorption behaviour of phenol and trichloroethylene, two organic compounds with different structures, onto cetyltrimethylammonium bromide (CTAB)-montmorillonite was studied. The monolayer Langmuir model (MLM) and empirical Freundlich model (EFM) were applied to the single-solute sorption of phenol or trichloroethylene from water onto monolayer or multilayer CTAB-montmorillonite. The parameters contained in the MLM and EFM were determined for each solute by fitting to the single-solute isotherm data, and subsequently utilized in binary sorption. The extended Langmuir model (ELM) coupled with the single-solute MLM and the ideal adsorbed solution theory (IAST) coupled with the single-solute EFM were used to predict the binary sorption of phenol and trichloroethylene onto CTAB-montmorillonite. It was found that the EFM was better than the MLM at describing single-solute sorption from water onto CTAB-montmorillonite, and the IAST was better than the ELM at describing the binary sorption from water onto CTAB-montmorillonite.

Prediction of ice content in biological model solutions when frozen under high pressure.

PubMed

Guignon, B; Aparicio, C; Otero, L; Sanz, P D

2009-01-01

High pressure is, at least, as effective as cryoprotective agents (CPAs) and are used for decreasing both homogenous nucleation and freezing temperatures. This fact gives rise to a great variety of possible cryopreservation processes under high pressure. They have not been optimized yet, since they are relatively recent and are mainly based on the pressure-temperature phase diagram of pure water. Very few phase diagrams of biological material are available under pressure. This is owing to the lack of suitable equipment and to the difficulties encountered in carrying out the measurements. Different aqueous solutions of salt and CPAs as biological models are studied in the range of 0 degrees C down to -35 degrees C, 0.1 up to 250 MPa, and 0-20% w/w total solute concentration. The phase transition curves of glycerol and of sodium chloride with either glycerol or sucrose in aqueous solutions are determined in a high hydrostatic pressure vessel. The experimental phase diagrams of binary solutions were well described by a third-degree polynomial equation. It was also shown that Robinson and Stokes' equation at high pressure succeeds in predicting the phase diagrams of both binary and ternary solutions. The solute cryoconcentration and the ice content were calculated as a function of temperature and pressure conditions during the freezing of a binary solution. This information should provide a basis upon which high-pressure cryopreservation processes may be performed and the damages derived from ice formation evaluated. (c) 2009 American Institute of Chemical Engineers Biotechnol.

Hydrophobic interactions between polymethacrylic acid and sodium laureth sulfate in aqueous solutions

NASA Astrophysics Data System (ADS)

Yaremko, Z. M.; Fedushinskaya, L. B.; Burka, O. A.; Soltys, M. N.

2014-09-01

The role of hydrophobic interaction in the development of associative processes is demonstrated, based on the concentration dependences of the viscosity and pH of binary solutions of polymethacrylic acid as an anionic polyelectrolyte and sodium laureth sulfate as an anionic surfactant. It is found that the inflection point on the dependence of the difference between the pH values of binary solutions of polymethacrylic acid and sodium laureth sulfate on the polyelectrolyte concentration is a criterion for determining the predominant contribution from hydrophobic interaction, as is the inflection point on the dependence of pH of individual solutions of polymethacrylic acid on the polyelectrolyte concentration.

Thermodynamic Parameters of the Dissolution of 4-Hydroxy-L-Proline and L-Phenylalanine in Mixed Aqueous Solvents at 298 K

NASA Astrophysics Data System (ADS)

Smirnov, V. I.; Badelin, V. G.

2018-01-01

The enthalpies of solution of 4-hydroxy-L-proline and L-phenylalanine in binary mixed aqueous solvents containing acetonitrile (AN), 1,4-dioxane (1,4-DO), or acetone (AC) at mole fractions of 0 to 0.25 are determined at T = 298.15 K via isothermal calorimetry. The standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of 4-hydroxy-L-proline and L-phenylalanine from water to mixed aqueous solvents are calculated using the experimental calorimetric data, as are the enthalpy coefficients of paired interactions ( h xy ) between the molecules of the investigated amino acids and the organic solvents. The effects the mixed aqueous solvent composition and the structure of the organic solvent molecules have on the enthalpies of solution and transfer for the investigated amino acids are considered. The correlation between the enthalpy of solution of the amino acids and the electron-donating properties of the organic solvents in the mixed aqueous solvent systems is established.

Hexadecyltrimethylammonium bromide (CTA-Br) and 1-butyl-3-methylimidazolium tetrafluoroborate (bmim-BF4) in aqueous solution: An ephemeral binary system.

PubMed

Comelles, Francesc; Ribosa, Isabel; Gonzalez, Juan José; Garcia, M Teresa

2017-03-15

Mixtures of the cationic surfactant hexadecyltrimethylammonium bromide (CTA-Br) and the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (bmim-BF 4 ) in aqueous solutions are expected to behave as typical binary cationic surfactant system taking into account the surface activity displayed by the ionic liquid, instead of considering the IL as a water cosolvent. Surface tension and conductivity measurements have been conducted as a function of the total concentration of the mixtures at different surfactant mole fraction (α CTA-Br ) to investigate the surface active properties. Turbidity immediately appearing when the compounds are mixed in water suggests the spontaneous formation of the low soluble compound hexadecyltrimethylammonium tetrafluoroborate (CTA-BF 4 ), together with the salt formed by the respective counterions bmim + and Br - in solution. For α CTA-Br ≠0.5, furthermore of the mentioned compounds, the spare bmim-BF 4 (for α CTA-Br <0.5) or CTA-Br (for α CTA-Br >0.5), are also present in the aqueous solution. Systems containing excess of bmim-BF 4 show a low critical aggregate concentration (cac), but an unexpected high surface tension at cac (γ cac ≈53-56mN/m), as pure CTA-BF 4 . For systems containing excess of CTA-Br, cac increases but γ cac decreases up to 36mN/m. Mixtures of pure CTA-BF 4 and bmim-BF 4 or CTA-Br behave as typical binary surfactant systems. Copyright © 2016 Elsevier Inc. All rights reserved.

Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita

To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of themore » Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.« less

Non-Ideality in Solvent Extraction Systems: PNNL FY 2014 Status Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levitskaia, Tatiana G.; Chatterjee, Sayandev; Pence, Natasha K.

The overall objective of this project is to develop predictive modeling capabilities for advanced fuel cycle separation processes by gaining a fundamental quantitative understanding of non-ideality effects and speciation in relevant aqueous and organic solutions. Aqueous solutions containing actinides and lanthanides encountered during nuclear fuel reprocessing have high ionic strength and do not behave as ideal solutions. Activity coefficients must be calculated to take into account the deviation from ideality and predict their behavior. In FY 2012-2013, a convenient method for determining activity effects in aqueous electrolyte solutions was developed. Our initial experiments demonstrated that water activity and osmotic coefficientsmore » of the electrolyte solutions can be accurately measured by the combination of two techniques, a Water Activity Meter and Vapor Pressure Osmometry (VPO). The water activity measurements have been conducted for binary lanthanide solutions in wide concentration range for all lanthanides (La-Lu with the exception of Pm). The osmotic coefficients and Pitzer parameters for each binary system were obtained by the least squares fitting of the water activity data. However, application of Pitzer model for the quantitative evaluation of the activity effects in the multicomponent mixtures is difficult due to the large number of the required interaction parameters. In FY 2014, the applicability of the Bromley model for the determination of the Ln(NO 3) 3 activity coefficients was evaluated. The new Bromley parameters for the binary Ln(NO 3) 3 electrolytes were obtained based on the available literature and our experimental data. This allowed for the accurate prediction of the Ln(NO 3) 3 activity coefficients for the binary Ln(NO 3) 3 electrolytes. This model was then successfully implemented for the determination of the Ln(NO 3) 3 activity coefficients in the ternary Nd(NO 3) 3/HNO 3/H2O, Eu(NO 3) 3/HNO 3/H 2O, and Eu(NO 3) 3/NaNO 3/H 2O systems. The main achievement of this work is the verified pathway for the estimation of the activity coefficients in the multicomponent aqueous electrolyte systems. The accurate Bromley electrolytes contributions obtained in this work for the entire series of lanthanide(III) nitrates (except Pm) can be applied for predicting activity coefficients and non-ideality effects for multi-component systems containing these species. This work also provides the proof-of-principle of extending the model to more complex multicomponent systems. Moreover, this approach can also be applied to actinide-containing electrolyte systems, for determination of the activity coefficients in concentrated radioactive solutions.« less

Single and binary adsorption of heavy metal ions from aqueous solutions using sugarcane cellulose-based adsorbent.

PubMed

Wang, Futao; Pan, Yuanfeng; Cai, Pingxiong; Guo, Tianxiang; Xiao, Huining

2017-10-01

A high efficient and eco-friendly sugarcane cellulose-based adsorbent was prepared in an attempt to remove Pb 2+ , Cu 2+ and Zn 2+ from aqueous solutions. The effects of initial concentration of heavy metal ions and temperature on the adsorption capacity of the bioadsorbent were investigated. The adsorption isotherms showed that the adsorption of Pb 2+ , Cu 2+ and Zn 2+ followed the Langmuir model and the maximum adsorptions were as high as 558.9, 446.2 and 363.3mg·g -1 , respectively, in single component system. The binary component system was better described with the competitive Langmuir isotherm model. The three dimensional sorption surface of binary component system demonstrated that the presence of Pb 2+ decreased the sorption of Cu 2+ , but the adsorption amount of other metal ions was not affected. The result from SEM-EDAX revealed that the adsorption of metal ions on bioadsorbent was mainly driven by coordination, ion exchange and electrostatic association. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermodynamics of the complex formation of copper(II) with L-phenylalanine in aqueous ethanol solutions

NASA Astrophysics Data System (ADS)

Burov, D. M.; Ledenkov, S. F.; Vandyshev, V. N.

2013-05-01

Constants of the acid dissociation and complexation of L-phenylalanine (HPhe) with copper(II) ions are determined by potentiometry in aqueous ethanol solutions containing 0 to 0.7 molar fraction of alcohol. Changes in the Gibbs energy for the transfer from water to a binary solvent of L-phenylalanine, Phe- anion, and [CuPhe]+ complex are calculated. It is found that the weakening of solvation of the ligand donor groups in solvents with high ethanol contents is accompanied by an increase in the stability of [CuPhe]+ complex.

Viscosity, density, and surface tension of binary mixtures of water and N-methyldiethanolamine and water and diethanolamine and tertiary mixtures of these amines with water over the temperature range 20--100[degree]C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rinker, E.B.; Oelschlager, D.W.; Colussi, A.T.

1994-04-01

Aqueous solutions of N-methyldiethanolamine (MDEA) and diethanolamine (DEA) are widely used in the industrial treatment of acid gas streams containing H[sub 2]S and CO[sub 2]. The density and viscosity of aqueous solutions of N-methyldiethanolamine were measured over the temperature range 60--100 C. The density and viscosity of aqueous solutions of diethanolamine and diethanolamine + N-methyldiethanolamine were measured over the temperature range 20--100 C. The surface tension of aqueous solutions of the above mixtures was measured over the temperature range 20--80 C. The concentration ranges were 10--50 mass % N-methyldiethanolamine, 10--30 mass % diethanolamine, and 50 mass % total amine concentrationmore » with mass ratios of 0.0441--0.5883 (diethanolamine to N-methyldiethanolamine). The measured quantities were found to be in agreement with the literature where data were available.« less

Separation of Pr and Nd from La in chloride solution by extraction with a mixture of Cyanex 272 and Alamine 336

NASA Astrophysics Data System (ADS)

Liu, Yang; Jeon, Ho Seok; Lee, Man Seung

2015-09-01

The possibility of separation of Pr and Nd from La in a chloride leaching solution of monazite sand has been investigated by using a binary mixture of Cyanex 272 (bis(2,4,4-trimethylpentyl) phosphinic acid) and Alamine 336 (tri-octyl/decyl amine). The binary mixture showed synergism on the extraction of the three metals and led to an increase in the separation factor between Pr/Nd and La compared to Cyanex 272 alone. Although the addition of chloride ion into aqueous increased the extraction of the metals, this addition had negative effect on the separation of Nd/Pr and La. McCabe-Thiele diagrams for the extraction of Pr and Nd with the binary mixture were constructed. Stripping of metals from the loaded organic phase was achieved with 0.7 M HCl. The difference in the solvent extraction of the rare earth elements from chloride solution between the binary mixture and saponified extractants was also discussed.

Volume properties and refraction of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids lysine, threonine, and oxyproline (C60(C6H13N2O2)2, C60(C4H8NO3)2, and C60(C5H9NO2)2) at 25°C

NASA Astrophysics Data System (ADS)

Semenov, K. N.; Ivanova, N. M.; Charykov, N. A.; Keskinov, V. A.; Kalacheva, S. S.; Duryagina, N. N.; Garamova, P. V.; Kulenova, N. A.; Nabieva, A.

2017-02-01

Concentration dependences of the density of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids are studied by pycnometry. Concentration dependences of the average molar volumes and partial volumes of components (H2O and corresponding bisadducts) are calculated for C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems at 25°C. Concentration dependences of the indices of refraction of C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems are determined at 25°C. The concentration dependences of specific refraction and molar refraction of bisadducts and aqueous solutions of them are calculated.

Thermal and volumetric properties of complex aqueous electrolyte solutions using the Pitzer formalism - The PhreeSCALE code

NASA Astrophysics Data System (ADS)

Lach, Adeline; Boulahya, Faïza; André, Laurent; Lassin, Arnault; Azaroual, Mohamed; Serin, Jean-Paul; Cézac, Pierre

2016-07-01

The thermal and volumetric properties of complex aqueous solutions are described according to the Pitzer equation, explicitly taking into account the speciation in the aqueous solutions. The thermal properties are the apparent relative molar enthalpy (Lϕ) and the apparent molar heat capacity (Cp,ϕ). The volumetric property is the apparent molar volume (Vϕ). Equations describing these properties are obtained from the temperature or pressure derivatives of the excess Gibbs energy and make it possible to calculate the dilution enthalpy (∆HD), the heat capacity (cp) and the density (ρ) of aqueous solutions up to high concentrations. Their implementation in PHREEQC V.3 (Parkhurst and Appelo, 2013) is described and has led to a new numerical tool, called PhreeSCALE. It was tested first, using a set of parameters (specific interaction parameters and standard properties) from the literature for two binary systems (Na2SO4-H2O and MgSO4-H2O), for the quaternary K-Na-Cl-SO4 system (heat capacity only) and for the Na-K-Ca-Mg-Cl-SO4-HCO3 system (density only). The results obtained with PhreeSCALE are in agreement with the literature data when the same standard solution heat capacity (Cp0) and volume (V0) values are used. For further applications of this improved computation tool, these standard solution properties were calculated independently, using the Helgeson-Kirkham-Flowers (HKF) equations. By using this kind of approach, most of the Pitzer interaction parameters coming from literature become obsolete since they are not coherent with the standard properties calculated according to the HKF formalism. Consequently a new set of interaction parameters must be determined. This approach was successfully applied to the Na2SO4-H2O and MgSO4-H2O binary systems, providing a new set of optimized interaction parameters, consistent with the standard solution properties derived from the HKF equations.

Removal of barium and strontium from aqueous solution using zeolite 4A.

PubMed

Araissi, Manel; Ayed, Imen; Elaloui, Elimame; Moussaoui, Younes

2016-01-01

The adsorption efficiency of Sr(2+) and Ba(2+) from aqueous solutions by zeolite 4A was investigated. Adsorption studies were carried out both in single and binary component systems. The single ion equilibrium adsorption data were fitted to three isotherm models: Langmuir, Freundlich and Dubinin-Radushkevich. The Langmuir model represents the equilibrium data better than the Freundlich model in the studied initial metal concentration (0.3-25 mmol L(-1)) in both the single and binary component systems. The obtained RL (separation factor or Langmuir parameter) values were in the range of 0-1 indicating that Sr(2+) and Ba(2+) sorption were favorable. The obtained mean free energy value for adsorption of Ba(2+) and Sr(2+) was 8.45 kJ mol(-1) and 9.12 kJ mol(-1), respectively, indicating that both ions were uptaken through an ion exchange process. The maximum adsorption capacities (Qmax) were 2.25 mmol g(-1) and 2.34 mmol g(-1) for Ba(2+) and Sr(2+) ions, respectively. Also, the study of the competitive sorption of ions in the binary system showed that zeolite 4A preferentially adsorbs cations in the following order: Ba(2+) < Sr(2+).

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

Measurement of Setschenow constants for six hydrophobic compounds in simulated brines and use in predictive modeling for oil and gas systems.

PubMed

Burant, Aniela; Lowry, Gregory V; Karamalidis, Athanasios K

2016-02-01

Treatment and reuse of brines, produced from energy extraction activities, requires aqueous solubility data for organic compounds in saline solutions. The presence of salts decreases the aqueous solubility of organic compounds (i.e. salting-out effect) and can be modeled using the Setschenow Equation, the validity of which has not been assessed in high salt concentrations. In this study, we used solid-phase microextraction to determine Setschenow constants for selected organic compounds in aqueous solutions up to 2-5 M NaCl, 1.5-2 M CaCl2, and in Na-Ca binary electrolyte solutions to assess additivity of the constants. These compounds exhibited log-linear behavior up to these high NaCl concentrations. Log-linear decreases in solubility with increasing salt concentration were observed up to 1.5-2 M CaCl2 for all compounds, and added to a sparse database of CaCl2 Setschenow constants. Setschenow constants were additive in binary electrolyte mixtures. New models to predict CaCl2 and KCl Setschenow constants from NaCl Setschenow constants were developed, which successfully predicted the solubility of the compounds measured in this study. Overall, data show that the Setschenow Equation is valid for a wide range of salinity conditions typically found in energy-related technologies. Copyright © 2015 Elsevier Ltd. All rights reserved.

pH-specific hydrothermal assembly of binary and ternary Pb(II)-(O,N-carboxylic acid) metal organic framework compounds: correlation of aqueous solution speciation with variable dimensionality solid-state lattice architecture and spectroscopic signatures.

PubMed

Gabriel, C; Perikli, M; Raptopoulou, C P; Terzis, A; Psycharis, V; Mateescu, C; Jakusch, T; Kiss, T; Bertmer, M; Salifoglou, A

2012-09-03

Hydrothermal pH-specific reactivity in the binary/ternary systems of Pb(II) with the carboxylic acids N-hydroxyethyl-iminodiacetic acid (Heida), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (Dpot), and 1,10-phenanthroline (Phen) afforded the new well-defined crystalline compounds [Pb(Heida)](n)·nH(2)O(1), [Pb(Phen)(Heida)]·4H(2)O(2), and [Pb(3)(NO(3))(Dpot)](n)(3). All compounds were characterized by elemental analysis, FT-IR, solution or/and solid-state NMR, and single-crystal X-ray diffraction. The structures in 1-2 reveal the presence of a Pb(II) center coordinated to one Heida ligand, with 1 exhibiting a two-dimensional (2D) lattice extending to a three-dimensional (3D) one through H-bonding interactions. The concurrent aqueous speciation study of the binary Pb(II)-Heida system projects species complementing the synthetic efforts, thereby lending credence to a global structural speciation strategy in investigating binary/ternary Pb(II)-Heida/Phen systems. The involvement of Phen in 2 projects the significance of nature and reactivity potential of N-aromatic chelators, disrupting the binary lattice in 1 and influencing the nature of the ultimately arising ternary 3D lattice. 3 is a ternary coordination polymer, where Pb(II)-Dpot coordination leads to a 2D metal-organic-framework material with unique architecture. The collective physicochemical properties of 1-3 formulate the salient features of variable dimensionality metal-organic-framework lattices in binary/ternary Pb(II)-(hydroxy-carboxylate) structures, based on which new Pb(II) materials with distinct architecture and spectroscopic signature can be rationally designed and pursued synthetically.

UV-Vis spectroscopic study and DFT calculation on the solvent effect of trimethoprim in neat solvents and aqueous mixtures.

PubMed

Almandoz, M C; Sancho, M I; Duchowicz, P R; Blanco, S E

2014-08-14

The solvatochromic behavior of trimethoprim (TMP) was analyzed using UV-Vis spectroscopy and DFT methods in neat and binary aqueous solvent mixtures. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions on the absorption maxima were evaluated by means of the linear solvation energy relationship concept of Kamlet and Taft. This analysis indicated that both interactions play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra of TMP and TMP:(solvent)n complexes in ACN and H2O using TD-DFT methods were in agreement with the experimental ones. Binary aqueous mixtures containing as co-solvents DMSO, ACN and EtOH were studied. Preferential solvation was detected as a nonideal behavior of the wavenumber curve respective to the analytical mole fraction of co-solvent in all binary systems. TMP molecules were preferentially solvated by the organic solvent over the whole composition range. Index of preferential solvation, as well as the influence of solvent parameters were calculated as a function of solvent composition. Copyright © 2014 Elsevier B.V. All rights reserved.

Marangoni Flow Induced Evaporation Enhancement on Binary Sessile Drops.

PubMed

Chen, Pin; Harmand, Souad; Ouenzerfi, Safouene; Schiffler, Jesse

2017-06-15

The evaporation processes of pure water, pure 1-butanol, and 5% 1-butanol aqueous solution drops on heated hydrophobic substrates are investigated to determine the effect of temperature on the drop evaporation behavior. The evolution of the parameters (contact angle, diameter, and volume) during evaporation measured using a drop shape analyzer and the infrared thermal mapping of the drop surface recorded by an infrared camera were used in investigating the evaporation process. The pure 1-butanol drop does not show any thermal instability at different substrate temperatures, while the convection cells created by the thermal Marangoni effect appear on the surface of the pure water drop from 50 °C. Because 1-butanol and water have different surface tensions, the infrared video of the 5% 1-butanol aqueous solution drop shows that the convection cells are generated by the solutal Marangoni effect at any substrate temperature. Furthermore, when the substrate temperature exceeds 50 °C, coexistence of the thermal and solutal Marangoni flows is observed. By analyzing the relation between the ratio of the evaporation rate of pure water and 1-butanol aqueous solution drops and the Marangoni number, a series of empirical equations for predicting the evaporation rates of pure water and 1-butanol aqueous solution drops at the initial time as well as the equations for the evaporation rate of 1-butanol aqueous solution drop before the depletion of alcohol are derived. The results of these equations correspond fairly well to the experimental data.

Uranyl(VI) nitrate salts: modeling thermodynamic properties using the binding mean spherical approximation theory and determination of "fictive" binary data.

PubMed

Ruas, Alexandre; Bernard, Olivier; Caniffi, Barbara; Simonin, Jean-Pierre; Turq, Pierre; Blum, Lesser; Moisy, Philippe

2006-02-23

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O as a "simple" solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of "simple" solution, values for density and water activity for the binary system UO(2)(NO(3))(2)/H(2)O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O. This new set of binary data is "fictive" in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.

Densities and viscosities for binary mixtures of N-methyldiethanolamine + triethylene glycol monomethyl ether from 25 C to 70 C and N-methyldiethanolamine + ethanol mixtures at 40 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henni, A.; Maham, Y.; Tontiwachwuthikul, P.

2000-04-01

Recent studies done on the absorption and desorption of acid gases (CO{sub 2}, H{sub 2}S) from natural gas, petroleum, and ammonia synthesis streams have shown that aqueous solutions of N-methyldiethanolamine (MDEA) can be used effectively for the selective removal of H{sub 2}S. This paper reports the measured values of the density and viscosity of binary mixtures of N-methyldiethanolamine (MDEA) and triethylene glycol monomethyl ether (TEGMME) at five temperatures in the range 25 C to 70 C over the whole concentration range. The authors also report the density and viscosity of the binary mixture MDEA + ethanol at 40 C. Themore » results are compared with data for aqueous mixtures and other alkanolamines when these are available. The derived excess molar volumes and viscosity deviations were correlated as a function of composition. The Grunberg-Nissan interaction energy constants are also reported.« less

Surface tension of dilute alcohol-aqueous binary fluids: n-Butanol/water, n-Pentanol/water, and n-Hexanol/water solutions

NASA Astrophysics Data System (ADS)

Cheng, Kuok Kong; Park, Chanwoo

2017-07-01

Surface tension of pure fluids, inherently decreasing with regard to temperature, creates a thermo-capillary-driven (Marangoni) flow moving away from a hot surface. It has been known that few high-carbon alcohol-aqueous solutions exhibit an opposite behavior of the surface tension increasing with regard to temperature, such that the Marangoni flow moves towards the hot surface (self-rewetting effect). We report the surface tensions of three dilute aqueous solutions of n-Butanol, n-Pentanol and n-Hexanol as self-rewetting fluids measured for ranges of alcohol concentration (within solubility limits) and fluid temperatures (25-85 °C). A maximum bubble pressure method using a leak-tight setup was used to measure the surface tension without evaporation losses of volatile components. It was found from this study that the aqueous solutions with higher-carbon alcohols exhibit a weak self-rewetting behavior, such that the surface tensions remain constant or slightly increases above about 60 °C. These results greatly differ from the previously reported results showing a strong self-rewetting behavior, which is attributed to the measurement errors associated with the evaporation losses of test fluids during open-system experiments.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

NASA Astrophysics Data System (ADS)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

Entropy-driven complex formation of malvidin-3- O-glucoside with common polyphenols in ethanol-water binary solutions

NASA Astrophysics Data System (ADS)

Kunsági-Máté, Sándor; Ortmann, Erika; Kollár, László; Nikfardjam, Martin Pour

2008-09-01

The complex formation of malvidin-3- O-glucoside with several polyphenols, the so-called "copigmentation" phenomenon, was studied in aqueous solutions. To simulate the copigmentation process during fermentation, the stability of the formed complexes was examined in dependence of the ethanol content of the aqueous solution. Results indicate that stronger and larger complexes are formed, when the ethanol content exceeds a critical margin of 8 vol.% However, the size of complexes of malvidin/procyanidin and malvidin/epicatechin is drastically reduced above this critical concentration. Fluorescence lifetime and solvent relaxation measurements give insight into the particular processes at molecular level and will help us comprehend the first important steps during winemaking in order to recommend an optimized winemaking technology to ensure extraordinary colour stability in red wines.

Glass transition behavior of ternary disaccharide-ethylene glycol-water solutions

NASA Astrophysics Data System (ADS)

Yu, Tongxu; Zhao, Lishan; Wang, Qiang; Cao, Zexian

2017-06-01

Glass transition behavior of ternary disaccharide-ethylene glycol-water solutions, in reference to that of the binary combinations, has been investigated towards a better understanding of their cryoprotective ability. In water-deficient solutions, the disaccharides, including trehalose, sucrose and maltose, can associate with more than 100 ethylene glycol molecules to form amorphous complex, one order of magnitude larger than the corresponding hydration numbers. In water-rich solutions, a second glass transition emerges with increasing molar fraction of ethylene glycol, indicating the possible synergy of disaccharides and ethylene glycol in vitrification of the ternary aqueous solution.

Three-Phase Melting Curves in the Binary System of Carbon Dioxide and Water

NASA Astrophysics Data System (ADS)

Abramson, E. H.

2017-10-01

Invariant, three-phase melting curves, of ice VI in equilibrium with solid CO2, of ice VII in equilibrium with solid CO2, and of solid CO2 in simultaneous equilibrium with a majority aqueous and a majority CO2 fluid, were explored in the binary system of carbon dioxide and water. Diamond-anvil cells were used to develop pressures of 5 GPa. Water exhibits a large melting temperature depression (73°C less than its pure melting temperature of 253°C at 5 GPa) indicative of large concentrations of CO2 in the aqueous solution. The melting point of water-saturated CO2 does not show a measureable departure from that of the pure system at temperatures lower than ∼200°C and only 10°C at 5 GPa (from 327°C).

The surface alloying effect of silicon in a binary NiTi-base alloy on the corrosion resistance and biocompatibility of the material

NASA Astrophysics Data System (ADS)

Psakhie, S. G.; Lotkov, A. I.; Meisner, L. L.; Meisner, S. N.; Matveeva, V. A.

2013-02-01

The corrosion resistance behavior and cytotoxicity of binary NiTi-base alloy specimens subjected to surface modification by silicon ion beams and the proliferative ability of mesenchymal stem cells of rat marrow on an ion-implanted surface of the alloy have been studied. The silicon ion beam processing of specimen surfaces is shown to bring about a nearly two-fold improvement in the corrosion resistance of the material to attack by aqueous solutions of NaCl (artificial body fluid) and human plasma and a drastic decrease in the nickel concentration after immersion of the specimens into the solutions for ˜3400 and ˜6000 h, respectively (for the artificial plasma solution, a nearly 20-fold decrease in the Ni concentration is observed.)

Metal biosorption equilibria in a ternary system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chong, K.H.; Volesky, B.

Equilibrium metal uptake performance of a biosorbent prepared from Ascophyllum nodosum seaweed biomass was studied using aqueous solutions containing copper, cadmium, and zinc ions in binary and ternary mixtures. Triangular equilibrium diagrams can graphically represent all the ternary equilibrium sorption data. Application of the multicomponent Langmuir model to describe the three-metal system revealed its nonideal characteristics, whereby the value of apparent dissociation constants for the respective metals differed for each system. This restricted the prediction of the ternary equilibria from the binary systems. However, some predictions of the ternary system behavior from the model were consistent with experimental data andmore » with conclusions postulated from the three possible binary subsystems.« less

Thermodynamic studies of drug-alpha-cyclodextrin interactions in water at 298.15 K: promazine hydrochloride/chlorpromazine hydrochloride + alpha-cyclodextrin + H(2)O systems.

PubMed

Terdale, Santosh S; Dagade, Dilip H; Patil, Kesharsingh J

2007-12-06

Data on osmotic coefficients have been obtained for a binary aqueous solution of two drugs, namely, promazine hydrochloride (PZ) and chlorpromazine hydrochloride (CPZ) using a vapor pressure osmometer at 298.15 K. The observed critical micelle concentration (cmc) agrees excellently with the available literature data. The measurements are extended to aqueous ternary solutions containing fixed a concentration of alpha-cyclodextrin (alpha-CD) of 0.1 mol kg(-1) and varied concentrations (approximately 0.005-0.2 mol kg(-1)) of drugs at 298.15 K. It has been found that the cmc values increase by the addition of alpha-CD. The mean molal activity coefficients of the ions and the activity coefficient of alpha-CD in binary as well as ternary solutions were obtained, which have been further used to calculate the excess Gibbs free energies and transfer Gibbs free energies. The lowering of the activity coefficients of ions and of alpha-CD is attributed to the existence of host-guest (inclusion)-type complex equilibria. It is suggested that CPZ forms 2:1 and 1:1 complexed species with alpha-CD, while PZ forms only 1:1 complexed species. The salting constant (ks) values are determined at 298.15 K for promazine-alpha-CD and chlorpromazine-alpha-CD complexes, respectively, by following the method based on the application of the McMillan-Mayer theory of virial coefficients to transfer free energy data. It is noted that the presence of chlorine in the drug molecule imparts better complexing capacity, the effect of which gets attenuated as a result of hydrophobic interaction. The results are discussed from the point of view of associative equilibria before the cmc and complexed equilibria for binary and ternary solutions, respectively.

Effect of solution non-ideality on erythrocyte volume regulation.

PubMed

Levin, R L; Cravalho, E G; Huggins, C E

1977-03-01

A non-ideal, hydrated, non-dilute pseudo-binary salt-protein-water solution model of the erythrocyte intracellular solution is presented to describe the osmotic behavior of human erythrocytes. Existing experimental activity data for salts and proteins in aqueous solutions are used to formulate van Laar type expressions for the solvent and solute activity coefficients. Reasonable estimates can therefore be made of the non-ideality of the erythrocyte intracellular solution over a wide range of osmolalities. Solution non-ideality is shown to affect significantly the degree of solute polarization within the erythrocyte intracellular solution during freezing. However, the non-ideality has very little effect upon the amount of water retained within erythrocytes cooled at sub-zero temperatures.

Energetics of the molecular interactions of L-alanine and L-serine with xylitol, D-sorbitol, and D-mannitol in aqueous solutions at 298.15 K

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2013-04-01

Integral enthalpies of dissolution Δsol H m of L-alanine and L-serine are measured via the calorimetry of dissolution in aqueous solutions of xylitol, D-sorbitol, and D-mannitol. Standard enthalpies of dissolution (Δsol H ○) and the transfer (Δtr H ○) of amino acids from water to binary solvent are calculated from the experimental data. Using the McMillan-Mayer theory, enthalpy coefficients of pairwise interactions h xy of amino acids with molecules of polyols are calculated that are negative. The obtained results are discussed within the theory of the prevalence of different types of interactions in mixed solutions and the effect of the structural features of interacting biomolecules on the thermochemical parameters of dissolution of amino acids.

Performance and mechanism of simultaneous removal of Cd(II) and Congo red from aqueous solution by hierarchical vaterite spherulites

NASA Astrophysics Data System (ADS)

Chen, Yuan-Yuan; Yu, Sheng-Hui; Jiang, Hao-Fan; Yao, Qi-Zhi; Fu, Sheng-Quan; Zhou, Gen-Tao

2018-06-01

Hierarchical vaterite spherulites, synthesized by a simple injection-precipitation method at room temperature, were applied for the simultaneous removal of heavy metal Cd(II) and dye Congo red (CR) from aqueous solution. Batch experiments reveal that the maximum removal capacities of as-prepared vaterite spherulites to Cd(II) and CR are 984.5 and 89.0 mg/g, respectively, showing excellent removal performance for Cd(II) and CR. Furthermore, in the binary Cd(II)-CR system, the removal capacity of vaterite to Cd(II) is significantly enhanced at lower CR concentration (<100 mg/L), but inhibited at higher CR concentration (>100 mg/L). In contrast, the concurrent Cd(II) shows negligible effect on the CR removal. The simultaneous removal mechanism was investigated by FESEM, EDX, XRD, FT-IR and XPS techniques. The simultaneous removal of Cd(II) and CR in the binary system is shown to be a multistep process, involving the preferential adsorption of dye CR, stabilization of CR to vaterite, coordination of the adsorbed CR molecules with Cd(II), and transformation of vaterite into otavite. Given the facile and green synthesis procedure, and effective removal of Cd(II) and CR in the binary system, the obtained vaterite spherulites have considerable practical interest in integrative treatment of wastewater contaminated by heavy metals and dyes.

Kinetics and equilibrium studies for the removal of heavy metals in both single and binary systems using hydroxyapatite

NASA Astrophysics Data System (ADS)

Ramesh, S. T.; Rameshbabu, N.; Gandhimathi, R.; Nidheesh, P. V.; Srikanth Kumar, M.

2012-09-01

Removal of heavy metals is very important with respect to environmental considerations. This study investigated the sorption of copper (Cu) and zinc (Zn) in single and binary aqueous systems onto laboratory prepared hydroxyapatite (HA) surfaces. Batch experiments were carried out using synthetic HA at 30 °C. Parameters that influence the adsorption such as contact time, adsorbent dosage and pH of solution were investigated. The maximum adsorption was found at contact time of 12 and 9 h, HA dosage of 0.4 and 0.7 g/l and pH of 6 and 8 for Cu and Zn, respectively, in single system. Adsorption kinetics data were analyzed using the pseudofirst-, pseudosecond-order and intraparticle diffusion models. The results indicated that the adsorption kinetic data were best described by pseudosecond-order model. Langmuir and Freundlich isotherm models were applied to analyze adsorption data, and Langmuir isotherm was found to be applicable to this adsorption system, in terms of relatively high regression values. The removal capacity of HA was found to be 125 mg of Cu/g, 30.3 mg of Zn/g in single system and 50 mg of Cu/g, 15.16 mg of Zn/g in binary system. The results indicated that the HA used in this work proved to be effective material for removing Cu and Zn from aqueous solutions.

Equilibrium isotherm and kinetic studies for the simultaneous removal of phenol and cyanide by use of S. odorifera (MTCC 5700) immobilized on coconut shell activated carbon

NASA Astrophysics Data System (ADS)

Singh, Neetu; Balomajumder, Chandrajit

2017-10-01

In this study, simultaneous removal of phenol and cyanide by a microorganism S. odorifera (MTCC 5700) immobilized onto coconut shell activated carbon surface (CSAC) was studied in batch reactor from mono and binary component aqueous solution. Activated carbon was derived from coconut shell by chemical activation method. Ferric chloride (Fecl3), used as surface modification agents was applied to biomass. Optimum biosorption conditions were obtained as a function of biosorbent dosage, pH, temperature, contact time and initial phenol and cyanide concentration. To define the equilibrium isotherms, experimental data were analyzed by five mono component isotherm and six binary component isotherm models. The higher uptake capacity of phenol and cyanide onto CSAC biosorbent surface was 450.02 and 2.58 mg/g, respectively. Nonlinear regression analysis was used for determining the best fit model on the basis of error functions and also for calculating the parameters involved in kinetic and isotherm models. The kinetic study results revealed that Fractal-like mixed first second order model and Brouser-Weron-Sototlongo models for phenol and cyanide were capable to offer accurate explanation of biosorption kinetic. According to the experimental data results, CSAC with immobilization of bacterium S. odorifera (MTCC 5700) seems to be an alternative and effective biosorbent for the elimination of phenol and cyanide from binary component aqueous solution.

Modeling CO2 mass transfer in amine mixtures: PZ-AMP and PZ-MDEA.

PubMed

Puxty, Graeme; Rowland, Robert

2011-03-15

The most common method of carbon dioxide (CO(2)) capture is the absorption of CO(2) into a falling thin film of an aqueous amine solution. Modeling of mass transfer during CO(2) absorption is an important way to gain insight and understanding about the underlying processes that are occurring. In this work a new software tool has been used to model CO(2) absorption into aqueous piperazine (PZ) and binary mixtures of PZ with 2-amino-2-methyl-1-propanol (AMP) or methyldiethanolamine (MDEA). The tool solves partial differential and simultaneous equations describing diffusion and chemical reaction automatically derived from reactions written using chemical notation. It has been demonstrated that by using reactions that are chemically plausible the mass transfer in binary mixtures can be fully described by combining the chemical reactions and their associated parameters determined for single amines. The observed enhanced mass transfer in binary mixtures can be explained through chemical interactions occurring in the mixture without need to resort to using additional reactions or unusual transport phenomena such as the "shuttle mechanism".

C–IBI: Targeting cumulative coordination within an iterative protocol to derive coarse-grained models of (multi-component) complex fluids

DOE PAGES

de Oliveira, Tiago E.; Netz, Paulo A.; Kremer, Kurt; ...

2016-05-03

We present a coarse-graining strategy that we test for aqueous mixtures. The method uses pair-wise cumulative coordination as a target function within an iterative Boltzmann inversion (IBI) like protocol. We name this method coordination iterative Boltzmann inversion (C–IBI). While the underlying coarse-grained model is still structure based and, thus, preserves pair-wise solution structure, our method also reproduces solvation thermodynamics of binary and/or ternary mixtures. In addition, we observe much faster convergence within C–IBI compared to IBI. To validate the robustness, we apply C–IBI to study test cases of solvation thermodynamics of aqueous urea and a triglycine solvation in aqueous urea.

Study on Colloid Vibration Current in Aqueous Solution of Binary Surfactant Mixtures: Effects of Counterions and Hydrophobic Chains.

PubMed

Takata, Youichi; Hyono, Atsushi; Ohshima, Hiroyuki

2016-11-01

In order to elucidate an electroacoustic phenomenon of mixed micelles in an aqueous solution, we measured the colloid vibration current (CVI) in aqueous solutions of binary surfactant mixtures. Based on the thermodynamic treatment of critical micelle concentration (cmc) values determined by conductivity measurements, it was expected that dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium chloride (DTAC) molecules would mix ideally in the micelle. However, the micelle composition as evaluated from the CVI measurement, based on the linear dependence of the CVI value on the micelle composition, differed from the aforementioned ideality. Considering these observations, we concluded that the CVI measurement was more sensitive to the counterion distribution near the micelle surface, whereas the thermodynamically determined micelle composition included the counterions more loosely bound in the diffuse double layer due to the electroneutrality condition included in its assumption. On the other hand, the phase diagram illustrating micelle formation in the lithium dodecyl sulfate (LiDS) - lithium perfluorooctane sulfonate (LiFOS) mixture system showed a heteroazeotropic point arising from the stronger interactions between homologous surfactants than between heterologous ones. Although the concentration dependence of CVI values was expected to drastically change at a heteroazeotropic point due to the enormous variation in the density of the micelle core, the results showed a monotonous change, which suggests that the density of the micelle core varies continuously. By taking the partial molar volume of fluorocarbon compounds in the hydrocarbon compounds into account, the density of the micelle core was affected by the size of the micelle as well as its constituents.

The self-organization and functional activity of binary system based on erucyl amidopropyl betaine - alkylated polyethyleneimine

NASA Astrophysics Data System (ADS)

Gaynanova, Gulnara A.; Valiakhmetova, Alsu R.; Kuryashov, Dmitry A.; Kudryashova, Yuliana R.; Lukashenko, Svetlana S.; Syakaev, Victor V.; Latypov, Shamil K.; Bukharov, Sergey V.; Bashkirtseva, Natalia Yu.; Zakharova, Lucia Ya.

2013-11-01

The self-organization in individual and binary aqueous solutions of a zwitterionic surfactant erucyl amidopropyl betaine and alkylated polyethyleneimine is carried out with a wide range of physical and chemical methods, including tensiometry, conductometry, dynamic light scattering, pH-metry, spectrophotometry, and fluorescence spectroscopy. The data obtained strongly support the formation of nanosized aggregates in the systems and provide information on their structure and probable morphological transitions. High solubilization capacity and data on the contact angle showed a possibility of the application of these systems as nanocontainers or oil wetting agents in the oil recovery.

Thermodynamic studies of aqueous solutions of 2,2,2-cryptand at 298.15 K: enthalpy-entropy compensation, partial entropies, and complexation with K+ ions.

PubMed

Shaikh, Vasim R; Terdale, Santosh S; Ahamad, Abdul; Gupta, Gaurav R; Dagade, Dilip H; Hundiwale, Dilip G; Patil, Kesharsingh J

2013-12-19

The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.

On the adequacy of modeling the concentration dependences of the activity coefficients for the components of solutions

NASA Astrophysics Data System (ADS)

Sergievskii, V. V.; Rudakov, A. M.

2006-11-01

An analysis of the accepted methods for calculating the activity coefficients for the components of binary aqueous solutions was performed. It was demonstrated that the use of the osmotic coefficients in auxiliary calculations decreases the accuracy of estimates of the activity coefficients. The possibility of calculating the activity coefficient of the solute from the concentration dependence of the water activity was examined. It was established that, for weak electrolytes, the interpretation of data on heterogeneous equilibria within the framework of the standard assumption that the dissociation is complete encounters serious difficulties.

Grafting of vinyl acetate-ethylacrylate binary monomer mixture onto guar gum.

PubMed

Singh, Vandana; Singh, Angela; Joshi, Sneha; Malviya, Tulika

2016-03-01

Present article reports on guar gum (GG) functionalization through graftcopolymerization of vinylacetate (VAC) and ethylacrylate (EA) from their binary mixtures. The potassium persulfate/ascorbic acid (KPS/AA) redox initiator system has been used for the binary grafting under the previously optimized conditions for VAC grafting at guar gum. The concentration of ascorbic acid (AA), persulfate (KPS), and grafting temperature were varied to optimize the binary grafting. A preliminary investigation revealed that the copolymer has excellent ability to capture Hg(II) from aqueous solution. It was observed that the optimum % grafting sample (CP3) was best at Hg(II) adsorption. CP3 and mercury loaded CP3 (CP3-Hg) have been extensively characterized using Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), and Thermo gravimetric analysis (TGA) and a plausible mechanism for the grafting has been proposed. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparison of adsorption and photo-Fenton processes for phenol and paracetamol removing from aqueous solutions: Single and binary systems

NASA Astrophysics Data System (ADS)

Rad, Leila Roshanfekr; Haririan, Ismaeil; Divsar, Faten

2015-02-01

In the present study, adsorption and photo-Fenton processes have been compared for the removal of phenol and paracetamol from aqueous solutions in a single and binary systems. NaX nanozeolites and cobalt ferrite nanoparticles were used during adsorption and photo-Fenton processes, respectively. Both nanoparticles were synthesized using microwave heating method. The synthesized nanoparticles were characterized using powder X-ray diffraction (XRD) and scanning electronic microscopy (SEM) analysis. Based on results, more than 99% removing percentages of phenol and paracetamol were obtained during photo-Fenton process at initial concentrations of 10, 20, 50, 100 and 200 mg/L of phenol and paracetamol. Moreover, the complete removing of phenol and paracetamol was only achieved at lower initial concentrations than 10 mg/L for phenol and paracetamol during adsorption process. The results showed a significant dependence of the phenol and paracetamol removing on the initial concentrations of phenol and paracetamol for selection of process. The photo-Fenton process could be considered an alternative method in higher initial concentrations of phenol and paracetamol. However, the adsorption process due to economical issue was preferred for phenol and paracetamol removing at lower initial concentrations. The kinetic data of photo-Fenton and adsorption processes were well described using first-order and pseudo-second-order kinetic models. The results of phenol and paracetamol removing in a binary system confirmed the obtained results of single removing of phenol and paracetamol in selection of process.

Unravelling the Composition Dependent Anomalies of Pair Hydrophobicity in Water-Ethanol Binary Mixtures.

PubMed

Halder, Ritaban; Jana, Biman

2018-06-05

Aqueous binary mixtures have received immense attention in recent years because of their extensive application in several biological and industrial processes. Water-ethanol binary mixture serves as a unique system because it exhibits composition dependent alteration of dynamic and thermodynamic properties. Our present work demonstrates how different compositions of water-ethanol binary mixtures affect the pair hydrophobicity of different hydrophobes. Pair hydrophobicity is measured by the depth of the first minimum (contact minima) of potential of mean force (PMF) profile between two hydrophobes. The pair hydrophobicity is found to be increased with addition of ethanol to water up to mole fraction of 0.10 and decreased with further addition of ethanol. This observation is shown to be true for three different pairs of hydrophobes. Decomposition of PMF into enthalpic and entropic contribution indicates a switch from entropic to enthalpic stabilization of the contact minimum upon addition of ethanol to water. The gain in mixing enthalpy of the binary solvent system upon association of two hydrophobes is found to be the determining factor for the stabilization of contact minimum. Several static/dynamics quantities (average composition fluctuations, diffusion coefficients, fluctuations in total dipole moment, propensity of ethyl-ethyl association, etc) of the ethanol-water binary mixture also show irregularities around xEtOH =0.10-0.15. We have also discovered that the hydrogen bonding pattern of ethanol rather than water reveals a change in trend near the similar composition range. As the anomalous behaviour of the physical/dynamical properties along with the pair hydrophobicity in aqueous binary mixture of amphiphilic solutes is common phenomena, our results may provide a general viewpoint on these aspects.

A study of the kinetics and isotherms for Cr(VI) adsorption in a binary mixture of Cr(VI)-Ni(II) using hierarchical porous carbon obtained from pig bone.

PubMed

Li, Chengxian; Huang, Zhe; Huang, Bicheng; Liu, Changfeng; Li, Chengming; Huang, Yaqin

2014-01-01

Cr(VI) adsorption in a binary mixture Cr(VI)-Ni(II) using the hierarchical porous carbon prepared from pig bone (HPC) was investigated. The various factors affecting adsorption of Cr(VI) ions from aqueous solutions such as initial concentration, pH, temperature and contact time were analyzed. The results showed excellent efficiency of Cr(VI) adsorption by HPC. The kinetics and isotherms for Cr(VI) adsorption from a binary mixture Cr(VI)-Ni(II) by HPC were studied. The adsorption equilibrium described by the Langmuir isotherm model is better than that described by the Freundlich isotherm model for the binary mixture in this study. The maximum adsorption capacity was reliably found to be as high as 192.68 mg/g in the binary mixture at pH 2. On fitting the experimental data to both pseudo-first- and second-order equations, the regression analysis of the second-order equation gave a better R² value.

Solute transport with equilibrium aqueous complexation and either sorption or ion exchange: Simulation methodology and applications

USGS Publications Warehouse

Lewis, F.M.; Voss, C.I.; Rubin, J.

1987-01-01

Methodologies that account for specific types of chemical reactions in the simulation of solute transport can be developed so they are compatible with solution algorithms employed in existing transport codes. This enables the simulation of reactive transport in complex multidimensional flow regimes, and provides a means for existing codes to account for some of the fundamental chemical processes that occur among transported solutes. Two equilibrium-controlled reaction systems demonstrate a methodology for accommodating chemical interaction into models of solute transport. One system involves the sorption of a given chemical species, as well as two aqueous complexations in which the sorbing species is a participant. The other reaction set involves binary ion exchange coupled with aqueous complexation involving one of the exchanging species. The methodology accommodates these reaction systems through the addition of nonlinear terms to the transport equations for the sorbing species. Example simulation results show (1) the effect equilibrium chemical parameters have on the spatial distributions of concentration for complexing solutes; (2) that an interrelationship exists between mechanical dispersion and the various reaction processes; (3) that dispersive parameters of the porous media cannot be determined from reactive concentration distributions unless the reaction is accounted for or the influence of the reaction is negligible; (4) how the concentration of a chemical species may be significantly affected by its participation in an aqueous complex with a second species which also sorbs; and (5) that these coupled chemical processes influencing reactive transport can be demonstrated in two-dimensional flow regimes. ?? 1987.

Surface tension of binary mixtures of water + N-methyldiethanolamine and ternary mixtures of this amine and water with monoethanolamine, diethanolamine, and 2-amino-2-methyl-1-propanol from 25 to 50 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alvarez, E.; Rendo, R.; Sanjurjo, B.

1998-11-01

The surface tension of aqueous solutions of N-methyldiethanolamine and diethanolamine + N-methyldiethanolamine, monoethanolamine + N-methyldiethanolamine and 2-amino-2-methyl-1-propanol + N-methyldiethanolamine was measured at temperatures from 25 C to 50 C. For binary mixtures the concentration range was 0--50 mass % N-methyldiethanolamine, and for the tertiary mixtures the concentration range for each amine was 0--50 mass %. The experimental values were correlated with temperature and mole fraction. The maximum deviation in both cases was always less than 0.5%.

The susceptibility critical exponent for a nonaqueous ionic binary mixture near a consolute point

NASA Technical Reports Server (NTRS)

Zhang, Kai C.; Briggs, Matthew E.; Gammon, Robert W.; Levelt Sengers, J. M. H.

1992-01-01

We report turbidity measurements of a nonaqueous ionic solution of triethyl n-hexylammonium triethyl n-hexylboride in diphenyl ether. A classical susceptibility critical exponent gamma = 1.01 +/- 0.01 is obtained over the reduced temperature range t between values of 0.1 and 0.0001. The best fits of the sample transmission had a standard deviation of 0.39 percent over this range. Ising and spherical model critical exponents are firmly excluded. The correlation length amplitude xi sub 0 from fitting is 1.0 +/- 0.2 nm which is much larger than values found in neutral fluids and some aqueous binary mixtures.

Smart worm-like micelles responsive to CO2/N2 and light dual stimuli.

