WorldWideScience

Sample records for metastable liquid-liquid coexistence

  1. Metastable liquid-liquid transition in a molecular model of water

    Science.gov (United States)

    Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang; Car, Roberto; Panagiotopoulos, Athanassios Z.; Debenedetti, Pablo G.

    2014-06-01

    Liquid water's isothermal compressibility and isobaric heat capacity, and the magnitude of its thermal expansion coefficient, increase sharply on cooling below the equilibrium freezing point. Many experimental, theoretical and computational studies have sought to understand the molecular origin and implications of this anomalous behaviour. Of the different theoretical scenarios put forward, one posits the existence of a first-order phase transition that involves two forms of liquid water and terminates at a critical point located at deeply supercooled conditions. Some experimental evidence is consistent with this hypothesis, but no definitive proof of a liquid-liquid transition in water has been obtained to date: rapid ice crystallization has so far prevented decisive measurements on deeply supercooled water, although this challenge has been overcome recently. Computer simulations are therefore crucial for exploring water's structure and behaviour in this regime, and have shown that some water models exhibit liquid-liquid transitions and others do not. However, recent work has argued that the liquid-liquid transition has been mistakenly interpreted, and is in fact a liquid-crystal transition in all atomistic models of water. Here we show, by studying the liquid-liquid transition in the ST2 model of water with the use of six advanced sampling methods to compute the free-energy surface, that two metastable liquid phases and a stable crystal phase exist at the same deeply supercooled thermodynamic condition, and that the transition between the two liquids satisfies the thermodynamic criteria of a first-order transition. We follow the rearrangement of water's coordination shell and topological ring structure along a thermodynamically reversible path from the low-density liquid to cubic ice. We also show that the system fluctuates freely between the two liquid phases rather than crystallizing. These findings provide unambiguous evidence for a liquid-liquid transition in

  2. Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man's land

    Science.gov (United States)

    Handle, Philip H.; Loerting, Thomas; Sciortino, Francesco

    2017-12-01

    We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water-water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid-liquid transition that could take place in the no-man's land, the temperature-pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form.

  3. Heat capacities and asymmetric criticality of the (liquid + liquid) coexistence curves for {dimethyl carbonate + n-undecane, or n-tridecane}

    International Nuclear Information System (INIS)

    Chen, Zhiyun; Shi, Aiqin; Liu, Shixia; Yin, Tianxiang; Shen, Weiguo

    2014-01-01

    Highlights: • Coexistence curves of dimethyl carbonate + n-undecane (or + n-tridecane) were measured. • Isobaric heat capacity per unit volume of critical binary solutions dimethyl carbonate + n-undecane (or + n-tridecane) were determined. • The critical exponent β are consistent with the 3D-Ising value. • The asymmetry of the coexistence curves were discussed by the complete scaling theory. - Abstract: The (liquid + liquid) coexistences and the critical behavior of isobaric heat capacity per unit volume for critical binary solutions {dimethyl carbonate + n-undecane, or n-tridecane} have been studied. The critical exponents β and α were deduced and found to be consistent with the 3D-Ising values. The critical amplitudes were determined and used to test the asymmetric criticality of coexistence curves. It was found that the heat capacity does play an important role in describing the asymmetric criticality of the coexistence curves

  4. Behavior of supercooled aqueous solutions stemming from hidden liquid-liquid transition in water.

    Science.gov (United States)

    Biddle, John W; Holten, Vincent; Anisimov, Mikhail A

    2014-08-21

    A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid-liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid-liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H2O-NaCl and H2O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid-liquid transition. We elucidate the non-conserved nature of the order parameter (extent of "reaction" between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

  5. Erasing no-man's land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles.

    Science.gov (United States)

    Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

    2014-09-01

    One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point [1] located in the "no-man's land" [2]. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, since spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water [3, 4]. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon [5], carbon [6] and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

  6. Erasing no-man’s land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles

    Science.gov (United States)

    Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

    2014-09-01

    One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point located in the `no-man’s land’. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, as spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon, carbon and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

  7. Decompression-induced melting of ice IV and the liquid-liquid transition in water

    Science.gov (United States)

    Mishima, Osamu; Stanley, H. Eugene

    1998-03-01

    Although liquid water has been the focus of intensive research for over 100 years, a coherent physical picture that unifies all of the known anomalies of this liquid, is still lacking. Some of these anomalies occur in the supercooled region, and have been rationalized on the grounds of a possible retracing of the liquid-gas spinodal (metastability limit) line into the supercooled liquid region, or alternatively the presence of a line of first-order liquid-liquid phase transitions in this region which ends in a critical point,. But these ideas remain untested experimentally, in part because supercooled water can be probed only above the homogeneous nucleation temperature TH at which water spontaneously crystallizes. Here we report an experimental approach that is not restricted by the barrier imposed by TH, involving measurement of the decompression-induced melting curves of several high-pressure phases of ice in small emulsified droplets. We find that the melting curve for ice IV seems to undergo a discontinuity at precisely the location proposed for the line of liquid-liquid phase transitions. This is consistent with, but does not prove, the coexistence of two different phases of (supercooled) liquid water. From the experimental data we calculate a possible Gibbs potential surface and a corresponding equation of state for water, from the forms of which we estimate the coordinates of the liquid-liquid critical point to be at pressure Pc ~ 0.1GPa and temperature Tc ~ 220K.

  8. Liquid-liquid and liquid-solid phase separation and flocculation for a charged colloidal dispersion

    International Nuclear Information System (INIS)

    Lai, S.K.; Wu, K.L.

    2002-01-01

    We model the intercolloidal interaction by a hard-sphere Yukawa repulsion to which is added the long-range van der Waals attraction. In comparison with the Derjaguin-Landau-Verwey-Overbeek repulsion, the Yukawa repulsion explicitly incorporates the spatial correlations between colloids and small ions. As a result, the repulsive part can be expressed analytically and has a coupling strength depending on the colloidal volume fraction. By use of this two-body potential of mean force and in conjunction with a second-order thermodynamic perturbation theory, we construct the colloidal Helmholtz free energy and use it to calculate the thermodynamic quantities, pressure and chemical potential, needed in the determination of the liquid-liquid and liquid-solid phase diagrams. We examine, in an aqueous charged colloidal dispersion, the effects of the Hamaker constant and particle size on the conformation of a stable liquid-liquid phase transition calculated with respect to the liquid-solid coexistence phases. We find that there exists a threshold Hamaker constant or particle size whose value demarcates the stable liquid-liquid coexistence phases from their metastable counterparts. Applying the same technique and using the energetic criterion, we extend our calculations to study the flocculation phenomenon in aqueous charged colloids. Here, we pay due attention to determining the loci of a stability curve stipulated for a given temperature T 0 , and obtain the parametric phase diagram of the Hamaker constant vs the coupling strength or, at given surface potential, the particle size. By imposing T 0 to be the critical temperature T c , i.e., setting k B T 0 (=k B T c ) equal to a reasonable potential barrier, we arrive at the stability curve that marks the irreversible reversible phase transition. The interesting result is that there occurs a minimum size for the colloidal particles below (above) which the colloidal dispersion is driven to an irreversible (reversible) phase

  9. Evaluating the Liquid Liquid Phase Transition Hypothesis of Supercoooled Water

    Science.gov (United States)

    Limmer, David; Chandler, David

    2011-03-01

    To explain the anomalous behavior of supercooled water it has been conjectured that buried within an experimentally inaccessible region of liquid water's phase diagram there exists a second critical point, which is the terminus of a first order transition line between two distinct liquid phases. The so-called liquid-liquid phase transition (LLPT) has since generated much study, though to date there is no consensus on its existence. In this talk, we will discuss our efforts to systematically study the metastable phase diagram of supercooled water through computer simulation. By employing importance-sampling techniques, we have calculated free energies as a function of the density and long-range order to determine unambiguously if two distinct liquid phases exist. We will argue that, contrary to the LLPT hypothesis, the observed phenomenology can be understood as a consequence of the limit of stability of the liquid far away from coexistence. Our results suggest that homogeneous nucleation is the cause of the increased fluctuations present upon supercooling. Further we will show how this understanding can be extended to explain experimental observations of hysteresis in confined supercooled water systems.

  10. Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

    Directory of Open Access Journals (Sweden)

    A. Zuend

    2010-08-01

    Full Text Available Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008. This model allows the reliable computation of the liquid-liquid coexistence curve (binodal, corresponding tie-lines, the limit of stability/metastability (spinodal, and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six

  11. Electrophoretic transport of biomolecules across liquid-liquid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hahn, Thomas; Hardt, Steffen [Center of Smart Interfaces, TU Darmstadt, Petersenstrasse 32, D-64287 Darmstadt (Germany); Muenchow, Goetz, E-mail: hardt@csi.tu-darmstadt.de [Institut fuer Mikrotechnik Mainz GmbH, Carl-Zeiss-Strasse 18-20, D-55129 Mainz (Germany)

    2011-05-11

    The mass transfer resistance of a liquid-liquid interface in an aqueous two-phase system composed of poly(ethylene glycol) and dextran is investigated. Different types of proteins and DNA stained with fluorescent dyes serve as probes to study the transport processes close to the interface. A microfluidic device is employed to enable the electrophoretic transport of biomolecules from one phase to another. The results obtained for proteins can be explained solely via the different electrophoretic mobilities and different affinities of the molecules to the two phases, without any indications of a significant mass transfer resistance of the liquid-liquid interface. By contrast, DNA molecules adsorb to the interface and only desorb under an increased electric field strength. The desorption process carries the signature of a thermally activated escape from a metastable state, as reflected in the exponential decay of the fluorescence intensity at the interface as a function of time.

  12. Solid-Liquid and Liquid-Liquid Equilibrium in the Formamide-Acetophenone System.

    Czech Academy of Sciences Publication Activity Database

    Malijevská, I.; Sedláková, Zuzana; Řehák, K.; Vrbka, P.

    2006-01-01

    Roč. 71, 9 (2006) , s. 1350-1358 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40720504 Keywords : solid-liquid equilibria * liquid-liquid equilibria * metastable Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.881, year: 2006

  13. Erasing no-man's land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles

    NARCIS (Netherlands)

    Smallenburg, Frank; Filion, Laura|info:eu-repo/dai/nl/326823484; Sciortino, Francesco

    2014-01-01

    One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point located in the 'no-man's land'. In this scenario, two liquids with distinct local structure

  14. PREFACE: Functionalized Liquid Liquid Interfaces

    Science.gov (United States)

    Girault, Hubert; Kornyshev, Alexei A.; Monroe, Charles W.; Urbakh, Michael

    2007-09-01

    Most natural processes take place at interfaces. For this reason, surface science has been a focal point of modern research. At solid-liquid interfaces one can induce various species to adsorb or react, and thus may study interactions between the substrate and adsorbates, kinetic processes, optical properties, etc. Liquid-liquid interfaces, formed by immiscible liquids such as water and oil, have a number of distinctive features. Both sides of the interface are amenable to detailed physical and chemical analysis. By chemical or electrochemical means, metal or semiconductor nanoparticles can be formed or localised at the interface. Surfactants can be used to tailor surface properties, and also to place organic molecular or supermolecular constructions at the boundary between the liquids. Electric fields can be used to drive ions from one fluid to another, or even change the shape of the interface itself. In many cases, both liquids are optically transparent, making functionalized liquid-liquid interfaces promising for various optical applications based on the transmission or reflection of light. An advantage common to most of these systems is self-assembly; because a liquid-liquid interface is not mechanically constrained like a solid-liquid interface, it can easily access its most stable state, even after it has been driven far from equilibrium. This special issue focuses on four modes of liquid-liquid interfacial functionalization: the controlled adsorption of molecules or nanoparticles, the formation of adlayers or films, electrowetting, and ion transfer or interface-localized reactions. Interfacial adsorption can be driven electrically, chemically, or mechanically. The liquid-liquid interface can be used to study how anisotropic particles orient at a surface under the influence of a field, how surfactants interact with other adsorbates, and how nanoparticles aggregate; the transparency of the interface also makes the chirality of organic adsorbates amenable to

  15. LIQUID-LIQUID EXTRACTION COLUMNS

    Science.gov (United States)

    Thornton, J.D.

    1957-12-31

    This patent relates to liquid-liquid extraction columns having a means for pulsing the liquid in the column to give it an oscillatory up and down movement, and consists of a packed column, an inlet pipe for the dispersed liquid phase and an outlet pipe for the continuous liquid phase located in the direct communication with the liquid in the lower part of said column, an inlet pipe for the continuous liquid phase and an outlet pipe for the dispersed liquid phase located in direct communication with the liquid in the upper part of said column, a tube having one end communicating with liquid in the lower part of said column and having its upper end located above the level of said outlet pipe for the dispersed phase, and a piston and cylinder connected to the upper end of said tube for applying a pulsating pneumatic pressure to the surface of the liquid in said tube so that said surface rises and falls in said tube.

  16. Liquid-liquid equilibria for binary and ternary polymer solutions with PC-SAFT

    DEFF Research Database (Denmark)

    Lindvig, Thomas; Michelsen, Michael Locht; Kontogeorgis, Georgios

    2004-01-01

    concentration coexistence curves at fixed pressure and temperature. The algorithms automatically trace the entire liquid-liquid coexistence curves in steps by adjusting the step size, generating initial estimates, and subsequently solving the phase-equilibrium problem by a second-order method. The algorithms...... are used for investigating the correlative and predictive capabilities of the thermodynamic model PC-SAFT. The investigation shows that the model correlates well experimental LLE data for binary as well as ternary systems but further predicts the behavior of the ternary systems with reasonably good...

  17. Metastable hydrogen

    International Nuclear Information System (INIS)

    Dose, V.

    1982-01-01

    This paper deals with the basic physical properties of the metastable 2 2 sub(1/2) state of atomic hydrogen. Applications relying on its special properties, including measurement of the Lamb shift, production of spin-polarized protons and the measurement of molecular electric moments, are discussed. (author)

  18. Liquid--liquid contact in vapor explosion

    International Nuclear Information System (INIS)

    Segev, A.