PubMed

Jiang, Jianzhong; Wang, Guozheng; Ma, Yuxuan; Cui, Zhenggang; Binks, Bernard P

2017-04-12

CO 2 /N 2 and light dual stimuli-responsive worm-like micelles (WLMs) were obtained by addition of a relatively small amount of a switchable surfactant, 4-butyl-4'-(4-N,N-dimethylhexyloxy-amine) azobenzene bicarbonate (AZO-B6-CO 2 ), sensitive to the same triggers to a binary aqueous solution of cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal).

Measurement of Soret and Fickian diffusion coefficients by orthogonal phase-shifting interferometry and its application to protein aqueous solutions

NASA Astrophysics Data System (ADS)

Torres, Juan F.; Komiya, Atsuki; Henry, Daniel; Maruyama, Shigenao

2013-08-01

We have developed a method to measure thermodiffusion and Fickian diffusion in transparent binary solutions. The measuring instrument consists of two orthogonally aligned phase-shifting interferometers coupled with a single rotating polarizer. This high-resolution interferometer, initially developed to measure isothermal diffusion coefficients in liquid systems [J. F. Torres, A. Komiya, E. Shoji, J. Okajima, and S. Maruyama, Opt. Lasers Eng. 50, 1287 (2012)], was modified to measure transient concentration profiles in binary solutions subject to a linear temperature gradient. A convectionless thermodiffusion field was created in a binary solution sample that is placed inside a Soret cell. This cell consists of a parallelepiped cavity with a horizontal cross-section area of 10 × 20 mm2, a variable height of 1-2 mm, and transparent lateral walls. The small height of the cell reduces the volume of the sample, shortens the measurement time, and increases the hydrodynamic stability of the system. An additional free diffusion experiment with the same optical apparatus provides the so-called contrast factors that relate the unwrapped phase and concentration gradients, i.e., the measurement technique is independent and robust. The Soret coefficient is determined from the concentration and temperature differences between the upper and lower boundaries measured by the interferometer and thermocouples, respectively. The Fickian diffusion coefficient is obtained by fitting a numerical solution to the experimental concentration profile. The method is validated through the measurement of thermodiffusion in the well-known liquid pairs of ethanol-water (ethanol 39.12 wt.%) and isobutylbenzene-dodecane (50.0 wt.%). The obtained coefficients agree with the literature values within 5.0%. Finally, the developed technique is applied to visualize biomolecular thermophoresis. Two protein aqueous solutions at 3 mg/ml were used as samples: aprotinin (6.5 kDa)-water and lysozyme (14.3 kDa)-water. It was found that the former protein molecules are thermophilic and the latter thermophobic. In contrast to previously reported methods, this technique is suitable for both short time and negative Soret coefficient measurements.

Preferential solvatation of human serum albumin in dimethylsulfoxide-H2O binary solution

NASA Astrophysics Data System (ADS)

Grigoryan, K. R.

2009-12-01

The preferential solvatation of human serum albumin (HSA) in dimethylsulfoxide (DMSO) aqueous solutions were studied using the densitometry method. It has been shown that at DMSO low concentrations HSA undergoes to preferential hydration, but at DMSO higher concentrations preferential binding of DMSO molecules to protein occurs. It has been estimated that DMSO exhibits stabilizing/destabilizing effect on HSA structure which is explained in terms of hydration/solvatation of protein, on the one hand, and the medium structure enhancement/disruption around the protein molecule, on the other hand.

Evaporative cooling by a pulsed jet spray of binary ethanol-water mixture

NASA Astrophysics Data System (ADS)

Karpov, P. N.; Nazarov, A. D.; Serov, A. F.; Terekhov, V. I.

2015-07-01

We have experimentally studied the heat transfer under conditions of pulsed multinozzle jet spray impact onto a vertical surface. The working coolant fluid was aqueous ethanol solution in a range of concentrations K 1 = 0-96%. The duration of spray pulses was τ = 2, 4, and 10 ms at a repetition frequency of 10 Hz. The maximum heat transfer coefficient was achieved at an ethanol solution concentration within 50-60%. The thermal efficiency of pulsed spray cooling grows with increasing ethanol concentration and decreasing jet spray pulse duration.

Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water.

PubMed

Reschke, Thomas; Zherikova, Kseniya V; Verevkin, Sergey P; Held, Christoph

2016-03-01

Benzoic acid is a model compound for drug substances in pharmaceutical research. Process design requires information about thermodynamic phase behavior of benzoic acid and its mixtures with water and organic solvents. This work addresses phase equilibria that determine stability and solubility. In this work, Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) was used to model the phase behavior of aqueous and organic solutions containing benzoic acid and chlorobenzoic acids. Absolute vapor pressures of benzoic acid and 2-, 3-, and 4-chlorobenzoic acid from literature and from our own measurements were used to determine pure-component PC-SAFT parameters. Two binary interaction parameters between water and/or benzoic acid were used to model vapor-liquid and liquid-liquid equilibria of water and/or benzoic acid between 280 and 413 K. The PC-SAFT parameters and 1 binary interaction parameter were used to model aqueous solubility of the chlorobenzoic acids. Additionally, solubility of benzoic acid in organic solvents was predicted without using binary parameters. All results showed that pure-component parameters for benzoic acid and for the chlorobenzoic acids allowed for satisfying modeling phase equilibria. The modeling approach established in this work is a further step to screen solubility and to predict the whole phase region of mixtures containing pharmaceuticals. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Solidification and microstructures of binary ice-I/hydrate eutectic aggregates

USGS Publications Warehouse

McCarthy, C.; Cooper, R.F.; Kirby, S.H.; Rieck, K.D.; Stern, L.A.

2007-01-01

The microstructures of two-phase binary aggregates of ice-I + salt-hydrate, prepared by eutectic solidification, have been characterized by cryogenic scanning electron microscopy (CSEM). The specific binary systems studied were H2O-Na2SO4, H2O-MgSO4, H2O-NaCl, and H2O-H2SO4; these were selected based on their potential application to the study of tectonics on the Jovian moon Europa. Homogeneous liquid solutions of eutectic compositions were undercooled modestly (??T - 1-5 ??C); similarly cooled crystalline seeds of the same composition were added to circumvent the thermodynamic barrier to nucleation and to control eutectic growth under (approximately) isothermal conditions. CSEM revealed classic eutectic solidification microstructures with the hydrate phase forming continuous lamellae, discontinuous lamellae, or forming the matrix around rods of ice-I, depending on the volume fractions of the phases and their entropy of dissolving and forming a homogeneous aqueous solution. We quantify aspects of the solidification behavior and microstructures for each system and, with these data articulate anticipated effects of the microstructure on the mechanical responses of the materials.

Isopiestic Determination of the Osmotic Coefficients of NaNO3 + Eu(NO3)3 + H2O at 298.15 K and Representation with an Extended Ion-Interaction (Pitzer) Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peter R. Zalupski; Rocklan McDowell; Simon L. Clegg

Isopiestic vapor pressures were measured at 298.15 K for aqueous NaNO3 + Eu(NO3)3 solutions, using NaCl(aq) as the reference standard. Measurements were made for both binary (single salt) solutions and for ternary solutions of the following NaNO3 ionic strength fractions: 0.05995, 0.08749, 0.16084, 0.27709, and 0.36313 over the water activity range 0.8951 = aw = 0.9832. (These ionic strength fractions correspond to NaNO3 molality fractions 0.27675, 0.36519, 0.53489, 0.69695, and 0.77381, respectively.) The results, and those of other studies for the two pure aqueous solutions, were used to determine the Pitzer model parameters for aqueous Eu(NO3)3 for molalities up tomore » 3 mol kg–1 and the two ternary (mixture) parameters ?Eu,Na = 0.367 ± 0.0035 and ?Eu,Na,NO3 = -0.0743 ± 0.0014. Some deviations of the measurements from the fitted model, of the order of +0.0075 in the osmotic coefficient, were noted for mixtures containing less than about 1 mol kg–1 total NO3–. The use of the mixture parameters in the Pitzer model yields predicted trace activity coefficients of Eu3+ in 1 mol kg–1 aqueous NaNO3 almost a factor of 2 greater than if they are omitted.« less

Nanostructured iron(III)-copper(II) binary oxide: a novel adsorbent for enhanced arsenic removal from aqueous solutions.

PubMed

Zhang, Gaosheng; Ren, Zongming; Zhang, Xiwang; Chen, Jing

2013-08-01

To obtain a highly efficient and low-cost adsorbent for arsenic removal from water, a novel nanostructured Fe-Cu binary oxide was synthesized via a facile co-precipitation method. Various techniques including BET surface area measurement, powder XRD, SEM, and XPS were used to characterize the synthetic Fe-Cu binary oxide. It showed that the oxide was poorly crystalline, 2-line ferrihydrite-like and was aggregated with many nanosized particles. Laboratory experiments were performed to investigate adsorption kinetics, adsorption isotherms, pH adsorption edge and regeneration of spent adsorbent. The results indicated that the Fe-Cu binary oxide with a Cu: Fe molar ratio of 1:2 had excellent performance in removing both As(V) and As(III) from water, and the maximal adsorption capacities for As(V) and As(III) were 82.7 and 122.3 mg/g at pH 7.0, respectively. The values are favorable, compared to those reported in the literature using other adsorbents. The coexisting sulfate and carbonate had no significant effect on arsenic removal. However, the presence of phosphate obviously inhibited the arsenic removal, especially at high concentrations. Moreover, the Fe-Cu binary oxide could be readily regenerated using NaOH solution and be repeatedly used. The Fe-Cu binary oxide could be a promising adsorbent for both As(V) and As(III) removal because of its excellent performance, facile and low-cost synthesis process, and easy regeneration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Study of a binary interpenetrated polymeric complex by correlation of rheological parameters with zeta potential and conductivity.

PubMed

Nita, Loredana Elena; Chiriac, Aurica P; Neamtu, Iordana; Bercea, Maria

2010-03-01

The interpenetrated macromolecular chains complexation between poly(aspartic acid) and poly(vinyl alcohol) in aqueous solution it was investigated. The interpolymer complexation process was evaluated through dynamic rheology. The aspects concerning the stability of the tested homopolymers and the prepared interpolymeric complex there were achieved from the evaluation of the aqueous solutions'zeta potential and also by determining the pH influence upon the zeta potential and the conductivity. The data obtained through the rheological dynamic measurements were correlated with the composition of the polymeric mixture, the dependence of zeta potential and conductivity. The study reveals the conditions for the formation of interpenetrated polymeric complex as being a ratio of 70wt.% PAS to 30wt.% PVA at 22 degrees C and 50/50 PAS/PVA ratio at 37 degrees C temperature. From the pH influence upon the zeta potential values it was evidenced the PAS aqueous solution does not reach the isoelectric point. At the same time, PVA solution and the complex PAS/PVA reaches the isoelectric point at strongly acid pH. The better stability of PAS, PVA and their mixture in solution is recorded in the alkaline domain (7.5or=12). The conductivity increases with the rising of the PAS content, pH and temperature. Other characteristics of the prepared interpenetrated polymeric structure, as for example thermal stability, there are also presented.

Predicting the Kinetics of Ice Recrystallization in Aqueous Sugar Solutions

PubMed Central

2018-01-01

The quality of stored frozen products such as foods and biomaterials generally degrades in time due to the growth of large ice crystals by recrystallization. While there is ample experimental evidence that recrystallization within such products (or model systems thereof) is often dominated by diffusion-limited Ostwald ripening, the application of Ostwald-ripening theories to predict measured recrystallization rates has only met with limited success. For a model system of polycrystalline ice within an aqueous solution of sugars, we here show recrystallization rates can be predicted on the basis of Ostwald ripening theory, provided (1) the theory accounts for the fact the solution can be nonideal, nondilute and of different density than the crystals, (2) the effect of ice-phase volume fraction on the diffusional flux of water between crystals is accurately described, and (3) all relevant material properties (involving binary Fick diffusion coefficients, the thermodynamic factor of the solution, and the surface energy of ice) are carefully estimated. To enable calculation of material properties, we derive an alternative formulation of Ostwald ripening in terms of the Maxwell–Stefan instead of the Fick approach to diffusion. First, this leads to a cancellation of the thermodynamic factor (a measure for the nonideality of a solution), which is a notoriously difficult property to obtain. Second, we show that Maxwell–Stefan diffusion coefficients can to a reasonable approximation be related to self-diffusion coefficients, which are relatively easy to measure or predict in comparison to Fick diffusion coefficients. Our approach is validated for a binary system of water and sucrose, for which we show predicted recrystallization rates of ice compare well to experimental results, with relative deviations of at most a factor of 2. PMID:29651228

Predicting the Kinetics of Ice Recrystallization in Aqueous Sugar Solutions.

PubMed

van Westen, Thijs; Groot, Robert D

2018-04-04

The quality of stored frozen products such as foods and biomaterials generally degrades in time due to the growth of large ice crystals by recrystallization. While there is ample experimental evidence that recrystallization within such products (or model systems thereof) is often dominated by diffusion-limited Ostwald ripening, the application of Ostwald-ripening theories to predict measured recrystallization rates has only met with limited success. For a model system of polycrystalline ice within an aqueous solution of sugars, we here show recrystallization rates can be predicted on the basis of Ostwald ripening theory, provided (1) the theory accounts for the fact the solution can be nonideal, nondilute and of different density than the crystals, (2) the effect of ice-phase volume fraction on the diffusional flux of water between crystals is accurately described, and (3) all relevant material properties (involving binary Fick diffusion coefficients, the thermodynamic factor of the solution, and the surface energy of ice) are carefully estimated. To enable calculation of material properties, we derive an alternative formulation of Ostwald ripening in terms of the Maxwell-Stefan instead of the Fick approach to diffusion. First, this leads to a cancellation of the thermodynamic factor (a measure for the nonideality of a solution), which is a notoriously difficult property to obtain. Second, we show that Maxwell-Stefan diffusion coefficients can to a reasonable approximation be related to self-diffusion coefficients, which are relatively easy to measure or predict in comparison to Fick diffusion coefficients. Our approach is validated for a binary system of water and sucrose, for which we show predicted recrystallization rates of ice compare well to experimental results, with relative deviations of at most a factor of 2.

Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O

NASA Astrophysics Data System (ADS)

Pabalan, Roberto T.; Pitzer, Kenneth S.

1987-09-01

Mineral solubilities in binary and ternary electrolyte mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O are calculated to high temperatures using available thermodynamic data for solids and for aqueous electrolyte solutions. Activity and osmotic coefficients are derived from the ion-interaction model of Pitzer (1973, 1979) and co-workers, the parameters of which are evaluated from experimentally determined solution properties or from solubility data in binary and ternary mixtures. Excellent to good agreement with experimental solubilities for binary and ternary mixtures indicate that the model can be successfully used to predict mineral-solution equilibria to high temperatures. Although there are currently no theoretical forms for the temperature dependencies of the various model parameters, the solubility data in ternary mixtures can be adequately represented by constant values of the mixing term θ ij and values of ψ ijk which are either constant or have a simple temperature dependence. Since no additional parameters are needed to describe the thermodynamic properties of more complex electrolyte mixtures, the calculations can be extended to equilibrium studies relevant to natural systems. Examples of predicted solubilities are given for the quaternary system NaCl-KCl-MgCl 2-H 2O.

Exploring the Counteracting Mechanism of Trehalose on Urea Conferred Protein Denaturation: A Molecular Dynamics Simulation Study.

PubMed

Paul, Subrata; Paul, Sandip

2015-07-30

To provide the underlying mechanism of the inhibiting effect of trehalose on the urea denatured protein, we perform classical molecular dynamics simulations of N-methylacetamide (NMA) in aqueous urea and/or trehalose solution. The site-site radial distribution functions and hydrogen bond properties indicate in binary urea solution the replacement of NMA-water hydrogen bonds by NMA-urea hydrogen bonds. On the other hand, in ternary urea and trehalose solution, trehalose does not replace the NMA-urea hydrogen bonds significantly; rather, it forms hydrogen bonds with the NMA molecule. The calculation of a preferential interaction parameter shows that, at the NMA surface, trehalose molecules are preferred and the preference for urea decreases slightly in ternary solution with respect to the binary solution. The exclusion of urea molecules in the ternary urea-NMA-trehalose system causes alleviation in van der Waals interaction energy between urea and NMA molecules. Our findings also reveal the following: (a) trehalose and urea induced second shell collapse of water structure, (b) a reduction in the mean trehalose cluster size in ternary solution, and (c) slowing down of translational motion of solution species in the presence of osmolytes. Implications of these results for the molecular explanations of the counteracting mechanism of trehalose on urea induced protein denaturation are discussed.

Improved Aqueous Solubility and Antihypercholesterolemic Activity of Ezetimibe on Formulating with Hydroxypropyl-β-Cyclodextrin and Hydrophilic Auxiliary Substances.

PubMed

Srivalli, Kale Mohana Raghava; Mishra, Brahmeshwar

2016-04-01

The purpose of this study was to improve the aqueous solubility, dissolution, and pharmacodynamic properties of a BCS class II drug, ezetimibe (Eze) by preparing ternary cyclodextrin complex systems. We investigated the potential synergistic effect of two novel hydrophilic auxiliary substances, D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) and L-ascorbic acid-2-glucoside (AA2G) on hydroxypropyl-β-cyclodextrin (HPBCD) solubilization of poorly water-soluble hypocholesterolemic drug, Eze. In solution state, the binary and ternary systems were analyzed by phase solubility studies and Job's plot. The solid complexes prepared by freeze-drying were characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), nuclear magnetic resonance (NMR), and scanning electron microscopy (SEM). The log P values, aqueous solubility, dissolution, and antihypercholesterolemic activity of all systems were studied. The analytical techniques confirmed the formation of inclusion complexes in the binary and ternary systems. HPBCD complexation significantly (p < 0.05) reduced the log P and improved the solubility, dissolution, and hypocholesterolemic properties of Eze, and the addition of ternary component produced further significant improvement (p < 0.05) even compared to binary system. The remarkable reduction in log P and enhancement in solubility, dissolution, and antihypercholesterolemic activity due to the addition of TPGS or AA2G may be attributed to enhanced wetting, dispersibility, and complete amorphization. The use of TPGS or AA2G as ternary hydrophilic auxiliary substances improved the HPBCD solubilization and antihypercholesterolemic activity of Eze.

Modelling of ceramide interactions with porous graphite carbon in non-aqueous liquid chromatography.

PubMed

West, C; Cilpa, G; Gaudin, K; Chaminade, P; Lesellier, E

2005-09-16

Interactions of solutes on porous graphitic carbon (PGC) with non-aqueous mobile phases are studied by the linear solvation energy relationship (LSER). Studies have been carried out with eight binary mixtures composed of a weak solvent (acetonitrile or methanol) and a strong solvent (tetrahydrofuran, n-butanol, CH2Cl2, 1,1,2-trichloro-2,2,1-trifluoroethane). The systematic analysis of a set of test compounds was performed for each solvent mixture in isocratic mode (50:50). The results were compared to those obtained on PGC with hydro-organic liquids and supercritical fluids. They were then correlated with the observed retention behaviour of lipid compounds, more particularly ceramides.

Removal of thallium from aqueous solutions using Fe-Mn binary oxides.

PubMed

Li, Huosheng; Chen, Yongheng; Long, Jianyou; Li, Xiuwan; Jiang, Daqian; Zhang, Ping; Qi, Jianying; Huang, Xuexia; Liu, Juan; Xu, Ruibing; Gong, Jian

2017-09-15

In this study, Fe-Mn binary oxides, which harbor the strong oxidative power of manganese dioxide and the high adsorption capacity of iron oxides, were synthesized for Tl(I) removal using a concurrent chemical oxidation and precipitation method. The adsorption of Tl onto the Fe-Mn adsorbent was fast, effective, and selective, with equilibrium sorption reaching over 95% under a broad operating pH (3-12), and high ionic strength (0.1-0.5mol/L). The adsorption can be well fitted with both Langmuir and Freundlich isotherms, and the kinetics can be well described by the pseudo-second-order model. Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) spectra suggest that surface complexation, oxidation and precipitation were the main mechanisms for the removal of Tl. This study shows that the Fe-Mn binary oxides could be a promising adsorbent for Tl removal. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of concentration boundary layers on passive solute flows in a system of two polymeric membranes positioned in vertical planes.

PubMed

Slezak, Andrzej; Jasik-Slezak, Jolanta; Dworecki, Kazimierz

2003-01-01

The results of studies of influence of concentration boundary layers on passive diffusive transport in a double-membrane osmo-diffusive cell, containing a series of two (Ml and M(r)) vertically positioned, flat, microporous and symmetric polymer membranes (Nephrophane and Cellulose IMP-1) are presented in this paper. The membranes separated three compartments (l, m, r) containing binary, heterogeneous and non-ionic solutions (aqueous solutions of glucose or ethanol) or ternary non-electrolyte solutions (glucose solutions in 0.75 mol.l-1 solution of ethanol or ethanol solutions in 0.1 mol.l-1 aqueous solution of glucose). Solution concentrations fulfilled the condition C(k)l > C(k)m > C(k)r. The intermembrane compartment (m) was an infinitesimal solution layer. The volume of the m compartment and the volumes of the external (l and r) compartments fulfilled the condition Vl = Vr approximately 170 Vm. The tests were performed for configurations A and B of a double-membrane osmo-diffusive cell. In configuration A, the solution was located behind the M(r) membrane, and water was placed behind the Ml membrane, while in configuration B this sequence was reversed. The results obtained during experiment were interpreted in the categories of convective instability, which increased the value of diffusive permeability coefficient of the system: concentration boundary layer/membrane/concentration boundary layer.

[Computer modeling the hydrostatic pressure characteristics of the membrane potential for polymeric membrane, separated non-homogeneous electrolyte solutions].

PubMed

Slezak, Izabella H; Jasik-Slezak, Jolanta; Rogal, Mirosława; Slezak, Andrzej

2006-01-01

On the basis of model equation depending the membrane potential deltapsis, on mechanical pressure difference (deltaP), concentration polarization coefficient (zetas), concentration Rayleigh number (RC) and ratio concentration of solutions separated by membrane (Ch/Cl), the characteristics deltapsis = f(deltaP)zetas,RC,Ch/Cl for steady values of zetas, RC and Ch/Cl in single-membrane system were calculated. In this system neutral and isotropic polymeric membrane oriented in horizontal plane, the non-homogeneous binary electrolytic solutions of various concentrations were separated. Nonhomogeneity of solutions is results from creations of the concentration boundary layers on both sides of the membrane. Calculations were made for the case where on a one side of the membrane aqueous solution of NaCl at steady concentration 10(-3) mol x l(-1) (Cl) was placed and on the other aqueous solutions of NaCl at concentrations from 10(-3) mol x l(-1) to 2 x 10(-2) mol x l(-1) (Ch). Their densities were greater than NaCl solution's at 10(-3) mol x l(-1). It was shown that membrane potential depends on hydrodynamic state of a complex concentration boundary layer-membrane-concentration boundary layer, what is controlled by deltaP, Ch/Cl, RC and zetas.

Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures

NASA Astrophysics Data System (ADS)

Almandoz, M. C.; Sancho, M. I.; Blanco, S. E.

2014-01-01

The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π*). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture.

Study of complexation process between 4'-nitrobenzo-15-crown-5 and yttrium(III) cation in binary mixed non-aqueous solvents using conductometric method

NASA Astrophysics Data System (ADS)

Habibi, N.; Rounaghi, G. H.; Mohajeri, M.

2012-12-01

The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

Gex-Model Using Local Area Fraction for Binary Electrolyte Systems

NASA Astrophysics Data System (ADS)

Haghtalab, Ali; Joda, Marzieh

2007-06-01

The correlation and prediction of phase equilibria of electrolyte systems are essential in the design and operation of many industrial processes such as downstream processing in biotechnology, desalination, hydrometallurgy, etc. In this research, the local composition non-random two liquid-nonrandom factor (NRTL-NRF) model of Haghtalab and Vera was extended for uni-univalent aqueous electrolyte solutions. Based on the assumptions of the NRTL-NRF model, excess Gibbs free energy ( g E) functions were derived for binary electrolyte systems. In this work, the local area fraction was applied and the modified model of NRTL-NRF was developed with either an equal or unequal surface area of an anion to the surface area of a cation. The modified NRTL-NRF models consist of two contributions, one due to long-range forces represented by the Debye-Hückel theory, and the other due to short-range forces, represented by local area fractions of species through nonrandom factors. Each model contains only two adjustable parameters per electrolyte. In addition, the model with unequal surface area of ionic species gives better results in comparison with the second new model with equal surface area of ions. The results for the mean activity coefficients for aqueous solutions of uni-univalent electrolytes at 298.15 K showed that the present model is more accurate than the original NRTL-NRF model.

Photo-degradation of basic green 1 and basic red 46 dyes in their binary solution by La2O3-Al2O3nanocomposite using first-order derivative spectra and experimental design methodology.

PubMed

Fahimirad, Bahareh; Asghari, Alireza; Rajabi, Maryam

2017-05-15

In this work, the lanthanum oxide-aluminum oxide (La 2 O 3 -Al 2 O 3 ) nanocomposite is introduced as an efficient photocatalyst for the photo-degradation of the dyes basic green 1 (BG1) and basic red 46 (BR46) in their binary aqueous solution under the UV light irradiation. The properties of this catalyst are determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and UV-visible spectrophotometry. The first-order derivative spectra are used for the simultaneous analysis of the dyes in their binary solution. The screening investigations indicate that five parameters including the catalyst dosage, concentration of the dyes, irradiation time, and solution pH have significant effects on the photo-degradation of the dyes. The effects of these variables together with their interactions in the photo-degradation of the dyes are studied using the Box-Behnken design (BBD). Under the optimum experimental conditions, obtained via the desirability function, the photo-catalytic activities of La 2 O 3 -Al 2 O 3 and pure Al 2 O 3 are also investigated. The results obtained show an enhancement in the photo-catalytic activity when La 2 O 3 nanoparticles are loaded on the surface of Al 2 O 3 nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

Competition and enhancement effect in coremoval of atenolol and copper by an easily regenerative magnetic cation exchange resin.

PubMed

Li, Qimeng; Wang, Zheng; Li, Qiang; Shuang, Chendong; Zhou, Qing; Li, Aimin; Gao, Canzhu

2017-07-01

This paper aimed to investigate the removal of combined Cu 2+ and atenolol (ATL) in aqueous solution by using a newly synthesized magnetic cation exchange resin (MCER) as the adsorbent. The MCER exhibited efficient removal performance in sole, binary, pre-loading and saline systems. The adsorption kinetics of Cu 2+ and ATL fitted both pseudo-first-order and pseudo-second order model, while better described by pseudo-second order model in binary system. In mixed Cu 2+ and ATL solution, the adsorption of ATL was suppressed due to direct competition of carboxylic groups, while Cu 2+ adsorption was enhanced because of the formation of surface complexes. This increasing in heterogeneity was demonstrated by adsorption isotherms, which were more suitable for Freundlich model in binary system, while better described by Langmuir model in sole system. As proved by FTIR and XPS spectra, both amino and hydroxyl groups of ATL could form complexes with Cu 2+ . Decomplexing-bridging interaction was elucidated as the leading mechanism in coremoval of Cu 2+ and ATL, which involved [Cu-ATL] decomplexing and newly created Cu- or ATL sites for additional bridging. For saline system, the resulting competition and enhancement effects in mixed solution were amplified with the addition of co-existing cations. Moreover, the MCER could be effectively regenerated by 0.01 M HCl solution and maintain high stability over 5 adsorption-desorption cycles, which render it great potential for practical applications. Copyright © 2017. Published by Elsevier Ltd.

Corrosion behavior of binary titanium aluminide intermetallics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saffarian, H.M.; Gan, Q.; Hadkar, R.

1996-08-01

The corrosion behavior of arc-melted binary titanium aluminide intermetallics TiAl, Ti{sub 2}Al, and TiAl{sub 3} in aqueous sodium sulfate and sodium chloride solutions was measured and compared to that of pure Ti and Al. Effects of electrolyte composition (e.g., sulfate [0.25 M SO{sub 4}{sup 2}{sup {minus}}], chloride [0.1 to 1.0 M Cl{sup {minus}}], and pH [3 to 10]) were examined. Anodic polarization of titanium aluminides in aqueous SO{sub 4}{sup 2}{sup {minus}} solutions was similar (showing passive behavior), but no pitting or pitting potential (E{sub pit}) was observed. In aqueous NaCl, however, titanium aluminides were susceptible to pitting, and E{sub pit}more » decreased with increasing Al content (i.e., Ti{sub 3}Al had the highest E{sub pit} and, therefore, a greater resistance to pitting, followed by TiAl and TiAl{sub 3}). For TiAl, E{sub pit} was slightly dependent upon pH or Cl{sup {minus}} concentration. Pit morphology and E{sub pit} values were quite different for TiAl compared to Ti{sub 3}Al. TiAl showed numerous small pits, whereas Ti{sub 3}Al exhibited fewer but larger and deeper pits. The larger pit density for TiAl was associated with Al-rich interdendrite regions. One interesting feature of the anodic polarization curves for Ti{sub 3}Al was a small anodic peak frequently observed at {approximately}1.4 V{sub SCE} to 1.8 V{sub SCE}. Results suggested this peak was associated with pit initiation, since pitting initiated concurrently with the peak or immediately afterward.« less

pH-specific synthesis and spectroscopic, structural, and magnetic studies of a chromium(III)-citrate species. Aqueous solution speciation of the binary chromium(III)-citrate system.

PubMed

Gabriel, C; Raptopoulou, C P; Terzis, A; Tangoulis, V; Mateescu, C; Salifoglou, A

2007-04-16

In an attempt to understand the aqueous interactions of Cr(III) with the low-molecular-mass physiological ligand citric acid, the pH-specific synthesis in the binary Cr(III)-citrate system was explored, leading to the complex (NH4)4[Cr(C6H4O7)(C6H5O7)].3H2O (1). 1 crystallizes in the monoclinic space group I2/a, with a = 19.260(10) A, b = 10.006(6) A, c = 23.400(10) A, beta = 100.73(2) degrees , V = 4431(4) A3, and Z = 8. 1 was characterized by elemental analysis and spectroscopic, structural, thermal, and magnetic susceptibility studies. Detailed aqueous speciation studies in the Cr(III)-citrate system suggest the presence of a number of species, among which is the mononuclear [Cr(C6H4O7)(C6H5O7)]4- complex, optimally present around pH approximately 5.5. The structure of 1 reveals a mononuclear octahedral complex of Cr(III) with two citrate ligands bound to it. The two citrate ligands have different deprotonation states, thus signifying the importance of the mixed deprotonation state in the coordination sphere of the Cr(III) species in aqueous speciation. The latter reveals the distribution of numerous species, including 1, for which the collective structural, spectroscopic, and magnetic data point out its physicochemical profile in the solid state and in solution. The importance of the synthetic efforts linked to 1 and the potential ramifications of Cr(III) reactivity toward both low- and high-molecular-mass biotargets are discussed in light of (a) the quest for well-characterized soluble Cr(III) species that could be detected and identified in biologically relevant fluids, (b) ongoing efforts to delineate the aqueous speciation of the Cr(III)-citrate system and its link to biotoxic Cr(III) manifestations, and (c) the synthetic utility of convenient Cr(III) precursors in the synthesis of advanced materials.

Effect of the interfacial tension and ionic strength on the thermodynamic barrier associated to the benzocaine insertion into a cell membrane.

PubMed

López Cascales, J J; Oliveira Costa, S D

2013-02-01

The insertion of local anaesthetics into a cell membrane is a key aspect for explaining their activity at a molecular level. It has been described how the potency and response time of local anaesthetics is improved (for clinical applications) when they are dissolved in a solution of sodium bicarbonate. With the aim of gaining insight into the physico-chemical principles that govern the action mechanism of these drugs at a molecular level, simulations of benzocaine in binary lipid bilayers formed by DPPC/DPPS were carried out for different ionic strengths of the aqueous solution. From these molecular dynamic simulations, we observed how the thermodynamic barrier associated with benzocaine insertion into the lipid bilayers diminished exponentially as the fraction of DPPS in the bilayer increased, especially when the ionic strength of the aqueous solution increased. In line with these results, we also observed how this thermodynamic barrier diminished exponentially with the phospholipid/water interfacial tension. Copyright © 2012 Elsevier B.V. All rights reserved.

Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

Remediation of groundwater contaminated with the lead-phenol binary system by granular dead anaerobic sludge-permeable reactive barrier.

PubMed

Faisal, Ayad A H; Abd Ali, Ziad T

2017-10-01

Computer solutions (COMSOL) Multiphysics 3.5a software was used for simulating the one-dimensional equilibrium transport of the lead-phenol binary system including the sorption process through saturated sandy soil as the aquifer and granular dead anaerobic sludge (GDAS) as the permeable reactive barrier. Fourier-transform infrared spectroscopy analysis proved that the carboxylic and alcohol groups are responsible for the bio-sorption of lead onto GDAS, while phosphines, aromatic and alkane are the functional groups responsible for the bio-sorption of phenol. Batch tests have been performed to characterize the equilibrium sorption properties of the GDAS and sandy soil in lead and/or phenol containing aqueous solutions. Numerical and experimental results proved that the barrier plays a potential role in the restriction of the contaminant plume migration and there is a linear relationship between longevity and thickness of the barrier. A good agreement between these results was recognized with root mean squared error not exceeding 0.04.

Effect of stirring on the safety of flammable liquid mixtures.

PubMed

Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

2010-05-15

Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Potentiometric study of binary complexes of 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride with some lanthanide ions in aqueous and mixed solutions

NASA Astrophysics Data System (ADS)

Sharma, S. S.; Kadia, M. V.

2014-12-01

The complexation of lanthanide ions (Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Gd3+, Tb3+, and Dy3+) with 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride was studied at different temperatures and different ionic strengths in aqueous solutions by Irving-Rossotti pH titration technique. Stepwise calculation, PKAS and BEST Fortran IV computer programs were used for determination of proton-ligand and metal-ligand stability constants. The formation of species like MA, MA2, and MA(OH) is considered in SPEPLOT. Thermodynamic parameters of complex formation (Δ G, Δ H, and Δ S) are also evaluated. Negative Δ G and Δ H values indicate that complex formation is favourable in these experimental conditions. The stability of complexes is also studied at in different solvent-aqueous (vol/vol). The stability series of lanthanide complexes has shown to have the "gadolinium break." Stability of complexes decreases with increase in ionic strength and temperature. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained.

Applications of ionic liquids in biphasic separation: Aqueous biphasic systems and liquid-liquid equilibria.

PubMed

Shukla, Shashi Kant; Pandey, Shubha; Pandey, Siddharth

2018-07-20

Ionic liquids (ILs) have been receiving much attention in many fields of analytical chemistry because of their various interesting properties which distinguish them from volatile organic compounds. They offer both directional and non-directional forces towards a solute molecule and therefore act as excellent solvents for a wide range of polar and non-polar compounds. Because of the presence of various possible interactions, ILs easily undergo biphasic separation with water and other less polar/non-polar organic solvents. Their ability to create biphasic splitting makes them a promising candidate for liquid-liquid separation processes, such as aqueous biphasic systems and liquid-liquid equilibria. Various aspects of ILs in these separation methods are discussed in view of the origin of physical forces responsible for the biphasic interactions, the effect of structural components, temperature, pressure, pH and additives. The specific advantages of using ILs in aqueous biphasic systems and liquid-liquid equilibria in binary and ternary systems are discussed with a view to defining their future role in separation processes by giving major emphasis on developing non-toxic ILs with physical and solution properties tailored to the needs of specific sample preparation techniques. Copyright © 2017 Elsevier B.V. All rights reserved.

Dynamics of glycerine and water transport across human skin from binary mixtures.

PubMed

Ventura, S A; Kasting, G B

2017-04-01

Skin transport properties of glycerine and water from binary mixtures contacting human skin were determined to better understand the mechanism of skin moisturization by aqueous glycerine formulations. Steady-state permeation for 3 H 2 O and 14 C-glycerine across split-thickness human skin in vitro and desorption dynamics of the same permeants in isolated human stratum corneum (HSC) were experimentally determined under near equilibrium conditions. These data were compared to a priori values developed in the context of a thermodynamic model for binary mixtures of glycerine and water and a previously determined water sorption isotherm for HSC. This allowed the estimation of diffusion and partition coefficients for each permeant in the HSC, as well as HSC thickness, as a function of composition of the contacting solution. These data may be used to estimate water retention and associated HSC swelling related to the absorption and slow release of glycerine from the skin. It took 6+ days for glycerine to completely desorb from HSC immersed in glycerine/water binary solutions. Desorption of both 3 H 2 O and 14 C-glycerine from HSC was slower in pure water than from binary mixtures, a result that is largely explained by the greater swelling of HSC in water. Parametric relationships were developed for water and glycerine intradiffusivities in HSC as functions of HSC water content, and a mutual diffusion coefficient was estimated by analogy with glycerine/water binary solutions. The intradiffusivity of 14 C-glycerine in HSC as inferred from sorption/desorption experiments was shown to be approximately 10-fold less than that inferred from permeation experiments, whereas the corresponding values for 3 H 2 O were comparable. These studies confirm that glycerine enters HSC in substantial quantities and has a long residence time therein. The coupling between bulk water and glycerine transport projected from binary solution data suggests the net effect of glycerine is to slow water loss from the skin. The data support the concept of glycerine as a humectant with an excellent balance of skin penetration and retention characteristics; however, they do not rule out the possibility of an additional biological effect on skin barrier homoeostasis. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

[Computer modeling the dependences of the membrane potential for polymeric membrane separated non-homogeneous electrolyte solutions on concentration Rayleigh number].

PubMed

Slezak, Izabella H; Jasik-Slezak, Jolanta; Bilewicz-Wyrozumska, Teresa; Slezak, Andrzej

2006-01-01

On the basis of model equation describing the membrane potential delta psi(s) on concentration Rayleigh number (R(C)), mechanical pressure difference (deltaP), concentration polarization coefficient (zeta s) and ratio concentration of solutions separated by membrane (Ch/Cl), the characteristics delta psi(s) = f(Rc)(delta P, zeta s, Ch/Cl) for steady values of zeta s, R(C) and Ch/Cl in single-membrane system were calculated. In this system neutral and isotropic polymeric membrane oriented in horizontal plane, the non-homogeneous binary electrolytic solutions of various concentrations were separated. Nonhomogeneity of solutions is results from creations of the concentration boundary layers on both sides of the membrane. Calculations were made for the case where on a one side of the membrane aqueous solution of NaCl at steady concentration 10(-3) mol x l(-1) (Cl) was placed and on the other aqueous solutions of NaCl at concentrations from 10(-3) mol x l(-1) to 2 x 10(-2) mol x l(-1) (Ch). Their densities were greater than NaCl solution's at 10(-3) mol x l(-1). It was shown that membrane potential depends on hydrodynamic state of a complex concentration boundary layer-membrane-concentration boundary layer, what is controlled by deltaP, Ch/Cl, Rc and Zeta(s).

Predict the glass transition temperature of glycerol-water binary cryoprotectant by molecular dynamic simulation.

PubMed

Li, Dai-Xi; Liu, Bao-Lin; Liu, Yi-shu; Chen, Cheng-lung

2008-04-01

Vitrification is proposed to be the best way for the cryopreservation of organs. The glass transition temperature (T(g)) of vitrification solutions is a critical parameter of fundamental importance for cryopreservation by vitrification. The instruments that can detect the thermodynamic, mechanical and dielectric changes of a substance may be used to determine the glass transition temperature. T(g) is usually measured by using differential scanning calorimetry (DSC). In this study, the T(g) of the glycerol-aqueous solution (60%, wt/%) was determined by isothermal-isobaric molecular dynamic simulation (NPT-MD). The software package Discover in Material Studio with the Polymer Consortium Force Field (PCFF) was used for the simulation. The state parameters of heat capacity at constant pressure (C(p)), density (rho), amorphous cell volume (V(cell)) and specific volume (V(specific)) and radial distribution function (rdf) were obtained by NPT-MD in the temperature range of 90-270K. These parameters showed a discontinuity at a specific temperature in the plot of state parameter versus temperature. The temperature at the discontinuity is taken as the simulated T(g) value for glycerol-water binary solution. The T(g) values determined by simulation method were compared with the values in the literatures. The simulation values of T(g) (160.06-167.51K) agree well with the DSC results (163.60-167.10K) and the DMA results (159.00K). We drew the conclusion that molecular dynamic simulation (MDS) is a potential method for investigating the glass transition temperature (T(g)) of glycerol-water binary cryoprotectants and may be used for other vitrification solutions.

[Effect of solution environments on ceramic membrane microfiltration of model system of Chinese medicines].

PubMed

Zhang, Lianjun; Lu, Jin; Le, Kang; Fu, Tingming; Guo, Liwei

2010-07-01

To investigate the effect of differents solution environments on the ceramic membrane microfiltration of model system of Chinese medicines. Taking binary system of soybean protein-berberine as the research object, flux, transmittance of berberine and traping rate of protein as indexes, different solution environment on membrane process were investigated. When the concentration of soybean protein was under 1 g x L(-1), the membrane flux was minimum with the traping of berberine decreased slightly as the concentration increased. When pH was 4, the flux was maximum with the traping rate of protein was 99%, and the transmittance of berberine reached above 60%. The efficiency of membrane separation can be improved by optimizing the solution environment of water-extraction of chinese medicines. The efficiency of membrane separation is the best when adjust the pH to the isoelectric point of proteins for the proteins as the main pollutant in aqueous solution.

Effect of salts on the solubility of ionic liquids in water: experimental and electrolyte Perturbed-Chain Statistical Associating Fluid Theory†

PubMed Central

Mohammad, Sultan; Schleinitz, Miko; Coutinhoa, João A. P.; Freire, Mara G.

2016-01-01

Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg−1). At salt molalities higher than 0.2 mol kg−1, all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.20 mol kg−1. To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) was applied using ion-specific parameters. The gathered experimental data was modelled using ePC-SAFT parameters complemented by fitting a single binary parameter between K+ and the IL-ions to the IL solubility in K3PO4 aqueous solutions. Based on this approach, the description of anion-specific salting-out effects of the remaining potassium salts was found to be in good agreement with experimental data. Remarkably, ePC-SAFT is even able to predict the salting-in effect induced by K2HPO4, based on the single K+/IL-ions binary parameter which was fitted to an exclusively salting-out effect promoted by K3PO4. Finally, ePC-SAFT was applied to predict the influence of other sodium salts on the [C4C1im][NTf2] solubility in water, with experimental data taken from literature, leading to an excellent description of the liquid–liquid phase behaviour. PMID:26575280

Simultaneous adsorption of Cu2+ and Acid fuchsin (AF) from aqueous solutions by CMC/bentonite composite.

PubMed

Gong, Ning; Liu, Yanping; Huang, Ruihua

2018-04-21

Carboxymethyl-chitosan (CMC)/bentonite composite was prepared by the method of membrane-forming, and characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) techniques. The simultaneous adsorption of Cu 2+ and Acid fuchsin (AF) applying CMC/bentonite composite as an adsorbent in single or binary systems was investigated. The adsorption study was conducted systematically by varying the ratio of CMC to bentonite, adsorbent dosage, initial pH value, initial Cu 2+ (or AF) concentration, contact time and the interaction of two components in binary solutions. The results showed that the presence of Cu 2+ hindered the adsorption of AF, while the presence of AF almost had no influence on the adsorption of Cu 2+ in binary systems. The adsorption data of Cu 2+ and AF were both suitable for Langmuir isotherm model, and the maximum adsorption capacities of CMC/bentonite composite, according to the Langmuir isotherm model were 81.4 mg/g for Cu 2+ and 253.2 mg/g for AF at 298 K. The pseudo-second-order model could better describe the adsorption process of Cu 2+ and AF. Thermodynamic constant values illustrated that the adsorption of Cu 2+ was endothermic, while the adsorption process of AF was exothermic. Copyright © 2018. Published by Elsevier B.V.

Competitive adsorption of ibuprofen and amoxicillin mixtures from aqueous solution on activated carbons.

PubMed

Mansouri, Hayet; Carmona, Rocio J; Gomis-Berenguer, Alicia; Souissi-Najar, Souad; Ouederni, Abdelmottaleb; Ania, Conchi O

2015-07-01

This work investigates the competitive adsorption under dynamic and equilibrium conditions of ibuprofen (IBU) and amoxicillin (AMX), two widely consumed pharmaceuticals, on nanoporous carbons of different characteristics. Batch adsorption experiments of pure components in water and their binary mixtures were carried out to measure both adsorption equilibrium and kinetics, and dynamic tests were performed to validate the simultaneous removal of the mixtures in breakthrough experiments. The equilibrium adsorption capacities evaluated from pure component solutions were higher than those measured in dynamic conditions, and were found to depend on the porous features of the adsorbent and the nature of the specific/dispersive interactions that are controlled by the solution pH, density of surface change on the carbon and ionization of the pollutant. A marked roll-up effect was observed for AMX retention on the hydrophobic carbons, not seen for the functionalized adsorbent likely due to the lower affinity of amoxicillin towards the carbon adsorbent. Dynamic adsorption of binary mixtures from wastewater of high salinity and alkalinity showed a slight increase in IBU uptake and a reduced adsorption of AMX, demonstrating the feasibility of the simultaneous removal of both compounds from complex water matrices. Copyright © 2014 Elsevier Inc. All rights reserved.

The dynamics of solvation dictates the conformation of polyethylene oxide in aqueous, isobutyric acid and binary solutions.

PubMed

Dahal, Udaya R; Dormidontova, Elena E

2017-04-12

Polymers hydrogen-bonding with solvent represent an important broad class of polymers, properties of which depend on solvation. Using atomistic molecular dynamics simulations with the OPLS/AA force field we investigate the effect of hydrogen bonding on PEO conformation and chain mobility by comparing its behavior in isobutyric acid and aqueous solutions. In agreement with experimental data, we found that in isobutyric acid PEO forms a rather rigid extended helical structure, while in water it assumes a highly flexible coil conformation. We show that the difference in PEO conformation and flexibility is the result of the hydrogen bond stability and overall solvent dynamics near PEO. Isobutyric acid forms up to one hydrogen bond per repeat unit of PEO and interacts with PEO for a prolonged period of time, thereby stabilizing the helical structure of the polymer and reducing its segmental mobility. In contrast, water forms on average 1.2 hydrogen bonds per repeat unit of PEO (with 60% of water forming a single hydrogen bond and 40% of water forming two hydrogen bonds) and resides near PEO for a noticeably shorter time than isobutyric acid, leading to the well-documented high segmental mobility of PEO in water. We also analyze PEO conformation, hydrogen bonding and segmental mobility in binary water/isobutyric acid solutions and find that in the phase separated region PEO resides in the isobutyric-rich phase forming about 25% of its hydrogen bonds with isobutyric acid and 75% with water. We show that the dynamics of solvation affects the equilibrium properties of macromolecules, such as conformation, and by mixing of hydrogen bond-donating solvents one can significantly alter both polymer conformation and its local dynamics.

Ice Recrystallization in a Solution of a Cryoprotector and Its Inhibition by a Protein: Synchrotron X-Ray Diffraction Study.

PubMed

Zakharov, Boris; Fisyuk, Alexander; Fitch, Andy; Watier, Yves; Kostyuchenko, Anastasia; Varshney, Dushyant; Sztucki, Michael; Boldyreva, Elena; Shalaev, Evgenyi

2016-07-01

Ice formation and recrystallization is a key phenomenon in freezing and freeze-drying of pharmaceuticals and biopharmaceuticals. In this investigation, high-resolution synchrotron X-ray diffraction is used to quantify the extent of disorder of ice crystals in binary aqueous solutions of a cryoprotectant (sorbitol) and a protein, bovine serum albumin. Ice crystals in more dilute (10 wt%) solutions have lower level of microstrain and larger crystal domain size than these in more concentrated (40 wt%) solutions. Warming the sorbitol-water mixtures from 100 to 228 K resulted in partial ice melting, with simultaneous reduction in the microstrain and increase in crystallite size, that is, recrystallization. In contrast to sorbitol solutions, ice crystals in the BSA solutions preserved both the microstrain and smaller crystallite size on partial melting, demonstrating that BSA inhibits ice recrystallization. The results are consistent with BSA partitioning into quasi-liquid layer on ice crystals but not with a direct protein-ice interaction and protein sorption on ice surface. The study shows for the first time that a common (i.e., not-antifreeze) protein can have a major impact on ice recrystallization and also presents synchrotron X-ray diffraction as a unique tool for quantification of crystallinity and disorder in frozen aqueous systems. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Concentration Dependence of Solution Shear Viscosity and Solute Mass Diffusivity in Crystal Growth from Solutions

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.

1995-01-01

The physical properties of a supersaturated binary solution such as its density rho, shear viscosity eta, and solute mass diffusivity D are dependent on the solute concentration c: rho = rho(c), eta = eta(c), and D = D(c). The diffusion boundary layer equations related to crystal growth from solution are derived for the case of natural convection with a solution density, a shear viscosity, and a solute diffusivity that are all depen- dent on solute concentration. The solution of these equations has demonstrated the following. (1) At the vicinity of the saturation concentration c(sub s) the solution shear viscosity eta depends on rho as eta(sub s) = eta(rho(sub s))varies as square root of rho(c(sub s)). This theoretically derived result has been verified in experiments with several aqueous solutions of inorganic and organic salts. (2) The maximum solute mass transfer towards the growing crystal surface can be achieved for values of c where the ratio of d ln(D(c)/dc) to d ln(eta(c)/dc) is a maximum.

Evidence for the interactions occurring between ionic liquids and tetraethylene glycol in binary mixtures and aqueous biphasic systems.

PubMed

Tomé, Luciana I N; Pereira, Jorge F B; Rogers, Robin D; Freire, Mara G; Gomes, José R B; Coutinho, João A P

2014-05-01

The well-recognized advantageous properties of poly(ethylene glycol)s (PEGs) and ionic liquids (ILs) in the context of an increasing demand for safe and efficient biotechnological processes has led to a growing interest in the study of their combinations for a wide range of procedures within the framework of green chemistry. Recently, one of the most promising and attractive applications has been the novel IL/polymer-based aqueous biphasic systems (ABS) for the extraction and purification of biomolecules. There still lacks, however, a comprehensive picture of the molecular phenomena that control the phase behavior of these systems. In order to further delve into the interactions that govern the mutual solubilities between ILs and PEGs and the formation of PEG/IL-based ABS, (1)H NMR spectroscopy in combination with classical molecular dynamics (MD) simulations performed for binary mixtures of tetraethylene glycol (TEG) and 1-alkyl-3-methylimidazolium-chloride-based ILs and for the corresponding ternary TEG/IL/water solutions, at T = 298.15 K, were employed in this work. The results of the simulations show that the mutual solubilities of the ILs and TEG are mainly governed by the hydrogen bonds established between the chloride anion and the -OH group of the polymer in the binary systems. Additionally, the formation of IL/PEG-based ABS is shown to be controlled by a competition between water and chloride for the interactions with the hydroxyl group of TEG.

The influence of pressure on the activity coefficients of the solutes and on the solubility of minerals in the system Na-Ca-Cl-SO 4-H 2O to 200°C and 1 kbar and to high NaCl concentration

NASA Astrophysics Data System (ADS)

Monnin, Christophe

1990-12-01

A model is presented which is used to calculate the effect of pressure on activity coefficients of aqueous solutes in the system Na-Ca-Cl-SO 4-H 2O to 200°C. Literature data for the density and compressibility of aqueous binary solutions of Na 2SO 4 and CaCl 2 to 200°C are used to calculate the first and second pressure derivatives of Pitzer's ion interaction model parameters, as well as the standard molal compressibility and volume of these two salts. Empirical correlations between the apparent molal volume and compressibility of the aqueous electrolytes are used to guide the choice of the temperature dependent expressions used for the numerical representation of the derivatives of Pitzer's parameters with respect to pressure. For sodium sulfate solutions, such correlations are used to extrapolate compressibilities to 200°C. The change in the thermodynamic properties of the-CaSO 04 ion pair with pressure is taken into account by the variation of its dissociation constant. The volumetric properties (partial molal volumes and compressibilities) of multicomponent solutions in the Na-Ca-Cl-SO 4-H 2O system can be predicted from the information generated here and the volumetric equations of ROGERS and PITZER (1982) for NaCl. This model is then combined with the high temperature model of MOLLER (1988) of the same system in order to calculate activity coefficients at high pressures to 200°C. The resulting model is validated by comparing calculated and measured solubilities of anhydrite and gypsum in pure water and in NaCl solutions up to 6 M. The agreement between the calculated and measured solubilities of the calcium sulfates is typically better than 10% up to 200°C and 1 kbar. The relevance of temperature and pressure corrections to the activity coefficients of aqueous solutes is discussed in regard to the assumed accuracy with which geochemical models are able to calculate mineral solubilities.

Heterogeneous binary interactions of taste primaries: perceptual outcomes, physiology, and future directions.

PubMed

Wilkie, Lynn M; Capaldi Phillips, Elizabeth D

2014-11-01

Complex taste experiences arise from the combinations of five taste primaries. Here we review the literature on binary interactions of heterogeneous taste primaries, focusing on perceptual results of administering mixtures of aqueous solutions to human participants. Some interactions proved relatively consistent across tastants and experimental methods: sour acids enhanced saltiness, salts and sweeteners suppressed bitterness, sweeteners suppressed sourness, and sour acids enhanced bitterness. However, for the majority of interactions there were differential effects based on the tastants and their concentrations. Drawing conclusions about interactions with umami is currently not possible due to the low number of primary source studies investigating it and the confounding sodium ions in monosodium glutamate (MSG). Speculative physiological explanations are provided that fit the current data and suggestions for future research studies are proposed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Stable biomimetic super-hydrophobic engineering materials.

PubMed

Guo, Zhiguang; Zhou, Feng; Hao, Jingcheng; Liu, Weimin

2005-11-16

We describe a simple and inexpensive method to produce super-hydrophobic surfaces on aluminum and its alloy by oxidation and chemical modification. Water or aqueous solutions (pH = 1-14) have contact angles of 168 +/- 2 and 161 +/- 2 degrees on the treated surfaces of Al and Al alloy, respectively. The super-hydrophobic surfaces are produced by the cooperation of binary structures at micro- and nanometer scales, thus reducing the energies of the surfaces. Such super-hydrophobic properties will greatly extend the applications of aluminum and its alloy as lubricating materials.

IUPAC-NIST Solubility Data Series. 104. Lithium Sulfate and its Double Salts in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Sohr, Julia; Voigt, Wolfgang; Zeng, Dewen

2017-06-01

The solubility data for lithium sulfate and its double salts in water are reviewed. Where appropriate, binary, ternary, and multicomponent systems are critically evaluated. The best values were selected on basis of these evaluations and presented in tabular form. Fitting equations and plots are provided. The quantities, units, and symbols used are in accord with IUPAC recommendations. The original data have been reported and, if necessary, transferred into the units and symbols recommended by IUPAC. The literature on solubility data is covered up to the end of 2015.

Biomimetic superhydrophobic surface of high adhesion fabricated with micronano binary structure on aluminum alloy.

PubMed

Liu, Yan; Liu, Jindan; Li, Shuyi; Liu, Jiaan; Han, Zhiwu; Ren, Luquan

2013-09-25

Triggered by the microstructure characteristics of the surfaces of typical plant leaves such as the petals of red roses, a biomimetic superhydrophobic surface with high adhesion is successfully fabricated on aluminum alloy. The essential procedure is that samples were processed by a laser, then immersed and etched in nitric acid and copper nitrate, and finally modified by DTS (CH3(CH2)11Si(OCH3)3). The obtained surfaces exhibit a binary structure consisting of microscale crater-like pits and nanoscale reticula. The superhydrophobicity can be simultaneously affected by the micronano binary structure and chemical composition of the surface. The contact angle of the superhydrophobic surface reaches up to 158.8 ± 2°. Especially, the surface with micronano binary structure is revealed to be an excellent adhesive property with petal-effect. Moreover, the superhydrophobic surfaces show excellent stability in aqueous solution with a large pH range and after being exposed long-term in air. In this way, the multifunctional biomimetic structural surface of the aluminum alloy is fabricated. Furthermore, the preparation technology in this article provides a new route for other metal materials.

Multicomponent transport in membranes for redox flow batteries

NASA Astrophysics Data System (ADS)

Monroe, Charles

2015-03-01

Redox flow batteries (RFBs) incorporate separator membranes, which ideally prevent mixing of electrochemically active species while permitting crossover of inactive supporting ions. Understanding crossover and membrane selectivity may require multicomponent transport models that account for solute/solute interactions within the membrane, as well as solute/membrane interactions. Application of the Onsager-Stefan-Maxwell formalism allows one to account for all the dissipative phenomena that may accompany component fluxes through RFB membranes. The magnitudes of dissipative interactions (diffusional drag forces) are quantified by matching experimentally established concentration transients with theory. Such transients can be measured non-invasively using DC conductometry, but the accuracy of this method requires precise characterization of the bulk RFB electrolytes. Aqueous solutions containing both vanadyl sulfate (VOSO4) and sulfuric acid (H2SO4) are relevant to RFB technology. One of the first precise characterizations of aqueous vanadyl sulfate has been implemented and will be reported. To assess the viability of a separator for vanadium RFB applications with cell-level simulations, it is critical to understand the tendencies of various classes of membranes to absorb (uptake) active species, and to know the relative rates of active-species and supporting-electrolyte diffusion. It is also of practical interest to investigate the simultaneous diffusion of active species and supports, because interactions between solutes may ultimately affect the charge efficiency and power efficiency of the RFB system as a whole. A novel implementation of Barnes's classical model of dialysis-cell diffusion [Physics 5:1 (1934) 4-8] is developed to measure the binary diffusion coefficients and sorption equilibria for single solutes (VOSO4 or H2SO4) in porous membranes and cation-exchange membranes. With the binary diffusion and uptake measurement in hand, a computer simulation that extends the approach of Heintz, Wiedemann and Ziegler [J. Membrane Science 137:1-2 (1997) 121-132] is used to establish Onsager resistances that describe the drag forces VOSO4 and H2SO4 exert on each other as they interdiffuse. The ramifications of these interactions for different classes of membranes - and for RFB applications - will be discussed. NSF CBET-1253544.

Competitive removal of hazardous dyes from aqueous solution by MIL-68(Al): Derivative spectrophotometric method and response surface methodology approach

NASA Astrophysics Data System (ADS)

Tehrani, Mahnaz Saghanejhad; Zare-Dorabei, Rouholah

2016-05-01

MIL-68(Al) as a metal-organic framework (MOF) was synthesized and characterized by different techniques such as SEM, BET, FTIR, and XRD analysis. This material was then applied for simulations removal of malachite green (MG) and methylene blue (MB) dyes from aqueous solutions using second order derivative spectrophotometric method (SODS) which was applied to resolve the overlap between the spectra of these dyes. The dependency of dyes removal efficiency in binary solutions was examined and optimized toward various parameters including initial dye concentration, pH of the solution, adsorbent dosage and ultrasonic contact time using central composite design (CCD) under response surface methodology (RSM) approach. The optimized experimental conditions were set as pH 7.78, contact time 5 min, initial MB concentration 22 mg L- 1, initial MG concentration 12 mg L- 1 and adsorbent dosage 0.0055 g. The equilibrium data was fitted to isotherm models such as Langmuir, Freundlich and Tempkin and the results revealed the suitability of the Langmuir model. The maximum adsorption capacity of 666.67 and 153.85 mg g- 1 was obtained for MB and MG removal respectively. Kinetics data fitting to pseudo-first order, pseudo-second order and Elovich models confirmed the applicability of pseudo-second order kinetic model for description of the mechanism and adsorption rate. Dye-loaded MIL-68(Al) can be easily regenerated using methanol and applied for three frequent sorption/desorption cycles with high performance. The impact of ionic strength on removal percentage of both dyes in binary mixture was studied by using NaCl and KCl soluble salts at different concentrations. According to our findings, only small dosage of the proposed MOF is considerably capable to remove large amounts of dyes at room temperature and in very short time that is a big advantage of MIL-68(Al) as a promising adsorbent for adsorptive removal processes.

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films

DOE PAGES

Farzaneh, Amirfarrokh; DeJaco, Robert F.; Ohlin, Lindsay; ...

2017-08-02

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groupsmore » are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100–23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.« less

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farzaneh, Amirfarrokh; DeJaco, Robert F.; Ohlin, Lindsay

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groupsmore » are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100–23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.« less

Revisiting the Aqueous Solutions of Dimethyl Sulfoxide by Spectroscopy in the Mid- and Near-Infrared: Experiments and Car-Parrinello Simulations.

PubMed

Wallace, Victoria M; Dhumal, Nilesh R; Zehentbauer, Florian M; Kim, Hyung J; Kiefer, Johannes

2015-11-19

The infrared and near-infrared spectra of the aqueous solutions of dimethyl sulfoxide are revisited. Experimental and computational vibrational spectra are analyzed and compared. The latter are determined as the Fourier transformation of the velocity autocorrelation function of data obtained from Car-Parrinello molecular dynamics simulations. The experimental absorption spectra are deconvolved, and the excess spectra are determined. The two-dimensional excess contour plot provides a means of visualizing and identifying spectral regions and concentration ranges exhibiting nonideal behavior. In the binary mixtures, the analysis of the SO stretching band provides a semiquantitative picture of the formation and dissociation of hydrogen-bonded DMSO-water complexes. A maximum concentration of these clusters is found in the equimolar mixture. At high DMSO concentration, the formation of rather stable 3DMSO:1water complexes is suggested. The formation of 1DMSO:2water clusters, in which the water oxygen atoms interact with the sulfoxide methyl groups, is proposed as a possible reason for the marked depression of the freezing temperature at the eutectic point.

The effect of pH and triethanolamine on sulfisoxazole complexation with hydroxypropyl-beta-cyclodextrin.

PubMed

Gladys, Granero; Claudia, Garnero; Marcela, Longhi

2003-11-01

A novel complexation of sulfisoxazole with hydroxypropyl-beta-cyclodextrin (HP-beta-CD) was studied. Two systems were used: binary complexes prepared with HP-beta-CD and multicomponent system (HP-beta-CD and the basic compound triethanolamine (TEA)). Inclusion complex formation in aqueous solutions and in solid state were investigated by the solubility method, thermal analysis (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)), Fourier-transform infrared spectroscopy (FT-IR) and dissolution studies. The solid complexes of sulfisoxazole were prepared by freeze-drying the homogeneous concentrated aqueous solutions in molar ratios of sulfisoxazole:HP-beta-CD 1:1 and 1:2, and sulfisoxazole:TEA:HP-beta-CD 1:1:2. FT-IR and thermal analysis showed differences among sulfisoxazole:HP-beta-CD and sulfisoxazole:TEA:HP-beta-CD and their corresponding physical mixtures and individual components. The HP-beta-CD solubilization of sulfisoxazole could be improved by ionization of the drug molecule through pH adjustments. However, larger improvements of the HP-beta-CD solubilization are obtained when multicomponent systems are used, allowing to reduce the amount of CD necessary to prepare the target formulation.

Selective adsorption of Pb(II) from aqueous solution using porous biosilica extracted from marine diatom biomass: Properties and mechanism

NASA Astrophysics Data System (ADS)

Qi, Yarong; Wang, Jingfeng; Wang, Xin; Cheng, Jay Jiayang; Wen, Zhiyou

2017-02-01

Biosilica with a surface area of 143 m2 g-1 derived from marine diatoms was prepared using an easy two-step method involving washing with dilute acid and baking. The extracted biosilica was used to remove divalent lead ions, i.e., Pb(II), from aqueous solution. The effects on Pb(II) adsorption of initial pH, shaking speed, and adsorbent loading were investigated. The adsorption of Pb(II) in the presence of other ions was also investigated. The biosilica showed a high adsorption capacity with high selectivity for Pb(II). The experimental maximum adsorption capacity was 108.2-120.4 mg g-1 at an adsorbent loading of 1 g L-1. The adsorption process was best described by the Langmuir model. The adsorbent selectively adsorbed Pb(II) from binary ion systems in the presence of Cu(II), Cd(II), Ni(II), and Ag(I). The results of this study show that biosilica extracted from fresh marine diatoms is a more efficient and selective adsorbent for Pb(II) than other inorganic adsorbents.

User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

Selective Permeating Properties of Butanol and Water through Polystyrene- b-polydimethylsiloxane- b-polystyrene Pervaporation Membranes

NASA Astrophysics Data System (ADS)

Shin, Chaeyoung; Baer, Zachary; Chen, X. Chelsea; Ozcam, A. Evren; Clark, Douglas; Balsara, Nitash

2015-03-01

Polystyrene- b-polydimethylsiloxane- b-polystyrene (SDS) membranes have been studied in butanol-water binary pervaporation experiments and pervaporation experiments integrated with viable fermentation broths. Polydimethylsiloxane has been widely known to be a suitable material for separating organic chemicals from aqueous solutions, and it thus provides a continuous matrix phase in SDS membranes for permeation of small molecules. The polystyrene block provides mechanical stability to maintain the membrane structure in the pervaporation membranes. We take advantage of these features to fabricate a thin and butanol-selective SDS membrane for in situ product removal in fermentation.

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE PAGES

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

2017-05-12

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

StimuFrac Compressibility as a Function of CO2 Molar Fraction

DOE Data Explorer

Carlos A. Fernandez

2016-04-29

Compressibility values were obtained in a range of pressures at 250degC by employing a fixed volume view cell completely filled with PAA aqueous solution and injecting CO2 at constant flow rate (0.3mL/min). Pressure increase as a function of supercritical CO2 (scCO2) mass fraction in the mixture was monitored. The plot shows the apparent compressibility of Stimufrac as a function of scCO2 mass fraction obtained in a pressure range between 2100-7000 psi at 250degC. At small mass fractions of scCO2 the compressibility increases probably due to the dissolution/reaction of CO2 in aqueous PAA and reaches a maximum at mCO2/mH2O = 0.06. Then, compressibility decreases showing a linear relationship with scCO2 mass fraction due to the continuous increase in density of the binary fluid associated to the pressure increase.

Solid-solution aqueous-solution equilibria: thermodynamic theory and representation

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.

1990-01-01

Thorstenson and Plummer's (1977) "stoichiometric saturation' model is reviewed, and a general relation between stoichiometric saturation Kss constants and excess free energies of mixing is derived for a binary solid-solution B1-xCxA: GE = RT[ln Kss - xln(xKCA) - (l-x)ln((l-x)KBA)]. This equation allows a suitable excess free energy function, such as Guggenheim's (1937) sub-regular function, to be fitted from experimentally determined Kss constants. Solid-phase free energies and component activity-coefficients can then be determined from one or two fitted parameters and from the endmember solubility products KBA and KCA. A general form of Lippmann's (1977,1980) "solutus equation is derived from an examination of Lippmann's (1977,1980) "total solubility product' model. Lippmann's ??II or "total solubility product' variable is used to represent graphically not only thermodynamic equilibrium states and primary saturation states but also stoichiometric saturation and pure phase saturation states. -from Authors

Clinical pharmacokinetic study for the effect of glimepiride matrix tablets developed by quality by design concept.

PubMed

Ahmed, Tarek A; Suhail, Mohammad A A; Hosny, Khaled M; Abd-Allah, Fathy I

2018-01-01

Implementation of a new pharmaceutical technique to improve aqueous solubility and thus dissolution, enhancement of drug permeation, and finally formulation of a controlled release tablet loaded with glimepiride (GLMP). Improve GLMP bioavailability and pharmacokinetics in type II diabetic patients. Different polymers were used to enhance aqueous GLMP solubility of which a saturated polymeric drug solution was prepared and physically adsorbed onto silica. An experimental design was employed to optimize the formulation parameters affecting the preparation of GLMP matrix tablets. A compatibility study was conducted to study components interactions. Scanning electron microscope (SEM) was performed before and after the tablets were placed in the dissolution medium. An in vivo study in human volunteers was performed with the optimized GLMP tablets, which were compared to pure and marketed drug products. Enhancement of GLMP aqueous solubility, using the polymeric drug solution technique, by more than 6-7 times when compared with the binary system. All the studied formulation factors significantly affected the studied variables. No significant interaction was detected among components. SEM illustrated the surface and inner tablet structure, and confirmed the drug release which was attributed to diffusion mechanism. The volunteer group administered the optimized GLMP tablet exhibited higher drug plasma concentration (147.4 ng/mL), longer time to reach maximum plasma concentration (4 h) and longer t 1/2 (7.236 h) compared to other groups. Matrix tablet loaded with a physically modified drug form could represent a key solution for drugs with inconsistent dissolution and absorption profiles.

Mono-component versus binary isotherm models for Cu(II) and Pb(II) sorption from binary metal solution by the green alga Pithophora oedogonia.

PubMed

Kumar, Dhananjay; Singh, Alpana; Gaur, J P

2008-11-01

The sorption of Cu(II) and Pb(II) by Pithophora markedly decreased as the concentration of the secondary metal ion, Cu(II) or Pb(II), increased in the binary metal solution. However, the test alga showed a greater affinity to sorb Cu(II) than Pb(II) from the binary metal solution. Mono-component Freundlich, Langmuir, Redlich-Peterson and Sips isotherms successfully predicted the sorption of Cu(II) and Pb(II) from both single and binary metal solutions. None of the tested binary sorption isotherms could realistically predict Cu(II) and Pb(II) sorption capacity and affinity of the test alga for the binary metal solutions of varying composition, which mono-component isotherms could very well accomplish. Hence, mono-component isotherm modeling at different concentrations of the secondary metal ion seems to be a better option than binary isotherms for metal sorption from binary metal solution.

Influence of chain length and double bond on the aqueous behavior of choline carboxylate soaps.

PubMed

Rengstl, Doris; Diat, Olivier; Klein, Regina; Kunz, Werner

2013-02-26

In preceding studies, we demonstrated that choline carboxylates ChC(m) with alkyl chain lengths of m = 12 - 18 are highly water-soluble (for m = 12, soluble up to 93 wt % soap and 0 °C). In addition, choline soaps are featured by an extraordinary lyotropic phase behavior. With decreasing water concentration, the following phases were found: micellar phase (L(1)), discontinuous cubic phase (I(1)' and I(1)"), hexagonal phase (H(1)), bicontinuous cubic phase (V(1)), and lamellar phase (L(α)). The present work is also focused on the lyotropic phase behavior of choline soaps but with shorter alkyl chains or different alkyl chain properties. We have investigated the aqueous phase behavior of choline soaps with C(8) and C(10) chain-lengths (choline octanoate and choline decanoate) and with a C(18) chain-length with a cis-double bond (choline oleate). We found that choline decanoate follows the lyotropic phase behavior of the longer-chain homologues mentioned above. Choline octanoate in water shows no discontinuous cubic phases, but an extended, isotropic micellar solution phase. In addition, choline octanoate is at the limit between a surfactant and a hydrotrope. The double bond in choline oleate leads also to a better solubility in water and a decrease of the solubilization temperature. It also influences the Gaussian curvature of the aggregates which results in a loss of discontinuous cubic phases in the binary phase diagram. The different lyotropic mesophases were identified by the penetration scan technique with polarizing light microscope and visual observations. To clarify the structural behavior small (SAXS) and wide (WAXS) angle X-ray scattering were performed. To further characterize the extended, isotropic micellar solution phase in the binary phase diagram of choline octanoate viscosity and conductivity measurements were also carried out.

A new method for multicomponent activity coefficients of electrolytes in aqueous atmospheric aerosols

NASA Astrophysics Data System (ADS)

Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

2005-01-01

Three-dimensional models of atmospheric inorganic aerosols need accurate and computationally efficient parameterizations of activity coefficients of various electrolytes in multicomponent aqueous solutions. In this paper, we extend the Taylor's series expansion mixing rule used by C. Wagner in 1952 for estimating activity coefficients in dilute alloy solutions to aqueous electrolyte solutions at any concentration. The resulting method, called the multicomponent Taylor expansion method (MTEM), estimates the mean activity coefficient of an electrolyte in a multicomponent solution on the basis of its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. MTEM is applied here for atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+, SO42-, HSO4-, NO3-, and Cl- ions. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson (ZSR) method. For self-consistency, most of the MTEM and ZSR parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K and are valid for an aw range of 0.2-0.97. Because CaSO4 is sparingly soluble, it is treated as a solid in the model over the entire aw range. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols and is contrasted against the mixing rule of C. L. Kusik and H. P. Meissner and of L. A. Bromley and the newer approach of S. Metzger and colleagues. Predictions of MTEM are found to be generally within a factor of 0.8-1.25 of the comprehensive Pitzer-Simonson-Clegg model and are shown to be significantly more accurate than predictions of the other three methods. MTEM also yields a noniterative solution of the bisulfate ion dissociation in sulfate-rich systems: a major computational advantage over other ionic-strength-based methods that require an iterative solution. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.

Heteroaggregation of Silver Nanoparticles with Clay Minerals in Aqueous System

NASA Astrophysics Data System (ADS)

Liu, J.; Burrow, E.; Hwang, Y.; Lenhart, J.

2013-12-01

Nanoparticles are increasingly being used in industrial processes and consumer products that exploit their beneficial properties and improve our daily lives. Nevertheless, they also attract attention when released into natural environment due to their potential for causing adverse effects. The fate and transport of nanoparticles in aqueous systems have been the focus of intense study. However, their interactions with other natural particles have received only limited attention. Clay minerals are ubiquitous in most aquatic systems and their variably charged surfaces can act as deposition sites that can alter the fate and transport of nanoparticles in natural aqueous environments. In this study, we investigated the homoaggregation of silver nanoparticles with different coating layers and their heteroaggregation behavior with clay minerals (illite, kaolinite, montmorillonite) in neutral pH solutions. Silver nanoparticles with a nominal diameter of 80 nm were synthesized with three different surface coating layers: uncoated, citrate-coated and Tween-coated. Illite (IMt-2), kaolinite (KGa-2), and montmorillonite (SWy-2) were purchased from the Clay Mineral Society (Indiana) and pretreated to obtain monocationic (Na-clay) and dicationic (Ca-clay) suspensions before the experiments. The change in hydrodynamic diameter as a function of time was monitored using dynamic light scattering (DLS) measurements in order to evaluate early stage aggregation as a function of electrolyte concentration in both the homo- and heteroaggregation scenarios. A shift in the critical coagulation concentration (CCC) values to lower electrolyte concentrations was observed in binary systems, compared to single silver nanoparticle and clay systems. The results also suggest more rapid aggregation in binary system during the early aggregation stage when compared to the single-particle systems. The behavior of citrate-coated silver nanoparticles was similar to that of the bare particles, while the Tween-coated silver nanoparticles showed high stability in both single and binary systems. There were no significant differences in early stage aggregation kinetics observed inthe Na-clay-nanoparticle or Ca-clay-nanoparticle systems, which suggested that the CCC values of the single Na- or Ca-clay suspensions depend only on the electrolyte concentration, not the original cations on the clay surface. These results provide a basic idea for understanding the heteroaggregation of different silver nanoparticles and clays, which can be utilized in further study of fate and transport of engineered nanoparticles in natural aqueous system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeshita, Kenji

A mathematical model to predict the extraction behavior of metal ion between a polymer gel and an aqueous solution was proposed. It consists of the Flory-Huggins formula for evaluating thermodynamically the physico-chemical properties of polymer gel, the modified Stokes-Einstein equation to evaluate the mass transfer rate of metal ion into polymer gel and the equation to evaluate the extraction equilibrium. The extraction of lanthanide elements, Nd(III), Sm(III) and Gd(III), from an aqueous solution containing nitrate ion was carried out by the use of SDB (styrene-divinylbenzene copolymer) gel swollen with a bidentate organophosphorus compound, CMP (dihexyl-N,N-diethylcarbamoylmethylpohosphonate). The binary extraction and themore » effect of the crosslinking degree of SDB gel on the extraction rate were examined. These experimental results were in agreement with the predictions calculated by the proposed model. It was confirmed that the extraction behavior of lanthanide ions into the SDB gel was predicted accurately, when the physico-chemical properties of SDB gel, such as the affinity between SDB and CMP ({chi}) and the crosslinking degree ({nu}{sub e}), and a coefficient defined in the modified Stokes-Einstein equation (K{sub 0}) were known. This model is available as a tool to design an extraction chromatographic process using polymer gel.« less

Effect of polyethylene glycol on the liquid–liquid phase transition in aqueous protein solutions

PubMed Central

Annunziata, Onofrio; Asherie, Neer; Lomakin, Aleksey; Pande, Jayanti; Ogun, Olutayo; Benedek, George B.

2002-01-01

We have studied the effect of polyethylene glycol (PEG) on the liquid–liquid phase separation (LLPS) of aqueous solutions of bovine γD-crystallin (γD), a protein in the eye lens. We observe that the phase separation temperature increases with both PEG concentration and PEG molecular weight. PEG partitioning, which is the difference between the PEG concentration in the two coexisting phases, has been measured experimentally and observed to increase with PEG molecular weight. The measurements of both LLPS temperature and PEG partitioning in the ternary γD-PEG-water systems are used to successfully predict the location of the liquid–liquid phase boundary of the binary γD-water system. We show that our LLPS measurements can be also used to estimate the protein solubility as a function of the concentration of crystallizing agents. Moreover, the slope of the tie-lines and the dependence of LLPS temperature on polymer concentration provide a powerful and sensitive check of the validity of excluded volume models. Finally, we show that the increase of the LLPS temperature with PEG concentration is due to attractive protein–protein interactions. PMID:12391331

Free energy of formation of a crystal nucleus in incongruent solidification: Implication for modeling the crystallization of aqueous nitric acid droplets in polar stratospheric clouds

NASA Astrophysics Data System (ADS)

Djikaev, Yuri S.; Ruckenstein, Eli

2017-04-01

Using the formalism of classical thermodynamics in the framework of the classical nucleation theory, we derive an expression for the reversible work W* of formation of a binary crystal nucleus in a liquid binary solution of non-stoichiometric composition (incongruent crystallization). Applied to the crystallization of aqueous nitric acid droplets, the new expression more adequately takes account of the effects of nitric acid vapor compared to the conventional expression of MacKenzie, Kulmala, Laaksonen, and Vesala (MKLV) [J. Geophys. Res.: Atmos. 102, 19729 (1997)]. The predictions of both MKLV and modified expressions for the average liquid-solid interfacial tension σls of nitric acid dihydrate (NAD) crystals are compared by using existing experimental data on the incongruent crystallization of aqueous nitric acid droplets of composition relevant to polar stratospheric clouds (PSCs). The predictions for σls based on the MKLV expression are higher by about 5% compared to predictions based on our modified expression. This results in similar differences between the predictions of both expressions for the solid-vapor interfacial tension σsv of NAD crystal nuclei. The latter can be obtained by using the method based on the analysis of experimental data on crystal nucleation rates in aqueous nitric acid droplets; it exploits the dominance of the surface-stimulated mode of crystal nucleation in small droplets and its negligibility in large ones. Applying that method to existing experimental data, our expression for the free energy of formation provides an estimate for σsv of NAD in the range ≈92 dyn/cm to ≈100 dyn/cm, while the MKLV expression predicts it in the range ≈95 dyn/cm to ≈105 dyn/cm. The predictions of both expressions for W* become identical for the case of congruent crystallization; this was also demonstrated by applying our method for determining σsv to the nucleation of nitric acid trihydrate crystals in PSC droplets of stoichiometric composition.

[Intersection point rule for the retention value with mobile phase composition and boiling point of the homologues and chlorobenzenes in soil leaching column chromatography].

PubMed

Xu, F; Liang, X; Lin, B; Su, F

1999-03-01

Based on the linear retention equation of the logarithm of the capacity factor (logk') vs. the methanol volume fraction (psi) of aqueous binary mobile phase in soil leaching column chromatography, the intersection point rule for the logk' of homologues and weak polar chlorobenzenes, with psi, as well as with boiling point, has been derived due to existence of the similar interactions among solutes of the same series, stationary phase (soil) and eluent (methanol-water). These rules were testified by experimental data of homologues (n-alkylbenzenes, methylbenzenes) and weak polar chlorobenzenes.

IUPAC-NIST Solubility Data Series. 89. Alkali Metal Nitrates. Part 2. Sodium Nitrate

NASA Astrophysics Data System (ADS)

Eysseltová, Jitka; Zbranek, Vladimír; Skripkin, Mikhail Yurievich; Sawada, Kiyoshi; Tepavitcharova, Stefka

2017-03-01

The solubility data at 1 bar or saturation pressure for sodium nitrate are reviewed. Where appropriate, binary, ternary, and multicomponent systems are critically evaluated. The solubility results were obtained in water or aqueous solutions. All data were critically examined for their reliability. The best values were selected on the basis of critical evaluations and presented in tabular form. Fitting equations and plots are also provided. The quantities, units, and symbols used are in accord with IUPAC recommendations. The original data have been reported and, if necessary, transferred into the units and symbols recommended by IUPAC. The literature on solubility data was researched through 2014.

Linear adsorption of nonionic organic compounds from water onto hydrophilic minerals: Silica and alumina

USGS Publications Warehouse

Su, Y.-H.; Zhu, Y.-G.; Sheng, G.; Chiou, C.T.

2006-01-01

To characterize the linear adsorption phenomena in aqueous nonionic organic solute-mineral systems, the adsorption isotherms of some low-molecular- weightnonpolar nonionic solutes (1,2,3-trichlorobenzene, lindane, phenanthrene, and pyrene) and polar nonionic solutes (1,3-dinitrobenzene and 2,4-dinitrotoluene) from single-and binary-solute solutions on hydrophilic silica and alumina were established. Toward this objective, the influences of temperature, ionic strength, and pH on adsorption were also determined. It is found that linear adsorption exhibits low exothermic heats and practically no adsorptive competition. The solute-solid configuration and the adsorptive force consistent with these effects were hypothesized. For nonpolar solutes, the adsorption occurs presumably by London (dispersion) forces onto a water film above the mineral surface. For polar solutes, the adsorption is also assisted by polar-group interactions. The reduced adsorptive forces of solutes with hydrophilic minerals due to physical separation by the water film and the low fractions of the water-film surface covered by solutes offer a theoretical basis for linear solute adsorption, low exothermic heats, and no adsorptive competition. The postulated adsorptive forces are supported by observations that ionic strength or pH poses no effect on the adsorption of nonpolar solutes while it exhibits a significant effect on the uptake of polar solutes. ?? 2006 American Chemical Society.

Structural anomaly and dynamic heterogeneity in cycloether/water binary mixtures: Signatures from composition dependent dynamic fluorescence measurements and computer simulations

NASA Astrophysics Data System (ADS)

Indra, Sandipa; Guchhait, Biswajit; Biswas, Ranjit

2016-03-01

We have performed steady state UV-visible absorption and time-resolved fluorescence measurements and computer simulations to explore the cosolvent mole fraction induced changes in structural and dynamical properties of water/dioxane (Diox) and water/tetrahydrofuran (THF) binary mixtures. Diox is a quadrupolar solvent whereas THF is a dipolar one although both are cyclic molecules and represent cycloethers. The focus here is on whether these cycloethers can induce stiffening and transition of water H-bond network structure and, if they do, whether such structural modification differentiates the chemical nature (dipolar or quadrupolar) of the cosolvent molecules. Composition dependent measured fluorescence lifetimes and rotation times of a dissolved dipolar solute (Coumarin 153, C153) suggest cycloether mole-fraction (XTHF/Diox) induced structural transition for both of these aqueous binary mixtures in the 0.1 ≤ XTHF/Diox ≤ 0.2 regime with no specific dependence on the chemical nature. Interestingly, absorption measurements reveal stiffening of water H-bond structure in the presence of both the cycloethers at a nearly equal mole-fraction, XTHF/Diox ˜ 0.05. Measurements near the critical solution temperature or concentration indicate no role for the solution criticality on the anomalous structural changes. Evidences for cycloether aggregation at very dilute concentrations have been found. Simulated radial distribution functions reflect abrupt changes in respective peak heights at those mixture compositions around which fluorescence measurements revealed structural transition. Simulated water coordination numbers (for a dissolved C153) and number of H-bonds also exhibit minima around these cosolvent concentrations. In addition, several dynamic heterogeneity parameters have been simulated for both the mixtures to explore the effects of structural transition and chemical nature of cosolvent on heterogeneous dynamics of these systems. Simulated four-point dynamic susceptibility suggests formation of clusters inducing local heterogeneity in the solution structure.

Aqueous electrolytes for redox flow battery systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

An aqueous redox flow battery system includes an aqueous catholyte and an aqueous anolyte. The aqueous catholyte may comprise (i) an optionally substituted thiourea or a nitroxyl radical compound and (ii) a catholyte aqueous supporting solution. The aqueous anolyte may comprise (i) metal cations or a viologen compound and (ii) an anolyte aqueous supporting solution. The catholyte aqueous supporting solution and the anolyte aqueous supporting solution independently may comprise (i) a proton source, (ii) a halide source, or (iii) a proton source and a halide source.

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

NASA Astrophysics Data System (ADS)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Adsorption of Selected Pharmaceutical Compounds onto Activated Carbon in Dilute Aqueous Solutions Exemplified by Acetaminophen, Diclofenac, and Sulfamethoxazole.

PubMed

Chang, E-E; Wan, Jan-Chi; Kim, Hyunook; Liang, Chung-Huei; Dai, Yung-Dun; Chiang, Pen-Chi

2015-01-01

The adsorption of three pharmaceuticals, namely, acetaminophen, diclofenac, and sulfamethoxazole onto granular activated carbon (GAC), was investigated. To study competitive adsorption, both dynamic and steady-state adsorption experiments were conducted by careful selection of pharmaceuticals with various affinities and molecular size. The effective diffusion coefficient of the adsorbate was increased with decease in particle size of GAC. The adsorption affinity represented as Langmuir was consistent with the ranking of the octanol-water partition coefficient, K(ow). The adsorption behavior in binary or tertiary systems could be described by competition adsorption. In the binary system adsorption replacement occurred, under which the adsorbate with the smaller K(ow) was replaced by the one with larger K(ow). Results also indicated that portion of the micropores could be occupied only by the small target compound, but not the larger adsorbates. In multiple-component systems the competition adsorption might significantly be affected by the macropores and less by the meso- or micropores.

Adsorption of Selected Pharmaceutical Compounds onto Activated Carbon in Dilute Aqueous Solutions Exemplified by Acetaminophen, Diclofenac, and Sulfamethoxazole

PubMed Central

Chang, E.-E.; Wan, Jan-Chi; Liang, Chung-Huei; Dai, Yung-Dun; Chiang, Pen-Chi

2015-01-01

The adsorption of three pharmaceuticals, namely, acetaminophen, diclofenac, and sulfamethoxazole onto granular activated carbon (GAC), was investigated. To study competitive adsorption, both dynamic and steady-state adsorption experiments were conducted by careful selection of pharmaceuticals with various affinities and molecular size. The effective diffusion coefficient of the adsorbate was increased with decease in particle size of GAC. The adsorption affinity represented as Langmuir was consistent with the ranking of the octanol-water partition coefficient, K ow. The adsorption behavior in binary or tertiary systems could be described by competition adsorption. In the binary system adsorption replacement occurred, under which the adsorbate with the smaller K ow was replaced by the one with larger K ow. Results also indicated that portion of the micropores could be occupied only by the small target compound, but not the larger adsorbates. In multiple-component systems the competition adsorption might significantly be affected by the macropores and less by the meso- or micropores. PMID:26078989

Oil-soluble and water-soluble BTPhens and their europium complexes in octanol/water solutions: interface crossing studied by MD and PMF simulations.

PubMed

Benay, G; Wipff, G

2013-01-31

Bistriazinyl-phenantroline "BTPhen" ligands L display the remarkable feature to complex trivalent lanthanide and actinide ions, with a marked selectivity for the latter. We report on molecular dynamics studies of tetrasubstituted X(4)BTPhens: L(4+) (X = (+)Et(3)NCH(2)-), L(4-) (X = (-)SO(3)Ph-), and L(0) (X = CyMe(4)) and their complexes with Eu(III) in binary octanol/water solutions. Changes in free energies upon interface crossing are also calculated for typical solutes by potential of mean force PMF simulations. The ligands and their complexes partition, as expected, to either the aqueous or the oil phase, depending on the "solubilizing" group X. Furthermore, most of them are found to be surface active. The water-soluble L(4+) and L(4-) ligands and their (L)Eu(NO(3))(3) complexes adsorb at the aqueous side of the interface, more with L(4-) than with L(4+). The oil soluble ligand L(0) is not surface active in its endo-endo form but adsorbs on the oil side of the interface in its most polar endo-exo form, as well as in its protonated L(0)H(+) and complexed (L(0))Eu(NO(3))(3) states. Furthermore, comparing PMFs of the Eu(III) complexes with and without nitric acid shows that acidifying the aqueous phase has different effects, depending on the ligand charge. In particular, acid promotes the Eu(III) extraction by L(0) via the (L(0))(2)Eu(NO(3))(2+) complex, as observed experimentally. Overall, the results point to the importance of interfacial adsorption for the liquid-liquid extraction of trivalent lanthanide and actinide cations by BTPhens and analogues.

Grafting of GMA and some comonomers onto chitosan for controlled release of diclofenac sodium.

PubMed

Sharma, Rajeev Kr; Lalita; Singh, Anirudh P; Chauhan, Ghanshyam S

2014-03-01

In order to develop pH sensitive hydrogels for controlled drug release we have graft copolymerized glycidyl methacrylate (GMA) with comonomers acrylic acid, acrylamide and acrylonitrile, onto chitosan (Ch) by using potassium persulphate (KPS) as free radical initiator in aqueous solution. The optimum percent grafting for GMA was recorded for 1g chitosan at [KPS]=25.00 × 10(-3)mol/L, [GMA]=0.756 × 10(-3)mol/L, reaction temperature=60 °C and reaction time=1h in 20 mL H2O. Binary monomers were grafted for five different concentrations at optimum grafting conditions evaluated for GMA alone onto chitosan. The graft copolymers were characterized by FTIR, XRD, TGA and SEM. The swelling properties of chitosan and graft copolymers were investigated at different pH to define their end uses in sustained release of an anti-inflammatory drug, diclofenac sodium. Percent drug release w.r.t. drug loaded in polymeric sample was studied as function of time in buffer solutions of pH 2.0 and 7.4. In vitro release data was analyzed using Fick's Law. Chitosan grafted with binary monomers, GMA-co-AAm and GMA-co-AN showed very good results for sustained release of drug at 7.4 pH. Copyright © 2014 Elsevier B.V. All rights reserved.

Counteraction of Trehalose on N, N-Dimethylformamide-Induced Candida rugosa Lipase Denaturation: Spectroscopic Insight and Molecular Dynamic Simulation

PubMed Central

Yang, Xin; Jia, Yigang; Hu, Yi; Xu, Qing; Xu, Xian

2016-01-01

Candida rugosa lipase (CRL) has been widely used as a biocatalyst for non-aqueous synthesis in biotechnological applications, which, however, often suffers significant loss of activity in organic solvent. Experimental results show that trehalose could actively counteract the organic-solvent-induced protein denaturation, while the molecular mechanisms still don’t unclear. Herein, CRL was used as a model enzyme to explore the effects of trehalose on the retention of enzymatic activity upon incubation in N,N-dimethylformamide (DMF). Results showed that both catalytic activity and conformation changes of CRL influenced by DMF solvent were inhibited by trehalose in a dose-dependent fashion. The simulations further indicated that the CRL protein unfolded in binary DMF solution, but retained the native state in the ternary DMF/trehalose system. Trehalose as the second osmolyte added into binary DMF solution decreased DMF-CRL hydrogen bonds efficiently, whereas increased the intermolecular hydrogen bondings between DMF and trehalose. Thus, the origin of its denaturing effects of DMF on protein is thought to be due to the preferential exclusion of trehalose as well as the intermolecular hydrogen bondings between trehalose and DMF. These findings suggest that trehalose protect the CRL protein from DMF-induced unfolding via both indirect and direct interactions. PMID:27031946

Spectral studies on the interaction of pinacyanol chloride with binary surfactants in aqueous medium.

PubMed

Manna, Kausik; Panda, Amiya Kumar

2009-12-01

Interaction of pinacyanol chloride (PIN) with pure and binary mixtures of cetyltrimethylammonium bromide (CTAB) and sodium deoxycholate (NaDC) was spectroscopically studied. Interaction of PIN with pure NaDC produced a blue shifted metachromatic band (at approximately 502 nm), which gradually shifted to higher wavelength region as the concentration of NaDC increased in the pre-micellar stage. For CTAB only intensity of both the bands increased without any shift. Mixed surfactant systems behaved differently than the pure components. Absorbance of monomeric band with a slight red-shift, and a simultaneous decrease in the absorbance of dimeric band of PIN, were observed for all the combinations in the post-micellar region. PIN-micelle binding constant (K(b)) for pure as well as mixed was determined from spectral data using Benesi-Hildebrand equation. Using the idea of Regular Solution Theory, micellar aggregates were assumed to be predominant than other aggregated state, like vesicles. Aggregation number was determined by fluorescence quenching method. Spectral analyses were also done to evaluate CMC values. Rubinigh's model for Regular Solution Theory was employed to evaluate the interaction parameters and micellar composition. Strong synergistic interaction between the oppositely charged surfactants was noted. Bulkier nature of NaDC lowered down its access in mixed micellar system.

New analytical technique for carbon dioxide absorption solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pouryousefi, F.; Idem, R.O.

2008-02-15

The densities and refractive indices of two binary systems (water + MEA and water + MDEA) and three ternary systems (water + MEA + CO{sub 2}, water + MDEA + CO{sub 2}, and water + MEA + MDEA) used for carbon dioxide (CO{sub 2}) capture were measured over the range of compositions of the aqueous alkanolamine(s) used for CO{sub 2} absorption at temperatures from 295 to 338 K. Experimental densities were modeled empirically, while the experimental refractive indices were modeled using well-established models from the known values of their pure-component densities and refractive indices. The density and Gladstone-Dale refractive indexmore » models were then used to obtain the compositions of unknown samples of the binary and ternary systems by simultaneous solution of the density and refractive index equations. The results from this technique have been compared with HPLC (high-performance liquid chromatography) results, while a third independent technique (acid-base titration) was used to verify the results. The results show that the systems' compositions obtained from the simple and easy-to-use refractive index/density technique were very comparable to the expensive and laborious HPLC/titration techniques, suggesting that the refractive index/density technique can be used to replace existing methods for analysis of fresh or nondegraded, CO{sub 2}-loaded, single and mixed alkanolamine solutions.« less

Counteraction of Trehalose on N, N-Dimethylformamide-Induced Candida rugosa Lipase Denaturation: Spectroscopic Insight and Molecular Dynamic Simulation.

PubMed

Yang, Xin; Jiang, Ling; Jia, Yigang; Hu, Yi; Xu, Qing; Xu, Xian; Huang, He

2016-01-01

Candida rugosa lipase (CRL) has been widely used as a biocatalyst for non-aqueous synthesis in biotechnological applications, which, however, often suffers significant loss of activity in organic solvent. Experimental results show that trehalose could actively counteract the organic-solvent-induced protein denaturation, while the molecular mechanisms still don't unclear. Herein, CRL was used as a model enzyme to explore the effects of trehalose on the retention of enzymatic activity upon incubation in N,N-dimethylformamide (DMF). Results showed that both catalytic activity and conformation changes of CRL influenced by DMF solvent were inhibited by trehalose in a dose-dependent fashion. The simulations further indicated that the CRL protein unfolded in binary DMF solution, but retained the native state in the ternary DMF/trehalose system. Trehalose as the second osmolyte added into binary DMF solution decreased DMF-CRL hydrogen bonds efficiently, whereas increased the intermolecular hydrogen bondings between DMF and trehalose. Thus, the origin of its denaturing effects of DMF on protein is thought to be due to the preferential exclusion of trehalose as well as the intermolecular hydrogen bondings between trehalose and DMF. These findings suggest that trehalose protect the CRL protein from DMF-induced unfolding via both indirect and direct interactions.

Densities of aqueous blended amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsu, C.H.; Li, M.H.

1997-05-01

Solutions of alkanolamines are an industrially important class of compounds used in the natural gas and synthetic ammonia industries and petroleum chemical plants for the removal of CO{sub 2} and H{sub 2}S from gas streams. The densities of aqueous mixtures of diethanolamine (DEA) + N-methyldiethanolamine (MDEA) + water, DEA + 2-amino-2-methyl-1-propanol (AMP) + water, and monoethanolamine (MEA) + 2-piperidineethanol (2-PE) + water were measured from 30 C to 80 C. A Redlich-Kister equation of the excess volume was applied to represent the density. Based on the available density data for five ternary systems: MEA + MDEA + H{sub 2}O, MEAmore » + AMP + H{sub 2}O, DEA + MDEA + H{sub 2}O, DEA + AMP + H{sub 2}O, and MEA + 2-PE + H{sub 2}O, a generalized set of binary parameters were determined. The density calculations show quite satisfactory results. The overall average absolute percent deviation is about 0.04% for a total of 686 data points.« less

Viscosities of aqueous blended amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsu, C.H.; Li, M.H.

1997-07-01

Solutions of alkanolamines are an industrially important class of compounds used in the natural gas, oil refineries, petroleum chemical plants, and synthetic ammonia industries for the removal of acidic components like CO{sub 2} and H{sub 2}S from gas streams. The viscosities of aqueous mixtures of diethanolamine (DEA) + N-methyldiethanolamine (MDEA), DEA + 2-amino-2-methyl-1-propanol (AMP), and monoethanolamine (MEA) + 2-piperidineethanol (2-PE) were measured from 30 C to 80 C. A Redlich-Kister equation for the viscosity deviation was applied to represent the viscosity. On the basis of the available viscosity data for five ternary systems, MEA + MDEA + H{sub 2}O, MEAmore » + AMP + H{sub 2}O, DEA + MDEA + H{sub 2}O, DEA + AMP + H{sub 2}O, and MEA + 2-PE + H{sub 2}O, a generalized set of binary parameters were determined. For the viscosity calculation of the systems tested, the overall average absolute percent deviation is about 1.0% for a total of 499 data points.« less

On the calculation of solubilities via direct coexistence simulations: Investigation of NaCl aqueous solutions and Lennard-Jones binary mixtures.

PubMed

Espinosa, J R; Young, J M; Jiang, H; Gupta, D; Vega, C; Sanz, E; Debenedetti, P G; Panagiotopoulos, A Z

2016-10-21

Direct coexistence molecular dynamics simulations of NaCl solutions and Lennard-Jones binary mixtures were performed to explore the origin of reported discrepancies between solubilities obtained by direct interfacial simulations and values obtained from the chemical potentials of the crystal and solution phases. We find that the key cause of these discrepancies is the use of crystal slabs of insufficient width to eliminate finite-size effects. We observe that for NaCl crystal slabs thicker than 4 nm (in the direction perpendicular to the interface), the same solubility values are obtained from the direct coexistence and chemical potential routes, namely, 3.7 ± 0.2 molal at T = 298.15 K and p = 1 bar for the JC-SPC/E model. Such finite-size effects are absent in the Lennard-Jones system and are likely caused by surface dipoles present in the salt crystals. We confirmed that μs-long molecular dynamics runs are required to obtain reliable solubility values from direct coexistence calculations, provided that the initial solution conditions are near the equilibrium solubility values; even longer runs are needed for equilibration of significantly different concentrations. We do not observe any effects of the exposed crystal face on the solubility values or equilibration times. For both the NaCl and Lennard-Jones systems, the use of a spherical crystallite embedded in the solution leads to significantly higher apparent solubility values relative to the flat-interface direct coexistence calculations and the chemical potential values. Our results have broad implications for the determination of solubilities of molecular models of ionic systems.

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Use of spectroscopic technique to develop a reagent for Mo(VI) utilizing micellar effects on complex formation

NASA Astrophysics Data System (ADS)

Taşcioğlu, Sülin; Kaki, E.; Taşcioğlu, Senay

2012-09-01

Ultraviolet and visible spectral properties of aqueous solutions of molybdenum(VI) (Mo), gallic acid (GA), Lalanine (Ala), and L-Phenylalanine (Phe), and of their binary and ternary solutions were investigated in the absence and presence of anionic, cationic, and nonionic surfactant micelles. Evaluation of the spectra in a comparative way revealed that both Ala and Phe form ternary complexes with Mo and GA. The formation of a quaternary complex between Mo, GA, Phe, and cetyltrimethylammonium bromide at pH 4.5 provided a reagent system with a strikingly high sensitivity (1.2•106 l/(mol•cm)) for use in the spectrophotometric determination of Mo. A mechanism of micellar effects was discussed in terms of the substrate molecular charge and hydrophobicity, and rationalized on the basis of the spectral data obtained above and below the isoelectric pH of the amino acids.

Effect of co-existing copper and calcium on the removal of As(V) by reused aluminum oxides.

PubMed

Yang, J K; Park, Y J; Kim, K H; Lee, H Y; Min, K C; Lee, S M

2013-01-01

Among the various heavy metals, arsenic is frequently found in abandoned mine drainage and the environmental fate of arsenic in real aqueous solutions can be highly dependent on the presence of co-existing ions. In this study, removal of arsenate through adsorption on the reused aluminum oxide or through precipitation was investigated in a single and in a binary system as a function of pH and concentration. Different removal behaviors of arsenate were observed in the presence of different cations as well as a variation of the molar ratios of arsenate to cations. Co-operative effects on arsenate removal by precipitation in solution occurred with an increase of copper concentration, while a decrease of arsenate removal resulted in increasing calcium concentration. It was observed that the arsenate removal in the presence of calcium would be highly dependent on the molar ratios of both elements.

PROCESS OF REMOVING PLUTONIUM VALUES FROM SOLUTION WITH GROUP IVB METAL PHOSPHO-SILICATE COMPOSITIONS

DOEpatents

Russell, E.R.; Adamson, A.W.; Schubert, J.; Boyd, G.E.

1957-10-29

A process for separating plutonium values from aqueous solutions which contain the plutonium in minute concentrations is described. These values can be removed from an aqueous solution by taking an aqueous solution containing a salt of zirconium, titanium, hafnium or thorium, adding an aqueous solution of silicate and phosphoric acid anions to the metal salt solution, and separating, washing and drying the precipitate which forms when the two solutions are mixed. The aqueous plutonium containing solution is then acidified and passed over the above described precipi-tate causing the plutonium values to be adsorbed by the precipitate.