    1978-08-01

    The contact of two liquid materials, one of which is at a temperature substantially above the boiling point of the other, can lead to fast energy conversion and a subsequent shock wave. This well-known phenomenon is called a ''vapor explosion.'' One method of producing intimate, liquid--liquid contact (which is known to be a necessary condition for vapor explosion) is a shock tube configuration. Such experiments in which water was impacted upon molten aluminum showed that very high pressures, even larger than the thermodynamic critical pressure, could occur. The mechanism by which such sharp pressure pulses are generated is not yet clear. In this experiment cold liquids (Freon-11, Freon-22, water, or butanol) were impacted upon various hot materials (mineral oil, silicone oil, water, mercury, molten Wood's metal or molten salt mixture). The main conclusion from the experimental study is that hydrodynamic effects may be very significant in any shock tube analyses, especially when multiple interactions are observed. A theoretical study was performed to check the possibility of vapor film squeezing (between a drop in film boiling and a surface) as a controlling mechanism for making liquid--liquid contact. Using experimental data, the film thickness was calculated and it was found to be too thick for any conceivable film rupture mechanism. It was suggested that the coalescence is a two-stage process, in which the controlling stage depends mainly on temperature and surface properties and can be described as the ability of cold liquid to spread on a hot surface

  19. Liquid-liquid phase transition in Stillinger-Weber silicon

    International Nuclear Information System (INIS)

    Beaucage, Philippe; Mousseau, Normand

    2005-01-01

    It was recently demonstrated that Stillinger-Weber silicon undergoes a liquid-liquid first-order phase transition deep into the supercooled region (Sastry and Angell 2003 Nat. Mater. 2 739). Here we study the effects of perturbations on this phase transition. We show that the order of the liquid-liquid transition changes with negative pressure. We also find that the liquid-liquid transition disappears when the three-body term of the potential is strengthened by as little as 5%. This implies that the details of the potential could affect strongly the nature and even the existence of the liquid-liquid phase

  20. (Liquid + liquid) phase equilibrium and critical behavior of binary solution {heavy water + 2,6-dimethylpyridine}

    International Nuclear Information System (INIS)

    Xu, Chen; Chai, Shouning; Yin, Tianxiang; Chen, Zhiyun; Shen, Weiguo

    2015-01-01

    Highlights: • Coexistence curves, heat capacities and turbidities were measured. • Deuterium effect on coexistence curves was discussed. • Universal critical amplitude ratios were tested. • Asymmetry of coexistence curves was analyzed by the complete scaling theory. - Abstract: The (liquid + liquid) coexistence curves, the isobaric heat capacities per unit volume and the turbidities for the binary solution of {heavy water + 2,6-dimethylpyridine} have been precisely measured. The values of the critical exponents were obtained, which confirmed the 3D-Ising universality. It was found that the critical temperature dropped by 5.9 K and the critical amplitude of the coexistence curve significantly increased as compared to the binary solution of {water + 2,6-dimethylpyridine}. The complete scaling theory was applied to well describe the asymmetric behavior of the diameter of the coexistence curve as the heat capacity contribution was considered. Moreover, the values of the critical amplitudes of the correlation length and the osmotic compressibility were deduced, which together with the critical amplitudes of the coexistence curve and the heat capacity to test universal amplitude ratios

  1. Liquid-liquid contact in vapor explosion

    International Nuclear Information System (INIS)

    Segev, A.

    1978-08-01

    The contact of two liquid materials, one of which is at a temperature substantially above the boiling point of the other, can lead to fast energy conversion and a subsequent shock wave. This phenomenon is called a vapor explosion. One method of producing intimate, liquid-liquid contact (which is known to be a necessary condition for vapor explosion) is a shock tube configuration. Such experiments in which water was impacted upon molten aluminum showed that very high pressures, even larger than the thermodynamic critical pressure, could occur. The mechanism by which such sharp pressure pulses are generated is not yet clear. The report describes experiments in which cold liquids (Freon-11, Freon-22, water, or butanol) were impacted upon various hot materials

  2. Plate performance in liquid-liquid extraction

    International Nuclear Information System (INIS)

    Wadkins, R.P.

    1984-01-01

    The relative effectiveness of perforated, nozzle, and burred plates from a capacity and extraction standpoint were studied in a pulsed liquid-liquid extraction system. The experiments were conducted in a 3.8 x 10 -2 m diameter column using a mixture of aluminum nitrate, nitric acid, and uranyl nitrate as the aqueous phase, and tributyl phosphate dissolved in AMSCO 125-90 W as the organic phase. The uranium was extracted from the aqueous phase to the organic phase. A standard cartridge was made for each type of plate and consisted of an assembly of plates spaced 5.08 x 10 -2 m apart. Each plate had 3.2 x 10 -3 m holes spaced on 6.1 x 10 -3 -m centers, and contained 23% free area. 16 references, 4 figures, 1 table

  3. Complexity, Metastability and Nonextensivity

    Science.gov (United States)

    Beck, C.; Benedek, G.; Rapisarda, A.; Tsallis, C.

    the glass transition in thermal systems / A. Coniglio ... [et al.] -- Supersymmetry and metastability in disordered systems / I. Giardinu, A. Cavagna and G. Parisi -- The metastable liquid-liquid phase transition: from water to colloids and liquid metals / G. Franzese and H. E. Stanley -- Optimization by thermal cycling / A. Möbius, K. H. Hoffmann and C. Schön -- Ultra-thin magnetic films and the structural glass transition: a modelling analogy / S. A. Cannas ... [et al.] -- Non-extensivity of inhomogeneous magnetic systems / M. S. Reis ... [et al.] -- Multifractal analysis of turbulence and granular flow / T. Arimitsu and N. Arimitsu -- Application of superstatistics to atmospheric turbulence / S. Rizzo and A. Rapisarda -- Complexity of perceptual processes / F. T. Arecchi -- Energetic model of tumor growth / P. Castorina and D. Zappalá -- Active Brownian motion - stochastic dynamics of swarms / W. Ebeling and U. Erdmann -- Complexity in the collective behaviour of humans / T. Vicsek -- Monte Carlo simulations of opinion dynamics / S. Fortunato -- A Merton-like approach to pricing debt based on a non-Gaussian asset model / L. Borland, J. Evnine and B. Pochart -- The subtle nature of market efficiency / J.-P. Bouchaud -- Correlation based hierarchical clustering in financial time series / S. Miccichè, F. Lillo and R. N. Mantegna -- Path integrals and exotic options: methods and numerical results / G. Bormetti ... [et al.] -- Aging of event-event correlation of earthquake aftershocks / S. Abe and N. Suzuki -- Aging in earthquakes model / U. Tirnakli -- The Olami-Feder-Christensen model on a small-world topology / F. Caruso ... [et al.] -- Networks as Renormalized models for emergent behavior in physical systems / M. Paczuski -- Energy landscapes, scale-free networks and Apollonian packings / J. P. K. Doye and C. P. Massen -- Epidemic modeling and complex realities / M. Barthélemy ... [et al.] -- The importance of being central / P. Crucitti and V. Latora.

  4. Macromolecular sensing at the liquid-liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Herzog, Gregoire; Flynn, Shane [Tyndall National Institute, Lee Maltings, University College, Cork (Ireland); Arrigan, Damien W M, E-mail: gregoire.herzog@tyndall.ie [Nanochemistry Research Institute, Department of Chemistry, Curtin University, Perth (Australia)

    2011-08-17

    We report here the electrochemical sensing of macromolecules, such as polyLysine dendrimers, at the polarised liquid | liquid interface. Electrochemistry at the liquid | liquid interface is a powerful analytical technique which allows the detection of non-redox active molecules via ion transfer reactions at a polarised water - oil interface. We demonstrate here that different parameters of the polyLysine dendrimers (charge number, molecular weight) have a strong influence on the sensitivity and limit of detection of these macromolecules. This work will help to the development of sensors based on charge transfer at the liquid | liquid interface.

  5. Macromolecular sensing at the liquid-liquid interface

    International Nuclear Information System (INIS)

    Herzog, Gregoire; Flynn, Shane; Arrigan, Damien W M

    2011-01-01

    We report here the electrochemical sensing of macromolecules, such as polyLysine dendrimers, at the polarised liquid | liquid interface. Electrochemistry at the liquid | liquid interface is a powerful analytical technique which allows the detection of non-redox active molecules via ion transfer reactions at a polarised water - oil interface. We demonstrate here that different parameters of the polyLysine dendrimers (charge number, molecular weight) have a strong influence on the sensitivity and limit of detection of these macromolecules. This work will help to the development of sensors based on charge transfer at the liquid | liquid interface.

  6. Use of micro-emulsions in liquid-liquid extraction

    International Nuclear Information System (INIS)

    Komornicki, Jacques

    1982-01-01

    As liquid-liquid extraction of metallic cations is an important method of separation and concentration of metals present in diluted aqueous solutions, and as the extraction rate is limited by one or several steps of matter transfer at the liquid-liquid interface, the extraction kinetics can be improved by creating a wide surface interface and by allowing an increased reactivity between species. In this research thesis, the author aims at determining to which extent systems of interface with a wide surface obtained by using for example amphiphile molecules to create micro-emulsions, can be used as reaction media for physical-chemical processes of liquid-liquid extraction. He also aims at identifying their applicability limitations and problems which might arise with their application. The author notably focuses of the liquid-liquid extraction of metallic cations exhibiting particularly slow extraction kinetics

  7. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II

    Science.gov (United States)

    Limmer, David T.; Chandler, David

    2013-06-01

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys. 135, 134503 (2011), 10.1063/1.3643333 and preprint arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light.

  8. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II

    International Nuclear Information System (INIS)

    Limmer, David T.; Chandler, David

    2013-01-01

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys.135, 134503 (2011) and preprint http://arxiv.org/abs/arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light

  9. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II

    Energy Technology Data Exchange (ETDEWEB)

    Limmer, David T.; Chandler, David, E-mail: chandler@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States)

    2013-06-07

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys.135, 134503 (2011) and preprint http://arxiv.org/abs/arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light.

  10. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II.

    Science.gov (United States)

    Limmer, David T; Chandler, David

    2013-06-07

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys. 135, 134503 (2011) and preprint arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light.

  11. Liquid-liquid phase equilibrium and heat capacity of binary solution {2-propanol + 1-octyl-3-methylimidazolium hexafluorophosphate}

    International Nuclear Information System (INIS)

    Guo, Yimin; Zhang, Xianshuo; Xu, Chen; Shen, Weiguo

    2017-01-01

    Highlights: • Liquid-liquid equilibrium of binary {2-propanol + RTIL} solution was measured. • The critical exponents were deduced and found to belong to 3D-Ising universality. • Asymmetry of the coexistence curve was analyzed by the complete scaling theory. • The dependences of critical parameters on the permittivity of alkanols were discussed. - Abstract: The liquid-liquid coexistence curve and the heat capacity for binary solution of {2-propanol + 1-octyl-3-methylimidazolium hexafluorophosphate} have been precisely measured. The values of the critical exponents α and β, characterizing the critical anomalies of the heat capacity and the coexistence curve respectively, were deduced and found to be consistent with theoretical predictions. The asymmetric behavior of the diameter of the coexistence curve was studied in the frame of the complete scaling theory, demonstrating that the heat capacity related term is of importance. Furthermore, the restricted primitive model (RPM) was used to calculate the reduced upper consolute temperature and density, which together with a comparative larger value of A + indicated a character of solvophobic criticality.

  12. Liquid-liquid interfacial properties of a symmetrical Lennard-Jones binary mixture

    Energy Technology Data Exchange (ETDEWEB)

    Martínez-Ruiz, F. J.; Blas, F. J., E-mail: felipe@uhu.es [Laboratorio de Simulación Molecular y Química Computacional, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Física Aplicada, Universidad de Huelva, 21007 Huelva (Spain); Moreno-Ventas Bravo, A. I. [Laboratorio de Simulación Molecular y Química Computacional, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Geología, Universidad de Huelva, 21007 Huelva (Spain)

    2015-09-14

    We determine the interfacial properties of a symmetrical binary mixture of equal-sized spherical Lennard-Jones molecules, σ{sub 11} = σ{sub 22}, with the same dispersive energy between like species, ϵ{sub 11} = ϵ{sub 22}, but different dispersive energies between unlike species low enough to induce phase separation. We use the extensions of the improved version of the inhomogeneous long-range corrections of Janecek [J. Phys. Chem. B 110, 6264 (2006)], presented recently by MacDowell and Blas [J. Chem. Phys. 131, 074705 (2009)] and Martínez-Ruiz et al. [J. Chem. Phys. 141, 184701 (2014)], to deal with the interaction energy and microscopic components of the pressure tensor. We perform Monte Carlo simulations in the canonical ensemble to obtain the interfacial properties of the symmetrical mixture with different cut-off distances r{sub c} and in combination with the inhomogeneous long-range corrections. The pressure tensor is obtained using the mechanical (virial) and thermodynamic route. The liquid-liquid interfacial tension is also evaluated using three different procedures, the Irving-Kirkwood method, the difference between the macroscopic components of the pressure tensor, and the test-area methodology. This allows to check the validity of the recent extensions presented to deal with the contributions due to long-range corrections for intermolecular energy and pressure tensor in the case of binary mixtures that exhibit liquid-liquid immiscibility. In addition to the pressure tensor and the surface tension, we also obtain density profiles and coexistence densities and compositions as functions of pressure, at a given temperature. According to our results, the main effect of increasing the cut-off distance r{sub c} is to sharpen the liquid-liquid interface and to increase the width of the biphasic coexistence region. Particularly interesting is the presence of a relative minimum in the total density profiles of the symmetrical mixture. This minimum is related

  13. Liquid-liquid interfacial properties of a symmetrical Lennard-Jones binary mixture

    International Nuclear Information System (INIS)

    Martínez-Ruiz, F. J.; Blas, F. J.; Moreno-Ventas Bravo, A. I.

    2015-01-01

    We determine the interfacial properties of a symmetrical binary mixture of equal-sized spherical Lennard-Jones molecules, σ 11 = σ 22 , with the same dispersive energy between like species, ϵ 11 = ϵ 22 , but different dispersive energies between unlike species low enough to induce phase separation. We use the extensions of the improved version of the inhomogeneous long-range corrections of Janecek [J. Phys. Chem. B 110, 6264 (2006)], presented recently by MacDowell and Blas [J. Chem. Phys. 131, 074705 (2009)] and Martínez-Ruiz et al. [J. Chem. Phys. 141, 184701 (2014)], to deal with the interaction energy and microscopic components of the pressure tensor. We perform Monte Carlo simulations in the canonical ensemble to obtain the interfacial properties of the symmetrical mixture with different cut-off distances r c and in combination with the inhomogeneous long-range corrections. The pressure tensor is obtained using the mechanical (virial) and thermodynamic route. The liquid-liquid interfacial tension is also evaluated using three different procedures, the Irving-Kirkwood method, the difference between the macroscopic components of the pressure tensor, and the test-area methodology. This allows to check the validity of the recent extensions presented to deal with the contributions due to long-range corrections for intermolecular energy and pressure tensor in the case of binary mixtures that exhibit liquid-liquid immiscibility. In addition to the pressure tensor and the surface tension, we also obtain density profiles and coexistence densities and compositions as functions of pressure, at a given temperature. According to our results, the main effect of increasing the cut-off distance r c is to sharpen the liquid-liquid interface and to increase the width of the biphasic coexistence region. Particularly interesting is the presence of a relative minimum in the total density profiles of the symmetrical mixture. This minimum is related with a desorption of the

  14. Separation of Asphaltenes by Polarity using Liquid-Liquid Extraction

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar

    1997-01-01

    In order to investigate the nature of petroleum asphaltenes in terms of polarity a process was developed using initial liquid-liquid extraction of the oil phase followed by precipitation of the asphaltenes using n-heptane. The liquid-liquid extraction was performed using toluene-methanol mixtures...... phase. The asphaltenes were analysed using FTir, Elemental analysis, and HPLC-SEC with a diode array detector. With increasing content of toluene in the methanol the molecular weight distribution of the asphaltenes significantly move to higher molecular weights. The content of nitrogen and sulfur...

  15. Two-state thermodynamics and the possibility of a liquid-liquid phase transition in supercooled TIP4P/2005 water

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Rakesh S.; Debenedetti, Pablo G. [Department of Chemical & Biological Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Biddle, John W.; Anisimov, Mikhail A., E-mail: anisimov@umd.edu [Institute of Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

    2016-04-14

    Water shows intriguing thermodynamic and dynamic anomalies in the supercooled liquid state. One possible explanation of the origin of these anomalies lies in the existence of a metastable liquid-liquid phase transition (LLPT) between two (high and low density) forms of water. While the anomalies are observed in experiments on bulk and confined water and by computer simulation studies of different water-like models, the existence of a LLPT in water is still debated. Unambiguous experimental proof of the existence of a LLPT in bulk supercooled water is hampered by fast ice nucleation which is a precursor of the hypothesized LLPT. Moreover, the hypothesized LLPT, being metastable, in principle cannot exist in the thermodynamic limit (infinite size, infinite time). Therefore, computer simulations of water models are crucial for exploring the possibility of the metastable LLPT and the nature of the anomalies. In this work, we present new simulation results in the NVT ensemble for one of the most accurate classical molecular models of water, TIP4P/2005. To describe the computed properties and explore the possibility of a LLPT, we have applied two-structure thermodynamics, viewing water as a non-ideal mixture of two interconvertible local structures (“states”). The results suggest the presence of a liquid-liquid critical point and are consistent with the existence of a LLPT in this model for the simulated length and time scales. We have compared the behavior of TIP4P/2005 with other popular water-like models, namely, mW and ST2, and with real water, all of which are well described by two-state thermodynamics. In view of the current debate involving different studies of TIP4P/2005, we discuss consequences of metastability and finite size in observing the liquid-liquid separation. We also address the relationship between the phenomenological order parameter of two-structure thermodynamics and the microscopic nature of the low-density structure.

  16. Two-state thermodynamics and the possibility of a liquid-liquid phase transition in supercooled TIP4P/2005 water

    International Nuclear Information System (INIS)

    Singh, Rakesh S.; Debenedetti, Pablo G.; Biddle, John W.; Anisimov, Mikhail A.

    2016-01-01

    Water shows intriguing thermodynamic and dynamic anomalies in the supercooled liquid state. One possible explanation of the origin of these anomalies lies in the existence of a metastable liquid-liquid phase transition (LLPT) between two (high and low density) forms of water. While the anomalies are observed in experiments on bulk and confined water and by computer simulation studies of different water-like models, the existence of a LLPT in water is still debated. Unambiguous experimental proof of the existence of a LLPT in bulk supercooled water is hampered by fast ice nucleation which is a precursor of the hypothesized LLPT. Moreover, the hypothesized LLPT, being metastable, in principle cannot exist in the thermodynamic limit (infinite size, infinite time). Therefore, computer simulations of water models are crucial for exploring the possibility of the metastable LLPT and the nature of the anomalies. In this work, we present new simulation results in the NVT ensemble for one of the most accurate classical molecular models of water, TIP4P/2005. To describe the computed properties and explore the possibility of a LLPT, we have applied two-structure thermodynamics, viewing water as a non-ideal mixture of two interconvertible local structures (“states”). The results suggest the presence of a liquid-liquid critical point and are consistent with the existence of a LLPT in this model for the simulated length and time scales. We have compared the behavior of TIP4P/2005 with other popular water-like models, namely, mW and ST2, and with real water, all of which are well described by two-state thermodynamics. In view of the current debate involving different studies of TIP4P/2005, we discuss consequences of metastability and finite size in observing the liquid-liquid separation. We also address the relationship between the phenomenological order parameter of two-structure thermodynamics and the microscopic nature of the low-density structure.

  17. Mechanism of Lecithin Adsorption at a Liquid/Liquid Interface

    Czech Academy of Sciences Publication Activity Database

    Mareček, Vladimír; Lhotský, Alexandr; Jänchenová, Hana

    2003-01-01

    Roč. 107, č. 19 (2003), s. 4573-4578 ISSN 1089-5647 R&D Projects: GA ČR GA203/00/0636 Institutional research plan: CEZ:AV0Z4040901 Keywords : adsorption * mechanism of lecithin * liquid/liquid interface Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2003

  18. Liquid-liquid interfacial tension of electrolyte solutions

    NARCIS (Netherlands)

    Bier, Markus; Zwanikken, J.W.; van Roij, R.H.H.G.

    2008-01-01

    It is theoretically shown that the excess liquid-liquid interfacial tension between two electrolyte solutions as a function of the ionic strength I behaves asymptotically as (-) for small I and as (±I) for large I. The former regime is dominated by the electrostatic potential due to an unequal

  19. Dynamics of solid nanoparticles near a liquid-liquid interface

    Science.gov (United States)

    Daher, Ali; Ammar, Amine; Hijazi, Abbas

    2018-05-01

    The liquid - liquid interface can be used as a suitable medium for generating some nanostructured films of metals, or inorganic materials such as semi conducting metals. This process can be controlled well if we study the dynamics of nanoparticles (NPs) at the liquid-liquid interface which is a new field of study, and is not understood well yet. The dynamics of NPs at liquid-liquid interfaces is investigated by solving the fluid-particle and particle-particle interactions. Our work is based on the Molecular Dynamics (MD) simulation in addition to Phase Field (PF) method. We modeled the liquid-liquid interface using the diffuse interface model, where the interface is considered to have a characteristic thickness. We have shown that the concentration gradient of one fluid in the other gives rise to a hydrodynamic force that drives the NPs to agglomerate at the interface. These obtained results may introduce new applications where certain interfaces can be considered to be suitable mediums for the synthesis of nanostructured materials. In addition, some liquid interfaces can play the role of effective filters for different species of biological NPs and solid state waste NPs, which will be very important in many industrial and biomedical domains.

  20. Transuranium element purification by liquid-liquid extraction

    International Nuclear Information System (INIS)

    Madic, C.; Koehly, G.

    1976-01-01

    In the transuranium element production, the liquid-liquid extraction purification is presented. The affinity of TBP and trilaurylammonium nitrate for these elements is given. Exemples of NP/Pu, Pu/Np, U/Pu, Am/Cm, Am and Cm/Ln separation are presented [fr

  1. CATION-EXCHANGE SOLID-PHASE AND LIQUID-LIQUID ...

    African Journals Online (AJOL)

    B. S. Chandravanshi

    An existing liquid-liquid extraction (LLE) method was improved in terms of ... clean-up of the alkaloids from khat leaves, prior to HPLC-DAD detection. Despite .... The limits of detection (LOD) and quantification (LOQ) were calculated using the.

  2. Liquid-liquid extraction by reversed micelles in biotechnological processes

    Directory of Open Access Journals (Sweden)

    Kilikian B. V.

    2000-01-01

    Full Text Available In biotechnology there is a need for new purification and concentration processes for biologically active compounds such as proteins, enzymes, nucleic acids, or cells that combine a high selectivity and biocompatibility with an easy scale-up. A liquid-liquid extraction with a reversed micellar phase might serve these purposes owing to its capacity to solubilize specific biomolecules from dilute aqueous solutions such as fermentation and cell culture media. Reversed micelles are aggregates of surfactant molecules containing an inner core of water molecules, dispersed in a continuous organic solvent medium. These reversed micelles are capable of selectively solubilizing polar compounds in an apolar solvent. This review gives an overview of liquid-liquid extraction by reversed micelles for a better understanding of this process.

  3. Haze Formation and Behavior in Liquid-Liquid Extraction Processes

    International Nuclear Information System (INIS)

    Arm, Stuart T.; Jenkins, J. A.

    2006-01-01

    Aqueous haze formation and behavior was studied in the liquid-liquid system tri-n-butyl phosphate in odorless kerosene and 3M nitric acid with uranyl nitrate and cesium nitrate representing the major solute and an impurity, respectively. A pulsed column, mixer-settler and centrifugal contactor were chosen to investigate the effect of different turbulence characteristics on the manifestation of haze since these contactors exhibit distinct mixing phenomena. The dispersive processes of drop coalescence and breakage, and water precipitation in the organic phase were observed to lead to the formation of haze drops of ∼1 um in diameter. The interaction between the haze and primary drops of the dispersion was critical to the separation efficiency of the liquid-liquid extraction equipment. Conditions of high power input and spatially homogeneous mixing enabled the haze drops to become rapidly assimilated within the dispersion to maximize the scrub performance and separation efficiency of the equipment

  4. Recycling of Metal Containing Waste by Liquid-Liquid Extraction

    International Nuclear Information System (INIS)

    Reinhardt, H.

    1999-01-01

    Through the years, a large number of liquid-liquid extraction have been proposed for metal waste recovery and recycling(1,2). However, few of them have achieved commercial application. In fact, relatively little information is available on practical operation and economic feasibility. This presentation will give complementary information by describing and comparing three processes, based on the Am MAR hydrometallurgical concept and representing three different modes of operation

  5. [High-performance liquid-liquid chromatography in beverage analysis].

    Science.gov (United States)

    Bricout, J; Koziet, Y; de Carpentrie, B

    1978-01-01

    Liquid liquid chromatography was performed with columns packed with stationary phases chemically bonded to silica microparticules. These columns show a high efficiency and are used very easily. Flavouring compounds like aromatic aldehydes which have a low volatility were analyzed in brandy using a polar phase alkylnitrile. Sapid substances like amarogentin in Gentiana lutea or glyryrrhizin in Glycyrrhiza glabra were determined by reversed phase chromatography. Finally ionizable substances like synthetic dyes can be analyzed by paired ion chromatography witha non polar stationary phase.

  6. Thermodynamics of mixtures containing alkoxyethanols. XXVIII: Liquid-liquid equilibria for 2-phenoxyethanol + selected alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, Victor; Garcia, Mario [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain); Gonzalez, Juan Antonio, E-mail: jagl@termo.uva.es [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain); Garcia De La Fuente, Isaias; Cobos, Jose Carlos [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain)

    2011-07-10

    Highlights: {yields} LLE coexistence curves were determined for mixtures of 2PhEE with alkanes. {yields} UCST values are higher for n-alkane systems than for solutions with cyclic alkanes. {yields} For the latter mixtures, UCST increases with the size of the alkyl group attached. {yields} Alkoxyethanol-alkoxyethanol interactions are enhanced by aromatic group in cellosolve. - Abstract: The coexistence curves of the liquid-liquid equilibria (LLE) for systems of 2-phenoxyethanol (2PhEE) with heptane, octane, cyclohexane, methylcyclohexane or ethylcyclohexane have been determined by the method of the critical opalescence using a laser scattering technique. All the curves show an upper critical solution temperature (UCST), have a rather horizontal top and their symmetry depends on the relative size of the mixture compounds. UCST values are higher for systems with linear alkanes than for solutions including cyclic alkanes. For these mixtures, the UCST increases with the size of the alkyl group attached to the cyclic part of the molecule. It is shown that interactions between alkoxyethanol molecules are stronger when the hydroxyether contains an aromatic group. Data are used to determine the critical exponent for the order parameter mole fraction. Values obtained are consistent with those provided by the Ising model or by the renormalization group theory.

  7. Thermodynamics of mixtures containing alkoxyethanols. XXVIII: Liquid-liquid equilibria for 2-phenoxyethanol + selected alkanes

    International Nuclear Information System (INIS)

    Alonso, Victor; Garcia, Mario; Gonzalez, Juan Antonio; Garcia De La Fuente, Isaias; Cobos, Jose Carlos

    2011-01-01

    Highlights: → LLE coexistence curves were determined for mixtures of 2PhEE with alkanes. → UCST values are higher for n-alkane systems than for solutions with cyclic alkanes. → For the latter mixtures, UCST increases with the size of the alkyl group attached. → Alkoxyethanol-alkoxyethanol interactions are enhanced by aromatic group in cellosolve. - Abstract: The coexistence curves of the liquid-liquid equilibria (LLE) for systems of 2-phenoxyethanol (2PhEE) with heptane, octane, cyclohexane, methylcyclohexane or ethylcyclohexane have been determined by the method of the critical opalescence using a laser scattering technique. All the curves show an upper critical solution temperature (UCST), have a rather horizontal top and their symmetry depends on the relative size of the mixture compounds. UCST values are higher for systems with linear alkanes than for solutions including cyclic alkanes. For these mixtures, the UCST increases with the size of the alkyl group attached to the cyclic part of the molecule. It is shown that interactions between alkoxyethanol molecules are stronger when the hydroxyether contains an aromatic group. Data are used to determine the critical exponent for the order parameter mole fraction. Values obtained are consistent with those provided by the Ising model or by the renormalization group theory.