Gradual crossover in molecular organization of stable liquid H2O at moderately high pressure and temperature

NASA Astrophysics Data System (ADS)

Koga, Yoshikata; Westh, Peter; Yoshida, Koh; Inaba, Akira; Nakazawa, Yasuhiro

2014-09-01

Using the literature raw data of the speed of sound and the specific volume, the isothermal compressibility, κT, a second derivative thermodynamic quantity of G, was evaluated for liquid H2O in the pressure range up to 350 MPa and the temperature to 50 °C. We then obtained its pressure derivative, dκT/dp, a third derivative numerically without using a fitting function to the κT data. On taking yet another p-derivative at a fixed T graphically without resorting to any fitting function, the resulting d2κT/dp2, a fourth derivative, showed a weak but clear step anomaly, with the onset of the step named point X and its end point Y. In analogy with another third and fourth derivative pair in binary aqueous solutions of glycerol, dαp/dxGly and d2αp/dxGly2, at 0.1 MPa (αp is the thermal expansivity and xGly the mole fraction of solute glycerol) in our recent publication [J. Solution Chem. 43, 663-674 (2014); DOI:10.1007/s10953-013-0122-7], we argue that there is a gradual crossover in the molecular organization of pure H2O from a low to a high p-regions starting at point X and ending at Y at a fixed T. The crossover takes place gradually spanning for about 100 MPa at a fixed temperature. The extrapolated temperature to zero p seems to be about 70 - 80 °C for points X and 90 - 110 °C for Y. Furthermore, the mid-points of X and Y seem to extrapolate to the triple point of liquid, ice Ih and ice III. Recalling that the zero xGly extrapolation of point X and Y for binary aqueous glycerol at 0.1 MPa gives about the same T values respectively, we suggest that at zero pressure the region below about 70 °C the hydrogen bond network is bond-percolated, while above about 90 °C there is no hydrogen bond network. Implication of these findings is discussed.

Perfluorooctane sulfonate adsorption on powder activated carbon: Effect of phosphate (P) competition, pH, and temperature.

PubMed

Qian, Jin; Shen, Mengmeng; Wang, Peifang; Wang, Chao; Li, Kun; Liu, Jingjing; Lu, Bianhe; Tian, Xin

2017-09-01

Powdered activated carbon (PAC), as an adsorbent, was applied to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Laboratory batch experiments were performed to investigate the influences of phosphate (P) competition, temperature, and pH for PFOS adsorption onto PAC. The results showed that higher temperature favored PFOS adsorption in single and binary systems. The kinetic data fitted very well to the pseudo second-order kinetic model. Thermodynamically, the endothermic enthalpy of the PFOS adsorption in single and binary systems were 125.07 and 21.25 kJ mol -1 , respectively. The entropy of the PFOS adsorption in single and binary systems were 0.479 and 0.092 kJ mol -1  K -1 , respectively. And the Gibbs constants were negative. These results indicated that the adsorption processes were spontaneous. The adsorption isotherms of PFOS agreed well with the Langmuir model. In the single system, PFOS adsorption decreased with increased pH value. The difference in the amount of PFOS adsorption between the single and binary systems increased at higher pH. Frustrated total internal reflection (FTIR) demonstrated that P competition increased the hydrophilicity of the PAC and the electrostatic repulsion between PFOS and PAC, then the PFOS adsorption amount decreased. It also demonstrated that, at higher temperature, increased PFOS adsorption was mainly due to the higher diffusion rate of PFOS molecules and greater number of active sites opened on the PAC surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

Application of experimental design and derivative spectrophotometry methods in optimization and analysis of biosorption of binary mixtures of basic dyes from aqueous solutions.

PubMed

Asfaram, Arash; Ghaedi, Mehrorang; Ghezelbash, Gholam Reza; Pepe, Francesco

2017-05-01

Simultaneous biosorption of malachite green (MG) and crystal violet (CV) on biosorbent Yarrowia lipolytica ISF7 was studied. An appropriate derivative spectrophotometry technique was used to evaluate the concentration of each dye in binary solutions, despite significant interferences in visible light absorbances. The effects of pH, temperature, growth time, initial MG and CV concentration in batch experiments were assessed using Design of Experiment (DOE) according to central composite second order response surface methodology (RSM). The analysis showed that the greatest biosorption efficiency (>99% for both dyes) can be obtained at pH 7.0, T=28°C, 24h mixing and 20mgL -1 initial concentrations for both MG and CV dyes. The quadratic constructed equation ability for fitting experimental data is judged based on criterions like R 2 values, significant p and lack-of-fit value strongly confirm its high adequacy and applicability for prediction of revel behavior of the system under study. The proposed model showed very high correlation coefficients (R 2 =0.9997 for CV and R 2 =0.9989 for MG), while supported by closeness of predicted and experimental value. A kinetic analysis was carried out, showing that for both dyes a pseudo-second order kinetic model adequately describes the available data. The Langmuir isotherm model in single and binary components has better performance for description of dyes biosorption with maximum monolayer biosorption capacity of 59.4 and 62.7mgg -1 in single component and 46.4 and 50.0mgg -1 for CV and MB in binary components, respectively. The surface structure of biosorbents and the possible biosorbents-dyes interactions between were also evaluated by Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The values of thermodynamic parameters including ΔG° and ΔH° strongly confirm which method is spontaneous and endothermic. Copyright © 2017. Published by Elsevier Inc.

Complexation and molecular modeling studies of europium(III)-gallic acid-amino acid complexes.

PubMed

Taha, Mohamed; Khan, Imran; Coutinho, João A P

2016-04-01

With many metal-based drugs extensively used today in the treatment of cancer, attention has focused on the development of new coordination compounds with antitumor activity with europium(III) complexes recently introduced as novel anticancer drugs. The aim of this work is to design new Eu(III) complexes with gallic acid, an antioxida'nt phenolic compound. Gallic acid was chosen because it shows anticancer activity without harming health cells. As antioxidant, it helps to protect human cells against oxidative damage that implicated in DNA damage, cancer, and accelerated cell aging. In this work, the formation of binary and ternary complexes of Eu(III) with gallic acid, primary ligand, and amino acids alanine, leucine, isoleucine, and tryptophan was studied by glass electrode potentiometry in aqueous solution containing 0.1M NaNO3 at (298.2 ± 0.1) K. Their overall stability constants were evaluated and the concentration distributions of the complex species in solution were calculated. The protonation constants of gallic acid and amino acids were also determined at our experimental conditions and compared with those predicted by using conductor-like screening model for realistic solvation (COSMO-RS) model. The geometries of Eu(III)-gallic acid complexes were characterized by the density functional theory (DFT). The spectroscopic UV-visible and photoluminescence measurements are carried out to confirm the formation of Eu(III)-gallic acid complexes in aqueous solutions. Copyright © 2016 Elsevier Inc. All rights reserved.

Trapping proton transfer intermediates in the disordered hydrogen-bonded network of cryogenic hydrofluoric acid solutions.

PubMed

Ayotte, Patrick; Plessis, Sylvain; Marchand, Patrick

2008-08-28

A molecular-level description of the structural and dynamical aspects that are responsible for the weak acid behaviour of dilute hydrofluoric acid solutions and their unusual increased acidity at near equimolar concentrations continues to elude us. We address this problem by reporting reflection-absorption infrared spectra (RAIRS) of cryogenic HF-H(2)O binary mixtures at various compositions prepared as nanoscopic films using molecular beam techniques. Optical constants for these cryogenic solutions [n(omega) and k(omega)] are obtained by iteratively solving Fresnel equations for stratified media. Modeling of the experimental RAIRS spectra allow for a quantitative interpretation of the complex interplay between multiple reflections, optical interference and absorption effects. The evolution of the strong absorption features in the intermediate 1000-3000 cm(-1) range with increasing HF concentration reveals the presence of various ionic dissociation intermediates that are trapped in the disordered H-bonded network of cryogenic hydrofluoric acid solutions. Our findings are discussed in light of the conventional interpretation of why hydrofluoric acid is a weak acid revealing molecular-level details of the mechanism for HF ionization that may be relevant to analogous elementary processes involved in the ionization of weak acids in aqueous solutions.

The use of synthesized aqueous solutions for determining strontium sorption isotherms

USGS Publications Warehouse

Liszewski, M.J.; Bunde, R.L.; Hemming, C.; Rosentreter, J.; Welhan, J.

1998-01-01

The use of synthesized aqueous solutions for determining experimentally derived strontium sorption isotherms of sediment was investigated as part of a study accessing strontium chemical transport properties. Batch experimental techniques were used to determine strontium sorption isotherms using synthesized aqueous solutions designed to chemically represent water from a natural aquifer with respect to major ionic character and pH. A strontium sorption isotherm for a sediment derived using a synthesized aqueous solution was found to be most comparable to an isotherm derived using natural water when the synthesized aqueous solution contained similar concentrations of calcium and magnesium. However, it is difficult to match compositions exactly due to the effects of disequilibrium between the solution and the sediment. Strong linear relations between sorbed strontium and solution concentrations of calcium and magnesium confirm that these cations are important co-constituents in these synthesized aqueous solutions. Conversely, weak linear relations between sorbed strontium and solution concentrations of sodium and potassium indicate that these constituents do not affect sorption of strontium. The addition of silica to the synthesized aqueous solution does not appreciably affect the resulting strontium sorption isotherm.

Single, binary and multi-component adsorption of some anions and heavy metals on environmentally friendly Carpobrotus edulis plant.

PubMed

Chiban, Mohamed; Soudani, Amina; Sinan, Fouad; Persin, Michel

2011-02-01

A low-cost adsorbent and environmentally friendly adsorbent from Carpobrotus edulis plant was used for the removal of NO(3)(-), H(2)PO(4)(-), Pb(2+) and Cd(2+) ions from single, binary and multi-component systems. The efficiency of the adsorbent was studied using batch adsorption technique under different experimental conditions by varying parameters such as pH, initial concentration and contact time. In single component systems, the dried C. edulis has the highest affinity for Pb(2+), followed by NO(3)(-), Cd(2+) and H(2)PO(4)(-), with adsorption capacities of 175mg/g, 125mg/g, 28mg/g and 26mg/g, respectively. These results showed that the adsorption of NO(3)(-) and H(2)PO(4)(-) ions from single and binary component systems can be successfully described by Langmuir and Freundlich isotherms. Freundlich adsorption model, showed the best fit to the single and binary experimental adsorption data. These results also indicated that the adsorption yield of Pb(2+) ion was reduced by the presence of Cd(2+) ion in binary metal mixture. The competitive adsorption of NO(3)(-), H(2)PO(4)(-), Pb(2+) and Cd(2+) ions on dried C. edulis plant shows that NO(3)(-) and H(2)PO(4)(-) anions are able to adsorb on different free binding sites and Pb(2+) and Cd(2+) cations are able to adsorb on the same active sites of C. edulis particles. The dried C. edulis was found to be efficient in removing nitrate, phosphate, cadmium and lead from aqueous solution as compared to other adsorbents already used for the removal of these ions. Copyright © 2010 Elsevier B.V. All rights reserved.

Synthetic investigation of binary-ternary Cr(III)-hydroxycarboxylic acid-aromatic chelator systems. Structure-specific influence on adipogenic biomarkers linked to insulin mimesis.

PubMed

Tsave, O; Gabriel, C; Kafantari, M; Yavropoulou, M; Yovos, J G; Raptopoulou, C P; Psycharis, V; Terzis, A; Mateescu, C; Salifoglou, A

2018-07-01

In an attempt to understand the aqueous interactions of Cr(III) with low-molecular mass physiological ligands and examine its role as an adipogenic metallodrug agent in Diabetes mellitus II, the pH-specific synthesis in the binary-ternary Cr(III)-(HA = hydroxycarboxylic acid)-(N,N)-aromatic chelator (AC) (HA = 2-hydroxyethyl iminodiacetic acid/heidaH 2 , quinic acid; AC = 1,10-phenanthroline/phen) systems was pursued, leading to four new crystalline compounds. All materials were characterized by elemental analysis, UV-Visible, FT-IR, and ESI-MS spectroscopy, cyclic voltammetry, and X-Ray crystallography. Concurrently, the aqueous speciation of the binary Cr(III)-(2-hydroxyethyl iminodiacetic acid) system, complemented by ESI-MS, provided key-details of the species in solution correlating with the solid-state species. The structurally distinct Cr(III) soluble species were subsequently used in an in vitro investigation of their cytotoxic activity in 3T3-L1 fibroblast cultures. Compound 1 exhibited solubility, bioavailability, and atoxicity over a wide concentration range (0.1-100 μΜ) in contrast to 3, which was toxic. The adipogenic potential of 1 was subsequently investigated toward transformation of pre-adipocytes into mature adipocytes. Confirmation of that capacity relied on molecular biological techniques a) involving genes (glucose transporter type 4, peroxisome proliferator-activated receptor gamma, glucokinase, and adiponectin) serving as sensors of the transformation process, b) comparing the Cr(III)-adipogenicity potential to that of insulin, and c) exemplifying the ultimate maturity of adipocytes poised to catabolize glucose. The collective effort points out salient structural features in the coordination sphere of Cr(III) inducing adipogenic transformation relevant to combating hyperglycemia. The multiply targeted mechanistic insight into such a process exemplifies the role of well-defined Cr(III) complex forms as potential insulin-mimetic adipogenic agents in Diabetes mellitus II. Copyright © 2018 Elsevier Inc. All rights reserved.

Membrane separation for non-aqueous solution

NASA Astrophysics Data System (ADS)

Widodo, S.; Khoiruddin; Ariono, D.; Subagjo; Wenten, I. G.

2018-01-01

Membrane technology has been widely used in a number of applications competing with conventional technologies in various ways. Despite the enormous applications, they are mainly used for the aqueous system. The use of membrane-based processes in a non-aqueous system is an emerging area. This is because developed membranes are still limited in separations involving aqueous solution which show several drawbacks when implemented in a non-aqueous system. The purpose of this paper is to provide a review of the current application of membrane processes in non-aqueous solutions, such as mineral oil treatment, vegetable oil processing, and organic solvent recovery. Developments of advanced membrane materials for the non-aqueous solutions such as super-hydrophobic and organic solvent resistant membranes are reviewed. In addition, challenges and future outlook of membrane separation for the non-aqueous solution are discussed.

Phase Equilibrium Investigation on 2-Phenylethanol in Binary and Ternary Systems: Influence of High Pressure on Density and Solid-Liquid Phase Equilibrium.

PubMed

Domańska, Urszula; Królikowski, Marek; Wlazło, Michał; Więckowski, Mikołaj

2018-05-30

Ionic liquids (ILs) are important new solvents proposed for applications in different separation processes. Herein, an idea of possible use of high pressure in a general strategy of production of 2-phenylethanol (PEA) is discussed. In this work, we present the influence of pressure on the density in binary systems of {1-hexyl-1-methylpyrrolidynium bis{(trifluoromethyl)sulfonyl}imide, [HMPYR][NTf 2 ], or 1-dodecyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [DoMIM][NTf 2 ] + PEA} in a wide range of temperatures (298.15-348.15 K) and pressures (0.1-40 MPa). The densities at ambient and high pressures are measured to present the physicochemical properties of the ILs used in the process of separation of PEA from aqueous phase. The Tait equation was used for the correlation of density of one-component and two-component systems as a function of mole fraction, temperature, and pressure. The influence of pressure is not significant. These systems exhibit mainly negative molar excess volumes, V E . The solid-liquid phase equilibrium (SLE) of [DoMIM][NTf 2 ] in PEA at atmospheric pressure was measured and compared to the SLE high-pressure results. Additionally, the ternary liquid-liquid phase equilibrium (LLE) at ambient pressure in the {[DoMIM][NTf 2 ] (1) + PEA (2) + water (3)} at temperature T = 308.15 K was investigated. The solubility of water in the [DoMIM][NTf 2 ] is quite high in comparison with that measured by us earlier for ILs ( x 3 = 0.403) at T = 308.15 K, which results in not very successful average selectivity of extraction of PEA from the aqueous phase. The [DoMIM][NTf 2 ] has shown strong interaction with PEA without the immiscibility region. The ternary system revealed Treybal's type phase equilibrium in which two partially miscible binaries ([DoMIM][NTf 2 ] + water) and (PEA + water) exist. From the results of LLE in the ternary system, the selectivity and the solute distribution ratio of separation of water/PEA were calculated and compared to the results obtained for the ILs measured earlier by us. The popular NRTL model was used to correlate the experimental tie-lines in ternary LLE. These results may help in a new technological project of "in situ" extraction of PEA from aqueous phase during the biosynthesis.

Water-soluble polymers for recovery of metal ions from aqueous streams

DOEpatents

Smith, Barbara F.; Robison, Thomas W.

1998-01-01

A process of selectively separating a target metal contained in an aqueous solution by contacting the aqueous solution containing a target metal with an aqueous solution including a water-soluble polymer capable of binding with the target metal for sufficient time whereby a water-soluble polymer-target metal complex is formed, and, separating the solution including the water-soluble polymer-target metal complex from the solution is disclosed.

Solar photocatalytic degradation of mono azo methyl orange and diazo reactive green 19 in single and binary dye solutions: adsorbability vs photodegradation rate.

PubMed

Ong, Soon-An; Min, Ohm-Mar; Ho, Li-Ngee; Wong, Yee-Shian

2013-05-01

The objective of this study was to examine the effects of adsorbability and number of sulfonate group on solar photocatalytic degradation of mono azo methyl orange (MO) and diazo Reactive Green 19 (RG19) in single and binary dye solutions. The adsorption capacity of MO and RG19 onto the TiO₂ was 16.9 and 26.8 mg/g, respectively, in single dye solution, and reduced to 5.0 and 23.1 mg/g, respectively, in the binary dye solution. The data obtained for photocatalytic degradation of MO and RG19 in single and binary dye solution were well fitted with the Langmuir-Hinshelwood kinetic model. The pseudo-first-order rate constants of diazo RG19 were significant higher than the mono azo MO either in single or binary dye solutions. The higher number of sulfonate group in RG19 contributed to better adsorption capacity onto the surface of TiO₂ than MO indicating greater photocatalytic degradation rate.

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.

Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Uda, Tetsuya

2016-04-01

This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

Screening hydroxyapatite for cadmium and lead immobilization in aqueous solution and contaminated soil: The role of surface area.

PubMed

Li, Hongying; Guo, Xisheng; Ye, Xinxin

2017-02-01

Hydroxyapatite (HAP) has been widely used to immobilize many cationic metals in water and soils. The specific reason why an increase in the surface area of HAP enhances cadmium (Cd) uptake, but has no effect on lead (Pb) uptake, is not clear. The aim of this study was to determine the factors causing the differences in sorption behavior between Cd and Pb by evaluating HAPs with different surface areas. We synthesized HAPs with two different surface areas, which were characterized by X-ray diffraction, N 2 adsorption, and scanning electron microscopy, and then evaluated them as sorbents for Cd and Pb removal by testing in single and binary systems. The sorption capacity of large surface area HAP (1.85mmol/g) for Cd in the single-metal system was higher than that of small surface area HAP (0.64mmol/g), but there were no differences between single- and binary-metal solutions containing Pb. After the Cd experiments, the HAP retained a stable structure and intact morphology, which promotes the accessibility of reactive sites for Cd. However, a newly formed precipitate covered the surface and blocked the channels in the presence of Pb, which reduced the number of potential adsorption sites on HAP for Cd and Pb. Remediation experiments using Cd- and Pb-contaminated soil produced similar results to the solution tests. These results indicate that alterations of the structure and morphology during the reaction is an important factor influencing metal sorption to HAP. Copyright © 2016. Published by Elsevier B.V.

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...

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.

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; 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.

Evaluation and enhancement of heavy metals bioremediation in aqueous solutions by Nocardiopsis sp. MORSY1948, and Nocardia sp. MORSY2014.

PubMed

El-Gendy, Mervat Morsy Abbas Ahmed; El-Bondkly, Ahmed Mohamed Ahmed

2016-01-01

An analysis of wastewater samples collected from different industrial regions of Egypt demonstrated dangerously high levels of nickel (0.27-31.50mgL(-1)), chromium (1.50-7.41mgL(-1)) and zinc (1.91-9.74mgL(-1)) in the effluents. Alarmingly, these heavy metals are among the most toxic knownones to humans and wildlife. Sixty-nine Actinomycete isolates derived from contaminated sites were evaluated under single, binary, and ternary systems for their biosorption capacity for Ni(2+), Cr(6+) and Zn(2+) from aqueous solutions. The results of the study identified isolates MORSY1948 and MORSY2014 as the most active biosorbents. Phenotypic and chemotypic characterization along with molecular phylogenetic evidence confirmed that the two strains are members of the Nocardiopsis and Nocardia genera, respectively. The results also proved that for both the strains, heavy metal reduction was more efficient with dead rather than live biomass. The affinity of the dead biomass of MORSY1948 strain for Ni(2+), Cr(6+) and Zn(2+) under the optimized pH conditions of 7, 8 and 7, respectively at 40°C temperature with 0.3% biosorbent dosage was found to be as follows: Ni(2+) (87.90%)>Zn(2+) (84.15%)>Cr(6+) (63.75%). However, the dead biomass of MORSY2014 strain under conditions of pH 8 and 50°C temperature with 0.3% biosorbent dose exhibited the highest affinity which was as follows: Cr(6+) (95.22%)>Ni(2+) (93.53%)>Zn(2+) (90.37%). All heavy metals under study were found to be removed from aqueous solutions in entirety when the sorbent dosage was increased to 0.4%. Copyright © 2016 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

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.

Phase-separable aqueous amide solutions as a thermal history indicator.

PubMed

Kitsunai, Makoto; Miyajima, Kentaro; Mikami, Yuzuru; Kim, Shokaku; Hirasawa, Akira; Chiba, Kazuhiro

2008-12-01

Aqueous solutions of several new amide compounds for use as simple thermal history indicators in the low-temperature transport of food and other products were synthesized. The phase transition temperatures of the aqueous solutions can be freely adjusted by changing the amide-water ratio in solution, the sodium chloride concentration of the water, and the type of amide compound. It is expected that these aqueous solutions can be applied as new thermal history indicators.

LASERS, ACTIVE MEDIA: The aqueous-polyelectrolyte dye solution as an active laser medium

NASA Astrophysics Data System (ADS)

Akimov, A. I.; Saletskii, A. M.

2000-11-01

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.

Solution-phase electronegativity scale: insight into the chemical behaviors of metal ions in solution.

PubMed

Li, Keyan; Li, Min; Xue, Dongfeng

2012-04-26

By incorporating the solvent effect into the Born effective radius, we have proposed an electronegativity scale of metal ions in aqueous solution with the most common oxidation states and hydration coordination numbers in terms of the effective ionic electrostatic potential. It is found that the metal ions in aqueous solution are poorer electron acceptors compared to those in the gas phase. This solution-phase electronegativity scale shows its efficiency in predicting some important properties of metal ions in aqueous solution such as the aqueous acidities of the metal ions, the stability constants of metal complexes, and the solubility product constants of the metal hydroxides. We have elaborated that the standard reduction potential and the solution-phase electronegativity are two different quantities for describing the processes of metal ions in aqueous solution to soak up electrons with different final states. This work provides a new insight into the chemical behaviors of the metal ions in aqueous solution, indicating a potential application of this electronegativity scale to the design of solution reactions.

Unraveling the cytotoxicity and metabolic pathways of binary natural deep eutectic solvent systems

PubMed Central

Mbous, Yves Paul; Hayyan, Maan; Wong, Won Fen; Looi, Chung Yeng; Hashim, Mohd Ali

2017-01-01

In this study, the anticancer potential and cytotoxicity of natural deep eutectic solvents (NADESs) were assessed using HelaS3, PC3, A375, AGS, MCF-7, and WRL-68 hepatic cell lines. NADESs were prepared from choline chloride, fructose, or glucose and compared with an N,N-diethyl ethanolammonium chloride:triethylene glycol DES. The NADESs (98 ≤ EC50 ≥ 516 mM) were less toxic than the DES (34 ≤ EC50 ≥ 120 mM). The EC50 values of the NADESs were significantly higher than those of the aqueous solutions of their individual components but were similar to those of the aqueous solutions of combinations of their chief elements. Due to the uniqueness of these results, the possibility that NADESs could be synthesized intracellularly to counterbalance the cytotoxicity of their excess principal constituents must be entertained. However, further research is needed to explore this avenue. NADESs exerted cytotoxicity by increasing membrane porosity and redox stress. In vivo, they were more destructive than the DES and induced liver failure. The potential of these mixtures was evidenced by their anticancer activity and intracellular processing. This infers that they can serve as tools for increasing our understanding of cell physiology and metabolism. It is likely that we only have begun to comprehend the nature of NADESs. PMID:28145498

Enhanced decolorization of methyl orange in aqueous solution using iron-carbon micro-electrolysis activation of sodium persulfate.

PubMed

Li, Peng; Liu, Zhipeng; Wang, Xuegang; Guo, Yadan; Wang, Lizhang

2017-08-01

Reactivity of sodium persulfate (PS) in the decolorization of methyl orange (MO) in aqueous solution using an iron-carbon micro-electrolysis (ICE) method was investigated. The effects of sodium persulfate doses, pH, Fe-to-C mass ratios, initial MO concentration as well as the reaction temperature were comprehensively studied in batch experiments. The ICE-PS coupled process was more suitable for wide ranges of pH, initial MO concentration and reaction temperature, accompanied by the reduction of Fe compared ICE. The MO removal efficiency improved substantially by ICE-PS technique, 76.03% for ICE and 91.27% for ICE-PS at experimental conditions of pH 3.0, Fe-to-C mass ratio 3:1, PS addition 10 mM and initial MO concentration 0.61 mM. Furthermore, the biodegradability index (BI) dramatically increased from 0.26 to 0.65. The binary hydroxyl and sulfate radicals that non-selectively degrade MO to the derivatives with small molecules are ascribed to ICE-PS method as detected by the UV-vis spectra. The PS activation resource was Fe 2+ through the hydroxyl radical quenching reaction by the additive tert-butanol (TBA). This study provides an in-depth theoretical understanding of the development and wide commercial application of the ICE technology to refractory industrial dye wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Unraveling the cytotoxicity and metabolic pathways of binary natural deep eutectic solvent systems

NASA Astrophysics Data System (ADS)

Mbous, Yves Paul; Hayyan, Maan; Wong, Won Fen; Looi, Chung Yeng; Hashim, Mohd Ali

2017-02-01

In this study, the anticancer potential and cytotoxicity of natural deep eutectic solvents (NADESs) were assessed using HelaS3, PC3, A375, AGS, MCF-7, and WRL-68 hepatic cell lines. NADESs were prepared from choline chloride, fructose, or glucose and compared with an N,N-diethyl ethanolammonium chloride:triethylene glycol DES. The NADESs (98 ≤ EC50 ≥ 516 mM) were less toxic than the DES (34 ≤ EC50 ≥ 120 mM). The EC50 values of the NADESs were significantly higher than those of the aqueous solutions of their individual components but were similar to those of the aqueous solutions of combinations of their chief elements. Due to the uniqueness of these results, the possibility that NADESs could be synthesized intracellularly to counterbalance the cytotoxicity of their excess principal constituents must be entertained. However, further research is needed to explore this avenue. NADESs exerted cytotoxicity by increasing membrane porosity and redox stress. In vivo, they were more destructive than the DES and induced liver failure. The potential of these mixtures was evidenced by their anticancer activity and intracellular processing. This infers that they can serve as tools for increasing our understanding of cell physiology and metabolism. It is likely that we only have begun to comprehend the nature of NADESs.

Preparation of graphene oxide-manganese dioxide for highly efficient adsorption and separation of Th(IV)/U(VI).

PubMed

Pan, Ning; Li, Long; Ding, Jie; Li, Shengke; Wang, Ruibing; Jin, Yongdong; Wang, Xiangke; Xia, Chuanqin

2016-05-15

Manganese dioxide decorated graphene oxide (GOM) was prepared via fixation of crystallographic MnO2 (α, γ) on the surface of graphene oxide (GO) and was explored as an adsorbent material for simultaneous removal of thorium/uranium ions from aqueous solutions. In single component systems (Th(IV) or U(VI)), the α-GOM2 (the weight ratio of GO/α-MnO2 of 2) exhibited higher maximum adsorption capacities toward both Th(IV) (497.5mg/g) and U(VI) (185.2 mg/g) than those of GO. In the binary component system (Th(IV)/U(VI)), the saturated adsorption capacity of Th(IV) (408.8 mg/g)/U(VI) (66.8 mg/g) on α-GOM2 was also higher than those on GO. Based on the analysis of various data, it was proposed that the adsorption process may involve four types of molecular interactions including coordination, electrostatic interaction, cation-pi interaction, and Lewis acid-base interaction between Th(IV)/U(VI) and α-GOM2. Finally, the Th(IV)/U(VI) ions on α-GOM2 can be separated by a two-stage desorption process with Na2CO3/EDTA. Those results displayed that the α-GOM2 may be utilized as an potential adsorbent for removing and separating Th(IV)/U(VI) ions from aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Systematic Approach to Electrostatically Induced 2D Crystallization of Nanoparticles at Liquid Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fukuto, M.; Kewalramani, S.; Wang, S.

2011-02-07

We report an experimental demonstration of a strategy for inducing two-dimensional (2D) crystallization of charged nanoparticles on oppositely charged fluid interfaces. This strategy aims to maximize the interfacial adsorption of nanoparticles, and hence their lateral packing density, by utilizing a combination of weakly charged particles and a high surface charge density on the planar interface. In order to test this approach, we investigated the assembly of cowpea mosaic virus (CPMV) on positively charged lipid monolayers at the aqueous solution surface, by means of in situ X-ray scattering measurements at the liquid-vapor interface. The assembly was studied as a function ofmore » the solution pH, which was used to vary the charge on CPMV, and of the mole fraction of the cationic lipid in the binary lipid monolayer, which set the interface charge density. The 2D crystallization of CPMV occurred in a narrow pH range just above the particle's isoelectric point, where the particle charge was weakly negative, and only when the cationic-lipid fraction in the monolayer exceeded a threshold. The observed 2D crystals exhibited nearly the same packing density as the densest lattice plane within the known 3D crystals of CPMV. The above electrostatic approach of maximizing interfacial adsorption may provide an efficient route to the crystallization of nanoparticles at aqueous interfaces.« less

The validity of the potential model in predicting the structural, dynamical, thermodynamic properties of the unary and binary mixture of water-alcohol: Methanol-water case

NASA Astrophysics Data System (ADS)

Obeidat, Abdalla; Abu-Ghazleh, Hind

2018-06-01

Two intermolecular potential models of methanol (TraPPE-UA and OPLS-AA) have been used in order to examine their validity in reproducing the selected structural, dynamical, and thermodynamic properties in the unary and binary systems. These two models are combined with two water models (SPC/E and TIP4P). The temperature dependence of density, surface tension, diffusion and structural properties for the unary system has been computed over specific range of temperatures (200-300K). The very good performance of the TraPPE-UA potential model in predicting surface tension, diffusion, structure, and density of the unary system led us to examine its accuracy and performance in its aqueous solution. In the binary system the same properties were examined, using different mole fractions of methanol. The TraPPE-UA model combined with TIP4P-water shows a very good agreement with the experimental results for density and surface tension properties; whereas the OPLS-AA combined with SPCE-water shows a very agreement with experimental results regarding the diffusion coefficients. Two different approaches have been used in calculating the diffusion coefficient in the mixture, namely the Einstein equation (EE) and Green-Kubo (GK) method. Our results show the advantageous of applying GK over EE in reproducing the experimental results and in saving computer time.

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

DOEpatents

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.

SEPARATION OF SCANDIUM VALUES FORM IRON VALUES BY SOLVENT EXTRACTION

DOEpatents

Kuhlman, C.W. Jr.; Lang, G.P.

1961-12-19

A process is given for separating scandium from trivalent iron values. In this process, an aqueous nitric acid solution is contacted with a water- immiscible alkyl phosphate solution, the aqueous solution containing the values to be separated, whereby the scandium is taken up by the alkyl phosphate. The aqueous so1ution is preferably saturated with magnesium nitrate to retain the iron in the aqueous solution. (AEC)

An ion-imprinted silica-supported organic-inorganic hybrid sorbent prepared by a surface imprinting technique combined with a polysaccharide incorporated sol-gel process for selective separation of cadmium(II) from aqueous solution.

PubMed

Li, Feng; Jiang, Hongquan; Zhang, Shusheng

2007-03-15

Ion-imprinting concept and polysaccharide incorporated sol-gel process were applied to the preparation of a new silica-supported organic-inorganic hybrid sorbent for selective separation of Cd(II) from aqueous solution. In the prepared shell/core composite sorbent, covalently surface coating on the supporting silica gel was achieved by using a Cd(II)-imprinting sol-gel process starting from an inorganic precursor, gamma-glycidoxypropyltrimethoxysiloxane (GPTMS), and a functional biopolymer, chitosan (CS). The sorbent was prepared through self-hydrolysis of GPTMS, self-condensation and co-condensation of silanol groups (Si-OH) from siloxane and silica gel surface, in combination with in situ covalent cross-linking of CS with partial amine shielded by Cd(II) complexation. Extraction of the imprinting molecules left a predetermined arrangement of ligands and tailored binding pockets for Cd(II). The prepared sorbent was characterized by using X-ray energy dispersion spectroscopy (EDX), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Batch experiments were conducted to study the sorption performance by removal of Cd(II) when present singly or in binary system, an aqueous Cd(II) and Zn(II) mixture. The ion-imprinted composite sorbent offered a fast kinetics for the sorption of Cd(II) and the maximum capacity was 1.14mmolg(-1). The uptake capacity of the imprinted sorbent and the selectivity coefficient were much higher than that of the non-imprinted sorbent. The imprinted sorbent exhibited high reusability. The prepared functional sorbent was shown to be promising for the preconcentration of cadmium in environmental and biological samples.

Determination of the antileukemic drug mitoguazone and seven other closely related bis(amidinohydrazones) in human blood serum by high-performance liquid chromatography.

PubMed

Koskinen, M; Elo, H; Lukkari, P; Riekkola, M L

1996-10-11

A reversed-phase (C18) HPLC method with diode-array detection was developed for the separation and determination of methylglyoxal bis(amidinohydrazone) (mitoguazone) and seven closely related aliphatic analogs thereof, namely the bis(amidinohydrazones) of glyoxal, dimethylglyoxal, ethylmethylglyoxal, methylpropylglyoxal, butylmethylglyoxal, diethylglyoxal and dipropylglyoxal. The mobile phase consisted of a non-linear binary gradient of methanol and 0.03 M aqueous sodium acetate buffer (pH 4.3). Good separation of the eight congeners was achieved. On increasing the methanol content of the eluent, the bis(amidinohydrazones) eluted in the order of increasing number of carbon atoms in the side-chains. The method was also applied to the quantitative analysis of the compounds in aqueous solution and, combined with ultrafiltration, for the separation of the eight congeners in spiked human blood serum. A separate simplified method for the quantitative determination of each of the compounds in spiked human blood serum samples was also developed. The methods developed made for the first time possible the simultaneous HPLC analysis of more than one bis(amidinohydrazones). The results obtained indicate that the bis(amidinohydrazones) studied obviously have a distinct tendency to form ion associates with acetate ions and probably also other carboxylate ions in aqueous solution. This aspect may be of biochemical significance, especially concerning the intracellular binding of the compounds. Each one of the compounds studied invariably gave rise to one peak only, this result supporting the theory that the conventional synthesis of each of the compounds gives rise to one geometrical isomer only. This result is completely in agreement with the results of previous proton and carbon NMR spectroscopic as well as X-ray diffraction studies.

Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

PubMed

Bohli, Thouraya; Ouederni, Abdelmottaleb

2016-08-01

Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.

Evolution of Spatial pH Distribution in Aqueous Solution induced by Atmospheric Pressure Plasma

NASA Astrophysics Data System (ADS)

Takahashi, Shigenori; Mano, Kakeru; Hayashi, Yui; Takada, Noriharu; Kanda, Hideki; Goto, Motonobu

2016-09-01

Discharge plasma at gas-liquid interface produces some active species, and then they affect chemical reactions in aqueous solution, where pH of aqueous solution is changed due to redox species. The pH change of aqueous solution is an important factor for chemical reactions. However, spatial pH distribution in a reactor during the discharge has not been clarified yet. Thus, this work focused on spatial pH distribution of aqueous solution when pulsed discharge plasma was generated from a copper electrode in gas phase to aqueous solution in a reactor. Experiments were conducted using positive unipolar pulsed power. The unipolar pulsed voltage at +8.0 kV was applied to the copper electrode and the bottom of the reactor was grounded. The size of the reactor was 80 mm wide, 10 mm deep, and 40 mm high. The electrode was set at distance of 2 mm from the solution surface. Anthocyanins were contained in the aqueous solution as a pH indicator. The change pH solution spread horizontally, and low pH region of 10 mm in depth was formed. After discharge for 10 minutes, the low pH region was diffused toward the bottom of the reactor. After discharge for 60 minutes, the pH of the whole solution decreased.

Hydrogen production by sodium borohydride in NaOH aqueous solution

NASA Astrophysics Data System (ADS)

Wang, Q.; Zhang, L. F.; Zhao, Z. G.

2018-01-01

The kinetics of hydrolysis reaction of NaBH4 in NaOH aqueous solution is studied. The influence of pH of the NaOH aqueous solution on the rate of hydrogen production and the hydrogen production efficiency are studied for the hydrolysis reaction of NaBH4. The results show that the activation energy of hydrolysis reaction of NaBH4 increased with the increase of the initial pH of NaOH aqueous solution.With the increasing of the initial pH of NaOH aqueous solution, the rate of hydrogen production and hydrogen production efficiency of NaBH4 hydrolysis decrease.

Assessment of Fenton's reagent and ozonation as pre-treatments for increasing the biodegradability of aqueous diethanolamine solutions from an oil refinery gas sweetening process.

PubMed

Durán-Moreno, A; García-González, S A; Gutiérrez-Lara, M R; Rigas, F; Ramírez-Zamora, R M

2011-02-28

The aim of this work was to evaluate the efficiency of three chemical oxidation processes for increasing the biodegradability of aqueous diethanolamine solutions (aqueous DEA solutions), to be used as pre-treatments before a biological process. The raw aqueous DEA solution, sourced from a sour gas sweetening plant at a Mexican oil refinery, was first characterized by standardized physico-chemical methods. Then experiments were conducted on diluted aqueous DEA solutions to test the effects of Fenton's reagent, ozone and ozone-hydrogen peroxide on the removal of some physicochemical parameters of these solutions. Lastly, biodegradability tests based on Dissolved Organic Carbon Die Away OECD301-A, were carried out on a dilution of the raw aqueous DEA solution and on the treated aqueous DEA solutions, produced by applying the best experimental conditions determined during the aforementioned oxidation tests. Experimental results showed that for aqueous DEA solutions treated with Fenton's reagent, the best degradation rate (70%) was obtained at pH 2.8, with Fe(2+) and H(2)O(2) at doses of 1000 and 10,000 mg/L respectively. In the ozone process, the best degradation (60%) was observed in aqueous DEA solution (100 mg COD/L), using 100 mg O(3)/L at pH 5. In the ozone-hydrogen peroxide process, no COD or DOC removals were observed. The diluted spent diethanolamine solution showed its greatest increase in biodegradability after a reaction period of 28 days when treated with Fenton's reagent, but after only 15 days in the case of ozonation. Copyright © 2011 Elsevier B.V. All rights reserved.

Cryo-irradiation as a terminal method for the sterilization of drug aqueous solutions.

PubMed

Maquille, Aubert; Habib Jiwan, Jean-Louis; Tilquin, Bernard

2008-05-01

The aim of this study is to evaluate the specificities of the irradiation of drugs in frozen aqueous solution. The structures of the degradation products were determined to gain insight into the radiolysis mechanisms occurring in frozen aqueous solutions. Metoclopramide hydrochloride and metoprolol tartrate were chosen as models. The frozen solutions were irradiated at dry ice temperature by high energy electrons at various doses. The drug purity (chemical potency) and the radiolysis products were quantified by HPLC-DAD. Characterization of the degradation products was performed by LC-APCI-MS-MS. The structures of the radiolysis products detected in irradiated frozen aqueous solutions were compared to those detected in solid-state and aqueous solutions (previous studies). For both metoclopramide and metoprolol, solute loss upon irradiation of frozen aqueous solutions was negligible. Five radiolysis products present in traces were identified in irradiated metoclopramide frozen solutions. Three of them were previously identified in solid-state irradiated metoclopramide crystals. The two others were formed following reactions with the hydroxyl radical (indirect effect). Only one fragmentation product was observed in irradiated metoprolol frozen solutions. For both drugs, radiosterilization of frozen solutions, even at high doses (25 kGy), was found to be possible.

Noble metal superparticles and methods of preparation thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yugang; Hu, Yongxing

A method comprises heating an aqueous solution of colloidal silver particles. A soluble noble metal halide salt is added to the aqueous solution which undergoes a redox reaction on a surface of the silver particles to form noble metal/silver halide SPs, noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs on the surface of the silver particles. The heat is maintained for a predetermined time to consume the silver particles and release the noble metal/silver halide SPs, the noble metal halide/silver halide SPs or the noble metal oxide/silver halide SPs into the aqueous solution. The aqueous solution ismore » cooled. The noble metal/silver halide SPs, the noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs are separated from the aqueous solution. The method optionally includes adding a soluble halide salt to the aqueous solution.« less

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One systemmore » operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.« less

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-07-14

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

PubMed

El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) < Ni(2+) < Cu(2+) > Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands

PubMed Central

El-Sherif, Ahmed A.; Shehata, Mohamed R.; Shoukry, Mohamed M.; Barakat, Mohammad H.

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO3) using a potentiometric technique. The order of –ΔG0 and –ΔH0 was found to obey Co2+ < Ni2+ < Cu2+ > Zn2+, in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K. PMID:23226992

Excitation energy transfer in europium chelate with doxycycline in the presence of a second ligand in micellar solutions of nonionic surfactants

NASA Astrophysics Data System (ADS)

Smirnova, T. D.; Shtykov, S. N.; Kochubei, V. I.; Khryachkova, E. S.

2011-01-01

The complexation of Eu3+ with doxycycline (DC) antibiotic in the presence of several second ligands and surfactant micelles of different types is studied by the spectrophotometric and luminescence methods. It is found that the efficiency of excitation energy transfer in Eu3+-DC chelate depends on the nature of the second ligand and surfactant micelles. Using thenoyltrifluoroacetone (TTA) as an example, it is shown that the second ligand additionally sensitizes the europium fluorescence, and the possibility of intermediate sensitization of DC and then of europium is shown by the example of 1,10-phenanthroline. In all cases, the excitation energy transfer efficiency was increased due to the so-called antenna effect. The decay kinetics of the sensitized fluorescence of the binary and mixed-ligand chelates in aqueous and micellar solutions of nonionic surfactants is studied and the relative quantum yields and lifetimes of fluorescence are determined.

Solubility enhancement of miconazole nitrate: binary and ternary mixture approach.

PubMed

Rai, Vineet Kumar; Dwivedi, Harinath; Yadav, Narayan Prasad; Chanotiya, Chandan Singh; Saraf, Shubhini A

2014-08-01

Enhancement of aqueous solubility of very slightly soluble Miconazole Nitrate (MN) is required to widen its application from topical formulation to oral/mucoadhesive formulations. Aim of the present investigation was to enhance the aqueous solubility of MN using binary and ternary mixture approach. Binary mixtures such as solvent deposition, inclusion complexation and solid dispersion were adopted to enhance solubility using different polymers like lactose, beta-cyclodextrin (β-CD) and polyethylene-glycol 6000 (PEG 6000), respectively. Batches of binary mixtures with highest solubility enhancement potentials were further mixed to form ternary mixture by a simple kneading method. Drug polymer interaction and mixture morphology was studied using the Fourier transform infrared spectroscopy and the scanning electron microscopy, respectively along with their saturation solubility studies and drug release. An excellent solubility enhancement, i.e. up to 72 folds and 316 folds of MN was seen by binary and ternary mixture, respectively. Up to 99.5% drug was released in 2 h from the mixtures of MN and polymers. RESULTS revealed that solubility enhancement by binary mixtures is achieved due to surface modification and by increasing wettability of MN. Tremendous increase in solubility of MN by ternary mixture could possibly be due to blending of water soluble polymers, i.e. lactose and PEG 6000 with β-CD which was found to enhance the solubilizing nature of β-CD. Owing to the excellent solubility enhancement potential of ternary mixtures in enhancing MN solubility from 110.4 μg/ml to 57640.0 μg/ml, ternary mixture approach could prove to be promising in the development of oral/mucoadhesive formulations.

Spontaneous formation of nanometer scale tubular vesicles in aqueous mixtures of lipid and block copolymer amphiphiles.

PubMed

Lim, Seng Koon; Wong, Andrew S W; de Hoog, Hans-Peter M; Rangamani, Padmini; Parikh, Atul N; Nallani, Madhavan; Sandin, Sara; Liedberg, Bo

2017-02-08

Many common amphiphiles self-assemble in water to produce heterogeneous populations of discrete and symmetric but polydisperse and multilamellar vesicles isolating the encapsulated aqueous core from the surrounding bulk. But when mixtures of amphiphiles of vastly different elastic properties co-assemble, their non-uniform molecular organization can stabilize lower symmetries and produce novel shapes. Here, using high resolution electron cryomicroscopy and tomography, we identify the spontaneous formation of a membrane morphology consisting of unilamellar tubular vesicles in dilute aqueous solutions of binary mixtures of two different amphiphiles of vastly different origins. Our results show that aqueous phase mixtures of a fluid-phase phospholipid and an amphiphilic block copolymer spontaneously assume a bimodal polymorphic character in a composition dependent manner: over a broad range of compositions (15-85 mol% polymer component), a tubular morphology co-exists with spherical vesicles. Strikingly, in the vicinity of equimolar compositions, an exclusively tubular morphology (L t ; diameter, ∼15 nm; length, >1 μm; core, ∼2.0 nm; wall, ∼5-6 nm) emerges in an apparent steady state. Theory suggests that the spontaneous stabilization of cylindrical vesicles, unaided by extraneous forces, requires a significant spontaneous bilayer curvature, which in turn necessitates a strongly asymmetric membrane composition. We confirm that such dramatic compositional asymmetry is indeed produced spontaneously in aqueous mixtures of a lipid and polymer through two independent biochemical assays - (1) reduction in the quenching of fluorophore-labeled lipids and (2) inhibition in the activity of externally added lipid-hydrolyzing phospholipase A2, resulting in a significant enrichment of the polymer component in the outer leaflet. Taken together, these results illustrate the coupling of the membrane shape with local composition through spontaneous curvature generation under conditions of asymmetric distribution of mixtures of disparate amphiphiles.

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

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.

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.

RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

DOEpatents

Ader, M.

1963-11-19

A process of recovering actinides is presented. Tetravalent actinides are extracted from rare earths in an aqueous nitric acid solution with a ketone and back-extracted from the ketone into an aqueous medium. The aqueous actinide solution thus obtained, prior to concentration by boiling, is sparged with steam to reduce its ketone to a maximum content of 3 grams per liter. (AEC)

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...

Metal separations using aqueous biphasic partitioning systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaiko, D.J.; Zaslavsky, B.; Rollins, A.N.

1996-05-01

Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that the authors have studied are generated by combining an aqueous salt solution with an aqueous polymer solution. They have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. They have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS). In this report they reviewmore » the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.« less

Raman spectroscopic study of the conformation of dicarboxylic acid salts in aqueous solutions

NASA Astrophysics Data System (ADS)

Fukushima, Kunio; Watanabe, Toshiaki; Umemura, Matome

1986-08-01

It is already known that the molecules of long chain monocarboxylic acid salts have a tendency to form micelles in aqueous solutions, the molecular chain taking the all- trans zigzag structure. However it is considered difficult for dicarboxylic acid salts to adopt the same structure as the monocarboxylic acid salts as they have two carboxyl groups, one on each end of the molecular chain. Therefore, a special structure is expected to exist for dicarboxylic acid salts in aqueous solution. In order to examine this, Raman spectra of suberic acid salt and azelaic acid salt in aqueous solution were measured and the normal vibrational calculation carried out, showing that dicarboxylic acid salts have a helical structure in aqueous solution.

Effective simultaneous removal of Pb(II) and Cd(II) ions by a new magnetic zeolite prepared from stem sweep

NASA Astrophysics Data System (ADS)

Safinejad, A.; Goudarzi, N.; Arab Chamjangali, M.; Bagherian, G.

2017-11-01

In this work, we prepared a new magnetic zeolite (MZ), as a sorbent, from stem sweep and used for the removal of lead and cadmium ions from aqueous solutions. Then the effective parameters involved in the removal efficiency of the studied ions were investigated. The synthetic MZ was characterized using x-ray diffraction (XRD) and field emission-scanning electron microscopy (FE-SEM). The best conditions for the preparation of MZ were found to be as follow: %Fe3O4 loaded  =  25, Si/Al  =  1.5, Na2O/SiO2  =  2.0, H2O/Na2O  =  75.0, crystallization time  =  20.0 h, and crystallization temperature  =  110 °C. The magnetic adsorbent was obtained by coating the zeolite with iron oxide nanoparticles. To study the sorption performance of the synthetic adsorbent, the single and binary systems including Pb(II) and Cd(II) ions were used. The effects of various parameters such as the solution pH, initial metal ion concentrations, amount of adsorbent, and contact time on the removal efficiency of the metal ions were studied. The results obtained showed that the adsorption isotherm data fitted well to the Langmuir isotherm, and that the adsorption kinetics of the metal ions in a binary system followed a pseudo-second order kinetic model.

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

DOEpatents

Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

1962-08-14

A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

Binary ferrihydrite catalysts

DOEpatents

Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

1996-01-01

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

Sulfur and nitrogen binary doped carbon dots derived from ammonium thiocyanate for selective probing doxycycline in living cells and multicolor cell imaging.

PubMed

Xue, Mingyue; Zhang, Liangliang; Zhan, Zhihua; Zou, Mengbing; Huang, Yong; Zhao, Shulin

2016-04-01

A novel sulfur and nitrogen binary doped carbon dots (S,N-CDs) was synthesized by one-step manner through the hydrothermal treatment of citric acid (CA) and ammonium thiocyanate, and the procedures for biomedical applications, including probing doxycycline in living cells and multicolor cell imaging were developed. The obtained S,N-CDs are stable in aqueous solution, possess a very high quantum yield (QY, 74.15%) and good photostability. The fluorescence of S,N-CDs can be specifically quenched by doxycycline, providing a convenient turn-off assay of doxycycline. This assay shows a wide linear detection range from 0.08 to 60 μM with a low detection limit of 20 nM. The present method also displays a good selectivity. More importantly, the S,N-CDs have an excellent biocompatibility and low cytotoxicity, allowing the multicolor cell imaging and doxycycline detection in living cells. Consequently, the developed doxycycline methods is facile, low-cost, biocompatible, sensitive and selective, which may hold the potential applications in the fields of food safety and environmental monitoring, as well as cancer therapy and related mechanism research. Copyright © 2015 Elsevier B.V. All rights reserved.