  8. The accuracy of liquid-liquid phase transition temperatures determined from semiautomated light scattering measurements

    Science.gov (United States)

    Dean, Kevin M.; Babayco, Christopher B.; Sluss, Daniel R. B.; Williamson, J. Charles

    2010-08-01

    The synthetic-method determination of liquid-liquid coexistence curves using semiautomated light scattering instrumentation and stirred samples is based on identifying the coexistence curve transition temperatures (Tcx) from sudden changes in turbidity associated with droplet formation. Here we use a thorough set of such measurements to evaluate the accuracy of several different analysis methods reported in the literature for assigning Tcx. More than 20 samples each of weakly opalescent isobutyric acid+water and strongly opalescent aniline+hexane were tested with our instrumentation. Transmitted light and scattering intensities at 2°, 24°, and 90° were collected simultaneously as a function of temperature for each stirred sample, and the data were compared with visual observations and light scattering theory. We find that assigning Tcx to the onset of decreased transmitted light or increased 2° scattering has a potential accuracy of 0.01 K or better for many samples. However, the turbidity due to critical opalescence obscures the identification of Tcx from the light scattering data of near-critical stirred samples, and no simple rule of interpretation can be applied regardless of collection geometry. At best, when 90° scattering is collected along with transmitted or 2° data, the accuracy of Tcx is limited to 0.05 K for near-critical samples. Visual determination of Tcx remains the more accurate approach in this case.

  9. (Liquid + liquid) equilibria of perfluorocarbons with fluorinated ionic liquids

    International Nuclear Information System (INIS)

    Martinho, S.; Araújo, J.M.M.; Rebelo, L.P.N.; Pereiro, A.B.; Marrucho, I.M.

    2013-01-01

    Highlights: • (Liquid + liquid) equilibria perfluorocarbons and fluorinated ionic liquids. • Non-Random Two Liquid model was successfully applied. • Thermodynamic functions that describe the solvation process were calculated. -- Abstract: In order to evaluate the feasibility of partially replace perfluorocarbons (PFCs) with fluorinated ionic liquids (FILs) in PFCs-in-water emulsions, usually used for biomedical purposes, herein the (liquid + liquid) phase equilibria of FILs containing fluorinated chains longer than four carbons with PFCs were carried out in a wide range of temperatures. With this goal in mind, two PFCs (perfluorooctane and perfluorodecalin) were selected and the (liquid + liquid) equilibria of the binary mixtures of these PFCs and FILs were studied at atmospheric pressure in a temperature range from T (293.15 to 343.15) K. For these studies, FILs containing ammonium, pyridinium and imidazolium cations and different anions with fluorocarbon alkyl chains between 4 and 8 were included. Additionally, Non-Random Two Liquid (NRTL) thermodynamic model was successfully applied to correlate the behaviour of the PFCs + FILs binary mixtures. Moreover, thermodynamic functions that describe the solvation process were calculated from the experimental data

  10. The Putative Liquid-Liquid Transition is a Liquid-Solid Transition in Atomistic Models of Water

    Science.gov (United States)

    Chandler, David; Limmer, David

    2013-03-01

    Our detailed and controlled studies of free energy surfaces for models of water find no evidence for reversible polyamorphism, and a general theoretical analysis of the phase behavior of cold water in nano pores shows that measured behaviors of these systems reflect surface modulation and dynamics of ice, not a liquid-liquid critical point. A few workers reach different conclusions, reporting evidence of a liquid-liquid critical point in computer simulations of supercooled water. In some cases, it appears that these contrary results are based upon simulation algorithms that are inconsistent with principles of statistical mechanics, such as using barostats that do not reproduce the correct distribution of volume fluctuations. In other cases, the results appear to be associated with difficulty equilibrating the supercooled material and mistaking metastability for coarsening of the ordered ice phase. In this case, sufficient information is available for us to reproduce the contrary results and to establish that they are artifacts of finite time sampling. This finding leads us to the conclusion that two distinct, reversible liquid phases do not exist in models of supercooled water.

  11. Liquid-liquid interfacial tension of electrolyte solutions

    OpenAIRE

    Bier, Markus; Zwanikken, Jos; van Roij, Rene

    2008-01-01

    It is theoretically shown that the excess liquid-liquid interfacial tension between two electrolyte solutions as a function of the ionic strength I behaves asymptotically as O(- I^0.5) for small I and as O(+- I) for large I. The former regime is dominated by the electrostatic potential due to an unequal partitioning of ions between the two liquids whereas the latter regime is related to a finite interfacial thickness. The crossover between the two asymptotic regimes depends sensitively on mat...

  12. (Liquid + liquid) equilibria of binary systems containing hyperbranched polymer Boltorn (registered) H2004 - Experimental study and modelling in terms of lattice-cluster theory

    International Nuclear Information System (INIS)

    Domanska, Urszula; Paduszynski, Kamil; Zolek-Tryznowska, Zuzanna

    2011-01-01

    (Liquid + liquid) phase equilibria (LLE) of binary mixtures containing hyperbranched polymer Boltorn (registered) H2004 and n-alkanes (n-hexane, n-heptane, n-octane, and n-decane) were studied over the temperature range from about (260 up to 360) K. The polymer is partially miscible with n-alkanes and the solubility decreases with an increase of the chain length of the solvent. Corresponding LLE phase diagrams including spinodal and binodal (liquid + liquid) coexistence curves were calculated in terms of the statistical mechanics - based on the lattice-cluster theory, based only on the upper critical solution temperature, and the polymer chain architecture. The results show semi-qualitative agreement of predicted and experimental equilibrium compositions and temperatures. Boltorn (registered) H2004 reveals complete miscibility in the liquid phase with alcohols (C 1 -C 8 ), aromatic hydrocarbons (benzene, toluene, and thiophene), and ethers (methyl tetra-butyl ether, ethyl tetra-butyl ether, and tetrahydrofurane).

  13. The role of ultrasound in controlling the liquid-liquid phase separation and nucleation of vanillin polymorphs I and II

    Science.gov (United States)

    Parimaladevi, P.; Supriya, S.; Srinivasan, K.

    2018-02-01

    The influence of ultrasound on liquid-liquid phase separation (LLPS) and polymorphism of vanillin in aqueous solution has been investigated for the first time by varying the ultrasonic parameters such as power, pulse rate and insonation time at ambient condition. Results reveal that the application of ultrasound controls the impact of LLPS and accelerates the nucleation of vanillin within a short period at lower levels of ultrasonic process parameters, and also enhances the quality of the nucleated crystals. Moreover, the application of ultrasound induces the nucleation of rare and metastable polymorph of vanillin Form II in aqueous solution. But, at higher levels of power, pulse rate and insonation time, the rate of LLPS is found increased and the quality of the crystals becomes deteriorated. Morphology of the nucleated polymorphs were identified through optical microscopy and confirmed by optical goniometry. The internal structure and thermal stability of the grown stable Form I and metastable Form II of vanillin were confirmed through powder X-ray diffraction (PXRD) and differential scanning calorimetry (DSC) analyses. Further, results suggest that the ultrasound has profound effect in controlling the LLPS and nucleation of vanillin polymorphs in aqueous solution.

  14. SISAK liquid-liquid extraction experiments with preseparated 257Rf

    International Nuclear Information System (INIS)

    Omtvedt, Jon Petter; Alstad, J.; Breivik, H.; Dyve, J.E.; Eberhardt, K.; Folden III, C.M.; Ginter, T.; Gregorich, K.E.; Hult, E.A.; Johansson, M.; Kirbach, U.W.; Lee, D.M.; Mendel, M.; Nahler, A.; Ninov, V.; Omtvedt, L.A.; Patin, J.B.; Skarnemark, G.; Stavsetra, L.; Sudowe, R.; Wiehl, N.; Wierczinski, B.; Wilk, P.A.; Zielinski, P.M.; Kratz, J.V.; Trautmann, N.; Nitsche, H.; Hoffman, D.C.

    2002-01-01

    The SISAK liquid-liquid extraction system was used to extract 4.0-s 257Rf. The 257Rf was produced in the reaction 208Pb(50Ti, 1n)257Rf with 237-MeV beam energy on target, separated in the Berkeley Gas-filled Separator (BGS) and transferred to a gas jet using the Recoil Transfer Chamber (RTC). The activity delivered by the gas jet was dissolved in 6-M HNO3 and Rf was extracted into 0.25-M dibutyl-phosphoric acid in toluene. This was the first time a transactinide, i.e., an element with Z >= 104, was extracted and unequivocally identified by the SISAK system. Thus, this pilot experiment demonstrates that the fast liquid-liquid extraction system SISAK, in combination with liquidscintillation detectors, can be used for investigating the chemical properties of the transactinides. The extraction result is in accordance with the behaviour shown by the Rf group IV homologues Zr and Hf

  15. Liquid-liquid extraction in flow analysis: A critical review

    Energy Technology Data Exchange (ETDEWEB)

    Silvestre, Cristina I.C.; Santos, Joao L.M. [REQUIMTE, Servico de Quimica-Fisica, Faculdade de Farmacia, Universidade do Porto, R. Anibal Cunha, 164, 4099-030 Porto (Portugal); Lima, Jose L.F.C., E-mail: limajlfc@ff.up.pt [REQUIMTE, Servico de Quimica-Fisica, Faculdade de Farmacia, Universidade do Porto, R. Anibal Cunha, 164, 4099-030 Porto (Portugal); Zagatto, Elias A.G. [Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, P.O. Box 96, Piracicaba 13400-970 (Brazil)

    2009-10-12

    Liquid-liquid extractions (LLE) are a common sample pre-treatment in many analytical applications. This review aims at providing a critical overview of the distinct automated continuous flow-based approaches that were developed for liquid-liquid extraction with the purpose of pre-concentration and/or separation of multiple analytes, such as ultra-trace metal and metalloid species, phenolic compounds, surfactants, pharmaceuticals, etc., hyphenated with many detection technique such as UV/vis spectrophotometry, atomic spectrometric detection systems and luminescent detectors, including distinct extraction strategies and applications like single and multiple extraction schemes, wetting film extraction, supported liquid membrane extraction, back extraction, closed-loop systems and the utilisation of zone sampling, chromatomembranes and iterative reversal techniques. The analytical performance of the developed flow-based LLE methods and the influence of flow manifold components such as the segmenter, extraction coil and phase separator, is emphasised and object of discussion. An overall presentation of each system components, selectivity, advantages and shortcomings is carried out and exemplified with selected applications.

  16. The use of ultrasonic instrumentation in liquid/liquid extraction plant

    International Nuclear Information System (INIS)

    Asher, R.C.; Bradshaw, L.; Tolchard, A.C.

    1984-01-01

    Ultrasonic instruments can be used to determine many of the parameters of interest in a liquid/liquid extraction plant, eg liquid levels, the position of interfaces between immiscible liquids and the concentration of solutions. The determinations can often be made non-invasively. A number of instruments developed for a liquid/liquid extraction plant used for nuclear fuel reprocessing is described. These instruments have a wider application in liquid/liquid extraction plant in general. (author)

  17. Electrochemical detection of dopamine using arrays of liquid-liquid micro-interfaces created within micromachined silicon membranes

    International Nuclear Information System (INIS)

    Berduque, Alfonso; Zazpe, Raul; Arrigan, Damien W.M.

    2008-01-01

    The detection of protonated dopamine by differential pulse voltammetry (DPV) and square wave voltammetry (SWV) at arrays of micro-interfaces between two immiscible electrolyte solutions (μITIES) is presented. Microfabricated porous silicon membranes (consisting of eight pores, 26.6 μm in radius and 500 μm pore-pore separation, in a hexagonal layout) were prepared by photolithographic and etching procedures. The membrane pores were fabricated with hydrophobic internal walls so that the organic phase filled the pores and created the liquid interface at the aqueous side of the membrane. These were used for harnessing the benefits of three-dimensional diffusion to the interface and for interface stabilisation. The liquid-liquid interface provides a simple method to overcome the major problem in the voltammetric detection of dopamine at solid electrodes due to the co-existence of ascorbate at higher concentrations. Selectivity for dopamine over ascorbate was achieved by the use of dibenzo-18-crown-6 (DB18C6) for the facilitated ion transfer of dopamine across the μITIES array. Under these conditions, the presence of ascorbate in excess did not interfere in the detection of dopamine and the lowest concentration detectable was ca. 0.5 μM. In addition, the drawback of current signal saturation (non-linear increase of the peak current with the concentration of dopamine) observed at conventional (millimetre-sized) liquid-liquid interfaces was overcome using the microfabricated porous membranes

  18. Opalescence of an IgG2 monoclonal antibody solution as it relates to liquid-liquid phase separation.

    Science.gov (United States)

    Mason, Bruce D; Zhang, Le; Remmele, Richard L; Zhang, Jifeng

    2011-11-01

    Opalescence for a monoclonal antibody solution was systematically studied with respect to temperature, protein concentration, ionic strength (using KCl), and pH conditions. Multiple techniques, including measurement of light scattering at 90° and transmission, Tyndall test, and microscopy, were deployed to examine the opalescence behavior. Near the vicinity of the critical point on the liquid-liquid coexistence curve in the temperature-protein concentration phase diagram, the enhanced concentration fluctuations significantly contributed to the critical opalescence evidently by formation of small liquid droplets. Furthermore, our data confirm that away from the critical point, the opalescence behavior is related to the antibody self-association (agglomeration) caused by the attractive antibody-antibody interactions. As expected, at a pH near the pI of the antibody, the solution became less opalescent as the ionic strength increased. However, at a pH below the pI, the opalescence of the solution became stronger, reached a maximum, and then began to drop as the ionic strength further increased. The change in the opalescence correlated well with the trends of protein-protein interactions revealed by the critical temperature from the liquid-liquid phase separation. Copyright © 2011 Wiley-Liss, Inc.

  19. Experimental measurement and prediction of (liquid + liquid + liquid) equilibrium for the system (n-hexadecane + water + triacetin)

    International Nuclear Information System (INIS)

    Revellame, Emmanuel D.; Holmes, William E.; Hernandez, Rafael; French, W. Todd; Forks, Allison; Ashe, Taylor; Estévez, L. Antonio

    2016-01-01

    Highlights: • Phase diagram for the system n-hexadecane + water + triacetin was established at T = 296.15 K and atmospheric pressure (0.1 MPa). • Both NRTL and UNIQUAC activity coefficient model adequately predicts the LLLE of the ternary system. • The phase equilibrium of the system is predominantly dictated by enthalpic contributions to the activity coefficient. - Abstract: The phase diagram for the ternary system containing (n-hexadecane + water + triacetin) was obtained experimentally at T = 296.15 K and ambient pressure. Results show that this system is of Type 3 according to the Treybal classification of ternary system. NRTL and UNIQUAC interaction parameters were calculated from binary phase equilibrium values and were used to predict the (liquid + liquid + liquid) equilibrium (LLLE) region. Results indicated that both NRTL and UNIQUAC could predict the LLLE region of the system with similar precision as indicated by the comparable standard deviations. This indicates that the enthalpic contribution to the activity coefficient is predominant and entropic contributions can be neglected.

  20. RECOVERY OF CARBOXYLIC ACIDS FROM AQUEOUS SOLUTIONS BY LIQUID-LIQUID EXTRACTION WITH A TRIISOOCTYLAMINE DILUENT SYSTEM

    Directory of Open Access Journals (Sweden)

    G. Malmary

    2001-12-01

    Full Text Available Tertiary alkylamines in solution with organic diluents are attractive extractants for the recovery of carboxylic acids from dilute aqueous phases. The aim of this study was to investigate the mechanism for extraction of organic acids from water by a long-chain aliphatic tertiary amine. In order to attain this objective, we studied the liquid-liquid equilibria between the triisooctylamine + 1-octanol + n-heptane system as solvent and an aqueous solution of an individual carboxylic acid such as citric, lactic and malic acids. The experiments showed that the partition coefficient for a particular organic acid depends on the kind of solute, notably when the acid concentration in the aqueous phase is low. A mathematical model, where both chemical association and physical distribution are taken into consideration, is proposed. The model suggests that the various complexes obtained between amine and organic acids contribute to the distribution of the solute between the coexisting phases in equilibrium.

  1. Liquid-liquid contact in vapor explosion. [LMFBR

    Energy Technology Data Exchange (ETDEWEB)

    Segev, A.

    1978-08-01

    The contact of two liquid materials, one of which is at a temperature substantially above the boiling point of the other, can lead to fast energy conversion and a subsequent shock wave. This phenomenon is called a vapor explosion. One method of producing intimate, liquid-liquid contact (which is known to be a necessary condition for vapor explosion) is a shock tube configuration. Such experiments in which water was impacted upon molten aluminum showed that very high pressures, even larger than the thermodynamic critical pressure, could occur. The mechanism by which such sharp pressure pulses are generated is not yet clear. The report describes experiments in which cold liquids (Freon-11, Freon-22, water, or butanol) were impacted upon various hot materials (mineral oil, silicone oil, water, mercury, molten Wood's metal or molten salt mixture).

  2. Separation of rare earths by liquid-liquid extraction

    International Nuclear Information System (INIS)

    Helgorsky, M.; Leveque, M.

    1978-01-01

    The elements of the rare earth family are characterised by very similar chemical properties connected with their special electronic structure. The purification of the rare earths sold by RHONE-POULENC is now done by the liquid-liquid extraction technique. The development of different extracting agents and also counter-current techniques have led to solvent extraction replacing the other fractionation techniques because of its efficiency and low cost. There are usually several possible solutions to the main problem of choosing the extracting agent and its mode of use. The difficulty is to find the most economical one taking account of the thermodynamic and hydrodynamic constraints of the solvent. It is shown how ideas about the separation have changed over the course of the development of the uses of the rare earths, ending finally in an integrated scheme that makes RHONE-POULENC a world leader of manufacturers of separated rare earths [fr

  3. (Liquid + liquid) phase behavior for systems containing (aromatic + TBA + methylcyclohexane)

    International Nuclear Information System (INIS)

    Ghanadzadeh, H.; Ghanadzadeh, A.

    2004-01-01

    The determination region of solubility of TBA (tert-butanol) with representative compounds of the gasoline was investigated experimentally at temperature of 298.2 K. Type 1 (liquid + liquid) phase diagrams were obtained for (methylcyclohexane + TBA + aromatic compounds). These results were correlated simultaneously by the UNIQUAC model. The values of the interaction parameters between each pair of components in the systems were obtained for the UNIQUAC model using the experimental result. The root mean square deviation (RMSD) between the observed and calculated mole percents was 1.88 for (methylcyclohexane + TBA + benzene), 2.45 for (methylcyclohexane + TBA + toluene) and 2.86 for (methylcyclohexane + TBA + ethylbenzene). The mutual solubility of methylcyclohexane and aromatic compounds (e.g., benzene toluene and ethylbenzene (BTE)) was also investigated by the addition of TBA at temperature of 298.2 K

  4. PERFORMANCE OF A PACKED LIQUID-LIQUID EXTRACTION COLUMN

    Directory of Open Access Journals (Sweden)

    İ. Metin HASDEMİR

    1999-03-01

    Full Text Available The influence of feed ratios ((LE/LR on the performance of a packed liquid-liquid extraction column, with a diameter of 5.86 cm and a column height of 132 cm was investigated. The column is made of borosilicate glass and packed with 10 x 10 mm glass Raschig rings. In this study, a ternary system composed of water + propionic acid + trichloroethylene was used. The data used to triangular diagram were obtained experimentally. The overall mass transfer coefficients, the numbers of overall mass transfer units, the heights of mass transfer units, the numbers of theoretical stages and height equivalent to a theoretical stage (H. E. T. S. values were calculated and compared with each other.

  5. Liquid-Liquid Phase Separation in Model Nuclear Waste Glasses: A Solid-State Double-Resonance NMR Study

    Energy Technology Data Exchange (ETDEWEB)

    Martineau, Ch.; Michaelis, V.K.; Kroeker, S. [Univ Manitoba, Dept Chem, Winnipeg, MB R3T 2N2 (Canada); Schuller, S. [CEA Valrho Marcoule, LDMC, SECM, DTCD, DEN, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    Double-resonance nuclear magnetic resonance (NMR) techniques are used in addition to single-resonance NMR experiments to probe the degree of mixing between network-forming cations Si and B, along with the modifier cations Cs{sup +} and Na{sup +} in two molybdenum-bearing model nuclear waste glasses. The double-resonance experiments involving {sup 29}Si in natural abundance are made possible by the implementation of a CPMG pulse-train during the acquisition period of the usual REDOR experiments. For the glass with lower Mo content, the NMR results show a high degree of Si-B mixing, as well as an homogeneous distribution of the cations within the borosilicate network, characteristic of a non-phase-separated glass. For the higher-Mo glass, a decrease of B-Si(Q{sup 4}) mixing is observed, indicating phase separation. {sup 23}Na and {sup 133}Cs NMR results show that although the Cs{sup +} cations, which do not seem to be influenced by the molybdenum content, are spread within the borate network, there is a clustering of the Na{sup +} cations, very likely around the molybdate units. The segregation of a Mo-rich region with Na{sup +} cations appears to shift the bulk borosilicate glass composition toward the metastable liquid liquid immiscibility region and induce additional phase separation. Although no crystallization is observed in the present case, this liquid liquid phase separation is likely to be the first stage of crystallization that can occur at higher Mo loadings or be driven by heat treatment. From this study emerges a consistent picture of the nature and extent of such phase separation phenomena in Mo-bearing glasses, and demonstrates the potential of double-resonance NMR methods for the investigation of phase separation in amorphous materials. (authors)

  6. Stable, metastable, and kinetically trapped amyloid aggregate phases.

    Science.gov (United States)

    Miti, Tatiana; Mulaj, Mentor; Schmit, Jeremy D; Muschol, Martin

    2015-01-12

    Self-assembly of proteins into amyloid fibrils plays a key role in a multitude of human disorders that range from Alzheimer's disease to type II diabetes. Compact oligomeric species, observed early during amyloid formation, are reported as the molecular entities responsible for the toxic effects of amyloid self-assembly. However, the relation between early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. We show that these different structures occupy well-defined regions in a peculiar phase diagram. Lysozyme amyloid oligomers and their curvilinear fibrils only form after they cross a salt and protein concentration-dependent threshold. We also determine a boundary for the onset of amyloid oligomer precipitation. The oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. These experimentally determined boundaries match well with colloidal model predictions that account for salt-modulated charge repulsion. The model also incorporates the metastable and kinetic character of oligomer phases. Similarities and differences of amyloid oligomer assembly to metastable liquid-liquid phase separation of proteins and to surfactant aggregation are discussed.

  7. Liquid-liquid extraction. Choice, calculation and design of devices

    International Nuclear Information System (INIS)

    Leybros, J.

    2005-01-01

    The aim of this work is to study the problematic due to the choice of an equipment, to its size and to its industrial bringing into operation. Besides its efficiency to carry out a mass transfer, the economical interest of an industrial device will be proportional to its specific rate (volume treated by surface unit of the cross section of the extractor). Nevertheless, as it seems to be logic to maximize the three parameters which have an influence on it (transfer coefficient, interfacial surface and transfer potential), there exists no device which can modify separately any of these parameters. In order to satisfy these aims, a great diversity of devices have been put on the market. Indeed, it exists about twenty different industrial devices. This diversity leads the engineer, during the design of a solvent extraction device, to take difficult and subjective decisions without pilot experiment on the considered system. The main problem of an economical and optimized calculation of the liquid-liquid extractors from theoretical data has still not found totally satisfying solutions. Thus, except in some cases where we have empirical correlations, the recourse to prototype experiments is required and the most recent advances have resulted essentially to define more reliable rules for the extrapolation of these experiments for the size of industrial devices. (O.M.)

  8. Mixing-settling apparatus for liquid-liquid extraction

    International Nuclear Information System (INIS)

    Skolokin, L.I.; Leif, V.E.; Sednev, J.M.

    1989-01-01

    A mixing-settling apparatus for liquid-liquid extraction comprises a casing. A first partition is mounted along its longitudinal axis and above an overflow device. The mixing device is connected to a means of feeding at least one of the phases and is shaped as at least one hollow element mounted essentially perpendicularly to the longitudinal axis of the casing. The walls of the hollow element are provided with openings, the outlet cross-sections of which are directed to the first partition. The first partition is provided with a means for regulating the height of the layer of the mixed phases M in the mixing zone, said means being located in the partition at the point most distant from the means for feeding phases L, S in the longitudinal direction. A second transporting device is mounted in the settling zone. It is fixed on to the casing and is located after the overflow device in the direction of movement of the light phase l. (author) 10 figs

  9. Investigation of metastable immiscibility in nuclear-waste-glasses. I-III

    International Nuclear Information System (INIS)

    Egnell, J.; Larsen, J.G.; Moeller, L.; Roed, G.

    1981-12-01

    Metastable liquid-liquid separation in glasses can often cause significant changes in physical and chemical properties of the original homogeneous glass. In some technical borosilicate glasses this phenomenon is used to change the chemical durability of the glass. For potential nuclear-waste-glasses the slow cooling through the temperature range 550 0 C - 700 0 C may lead to such a liquid-liquid phase separation. In order to investigate the susceptibility of phase separation of nuclear-waste-glasses, two KBS model glasses, ABS-39 and ABS-41, were investigated. Two of the subsequent reports are concerned with this problem. The third report also takes into consideration the effects of MoO 3 on the immiscibility gap. The maximum amount of MoO 3 that can be dissolved in ABS-39 and ABS 41 is also determined. (Auth.)

  10. Metastable superconducting alloys

    International Nuclear Information System (INIS)

    Johnson, W.L.

    1978-07-01

    The study of metastable metals and alloys has become one of the principal activities of specialists working in the field of superconducting materials. Metastable crystalline superconductors such as the A15-type materials have been given much attention. Non-crystalline superconductors were first studied over twenty years ago by Buckel and Hilsch using the technique of thin film evaporation on a cryogenic substrate. More recently, melt-quenching, sputtering, and ion implantation techniques have been employed to produce a variety of amorphous superconductors. The present article presents a brief review of experimental results and a survey of current work on these materials. The systematics of superconductivity in non-crystalline metals and alloys are described along with an analysis of the microscopic parameters which underlie the observed trends. The unique properties of these superconductors which arise from the high degree of structural disorder in the amorphous state are emphasized

  11. Metastable dark energy

    Directory of Open Access Journals (Sweden)

    Ricardo G. Landim

    2017-01-01

    Full Text Available We build a model of metastable dark energy, in which the observed vacuum energy is the value of the scalar potential at the false vacuum. The scalar potential is given by a sum of even self-interactions up to order six. The deviation from the Minkowski vacuum is due to a term suppressed by the Planck scale. The decay time of the metastable vacuum can easily accommodate a mean life time compatible with the age of the universe. The metastable dark energy is also embedded into a model with SU(2R symmetry. The dark energy doublet and the dark matter doublet naturally interact with each other. A three-body decay of the dark energy particle into (cold and warm dark matter can be as long as large fraction of the age of the universe, if the mediator is massive enough, the lower bound being at intermediate energy level some orders below the grand unification scale. Such a decay shows a different form of interaction between dark matter and dark energy, and the model opens a new window to investigate the dark sector from the point-of-view of particle physics.

  12. Design and operation of liquid-liquid extractors

    International Nuclear Information System (INIS)

    Wangquian Zhao.