Aqueous Plasma Pharmacy: Preparation Methods, Chemistry, and Therapeutic Applications

PubMed Central

Joslin, Jessica M.; McCall, James R.; Bzdek, Justin P.; Johnson, Derek C.; Hybertson, Brooks M.

2017-01-01

Plasma pharmacy is a subset of the broader field of plasma medicine. Although not strictly defined, the term aqueous plasma pharmacy (APP) is used to refer to the generation and distribution of reactive plasma-generated species in an aqueous solution followed by subsequent administration for therapeutic benefits. APP attempts to harness the therapeutic effects of plasma-generated oxidant species within aqueous solution in various applications, such as disinfectant solutions, cell proliferation related to wound healing, and cancer treatment. The subsequent use of plasma-generated solutions in the APP approach facilitates the delivery of reactive plasma species to internal locations within the body. Although significant efforts in the field of plasma medicine have concentrated on employing direct plasma plume exposure to cells or tissues, here we focus specifically on plasma discharge in aqueous solution to render the solution biologically active for subsequent application. Methods of plasma discharge in solution are reviewed, along with aqueous plasma chemistry and the applications for APP. The future of the field also is discussed regarding necessary research efforts that will enable commercialization for clinical deployment. PMID:28428835

Photoproduction of hydroxyl radicals in aqueous solution with algae under high-pressure mercury lamp.

PubMed

Liu, Xianli; Wu, Feng; Deng, Nansheng

2004-01-01

Photoproduction of hydroxyl radicals (*OH) could be induced in aqueous solution with algae (Nitzschia hantzschiana, etc.) and (or not) Fe3+ under high-pressure mercury lamp with an exposure time of 4 h. *OH was determined by HPLC using benzene as a probe. The photoproduction of *OH increased with increasing algae concentration. Fe3+ could enhance the photoproduction of *OH in aqueous solution with algae. The results showed that the photoproduction of *OH in algal solution with Fe3+ was greater than that in algal solution without Fe3+. The light intensity and pH affected the photoproduction of *OH in aqueous solution with algae with/without Fe3+. The photoproduction of *OH in aqueous solution with algae and Fe3+ under 250 W was greater than that under 125 W HPML. The photoproduction of *OH in algal solution (pH ranged from 4.0 to 7.0) with (or not) Fe3+ at pH 4 was the greatest.

Germanium films by polymer-assisted deposition

DOEpatents

Jia, Quanxi; Burrell, Anthony K.; Bauer, Eve; Ronning, Filip; McCleskey, Thomas Mark; Zou, Guifu

2013-01-15

Highly ordered Ge films are prepared directly on single crystal Si substrates by applying an aqueous coating solution having Ge-bound polymer onto the substrate and then heating in a hydrogen-containing atmosphere. A coating solution was prepared by mixing water, a germanium compound, ethylenediaminetetraacetic acid, and polyethyleneimine to form a first aqueous solution and then subjecting the first aqueous solution to ultrafiltration.

Synthesis and application of selective adsorbent for pirimicarb pesticides in aqueous media using allyl-β-cyclodextrin based binary functional monomers.

PubMed

He, Chengzijing; Lay, Sovichea; Yu, Haining; Shen, Shengrong

2018-04-01

Binary functional monomers, allyl-β-cyclodextrin (allyl-β-CD) and methacrylic acid (MAA) or allyl-β-CD and acrylonitrile (AN), were exploited in a fabrication of molecularly imprinted polymers (MIPs) for selective recognition and large enrichment of pirimicarb from aqueous media. Special attention was paid to the computational simulation of the imprinting molecular and functional monomers. The morphological characteristics of MIPs made of allyl-β-CD and MAA (M-MAA) were characterised by scanning electron microscopy. The effect of binding capacity of MAA-linked allyl-β-CD MIPs (M-MAA) demonstrated higher efficiency than that of AN-linked allyl-β-CD MIPs (M-AN) when tested in binding specificity. Finally, M-MAA was chosen to run through molecularly imprinted solid-phase extraction (MISPE) to analyse the spiked fresh leafy vegetables of pirimicarb. The present proposed technique is a promising tool for the preparation of the receptors which could recognise pirimicarb pesticide in aqueous media. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

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)

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.

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.

Mega-solubility of quartz resulting from highly alkaline fluids produced by dissolved albite in H2O at deep crustal conditions

NASA Astrophysics Data System (ADS)

Makhluf, A. R.; Manning, C. E.

2017-12-01

Models of H2O-rich fluids equilibrated with rocks at high P and T fail to predict the high solubilities observed experimentally, chiefly because thermodynamic data for the most abundant solutes is lacking. We investigated the effects of dissolved albite (Ab) on the solubility of quartz (Qz) at 1.0 GPa and 675-900 °C using a piston-cylinder apparatus to quantify possible mineral buffering or enhancement effects. We found a very large enhancement effect on the solubility of Qz when dissolved in dilute aqueous Ab solutions. SiO2 concentrations are similar to Qz solubility in strongly alkaline KOH solutions. At the highest temperature of 900 °C, we found that the solubility of Qz in 1.0 molal Ab solution increases by of factor of 4.5 over that in pure H2O, which corresponds to 10.7 molal SiO2. The nearly identical solubility of Qz in KOH(aq) and Ab solutions of the same concentration, P, and T, strongly suggest that NaOH(aq) liberated from NaAlSi3O8 in H2O fluids effects SiO2 solubility in a similar manner to that of KOH(aq). The deprotonated silica dimer was found to be a key species responsible for the high solubility of Qz in KOH(aq) and is likely responsible for the high solubility of Qz in Ab solutions. While the binaries Qz-H2O, Ab-H2O, and Qz-Ab are well known at 1.0 GPa, little data exists on the ternary system. The new results help quantify the ternary relations in the Ab-Qz-H2O system, which can be used as a simple model for liquid-vapor immiscibility granitic magmas. In addition, these highly alkaline solute-rich aqueous fluids suggest a mechanism for Ab-Qz metasomatism in subduction zones, such as in the Catalina schist (Bebout and Barton 1993), which provides an alternative to high P-T magmas. Our results show that subduction zone and metasomatic fluids may be much more alkaline and have significantly higher dissolving power than previously thought.

Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

PubMed

Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

2017-08-10

Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

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

PubMed Central

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

2014-01-01

Acemetacin (ACM) is a non-steroidal anti-inflammatory drug (NSAID), which causes reduced gastric damage compared with indomethacin. However, acemetacin has a tendency to form a less soluble hydrate in the aqueous medium. We noted difficulties in the preparation of cocrystals and salts of acemetacin by mechanochemical methods, because this drug tends to form a hydrate during any kind of solution-based processing. With the objective to discover a solid form of acemetacin that is stable in the aqueous medium, binary adducts were prepared by the melt method to avoid hydration. The coformers/salt formers reported are pyridine carboxamides [nicotinamide (NAM), isonicotinamide (INA), and picolinamide (PAM)], caprolactam (CPR), p-aminobenzoic acid (PABA), and piperazine (PPZ). The structures of an ACM–INA cocrystal and a binary adduct ACM–PABA were solved using single-crystal X-ray diffraction. Other ACM cocrystals, ACM–PAM and ACM–CPR, and the piperazine salt ACM–PPZ were solved from high-resolution powder X-ray diffraction data. The ACM–INA cocrystal is sustained by the acid⋯pyridine heterosynthon and N—H⋯O catemer hydrogen bonds involving the amide group. The acid⋯amide heterosynthon is present in the ACM–PAM cocrystal, while ACM–CPR contains carboxamide dimers of caprolactam along with acid–carbonyl (ACM) hydrogen bonds. The cocrystals ACM–INA, ACM–PAM and ACM–CPR are three-dimensional isostructural. The carboxyl⋯carboxyl synthon in ACM–PABA posed difficulty in assigning the position of the H atom, which may indicate proton disorder. In terms of stability, the salts were found to be relatively stable in pH 7 buffer medium over 24 h, but the cocrystals dissociated to give ACM hydrate during the same time period. The ACM–PPZ salt and ACM–nicotinamide cocrystal dissolve five times faster than the stable hydrate form, whereas the ACM–PABA adduct has 2.5 times faster dissolution rate. The pharmaceutically acceptable piperazine salt of acemetacin exhibits superior stability, faster dissolution rate and is able to overcome the hydration tendency of the reference drug. PMID:25075330

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

PubMed

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

2014-03-01

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

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

NASA Technical Reports Server (NTRS)

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

Cyclodextrin based ternary system of modafinil: Effect of trimethyl chitosan and polyvinylpyrrolidone as complexing agents.

PubMed

Patel, Parth; Agrawal, Y K; Sarvaiya, Jayrajsinh

2016-03-01

Modafinil is an approved drug for the treatment of narcolepsy and have a strong market presence in many countries. The drug is widely consumed for off-label uses and currently listed as a restricted drug. Modafinil has very low water solubility. To enhance the aqueous solubility of modafinil by the formation of a ternary complex with Hydroxypropyl-β-cyclodextrin and two hydrophilic polymers was the main objective of the present study. Pyrrolidone (PVP K30) and a water soluble chitosan derivative, trimethyl chitosan (TMC) were studied by solution state and solid state characterization methods for their discriminatory efficiency in solubility enhancement of modafinil. Phase solubility study depicted the highest complexation efficiency (2.22) of cyclodextrin derivative in the presence of TMC compared to the same in the presence of PVP K30 (0.08) and in the absence of any polymer (0.92). FT-IR analysis of binary and ternary complex expressed comparable contribution of both polymers in formation of inclusion complex. The thermal behaviour of binary and ternary complex, involving individual polymers disclosed the influence of TMC on polymorphism of the drug. DSC study revealed efficiency of TMC to prevent conversion of metastable polymorphic form to stable polymorphic form. Ternary complex, involving TMC enhanced water solubility of the drug 1.5 times more compared to the binary complex of the drug whereas PVP K30 reduced the Solubility. Copyright © 2015 Elsevier B.V. All rights reserved.

Physical Absorption of Green House Gases in Amines: The Influence of Functionality, Structure, and Cross-Interactions.

PubMed

Orozco, Gustavo A; Lachet, Véronique; Mackie, Allan D

2016-12-29

Monte Carlo simulations were performed in the isothermal-isobaric ensemble (NPT) to calculate the Henry constants of methane (CH 4 ), nitrous oxide (N 2 O), and carbon dioxide (CO 2 ) in pure H 2 O, amines, and alkanolamines using the classical Lorentz-Berthelot combining rules (L-B). The Henry constants of N 2 O and CO 2 in water are highly overestimated and motivated us to propose a new set of unlike interactions. Contrarily, the Henry constant of N 2 O in MEA is underestimated by around 40%, and again, a new reoptimized cross unlike parameter is able to reproduce the constant to within 10%. An analysis is given of the relationship between the physical absorption of these gases and the chemical structure or functionality of 12 molecules including amines and alkanolamines using the anisotropic united atom intermolecular potential (AUA4). Finally, the solubility of N 2 O in an aqueous solution of monoethanolamine (MEA) at 30% (wt) was also studied. A Henry constant within 7% of the experimental value was found by using the reoptimized parameters along with L-B to account for the MEA + H 2 O unlike interactions. This very good agreement without additional adjustments for the MEA + H 2 O system may be attributed to the good excess properties predictions found in previous works for the binary mixture (MEA + H 2 O). However, further work, including additional alkanolamines in aqueous solutions at several concentrations, is required to verify this particular point.

Interactions of carbon nanotubes with the nitromethane-water mixture governing selective adsorption of energetic molecules from aqueous solution.

PubMed

Liu, Yingzhe; Lai, Weipeng; Yu, Tao; Kang, Ying; Ge, Zhongxue

2015-03-14

The structure and dynamics of the nitromethane-water (NM-WT) binary mixture surrounding single walled carbon nanotubes (SWNTs) have been investigated by molecular dynamics simulations. The simulation trajectories show that the NM molecules can be selectively adsorbed both outside the surface and inside the cavity of SWNTs mainly dominated by van der Waals attractions because SWNTs have a higher binding affinity for NM than WT. The binding energies of SWNTs with NM and WT obtained from electronic structure calculations at the M06-2X/6-31+G* level are 15.31 and 5.51 kcal mol(-1), respectively. Compared with the SWNT exterior, the selective adsorption of NM is preferentially occurred in the SWNT interior due to the hydrophobic interactions and the dipole-dipole interactions, which induces the decrease of the hydrogen-bond number of NM with WT and ordered structures of NM with preferred intermolecular orientation in the SWNT cavity. Furthermore, the selective adsorption dynamics of NM from the aqueous solution is regardless of the chirality and radius of SWNTs. The SWNT radius plays a negligible role in the mass density distributions of NM outside the SWNTs, while the mass density of NM in the SWNT interior decreases gradually as the SWNT radius increases. The structural arrangements and intermolecular orientations of NM in the SWNT cavity are greatly dependent on the SWNT radius due to the size effect.

Binary ferrihydrite catalysts

DOEpatents

Huffman, G.P.; Zhao, J.; Feng, Z.

1996-12-03

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

Removal of reactive red-120 and 4-(2-pyridylazo) resorcinol from aqueous samples by Fe3O4 magnetic nanoparticles using ionic liquid as modifier.

PubMed

Absalan, Ghodratollah; Asadi, Mozaffar; Kamran, Sedigheh; Sheikhian, Leila; Goltz, Douglas M

2011-08-30

The nanoparticles of Fe(3)O(4) as well as the binary nanoparticles of ionic liquid and Fe(3)O(4) (IL-Fe(3)O(4)) were synthesized for removal of reactive red 120 (RR-120) and 4-(2-pyridylazo) resorcinol (PAR) as model azo dyes from aqueous solutions. The mean size and the surface morphology of the nanoparticles were characterized by TEM, DLS, XRD, FTIR and TGA techniques. Adsorption of RR-120 and PAR was studied in a batch reactor at different experimental conditions such as nanoparticle dosage, dye concentration, pH of the solution, ionic strength, and contact time. Experimental results indicated that the IL-Fe(3)O(4) nanoparticles had removed more than 98% of both dyes under the optimum operational conditions of a dosage of 60mg, a pH of 2.5, and a contact time of 2min when initial dyes concentrations of 10-200mg L(-1) were used. The maximum adsorption capacity of IL-Fe(3)O(4) was 166.67 and 49.26mg g(-1) for RR-120 and PAR, respectively. The isotherm experiments revealed that the Langmuir model attained better fits to the equilibrium data than the Freundlich model. The Langmuir adsorption constants were 5.99 and 3.62L mg(-1) for adsorptions of RR-120 and PAR, respectively. Both adsorption processes were endothermic and dyes could be desorbed from IL-Fe(3)O(4) by using a mixed NaCl-acetone solution and adsorbent was reusable. Copyright © 2011 Elsevier B.V. All rights reserved.

Chemical unfolding of chicken villin headpiece in aqueous dimethyl sulfoxide solution: cosolvent concentration dependence, pathway, and microscopic mechanism.

PubMed

Roy, Susmita; Bagchi, Biman

2013-04-25

Unfolding of a protein often proceeds through partial unfolded intermediate states (PUIS). PUIS have been detected in several experimental and simulation studies. However, complete analyses of transitions between different PUIS and the unfolding trajectory are sparse. To understand such dynamical processes, we study chemical unfolding of a small protein, chicken villin head piece (HP-36), in aqueous dimethyl sulfoxide (DMSO) solution. We carry out molecular dynamics simulations at various solution compositions under ambient conditions. In each concentration, the initial step of unfolding involves separation of two adjacent native contacts, between phenyl alanine residues (11-18 and 7-18). This first step induces, under appropriate conditions, subsequent separation among other hydrophobic contacts, signifying a high degree of cooperativity in the unfolding process. The observed sequence of structural changes in HP-36 on increasing DMSO concentration and the observed sequence of PUIS, are in approximate agreement with earlier simulation results (in pure water) and experimental observations on unfolding of HP-36. Peculiar to water-DMSO mixture, an intervening structural transformation (around 15% of DMSO) in the binary mixture solvent retards the progression of unfolding as composition is increased. This is reflected in a remarkable nonmonotonic composition dependence of RMSD, radius of gyration and the fraction of native contacts. At 30% mole fraction of DMSO, we find the extended randomly coiled structure of the unfolded protein. The molecular mechanism of DMSO induced unfolding process is attributed to the initial preferential solvation of the hydrophobic side chain atoms through the methyl groups of DMSO, followed by the hydrogen bonding of the oxygen atom of DMSO to the exposed backbone NH groups of HP-36.

Adsorption of transition metal ions from aqueous solutions onto a novel silica gel matrix inorganic-organic composite material.

PubMed

Yin, Ping; Xu, Qiang; Qu, Rongjun; Zhao, Guifang; Sun, Yanzhi

2010-01-15

A novel inorganic-organic composite material silica gel microspheres encapsulated by imidazole functionalized polystyrene (SG-PS-azo-IM) has been synthesized and characterized. This composite material was used to investigate the adsorption of Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II), Hg(II), Pb(II), Pd(II), Pt(II), Ag(I), and Au(III) from aqueous solutions, and the research results displayed that SG-PS-azo-IM has the highest adsorption capacity for Au(III). Langmuir and Freundlich isotherm models were applied to analyze the experimental data, the best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Au(III) is 1.700 mmol/g. The adsorption selectivity, the dynamic adsorption and desorption properties of SG-PS-azo-IM for Au(III) have also been studied. The results showed that SG-PS-azo-IM had excellent adsorption for Au(III) in four binary ions system, especially in the systems of Au(III)-Zn(II) and Au(III)-Cu(II), and almost Au(III) could be desorbed with the eluent solution of 0.5% thiourea in 1 mol/L HCl. Moreover, this novel composite material was used to preconcentrate Au(III) before its determination by flame atomic adsorption spectrometry. In the initial concentration range of 0.10-0.20 microg/mL, multiple of enrichment could reach 5.28. Thus, silica gel encapsulated by polystyrene coupling with imidazole (SG-PS-azo-IM) is favorable and useful for the removal of transition metal ions, and the high adsorption capacity makes it a good promising candidate material for Au(III) removal.

Arsenic removal in aqueous solution by a novel Fe-Mn modified biochar composite: Characterization and mechanism.

PubMed

Lin, Lina; Qiu, Weiwen; Wang, Di; Huang, Qing; Song, Zhengguo; Chau, Henry Wai

2017-10-01

The aim of this study was to develop a cost-effective method for As removal from aqueous systems. To this end, pristine biochar (BC) was impregnated with Fe-Mn oxides and a comparative analysis was conducted on the adsorption capacities of BC, Fe-Mn binary oxide (FMO), and Fe/Mn modified biochar (FMBC). The ferromanganese oxides increased the specific surface areas of BC. FMBC presented greater adsorption of As (Q max = 8.25mgg -1 ) than FMO and BC. Energy dispersive spectrometer analysis and electron microscope scanning revealed numerous pores of FMBC with the existence of Fe-Mn oxide using. Distinguished binding energy shifting of the As3d, Fe2p, O1s, and Mn2p3/2 regions after As sorption were found, indicating that Mn(III) oxidation and interaction of oxygen-containing function groups in the FMBC promoted the conversion of As(III) to As(V). Furthermore, chemisorption was found to be the main mechanism for As sorption on FMBC. Thus, the results suggest that FMBC could be used as an inexpensive and highly efficient adsorbent for As removal from water environment. Copyright © 2017 Elsevier Inc. All rights reserved.

Characteristics of regenerated nanocellulosic fibers from cellulose dissolution in aqueous solutions for wood fiber/polypropylene composites

Treesearch

Sangyeob Lee; Hui Pan; Chung Y. Hse; Alfred R. Gunasekaran; Todd F. Shupe

2014-01-01

The effects of aqueous solutions were evaluated on the properties of regenerated cellulosic nanofibers prepared from pure cellulose fibers in various formulations of aqueous solutions. Thermoplastic composites were prepared with reinforcement of the regenerated cellulosic nanofibers. The regenerated cellulosic fibers from cellulosic woody biomass were obtained from...

URANIUM SEPARATION PROCESS

DOEpatents

McVey, W.H.; Reas, W.H.

1959-03-10

The separation of uranium from an aqueous solution containing a water soluble uranyl salt is described. The process involves adding an alkali thiocyanate to the aqueous solution, contacting the resulting solution with methyl isobutyl ketons and separating the resulting aqueous and organic phase. The uranium is extracted in the organic phase as UO/sub 2/(SCN)/sub/.

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.

SE-72/AS-72 generator system based on Se extraction/ As reextraction

DOEpatents

Fassbender, Michael Ernst; Ballard, Beau D

2013-09-10

The preparation of a .sup.72Se/.sup.72As radioisotope generator involves forming an acidic aqueous solution of an irradiated alkali bromide target such as a NaBr target, oxidizing soluble bromide in the solution to elemental bromine, removing the elemental bromine, evaporating the resulting solution to a residue, removing hydrogen chloride from the residue, forming an acidic aqueous solution of the residue, adding a chelator that selectively forms a chelation complex with selenium, and extracting the chelation complex from the acidic aqueous solution into an organic phase. As the .sup.72Se generates .sup.72As in the organic phase, the .sup.72As may be extracted repeatedly from the organic phase with an aqueous acid solution.

Methods and systems for utilizing carbide lime or slag

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devenney, Martin; Fernandez, Miguel; Chen, Irvin

Provided herein are methods comprising a) treating a slag solid or carbide lime suspension with an ammonium salt in water to produce an aqueous solution comprising calcium salt, ammonium salt, and solids; b) contacting the aqueous solution with carbon dioxide from an industrial process under one or more precipitation conditions to produce a precipitation material comprising calcium carbonate and a supernatant aqueous solution wherein the precipitation material and the supernatant aqueous solution comprise residual ammonium salt; and c) removing and optionally recovering ammonia and/or ammonium salt using one or more steps of (i) recovering a gas exhaust stream comprising ammoniamore » during the treating and/or the contacting step; (ii) recovering the residual ammonium salt from the supernatant aqueous solution; and (iii) removing and optionally recovering the residual ammonium salt from the precipitation material.« less

Unique role of ionic liquid [bmin][BF 4] during curcumin-surfactant association and micellization of cationic, anionic and non-ionic surfactant solutions

NASA Astrophysics Data System (ADS)

Patra, Digambara; Barakat, Christelle

2011-09-01

Hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroburate, modified the properties of aqueous surfactant solutions associated with curcumin. Because of potential pharmaceutical applications as an antioxidant, anti-inflammatory and anti-carcinogenic agent, curcumin has received ample attention as potential drug. The interaction of curcumin with various charged aqueous surfactant solutions showed it exists in deprotonated enol form in surfactant solutions. The nitro and hydroxyl groups of o-nitrophenol interact with the carbonyl and hydroxyl groups of the enol form of curcumin by forming ground state complex through hydrogen bonds and offered interesting information about the nature of the interactions between the aqueous surfactant solutions and curcumin depending on charge of head group of the surfactant. IL[bmin][BF 4] encouraged early formation of micelle in case of cationic and anionic aqueous surfactant solutions, but slightly prolonged micelle formation in the case of neutral aqueous surfactant solution. However, for curcumin IL [bmin][BF 4] favored strong association (7-fold increase) with neutral surfactant solution, marginally supported association with anionic surfactant solution and discouraged (˜2-fold decrease) association with cationic surfactant solution.

Theory of Metastable State Relaxation in a Gravitational Field for Non-Critical Binary Systems with Non-Conserved Order Parameter

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.

1993-01-01

A new mathematical ansatz is developed for solution of the time-dependent Ginzburg-Landau nonlinear partial differential equation describing metastable state relaxation in binary (solute+solvent) non-critical solutions with non-conserved scalar order parameter in presence of a gravitational field. It has been demonstrated analytically that in such systems metastability initiates heterogeneous solute redistribution which results in the formation of a non-equilibrium singly-periodic spatial solute structure in the new solute-rich phase. The critical radius of nucleation and the induction time in these systems are gravity-dependent. It has also been proved that metastable state relaxation in vertical columns of supersaturated non-critical binary solutions leads to formation of the solute concentration gradient. Analytical expression for this concentration gradient is found and analysed. It is concluded that gravity can initiate phase separation (nucleation or spinodal decomposition).

Theoretical analysis of aqueous solutions of mixed strong electrolytes by a smaller-ion shell electrostatic model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fraenkel, Dan, E-mail: dfraenkel@eltronresearch.com

2014-02-07

In spite of the great importance of mixed electrolytes in science and technology, no compelling theoretical explanation has been offered yet for the thermodynamic behavior of such systems, such as their deviation from ideality and the variation of their excess functions with ionic composition and concentration. Using the newly introduced Smaller-ion Shell treatment – an extension of the Debye–Hückel theory to ions of dissimilar size (hence DH–SiS) – simple analytic mathematical expressions can be derived for the mean and single-ion activity coefficients of binary electrolyte components of ternary ionic systems. Such expressions are based on modifying the parallel DH–SiS equationsmore » for pure binary ionic systems, by adding to the three ion-size parameters – a (of counterions), b{sub +} (of positive coions), and b{sub −} (of negative coions) – a fourth parameter. For the (+ + −) system, this is “b{sub ++},” the contact distance between non-coion cations. b{sub ++} is derived from fits with experiment and, like the other b’s, is constant at varying ion concentration and combination. Four case studies are presented: (1) HCl–NaCl–H{sub 2}O, (2) HCl–NH{sub 4}Cl–H{sub 2}O, (3) (0.01 M HX)–MX–H{sub 2}O with X = Cl, Br, and with M = Li, Na, K, Cs, and (4) HCl–MCl{sub n}–H{sub 2}O with n = 2, M = Sr, Ba; and n = 3, M = Al, Ce. In all cases, theory is fully consistent with experiment when using a of the measured binary electrolyte as the sole fitting parameter. DH–SiS is thus shown to explain known “mysteries” in the behavior of ternary electrolytes, including Harned rule, and to adequately predict the pH of acid solutions in which ionized salts are present at different concentrations.« less

Treatment of infectious skin defects or ulcers with electrolyzed strong acid aqueous solution.

PubMed

Sekiya, S; Ohmori, K; Harii, K

1997-01-01

A chronic ulcer with an infection such as methicillin-resistant Staphylococcus aureus is hard to heal. Plastic and reconstructive surgeons often encounter such chronic ulcers that are resistant to surgical or various conservative treatments. We applied conservative treatment using an electrolyzed strong acid aqueous solution and obtained satisfactory results. The lesion was washed with the solution or soaked in a bowl of the solution for approximately 20 min twice a day. Fresh electrolyzed strong acid aqueous solution is unstable and should be stored in a cool, dark site in a sealed bottle. It should be used within a week after it has been produced. Here we report on 15 cases of infectious ulcers that were treated by electrolyzed strong acid aqueous solution. Of these cases, 7 patients were healed, 3 were granulated, and in 5, infection subsided. In most cases the lesion became less reddish and less edematous. Discharge or foul odor from the lesion was decreased. Electrolyzed strong acid aqueous solution was especially effective for treating a chronic refractory ulcer combined with diabetes melitus or peripheral circulatory insufficiency. This clinically applied therapy of electrolyzed strong acid aqueous solution was found to be effective so that this new therapeutic technique for ulcer treatment can now be conveniently utilized.

Preparing polymeric matrix composites using an aqueous slurry technique

NASA Technical Reports Server (NTRS)

Johnston, Norman J. (Inventor); Towell, Timothy W. (Inventor)

1993-01-01

An aqueous process was developed to prepare a consolidated composite laminate from an aqueous slurry. An aqueous poly(amic acid) surfactant solution was prepared by dissolving a poly(amic acid) powder in an aqueous ammonia solution. A polymeric powder was added to this solution to form a slurry. The slurry was deposited on carbon fiber to form a prepreg which was dried and stacked to form a composite laminate. The composite laminate was consolidated using pressure and was heated to form the polymeric matrix. The resulting composite laminate exhibited high fracture toughness and excellent consolidation.

Insights into water-mediated ion clustering in aqueous CaSO4 solutions: pre-nucleation cluster characteristics studied by ab initio calculations and molecular dynamics simulations.

PubMed

Li, Hui-Ji; Yan, Dan; Cai, Hou-Qin; Yi, Hai-Bo; Min, Xiao-Bo; Xia, Fei-Fei

2017-05-10

The molecular structure of growth units building crystals is a fundamental issue in the crystallization processes from aqueous solutions. In this work, a systematic investigation of pre-nucleation clusters and their hydration characteristics in aqueous CaSO 4 solutions was performed using ab initio calculations and molecular dynamics (MD) simulations. The results of ab initio calculations and MD simulations indicate that the dominant species in aqueous CaSO 4 solutions are monodentate ion-associated structures. Compared with charged ion clusters, neutral clusters are more likely to be present in an aqueous CaSO 4 solution. Neutral (CaSO 4 ) m clusters are probably the growth units involved in the pre-nucleation or crystallization processes. Meanwhile, hydration behavior around ion associated species in aqueous CaSO 4 solutions plays an important role in related phase/polymorphism selections. Upon ion clustering, the residence of some water molecules around Ca 2+ in ion-associated species is weakened while that of some bridging waters is enhanced due to dual interaction by Ca 2+ and SO 4 2- . Some phase/polymorphism selections can be achieved in aqueous CaSO 4 solutions by controlling the hydration around pre-nucleation clusters. Moreover, the association trend between calcium and sulfate is found to be relatively strong, which hints at the low solubility of calcium sulfate in water.

[Analysis of parameters of serum concentration and pharmacokinetic of liposome and aqueous solution of toatal ginsenoside of ginseng stems and leaves in rats].

PubMed

Zha, Lin; Zhao, Yan; Zhu, Hong-Yan; Cai, En-Bo; Liu, Shuang-Li; Yang, He; Zhao, Ying; Gao, Yu-Gang; Zhang, Lian-Xue

2017-05-01

The experiment was aimed to investigate the difference of plasma concentration and pharmacokinetic parameters between liposome and aqueous solution of toatal ginsenoside of ginseng stems and leaves in rats, such as ginsenosides Rg₁, Re, Rf, Rb₁, Rg₂, Rc, Rb₂, Rb₃, Rd. After intravenous injection of liposome and aqueous solution in rats, the blood was taken from the femoral vein to detect the plasma concentration of the above 9 ginsenoside monomers in different time points by using HPLC. The concentration-time curve was obtained and 3p97 pharmacokinetic software was used to get the pharmacokinetic parameters. After the intravenous injection of ginsenosides to rats, nine ginsenosides were detected in plasma. In general, among these ginsenosides, the peak time of the aqueous solution was between 0.05 to 0.083 3 h, and the serum concentration peak of liposome usually appeared after 0.5 h. After software fitting, the aqueous solution of ginsenoside monomers Rg₁, Re, Rf, Rg₂, Rc, Rd, Rb₃ was two-compartment model, and the liposomes were one-compartment model; aqueous solution and liposome of ginsenoside monomers Rb₁ were three-compartment model; aqueous solution of ginsenoside monomers Rb₂ was three-compartment model, and its liposome was one-compartment model. Area under the drug time curve (AUC) of these 9 kinds of saponin liposomes was larger than that of aqueous solution, and the retention time of the liposomes was longer than that of the aqueous solution; the removal rate was slower than that of the aqueous solution, and the half-life was longer than that of the water solution. The results from the experiment showed that by intravenous administration, the pharmacokinetic parameters of two formulations were significantly different from each other; the liposomes could not only remain the drug for a longer time in vivo, but also reduce the elimination rate and increase the treatment efficacy. As compared with the traditional dosage forms, the total ginsenoside of ginseng stems and leaves can improve the sustained release of the drug, which is of great significance for the research and development of new dosage forms of ginsenosides in the future. Copyright© by the Chinese Pharmaceutical Association.

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

Thermodynamic properties of potassium chloride aqueous solutions

NASA Astrophysics Data System (ADS)

Zezin, Denis; Driesner, Thomas

2017-04-01

Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

Effect of ionic strength on the thermodynamic characteristics of complexation between Fe(III) ion and nicotinamide in water-ethanol and water-dimethyl sulfoxide mixtures

NASA Astrophysics Data System (ADS)

Gamov, G. A.; Grazhdan, K. V.; Gavrilova, M. A.; Dushina, S. V.; Sharnin, V. A.; Baranski, A.

2013-06-01

Solutions of iron(III) perchlorate in water, water-ethanol, and water-dimethyl sulfoxide solvents (x_{H_2 O} = 0.7 and 0.25 mole fractions) at ionic strength values I = 0.1, 0.25, and 0.5 are studied by IR spectroscopy. Analysis of the absorption bands of perchlorate ion shows that it does not participate in association processes. It is demonstrated that in the range of ionic strength values between 0 and 0.5 (NaClO4), it affects neither the results from potentiometric titration to determine the stability constants of the iron(III)-nicotinamide complex nor the thermal effects of complexation determined via direct calorimetry in a binary solvent containing 0.3 mole fractions (m.f.) of a non-aqueous component.

Facile Preparation of Nanostructured, Superhydrophobic Filter Paper for Efficient Water/Oil Separation

PubMed Central

Wang, Jianhua; Wong, Jessica X. H.; Kwok, Honoria; Li, Xiaochun; Yu, Hua-Zhong

2016-01-01

In this paper, we present a facile and cost-effective method to obtain superhydrophobic filter paper and demonstrate its application for efficient water/oil separation. By coupling structurally distinct organosilane precursors (e.g., octadecyltrichlorosilane and methyltrichlorosilane) to paper fibers under controlled reaction conditions, we have formulated a simple, inexpensive, and efficient protocol to achieve a desirable superhydrophobic and superoleophilic surface on conventional filter paper. The silanized superhydrophobic filter paper showed nanostructured morphology and demonstrated great separation efficiency (up to 99.4%) for water/oil mixtures. The modified filter paper is stable in both aqueous solutions and organic solvents, and can be reused multiple times. The present study shows that our newly developed binary silanization is a promising method of modifying cellulose-based materials for practical applications, in particular the treatment of industrial waste water and ecosystem recovery. PMID:26982055

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.

Exploratory studies on some electrochemical cell systems

NASA Astrophysics Data System (ADS)

Chaudhuri, Srikumar; Guha, D.

Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.

Stability indicating HPLC-DAD method for analysis of Ketorolac binary and ternary mixtures in eye drops: Quantitative analysis in rabbit aqueous humor.

PubMed

El Yazbi, Fawzy A; Hassan, Ekram M; Khamis, Essam F; Ragab, Marwa A A; Hamdy, Mohamed M A

2017-11-15

Ketorolac tromethamine (KTC) with phenylephrine hydrochloride (PHE) binary mixture (mixture 1) and their ternary mixture with chlorpheniramine maleate (CPM) (mixture 2) were analyzed using a validated HPLC-DAD method. The developed method was suitable for the in vitro as well as quantitative analysis of the targeted mixtures in rabbit aqueous humor. The analysis in dosage form (eye drops) was a stability indicating one at which drugs were separated from possible degradation products arising from different stress conditions (in vitro analysis). For analysis in aqueous humor, Guaifenesin (GUF) was used as internal standard and the method was validated according to FDA regulation for analysis in biological fluids. Agilent 5 HC-C18(2) 150×4.6mm was used as stationary phase with a gradient eluting solvent of 20mM phosphate buffer pH 4.6 containing 0.2% triethylamine and acetonitrile. The drugs were resolved with retention times of 2.41, 5.26, 7.92 and 9.64min for PHE, GUF, KTC and CPM, respectively. The method was sensitive and selective to analyze simultaneously the three drugs in presence of possible forced degradation products and dosage form excipients (in vitro analysis) and also with the internal standard, in presence of aqueous humor interferences (analysis in biological fluid), at a single wavelength (261nm). No extraction procedure was required for analysis in aqueous humor. The simplicity of the method emphasizes its capability to analyze the drugs in vivo (in rabbit aqueous humor) and in vitro (in pharmaceutical formulations). Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactantmore » fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.« less

Environment-Friendly Post-Treatment of PEDOT-Tos Films by Aqueous Vitamin C Solutions for Tuning of Thermoelectric Properties

NASA Astrophysics Data System (ADS)

Khan, Ezaz Hasan; Thota, Sammaiah; Wang, Yiwen; Li, Lian; Wilusz, Eugene; Osgood, Richard; Kumar, Jayant

2018-04-01

Aqueous vitamin C solution has been used as an environment-friendly reducing agent for tuning the thermoelectric properties of p-toluenesulfonate-doped poly(3,4-ethylenedioxythiophene) (PEDOT-Tos) films. The de-doping of the PEDOT-Tos films by aqueous vitamin C solutions led to a decrease in the electrical conductivity of the films. The measured ultraviolet-visible-near-infrared and x-ray photoelectron spectra clearly indicated the reduction in the oxidation level from 37 to 23% when the PEDOT-Tos films were treated with 5% (w/v) aqueous vitamin C solutions. An increase in the Seebeck coefficient was measured, resulting in an increase in the figure-of-merit (ZT). A 42% increase in ZT was determined for the 5% aqueous vitamin C solution-treated PEDOT-Tos films with respect to that of the untreated films.

Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-08-11

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

Application of Molecular Dynamics Simulations in Molecular Property Prediction II: Diffusion Coefficient

PubMed Central

Wang, Junmei; Hou, Tingjun

2011-01-01

In this work, we have evaluated how well the General AMBER force field (GAFF) performs in studying the dynamic properties of liquids. Diffusion coefficients (D) have been predicted for 17 solvents, 5 organic compounds in aqueous solutions, 4 proteins in aqueous solutions, and 9 organic compounds in non-aqueous solutions. An efficient sampling strategy has been proposed and tested in the calculation of the diffusion coefficients of solutes in solutions. There are two major findings of this study. First of all, the diffusion coefficients of organic solutes in aqueous solution can be well predicted: the average unsigned error (AUE) and the root-mean-square error (RMSE) are 0.137 and 0.171 ×10−5 cm−2s−1, respectively. Second, although the absolute values of D cannot be predicted, good correlations have been achieved for 8 organic solvents with experimental data (R2 = 0.784), 4 proteins in aqueous solutions (R2 = 0.996) and 9 organic compounds in non-aqueous solutions (R2 = 0.834). The temperature dependent behaviors of three solvents, namely, TIP3P water, dimethyl sulfoxide (DMSO) and cyclohexane have been studied. The major MD settings, such as the sizes of simulation boxes and with/without wrapping the coordinates of MD snapshots into the primary simulation boxes have been explored. We have concluded that our sampling strategy that averaging the mean square displacement (MSD) collected in multiple short-MD simulations is efficient in predicting diffusion coefficients of solutes at infinite dilution. PMID:21953689

Solid/liquid interfacial free energies in binary systems

NASA Technical Reports Server (NTRS)

Nason, D.; Tiller, W. A.

1973-01-01

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

Calculating excess volumes of binary solutions with allowance for structural differences between mixed components

NASA Astrophysics Data System (ADS)

Balankina, E. S.

2016-06-01

Analytical dependences of a volume's properties on the differences between the geometric structures of initial monosystems are obtained for binary systems simulated by a grain medium. The effect of microstructural parameter k (the ratio of volumes of molecules of mixed components) on the concentration behavior of the relative excess molar volume of different types of real binary solutions is analyzed. It is established that the contribution due to differences between the volumes of molecules and coefficients of the packing density of mixed components is ~80-100% for mutual solutions of n-alkanes and ~55-80% of the experimental value of the relative excess molar volume for water solutions of n-alcohols.

Electrophotolysis oxidation system for measurement of organic concentration in water

NASA Technical Reports Server (NTRS)

Winkler, H. E. (Inventor)

1981-01-01

Methods and apparatus for determining organic carbon in aqueous solution are described. The method comprises subjecting the aqueous solution to electrolysis, for generating oxygen from water, and simultaneously to ultraviolet radiation, for oxidation of substantially all organic carbon to carbon dioxide. The carbon dioxide is measured and the value is related to the concentration of organic carbon in the aqueous solution.

RECOVERY AND SEPARATION OF LITHIUM VALUES FROM SALVAGE SOLUTIONS

DOEpatents

Hansford, D.L.; Raabe, E.W.

1963-08-20

Lithium values can be recovered from an aqueous basic solution by reacting the values with a phosphate salt soluble in the solution, forming an aqueous slurry of the resultant aqueous insoluble lithium phosphate, contacting the slurry with an organic cation exchange resin in the acid form until the slurry has been clarified, and thereafter recovering lithium values from the resin. (AEC)

Prediction of the glass transition in aqueous solutions of simple amides by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kreck, Cara A.; Mandumpal, Jestin B.; Mancera, Ricardo L.

2011-01-01

Some simple amides in aqueous solution are used in the cryopreservation of biological tissues as they are believed to promote the vitrification of water, inhibiting its crystallisation and the ensuing damage from ice formation. Molecular dynamics annealing simulations reveal a broadening in the glass transition of aqueous acetamide and N-methylacetamide solutions, suggesting a thermodynamic stabilisation of the glassy state, which may be responsible for their increased tendency of vitrification and their cryoprotective ability. By contrast, aqueous formamide solutions do not exhibit broadening of the glass transition; instead, it is shifted to lower temperatures, which explains their lack of vitrification properties.

Ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine and N-acetyltryptophan in aqueous solution: proton-coupled electron transfer versus electron transfer.

PubMed

Zhang, Ying; Yuan, Shuwei; Lu, Rong; Yu, Anchi

2013-06-20

We studied the ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine (AcTyr) and N-acetyltryptophan (AcTrp) in aqueous solution with femtosecond transient absorption spectroscopy. We found that the charge-transfer rate between Atto655 and AcTyr is about 240 times smaller than that between Atto655 and AcTrp. The pH value and D2O dependences of the excited-state decay kinetics of Atto655 in the presence of AcTyr and AcTrp reveal that the quenching of Atto655 fluorescence by AcTyr in aqueous solution is via a proton-coupled electron-transfer (PCET) process and that the quenching of Atto655 fluorescence by AcTrp in aqueous solution is via an electron-transfer process. With the version of the semiclassical Marcus ET theory, we derived that the electronic coupling constant for the PCET reaction between Atto655 and AcTyr in aqueous solution is 8.3 cm(-1), indicating that the PCET reaction between Atto655 and AcTyr in aqueous solution is nonadiabatic.

Method and apparatus for synthesizing anhydrous HNO.sub.3

DOEpatents

Coon, Clifford L.; Harrar, Jackson E.; Pearson, Richard K.; McGuire, Raymond R.

1984-01-01

A method and apparatus for electrochemically synthesizing anhydrous HNO.sub.3 from an aqueous solution of HNO.sub.3 includes oxidizing a solution of N.sub.2 O.sub.4 /aqueous HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /aqueous HNO.sub.3 solution and the anode. A potential of about 1.80V vs. SCE is preferred. Anhydrous or aqueous HNO.sub.3 may be disposed at the cathode within the electrochemical cell. Aqueous HNO.sub.3 having a water content of up to about 12% by weight is utilized to synthesize anhydrous HNO.sub.3.

Method and apparatus for synthesizing anhydrous HNO/sub 3/. [Patent application

DOEpatents

Coon, C.L.; Harrar, J.E.; Pearson, R.K.; McGuire, R.R.

1982-07-20

A method and apparatus for electrochemically synthesizing anhydrous HNO/sub 3/ from an aqueous solution of HNO/sub 3/- includes oxidizing a solution of N/sub 2/O/sub 4//aqueous HNO/sub 3/ at an anode, while maintaining a controlled potential between the N/sub 2/O/sub 4//aqueous HNO/sub 3/ solution and the anode. A potential of about 1.80V vs. SCE is preferred. Anhydrous or aqueous HNO/sub 3/ may be disposed at the cathode within the electrochemical cell. Aqueous HNO/sub 3/ having a water content of up to about 12% by weight is utilized to synthesize anhydrous HNO/sub 3/.

Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water

PubMed Central

Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

2015-01-01

Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

Physico-chemical properties of aqueous drug solutions: From the basic thermodynamics to the advanced experimental and simulation results.

PubMed

Bellich, Barbara; Gamini, Amelia; Brady, John W; Cesàro, Attilio

2018-04-05

The physical chemical properties of aqueous solutions of model compounds are illustrated in relation to hydration and solubility issues by using three perspectives: thermodynamic, spectroscopic and molecular dynamics simulations. The thermodynamic survey of the fundamental backgrounds of concentration dependence and experimental solubility results show some peculiar behavior of aqueous solutions with several types of similar solutes. Secondly, the use of a variety of experimental spectroscopic devices, operating under different experimental conditions of dimension and frequency, has produced a large amount of structural and dynamic data on aqueous solutions showing the richness of the information produced, depending on where and how the experiment is carried out. Finally, the use of molecular dynamics computational work is presented to highlight how the different types of solute functional groups and surface topologies organize adjacent water molecules differently. The highly valuable contribution of computer simulation studies in providing molecular explanations for experimental deductions, either of a thermodynamic or spectroscopic nature, is shown to have changed the current knowledge of many aqueous solution processes. While this paper is intended to provide a collective view on the latest literature results, still the presentation aims at a tutorial explanation of the potentials of the three methodologies in the field of aqueous solutions of pharmaceutical molecules. Copyright © 2018. Published by Elsevier B.V.

Ion exchange of Group I metals by hydrous crystalline silicotitanates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Z.; Philip, C.V.; Anthony, R.G.

1996-11-01

A new hydrous crystalline silicotitanate, labeled TAM-5 or CST, was developed for removing radioactive Cs{sup +} from aqueous nuclear waste. This material is stable to radiation, highly selective for cesium relative to sodium, potassium, rubidium, and protons, and performs well in acidic, neutral, and basic solutions. Various experiments were conducted to determine the ion exchange properties of TAM-5. Two kinds of ion exchange sites exist in the solid, and cation exchange in one site affects the ion exchange properties of the other site. These two types of sites have different thermal effects: with increasing temperature the pH of one increasesmore » and the pH of the other one decreases. The total ion exchange capacity is 4.6 mequiv/g, but the cesium ion exchange capacity was less, which shows that not all of the ion exchange sites are available for cesium exchange. Step changes were observed in the ion exchange isotherms. The solid phase behaved ideally prior to the step changes. The apparent capacities within the ideal solid region were 0.57 mequiv/g for Cs{sup +}, 1.18 mequiv/g for Rb{sup +}, and 1.2 mequiv/g for K{sup +}. Both direct competition by rubidium and protons and indirect competition by protons and potassium were observed. The rational selectivities, which were measured from binary ion exchange data, can be used in different solutions including the multicomponent ion exchange systems, because they are constant for an ideal solid. Binary ion exchange isotherms were also developed using the rational selectivity as the parameter for the isotherms of cesium, rubidinium, and potassium.« less

Assorted interactions of amino acids prevailing in aqueous vitamin C solutions probed by physicochemical and ab-initio contrivances

NASA Astrophysics Data System (ADS)

Das, Koyeli; Roy, Milan Chandra; Rajbanshi, Biplab; Roy, Mahendra Nath

2017-11-01

Qualitative and quantitative analysis of molecular interaction prevailing in tyrosine and tryptophan in aqueous solution of vitamin C have been probed by thermophysical properties. The apparent molar volume (ϕV), viscosity B-coefficient, molal refraction (RM) of tyrosine and tryptophan have been studied in aqueous vitamin C solutions at diverse temperatures via Masson equation which deduced solute-solvent and solute-solute interactions, respectively. Spectroscopic study along with physicochemical and computational techniques provides lots of interesting and highly significant insights of the model biological systems. The overall results established strong solute-solvent interactions between studied amino acids and vitamin C mixture in the ternary solutions.

Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge.

PubMed

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-10-21

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm(-1)). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge

NASA Astrophysics Data System (ADS)

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-09-01

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm-1). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

In Situ Cross-Linking of Polyvinyl Alcohol Films

NASA Technical Reports Server (NTRS)

Philipp, W. H.; Shu, L. C.; May, C. E.

1984-01-01

Films or impregnated matrices readily made from aqueous polyvinyl alcohol solution. Controlled thickness films made by casting precise quantities of aqueous polymer solution on smooth surface, allowing water to evaporate and then removing film. Composite separators formed in similar fashion by impregnating cloth matrix with polyvinyl alcohol solution and drying composite. Insoluble thin hydrophilic membranes made from aqueous systems, and use of undesirable organic solvents not required.

Sediment Ecosystem Assessment Protocol (SEAP): An Accurate and Integrated Weight-of-Evidence Based System

DTIC Science & Technology

2011-01-01

polychaete Neanthes arenaceodentata from exposures to copper in aqueous solutions ...involved 96 h exposures in aqueous solutions , followed by a 1-2 hour (depending on size) feeding period on Artemia (brine shrimp) nauplii in clean seawater...EC50) based on post- exposure feeding of the polychaete Neanthes arenaceodentata from exposures to copper in aqueous solutions . Metric (µg/L) Worm age

Synthesis and Characterization of Functional Mesostructures Using Colloidal Crystal Templating

DTIC Science & Technology

2004-01-01

fluorescent probes in aqueous polymer solutions . Khoury and co-workers measured the diffusion coefficient of several fluorescein-labeled proteins in...diffraction naq refractive index of the aqueous solution phase xvii ni refractive index of component i ngel refractive index of the hydrogel...phase Tg glass transition temperature α angle of diffraction φaq volume fraction of the aqueous solution phase φi volume fraction of

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.

Influence of pH, temperature, and concentration on stabilization of aqueous hornet silk solution and fabrication of salt-free materials.

PubMed

Kameda, Tsunenori

2015-01-01

We found that an aqueous solution of silk from cocoons produced by hornet larvae (hornet silk) can be obtained when the solution is adjusted to basic conditions of pH > 9.2. It is known that native hornet cocoons can be dissolved in concentrated aqueous solution of salts, such as lithium bromide (LiBr) and calcium chloride (CaCl2). Upon the removal of these salts from solution by dialysis, solidification, gelation, or sedimentation of hornet silk is known to occur. In the present study, under basic conditions, however, no such solidification occurred, even after salt removal. In this study, ammonia was used for alkalization of solution because it is volatilized during the casting process and pure hornet silk materials can be obtained after drying. The effects of the concentrations of hornet silk and ammonia, as well as dialysis temperature, on preventing gelation during dialysis were investigated. Dialysis conditions that limit the degradation of hornet silk by hydrolysis in alkali solution were identified. Moreover, casting conditions to prepare flexible and transparent hornet silk film from aqueous ammonia solution were optimized. Molecular structural analysis of hornet silk in aqueous ammonia solution and cast film indicated the formation of α-helix conformations. © 2014 Wiley Periodicals, Inc.

Aspheric Solute Ions Modulate Gold Nanoparticle Interactions in an Aqueous Solution: An Optimal Way to Reversibly Concentrate Functionalized Nanoparticles

PubMed Central

Villarreal, Oscar D; Chen, Liao Y; Whetten, Robert L; Demeler, Borries

2015-01-01

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-mercapto-benzoate, pMBA) in eight aqueous solutions having ions of varying sizes and shapes (Na+, K+, tetramethylamonium cation TMA+, trisamonium 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 non-spherical 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. PMID:26581232

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.

Corrosion resistance of porous binary tantalum and titanium carbides of various composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Artyunina, N.P.; Komratov, G.N.; Bolonova, E.A.

1993-12-20

Resistance of porous binary tantalum and titanium carbides in solutions of mineral acids and their mixtures, of several organic acids, and of ammonium and potassium hydroxide was studied. It has been shown that as the content of tantalum in a material increases its resistance in solutions of oxidizing acids is improved, but it is reduced in solutions of sulfuric and hydrofluoric acids and also in solutions of potassium hydroxide.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1993-07-27

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1991-12-10

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

URANIUM RECOVERY PROCESS

DOEpatents

Hyman, H.H.; Dreher, J.L.

1959-07-01

The recovery of uranium from the acidic aqueous metal waste solutions resulting from the bismuth phosphate carrier precipitation of plutonium from solutions of neutron irradiated uranium is described. The waste solutions consist of phosphoric acid, sulfuric acid, and uranium as a uranyl salt, together with salts of the fission products normally associated with neutron irradiated uranium. Generally, the process of the invention involves the partial neutralization of the waste solution with sodium hydroxide, followed by conversion of the solution to a pH 11 by mixing therewith sufficient sodium carbonate. The resultant carbonate-complexed waste is contacted with a titanated silica gel and the adsorbent separated from the aqueous medium. The aqueous solution is then mixed with sufficient acetic acid to bring the pH of the aqueous medium to between 4 and 5, whereby sodium uranyl acetate is precipitated. The precipitate is dissolved in nitric acid and the resulting solution preferably provided with salting out agents. Uranyl nitrate is recovered from the solution by extraction with an ether such as diethyl ether.

Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

NASA Astrophysics Data System (ADS)

Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

2018-06-01

The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

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.

Synergies in Astrometry: Predicting Navigational Error of Visual Binary Stars

NASA Astrophysics Data System (ADS)

Gessner Stewart, Susan

2015-08-01

Celestial navigation can employ a number of bright stars which are in binary systems. Often these are unresolved, appearing as a single, center-of-light object. A number of these systems are, however, in wide systems which could introduce a margin of error in the navigation solution if not handled properly. To illustrate the importance of good orbital solutions for binary systems - as well as good astrometry in general - the relationship between the center-of-light versus individual catalog position of celestial bodies and the error in terrestrial position derived via celestial navigation is demonstrated. From the list of navigational binary stars, fourteen such binary systems with at least 3.0 arcseconds apparent separation are explored. Maximum navigational error is estimated under the assumption that the bright star in the pair is observed at maximum separation, but the center-of-light is employed in the navigational solution. The relationships between navigational error and separation, orbital periods, and observers' latitude are discussed.

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.

Dielectric study of aqueous solutions of sodium dodecyl sulfate in the frequency span 20 Hz to 2 MHz

NASA Astrophysics Data System (ADS)

Kadve, A. M.; Vankar, H. P.; Rana, V. A.

2017-05-01

Dielectric measurements were carried out for aqueous solutions of Sodium Dodecyl Sulfate (SDS) in the frequency span of 20 Hz to 2 MHz at 300.15 K temperature using precision LCR meter. Also the refractive indices were measured for the solutions at 300.15 K temperature using Abbe's refractometer. The measurements were done for ten different concentrations of SDS in distilled water. Determined values of complex permittivity as a function of frequency were used to evaluate other parameters like loss tangent and electric modulus for the liquid samples. The permittivity at optical frequency were also calculated from the measured refractive indices for the aqueous solutions. The effect of concentration variation of SDS in the aqueous solutions on the determined parameters is discussed.

Effective adsorption and collection of cesium from aqueous solution using graphene oxide grown on porous alumina

NASA Astrophysics Data System (ADS)

Entani, Shiro; Honda, Mitsunori; Shimoyama, Iwao; Li, Songtian; Naramoto, Hiroshi; Yaita, Tsuyoshi; Sakai, Seiji

2018-04-01

Graphene oxide (GO) with a large surface area was synthesized by the direct growth of GO on porous alumina using chemical vapor deposition to study the Cs adsorption mechanism in aqueous solutions. Electronic structure analysis employing in situ near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy measurements clarifies the Cs atoms bond via oxygen functional groups on GO in the aqueous solution. The Cs adsorption capacity was found to be as high as 650-850 mg g-1, which indicates that the GO/porous alumina acts as an effective adsorbent with high adsorption efficiency for radioactive nuclides in aqueous solutions.

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.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

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

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions 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 TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Method for selectively reducing plutonium values by a photochemical process

DOEpatents

Friedman, Horace A.; Toth, Louis M.; Bell, Jimmy T.

1978-01-01

The rate of reduction of Pu(IV) to Pu(III) in nitric acid solution containing a reducing agent is enhanced by exposing the solution to 200-500 nm electromagnetic radiation. Pu values are recovered from an organic extractant solution containing Pu(IV) values and U(VI) values by the method of contacting the extractant solution with an aqueous nitric acid solution in the presence of a reducing agent and exposing the aqueous solution to electromagnetic radiation having a wavelength of 200-500 nm. Under these conditions, Pu values preferentially distribute to the aqueous phase and U values preferentially distribute to the organic phase.

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

Thermodynamic characteristics of protolytic equilibria of L-serine in aqueous solutions

NASA Astrophysics Data System (ADS)

Kochergina, L. A.; Volkov, A. V.; Khokhlova, E. A.; Krutova, O. N.

2011-05-01

The heat effects of the reaction of aqueous solution of L-serine with aqueous solutions of HNO3 and KOH were determined by calorimetry at temperatures of 288.15, 298.15, and 308.15 K, and ionic strength values of 0.2, 0.5, and 1.0 (background electrolyte, KNO3). Standard thermodynamic characteristics (Δr H o, Δr G o, Δr S o, Δ C {/p o}) of the acid-base reactions in aqueous solutions of L-serine were calculated. The effect of the concentration of background electrolyte and temperature on the heats of dissociation of amino acid was considered. The combustion energy of L-serine by bomb calorimetry in the medium of oxygen was determined. The standard combustion and formation enthalpies of crystalline L-serine were calculated. The heats of dissolution of crystalline L-serine in water and solutions of potassium hydroxide at 298.15 K were measured by direct calorimetry. The standard enthalpies of formation of L-serine and products of its dissociation in aqueous solution were calculated.

IS NSVS 5066754 A NEAR-CONTACT OR A MARGINAL CONTACT BINARY?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samec, Ronald G.; Nyaude, Ropafadzo; Caton, Daniel B.

BVR{sub cIc} light curves of NSVS 5066754 were taken on 2014 May at Dark Sky Observatory in North Carolina. This variable is a solar-type eclipsing binary ( T 1 ∼ 5750 K) with a period of only 0.3751689(1) days. It appeared to be one of the shortest periods in Shaw’s list of near-contact binaries. The Binary Maker fits and our Wilson–Devinney solutions show that the binary could have both semidetached and marginal contact binary configurations. Five new times of minimum light were calculated, along with two minima determined from archived All Sky Automated Survey observations. From these minima and the discovery epoch, amore » quadratic ephemeris was determined. Thus, a magnetic braking scenario is possible. Both semidetached and contact models were explored. A marginal contact solution had the best sum of square residuals. It gave a mass ratio of ∼0.5, and a component temperature difference of ∼360 K, albeit somewhat large for a contact binary. Two substantial cool spots were determined in this solution with 37° and 28° radii and t-factors or 0.94 and 0.78 respectively. The fill-out is very shallow, ∼106%. It may have recently achieved contact.« less

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, W.Y.

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Efficient ensemble system based on the copper binding motif for highly sensitive and selective detection of cyanide ions in 100% aqueous solutions by fluorescent and colorimetric changes.

PubMed

Jung, Kwan Ho; Lee, Keun-Hyeung

2015-09-15

A peptide-based ensemble for the detection of cyanide ions in 100% aqueous solutions was designed on the basis of the copper binding motif. 7-Nitro-2,1,3-benzoxadiazole-labeled tripeptide (NBD-SSH, NBD-SerSerHis) formed the ensemble with Cu(2+), leading to a change in the color of the solution from yellow to orange and a complete decrease of fluorescence emission. The ensemble (NBD-SSH-Cu(2+)) sensitively and selectively detected a low concentration of cyanide ions in 100% aqueous solutions by a colorimetric change as well as a fluorescent change. The addition of cyanide ions instantly removed Cu(2+) from the ensemble (NBD-SSH-Cu(2+)) in 100% aqueous solutions, resulting in a color change of the solution from orange to yellow and a "turn-on" fluorescent response. The detection limits for cyanide ions were lower than the maximum allowable level of cyanide ions in drinking water set by the World Health Organization. The peptide-based ensemble system is expected to be a potential and practical way for the detection of submicromolar concentrations of cyanide ions in 100% aqueous solutions.

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.

Bidentate organophosphorus solvent extraction process for actinide recovery and partition

DOEpatents

Schulz, Wallace W.

1976-01-01

A liquid-liquid extraction process for the recovery and partitioning of actinide values from acidic nuclear waste aqueous solutions, the actinide values including trivalent, tetravalent and hexavalent oxidation states is provided and includes the steps of contacting the aqueous solution with a bidentate organophosphorous extractant to extract essentially all of the actinide values into the organic phase. Thereafter the respective actinide fractions are selectively partitioned into separate aqueous solutions by contact with dilute nitric or nitric-hydrofluoric acid solutions. The hexavalent uranium is finally removed from the organic phase by contact with a dilute sodium carbonate solution.

Adsorption of Cu(II) from aqueous solution on sulfuric acid treated palygorskite

NASA Astrophysics Data System (ADS)

Niu, Yan-Ning; Yuan, Yuan; Gao, Wei-Xin; Qian, Sheng; Sun, Wen

2018-03-01

The absorption behavior of Cu2+ from aqueous solution on sulfuric acid treated palygorskite were investigated, the results showed that palygorskite had high absorption ability for Cu2+ from aqueous solution. Effects of the shaking time, pH and the copper ion concentration on the removal rate were discussed. The absorption behavior of Cu2+ could be well imitated by the Langmuir isothermal equation.

Water purification using organic salts

DOEpatents

Currier, Robert P.

2004-11-23

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

Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution

DOE PAGES

Leggett, Christina J.; Parker, Bernard F.; Teat, Simon J.; ...

2016-01-14

A “bare” V 5+ complex with glutaroimide-dioxime (H 3L), a ligand for uranium recovery from seawater, was synthesized from aqueous solution as Na[V(L) 2]2H 2O and the structure determined by x-ray diffraction. It is the first non-oxo V(v) complex that has been directly synthesized in and crystallized from aqueous solution.

Measurement of Surface Forces

DTIC Science & Technology

1990-11-16

creating an electrical double-layer whenever a bare mica surface is in contact with an aqueous solution . The mica/electrolyte double-layer...between mica in aqueous solutions containing 10-5 to I M KNO 3 (From Reference 44. Copyright 0 1985 Royal Swedish Academy. Reprinted with permission of...can be observed in aqueous KNO 3 solutions at close separations and at high ion concentrations. For example, if the force curves in Figure 8 (top) for

Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leggett, Christina J.; Parker, Bernard F.; Teat, Simon J.

A “bare” V 5+ complex with glutaroimide-dioxime (H 3L), a ligand for uranium recovery from seawater, was synthesized from aqueous solution as Na[V(L) 2]2H 2O and the structure determined by x-ray diffraction. It is the first non-oxo V(v) complex that has been directly synthesized in and crystallized from aqueous solution.

Sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on the surface of porous graphitized carbon

NASA Astrophysics Data System (ADS)

Savchenkova, A. S.; Buryak, A. K.; Kurbatova, S. V.

2015-09-01

The sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on porous graphitized carbon was studied. The effect of the structure of analyte molecules and the eluent composition on the characteristics of retention under the conditions of RP HPLC was analyzed. The effect of pH of the eluent on the shift of equilibrium in aqueous acetonitrile solutions was investigated.

ADSORPTION PROCEDURE IN PREPARING U$sup 23$$sup 3$

DOEpatents

Stoughton, R.W.

1958-10-14

A process is presented for the separation of protoactinium and thorium from an aqueous nitric acid solution containing these metals. It comprises contacting the solution with a cation exchange phenol-formaldehyde resin containing sulfonic acid groups, and eluting the adsorbed thorium from the resin by means of aqueous nitric acid. Thereafter the adsorbed protoactinium is eluted from the resin by means of an aqueous solution of ammonium fluoride.

Observations and light curve solutions of a selection of middle-contact W UMa binaries

NASA Astrophysics Data System (ADS)

Kjurkchieva, Diana Petrova; Popov, Velimir Angelov; Lyubenova Vasileva, Doroteya; Petrov, Nikola Ivanov

2018-04-01

Photometric observations in Sloan g‧ and i‧ bands of W UMa binaries NSVS 4340949, T-Dra0–00959, GSC 03950–00707, NSVS 4665041, NSVS 4803568, MM Peg, MM Com and NSVS 4751449 are presented. The light curve solutions revealed that the components of each target are of G and K spectral types. The binaries of the sample have middle-contact configurations whose fillout factors are within the range 0.2–0.4. The only exception is NSVS 4751449 which is in deeper contact (fillout factor of 0.55). It precisely obeys the relation between mass ratio and fillout factor for deep, low mass ratio overcontact binaries. One of the eclipses of almost all targets (except MM Peg) is an occultation and their photometric mass ratios and solutions could be accepted with confidence. We found that the target components have almost equal temperatures but differ considerably in size and mass. The components of the partially-eclipsed MM Peg have close parameters. Our solutions reveal that NSVS 4340949, T-Dra0–00959, NSVS 4803568 and MM Com are of W subtype while GSC 03950–00707, NSVS 4665041, MM Peg and NSVS 4751449 are of A subtype. This subclassification is well-determined for all totally-eclipsed binaries. The targets confirm the trends in which W-subtype systems have smaller periods and lower temperatures than A subtype binaries.

Origin of the computational hardness for learning with binary synapses.

PubMed

Huang, Haiping; Kabashima, Yoshiyuki

2014-11-01

Through supervised learning in a binary perceptron one is able to classify an extensive number of random patterns by a proper assignment of binary synaptic weights. However, to find such assignments in practice is quite a nontrivial task. The relation between the weight space structure and the algorithmic hardness has not yet been fully understood. To this end, we analytically derive the Franz-Parisi potential for the binary perceptron problem by starting from an equilibrium solution of weights and exploring the weight space structure around it. Our result reveals the geometrical organization of the weight space; the weight space is composed of isolated solutions, rather than clusters of exponentially many close-by solutions. The pointlike clusters far apart from each other in the weight space explain the previously observed glassy behavior of stochastic local search heuristics.

KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

PubMed Central

Dong, Hui; Wang, Lili; Gao, Wei; Li, Xiaoyuan; Wang, Chao; Ji, Fang; Pan, Jinlong; Wang, Baorui

2017-01-01

A novel functional KH2PO4 (KDP) aqueous solution-in-oil (KDP aq/O) microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP) was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP) were applied to replace water in the traditional water-in-oil (W/O) microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR) with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM) as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR. PMID:28772632

KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal.

PubMed

Dong, Hui; Wang, Lili; Gao, Wei; Li, Xiaoyuan; Wang, Chao; Ji, Fang; Pan, Jinlong; Wang, Baorui

2017-03-09

A novel functional KH₂PO₄ (KDP) aqueous solution-in-oil (KDP aq/O) microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP) was prepared. The system, which consisted of decanol, Triton X-100, and KH₂PO₄ aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations ( c KDP ) were applied to replace water in the traditional water-in-oil (W/O) microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR) with the increasing of the c KDP . As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion ( c KDP was changed from 10 mM to 100 mM) as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

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.

Ceramic porous material and method of making same

DOEpatents

Liu, Jun; Kim, Anthony Y.; Virden, Jud W.

1997-01-01

The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors.

Ceramic porous material and method of making same

DOEpatents

Liu, J.; Kim, A.Y.; Virden, J.W.

1997-07-08

The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors. 21 figs.

Ultrasonic evidence of hydrophobic interactions. Effect of ultrasound on benzoin condensation and some other reactions in aqueous ethanol.

PubMed

Tuulmets, Ants; Hagu, Hannes; Salmar, Siim; Cravotto, Giancarlo; Järv, Jaak

2007-03-29

The kinetics of KCN-catalyzed benzoin condensation of benzaldehyde in water and ethanol-water binary mixtures was investigated both under ultrasound at 22 kHz and without sonication. Thermodynamic activation parameters were calculated from kinetic data obtained at 35, 50, and 65 degrees C. Evidence that ultrasound can retard reactions is reported and hence a direct proof that sonochemical processes occur in the bulk solution. Former results and literature data for ester hydrolyses and tert-butyl chloride solvolysis are involved in the discussion. A quantitative relationship between sonication effects and the hydrophobicity of reagents is presented for the first time. Ultrasound affects hydrophobic interactions with the solvent, which are not manifested in conventional kinetics. When it suppresses the stabilization of the encounter complexes between reagents, sonication hinders the reaction but accelerates it when it perturbs the hydrophobic stabilization of the ground state of a reagent.

Some aspects of multicomponent excess free energy models with subregular binaries

NASA Astrophysics Data System (ADS)

Cheng, Weiji; Ganguly, Jibamitra

1994-09-01

We have shown that two of the most commonly used multicomponent formulations of excess Gibbs free energy of mixing, those by WOHL (1946, 1953) and REDLICH and KISTER (1948), are formally equivalent if the binaries are constrained to have subregular properties, and also that other subregular multicomponent formulations developed in the mineralogical and geochemical literature are equivalent to, or higher order extensions of, these formulations. We have also presented a compact derivation of a multicomponent subregular solution leading to the same expression as derived by HELFFRICH and WOOD (1989). It is shown that Wohl's multicomponent formulation involves combination of binary excess free energies, which are calculated at compositions obtained by normal projection of the multicomponent composition onto the bounding binary joins, and is, thus, equivalent to the formulation developed by MUGGIANU et al. (1975). Finally, following the lead of HILLERT (1980), we have explored the limiting behavior of regular and subregular ternary solutions when a pair of components become energetically equivalent, and have, thus, derived an expression for calculating the ternary interaction parameter in a ternary solution from a knowledge of the properties of the bounding binaries, when one of these binaries is nearly ideal.

Chemical evolution of multicomponent aerosol particles during evaporation

NASA Astrophysics Data System (ADS)

Zardini, Alessandro; Riipinen, Ilona; Pagels, Joakim; Eriksson, Axel; Worsnop, Douglas; Switieckli, Erik; Kulmala, Markku; Bilde, Merete

2010-05-01

Atmospheric aerosol particles have an important but not well quantified effect on climate and human health. Despite the efforts made in the last decades, the formation and evolution of aerosol particles in the atmosphere is still not fully understood. The uncertainty is partly due to the complex chemical composition of the particles which comprise inorganic and organic compounds. Many organics (like dicarboxylic acids) can be present both in the gas and in the condensed phase due to their low vapor pressure. Clearly, an understanding of this partition is crucial to address any other issue in atmospheric physics and chemistry. Moreover, many organics are water soluble, and their influence on the properties of aqueous solution droplets is still poorly characterized. The solid and sub-cooled liquid state vapor pressures of some organic compounds have been previously determined by measuring the evaporation rate of single-compound crystals [1-3] or binary aqueous droplets [4-6]. In this work, we deploy the HTDMA technique (Hygroscopicity Tandem Differential Mobility Analyzer) coupled with a 3.5m laminar flow-tube and an Aerosol Mass Spectrometer (AMS) for determining the chemical evolution during evaporation of ternary droplets made of one dicarboxylic acid (succinic acid, commonly found in atmospheric samples) and one inorganic compound (sodium chloride or ammonium sulfate) in different mixing ratios, in equilibrium with water vapor at a fixed relative humidity. In addition, we investigate the evaporation of multicomponent droplets and crystals made of three organic species (dicarboxylic acids and sugars), of which one or two are semi-volatile. 1. Bilde M. and Pandis, S.N.: Evaporation Rates and Vapor Pressures of Individual Aerosol Species Formed in the Atmospheric Oxidation of alpha- and beta-Pinene. Environmental Science and Technology, 35, 2001. 2. Bilde M., et al.: Even-Odd Alternation of Evaporation Rates and Vapor Pressures of C3-C9 Dicarboxylic Acid Aerosols, Environmental. Science and Technology, 37, 2003. 5. Koponen I.K., et al.: Thermodynamic properties of malonic, succinic, and glutaric acids: Evaporation rates and saturation vapor pressures. Environmental Science and Technology, 41, 2007. 4. Zardini A.A., et al.: White light Mie resonance spectroscopy used to measure very low vapor pressures of substances in aqueous solution aerosol particles. Optics Express, 14, 2006. 3. Zardini A.A. and Krieger, U.K.: Evaporation kinetics of a non-spherical, levitated aerosol particle using optical resonance spectroscopy for precision sizing. Optics Express, 17, 2009. 6. Riipinen, I., et al.: Adipic and Malonic Acid Aqueous Solutions: Surface Tensions and Saturation Vapor Pressures, J. Phys. Chem., 111, 2007.

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.

SEPARATION PROCESS FOR TRANSURANIC ELEMENT AND COMPOUNDS THEREOF

DOEpatents

Magnusson, L.B.

1958-04-01

A process is described for the separation of neptunium, from aqueous solutions of neptunium, plutonium, uraniunn, and fission prcducts. This separation from an acidic aqueous solution of a tetravalent neptuniunn can be made by contacting the solution with a certain type of chelating,; agent, preferably dissolved in an organic solvent, to form a neptunium chelate compound. When the organic solvent is present, the neptunium chelate compound is extracted; otherwise, it precipitates from the aqueous solution and is separated by any suitable means. The chelating agent is a fluorinated BETA -diketone. such as trifluoroacetyl acetone.

Radiolysis of aqueous solutions of thiamine

NASA Astrophysics Data System (ADS)

Chijate, C.; Albarran, G.; Negron-Mendoza, A.

1998-06-01

The results of the radiolysis of aqueous solutions of thiamine (vitamin B 1) are presented. The yields for decomposition of thiamine and the product of radiolytic products were determined. The G values decrease as the dose increases. Some radiolytic products were identified. Decomposition of thiamine was slightly dependent on the presence of oxygen and on the pH of the solution. At pH 4.4 with a concentration of 2.5 × 10 -4 mol L -1 of thiamine in an oxygen free aqueous solution, the G 0 value for decomposition is 5.0.

ION EXCHANGE PROCESS FOR THE RECOVERY AND PURIFICATION OF MATERIALS

DOEpatents

Long, R.S.; Bailes, R.H.

1958-04-15

A process for the recovery of certain metallic ions from aqueous solutions by ion exchange techniques is described. It is applicable to elements such as vanadium, chromium, nnanganese, and the like, which are capable of forming lower valent cations soluble in aqueous solutions and which also form ldgher valent anions soluble in aqueous acidic solutions. For example, small amounts of vanadium occurring in phosphoric acid prepared from phosphate rock may be recovered by reducing the vanadium to a trivalent cation adsorbing; the vanadium in a cationic exchange resin, then treating the resin with a suitable oxidizing agent to convert the adsorbed vanadium to a higher valent state, and finally eluting; the vanadium as an anion from the resin by means of an aqueous acidic solution.

Removal of copper ions from aqueous solutions by a steel-making by-product.

PubMed

López, F A; Martín, M I; Pérez, C; López-Delgado, A; Alguacil, F J

2003-09-01

A study is made of the use of a steel-making by-product (rolling mill scale) as a material for removing Cu(2+) ions from aqueous solutions. The influence of contact time, initial copper ion concentration and temperature on removal capability is considered. The removal of Cu(2+) ions from an aqueous solution involves two processes: on the one hand, the adsorption of Cu(2+) ions on the surface of mill scale due to the iron oxides present in the latter; and on the other hand, the cementation of Cu(2+) onto metallic iron contained in the mill scale. Rolling mill scale is seen to be an effective material for the removal of copper ions from aqueous solutions.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

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

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions 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 TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

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 (R

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.

Hardness behavior of binary and ternary niobium alloys at 77 and 300 K

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1974-01-01

The effects of alloy additions of zirconium, hafnium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, and iridium on the hardness of niobium was determined. Both binary and ternary alloys were investigated by means of hardness tests at 77 K and 300 K. Results showed that atomic size misfit plays a dominant role in controlling hardness of binary niobium alloys. Alloy softening, which occurred at dilute solute additions, is most likely due to an extrinsic mechanism involving interaction between solute elements and interstitial impurities.

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.

PROCESS FOR SEPARATING PLUTONIUM BY REPEATED PRECIPITATION WITH AMPHOTERIC HYDROXIDE CARRIERS

DOEpatents

Faris, B.F.

1960-04-01

A multiple carrier precipitation method is described for separating and recovering plutonium from an aqueous solution. The hydroxide of an amphoteric metal is precipitated in an aqueous plutonium-containing solution. This precipitate, which carries plutonium, is then separated from the supernatant liquid and dissolved in an aqueous hydroxide solution, forming a second plutonium- containing solution. lons of an amphoteric metal which forms an insoluble hydroxide under the conditions existing in this second solution are added to the second solution. The precipitate which forms and which carries plutonium is separated from the supernatant liquid. Amphoteric metals which may be employed are aluminum, bibmuth, copper, cobalt, iron, lanthanum, nickel, and zirconium.

Mechanistic roles of soil humus and minerals in the sorption of nonionic organic compounds from aqueous and organic solutions

USGS Publications Warehouse

Chiou, C.T.; Shoup, T.D.; Porter, P.E.

1985-01-01

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral contents. In aqueous systems, observed sorptive characteristics suggest that solute partitioning into the soil-humic phase is the primary mechanism of soil uptake. By contrast, data obtained from organic solutions on dehydrated soil partitioning into humic phase and adsorption by soil minerals is influenced by the soil-moisture content and by the solvent medium from which the solute is sorbed. ?? 1985.

Binary black hole in a double magnetic monopole field

NASA Astrophysics Data System (ADS)

Rodriguez, Maria J.

2018-01-01

Ambient magnetic fields are thought to play a critical role in black hole jet formation. Furthermore, dual electromagnetic signals could be produced during the inspiral and merger of binary black hole systems. In this paper, we derive the exact solution for the electromagnetic field occurring when a static, axisymmetric binary black hole system is placed in the field of two magnetic or electric monopoles. As a by-product of this derivation, we also find the exact solution of the binary black hole configuration in a magnetic or electric dipole field. The presence of conical singularities in the static black hole binaries represent the gravitational attraction between the black holes that also drag the external two monopole field. We show that these off-balance configurations generate no energy outflows.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549

MARVELS Radial Velocity Solutions to Seven Kepler Eclipsing Binaries

NASA Astrophysics Data System (ADS)

Heslar, Michael Francis; Thomas, Neil B.; Ge, Jian; Ma, Bo; Herczeg, Alec; Reyes, Alan; SDSS-III MARVELS Team

2016-01-01

Eclipsing binaries serve momentous purposes to improve the basis of understanding aspects of stellar astrophysics, such as the accurate calculation of the physical parameters of stars and the enigmatic mass-radius relationship of M and K dwarfs. We report the investigation results of 7 eclipsing binary candidates, initially identified by the Kepler mission, overlapped with the radial velocity observations from the SDSS-III Multi-Object APO Radial-Velocity Exoplanet Large-Area Survey (MARVELS). The RV extractions and spectroscopic solutions of these eclipsing binaries were generated by the University of Florida's 1D data pipeline with a median RV precision of ~60-100 m/s, which was utilized for the DR12 data release. We performed the cross-reference fitting of the MARVELS RV data and the Kepler photometric fluxes obtained from the Kepler Eclipsing Binary Catalog (V2) and modelled the 7 eclipsing binaries in the BinaryMaker3 and PHOEBE programs. This analysis accurately determined the absolute physical and orbital parameters of each binary. Most of the companion stars were determined to have masses of K and M dwarf stars (0.3-0.8 M⊙), and allowed for an investigation into the mass-radius relationship of M and K dwarfs. Among the cases are KIC 9163796, a 122.2 day period "heartbeat star", a recently-discovered class of eccentric binaries known for tidal distortions and pulsations, with a high eccentricity (e~0.75) and KIC 11244501, a 0.29 day period, contact binary with a double-lined spectrum and mass ratio (q~0.45). We also report on the possible reclassification of 2 Kepler eclipsing binary candidates as background eclipsing binaries based on the analysis of the flux measurements, flux ratios of the spectroscopic and photometric solutions, the differences in the FOVs, the image processing of Kepler, and RV and spectral analysis of MARVELS.

New spectroscopic binary companions of giant stars and updated metallicity distribution for binary systems

NASA Astrophysics Data System (ADS)

Bluhm, P.; Jones, M. I.; Vanzi, L.; Soto, M. G.; Vos, J.; Wittenmyer, R. A.; Drass, H.; Jenkins, J. S.; Olivares, F.; Mennickent, R. E.; Vučković, M.; Rojo, P.; Melo, C. H. F.

2016-10-01

We report the discovery of 24 spectroscopic binary companions to giant stars. We fully constrain the orbital solution for 6 of these systems. We cannot unambiguously derive the orbital elements for the remaining stars because the phase coverage is incomplete. Of these stars, 6 present radial velocity trends that are compatible with long-period brown dwarf companions. The orbital solutions of the 24 binary systems indicate that these giant binary systems have a wide range in orbital periods, eccentricities, and companion masses. For the binaries with restricted orbital solutions, we find a range of orbital periods of between ~97-1600 days and eccentricities of between ~0.1-0.4. In addition, we studied the metallicity distribution of single and binary giant stars. We computed the metallicity of a total of 395 evolved stars, 59 of wich are in binary systems. We find a flat distribution for these binary stars and therefore conclude that stellar binary systems, and potentially brown dwarfs, have a different formation mechanism than planets. This result is confirmed by recent works showing that extrasolar planets orbiting giants are more frequent around metal-rich stars. Finally, we investigate the eccentricity as a function of the orbital period. We analyzed a total of 130 spectroscopic binaries, including those presented here and systems from the literature. We find that most of the binary stars with periods ≲30 days have circular orbits, while at longer orbital periods we observe a wide spread in their eccentricities. Based on observations collected at La Silla - Paranal Observatory under programs IDs IDs 085.C-0557, 087.C.0476, 089.C-0524, 090.C-0345, 096.A-9020 and through the Chilean Telescope Time under programs IDs CN2012A-73, CN2012B-47, CN2013A-111, CN2013B-51, CN2014A-52 and CN2015A-48.

How Does a Hydrophobic Macromolecule Respond to Mixed Osmolyte Environment?

PubMed

Tah, Indrajit; Mondal, Jagannath

2016-10-04

The role of the protecting osmolyte Trimethyl N-oxide (TMAO) in counteracting the denaturing effect of urea on a protein is quite well established. However, the mechanistic role of osmolytes on the hydrophobic interaction underlying protein folding is a topic of contention and is emerging as a key area of biophysical interest. Although recent experiment and computer simulation have established that individual aqueous solution of TMAO and urea respectively stabilizes and destabilizes the collapsed conformation of a hydrophobic polymer, it remains to be explored how a mixed aqueous solution of protecting and denaturing osmolytes influences the conformations of the polymer. In order to bridge the gap, we have simulated the conformational behavior of both a model hydrophobic polymer and a synthetic polymer polystyrene in an aqueous mixture of TMAO and urea. Intriguingly, our free energy based simulations on both the systems show that even though a pure aqueous solution of TMAO stabilizes the collapsed or globular conformation of the hydrophobic polymer, addition of TMAO to an aqueous solution of urea further destabilizes the collapsed conformation of the hydrophobic polymer. We also observe that the extent of destabilization in a mixed osmolyte solution is relatively higher than that in pure aqueous urea solution. The reinforcement of the denaturation effect of the hydrophobic macromolecule in a mixed osmolyte solution is in stark contrast to the well-known counteracting role of TMAO in proteins under denaturing condition of urea. In both model and realistic systems, our results show that in a mixed aqueous solution, greater number of cosolutes preferentially bind to the extended conformation of the polymer relative to that in the collapsed conformation, thereby complying with Tanford-Wyman preferential solvation theory disfavoring the collapsed conformation. The results are robust across a range of osmolyte concentrations and multiple cosolute forcefields. Our findings unequivocally imply that the action of mixed osmolyte solution on hydrophobic polymer is significantly distinct from that of proteins.

Simple introduction of carboxyl head group with alkyl spacer onto multiwalled carbon nanotubes by solution plasma process

NASA Astrophysics Data System (ADS)

Nemoto, Shimpei; Ueno, Tomonaga; Watthanaphanit, Anyarat; Hieda, Junko; Bratescu, Maria Antoaneta; Saito, Nagahiro

2017-09-01

A simple method of fabricating carboxyl-terminated multiwalled carbon nanotubes (MWCNTs) with alkyl spacers was developed to improve the dispersion quality of MWCNTs in aqueous solutions using solution plasma (SP) in a 6-aminocaproic acid solution. The formation of SP in the solution led to better dispersion of MWCNTs in aqueous solutions. Fourier transform infrared spectroscopy (FT-IR) results indicate that a carboxyl group with an alkyl spacer can be introduced by SP treatment in the 6-aminocaproic acid solution. Sedimentation tests show that the SP-treated MWCNTs in the 6-aminocaproic acid solution retained their good dispersion quality in aqueous solutions of pHs 5, 6, and 9. The alkyl spacer plays an important role in the preservation of dispersion states particularly at pH 6.

Optical analogue of relativistic Dirac solitons in binary waveguide arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tran, Truong X., E-mail: truong.tran@mpl.mpg.de; Max Planck Institute for the Science of Light, Günther-Scharowsky str. 1, 91058 Erlangen; Longhi, Stefano

2014-01-15

We study analytically and numerically an optical analogue of Dirac solitons in binary waveguide arrays in the presence of Kerr nonlinearity. Pseudo-relativistic soliton solutions of the coupled-mode equations describing dynamics in the array are analytically derived. We demonstrate that with the found soliton solutions, the coupled mode equations can be converted into the nonlinear relativistic 1D Dirac equation. This paves the way for using binary waveguide arrays as a classical simulator of quantum nonlinear effects arising from the Dirac equation, something that is thought to be impossible to achieve in conventional (i.e. linear) quantum field theory. -- Highlights: •An opticalmore » analogue of Dirac solitons in nonlinear binary waveguide arrays is suggested. •Analytical solutions to pseudo-relativistic solitons are presented. •A correspondence of optical coupled-mode equations with the nonlinear relativistic Dirac equation is established.« less

Aqueous penetration and biological activity of moxifloxacin 0.5% ophthalmic solution and gatifloxacin 0.3% solution in cataract surgery patients.

PubMed

Kim, Dianne H; Stark, Walter J; O'Brien, Terrence P; Dick, James D

2005-11-01

To measure the achievable perioperative aqueous concentration of the commercially available topically administered fourth generation fluoroquinolones, moxifloxacin 0.5% ophthalmic solution, and gatifloxacin 0.3% ophthalmic solution, and to correlate this concentration with the agents' biological efficacy in the aqueous humor of patients undergoing routine cataract surgery. Prospective, randomized, parallel, double-masked, clinical trial. Fifty patients undergoing cataract extraction. Patients (n = 25) were given perioperative topical moxifloxacin 0.5% or topical gatifloxacin 0.3% (n = 25). One drop of antibiotic was administered every 10 minutes for 4 doses beginning 1 hour prior to surgery. Aqueous humor was sampled via paracentesis and antibiotic concentrations were determined using validated high performance liquid chromatography (HPLC) procedures. Dilution analyses were performed to determine the biological efficacy of the agents in the aqueous against Staphylococcus epidermidis, the most common cause of postcataract endophthalmitis. Aqueous humor antibiotic concentrations were measured using HPLC and microdilution bioassay techniques. Biological activity was measured as minimal inhibitory dilution and minimal bactericidal dilution. Aqueous humor concentrations for moxifloxacin via HPLC analysis were 1.80 (+/-1.21) microg/ml, whereas those for gatifloxacin were 0.48 (+/-0.34) microg/ml. This 3.8-fold difference in aqueous humor antibiotic concentrations was statistically significant (P = 0.00003). Similarly, the biological dilution analysis of the aqueous humor samples showed that moxifloxacin attained an estimated activity of 2.1 microg/ml, whereas the gatifloxacin activity was approximately 0.4 mug/ml, which represented a 4.9-fold difference. This study demonstrated that after topically administered perioperative antibiotics with cataract surgery, moxifloxacin 0.5% ophthalmic solution achieved a statistically significantly higher concentration in aqueous humor compared with gatifloxacin (P = 0.00003). Results from the broth dilution analysis showed that moxifloxacin 0.5% was biologically more active against S. epidermidis than gatifloxacin 0.3% in aqueous humor after topical application. There were no adverse events reported, and incision wounds healed quickly and as expected.

Electromarking solution

DOEpatents

Bullock, Jonathan S.; Harper, William L.; Peck, Charles G.

1976-06-22

This invention is directed to an aqueous halogen-free electromarking solution which possesses the capacity for marking a broad spectrum of metals and alloys selected from different classes. The aqueous solution comprises basically the nitrate salt of an amphoteric metal, a chelating agent, and a corrosion-inhibiting agent.

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)

Ice growth from supercooled aqueous solutions of benzene, naphthalene, and phenanthrene.

PubMed

Liyana-Arachchi, Thilanga P; Valsaraj, Kalliat T; Hung, Francisco R

2012-08-23

Classical molecular dynamics (MD) were performed to investigate the growth of ice from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene. The main objective of this study is to explore the fate of those aromatic molecules after freezing of the supercooled aqueous solutions, i.e., if these molecules become trapped inside the ice lattice or if they are displaced to the QLL or to the interface with air. Ice growth from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene result in the formation of quasi-liquid layers (QLLs) at the air/ice interface that are thicker than those observed when pure supercooled water freezes. Naphthalene and phenanthrene molecules in the supercooled aqueous solutions are displaced to the air/ice interface during the freezing process at both 270 and 260 K; no incorporation of these aromatics into the ice lattice is observed throughout the freezing process. Similar trends were observed during freezing of supercooled aqueous solutions of benzene at 270 K. In contrast, a fraction of the benzene molecules become trapped inside the ice lattice during the freezing process at 260 K, with the rest of the benzene molecules being displaced to the air/ice interface. These results suggest that the size of the aromatic molecule in the supercooled aqueous solution is an important parameter in determining whether these molecules become trapped inside the ice crystals. Finally, we also report potential of mean force (PMF) calculations aimed at studying the adsorption of gas-phase benzene and phenanthrene on atmospheric air/ice interfaces. Our PMF calculations indicate the presence of deep free energy minima for both benzene and phenanthrene at the air/ice interface, with these molecules adopting a flat orientation at the air/ice interface.

Polymer-assisted aqueous deposition of metal oxide films

DOEpatents

Li, DeQuan [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM

2003-07-08

An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.

Recovering oil by injecting aqueous alkali, cosurfactant and gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reisberg, J.; Bielmowicz, L. J.; Thigpen, D. R.

1985-01-15

A process of recovering oil from a subterranean reservoir in which the oil is acidic but forms monovalent cation soaps of only relatively low interfacial activity when reacted with aqueous alkaline solutions, comprises displacing the oil toward a production location with a mixture of gas and cosurfactant-containing aqueous alkaline solution.

Membrane Treatment of Aqueous Film Forming Foam (AFFF) Wastes for Recovery of Its Active Ingredients

DTIC Science & Technology

1980-10-01

T ME1MBRANE TREATMENT OF AQUEOUS FILM FORMING FOAM~ (AFFF) WASTES FOR RECOVERY OFI Fts ACTIVE INGREDIENTS FINAL REPORT October 1980 by Edward S. K...OF THIS PAGEOPMn Date AVntr* d)__ ---- Ultrafiltration (UF) and Reverse Osmosis (RO) treatment of Aqueous Film Forming Foam (AFFF) solutions was...of Aqueous Film Forming Foam (AFFF) solutions was investigated to determine the feasibility of employing membrane processes to separate and recover

Atomistic modeling of the solid-state chemistry of actinide materials

NASA Astrophysics Data System (ADS)

Shuller, Lindsay C.

Materials that incorporate actinides are critical to the nuclear fuel cycle, either as nuclear fuels or nuclear waste forms. In this thesis, I examine four materials: i) ThO2-UO2 solid solutions, ii) binary ThO2-CeO2-ZrO2 solid solutions, iii) Np-doped studtite, iv) Np-doped boltwoodite. Computational methods, particularly density functional theory (DFT) calculations and Monte-Carlo (MC) simulations, are used to determine the energetics and structures of these actinide-bearing materials. The solid-solution behavior of nuclear fuels and nuclear waste forms indicate the thermodynamic stability of the material, which is important for understanding the in-reactor fuel properties and long-term stability of used fuel. The ThxU1-xO2 and ThxCe 1-xO2 binaries are almost completely miscible; however, DeltaGmix reveals a small tendency for the systems to exsolve (e.g., DeltaEexsoln(Th xU1-xO2) = 0.13 kJ/(mol cations) at 750 K). Kinetic hindrances (e.g., interfacial energy) may inhibit exsolution, especially at the low temperatures necessary to stabilize the nanoscale exsolution lamellae observed in the ThxU1-xO2 and Ce xZr1-xO2 binaries. Miscibility in the Zr-bearing binaries is limited. At 1400 °C, only 3.6 and 0.09 mol% ZrO2 is miscible in CeO2 and ThO2, respectively. The incorporation of minor amounts of Np5+,6+ into uranium alteration phases, e.g., studtite [UO2O2 (H2O)4] or boltwoodite [K(UO2)(SiO 3OH)(H2O)1.5] , may limit the mobility of aqueous neptunyl complexes released from oxidized nuclear fuels. Np6+-incorporation into studtite requires less energy than Np5+-incorporation (e.g., with source/sink = Np2O5/UO 3 DeltaEincorp(Np6+) = 0.42 eV and DeltaEincorp(Np5+) = 1.12 eV). In addition, Np6+ is completely miscible in studtite at room temperature with respect to a hypothetical Np6+-studtite. Electronic structure calculations provide insight into Np-bonding in studtite. The Np 5f orbitals are within the band gap of studtite, resulting in the narrowing of the band gap from 2.29 eV for studtite to 1.09 eV for Np-incorporated studtite. Three charge-balancing mechanisms for the substitution of Np5+ for U6+ were compared: i) addition of H+ [DeltaEincorp(bolt) = 0.79 eV; DeltaEincorp(stud) = 1.12 eV], ii) interlayer coupled substitution [DeltaEincorp (bolt) = 1.40 eV], iii) intra-layer coupled-substitution [DeltaEincorp(bolt) = 0.86 eV]. Solid-solution calculations of the intra-layer coupled-substitution mechanism, where Np 5+ and P5+ substitute for U6+ and Si 4+, predict an incorporation limit of 585 ppm at 300 °C.

Method for producing oxygen from lunar materials

NASA Technical Reports Server (NTRS)

Sullivan, Thomas A. (Inventor)

1993-01-01

This invention is related to producing oxygen from lunar or Martian materials, particularly from lunar ilmenite in situ. The process includes producing a slurry of the minerals and hot sulfuric acid, the acid and minerals reacting to form sulfates of the metal. Water is added to the slurry to dissolve the minerals into an aqueous solution, the first aqueous solution is separated from unreacted minerals from the slurry, and the aqueous solution is electrolyzed to produce the metal and oxygen.

A fluorescent sensor for selective detection of cyanide using mesoporous graphitic carbon(IV) nitride.

PubMed

Lee, Eun Zoo; Lee, Sun Uk; Heo, Nam-Su; Stucky, Galen D; Jun, Young-Si; Hong, Won Hi

2012-04-25

A turn-on fluorescence sensor, Cu(2+)-c-mpg-C(3)N(4), was developed for detection of CN(-) in aqueous solution by simply mixing cubic mesoporous graphitic carbon nitride (c-mpg-C(3)N(4)) and aqueous solution of Cu(NO(3))(2). The highly sensitive detection of CN(-) with a detection limit of 80 nM is not only possible in aqueous solution but also in human blood serum.

Stiffness-independent highly efficient on-chip extraction of cell-laden hydrogel microcapsules from oil emulsion into aqueous solution by dielectrophoresis

PubMed Central

Huang, Haishui; Sun, Mingrui; Heisler-Taylor, Tyler; Kiourti, Asimina; Volakis, John; Lafyatis, Gregory

2015-01-01

A dielectrophoresis (DEP)-based method is reported to achieve highly efficient on-chip extraction of cell-laden microcapsules of any stiffness from oil into aqueous solution. The hydrogel microcapsules can be extracted into the aqueous solution by DEP and interfacial tension (IFT) forces with no trapped oil while the encapsulated cells are free from the electrical damages due to the Faraday cage effect. PMID:26297051

SALICYLATE PROCESS FOR THORIUM SEPARATION FROM RARE EARTHS

DOEpatents

Cowan, G.A.

1959-08-25

The separation of thorium from rare earths is accomplished by forming an aqueous solution of salts of thorium and rare earths and sufficient acetate buffer to provide a pH of between 2 and 5, adding an ammonium salicylate to the aqueous buffered solution, contacting the resultant solution with a substantially water-immiscible organic solvent mixture of an ether and an ester, and separating the solvent extract phase containing thorium salicylate from the aqueous phase containing the rare earths.

Stability of GO Modified by Different Dispersants in Cement Paste and Its Related Mechanism.

PubMed

Long, Wu-Jian; Fang, Changle; Wei, Jingjie; Li, Haodao

2018-05-18

Graphene oxide (GO) is a potential material to be used as a nano-reinforcement in cement matrix. However, a prerequisite for GO to fulfill its function in the cement matrix is homogeneous dispersion. In this study, the effects of three different dispersing agents (DAs), including polycarboxylate-based high range water reducer (P-HRWR), naphthalene-based high range water reducer (N-HRWR), and air entraining agent (AEA) on the dispersion of GO in aqueous solution, simulated concrete pore solution (SCPS), and suspension of cement pastes were sequentially investigated. Results showed that the dispersion effect of GO in aqueous solutions was improved with different DAs. However, the homogeneous dispersion of GO in aqueous solution re-agglomerated in SCPS and suspension of cement pastes. It was concluded that as the cement content and pH of aqueous solutions increased, GOs re-agglomerated and precipitated in an alkaline solution. A possible mechanism was proposed in this study and it was believed that electrostatic interactions and steric hindrance provided by the P-HRWR further made GOs stable in aqueous solutions. The ions and pH of cement pastes increased with the increasing amount of cement, which caused the separation of P-HRWR from GOs. Therefore, GOs were re-agglomerated and absorbed on the surface of the cement particles, resulting in GOs sedimentation.

Defining microchannels and valves on a hydrophobic paper by low-cost inkjet printing of aqueous or weak organic solutions.

PubMed

Cai, Longfei; Zhong, Minghua; Li, Huolin; Xu, Chunxiu; Yuan, Biyu

2015-07-01

We describe a simple and cost-effective strategy for rapid fabrication of microfluidic paper-based analytical devices and valves by inkjet printing. NaOH aqueous solution was printed onto a hydrophobic filter paper, which was previously obtained by soaking in a trimethoxyoctadecylsilane-heptane solution, allowing selective wet etching of hydrophobic cellulose to create hydrophilic-hydrophobic contrast with a relatively good resolution. Hexadecyltrimethylammonium bromide (CTMAB)-ethanol solution was printed onto hydrophobic paper to fabricate temperature-controlled valves. At low temperature, CTMAB deposited on the paper is insoluble in aqueous fluid, thus the paper remains hydrophobic. At high temperature, CTMAB becomes soluble so the CTMAB-deposited channel becomes hydrophilic, allowing the wicking of aqueous solution through the valve. We believe that this strategy will be very attractive for the development of simple micro analytical devices for point-of-care applications, including diagnostic testing, food safety control, and environmental monitoring.

Adsorptive removal of antibiotics from aqueous solution using carbon materials.

PubMed

Yu, Fei; Li, Yong; Han, Sheng; Ma, Jie

2016-06-01

Antibiotics, an important type of environmental contamination, have attracted many researchers to the study of their removal from aqueous solutions. Adsorption technology is a fast, efficient, and economical physicochemical method that is extensively used in wastewater treatment. From original activated carbon and carbon nanotubes to the latest graphene-based materials, carbon-based materials have been widely used as highly effective adsorbents for contaminant removal from aqueous solution because of their large specific surface area, high porosity, and high reaction activity. In this article, adsorption removal methods for four major types of antibiotic (tetracyclines, sulfonamides, macrolides, and quinolones) are reviewed. We also provide an overview of the application development of carbon materials as adsorbents for antibiotic removal from aqueous solution. The most promising works are discussed, and the main challenges in preparing high-performance adsorbents and the development tendency of adsorbents are also analyzed. This work provides theoretical guidance for subsequent research in the design and modification of carbon materials for applications in the adsorption removal of antibiotics from aqueous solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of chromium(III) from aqueous waste solution by liquid-liquid extraction in a circular microchannel.

PubMed

Luo, Jian Hong; Li, Jun; Guo, Lei; Zhu, Xin Hua; Dai, Shuang; Li, Xing

2017-11-01

A new circular microchannel device has been proposed for the removal of chromium(III) from aqueous waste solution by using kerosene as a diluent and (2-ethylhexyl) 2-ethylhexyl phosphonate as an extractant. The proposed device has several advantages such as a flexible and easily adaptable design, easy maintenance, and cheap setup without the requirement of microfabrication. To study the extraction efficiency and advantages of the circular microchannel device in the removal of chromium(III), the effects of various operating conditions such as the inner diameter of the channel, the total flow velocity, the phase ratio, the initial pH of aqueous waste solution, the reaction temperature and the initial concentration of extractant on the extraction efficiency are investigated and the optimal process conditions are obtained. The results show that chromium(III) in aqueous waste solution can be effectively removed with (2-ethylhexyl) 2-ethylhexyl phosphonate in the circular microchannel. Under optimized conditions, an extraction efficiency of chromium(III) of more than 99% can be attained and the aqueous waste solution can be discharged directly, which can meet the Chinese national emission standards.

Thermodynamic and structure-property study of liquid-vapor equilibrium for aroma compounds.

PubMed

Tromelin, Anne; Andriot, Isabelle; Kopjar, Mirela; Guichard, Elisabeth

2010-04-14

Thermodynamic parameters (T, DeltaH degrees , DeltaS degrees , K) were collected from the literature and/or calculated for five esters, four ketones, two aldehydes, and three alcohols, pure compounds and compounds in aqueous solution. Examination of correlations between these parameters and the range values of DeltaH degrees and DeltaS degrees puts forward the key roles of enthalpy for vaporization of pure compounds and of entropy in liquid-vapor equilibrium of compounds in aqueous solution. A structure-property relationship (SPR) study was performed using molecular descriptors on aroma compounds to better understand their vaporization behavior. In addition to the role of polarity for vapor-liquid equilibrium of compounds in aqueous solution, the structure-property study points out the role of chain length and branching, illustrated by the correlation between the connectivity index CHI-V-1 and the difference between T and log K for vaporization of pure compounds and compounds in aqueous solution. Moreover, examination of the esters' enthalpy values allowed a probable conformation adopted by ethyl octanoate in aqueous solution to be proposed.