    1996-01-01

    The performance of liquid-liquid extraction columns, with regard to design and operation, has been theoretically and experimentally studied in this work. Under the assumption of plug flow conditions, simple models for both differential and stagewise columns have been developed to establish quantitative relationships between the variables involved for the purpose of the prediction of extraction column performance. Although both models were developed at the beginning of the century, the analytical solutions are available only for the case of linear equilibria. This restriction is relaxed in this work by deriving analytical solutions for the case of curved equilibria. Two reliable models, namely the diffusion and backflow models, which allow for the effect of axial mixing on mass transfer, are available. Under the assumption of constant parameters, the analytical solutions of both models can be obtained. However, these analytical solutions for both models have complex form and are difficult to use in design since iterative solutions are required. To overcome this difficulty, approximate design equations with acceptable accuracy for both models are presented in this work which enable column height or the number of real stages to be obtained directly from specified separation, operating conditions, mass transfer and eddy diffusion coefficients and system properties. The proposed design equations are simple and suitable for manual calculation. They are preferable to previous simplified methods and purely empirical methods. The analytical solutions are restricted to constant parameters and simple linear equilibrium relationship. In order to design columns more accurately and to predict their performance more confidently, the axial variations of parameters and nonlinear relationship must be taken into account. In this work, a mathematical model based on population balance equation is formulated for the prediction of variations of drop size and holdup along the column

  13. Continuous gas/liquid–liquid/liquid flow synthesis of 4-fluoropyrazole derivatives by selective direct fluorination

    Directory of Open Access Journals (Sweden)

    Jessica R. Breen

    2011-08-01

    Full Text Available 4-Fluoropyrazole systems may be prepared by a single, sequential telescoped two-step continuous gas/liquid–liquid/liquid flow process from diketone, fluorine gas and hydrazine starting materials.

  14. Comment on "Spontaneous liquid-liquid phase separation of water"

    Science.gov (United States)

    Limmer, David T.; Chandler, David

    2015-01-01

    Yagasaki et al. [Phys. Rev. E 89, 020301 (2014), 10.1103/PhysRevE.89.020301] present results from a molecular dynamics trajectory illustrating coarsening of ice, which they interpret as evidence of transient coexistence between two distinct supercooled phases of liquid water. We point out that neither two distinct liquids nor criticality are demonstrated in this simulation study. Instead, the illustrated trajectory is consistent with coarsening behaviors analyzed and predicted in earlier work by others.

  15. Comment on "Spontaneous liquid-liquid phase separation of water".

    Science.gov (United States)

    Limmer, David T; Chandler, David

    2015-01-01

    Yagasaki et al. [Phys. Rev. E 89, 020301 (2014)] present results from a molecular dynamics trajectory illustrating coarsening of ice, which they interpret as evidence of transient coexistence between two distinct supercooled phases of liquid water. We point out that neither two distinct liquids nor criticality are demonstrated in this simulation study. Instead, the illustrated trajectory is consistent with coarsening behaviors analyzed and predicted in earlier work by others.

  16. Liquid-Liquid Extraction in Systems Containing Butanol and Ionic Liquids – A Review

    OpenAIRE

    Kubiczek Artur; Kamiński Władysław

    2017-01-01

    Room-temperature ionic liquids (RTILs) are a moderately new class of liquid substances that are characterized by a great variety of possible anion-cation combinations giving each of them different properties. For this reason, they have been termed as designer solvents and, as such, they are particularly promising for liquid-liquid extraction, which has been quite intensely studied over the last decade. This paper concentrates on the recent liquid-liquid extraction studies involving ionic liqu...

  17. Novel routes to metal nanoparticles : electrodeposition and reactions at liquid-liquid interfaces

    OpenAIRE

    Johans, Christoffer

    2003-01-01

    This thesis considers the nucleation and growth, synthesis, and catalytic application of metallic nanoparticles at liquid|liquid interfaces. It comprises five publications, a previously unpublished synthesis of polymer coated palladium nanoparticles, and an introduction to the relevant literature. Three publications are concerned with electrodeposition of metal nanoparticles at liquid|liquid interfaces. One publication and the results presented here consider the synthesis of silver and pallad...

  18. Membrane assisted liquid-liquid extraction of cerium

    International Nuclear Information System (INIS)

    Soldenhoff, K.M.

    2000-02-01

    Membrane assisted liquid-liquid extraction of cerium was investigated, with emphasis placed on the study of the reaction chemistry and the kinetics of non-dispersive solvent extraction and stripping with microporous membranes. A bulk liquid membrane process was developed for the purification of cerium(IV) from sulfate solutions containing other rare earth elements. The cerium process was studied in both a flat sheet contained liquid membrane configuration and with hollow fibre contactors. Di-2-ethylhexyl phosphoric acid (DEHPA) was identified as a suitable extractant for cerium(IV) from sulfuric acid solution, with due consideration of factors such as extraction ability, resistance to degradation, solvent selectivity and potential for sulfate transfer into a strip solution. A detailed study of the extraction of cerium(IV) with DEHPA defined the extraction reaction chemistry. The Ce/DEHPA/sulfate system was also investigated with a flat sheet bulk liquid membrane configuration, using both sulfuric and hydrochloric acid as receiver solutions. These tests identified that hydrophobic membranes provide better mass transfer for extraction and hydrophilic membranes are better for stripping. The presence of an impurity, mono 2-ethylhexyl phosphoric acid (MEHPA), was found to have a dramatic accelerating effect on the rate of the chemical extraction reaction. This was attributed to its higher interfacial activity and population compared to DEHPA, and the fact that MEHPA was also found to be an active carrier for cerium(IV). The mass transfer rate of membrane assisted extraction and stripping of cerium, using hydrophobic and hydrophilic microporous membranes, respectively, was investigated using a modified Lewis-type cell. It was quantitatively demonstrated that the extraction process was mainly controlled by membrane diffusion and the stripping process was controlled by the chemical reaction rate, with membrane diffusion becoming important at low distribution coefficients

  19. Topodynamics of metastable brains

    Science.gov (United States)

    Tozzi, Arturo; Peters, James F.; Fingelkurts, Andrew A.; Fingelkurts, Alexander A.; Marijuán, Pedro C.

    2017-07-01

    The brain displays both the anatomical features of a vast amount of interconnected topological mappings as well as the functional features of a nonlinear, metastable system at the edge of chaos, equipped with a phase space where mental random walks tend towards lower energetic basins. Nevertheless, with the exception of some advanced neuro-anatomic descriptions and present-day connectomic research, very few studies have been addressing the topological path of a brain embedded or embodied in its external and internal environment. Herein, by using new formal tools derived from algebraic topology, we provide an account of the metastable brain, based on the neuro-scientific model of Operational Architectonics of brain-mind functioning. We introduce a ;topodynamic; description that shows how the relationships among the countless intertwined spatio-temporal levels of brain functioning can be assessed in terms of projections and mappings that take place on abstract structures, equipped with different dimensions, curvatures and energetic constraints. Such a topodynamical approach, apart from providing a biologically plausible model of brain function that can be operationalized, is also able to tackle the issue of a long-standing dichotomy: it throws indeed a bridge between the subjective, immediate datum of the naïve complex of sensations and mentations and the objective, quantitative, data extracted from experimental neuro-scientific procedures. Importantly, it opens the door to a series of new predictions and future directions of advancement for neuroscientific research.

  20. Desensitization of metastable intermolecular composites

    Science.gov (United States)

    Busse, James R [South Fork, CO; Dye, Robert C [Los Alamos, NM; Foley, Timothy J [Los Alamos, NM; Higa, Kelvin T [Ridgecrest, CA; Jorgensen, Betty S [Jemez Springs, NM; Sanders, Victor E [White Rock, NM; Son, Steven F [Los Alamos, NM

    2011-04-26

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  1. Active liquid/liquid interfaces: contributions of non linear optics and tensiometry

    International Nuclear Information System (INIS)

    Gassin, P.M.

    2013-01-01

    Liquid-liquid extraction processes are widely used in the industrial fields of selective separation. Despite its numerous applications, the microscopic mechanisms which occur during a liquid-liquid extraction processes are really unknown specially at the liquid/liquid interface. Thus, this work deals on the understanding of the phenomena which drive the mass transfer across a liquid/liquid interface. Two experimental techniques were used in this work: dynamic interfacial tension measurement and non-linear optical experiments. Along with the use of this experimental approach, a numerical model describing the mass transfer dynamic has been developed. This model works under the assumption that both diffusion and a chemical step describing adsorption and desorption processes contribute to the global transfer kinetics. Model systems of surfactant molecules, chromophore molecules and complexing molecule were investigated at liquid/liquid and air/liquid interface. Interfacial phenomena like adsorption, surface aggregation and ion complexing were studied. Finally, the methodology developed in this work was applied to studied an extractant molecule with potential industrial application. (author) [fr

  2. (Liquid + liquid) equilibria for (water + 1-propanol or acetone + β-citronellol) at different temperatures

    International Nuclear Information System (INIS)

    Li, Hengde; Han, Yongtao; Huang, Cheng; Yang, Chufen

    2015-01-01

    Graphical abstract: (Liquid + liquid) equilibrium data for systems composed of β-citronellol and aqueous 1-propanol or acetone are presented. Distribution ratios of 1-propanol and acetone in the mixtures are examined. The effect of the temperature on the ternary (liquid + liquid) equilibria is evaluated and discussed. - Highlights: • Ternary (liquid + liquid) equilibria containing β-citronellol are presented. • Distribution ratios of 1-propanol and acetone in the mixtures are examined. • The effect on the temperature of the systems is evaluated and discussed. - Abstract: On this paper, experimental (liquid + liquid) equilibrium (LLE) results are presented for systems composed of β-citronellol and aqueous 1-propanol or acetone. To evaluate the phase separation properties of β-citronellol in aqueous mixtures, LLE values for the ternary systems (water + 1-propanol + β-citronellol) and (water + acetone + β-citronellol) were determined with a tie-line method at T = (283.15, 298.15, and 313.15 ± 0.02) K and atmospheric pressure. The reliability of the experimental tie-lines was verified by the Hand and Bachman equations. Ternary phase diagrams, distribution ratios of 1-propanol and acetone in the mixtures are shown. The effect of the temperature on the ternary (liquid + liquid) equilibria was examined and discussed. The experimental LLE values were satisfactorily correlated by extended UNIQUAC and modified UNIQUAC models

  3. Photodetachment of metastable He-

    International Nuclear Information System (INIS)

    Thompson, J.S.; Dellwo, J.; Compton, R.N.

    1990-01-01

    A crossed-beams apparatus has been used to measure angular distributions and cross sections for photoelectron detachment from metastable He - . Energy- and angle-resolved electron spectroscopy was used to investigate the spectral dependences of the angular distribution of the photoelectrons. The angular distributions along with photoelectron yield measurements were used to determine the cross sections for photodetachment of He - (2 4 P) via the energy resolved He(2 3 P) and He(2 3 S) exit channels. The precision of the cross section measurements was enhanced by exploiting the kinematic effects associated with detachment from a fast beam source. Calculated cross sections for the photodetachment of H - were used to establish an absolute scale for the He - cross section measurements

  4. On Metastability in FPU

    CERN Document Server

    Bambusi, D

    2005-01-01

    We present an analytical study of the Fermi--Pasta--Ulam (FPU) $\\alpha$--model with periodic boundary conditions. We analyze the dynamics corresponding to initial data with some low frequency Fourier modes excited. We show that, correspondignly, a pair of KdV equations constitute the resonant normal form of the system. We also use such a normal form in order to prove the existence of a metastability phenomenon. More precisely, we show that the time average of the modal energy spectrum rapidly attains a well defined distribution corresponding to a packet of low frequencies modes. Subsequently, the distribution remains unchanged up to the time scales of validity of our approximation. The phenomenon is controlled by the specific energy.

  5. Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

    Science.gov (United States)

    Xu, Weinan; Ledin, Petr A; Shevchenko, Valery V; Tsukruk, Vladimir V

    2015-06-17

    Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

  6. On the prediction of spray angle of liquid-liquid pintle injectors

    Science.gov (United States)

    Cheng, Peng; Li, Qinglian; Xu, Shun; Kang, Zhongtao

    2017-09-01

    The pintle injector is famous for its capability of deep throttling and low cost. However, the pintle injector has been seldom investigated. To get a good prediction of the spray angle of liquid-liquid pintle injectors, theoretical analysis, numerical simulations and experiments were conducted. Under the hypothesis of incompressible and inviscid flow, a spray angle formula was deduced from the continuity and momentum equations based on a control volume analysis. The formula was then validated by numerical and experimental data. The results indicates that both geometric and injection parameters affect the total momentum ratio (TMR) and then influence the spray angle formed by liquid-liquid pintle injectors. TMR is the pivotal non-dimensional number that dominates the spray angle. Compared with gas-gas pintle injectors, spray angle formed by liquid-liquid injectors is larger, which benefits from the local high pressure zone near the pintle wall caused by the impingement of radial and axial sheets.

  7. Pressure Dependence of the Liquid-Liquid Phase Transition of Nanopore Water Doped Slightly with Hydroxylamine, and a Phase Behavior Predicted for Pure Water

    Science.gov (United States)

    Nagoe, Atsushi; Iwaki, Shinji; Oguni, Masaharu; Tôzaki, Ken-ichi

    2014-09-01

    Phase transition behaviors of confined pure water and confined water doped with a small amount of hydroxylamine (HA) with a mole fraction of xHA = 0.03 were examined by high-pressure differential thermal analyses at 0.1, 50, 100, and 150 MPa; the average diameters of silica pores used were 2.0 and 2.5 nm. A liquid-liquid phase transition (LLPT) of the confined HA-doped water was clearly observed and its pressurization effect could be evaluated, unlike in the experiments on undoped water. It was found that pressurization causes the transition temperature (Ttrs) to linearly decrease, indicating that the low-temperature phase has a lower density than the high-temperature one. Transition enthalpy (ΔtrsH) decreased steeply with increasing pressure. Considering the linear decrease in Ttrs with increasing pressure, the steep decrease in ΔtrsH indicates that the LLPT effect of the HA-doped water attenuates with pressure. We present a new scenario of the phase behavior concerning the LLPT of pure water based on the analogy from the behavior of slightly HA-doped water, where a liquid-liquid critical point (LLCP) and a coexistence line are located in a negative-pressure regime but not in a positive-pressure one. It is reasonably understood that doping a small amount of HA into water results in negative chemical pressurization and causes the LLPT to occur even at ambient pressure.