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

Dutcher, Cari S; Wexler, Anthony S; Clegg, Simon L

2010-11-25

A semiempirical model is presented that predicts surface tensions (σ) of aqueous electrolyte solutions and their mixtures, for concentrations ranging from infinitely dilute solution to molten salt. The model requires, at most, only two temperature-dependent terms to represent surface tensions of either pure aqueous solutions, or aqueous or molten mixtures, over the entire composition range. A relationship was found for the coefficients of the equation σ = c(1) + c(2)T (where T (K) is temperature) for molten salts in terms of ion valency and radius, melting temperature, and salt molar volume. Hypothetical liquid surface tensions can thus be estimated for electrolytes for which there are no data, or which do not exist in molten form. Surface tensions of molten (single) salts, when extrapolated to normal temperatures, were found to be consistent with data for aqueous solutions. This allowed surface tensions of very concentrated, supersaturated, aqueous solutions to be estimated. The model has been applied to the following single electrolytes over the entire concentration range, using data for aqueous solutions over the temperature range 233-523 K, and extrapolated surface tensions of molten salts and pure liquid electrolytes: HCl, HNO(3), H(2)SO(4), NaCl, NaNO(3), Na(2)SO(4), NaHSO(4), Na(2)CO(3), NaHCO(3), NaOH, NH(4)Cl, NH(4)NO(3), (NH(4))(2)SO(4), NH(4)HCO(3), NH(4)OH, KCl, KNO(3), K(2)SO(4), K(2)CO(3), KHCO(3), KOH, CaCl(2), Ca(NO(3))(2), MgCl(2), Mg(NO(3))(2), and MgSO(4). The average absolute percentage error between calculated and experimental surface tensions is 0.80% (for 2389 data points). The model extrapolates smoothly to temperatures as low as 150 K. Also, the model successfully predicts surface tensions of ternary aqueous mixtures; the effect of salt-salt interactions in these calculations was explored.

Friction and wear of iron-base binary alloys in sliding contact with silicon carbide in vacuum

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1980-01-01

Multipass sliding friction experiments were conducted with various iron base binary alloys in contact with a single crystal silicon carbide surface in vacuum. Results indicate that the atomic size and concentration of alloy elements play important roles in controlling the transfer and friction properties of iron base binary alloys. Alloys having high solute concentration produce more transfer than do alloys having low solute concentration. The coefficient of friction during multipass sliding generally increases with an increase in the concentration of alloying element. The change of friction with succeeding passes after the initial pass also increases as the solute to iron, atomic radius ratio increases or decreases from unity.

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)

EXTRACTION METHOD FOR SEPARATING URANIUM, PLUTONIUM, AND FISSION PRODUCTS FROM COMPOSITIONS CONTAINING SAME

DOEpatents

Seaborg, G.T.

1957-10-29

Methods for separating plutonium from the fission products present in masses of neutron irradiated uranium are reported. The neutron irradiated uranium is first dissolved in an aqueous solution of nitric acid. The plutonium in this solution is present as plutonous nitrate. The aqueous solution is then agitated with an organic solvent, which is not miscible with water, such as diethyl ether. The ether extracts 90% of the uraryl nitrate leaving, substantially all of the plutonium in the aqueous phase. The aqueous solution of plutonous nitrate is then oxidized to the hexavalent state, and agitated with diethyl ether again. In the ether phase there is then obtained 90% of plutonium as a solution of plutonyl nitrate. The ether solution of plutonyl nitrate is then agitated with water containing a reducing agent such as sulfur dioxide, and the plutonium dissolves in the water and is reduced to the plutonous state. The uranyl nitrate remains in the ether. The plutonous nitrate in the water may be recovered by precipitation.

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

DOE PAGES

Reynolds, Jacob G.; Mauss, Billie M.; Daniel, Richard C.

2018-05-09

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms ofmore » quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.« less

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, Jacob G.; Mauss, Billie M.; Daniel, Richard C.

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms ofmore » quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.« less

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, Wen Y.

1984-01-01

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems.

PubMed

Kajiwara, K; Motegi, A; Murase, N

2001-01-01

The freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems was investigated by differential scanning calorimetry (DSC). In the aqueous NaCl-glucose solution system, single or double glass transitions followed by the corresponding devitrification exotherms were observed during rewarming. In the aqueous KCl-glucose solution system, on the other hand, a single glass transition followed by an exotherm was observed during rewarming. The presence of double glass transitions observed for a certain composition of the aqueous NaCl-glucose solution was taken as an evidence for the liquid-liquid immiscibility at low temperatures. Two kinds of crystallisation accompanied by exotherms during rewarming were identified by X-ray diffraction as ice and ice/NaCl x 2H(2)O, or ice/KCl eutectic component.

Preference for internucleotide linkages as a function of the number of constituents in a mixture

NASA Technical Reports Server (NTRS)

Kanavarioti, A.

1998-01-01

Phosphoimidazolide-activated ribomononucleotides (*pN; see Scheme I) are useful substrates for the nonenzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous solutions of *pN (0.01 M) typically yield only small amounts of dimers and traces of oligomers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the percentage yield of the condensation products increases and the yield of the hydrolysis product correspondingly decreases with *pN concentration (Kanavarioti 1997). Here we report product distributions in reactions with one, two, or three reactive components at the same total nucleotide concentration. *pN used as substrates were the nucleoside 5'-phosphate 2-methylimidazolides, 2-MeImpN, with N = cytidine (C), uridine (U), or guanosine (G). Reactions were conducted as self-condensations, i. e., one nucleotide only, with two components in the three binary U,C, U,G, and C,G mixtures, and with three components in the ternary U,C, G mixture. The products are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3', 5'-linked dimers, cyclic dimers, and a small percentage of longer oligomers. The surprising finding was that, under identical conditions, including the same total monomer concentration, the product distribution differs substantially from one reaction to another, most likely due to changing intermolecular interactions depending on the constituents. Even more unexpected was the observed trend according to which reactions of the U,C,G mixture produce the highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the approximately two-fold increase in the percentage yield of internucleotide-linked dimers is not due to a concentration effect or a catalyst, but to the increased complexity of the system from a single to two and three components. These observations, perhaps, provide an example of how increased complexity in relatively simple chemical systems leads to organization of the material and consequently to chemical evolution. A possible link between prebiotic chemistry and the postulated RNA world is discussed.

Exploring Solute-Solvent Interactions of -Amino Acids in Aqueous [] Arrangements by Volumetric, Viscometric, Refractometric, and Acoustic Approach

NASA Astrophysics Data System (ADS)

Roy, Mahendra Nath; Roy, Milan Chandra; Basak, Saptarshi

2014-05-01

Qualitative and quantitative analysis of molecular interaction prevailing in glycine, l-alanine, l-valine, and aqueous solution of ionic liquid (IL) [1-ethylpyridinium tetrafluoroborate (] have been investigated by thermophysical properties. The apparent molar volume (), viscosity -coefficient, molal refraction (), and adiabatic compressibility ( of glycine, l-alanine, and l-valine have been studied in 0.001 mol , 0.003 mol , and 0.005 mol aqueous 1-ethylpyridinium tetrafluoroborate [] solutions at 298.15 K from the values of densities , viscosities (), refractive index (, and speed of sound , respectively. The extent of interaction, i.e., the solute-solvent interaction is expressed in terms of the limiting apparent molar volume (, viscosity -coefficient, and limiting apparent molar adiabatic compressibility (. The limiting apparent molar volumes (, experimental slopes ( derived from the Masson equation, and viscosity - and -coefficients using the Jones-Dole equation have been interpreted in terms of ion-ion and ion-solvent interactions, respectively. Molal refractions ( have been calculated with the help of the Lorentz-Lorenz equation. The role of the solvent (aqueous IL solution) and the contribution of solute-solute and solute-solvent interactions to the solution complexes have also been analyzed through the derived properties.

Selected specific rates of reactions of transients from water in aqueous solution. Hydrated electron, supplemental data. [Reactions with transients from water, with inorganic solutes, and with solutes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, A.B.

1975-06-01

A compilation of rates of reactions of hydrated electrons with other transients and with organic and inorganic solutes in aqueous solution appeared in NSRDS-NBS 43, and covered the literature up to early 1971. This supplement includes additional rates which have been published through July 1973.

Method for loading resin beds

DOEpatents

Notz, Karl J.; Rainey, Robert H.; Greene, Charles W.; Shockley, William E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H.sup.+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145.degree.-200.degree. C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145.degree. C with a second aqueous component to provide a gaseous phase containing HNO.sub.3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate.

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

NASA Technical Reports Server (NTRS)

T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor); Huang, Cunping (Inventor)

2014-01-01

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

SEPARATION OF HAFNIUM FROM ZIRCONIUM

DOEpatents

Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

1960-05-31

The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

RECOVERY OF PROTACTINIUM

DOEpatents

Kraus, K.A.; Moore, G.E.

1959-02-01

A process is presented for the separation of protactinium values from an aqueous solution containing Pa and Th values comprising establishing in the solution a HCl concentration of from 4 to 11 molar, contacting the resulting solution with an anion-exchange adsorbent, such as a polystyrene divinyl benzene polymer with quatenary amines as the active exchange group, to effect the adsorption of Pa values upon the adsorbent while leaving Th values in the solution, and then washlng the separated Pa bearing adsorbent with an aqueous solution of HCl of less than 4M to exclusively elute Pa values from the adsorbent. If hexavalent U values are contained in the original solution thcy are adsorbed on the resin together with Pa. A separation is offected chromatographically by percolating the resin with aqueous HCl.

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)

Binary classification of aqueous solubility using support vector machines with reduction and recombination feature selection.

PubMed

Cheng, Tiejun; Li, Qingliang; Wang, Yanli; Bryant, Stephen H

2011-02-28

Aqueous solubility is recognized as a critical parameter in both the early- and late-stage drug discovery. Therefore, in silico modeling of solubility has attracted extensive interests in recent years. Most previous studies have been limited in using relatively small data sets with limited diversity, which in turn limits the predictability of derived models. In this work, we present a support vector machines model for the binary classification of solubility by taking advantage of the largest known public data set that contains over 46 000 compounds with experimental solubility. Our model was optimized in combination with a reduction and recombination feature selection strategy. The best model demonstrated robust performance in both cross-validation and prediction of two independent test sets, indicating it could be a practical tool to select soluble compounds for screening, purchasing, and synthesizing. Moreover, our work may be used for comparative evaluation of solubility classification studies ascribe to the use of completely public resources.

Can an ammonium-based room temperature ionic liquid counteract the urea-induced denaturation of a small peptide?

PubMed

Ghosh, Soumadwip; Dey, Souvik; Patel, Mahendra; Chakrabarti, Rajarshi

2017-03-15

The folding/unfolding equilibrium of proteins in aqueous medium can be altered by adding small organic molecules generally termed as co-solvents. Denaturants such as urea are instrumental in the unfolding of proteins while protecting osmolytes favour the folded ensemble. Recently, room temperature ionic liquids (ILs) have been shown to counteract the deleterious effect of urea on proteins. In this paper, using atomistic molecular dynamics we show that a ternary mixture containing a particular ammonium-based IL, triethylammonium acetate (TEAA), and urea (in 1 : 5 molar ratio) helps a small 15-residue S-peptide analogue regain most of its native structure, whereas a binary aqueous mixture containing a large amount of urea alone completely distorts it. Our simulations show that the denaturant urea directly interacts with the peptide backbone in the binary mixture while for the ternary mixture both urea as well as the IL are preferentially excluded from the peptide surface.

Thermodynamic studies of aqueous and CCl4 solutions of 15-crown-5 at 298.15 K: an application of McMillan-Mayer and Kirkwood-Buff theories of solutions.

PubMed

Dagade, Dilip H; Shetake, Poonam K; Patil, Kesharsingh J

2007-07-05

The density and osmotic coefficient data for solutions of 15-crown-5 (15C5) in water and in CCl4 solvent systems at 298.15 K have been reported using techniques of densitometry and vapor pressure osmometry in the concentration range of 0.01-2 mol kg-1. The data are used to obtain apparent molar and partial molar volumes, activity coefficients of the components as a function of 15C5 concentration. Using the literature heat of dilution data for aqueous system, it has become possible to calculate entropy of mixing (DeltaS(mix)), excess entropy of solution (DeltaS(E)), and partial molar entropies of the components at different concentrations. The results of all these are compared to those obtained for aqueous 18-crown-6 solutions reported earlier. It has been observed that the partial molar volume of 15C5 goes through a minimum and that of water goes through a maximum at approximately 1.2 mol kg(-1) in aqueous solutions whereas the opposite is true in CCl4 medium but at approximately 0.5 mol kg(-1). The osmotic and activity coefficients of 15C5 and excess free energy change for solution exhibit distinct differences in the two solvent systems studied. These results have been explained in terms of hydrophobic hydration and interactions in aqueous solution while weak solvophobic association of 15C5 molecules in CCl4 solutions is proposed. The data are further subjected to analysis by applying McMillan-Mayer and Kirkwood-Buff theories of solutions. The analysis shows that osmotic second virial coefficient value for 15C5 is marginally less than that of 18C6 indicating that reduction in ring flexibility does not affect the energetics of the interactions much in aqueous solution while the same gets influenced much in nonpolar solvent CCl4.

Disproportionation of a crystalline citrate salt of a developmental pharmaceutical compound: characterization of the kinetics using pH monitoring and online Raman spectroscopy plus quantitation of the crystalline free base form in binary physical mixtures using FT-Raman, XRPD and DSC.

PubMed

Skrdla, Peter J; Zhang, Dan

2014-03-01

The crystalline citrate salt (CS) of a developmental pharmaceutical compound, MK-Q, was investigated in this work from two different, but related, perspectives. In the first part of the paper, the apparent disproportionation kinetics were surveyed using two different slurry systems, one containing water and the other a pH 6.9 phosphate buffer, using time-dependent measurements of the solution pH or by acquiring online Raman spectra of the solids. While the CS is generally stable when stored as a solid under ambient conditions of temperature and humidity, its low pHmax (<3) facilitates rapid disproportionation in aqueous solution, particularly at higher pH values. The rate of disappearance of the CS was found to obey first-order (Noyes-Whitney/dissolution rate-limited) kinetics, however, the formation of the crystalline product form in the slurry system was observed to exhibit kinetics consistent with a heterogeneous nucleation-and-growth mechanism. In the second part of this paper, more sensitive offline measurements made using XRPD, DSC and FT-Raman spectroscopy were applied to the characterization of binary physical mixtures of the CS and free base (FB) crystalline forms of MK-Q to obtain a calibration curve for each technique. It was found that all calibration plots exhibited good linearity of response, with the limit of detection (LOD) for each technique estimated to be ≤7 wt% FB. While additional calibration curves would need to be constructed to allow for accurate quantitation in various slurry systems, the general feasibility of these techniques is demonstrated for detecting low levels of CS disproportionation. Copyright © 2013 Elsevier B.V. All rights reserved.

Stiffness-Independent Highly Efficient On-Chip Extraction of Cell-Laden Hydrogel Microcapsules from Oil Emulsion into Aqueous Solution by Dielectrophoresis.

PubMed

Huang, Haishui; Sun, Mingrui; Heisler-Taylor, Tyler; Kiourti, Asimina; Volakis, John; Lafyatis, Gregory; He, Xiaoming

2015-10-28

A dielectrophoresis (DEP)-based method achieves highly efficient on-chip extraction of cell-laden microcapsules of any stiffness from oil into aqueous solution. The hydrogel microcapsules can be extracted into the aqueous solution by DEP and interfacial tension forces with no trapped oil, while the encapsulated cells are free from electrical damage due to the Faraday cage effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SOLVENT EXTRACTION PROCESS FOR PLUTONIUM

DOEpatents

Seaborg, G.T.

1959-04-14

The separation of plutonium from aqueous inorganic acid solutions by the use of a water immiscible organic extractant liquid is described. The plutonium must be in the oxidized state, and the solvents covered by the patent include nitromethane, nitroethane, nitropropane, and nitrobenzene. The use of a salting out agents such as ammonium nitrate in the case of an aqueous nitric acid solution is advantageous. After contacting the aqueous solution with the organic extractant, the resulting extract and raffinate phases are separated. The plutonium may be recovered by any suitable method.

Aqueous solution-chemical derived Nisbnd Al2O3 solar selective absorbing coatings. 2. Wetting agents and spreading of aqueous solutions on aluminum substrate

NASA Astrophysics Data System (ADS)

Li, Zhenxiang; Zhao, Jianxi

2013-03-01

Wettability of aluminum substrate by the aqueous solutions containing ethoxylated alcohol nonionic surfactants C12En- or Triton X-series was studied using dynamic contact angle measurements. The efficiency of wetting was found to strongly depend on the length of polyoxyethylene (POE) chain of C12En- or Triton X surfactants. For C12E4 that has a very short POE chain, it hardly made the aqueous solution spreading over aluminum. The others with a long POE chain were indeed very efficient in promoting the solution spreading. Moreover, all the spreading process could be completed within 10 s. The single-layer Nisbnd Al2O3 coatings were fabricated from the precursor solutions containing C12En- or Triton X surfactants and the reflectance spectra were measured by a UV/vis spectrophotometer equipped with an integrating sphere. The results indicated that the precursor solution with a long POE chain surfactant as wetting agent favored to fabricate a uniform film on the aluminum substrate and therefore to get a high solar absorptance.

Reaction behaviors of decomposition of monocrotophos in aqueous solution by UV and UV/O processes.

PubMed

Ku, Y; Wang, W; Shen, Y S

2000-02-01

The decomposition of monocrotophos (cis-3-dimethoxyphosphinyloxy-N-methyl-crotonamide) in aqueous solution by UV and UV/O(3) processes was studied. The experiments were carried out under various solution pH values to investigate the decomposition efficiencies of the reactant and organic intermediates in order to determine the completeness of decomposition. The photolytic decomposition rate of monocrotophos was increased with increasing solution pH because the solution pH affects the distribution and light absorbance of monocrotophos species. The combination of O(3) with UV light apparently promoted the decomposition and mineralization of monocrotophos in aqueous solution. For the UV/O(3) process, the breakage of the >C=C< bond of monocrotophos by ozone molecules was found to occur first, followed by mineralization by hydroxyl radicals to generate CO(3)(2-), PO4(3-), and NO(3)(-) anions in sequence. The quasi-global kinetics based on a simplified consecutive-parallel reaction scheme was developed to describe the temporal behavior of monocrotophos decomposition in aqueous solution by the UV/O(3) process.

Process for the extraction of technetium from uranium

DOEpatents

Gong, Cynthia-May S.; Poineau, Frederic; Czerwinski, Kenneth R.

2010-12-21

A spent fuel reprocessing method contacts an aqueous solution containing Technetium(V) and uranyl with an acidic solution comprising hydroxylamine hydrochloride or acetohydroxamic acid to reduce Tc(V) to Tc(II, and then extracts the uranyl with an organic phase, leaving technetium(II) in aqueous solution.

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)

Method for separating water soluble organics from a process stream by aqueous biphasic extraction

DOEpatents

Chaiko, David J.; Mego, William A.

1999-01-01

A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

Structural transformations, composition anomalies and a dramatic collapse of linear polymer chains in dilute ethanol-water mixtures.

PubMed

Banerjee, Saikat; Ghosh, Rikhia; Bagchi, Biman

2012-03-29

Water-ethanol mixtures exhibit many interesting anomalies, such as negative excess partial molar volume of ethanol, excess sound absorption coefficient at low concentrations, and positive deviation from Raoult's law for vapor pressure, to mention a few. These anomalies have been attributed to different, often contradictory origins, but a quantitative understanding is still lacking. We show by computer simulation and theoretical analyses that these anomalies arise from the sudden emergence of a bicontinuous phase that occurs at a relatively low ethanol concentration of x(eth) ≈ 0.06-0.10 (that amounts to a volume fraction of 0.17-0.26, which is a significant range!). The bicontinuous phase is formed by aggregation of ethanol molecules, resulting in a weak phase transition whose nature is elucidated. We find that the microheterogeneous structure of the mixture gives rise to a pronounced nonmonotonic composition dependence of local compressibility and nonmonotonic dependence in the peak value of the radial distribution function of ethyl groups. A multidimensional free energy surface of pair association is shown to provide a molecular explanation of the known negative excess partial volume of ethanol in terms of parallel orientation and hence better packing of the ethyl groups in the mixture due to hydrophobic interactions. The energy distribution of the ethanol molecules indicates additional energy decay channels that explain the excess sound attenuation coefficient in aqueous alcohol mixtures. We studied the dependence of the solvation of a linear polymer chain on the composition of the water-ethanol solvent. We find that there is a sudden collapse of the polymer at x(eth) ≈ 0.05-a phenomenon which we attribute to the formation of the microheterogeneous structures in the binary mixture at low ethanol concentrations. Together with recent single molecule pulling experiments, these results provide new insight into the behavior of polymer chain and foreign solutes, such as enzymes, in aqueous binary mixtures.

Theory of Metastable State Relaxation for Non-Critical Binary Systems with Non-Conserved Order Parameter

NASA Technical Reports Server (NTRS)

Izmailov, Alexander; Myerson, Allan S.

1993-01-01

A new mathematical ansatz for a solution of the time-dependent Ginzburg-Landau non-linear partial differential equation is developed for non-critical systems such as non-critical binary solutions (solute + solvent) described by the non-conserved scalar order parameter. It is demonstrated that in such systems metastability initiates heterogeneous solute redistribution which results in formation of the non-equilibrium singly-periodic spatial solute structure. It is found how the time-dependent period of this structure evolves in time. In addition, the critical radius r(sub c) for solute embryo of the new solute rich phase together with the metastable state lifetime t(sub c) are determined analytically and analyzed.

Use of solid phase extraction (SPE) to evaluate in vitro skin permeation of aescin.

PubMed

Montenegro, L; Carbone, C; Giannone, I; Puglisi, G

2007-05-01

The aim of this work was to evaluate the feasibility of assessing aescin in vitro permeation through human skin by determining the amount of aescin permeated using conventional HPLC procedures after extraction of skin permeation samples by means of solid phase extraction (SPE). Aescin in vitro skin permeation was assessed from aqueous solutions and gels using both Franz-type diffusion cells and flow-through diffusion cells. The SPE method used was highly accurate (mean accuracy 99.66%), highly reproducible (intra-day and inter-day variations lower than 2.3% and 2.2%, respectively) and aescin recovery from normal saline was greater than 99%. The use of Franz-type diffusion cells did not allow us to determine aescin flux values through excised human skin, therefore aescin skin permeation parameters could be calculated only using flow-through diffusion cells. Plotting the cumulative amount of aescin permeated as a function of time, linear relationships were obtained from both aqueous solution and gel using flow-through diffusion cells. Aescin flux values through excised human skin from aqueous gel were significantly lower than those observed from aqueous solution (p < 0.05). Calculating aescin percutaneous absorption parameters we evidenced that aescin partition coefficient was lower from the aqueous gel with respect to the aqueous solution. Therefore, the SPE method used in this study was suitable to determine aescin in vitro skin permeation parameters from aqueous solutions and gels using a conventional HPLC method for the analysis of the skin permeation samples.

21 CFR 163.112 - Breakfast cocoa.

Code of Federal Regulations, 2012 CFR

2012-04-01

... oxide, used as such, or in aqueous solution; (2) Neutralizing agents. Phosphoric acid, citric acid and L-tartaric acid, used as such, or in aqueous solution; (3) Spices, natural and artificial flavorings, and...

21 CFR 163.112 - Breakfast cocoa.

Code of Federal Regulations, 2014 CFR

2014-04-01

... oxide, used as such, or in aqueous solution; (2) Neutralizing agents. Phosphoric acid, citric acid and L-tartaric acid, used as such, or in aqueous solution; (3) Spices, natural and artificial flavorings, and...

21 CFR 163.112 - Breakfast cocoa.

Code of Federal Regulations, 2013 CFR

2013-04-01

... oxide, used as such, or in aqueous solution; (2) Neutralizing agents. Phosphoric acid, citric acid and L-tartaric acid, used as such, or in aqueous solution; (3) Spices, natural and artificial flavorings, and...

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.

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.

Poynting-Flux-Driven Bubbles and Shocks Around Merging Neutron Star Binaries

NASA Astrophysics Data System (ADS)

Medvedev, M. V.; Loeb, A.

2013-04-01

Merging binaries of compact relativistic objects are thought to be progenitors of short gamma-ray bursts. Because of the strong magnetic field of one or both binary members and high orbital frequencies, these binaries are strong sources of energy in the form of Poynting flux. The steady injection of energy by the binary forms a bubble filled with matter with the relativistic equation of state, which pushes on the surrounding plasma and can drive a shock wave in it. Unlike the Sedov-von Neumann-Taylor blast wave solution for a point-like explosion, the shock wave here is continuously driven by the ever-increasing pressure inside the bubble. We calculate from the first principles the dynamics and evolution of the bubble and the shock surrounding it, demonstrate that it exhibits finite time singularity and find the corresponding analytical solution. We predict that such binaries can be observed as radio sources a few hours before and after the merger.

Crystal growth in fused solvent systems

NASA Technical Reports Server (NTRS)

Ulrich, D. R.; Noone, M. J.; Spear, K. E.; White, W. B.; Henry, E. C.

1973-01-01

Research is reported on the growth of electronic ceramic single crystals from solution for the future growth of crystals in a microgravity environment. Work included growth from fused or glass solvents and aqueous solutions. Topics discussed include: crystal identification and selection; aqueous solution growth of triglycine sulphate (TGS); and characterization of TGS.

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 ...

Rheological characterization of solutions and thin films made from amylose-hexadecylammonium chloride inclusion complexes and polyvinyl alcohol

USDA-ARS?s Scientific Manuscript database

The rheological properties of aqueous solutions and films made from blends of polyvinyl alcohol (PVOH) and amylose-hexadecylammonium chloride inclusion complexes (Hex-Am) were investigated to better understand the polymer interactions and processing parameters. Aqueous solutions of Hex-Am displayed ...

Study on Latent Heat of Fusion of Ice in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Kumano, Hiroyuki; Asaoka, Tatsunori; Saito, Akio; Okawa, Seiji

In this study, latent heat of fusion of ice in aqueous solutions was measured to understand latent heat of fusion of ice slurries. Propylene glycol, ethylene glycol, ethanol, NaCl and NaNO3 solutions were examined as the aqueous solutions. In the measurement, pure ice was put into the solution, and the temperature variation of the solution due to the melting of the ice was measured. Then, the effective latent heat of fusion was calculated from energy balance equation. When ice melts in solution, the concentration of the solution varies due to the melting of the ice, and dilution heat must be considered. Therefore, the latent heat of fusion of ice in aqueous solutions was predicted by considering the effects of dilution and freezing-point depression. The latent heat of fusion was also measured by differential scanning calorimetry(DSC) to compare the results obtained from the experiments with that obtained by DSC. As the result, it was found that the effective latent heat of fusion of ice decreased with the increase of the concentration of solution, and the effective latent heat of fusion was calculated from latent heat of fusion of pure ice and the effects of freezing-point depression and the dilution heat.

Direct Detection of Aqueous CO2 by Infrared Waveguide Spectroscopy with an Amorphous Fluoropolymer Coating Rod.

PubMed

Hotta, Hiroki; Miki, Yuko; Kawaguchi, Yukiko; Tsunoda, Kin-Ichi; Nakaoka, Atsuko; Ko, Sho; Kimoto, Takashi

2017-01-01

Infrared waveguide spectroscopy using a sapphire rod coated with an amorphous fluoropolymer (Cytop, Asahi Glass Co., ltd, Japan) has been developed in order to directly observe CO 2 in aqueous solutions. Since the amorphous fluoropolymer has a relatively high gas-permeability and hydrophobic feature, the aqueous CO 2 transmits into the amorphous fluoropolymer coating film, but water cannot penetrate into the film. Good linearity of calibration curves for CO 2 in the gas and the aqueous solution were obtained.

POLONIUM SEPARATION PROCESS

DOEpatents

Karraker, D.G.

1959-07-14

A liquid-liquid extraction process is presented for the recovery of polonium from lead and bismuth. According to the invention an acidic aqueous chloride phase containing the polonium, lead, and bismuth values is contacted with a tributyl phosphate ether phase. The polonium preferentially enters the organic phase which is then separated and washed with an aqueous hydrochloric solution to remove any lead or bismuth which may also have been extracted. The now highly purified polonium in the organic phase may be transferred to an aqueous solution by extraction with aqueous nitric acid.

Microbial solubilization of phosphate

DOEpatents

Rogers, R.D.; Wolfram, J.H.

1993-10-26

A process is provided for solubilizing phosphate from phosphate containing ore by treatment with microorganisms which comprises forming an aqueous mixture of phosphate ore, microorganisms operable for solubilizing phosphate from the phosphate ore and maintaining the aqueous mixture for a period of time and under conditions operable to effect the microbial solubilization process. An aqueous solution containing soluble phosphorus can be separated from the reacted mixture by precipitation, solvent extraction, selective membrane, exchange resin or gravity methods to recover phosphate from the aqueous solution. 6 figures.

Microbial solubilization of phosphate

DOEpatents

Rogers, Robert D.; Wolfram, James H.

1993-01-01

A process is provided for solubilizing phosphate from phosphate containing ore by treatment with microorganisms which comprises forming an aqueous mixture of phosphate ore, microorganisms operable for solubilizing phosphate from the phosphate ore and maintaining the aqueous mixture for a period of time and under conditions operable to effect the microbial solubilization process. An aqueous solution containing soluble phosphorous can be separated from the reacted mixture by precipitation, solvent extraction, selective membrane, exchange resin or gravity methods to recover phosphate from the aqueous solution.

Relation between the adsorbed quantity and the immersion enthalpy in catechol aqueous solutions on activated carbons.

PubMed

Moreno-Piraján, Juan Carlos; Blanco, Diego; Giraldo, Liliana

2012-01-01

An activated carbon, Carbochem(TM)-PS230, was modified by chemical and thermal treatment in flow of H(2), in order to evaluate the influence of the activated carbon chemical characteristics in the adsorption of the catechol. The catechol adsorption in aqueous solution was studied along with the effect of the pH solution in the adsorption process of modified activated carbons and the variation of immersion enthalpy of activated carbons in the aqueous solutions of catechol. The interaction solid-solution is characterized by adsorption isotherms analysis, at 298 K and pH 7, 9 and 11 in order to evaluate the adsorption value above and below that of the catechol pK(a). The adsorption capacity of carbons increases when the solution pH decreases. The retained amount increases slightly in the reduced carbon to maximum adsorption pH and diminishes in the oxidized carbon. Similar conclusions are obtained from the immersion enthalpies, whose values increase with the solute quantity retained. In granular activated carbon (CAG), the immersion enthalpies obtained are between 21.5 and 45.7 J·g(-1) for catechol aqueous solutions in a range of 20 at 1500 mg·L(-1).

Relation Between the Adsorbed Quantity and the Immersion Enthalpy in Catechol Aqueous Solutions on Activated Carbons

PubMed Central

Moreno-Piraján, Juan Carlos; Blanco, Diego; Giraldo, Liliana

2012-01-01

An activated carbon, CarbochemTM—PS230, was modified by chemical and thermal treatment in flow of H2, in order to evaluate the influence of the activated carbon chemical characteristics in the adsorption of the catechol. The catechol adsorption in aqueous solution was studied along with the effect of the pH solution in the adsorption process of modified activated carbons and the variation of immersion enthalpy of activated carbons in the aqueous solutions of catechol. The interaction solid-solution is characterized by adsorption isotherms analysis, at 298 K and pH 7, 9 and 11 in order to evaluate the adsorption value above and below that of the catechol pKa. The adsorption capacity of carbons increases when the solution pH decreases. The retained amount increases slightly in the reduced carbon to maximum adsorption pH and diminishes in the oxidized carbon. Similar conclusions are obtained from the immersion enthalpies, whose values increase with the solute quantity retained. In granular activated carbon (CAG), the immersion enthalpies obtained are between 21.5 and 45.7 J·g−1 for catechol aqueous solutions in a range of 20 at 1500 mg·L−1. PMID:22312237

75 FR 30844 - General Mills, Inc.; Withdrawal of Food Additive Petition

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-02

... for the reduction of pathogens and other microorganisms in aqueous sugar solutions and potable water... reduction of pathogens and other microorganisms in aqueous sugar solutions and potable water intended for...

Structural characterization of metal complexes in aqueous solutions: a XAS study of stannous fluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alsina, Marco A.; Gaillard, Jean-François

The identity and structure of tin(ii)-fluoride complexes formed in aqueous solutions are determined by combining X-ray absorption spectroscopy, thermodynamic modeling and quantum mechanical calculations.

Sorption of ochratoxin A from aqueous solutions using β-cyclodextrin-polyurethane polymer.

PubMed

Appell, Michael; Jackson, Michael A

2012-02-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1-10 μg·L(-1). These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples.

Superlubricity of a Mixed Aqueous Solution

NASA Astrophysics Data System (ADS)

Ma, Zhi-Zuo; Zhang, Chen-Hui; Luo, Jian-Bin; Lu, Xin-Chun; Wen, Shi-Zhu

2011-05-01

A super-low friction coefficient of 0.0028 is measured under a pressure of 300 MPa when the friction pair (the silicon nitride ball sliding on the silicate glass) is lubricated by the mixed aqueous solution of glycerol and boric acid. The morphorlogies of the hydroxylated glass plate are observed by an atomic force microscope (AFM) in deionized water, glycerol, boric acid and their mixed aqueous solution. Bonding peaks of the retained liquids adhered on the surface of the sliding track are detected by an infrared spectrum apparatus and a Raman spectrum apparatus. The mechanism of the superlubricity of the glycerol and boric acid mixed aqueous solution is discussed. It is deduced that the formation of the lubricant film has enough strength to support higher loads, the hydration effect offering the super lower shear resistance. Key words: superlubricity, water based lubricant, ultra-low friction

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.

Methods for separating medical isotopes using ionic liquids

DOEpatents

Luo, Huimin; Boll, Rose Ann; Bell, Jason Richard; Dai, Sheng

2014-10-21

A method for extracting a radioisotope from an aqueous solution, the method comprising: a) intimately mixing a non-chelating ionic liquid with the aqueous solution to transfer at least a portion of said radioisotope to said non-chelating ionic liquid; and b) separating the non-chelating ionic liquid from the aqueous solution. In preferred embodiments, the method achieves an extraction efficiency of at least 80%, or a separation factor of at least 1.times.10.sup.4 when more than one radioisotope is included in the aqueous solution. In particular embodiments, the method is applied to the separation of medical isotopes pairs, such as Th from Ac (Th-229/Ac-225, Ac-227/Th-227), or Ra from Ac (Ac-225 and Ra-225, Ac-227 and Ra-223), or Ra from Th (Th-227 and Ra-223, Th-229 and Ra-225).

Homogeneous Liquid–Liquid Extraction of Rare Earths with the Betaine—Betainium Bis(trifluoromethylsulfonyl)imide Ionic Liquid System

PubMed Central

Hoogerstraete, Tom Vander; Onghena, Bieke; Binnemans, Koen

2013-01-01

Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature. PMID:24169434

Organic component vapor pressures and hygroscopicities of aqueous aerosol measured by optical tweezers.

PubMed

Cai, Chen; Stewart, David J; Reid, Jonathan P; Zhang, Yun-hong; Ohm, Peter; Dutcher, Cari S; Clegg, Simon L

2015-01-29

Measurements of the hygroscopic response of aerosol and the particle-to-gas partitioning of semivolatile organic compounds are crucial for providing more accurate descriptions of the compositional and size distributions of atmospheric aerosol. Concurrent measurements of particle size and composition (inferred from refractive index) are reported here using optical tweezers to isolate and probe individual aerosol droplets over extended timeframes. The measurements are shown to allow accurate retrievals of component vapor pressures and hygroscopic response through examining correlated variations in size and composition for binary droplets containing water and a single organic component. Measurements are reported for a homologous series of dicarboxylic acids, maleic acid, citric acid, glycerol, or 1,2,6-hexanetriol. An assessment of the inherent uncertainties in such measurements when measuring only particle size is provided to confirm the value of such a correlational approach. We also show that the method of molar refraction provides an accurate characterization of the compositional dependence of the refractive index of the solutions. In this method, the density of the pure liquid solute is the largest uncertainty and must be either known or inferred from subsaturated measurements with an error of <±2.5% to discriminate between different thermodynamic treatments.

The influence of the preparation methods on the inclusion of model drugs in a beta-cyclodextrin cavity.

PubMed

Salústio, P J; Feio, G; Figueirinhas, J L; Pinto, J F; Cabral Marques, H M

2009-02-01

The work aims to prove the complexation of two model drugs (ibuprofen, IB and indomethacin, IN) by beta-cyclodextrin (betaCD), and the effect of water in such a process, and makes a comparison of their complexation yields. Two methods were considered: kneading of a binary mixture of the drug, betaCD, and inclusion of either IB or IN in aqueous solutions of betaCD. In the latter method water was removed by air stream, spray-drying and freeze-drying. To prove the formation of complexes in final products, optical microscopy, UV spectroscopy, IR spectroscopy, DSC, X-ray and NMR were considered. Each powder was added to an acidic solution (pH=2) to quantify the concentration of the drug inside betaCD cavity. Other media (pH=5 and 7) were used to prove the existence of drug not complexed in each powder, as the drugs solubility increases with the pH. It was observed that complexation occurred in all powders, and that the fraction of drug inside the betaCD did not depend neither on the method of complexation nor on the processes of drying considered.

Specific and Non-Specific Protein Association in Solution: Computation of Solvent Effects and Prediction of First-Encounter Modes for Efficient Configurational Bias Monte Carlo Simulations

PubMed Central

Cardone, Antonio; Pant, Harish; Hassan, Sergio A.

2013-01-01

Weak and ultra-weak protein-protein association play a role in molecular recognition, and can drive spontaneous self-assembly and aggregation. Such interactions are difficult to detect experimentally, and are a challenge to the force field and sampling technique. A method is proposed to identify low-population protein-protein binding modes in aqueous solution. The method is designed to identify preferential first-encounter complexes from which the final complex(es) at equilibrium evolves. A continuum model is used to represent the effects of the solvent, which accounts for short- and long-range effects of water exclusion and for liquid-structure forces at protein/liquid interfaces. These effects control the behavior of proteins in close proximity and are optimized based on binding enthalpy data and simulations. An algorithm is described to construct a biasing function for self-adaptive configurational-bias Monte Carlo of a set of interacting proteins. The function allows mixing large and local changes in the spatial distribution of proteins, thereby enhancing sampling of relevant microstates. The method is applied to three binary systems. Generalization to multiprotein complexes is discussed. PMID:24044772

Adsorption of heavy metals from aqueous solution by UV-mutant Bacillus subtilis loaded on biochars derived from different stock materials.

PubMed

Wang, Ting; Sun, Hongwen; Ren, Xinhao; Li, Bing; Mao, Hongjun

2018-02-01

Two kinds of biochars, one derived from corn straw (CBC) and one from pig manure (PBC), were used as the carriers of a bacterium (B38) to adsorb heavy metals in solution. CBC exhibited high affinity to Hg(II), while PBC showed large adsorption capacity of Pb(II). After loading with B38, the sorption capacity of the co-sorbents were enhanced for Pb(II), but weakened for Hg(II). In a binary system, the overall adsorption capacity to Hg-Pb (CBC+B38, 136.7mg/g; PBC+B38, 181.3mg/g) on co-sorbents was equal to the sum of the single-component values for Hg(II) and Pb(II). Electrostatic interactions and precipitation are the major mechanisms in the adsorption of Hg(II). In contrast, cation-π interactions and precipitation were involved in the sorption process of Pb(II). Moreover, the sorption sites of Hg(II) and Pb(II) partially overlapped on the biochar surface, but were different on co-sorbents. Hence, the co-sorbents have an advantage over the biochar alone in the removal of heavy metal mixtures. Copyright © 2017 Elsevier Inc. All rights reserved.

New Approach to Remove Metals from Chromated Copper Arsenate (CCA)-Treated Wood

Treesearch

Todd F. Shupe; Chung Y. Hse; Hui Pan

2012-01-01

Recovery of metals from chromated copper arsenate (CCA)-treated southern pine wood particles was investigated using binary acid solutions consisting of acetic, oxalic, and phosphoric acids in a microwave reactor. Formation of an insoluble copper oxalate complex in the binary solution containing oxalic acid was the major factor for low copper removal. Furthermore, the...

Densities of L-Glutamic Acid HCl Drug in Aqueous NaCl and KCl Solutions at Different Temperatures

NASA Astrophysics Data System (ADS)

Ryshetti, Suresh; Raghuram, Noothi; Rani, Emmadi Jayanthi; Tangeda, Savitha Jyostna

2016-04-01

Densities (ρ ) of (0.01 to 0.07) {mol}{\\cdot } {kg}^{-1} L-Glutamic acid HCl (L-HCl) drug in water, and in aqueous NaCl and KCl (0.5 and 1.0) {mol}{\\cdot } {kg}^{-1} solutions have been reported as a function of temperature at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure. The accurate density (ρ ) values are used to estimate the various parameters such as the apparent molar volume (V_{2,{\\upphi }}), the partial molar volume (V2^{∞}), the isobaric thermal expansion coefficient (α 2), the partial molar expansion (E2^{∞}), and Hepler's constant (partial 2V2^{∞}/partial T2)P. The Cosphere overlap model is used to understand the solute-solvent interactions in a ternary mixture (L-HCl drug + NaCl or KCl + water). Hepler's constant (partial 2V2^{∞}/partial T2)_P is utilized to interpret the structure-making or -breaking ability of L-HCl drug in aqueous NaCl and KCl solutions, and the results are inferred that L-HCl drug acts as a structure maker, i.e., kosmotrope in aqueous NaCl solutions and performs as a structure breaker, i.e., chaotrope in aqueous KCl solutions.

Heat capacity of alkanolamine aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiu, L.F.; Li, M.H.

1999-12-01

Heat capacities of monoethanoloamine, diglycolamine, diethanolamine, di-w propanolamine, triethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-l-propanol, and 2-piperidineethanol aqueous solutions were measured from 30 to 80 C with a differential scanning calorimeter (DSC). The mole fractions of alkanolamines studied are 0.2, 0.4, 0.6, and 0.8. Heat capacities of N-methyldiethanolamine aqueous solutions have been measured to verify the validity of C{sub p} measurements for alkanolamine aqueous solutions. The estimated uncertainty of the measured heat capacities is {plus{underscore}minus}3%, including the effect of up to 5% impurities in a substance. An excess molar heat capacity expression using the Redlich-Kister equation for the composition dependence is used to representmore » the measured C{sub p} of alkanolamine aqueous solutions. For a total of 374 data points, the calculation results for eight alkanolamine solutions give the overall average absolute deviations of 11.9% and 0.29% for the excess molar heat capacity and the heat capacity, respectively. The heat capacities presented in this study are, in general, of sufficient accuracy for most engineering-design calculations. Solutions of alkanolamines are industrially important mixtures used in the natural gas industry, oil refineries, petroleum chemical plants, and synthetic ammonia plants for the removal of acidic components such as CO{sub 2} and H{sub 2}S from gas streams.« less

METHOD OF APPLYING COPPER COATINGS TO URANIUM

DOEpatents

Gray, A.G.

1959-07-14

A method is presented for protecting metallic uranium, which comprises anodic etching of the uranium in an aqueous phosphoric acid solution containing chloride ions, cleaning the etched uranium in aqueous nitric acid solution, promptly electro-plating the cleaned uranium in a copper electro-plating bath, and then electro-plating thereupon lead, tin, zinc, cadmium, chromium or nickel from an aqueous electro-plating bath.

Pre-formulation and chemical stability studies of penethamate, a benzylpenicillin ester prodrug, in aqueous vehicles.

PubMed

Jain, Rohit; Wu, Zimei; Bork, Olaf; Tucker, Ian G

2012-01-01

Penethamate (PNT) is a diethylaminoethyl ester prodrug of benzylpenicillin used to treat bovine mastitis via the intramuscular route. Because of its instability, PNT products must be reconstituted before administration and the reconstituted injection has a short shelf life (7 days at 2-8°C). The purpose of this paper was to investigate whether the stability of PNT can be improved in order to achieve a chemically stable ready-to-use aqueous-based PNT formulation or at least to extend the shelf life of the reconstituted suspension. A chemical stability study of PNT in aqueous-based solutions as a function of pH, buffer strength, solvent mixtures and temperature, supported by studies of its solubility in mixed solvents, allowed predictions of the shelf life of PNT solution and suspension formulations. PNT degraded in aqueous solutions by several pathways over the pH range 2.0-9.3 with a V-shaped pH-rate profile and a minimum pH of around 4.5. The stability of PNT solutions in mixed solvents was greater than in aqueous solutions. For example, in propylene glycol:citrate buffer (60:40, v/v, pH 4.5), the half-life of PNT was 4.3 days compared with 1.8 days in aqueous buffer. However, solubility of PNT in the mixed solvent was higher than that in aqueous solution and this had an adverse effect on the stability of suspensions. By judicious choosing of pH and mixed solvent, it is possible to achieve a storage life of a PNT suspension of 5.5 months at 5°C, not sufficient for a ready-to-use product but a dramatic improvement in the storage life of the reconstituted product.

Absolute parameters and chemical composition of the binary star OU Gem

NASA Astrophysics Data System (ADS)

Glazunova, L. V.; Mishenina, T. V.; Soubiran, C.; Kovtyukh, V. V.

2014-10-01

The absolute parameters and chemical composition of the BY Dra-type spectroscopic binary OU Gem (HD 45088) were determined on the basis of 10 high-resolution spectra. A new orbital solution of the binary system was determined, the binary ephemerides were specified, and the main physical and atmospheric parameters of the binary components were obtained. The chemical composition of both components was estimated for the first time for the stars of such type.

Desorption of CO{sub 2} from MDEA and activated MDEA solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, G.W.; Zhang, C.F.; Qin, S.J.

1995-03-01

A packed column was used for investigating the desorption rate of CO{sub 2} from aqueous methyldiethanolamine (MDEA) and activated MDEA solutions. Experiments were conducted within the temperature range 30--70 C, the concentration of MDEA was 4.28 kmol/m{sup 3}, and the concentration of piperazine (PZ) was 0.10 kmol/m{sup 3} for aqueous activated MDEA solutions. Experimental data confirmed that the kinetics model of absorption CO{sub 2} into aqueous MDEA and activated MDEA solutions can be applicable to the situations in which desorption occurs, and the desorption rate of model predictions agree well with that of experimental determination.

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.

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

2014-06-01

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

Heat-induced morphological transformation of gold nanodumbbells in ionic surfactant solutions

NASA Astrophysics Data System (ADS)

Wen, Ting-Chun; Lu, Chung-Wen; Hsieh, Wei-Chi; Chang, Sheng-Te; Yang, Ya-Ting; Deng, Jin-Pei

2018-01-01

The thermal stability of gold nanodumbbells (NDs) is studied in aqueous solution of ionic surfactants. It is found in aqueous solution of cetyltrimethylammonium bromide that the blue-shift of longitudinal surface plasmon resonance band of gold NDs occurs at 75 °C and the new gold nanorods (NRs) with shortened aspect ratio are formed at the same time. The aspect ratio of the generated gold NRs gradually decreases and finally approaches ∼1.7 after repeated processing. Similarly, the same results are also obtained in aqueous solution of sodium dodecyl sulfate at room temperature. Mechanism is proposed for the shape transformation of gold NDs.

Laboratory studies of aqueous-phase oxidation of polyols in submicron particles

NASA Astrophysics Data System (ADS)

Daumit, K. E.; Carrasquillo, A. J.; Hunter, J. F.; Kroll, J. H.

2013-12-01

Aqueous-phase oxidation has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. However most aqueous oxidation studies are performed in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation is carried out within submicron particles, allowing for gas-particle partitioning of reactants, intermediates, and products. Using Fenton chemistry as a source of hydroxyl radicals, and a high-resolution aerosol mass spectrometer (AMS) for online characterization of particle composition, we find that aqueous oxidation can be quite rapid. The formation of high concentrations of oxalic acid is observed in the particle phase with some loss of carbon to the gas phase, indicating the formation of volatile products. We see a rapid degradation of condensed-phase oxidation products upon exposure to ultraviolet lights (centered at 350 nm) suggesting that these products may exist as iron(III)-oxalate complexes. Similar results are also seen when oxidation is carried out in bulk solution (with AMS analysis of the atomized solution); however in some cases the mass loss is less than is observed for submicron particles, likely due to differences in partitioning of early-generation products. Such products can partition out of the aqueous phase at the low liquid water contents in the chamber but remain in solution for further aqueous processing in bulk oxidation experiments. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different than those in bulk oxidation, pointing to the need to carry out aqueous oxidation studies under atmospherically relevant partitioning conditions (with liquid water contents mimicking those of cloud droplets or wet aerosol).

Evaporation of Binary Sessile Drops: Infrared and Acoustic Methods To Track Alcohol Concentration at the Interface and on the Surface.

PubMed

Chen, Pin; Toubal, Malika; Carlier, Julien; Harmand, Souad; Nongaillard, Bertrand; Bigerelle, Maxence

2016-09-27

Evaporation of droplets of three pure liquids (water, 1-butanol, and ethanol) and four binary solutions (5 wt % 1-butanol-water-based solution and 5, 25, and 50 wt % ethanol-water-based solutions) deposited on hydrophobic silicon was investigated. A drop shape analyzer was used to measure the contact angle, diameter, and volume of the droplets. An infrared camera was used for infrared thermal mapping of the droplet's surface. An acoustic high-frequency echography technique was, for the first time, applied to track the alcohol concentration in a binary-solution droplet. Evaporation of pure alcohol droplets was executed at different values of relative humidity (RH), among which the behavior of pure ethanol evaporation was notably influenced by the ambient humidity as a result of high hygrometry. Evaporation of droplets of water and binary solutions was performed at a temperature of 22 °C and a mean humidity of approximately 50%. The exhaustion times of alcohol in the droplets estimated by the acoustic method and the visual method were similar for the water-1-butanol mixture; however, the time estimated by the acoustic method was longer when compared with that estimated by the visual method for the water-ethanol mixture due to the residual ethanol at the bottom of the droplet.

Cyclic growth and dissolution of camphor crystals in quinary, ternary, and binary solutions: A study on crystal behavior in storm glass

NASA Astrophysics Data System (ADS)

Mitsuya, Takuro; Takahashi, Kyohei; Nagashima, Kazushige

2014-09-01

"Storm glass" is a hermetically sealed glass tube containing a solution of camphor. In 19th-century England, the pattern and quantity of the crystals were observed and interpreted as a weather forecasting tool. In the present study, the appearance of camphor crystals under cyclic temperature change was studied in three sample solutions, the storm glass solution (quinary system), camphor-ethanol-water (ternary system), and camphor-ethanol (binary system), to elucidate the effect of components in the storm glass on the appearance of camphor crystals. Equilibrium temperatures of camphor crystals as a function of the camphor concentration were also obtained to estimate the quantity of camphor crystals precipitated in the solutions. During the temperature cycles, the crystal height increased and decreased. The ranges (local maxima and minima) of crystal heights gradually decreased to approximately a constant range. Not only the crystal height but also the amplitude of the height variation in the quinary and ternary systems were much larger than those in the binary system, although the estimated weights of crystals precipitated in the quinary and ternary systems were smaller than that in the binary system. This fact resulted from the formation of dendrites in the quinary and ternary systems, which caused high porosity of sedimented crystals.