  8. One-step displacement dispersive liquid-liquid microextraction coupled with graphite furnace atomic absorption spectrometry for the selective determination of methylmercury in environmental samples.

    Science.gov (United States)

    Liang, Pei; Kang, Caiyan; Mo, Yajun

    2016-01-01

    A novel method for the selective determination of methylmercury (MeHg) was developed by one-step displacement dispersive liquid-liquid microextraction (D-DLLME) coupled with graphite furnace atomic absorption spectrometry. In the proposed method, Cu(II) reacted with diethyldithiocarbamate (DDTC) to form Cu-DDTC complex, which was used as the chelating agent instead of DDTC for the dispersive liquid-liquid microextraction (DLLME) of MeHg. Because the stability of MeHg-DDTC is higher than that of Cu-DDTC, MeHg can displace Cu from the Cu-DDTC complex and be preconcentrated in a single DLLME procedure. MeHg could be extracted into the extraction solvent phase at pH 6 while Hg(II) remained in the sample solution. Potential interference from co-existing metal ions with lower DDTC complex stability was largely eliminated without the need of any masking reagent. Under the optimal conditions, the limit of detection of this method was 13.6ngL(-1) (as Hg), and an enhancement factor of 81 was achieved with a sample volume of 5.0mL. The proposed method was successfully applied for the determination of trace MeHg in some environmental samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Determination of lead in environmental waters with dispersive liquid-liquid microextraction prior to atomic fluorescence spectrometry

    International Nuclear Information System (INIS)

    Zhou, Qingxiang; Zhao, Na; Xie, Guohong

    2011-01-01

    This paper established a new, rapid and sensitive method for the determination of lead in water samples preconcentrated by dispersive liquid-liquid microextraction (DLLME) prior to atomic fluorescence spectrometry. Dithizone was used as the chelating agent. In the DLLME procedure, lead formed lead-dithizone complex and migrated into the carbon tetrachloride micro-droplets. Important factors that would affect the extraction efficiency had been investigated including the kind and volume of extraction solvent and dispersive solvent, sample pH, the amount of chelating agent, extraction time and centrifugation time. The results showed that the coexisting ions containing in water samples had no obvious negative effect on the determination of lead. The experimental results indicated that the proposed method had a good linear range of 0.01-100 ng mL -1 (r 2 = 0.9990). The precision was 2.12% (RSD, n = 7) and the detection limit was 0.95 ng L -1 . Proposed method was validated with four real environmental samples and the results indicated that the proposed method was excellent for the future use and satisfied spiked recoveries were in the range of 92.9-97.4%.

  10. (Liquid + liquid), (solid + liquid), and (solid + liquid + liquid) equilibria of systems containing cyclic ether (tetrahydrofuran or 1,3-dioxolane), water, and a biological buffer MOPS

    International Nuclear Information System (INIS)

    Altway, Saidah; Taha, Mohamed; Lee, Ming-Jer

    2015-01-01

    Graphical abstract: - Highlights: • MOPS buffer induced liquid phase splitting for mixtures of water with THF or 1,3-dioxolane. • Phase boundaries of LLE, SLE, and SLLE were determined experimentally. • Tie-lines at LLE and at SLLE were also measured. • Phase diagrams of MOPS + water + THF or 1,3-dioxolane are prepared. • LLE tie-line data are correlated satisfactorily with the NRTL model. - Abstract: Two liquid phases were formed as the addition of a certain amount of biological buffer 3-(N-morpholino)propane sulfonic acid (MOPS) in the aqueous solutions of tetrahydrofuran (THF) or 1,3-dioxolane. To evaluate the feasibility of recovering the cyclic ethers from their aqueous solutions with the aid of MOPS, we determined experimentally the phase diagrams of the ternary systems of {cyclic ether (THF or 1,3-dioxolane) + water + MOPS} at T = 298.15 K under atmospheric pressure. In this study, the solubility data of MOPS in water and in the mixed solvents of water/cyclic ethers were obtained from the results of a series of density measurements, while the (liquid + liquid) and the (solid + liquid + liquid) phase boundaries were determined by visually inspection. Additionally, the tie-line results for (liquid + liquid) equilibrium (LLE) and for (solid + liquid + liquid) equilibrium (SLLE) were measured using an analytical method. The reliability of the experimental LLE tie-line results data was validated by using the Othmer–Tobias correlation. These LLE tie-line values were correlated well with the NRTL model. The phase diagrams obtained from this study reveal that MOPS is a feasible green auxiliary agent to recover the cyclic ethers from their aqueous solutions, especially for 1,3-dioxolane

  11. Metastable gravity on classical defects

    International Nuclear Information System (INIS)

    Ringeval, Christophe; Rombouts, Jan-Willem

    2005-01-01

    We discuss the realization of metastable gravity on classical defects in infinite-volume extra dimensions. In dilatonic Einstein gravity, it is found that the existence of metastable gravity on the defect core requires violation of the dominant energy condition for codimension N c =2 defects. This is illustrated with a detailed analysis of a six-dimensional hyperstring minimally coupled to dilaton gravity. We present the general conditions under which a codimension N c >2 defect admits metastable modes, and find that they differ from lower codimensional models in that, under certain conditions, they do not require violation of energy conditions to support quasilocalized gravity

  12. Liquid-liquid phase transition and glass transition in a monoatomic model system.

    Science.gov (United States)

    Xu, Limei; Buldyrev, Sergey V; Giovambattista, Nicolas; Stanley, H Eugene

    2010-01-01

    We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

  13. An inkjet-printed microfluidic device for liquid-liquid extraction.

    Science.gov (United States)

    Watanabe, Masashi

    2011-04-07

    A microfluidic device for liquid-liquid extraction was quickly produced using an office inkjet printer. An advantage of this method is that normal end users, who are not familiar with microfabrication, can produce their original microfluidic devices by themselves. In this method, the printer draws a line on a hydrophobic and oil repellent surface using hydrophilic ink. This line directs a fluid, such as water or xylene, to form a microchannel along the printed line. Using such channels, liquid-liquid extraction was successfully performed under concurrent and countercurrent flow conditions. © The Royal Society of Chemistry 2011

  14. Detection based on rainbow refractometry of droplet sphericity in liquid-liquid systems.

    Science.gov (United States)

    Lohner, H; Lehmann, P; Bauckhage, K

    1999-03-01

    The shape of droplets in liquid-liquid systems influences their mass and momentum transfer processes. The deviation from sphericity of rising droplets in liquid-liquid systems was investigated for different droplet sizes. Rainbow refractometry permits one to test, in this case, whether the use of laser-optical particle sizing will be correct or faulty. Since the assumption of spherical particle geometry is a general basis of laser-optical particle-sizing techniques such as rainbow refractometry or phase Doppler anemometry, deviation from the spherical shape results in a measuring error. A sphericity check based on rainbow refractometry is introduced.

  15. Experimental (solid + liquid) or (liquid + liquid) phase equilibria of (amine + nitrile) binary mixtures

    International Nuclear Information System (INIS)

    Domanska, Urszula; Marciniak, Malgorzata

    2007-01-01

    (Solid + liquid) phase diagrams have been determined for (hexylamine, or octylamine, or 1,3-diaminopropane + acetonitrile) mixtures. Simple eutectic systems have been observed in these mixtures. (Liquid + liquid) phase diagrams have been determined for (octylamine, or decylamine + propanenitrile, or + butanenitrile) mixtures. Mixtures with propanenitrile and butanenitrile show immiscibility in the liquid phase with an upper critical solution temperature, UCST. (Solid + liquid) phase diagrams have been correlated using NRTL, NRTL 1, Wilson and UNIQUAC equations. (Liquid + liquid) phase diagrams have been correlated using NRTL equation

  16. Friction and diffusion of a nano-colloidal disk in a two-dimensional solvent with a liquid-liquid transition.

    Science.gov (United States)

    Torres-Carbajal, Alexis; Castañeda-Priego, Ramón

    2018-03-07

    We report on the friction and diffusion of a single mobile nano-colloidal disk, whose size and mass are one and two orders of magnitude, respectively, greater than the molecules of the host solvent; all particles are restricted to move in a two-dimensional space. Using molecular dynamics simulations, the variation of the transport coefficients as a function of the thermodynamic state of the supporting fluid, in particular, around those states in the neighbourhood of the liquid-liquid phase coexistence, is investigated. The diffusion coefficient is determined through the fit of the mean-square displacement at long times and with the Green-Kubo relationship for the velocity autocorrelation function, whereas the friction coefficient is computed from the correlation of the fluctuating force. From the determination of the transport properties, the applicability of the Stokes-Einstein relation in two dimensions around the second critical point is discussed.

  17. Comparison of dispersive liquid-liquid microextraction and hollow fiber liquid-liquid-liquid microextraction for the determination of fentanyl, alfentanil, and sufentanil in water and biological fluids by high-performance liquid chromatography.

    Science.gov (United States)

    Saraji, Mohammad; Khalili Boroujeni, Malihe; Hajialiakbari Bidgoli, Ali Akbar

    2011-06-01

    Dispersive liquid-liquid microextraction (DLLME) and hollow fiber liquid-liquid-liquid microextraction (HF-LLLME) combined with HPLC-DAD have been applied for the determination of three narcotic drugs (alfentanil, fentanyl, and sufentanil) in biological samples (human plasma and urine). Different DLLME parameters influencing the extraction efficiency such as type and volume of the extraction solvent and the disperser solvent, concentration of NaOH, and salt addition were investigated. In the HF-LLLME, the effects of important parameters including organic solvent type, concentration of NaOH as donor solution, concentration of H(2)SO(4) as acceptor phase, salt addition, stirring rate, temperature, and extraction time were investigated and optimized. The results showed that both extraction methods exhibited good linearity, precision, enrichment factor, and detection limit. Under optimal condition, the limits of detection ranged from 0.4 to 1.9 μg/L and from 1.1 to 2.3 μg/L for DLLME and HF-LLLME, respectively. For DLLME, the intra- and inter-day precisions were 1.7-6.4% and 14.2-15.9%, respectively; and for HF-LLLME were 0.7-5.2% and 3.3-10.1%, respectively. The enrichment factors were from 275 to 325 and 190 to 237 for DLLME and HF-LLLME, respectively. The applicability of the proposed methods was investigated by analyzing biological samples. For analysis of human plasma and urine samples, HF-LLLME showed higher precision, more effective sample clean-up, higher extraction efficiency, lower organic solvent consumption than DLLME.

  18. Determination of Niacinamide in Lotions and Creams Using Liquid-Liquid Extraction and High-Performance Liquid Chromatography

    Science.gov (United States)

    Usher, Karyn M.; Simmons, Carolyn R.; Keating, Daniel W.; Rossi, Henry F., III

    2015-01-01

    Chemical separations are an important part of an undergraduate chemistry curriculum. Sophomore students often get experience with liquid-liquid extraction in organic chemistry classes, but liquid-liquid extraction is not as often introduced as a quantitative sample preparation method in honors general chemistry or quantitative analysis classes.…

  19. Elastic properties of surfactant monolayers at liquid-liquid interfaces: A molecular dynamics study

    DEFF Research Database (Denmark)

    Laradji, Mohamed; Mouritsen, Ole G.

    2000-01-01

    Using a simple molecular model based on the Lennard-Jones potential, we systematically study the elastic properties of liquid-liquid interfaces containing surfactant molecules by means of extensive and large-scale molecular dynamics simulations. The main elastic constants of the interface, corres...

  20. Luminescence screening of enrofloxacin and ciprofloxacin residues in swine liver after dispersive liquid - liquid microextraction cleanup

    Science.gov (United States)

    A rapid luminescence method was developed to screen residues of enrofloxacin (ENRO) and its metabolite, ciprofloxacin (CIPRO), in swine liver. Target analytes were extracted in acetonitrile-2.5% trifluoroacetic acid-NaCl, cleaned up by dispersive liquid-liquid microextraction (DLLME), and finally de...

  1. Purification process for aqueous solutions of rare earths by liquid-liquid extraction

    International Nuclear Information System (INIS)

    Rollat, A.; Sabot, J.L.; Burgard, M.; Delloye, T.

    1986-01-01

    Alkaline earth metals are removed by liquid-liquid extraction between on aqueous nitric phase of impure rare earth compounds and an organic phase of polyether (crown ether). This process is particularly suited to removal of Ca, Ba and Ra contained in nitric solutions of rare earths [fr

  2. Indication of liquid-liquid phase transition in CuZr-based melts

    DEFF Research Database (Denmark)

    Zhou, C.; Hu, L.N.; Sun, Q.J.

    2013-01-01

    We study the dynamic behavior of CuZr-based melts well above the liquidus temperature. The results show a discontinuous change in viscosity during cooling, which is attributed to an underlying liquid-liquid phase transition (LLPT) in these melts. The LLPT is further verified by thermodynamic...

  3. Ionizable polyethers as specific metal ion carriers in liquid-liquid extraction and liquid membrane separations

    International Nuclear Information System (INIS)

    Walkowiak, W.; Charewicz, W.A.; Bartsch, R.A.; Ndip, G.M.

    1988-01-01

    Consideration is given to results of investigations into competitive extraction and penetration through a liquid membrane of alkali and alkaline earth cations from aqueous solutions by a series of lipophilic and ionizable acyclic polyethers of various molecular structure. It is shown that specificity and selectiviy of cation carriers in liquid-liquid extraction and liquid membrane separation depend on molecular structure of acyclic polyethers

  4. CO2 Capture with Liquid-Liquid Phase Change Solvents: A Thermodynamic Study

    DEFF Research Database (Denmark)

    Waseem Arshad, Muhammad; Fosbøl, Philip Loldrup; von Solms, Nicolas

    2017-01-01

    by the quaternary H2O-DEEAMAPA-CO2 system which gives liquid-liquid phase split when reacted with carbon dioxide. A total of 94 model parameters and 6 thermodynamic properties were fitted to approximately 1500 equilibrium and thermal experimental data consisting of pureamine vapor pressure (Pvap), vapor...