An ex vivo human aqueous humor-concentration comparison of two commercial bromfenac formulations

PubMed Central

Walters, Thomas R; Smyth-Medina, Robert J; Cockrum, Paul C

2018-01-01

Purpose The purpose of this study was to quantify the concentration of bromfenac in the aqueous humor utilizing high-performance liquid chromatography mass spectrometry between two commercial nonsteroidal anti-inflammatory drugs, using aqueous humor concentrations to characterize pharmacokinetic proportional differences between 0.075% bromfenac ophthalmic solution in DuraSite (BromSite®) and 0.09% bromfenac ophthalmic solution (Bromday®). Methods In this multicenter, randomized, double-masked, two-arm, parallel-group, comparative, Phase II clinical trial, subjects were assigned to receive bromfenac in DuraSite or bromfenac ophthalmic solution in a 1:1 ratio. One drop of the masked test article was instilled into the study eye once a day for 2 days prior to and 3 hours prior (last instillation) to the subject’s cataract surgery. Aqueous humor samples were collected upon initial cataract incision for analysis of bromfenac levels. The primary end point was aqueous humor concentration of bromfenac at Day 3, at the initiation of cataract surgery. Aqueous humor samples were collected and analyzed for bromfenac levels. Results A total of 60 subjects completed the study, 30 in each group. The mean bromfenac aqueous humor concentration in subjects who received bromfenac in DuraSite was more than twice (49.33±41.87 ng/mL, P=0.004) that of subjects who received bromfenac ophthalmic solution (23.65±16.31 ng/mL) after three doses. Conclusion Mean bromfenac aqueous humor concentration in subjects receiving the DuraSite-containing bromfenac in DuraSite (0.075%) was significantly higher compared to subjects receiving bromfenac ophthalmic solution (0.09%) after 3 days of dosing. PMID:29849449

Theoretic Study on Dispersion Mechanism of Boron Nitride Nanotubes by Polynucleotides

PubMed Central

Liang, Lijun; Hu, Wei; Zhang, Zhisen; Shen, Jia-Wei

2016-01-01

Due to the unique electrical and mechanical properties of boron nitride nanotubes (BNNT), BNNT has been a promising material for many potential applications, especially in biomedical field. Understanding the dispersion of BNNT in aqueous solution by biomolecules is essential for its use in biomedical applications. In this study, BNNT wrapped by polynucleotides in aqueous solution was investigated by molecular dynamics (MD) simulations. Our results demonstrated that the BNNT wrapped by polynucleotides could greatly hinder the aggregation of BNNTs and improve the dispersion of BNNTs in aqueous solution. Dispersion of BNNTs with the assistance of polynucleotides is greatly affected by the wrapping manner of polynucleotides on BNNT, which mainly depends on two factors: the type of polynucleotides and the radius of BNNT. The interaction between polynucleotides and BNNT(9, 9) is larger than that between polynucleotides and BNNT(5, 5), which leads to the fact that dispersion of BNNT(9, 9) is better than that of BNNT(5, 5) with the assistance of polynucleotides in aqueous solution. Our study revealed the molecular-level dispersion mechanism of BNNT with the assistance of polynucleotides in aqueous solution. It shades a light on the understanding of dispersion of single wall nanotubes by biomolecules. PMID:28004832

Photolysis of Diazo Dye in Aqueous Solutions of Metal Nitrates

NASA Astrophysics Data System (ADS)

Volkova, N. A.; Evstrop'ev, S. K.; Istomina, O. V.; Kolobkova, E. V.

2018-04-01

The photolysis of Chicago Blue Sky diazo dye is studied. It is experimentally shown that the presence of metal nitrates in aqueous solutions changes the photolysis mechanism and sharply increases the photolysis rate.

Dynamics of aqueous binary glass-formers confined in MCM-41.

PubMed

Elamin, Khalid; Jansson, Helén; Swenson, Jan

2015-05-21

Dielectric permittivity measurements were performed on water solutions of propylene glycol (PG) and propylene glycol monomethyl ether (PGME) confined in 21 Å pores of the silica matrix MCM-41 C10 in wide frequency (10(-2)-10(6) Hz) and temperature (130-250 K) ranges. The aim was to elucidate how the formation of large hydrogen bonded structural entities, found in bulk solutions of PGME, was affected by the confined geometry, and to make comparisons with the dynamic behavior of the PG-water system. For all solutions the measurements revealed four almost concentration independent relaxation processes. The intensity of the fastest process is low compared to the other relaxation processes and might be caused by both hydroxyl groups of the pore surfaces and by local motions of water and solute molecules. The second fastest process contains contributions from both the main water relaxation as well as the intrinsic β-relaxation of the solute molecules. The third fastest process is the viscosity related α-relaxation. Its concentration independency is very different compared to the findings for the corresponding bulk systems, particularly for the PGME-water system. The experimental data suggests that the surface interactions induce a micro-phase separation of the two liquids, resulting in a full molecular layer of water molecules coordinating to the hydrophilic hydroxyl groups on the surfaces of the silica pores. This, in turn, increases the geometrical confinement effect for the remaining solution even more and prevents the building up of the same type of larger structural entities in the PGME-water system as in the corresponding bulk solutions. The slowest process is mainly hidden in the high conductivity contribution at low frequencies, but its temperature dependence can be extracted for the PGME-water system. However, its origin is not fully clear, as will be discussed.

Molecular interactions in ethyl acetate-chlorobenzene binary solution: Dielectric, spectroscopic studies and quantum chemical calculations.

PubMed

Karthick, N K; Kumbharkhane, A C; Joshi, Y S; Mahendraprabu, A; Shanmugam, R; Elangovan, A; Arivazhagan, G

2017-05-05

Dielectric studies using Time Domain Reflectometry method has been carried out on the binary solution of Ethyl acetate (EA) with Chlorobenzene (CBZ) over the entire composition range. Spectroscopic (FTIR and 13 C NMR) signatures of neat EA, CBZ and their equimolar binary solution have also been recorded. The results of the spectroscopic studies favour the presence of (CBZ) CH⋯OC (EA), (EA) methylene CH⋯π electrons (CBZ) and (EA) methyl CH⋯Cl (CBZ) contacts which have been validated using quantum chemical calculations. Dimerization of CBZ has been identified. Presence of β-clusters has been identified in all the solutions. Although EA and CBZ molecules have nearly equal molar volumes, CBZ molecules experience larger hindrance for the rotation than EA molecules. Very small excess dielectric constant (ε E ) values may be correlated with weak heteromolecular forces and/or closed heteromolecular association. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular interactions in ethyl acetate-chlorobenzene binary solution: Dielectric, spectroscopic studies and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Karthick, N. K.; Kumbharkhane, A. C.; Joshi, Y. S.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

2017-05-01

Dielectric studies using Time Domain Reflectometry method has been carried out on the binary solution of Ethyl acetate (EA) with Chlorobenzene (CBZ) over the entire composition range. Spectroscopic (FTIR and 13C NMR) signatures of neat EA, CBZ and their equimolar binary solution have also been recorded. The results of the spectroscopic studies favour the presence of (CBZ) Csbnd H ⋯ Odbnd C (EA), (EA) methylene Csbnd H ⋯ π electrons (CBZ) and (EA) methyl Csbnd H ⋯ Cl (CBZ) contacts which have been validated using quantum chemical calculations. Dimerization of CBZ has been identified. Presence of β-clusters has been identified in all the solutions. Although EA and CBZ molecules have nearly equal molar volumes, CBZ molecules experience larger hindrance for the rotation than EA molecules. Very small excess dielectric constant (εE) values may be correlated with weak heteromolecular forces and/or closed heteromolecular association.

The frequency-dependent response of single aerosol particles to vapour phase oscillations and its application in measuring diffusion coefficients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Preston, Thomas C.; Davies, James F.; Wilson, Kevin R.

A new method for measuring diffusion in the condensed phase of single aerosol particles is proposed and demonstrated. The technique is based on the frequency-dependent response of a binary particle to oscillations in the vapour phase of one of its chemical components. Here, we discuss how this physical situation allows for what would typically be a non-linear boundary value problem to be approximately reduced to a linear boundary value problem. For the case of aqueous aerosol particles, we investigate the accuracy of the closed-form analytical solution to this linear problem through a comparison with the numerical solution of the fullmore » problem. Then, using experimentally measured whispering gallery modes to track the frequency-dependent response of aqueous particles to relative humidity oscillations, we determine diffusion coefficients as a function of water activity. The measured diffusion coefficients are compared to previously reported values found using the two common experiments: (i) the analysis of the sorption/desorption of water from a particle after a step-wise change to the surrounding relative humidity and (ii) the isotopic exchange of water between a particle and the vapour phase. The technique presented here has two main strengths: first, when compared to the sorption/desorption experiment, it does not require the numerical evaluation of a boundary value problem during the fitting process as a closed-form expression is available. Second, when compared to the isotope exchange experiment, it does not require the use of labeled molecules. Therefore, the frequency-dependent experiment retains the advantages of these two commonly used methods but does not suffer from their drawbacks.« less

The frequency-dependent response of single aerosol particles to vapour phase oscillations and its application in measuring diffusion coefficients

DOE PAGES

Preston, Thomas C.; Davies, James F.; Wilson, Kevin R.

2017-01-13

A new method for measuring diffusion in the condensed phase of single aerosol particles is proposed and demonstrated. The technique is based on the frequency-dependent response of a binary particle to oscillations in the vapour phase of one of its chemical components. Here, we discuss how this physical situation allows for what would typically be a non-linear boundary value problem to be approximately reduced to a linear boundary value problem. For the case of aqueous aerosol particles, we investigate the accuracy of the closed-form analytical solution to this linear problem through a comparison with the numerical solution of the fullmore » problem. Then, using experimentally measured whispering gallery modes to track the frequency-dependent response of aqueous particles to relative humidity oscillations, we determine diffusion coefficients as a function of water activity. The measured diffusion coefficients are compared to previously reported values found using the two common experiments: (i) the analysis of the sorption/desorption of water from a particle after a step-wise change to the surrounding relative humidity and (ii) the isotopic exchange of water between a particle and the vapour phase. The technique presented here has two main strengths: first, when compared to the sorption/desorption experiment, it does not require the numerical evaluation of a boundary value problem during the fitting process as a closed-form expression is available. Second, when compared to the isotope exchange experiment, it does not require the use of labeled molecules. Therefore, the frequency-dependent experiment retains the advantages of these two commonly used methods but does not suffer from their drawbacks.« less

Ecotoxicological characterization of polyoxyethylene glycerol ester non-ionic surfactants and their mixtures with anionic and non-ionic surfactants.

PubMed

Ríos, Francisco; Fernández-Arteaga, Alejandro; Lechuga, Manuela; Fernández-Serrano, Mercedes

2017-04-01

This paper reports on a study that investigated the aquatic toxicity of new non-ionic surfactants derived from renewable raw materials, polyoxyethylene glycerol ester (PGE), and their binary mixtures with anionic and non-ionic surfactants. Toxicity of pure PGEs was determined using representative organisms from different trophic levels: luminescent bacteria (Vibrio fischeri), microalgae (Pseudokirchneriella subcapitata), and freshwater crustaceans (Daphnia magna). Relationships between toxicity and the structural parameters such as unit of ethylene oxide (EO) and hydrophilic-lipophilic balance (HLB) were evaluated. Critical micellar concentration (CMC) in the conditions of the toxicity test was also determined. It was found that the toxicity of the aqueous solutions of PGE decreased when the number of EO units in the molecule, HLB, and CMC increased. PGEs showed lower CMC in marine medium, and the toxicity to V. ficheri is lower when the CMC was higher. Given their non-polar nature, narcosis was expected to be the primary mode of toxic action of PGEs. For the mixture of surfactants, we observed that the mixtures with PGE that had the higher numbers of EO units were more toxic than the aqueous solutions of pure surfactants. Moreover, we found that concentration addition was the type of action more likely to occur for mixtures of PGE with lower numbers of EO units with non-ionic surfactants (alkylpolyglucoside and fatty alcohol ethoxylate), whereas for the mixture of PGE with lower EO units and anionic surfactant (ether carboxylic derivative), the most common response type was response addition. In case of mixtures involving amphoteric surfactants and PGEs with the higher numbers of EO units, no clear pattern with regard to the mixture toxicity response type could be observed.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

Multiple stimulus reversible hydrogels

DOEpatents

Gutowska, Anna; Krzyminski, Karol J.

2003-12-09

A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.

Multiple stimulus reversible hydrogels

DOEpatents

Gutowska, Anna; Krzyminski, Karol J.

2006-04-25

A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.

Removal of metal ions from aqueous solution

DOEpatents

Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

1990-01-01

A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

Removal of metal ions from aqueous solution

DOEpatents

Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

1990-11-13

A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat unit for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heayv metals from solution. This also results in the removal of the metals from the column in a concentrated form.

Long-term results of treatment with diquafosol ophthalmic solution for aqueous-deficient dry eye.

PubMed

Koh, Shizuka; Ikeda, Chikako; Takai, Yoshihiro; Watanabe, Hitoshi; Maeda, Naoyuki; Nishida, Kohji

2013-09-01

To evaluate the preliminary long-term efficacy of diquafosol ophthalmic solution for aqueous-deficient dry eye. Fifteen patients with mild-to-moderate aqueous-deficient dry eye were enrolled. After a washout period, the patients were treated with 3 % diquafosol ophthalmic solution for 6 months. We assessed 12 subjective dry eye symptoms, corneal and conjunctival staining with fluorescein, tear film break-up time (BUT), lower tear meniscus height measured with anterior-segment optical coherence tomography, Schirmer's testing, and adverse reactions at baseline and 1, 3, and 6 months after the start of treatment. Treatment with diquafosol ophthalmic solution significantly improved dry eye symptoms, corneal staining, BUT, and tear meniscus height at 1 month and maintained the effectiveness for 6 months. Conjunctival staining significantly improved 3 and 6 months after treatment. No significant adverse reactions developed. Prolonged use of diquafosol ophthalmic solution for 6 months produced significant improvement both subjectively (dry eye symptom score) and objectively (ocular staining score and tear function tests) for aqueous-deficient dry eye.

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION

DOEpatents

Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.

1960-08-23

A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments.

PubMed

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert; Bradforth, Stephen E; Schwegler, Eric; Galli, Giulia

2017-06-01

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecularmore » dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.« less

Mercury removal from aqueous solutions by zinc cementation.

PubMed

Ku, Young; Wu, Ming-Huan; Shen, Yung-Shen

2002-01-01

The main purpose of this research is to study the addition effect of the surfactant and other operating factors on the treatment of wastewater containing mercury ions in aqueous solution by cementation with sacrificing metal, zinc. The removal of mercury ions from aqueous solutions by cementation of zinc powder was found to be a function of solution pH and temperature, amount of zinc, concentration of mercury ion, contact time and the addition of several organic surfactants. Cementation of mercury was shown to be a feasible process to achieve a very high degree of mercury removal over a broad operational range within a fairly reasonable contact time. The reaction rate is approximately first order with respect to the concentration of mercury ion in aqueous solution. Among the surfactants used in this study, only the presence of SDS, an anionic surfactant, slightly enhanced the cementation rate of mercury. The presence of CTAB and Triton-X100 retarded the cementation of mercury by zinc.

Self-Assembly of Porphyrin J-Aggregates

NASA Astrophysics Data System (ADS)

Snitka, Valentinas; Rackaitis, Mindaugas; Navickaite, Gintare

2006-03-01

The porphyrin nanotubes were built by ionic self-assembly of two oppositely charged porphyrins in aqueous solution. The porphyrins in the acid aqueous solution self-assemble into J-aggregates, wheels or other structures. The electrostatic forces between these porphyrin blocks contribute to the formation of porphyrin aggregates in the form of nanotubes, enhance the structural stability of these nanostructures. The nanotubes were composed mixing aqueous solutions of the two porphyrins - anionic Meso-tetra(4- sulfonatophrnyl)porhine dihydrochloride (TPPS4) and cationic Meso-tetra(4-pyridyl)porphine (T4MPyP). The porphyrin nanotubes obtained are hollow structures with the length of 300 nm and diameter 50 nm. Photocatalytic porphyrins are used to reduce metal complexes from aqueous solution and to control the deposition of Au from AuHCl4 and Au nanoparticles colloid solutions onto porphyrin nanotubes. Porphyrin nanotubes are shown to reduce metal complexes and deposit the metal selectively onto the inner or outer surface of the tubes, leading to nanotube-metal composite structures.

Challenges in analysis of high-molar mass dextrans: comparison of HPSEC, AsFlFFF and DOSY NMR spectroscopy.

PubMed

Maina, Ndegwa Henry; Pitkänen, Leena; Heikkinen, Sami; Tuomainen, Päivi; Virkki, Liisa; Tenkanen, Maija

2014-01-01

Dilute solutions of various dextran standards, a high-molar mass (HMM) commercial dextran from Leuconostoc spp., and HMM dextrans isolated from Weissella confusa and Leuconostoc citreum were analyzed with high-performance size-exclusion chromatography (HPSEC), asymmetric flow field-flow fractionation (AsFlFFF), and diffusion-ordered NMR spectroscopy (DOSY). HPSEC analyses were performed in aqueous and dimethyl sulfoxide (DMSO) solutions, while only aqueous solutions were utilized in AsFlFFF and DOSY. The study showed that all methods were applicable to dextran analysis, but differences between the aqueous and DMSO-based solutions were obtained for HMM samples. These differences were attributed to the presence of aggregates in aqueous solution that were less prevalent in DMSO. The study showed that DOSY provides an estimate of the size of HMM dextrans, though calibration standards may be required for each experimental set-up. To our knowledge, this is the first study utilizing these three methods in analyzing HMM dextrans. Copyright © 2013 Elsevier Ltd. All rights reserved.

Quaternary complexes composed of plasmid DNA/protamine/fish sperm DNA/stearic acid grafted chitosan oligosaccharide micelles for gene delivery.

PubMed

Du, Yong-Zhong; Lu, Ping; Yuan, Hong; Zhou, Jian-Ping; Hu, Fu-Qiang

2011-01-01

Quaternary complexes with condensed core of plasmid DNA, protamine, fish sperm DNA and shell of stearic acid grafted chitosan oligosaccharide (CSO-SA), were prepared. The CSO-SA could self-assemble to form nano-sized micelles in aqueous solution and demonstrated excellent internalization ability of tumor cells. Dynamic light scattering (DLS) measurement and transmission electrostatic microscope (TEM) images showed that quaternary complexes had spherical shape with about 25 nm number average diameter, and the size of quaternary complexes was smaller than that of CSO-SA micelles and CSO-SA micelles/plasmid DNA binary complexes. The transfection efficiencies of quaternary complexes on HEK293 and MCF-7 cells increased with incubation time, and were significantly higher than that of CSO-SA micelles/plasmid DNA binary complexes. The optimal transfection efficiency of quaternary complexes on HEK293 and MCF-7 cells measured by flow cytometer after 96 h was 23.82% and 41.43%, respectively. Whereas, the transfection efficiency of Lipofectamine™ 2000 on HEK293 and MCF-7 cells after 96 h was 32.45% and 33.23%, respectively. The data of luciferease activity measurement showed that the optimal ratio of plasmid DNA:fish sperm DNA:protamine:CSO-SA was 1:1:5:5. The results indicated that the present quaternary complexes were potential non-viral gene delivery system. Copyright © 2010 Elsevier B.V. All rights reserved.

Final product analysis in the e-beam and gamma radiolysis of aqueous solutions of metoprolol tartrate

NASA Astrophysics Data System (ADS)

Slegers, Catherine; Tilquin, Bernard

2006-09-01

The radiostability of metoprolol tartrate aqueous solutions and the influence of the absorbed dose (0-50 kGy), dose rate (e-beam (EB) vs. gamma ( γ)) and radioprotectors (pharmaceutical excipients) are investigated by HPLC-UV analyses and through computer simulations. The use of radioprotecting excipients is more promising than an increase in the dose rate to lower the degradation of metoprolol tartrate aqueous solutions for applications such as radiosterilization. The decontamination of metoprolol tartrate from waste waters by EB processing appears highly feasible.

Vibrational spectroscopic study of nickel (II) formate, Ni(HCO 2) 2, and its aqueous solution

NASA Astrophysics Data System (ADS)

Edwards, H. G. M.; Knowles, A.

1992-04-01

A vibrational spectroscopic study of nickel (II) formate and its aqueous solution has been made. The vibrations characteristic of a formato—nickel complex have been assigned and it is concluded that the species Ni(HCO 2) +(HCO 2) - exists in the solid state, with monodentate ligand-to-metal bonding. The Raman spectrum of an aqueous solution of nickel (II) formate indicates that complete dissociation of the formato—nickel (II) species occurs to formate ions and nickel (II) hexa-aquo ions. Comparisons are made with other nickel (II) carboxylates.

Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, F; Ross, A B

1977-01-01

Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

Measurements of Atmospheric Aerosols: Experimental Methods and Results of Measurements off the East Coast of the United States.

DTIC Science & Technology

1983-07-19

Pruppacher and Klett, 1978) 2(rl ’. r R 1 F5S = a,, e (5) where a. is the water activity of the aqueous solution , (r is the surface tension of the droplet...desorption) of ions by the insoluble portion of the particle, which is assumed to be totally submerged in the aqueous solution . We denote the coefficient ...between the saturation ratio S (relative humidity/100) of the air and the equili- brium radius r of an aqueous solution droplet may be expressed as

Patents – Melvin Calvin

Science.gov Websites

plutonium from uranium and fission products in an aqueous acidic solution by use of a chelating agent. The concentration is adjusted to about 1 N bar. The aqueous solution is then contacted with a water-immiscible organic solvent solution and the chelating agent. The chelating agents covered by this invention comprise

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bunkin, N F; Shkirin, A V; Burkhanov, I S

Aqueous NaCl solutions with different concentrations have been investigated by dynamic scattering of laser radiation. It is experimentally shown that these solutions contain scattering particles with a wide size distribution in a range of ∼10 – 100 nm. The experimental results indirectly confirm the existence of quasi-stable gas nanobubbles in the bulk of aqueous ionic solutions. (light scattering)

NMR studies of water dynamics during sol-to-gel transition of poly (N-isopropylacrylamide) in concentrated aqueous solution

USDA-ARS?s Scientific Manuscript database

The thermo-sensitive polymer, poly(N-isopropylacrylamide) (PNIPAM) undergoes a coil-to-globule transition in an aqueous solution as the temperature is raised through the lower critical solution temperature. Thus far, little is known about the dynamical states of the water molecules that contribute ...

METHOD FOR ELECTRODEPOSITING POLONIUM

DOEpatents

Wehrmann, R.F.

1960-08-30

The deposition of a thick uniform layer of polonium metal from aqueous solutions can be carried out by electrolyzing an aqueous solution of 1 N hydrofluoric acid containing about 0.13 curie of polonium per cubic centimeter of solution with platinum electrodes and a current density of about 1.2 ma/cm/sup 2/ of cathode surface.

MECHANISTIC ROLES OF SOIL HUMUS AND MINERALS IN THE SORPTION OF NONIONIC ORGANIC COMPOUNDS FROM AQUEOUS AND ORGANIC SOLUTIONS

EPA Science Inventory

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral...

CO2 as a smart gelator for Pluronic aqueous solutions.

PubMed

Liu, Chengcheng; Mei, Qingqing; Zhang, Jianling; Kang, Xinchen; Peng, Li; Han, Buxing; Xue, Zhimin; Sang, Xinxin; Yang, Xiaogan; Wu, Zhonghua; Li, Zhihong; Mo, Guang

2014-11-25

It was found that CO2 could induce the gelation of Pluronic aqueous solutions, during which the microstructure of the solution transforms from randomly dispersed spherical micelles to cubic close packed micelles. The gelation switched by compressed CO2 has many advantages and can be applied in the synthesis of porous materials.

Method for aqueous radioactive waste treatment

DOEpatents

Bray, L.A.; Burger, L.L.

1994-03-29

Plutonium, strontium, and cesium found in aqueous waste solutions resulting from nuclear fuel processing are removed by contacting the waste solutions with synthetic zeolite incorporating up to about 5 wt % titanium as sodium titanate in an ion exchange system. More than 99.9% of the plutonium, strontium, and cesium are removed from the waste solutions. 3 figures.

Method for aqueous radioactive waste treatment

DOEpatents

Bray, Lane A.; Burger, Leland L.

1994-01-01

Plutonium, strontium, and cesium found in aqueous waste solutions resulting from nuclear fuel processing are removed by contacting the waste solutions with synthetic zeolite incorporating up to about 5 wt % titanium as sodium titanate in an ion exchange system. More than 99.9% of the plutonium, strontium, and cesium are removed from the waste solutions.

Direct evidence on the existence of [Mo132]Keplerate-type species in aqueous solution.

PubMed

Roy, Soumyajit; Planken, Karel L; Kim, Robbert; Mandele, Dexx v d; Kegel, Willem K

2007-10-15

We demonstrate the existence of discrete single molecular [Mo(132)] Keplerate-type clusters in aqueous solution. Starting from a discrete spherical [Mo(132)] cluster, the formation of an open-basket-type [Mo(116)] defect structure is shown for the first time in solution using analytical ultracentrifugation sedimentation velocity experiments.

Solubilization of polycyclic aromatic hydrocarbons in micellar nonionic surfactant solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edwards, D.A.; Luthy, R.G.; Liu, Zhongbao

1991-01-01

Experimental data are presented on the enhanced apparent solubilities of naphthalene, phenanthrene, and pyrene resulting from solubilization in aqueous solutions of four commercial, nonionic surfactants: an alkyl polyoxyethylene (POE) type, two octylphenol POE types, and a nonylphenol POE type. Apparent solubilities of the polycyclic aromatic hydrocarbon (PAH) compounds in surfactant solutions were determined by radiolabeled techniques. Solubilization of each PAH compound commenced at the surfactant critical micelle concentration and was proportional to the concentration of surfactant in micelle form. The partitioning of organic compounds between surfactant micelles and aqueous solution is characterized by a mole fraction micelle-phase/aqueous-phase partition coefficient, K{submore » m}. Values of log K{sub m} for PAH compounds in surfactant solutions of this study range from 4.57 to 6.53. Log K{sub m} appears to be a linear function of log K{sub ow} for a given surfactant solution. A knowledge of partitioning in aqueous surfactant systems is a prerequisite to understanding mechanisms affecting the behavior of hydrophobic organic compounds in soil-water systems in which surfactants play a role in contaminant remediation or facilitated transport.« less

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.

STRIPPING OF URANIUM FROM ORGANIC EXTRACTANTS

DOEpatents

Crouse, D.J. Jr.

1962-09-01

A liquid-liquid extraction method is given for recovering uranium values from uranium-containing solutions. Uranium is removed from a uranium-containing organic solution by contacting said organic solution with an aqueous ammonium carbonate solution substantially saturated in uranium values. A uranium- containing precipitate is thereby formed which is separated from the organic and aqueous phases. Uranium values are recovered from this separated precipitate. (AE C)

PROCESS OF ELIMINATING HYDROGEN PEROXIDE IN SOLUTIONS CONTAINING PLUTONIUM VALUES

DOEpatents

Barrick, J.G.; Fries, B.A.

1960-09-27

A procedure is given for peroxide precipitation processes for separating and recovering plutonium values contained in an aqueous solution. When plutonium peroxide is precipitated from an aqueous solution, the supernatant contains appreciable quantities of plutonium and peroxide. It is desirable to process this solution further to recover plutonium contained therein, but the presence of the peroxide introduces difficulties; residual hydrogen peroxide contained in the supernatant solution is eliminated by adding a nitrite or a sulfite to this solution.

Sol-gel type synthesis of Bi.sub.2 (Sr,Ta.sub.2)O.sub.9 using an acetate based system

DOEpatents

Boyle, Timothy J.

1997-01-01

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen.

Sol-gel type synthesis of Bi{sub 2}(Sr,Ta{sub 2})O{sub 9} using an acetate based system

DOEpatents

Boyle, T.J.

1997-11-04

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen. 6 figs.

Nominal vs. actual supersaturation of solutions

NASA Astrophysics Data System (ADS)

Borisenko, Alexander

2018-03-01

Following the formalism of the Classical Nucleation Theory beyond the dilute solution approximation, this paper considers a difference between the actual solute supersaturation (given by the present-to-saturated solute activity ratio) and the nominal supersaturation (given by the present-to-saturated solute concentration ratio) due to formation of subcritical transient solute clusters, called heterophase fluctuations. Based on their distribution function, we introduce an algebraic equation of supersaturation that couples the nominal supersaturation of a binary metastable solution with its actual supersaturation and a function of the specific interface energy and temperature. The applicability of this approach is validated by comparison to simulation data [(Clouet et al., Phys. Rev. B 69, 064109 (2004)] on nucleation of Al3Zr and Al3Sc in model binary Al alloys.

Piezoelectric Resonance Defined High Performance Sensors and Modulators

DTIC Science & Technology

2016-05-30

Lopez-Ribot, Amar S. Bhalla, Melissa Montes, Ruyan Guo. Properties of Silver and Copper Nanoparticle Containing Aqueous Suspensions and Evaluation of...Amar S. Bhalla, Ruyan Guo, “Properties of Silver and Copper Nanoparticle - Containing Aqueous Solutions and Their Anti-Biofilm Effects," (2015)Symposium...Properties of Silver and Copper Nanoparticle -Containing AqueousSolutions and Evaluation of their In Vitro Activity againstCandida albicans and

Kinetics of photobleaching of aqueous solutions of ricin agglutinin in the presence of guanidine chloride

NASA Astrophysics Data System (ADS)

Brandt, Nikolai N.; Chikishev, Andrey Y.

2002-05-01

Kinetics of background decay in Raman spectra of aqueous solutions of ricin agglutinin in the presence of guanidine chloride were measured. The differences in the kinetics of photobleaching are discussed.

Sensory evaluation of the synergism among odorants present in concentrations below their odor threshold in a Chinese jasmine green tea infusion.

PubMed

Ito, Yuriko; Kubota, Kikue

2005-01-01

The mechanism for the contribution of subthreshold aroma constituents to the overall jasmine tea odor impression was studied on the basis of a sensory evaluation. Binary model aqueous solutions containing the authentic odorants of a jasmine tea infusion, (E)-2-hexenyl hexanoate (I), (Z)-3-hexenol (II), and indole (III), were each prepared in a concentration below the odor threshold. Each solution had no aroma, but when 4-hexanolide replaced only 5% of each odorant, the odor intensity of each model solution was significantly strengthened. An astringent note and heavy note were recognized for each solution as the commonly perceived characteristics from the sensory evaluation. The concentration of 4-hexanolide added was also at the subthreshold level. The results suggest mutual interaction between odorants I, II, or III and 4-hexanolide. The effect on the overall odor sensation of a jasmine tea infusion by adding 4-hexanolide at a concentration below its odor threshold was also studied. In this case, the intensity of both the sweet and astringent notes was significantly strengthened in comparison with the odor impression of the original jasmine tea infusion. This phenomenon is considered to have been a synergistic effect between subthreshold odor compounds in the jasmine tea infusion. The results of this study clarify for the first time that the subthreshold aroma constituents play an important role in the characteristic flavor of a jasmine tea infusion.

Sorption of Ochratoxin A from Aqueous Solutions Using β-Cyclodextrin-Polyurethane Polymer

PubMed Central

Appell, Michael; Jackson, Michael A.

2012-01-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1–10 μg·L−1. These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples. PMID:22474569

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-interactive Chemicals Contained in Boundary Layer-targeted Emulsions

NASA Technical Reports Server (NTRS)

Richmond, Robert Chafee (Inventor); Schramm, Jr., Harry F. (Inventor); Defalco, Francis G. (Inventor)

2013-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Defalco, Francis G. (Inventor); Richmond, Robert Chaffee (Inventor); Schramm, Jr., Harry F. (Inventor)

2017-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, water, or a water-based lubricant. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Defalco, Francis G. (Inventor); Richmond, Robert Chaffee (Inventor); Schramm, Harry F., Jr. (Inventor)

2016-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometrymore » of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.« less

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

Rotational dynamics of trehalose in aqueous solutions studied by depolarized light scattering

NASA Astrophysics Data System (ADS)

Gallina, M. E.; Comez, L.; Morresi, A.; Paolantoni, M.; Perticaroli, S.; Sassi, P.; Fioretto, D.

2010-06-01

High resolution depolarized light scattering spectra, extended from 0.5 to 2×104 GHz by the combined used of a dispersive and an interferometric setup, give evidence of separated solute and solvent dynamics in diluted trehalose aqueous solutions. The slow relaxation process, located in the gigahertz frequency region, is analyzed as a function of temperature and concentration and assigned to the rotational diffusion of the sugar molecule. The results are discussed in comparison with the data obtained on glucose solutions and they are used to clarify the molecular origin of some among the several relaxation processes reported in literature for oligosaccharides solutions. The concentration dependence of relaxation time and of shear viscosity are also discussed, suggesting that the main effect of carbohydrate molecules on the structural relaxation of diluted aqueous solutions is the perturbation induced on the dynamics of the first hydration shell of each solute molecule.

LUT observations of the mass-transferring binary AI Dra

NASA Astrophysics Data System (ADS)

Liao, Wenping; Qian, Shengbang; Li, Linjia; Zhou, Xiao; Zhao, Ergang; Liu, Nianping

2016-06-01

Complete UV band light curve of the eclipsing binary AI Dra was observed with the Lunar-based Ultraviolet Telescope (LUT) in October 2014. It is very useful to adopt this continuous and uninterrupted light curve to determine physical and orbital parameters of the binary system. Photometric solutions of the spot model are obtained by using the W-D (Wilson and Devinney) method. It is confirmed that AI Dra is a semi-detached binary with secondary component filling its critical Roche lobe, which indicates that a mass transfer from the secondary component to the primary one should happen. Orbital period analysis based on all available eclipse times suggests a secular period increase and two cyclic variations. The secular period increase was interpreted by mass transfer from the secondary component to the primary one at a rate of 4.12 ×10^{-8}M_{⊙}/yr, which is in agreement with the photometric solutions. Two cyclic oscillations were due to light travel-time effect (LTTE) via the presence of two cool stellar companions in a near 2:1 mean-motion resonance. Both photometric solutions and orbital period analysis confirm that AI Dra is a mass-transferring binary, the massive primary is filling 69 % of its critical Roche lobe. After the primary evolves to fill the critical Roche lobe, the mass transfer will be reversed and the binary will evolve into a contact configuration.

Process for the combined removal of SO.sub.2 and NO.sub.x from flue gas

DOEpatents

Chang, Shih-Ger; Liu, David K.; Griffiths, Elizabeth A.; Littlejohn, David

1988-01-01

The present invention in one aspect relates to a process for the simultaneous removal of NO.sub.x and SO.sub.2 from a fluid stream comprising mixtures thereof and in another aspect relates to the separation, use and/or regeneration of various chemicals contaminated or spent in the process and which includes the steps of: (A) contacting the fluid stream at a temperature of between about 105.degree. and 180.degree. C. with a liquid aqueous slurry or solution comprising an effective amount of an iron chelate of an amino acid moiety having at least one --SH group; (B) separating the fluid stream from the particulates formed in step (A) comprising the chelate of the amino acid moiety and fly ash; (C) washing and separating the particulates of step (B) with an aqueous solution having a pH value of between about 5 to 8; (D) subsequently washing and separating the particulates of step (C) with a strongly acidic aqueous solution having a pH value of between about 1 to 3; (E) washing and separating the particulates of step (D) with an basic aqueous solution having a pH value of between about 9 to 12; (F) optionally adding additional amino acid moiety, iron (II) and alkali to the aqueous liquid from step (D) to produce an aqueous solution or slurry similar to that in step (A) having a pH value of between about 4 to 12; and (G) recycling the aqueous slurry of step (F) to the contacting zone of step (A). Steps (D) and (E) can be carried out in the reverse sequence, however the preferred order is (D) and then (E). In another preferred embodiment the present invention provides a process for the removal of NO.sub.x, SO.sub.2 and particulates from a fluid stream which includes the steps of (A) injecting into a reaction zone an aqueous solution itself comprising (i) an amino acid moiety selected from those described above; (ii) iron (II) ion; and (iii) an alkali, wherein the aqueous solution has a pH of between about 4 and 11; followed by solids separation and washing as is described in steps (B), (C), (D) and (E) above. The overall process is useful to reduce acid rain components from combustion gas sources.

Molecular dynamics simulation studies of the interactions between ionic liquids and amino acids in aqueous solution.

PubMed

Tomé, Luciana I N; Jorge, Miguel; Gomes, José R B; Coutinho, João A P

2012-02-16

Although the understanding of the influence of ionic liquids (ILs) on the solubility behavior of biomolecules in aqueous solutions is relevant for the design and optimization of novel biotechnological processes, the underlying molecular-level mechanisms are not yet consensual or clearly elucidated. In order to contribute to the understanding of the molecular interactions established between amino acids and ILs in aqueous media, classical molecular dynamics (MD) simulations were performed for aqueous solutions of five amino acids with different structural characteristics (glycine, alanine, valine, isoleucine, and glutamic acid) in the presence of 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonyl imide. The results from MD simulations enable to relate the properties of the amino acids, namely their hydrophobicity, to the type and strength of their interactions with ILs in aqueous solutions and provide an explanation for the direction and magnitude of the solubility phenomena observed in [IL + amino acid + water] systems by a mechanism governed by a balance between competitive interactions of the IL cation, IL anion, and water with the amino acids.

DISSOLUTION OF LANTHANUM FLUORIDE PRECIPITATES

DOEpatents

Fries, B.A.

1959-11-10

A plutonium separatory ore concentration procedure involving the use of a fluoride type of carrier is presented. An improvement is given in the derivation step in the process for plutonium recovery by carrier precipitation of plutonium values from solution with a lanthanum fluoride carrier precipitate and subsequent derivation from the resulting plutonium bearing carrier precipitate of an aqueous acidic plutonium-containing solution. The carrier precipitate is contacted with a concentrated aqueous solution of potassium carbonate to effect dissolution therein of at least a part of the precipitate, including the plutonium values. Any remaining precipitate is separated from the resulting solution and dissolves in an aqueous solution containing at least 20% by weight of potassium carbonate. The reacting solutions are combined, and an alkali metal hydroxide added to a concentration of at least 2N to precipitate lanthanum hydroxide concomitantly carrying plutonium values.

Sorption of tetracycline antibiotics on hyper-crosslinked polystyrene from aqueous and aqueous-organic media

NASA Astrophysics Data System (ADS)

Udalova, A. Yu.; Dmitrienko, S. G.; Apyari, V. V.

2015-06-01

The sorption of tetracycline, oxytetracycline, chlortetracycline, and doxycycline on hyper-cross-linked polystyrene from aqueous and aqueous-organic solutions is studied under static and dynamic conditions in order to extend the range of the sorbents suitable for sorption isolation and the preconcentration of tetracycline antibiotics. Features of tetracycline sorption depending on the acidity of a solution and the nature and concentration of the compounds are explained. It is shown that hyper-crosslinked polystyrene can be used for the group sorption preconcentration of these compounds.

Formation of the racemic compound of ephedrine base from a physical mixture of its enantiomers in the solid, liquid, solution, or vapor state.

PubMed

Duddu, S P; Grant, D J

1992-08-01

Physical mixtures (conglomerates) of the two enantiomers of ephedrine base, each containing 0.5% (w/w) of water, were observed to be converted to the 1:1 racemic compound in the solid, liquid, solution, or vapor state. From a geometrically mixed racemic conglomerate of particle size 250-300 microns (50-60 mesh), the formation of the racemic compound follows second-order kinetics (first order with respect to each enantiomer), with a rate constant of 392 mol-1 hr-1 at 22 degrees C. The reaction appears to proceed via the vapor phase as indicated by the growth of the crystals of the racemic compound between diametrically separated crystals of the two enantiomers in a glass petri dish. The observed kinetics of conversion in the solid state are explained by a homogeneous reaction model via the vapor and/or liquid states. Formation of the racemic compound from the crystals of ephedrine enantiomers in the solution state may explain why Schmidt et al. (Pharm. Res. 5:391-395, 1988) observed a consistently lower aqueous solubility of the mixture than of the pure enantiomers. The solid phase in equilibrium with the solution at the end of the experiment was found to be the racemic compound, whose melting point and heat of fusion are higher than those of the enantiomers. An association reaction, of measurable rate, between the opposite enantiomers in a binary mixture in the solid, liquid, solution, or vapor state to form the racemic compound may be more common than is generally realized.

Investigation of a 2-step agglomeration process performed in a rotary processor using polyethylene glycol solutions as the primary binder liquid.

PubMed

Kristensen, Jakob

2006-10-27

The purpose of this research was to investigate the use of polyethylene glycol (PEG) solutions as the primary binder liquid in a 2-step agglomeration process performed in a rotary processor and characterize the resulting granules and their tableting characteristics. This was done by granulation of binary mixtures of microcrystalline cellulose (MCC) and either lactose, calcium phosphate, acetaminophen, or theophylline, in a 1:3 ratio, using a 50% (wt/wt) aqueous solution of PEG and water as the binder liquid. Formulations containing lactose were agglomerated using 5 different amounts of the PEG binder solution, giving rise to a PEG content in the range of 6% to 43% (wt/wt). The process outcome was characterized according to adhesion, yield, and water requirement, and the prepared granules were characterized according to size, size distribution, and flow properties as well as tableting properties. The agglomeration of all mixtures resulted in high yields of free-flowing agglomerates and gave rise to good reproducibility of the investigated agglomerate characteristics. The process allowed for the incorporation of 42.5% (wt/wt) PEG, which is higher than the percentage of PEG reported for other equipment. Tablets of sufficient strength could be prepared with all investigated excipients using 20% wt/wt PEG; higher PEG contents gave rise to adhesion and prolonged disintegration. In conclusion, agglomeration in a torque-controlled rotary processor using solutions of PEG as the primary binder liquid was found to be a robust process, suitable for the incorporation of high contents of PEG and/or drug compounds.

Generalization of the binary structural phase field crystal model

NASA Astrophysics Data System (ADS)

Smith, Nathan; Provatas, Nikolas

2017-10-01

Two improvements to the binary structural phase field crystal (XPFC) theory are presented. The first is an improvement to the phenomenology for modelling density-density correlation functions and the second extends the free energy of the mixing term in the binary XPFC model beyond ideal mixing to a regular solution model. These improvements are applied to study kinetics of precipitation from solution. We observe a two-step nucleation pathway similar to recent experimental work [N. D. Loh, S. Sen, M. Bosman, S. F. Tan, J. Zhong, C. A. Nijhuis, P. Král, P. Matsudaira, and U. Mirsaidov, Nat. Chem. 9, 77 (2017), 10.1038/nchem.2618; A. F. Wallace, L. O. Hedges, A. Fernandez-Martinez, P. Raiteri, J. D. Gale, G. A. Waychunas, S. Whitelam, J. F. Banfield, and J. J. De Yoreo, Science 341, 885 (2013), 10.1126/science.1230915] in which the liquid solution first decomposes into solute-poor and solute-rich regions, followed by precipitate nucleation of the solute-rich regions. Additionally, we find a phenomenon not previously described in the literature in which the growth of precipitates is accelerated in the presence of uncrystallized solute-rich liquid regions.

NEPTUNIUM SOLVENT EXTRACTION PROCESS

DOEpatents

Dawson, L.R.; Fields, P.R.

1959-10-01

The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

The effect of deep eutectic solvents on catalytic function and structure of bovine liver catalase.

PubMed

Harifi-Mood, Ali Reza; Ghobadi, Roohollah; Divsalar, Adeleh

2017-02-01

Aqueous solutions of reline and glyceline, the most common deep eutectic solvents, were used as a medium for Catalase reaction. By some spectroscopic methods such as UV-vis, fluorescence and circular dichroism (CD) function and structure of Catalase were investigated in aqueous solutions of reline and glyceline. These studies showed that the binding affinity of the substrate to the enzyme increased in the presence of 100mM glyceline solution, which contrasts with reline solution that probably relates to instructive changes in secondary structure of protein. Meanwhile, enzyme remained nearly 70% and 80% active in this concentration of glyceline and reline solutions respectively. In the high concentration of DES solutions, enzyme became mainly inactive but surprisingly stayed in nearly 40% active in choline chloride solution, which is the common ion species in reline and glyceline solvents. It is proposed that the chaotropic nature of choline cation might stop the reducing trend of activity in concentrated choline chloride solutions but this instructive effect is lost in aqueous deep eutectic solvents. In this regard, the presence of various concentrations of deep eutectic solvents in the aqueous media of human cells would be an activity adjuster for this important enzyme in its different operation conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydration and dielectrical properties of aqueous pyrrolidinium trifluoroacetate solutions

NASA Astrophysics Data System (ADS)

Lyashchenko, A. K.; Balakaeva, I. V.; Simonova, Yu. A.; Timofeeva, L. M.

2017-10-01

Results from microwave measurements of the dielectrical properties of aqueous pyrrolidinium trifluoroacetate solutions at maximum water dispersion frequencies (13-25 GHz) and temperatures of 288, 298, and 308 K are given. The static dielectrical constants, times, and activation parameters of the dielectrical relaxation of solutions are calculated. The enthalpy and time of dielectrical relaxation activation are increased by deceleration of the motion of water molecules in the hydrate shells of ions. The changes in dielectrical parameters are in this case minimal in a series of aqueous solutions of diallylammonium salts with cations of different structures and degrees of substitution. It is shown that pyrrolidinium ions are characterized by weak hydrophobic hydration.

METHOD OF SEPARATING PLUTONIUM

DOEpatents

Heal, H.G.

1960-02-16

BS>A method of separating plutonium from aqueous nitrate solutions of plutonium, uranium. and high beta activity fission products is given. The pH of the aqueous solution is adjusted between 3.0 to 6.0 with ammonium acetate, ferric nitrate is added, and the solution is heated to 80 to 100 deg C to selectively form a basic ferric plutonium-carrying precipitate.

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.)

Separations by supported liquid membrane cascades

DOEpatents

Danesi, P.R.

1983-09-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solution and the supported liquid membranes are arranged to provide a continuous process.

Quenching characteristics of bathocuproinedisulfonic acid, disodium salt in aqueous solution and copper sulfate plating solution

NASA Astrophysics Data System (ADS)

Koga, Toshiaki; Hirakawa, Chieko; Takeshita, Michinori; Terasaki, Nao

2018-04-01

Bathocuproinedisulfonic acid, disodium salt (BCS) is generally used to detect Cu(I) through a color reaction. We newly found BCS fluorescence in the visible blue region in an aqueous solution. However, the fluorescence mechanism of BCS is not well known, so we should investigate its fundamental information. We confirmed that the characteristics of fluorescence are highly dependent on the molecular concentration and solvent properties. In particular, owing to the presence of the copper compound, the fluorescence intensity extremely decreases. By fluorescence quenching, we observed that a copper compound concentration of 10-6 mol/L or less could easily be measured in an aqueous solution. We also observed BCS fluorescence in copper sulfate plating solution and the possibility of detecting monovalent copper by fluorescence reabsorption.

DISTRIBUTION OF URANIUM, ZIRCONIUM, NIOBIUM, RUTHENIUM AND CERIUM BETWEEN NITRIC ACID SOLUTIONS AND 10% TLA-5% OCTYL ALCOHOL/SHELL SOL-T

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Menchero, E.; Centeno, J.; Magni, G.

1962-03-01

The extraction of traces of Ru, Zr, Nb, Ce, and U at low concentrations (5 mg/l in aqueous solution) from nitric acid solutions using trilauryl amine (TLA) has been experimentally studied. TLA will eventually be used for final purification of plutonium. Room-temperature data on plutonium contaminant distribution between aqueous solutions of varying nitric acid concentrations and a Shellsol-T solution containing l0% TlA and 5% octyl alcohol are presented. Within the temperature and nitric acid concentration ranges tested, the extractability of uranium increased with increased acid concentrations, although acid concentration in the aqueous phase had no effect on the decontamination factorsmore » for the main fission products. (H.G.G.)« less

Thin film superconductors and process for making same

DOEpatents

Nigrey, P.J.

1988-01-21

A process for the preparation of oxide superconductors from high-viscosity non-aqueous solution is described. Solutions of lanthanide nitrates, alkaline earth nitrates and copper nitrates in a 1:2:3 stoichiometric ratio, when added to ethylene glycol containing citric acid solutions, have been used to prepare highly viscous non-aqueous solutions of metal mixed nitrates-citrates. Thin films of these compositions are produced when a layer of the viscous solution is formed on a substrate and subjected to thermal decomposition.

The Solar-Type Hard-Binary Frequency and Distributions of Orbital Parameters in the Open Cluster M37

NASA Astrophysics Data System (ADS)

Geller, Aaron M.; Meibom, Soren; Barnes, Sydney A.; Mathieu, Robert D.

2014-02-01

Binary stars, and particularly the short-period ``hard'' binaries, govern the dynamical evolution of star clusters and determine the formation rates and mechanisms for exotic stars like blue stragglers and X-ray sources. Understanding the near-primordial hard-binary population of star clusters is of primary importance for dynamical models of star clusters, which have the potential to greatly advance our understanding of star cluster evolution. Yet the binary frequencies and distributions of binary orbital parameters (period, eccentricity, etc.) for young coeval stellar populations are poorly known, due to a lack of necessary observations. The young (~540 Myr) open cluster M37 hosts a rich binary population that can be used to empirically define these initial conditions. Importantly, this cluster has been the target of a comprehensive WIYN/Hydra radial-velocity (RV) survey, from which we have already identified a nearly complete sample of 329 solar-type (1.5 <=M [M_⊙] <=1.0) members in M37. Of these stars, 82 show significant RV variability, indicative of a binary companion. We propose to build upon these data with a multi-epoch RV survey using WIYN/Hydra to derive kinematic orbital solutions for these 82 binaries in M37. This project was granted time in 2013B and scheduled for later this year. We anticipate that about half of the detected binaries in M37 will acquire enough RV measurements (>=10) in 2013B to begin searching for orbital solutions. With this proposal and perhaps one additional semester we should achieve >=10 RV measurements for the remaining binaries.

CONTINUOUS CHELATION-EXTRACTION PROCESS FOR THE SEPARATION AND PURIFICATION OF METALS

DOEpatents

Thomas, J.R.; Hicks, T.E.; Rubin, B.; Crandall, H.W.

1959-12-01

A continuous process is presented for separating metal values and groups of metal values from each other. A complex mixture. e.g., neutron-irradiated uranium, can be resolved into component parts. In the present process the values are dissolved in an acidic solution and adjusted to the proper oxidation state. Thenceforth the solution is contacted with an extractant phase comprising a fluorinated beta -diketone in an organic solvent under centain pH conditions whereupon plutonium and zirconium are extracted. Plutonium is extracted from the foregoing extract with reducing aqueous solutions or under specified acidic conditions and can be recovered from the aqueous solution. Zirconium is then removed with an oxalic acid aqueous phase. The uranium is recovered from the residual original solution using hexone and hexone-diketone extractants leaving residual fission products in the original solution. The uranium is extracted from the hexone solution with dilute nitric acid. Improved separations and purifications are achieved using recycled scrub solutions and the "self-salting" effect of uranyl ions.