  5. Noise and ac impedance analysis of ion transfer kinetics at the micro liquid/liquid interface

    Czech Academy of Sciences Publication Activity Database

    Josypčuk, Oksana; Holub, Karel; Mareček, Vladimír

    2015-01-01

    Roč. 56, JUL 2015 (2015), s. 43-45 ISSN 1388-2481 R&D Projects: GA ČR GA13-04630S Institutional support: RVO:61388955 Keywords : noise analysis * liquid/liquid interface * ion transfer kinetics Subject RIV: CG - Electrochemistry Impact factor: 4.569, year: 2015

  6. Heat transfer on liquid-liquid interface of molten-metal and water

    International Nuclear Information System (INIS)

    Tanaka, T.; Saito, Yasushi; Mishima, Kaichiro

    2001-01-01

    Molten-core pool had been formed in the lower-head of TMI-2 pressure vessel at the severe accident. The lower head, however, didn't receive any damage by reactor core cooling. Heat transfer at outside of the lower head and boiling heat transfer at liquid-liquid interface of molten-metal and water, however, are important for initial cooling process of the molten-core pool. The heat transfer experiments for the liquid-liquid interface of molten-metal and water are carried out over the range of natural convection to film boiling region. Phenomenon on the heat transfer experiments are visualized by using of high speed video camera. Wood's metal and U-alloy 78 are used as molten-metal. The test section of the experiments consists of a copper block with heater, wood's metal, and water. Three thermocouple probes are used for temperature measurement of water side and the molten-metal side. Stability of the liquid-liquid interface is depended on the wetness of container wall for molten metal and the temperature distribution of the interface. Entrainment phenomena of molten-metal occurs by a fluctuation of the interface after boiling on the container wall surface. The boiling curves obtained from the liquid-liquid interface experiments are agree with the nucleate boiling and the film boiling correlations of solid-liquid system. (Suetake, M.)

  7. Hybrid Multiphase CFD Solver for Coupled Dispersed/Segregated Flows in Liquid-Liquid Extraction

    Directory of Open Access Journals (Sweden)

    Kent E. Wardle

    2013-01-01

    Full Text Available The flows in stage-wise liquid-liquid extraction devices include both phase segregated and dispersed flow regimes. As a additional layer of complexity, for extraction equipment such as the annular centrifugal contactor, free-surface flows also play a critical role in both the mixing and separation regions of the device and cannot be neglected. Traditionally, computional fluid dynamics (CFD of multiphase systems is regime dependent—different methods are used for segregated and dispersed flows. A hybrid multiphase method based on the combination of an Eulerian multifluid solution framework (per-phase momentum equations and sharp interface capturing using Volume of Fluid (VOF on selected phase pairs has been developed using the open-source CFD toolkit OpenFOAM. Demonstration of the solver capability is presented through various examples relevant to liquid-liquid extraction device flows including three-phase, liquid-liquid-air simulations in which a sharp interface is maintained between each liquid and air, but dispersed phase modeling is used for the liquid-liquid interactions.

  8. Liquid-Liquid Extraction in Systems Containing Butanol and Ionic Liquids – A Review

    Directory of Open Access Journals (Sweden)

    Kubiczek Artur

    2017-03-01

    Full Text Available Room-temperature ionic liquids (RTILs are a moderately new class of liquid substances that are characterized by a great variety of possible anion-cation combinations giving each of them different properties. For this reason, they have been termed as designer solvents and, as such, they are particularly promising for liquid-liquid extraction, which has been quite intensely studied over the last decade. This paper concentrates on the recent liquid-liquid extraction studies involving ionic liquids, yet focusing strictly on the separation of n-butanol from model aqueous solutions. Such research is undertaken mainly with the intention of facilitating biological butanol production, which is usually carried out through the ABE fermentation process. So far, various sorts of RTILs have been tested for this purpose while mostly ternary liquid-liquid systems have been investigated. The industrial design of liquid-liquid extraction requires prior knowledge of the state of thermodynamic equilibrium and its relation to the process parameters. Such knowledge can be obtained by performing a series of extraction experiments and employing a certain mathematical model to approximate the equilibrium. There are at least a few models available but this paper concentrates primarily on the NRTL equation, which has proven to be one of the most accurate tools for correlating experimental equilibrium data. Thus, all the presented studies have been selected based on the accepted modeling method. The reader is also shown how the NRTL equation can be used to model liquid-liquid systems containing more than three components as it has been the authors’ recent area of expertise.

  9. The liquid–liquid coexistence curves of {benzonitrile + n-pentadecane} and {benzonitrile + n-heptadecane} in the critical region

    International Nuclear Information System (INIS)

    Chen, Zhiyun; Bai, Yongliang; Yin, Tianxiang; An, Xueqin; Shen, Weiguo

    2012-01-01

    Highlights: ► Coexistence curves of (benzonitrile + n-pentadecane) and (benzonitrile + n-heptadecane) were measured. ► The values of the critical exponent β are consistent with that predicted by the 3D-Ising model. ► The coexistence curves are well described by the critical crossover model. ► The asymmetry of the diameters of the coexistence curves were discussed by the complete scaling theory. - Abstract: Liquid + liquid coexistence curves for the binary solutions of {benzonitrile + n-pentadecane} and {benzonitrile + n-heptadecane} have been measured in the critical region. The critical exponent β and the critical amplitudes have been deduced and the former is consistent with the theoretic prediction. It was found that the coexistence curves may be well described by the crossover model proposed by Gutkowski et al. The asymmetries of the diameters of the coexistence curves were also discussed in the frame of the complete scaling theory.

  10. Determination of desipramine in biological samples using liquid-liquid-liquid microextraction combined with in-syringe derivatization, gas chromatography, and nitrogen/phosphorus detection.

    Science.gov (United States)

    Saraji, Mohammad; Mehrafza, Narges; Bidgoli, Ali Akbar Hajialiakbari; Jafari, Mohammad Taghi

    2012-10-01

    A method was established for the determination of desipramine in biological samples using liquid-liquid-liquid microextraction followed by in-syringe derivatization and gas chromatography-nitrogen phosphorus detection. The extraction method was based on the use of two immiscible organic solvents. n-Dodecane was impregnated in the pores of the hollow fiber and methanol was placed inside the lumen of the fiber as the acceptor phase. Acetic anhydride was used as the reagent for the derivatization of the analyte inside the syringe barrel. Parameters that affect the extraction efficiency (composition of donor and acceptor phase, ionic strength, sample temperature, and extraction time) as well as derivatization efficiency (amount of acetic anhydride and reaction time and temperature) were investigated. The limit of detection was 0.02 μg/L with intra and interday RSDs of 2.6 and 7.7%, respectively. The linearity of the method was in the range of 0.2-20 μg/L (r(2) = 0.9986). The method was successfully applied to determine desipramine in human plasma and urine. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for Jatropha curcas biodiesel

    International Nuclear Information System (INIS)

    Silva, Juliana R.F.; Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Lanza, Marcelo; Priamo, Wagner L.; Vladimir Oliveira, J.

    2013-01-01

    Highlights: ► (Liquid + liquid) equilibrium data for multicomponent Jatropha curcas FAME and FAEE. ► Tie-lines, solubility curves (binodal curves) with low deviations from mass balance. ► Experimental data correlated with the UNIQUAC model. -- Abstract: Reported in this study are (liquid + liquid) equilibrium data for binary, ternary, and quaternary systems formed by fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) of Jatropha curcas oil, water, glycerol, methanol, and ethanol at temperatures of (303.15, 318.15, and 333.15) K. In general, all the systems investigated resulted in good agreement between phase compositions of crunodes of tie-lines, solubility curves (binodal curves) and overall compositions, hence indicating low deviations from mass balance. Experimental results were correlated with the UNIQUAC model, showing low deviations among experimental and calculated values

  12. Liquid-Liquid Phase Transition and Glass Transition in a Monoatomic Model System

    Directory of Open Access Journals (Sweden)

    Nicolas Giovambattista

    2010-12-01

    Full Text Available We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

  13. Ternary (liquid + liquid) equilibria of {trifluorotris(perfluoroethyl)phosphate based ionic liquids + thiophene + heptane}

    International Nuclear Information System (INIS)

    Marciniak, Andrzej; Królikowski, Marek

    2012-01-01

    Highlights: ► Ternary (liquid + liquid) equilibria for 3 ionic liquid + thiophene + heptane systems. ► The influence of ionic liquid structure on phase diagrams is discussed. ► High selectivity for separation of heptane/thiophene is observed. - Abstract: Ternary (liquid + liquid) equilibria for three systems containing ionic liquids {(4-(2-methoxyethyl)-4-methylmorpholinium trifluorotris(perfluoroethyl)phosphate, 1-(2-methoxyethyl)-1-methylpiperidinium trifluorotris(perfluoroethyl)phosphate, 1-(2-methoxyethyl)-1-methylpyrrolidinium trifluorotris(perfluoroethyl)phosphate) + thiophene + heptane} have been determined at T = 298.15 K. All systems showed high solubility of thiophene in the ionic liquid and low solubility of heptane. The solute distribution coefficient and the selectivity were calculated for all systems. High values of selectivity were obtained. The experimental results have been correlated using NRTL model. The influence of ionic liquid structure on phase equilibria is discussed.

  14. Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for castor oil biodiesel

    International Nuclear Information System (INIS)

    Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Lanza, Marcelo; Priamo, Wagner L.; Oliveira, J. Vladimir

    2013-01-01

    Highlights: ► (Liquid + liquid) equilibrium data for multicomponent castor oil FAME and FAEE castor oil. ► Tie-lines and solubility curves (binodal) by cloud-point method for FAME and FAEE systems. ► Experimental data correlated using the UNIQUAC model. -- Abstract: This work reports new liquid–liquid solubility values (binodal curves) as well as (liquid + liquid) equilibrium data for, ternary and quaternary systems containing fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) from castor oil, water, glycerol, methanol and anhydrous ethanol at T = (303.15, 318.15, and 333.15) K. Solubility curves (binodal) were also obtained by the cloud-point method for binary systems containing FAME, FAEE, water, or glycerol. All results obtained can be considered of good quality. The experimental values were correlated using the UNIQUAC model, whose results presented good performance and satisfactory fitting of equilibrium values

  15. Theoretical background and the flow fields in downhole liquid-liquid hydrocyclone (LLHC

    Directory of Open Access Journals (Sweden)

    Osei Harrison

    2014-07-01

    Full Text Available Hydrocyclone system for downhole oil-water separation provides an effective technique of enhancing the economic viability of higher water-cut wells while at the same time reducing the risk of environmental pollution. This paper describes the hydrodynamics of the liquid-liquid hydrocyclones and the flow fields within it are paramount for achieving successful separation process. Some of the important hydrodynamic flow phenomenon within the liquid-liquid hydrocyclone and how they influence the separation efficiency of water/oil was analyzed through analytical solution. The properties of the liquids were based on Bayan offshore field measured properties. The results indicated that there are two swirling zones separated by stagnant flow field. The inner is the light liquid zone, while the outer is the heavy liquid zone.

  16. On the application of the NRTL method to ternary (liquid + liquid) equilibria

    International Nuclear Information System (INIS)

    Alvarez Julia, Jorge; Barrero, Carmen R.; Corso, Maria E.; Grande, Maria del Carmen; Marschoff, Carlos M.

    2005-01-01

    The use of the NRTL method for correlating experimental data in ternary (liquid + liquid) equilibria is considered. It is concluded that parameters obtained by direct correlation techniques have not a direct physical meaning. Also, it is shown that the resulting values for these parameters depend on the number of experimental points considered and on the particular calculation method employed. Thus, it is very risky to employ such parameters in predicting equilibria of other ternary mixtures

  17. Liquid-liquid displacement in slippery liquid-infused membranes (SLIMs)

    OpenAIRE

    Bazyar, Hanieh; Lv, Pengyu; Wood, Jeffery A.; Porada, Slawomir; Lohse, Detlef; Lammertink, Rob G. H.

    2018-01-01

    Liquid-infused membranes inspired by slippery liquid-infused porous surfaces (SLIPS) have been recently introduced to membrane technology. The gating mechanism of these membranes is expected to give rise to anti-fouling properties and multi-phase transport capabilities. However, the long-term retention of the infusion liquid has not yet been explored. To address this issue, we investigate the retention of the infusion liquid in slippery liquid-infused membranes (SLIMs) via liquid-liquid displ...

  18. Scanning electrochemical microscopy determination of hydrogen flux at liquid|liquid interface with potentiometric probe

    OpenAIRE

    Jedraszko, Justyna; Nogala, Wojciech; Adamiak, Wojciech; Girault, Hubert H.; Opallo, Marcin

    2014-01-01

    Scanning electrochemical microscopy potentiometric determination of local hydrogen concentration and its flux next to the liquid|liquid interface was demonstrated. This method is based on the shift of open circuit potential of Pt-based reversible hydrogen electrode. The detection system was verified with a system generating hydrogen under galvanostatic conditions. Then, it was applied to aqueous|1,2-dichloroethane interface where hydrogen is produced with decamethylferrocene as electron donor.

  19. Further evidence of a liquid-liquid transition in interfacial water

    International Nuclear Information System (INIS)

    Zanotti, J-M; Bellissent-Funel, M C; Chen, S-H; Kolesnikov, A I

    2006-01-01

    In a previous paper we combined calorimetric, diffraction and high-resolution quasi-elastic neutron scattering data to show that after exhibiting a glass transition at 165 K, interfacial water experiences a first order liquid-liquid transition at 240 K from a low-density to a high-density liquid. Here we present further evidence of these transitions obtained by high-energy inelastic neutron scattering

  20. Kinetics of glycoalkaloid hydrolysis and solanidine extraction in liquid-liquid systems

    Directory of Open Access Journals (Sweden)

    Stanković Mihajlo Z.

    2002-01-01

    Full Text Available The kinetics of glycoalkaloid hydrolysis and solanidine extraction in Analyzed in this study. obtained from dried and milled potato haulm to to which hydrochlotic acid was added is the first liquid phase, while chloroform trichloroethylene or carbon tetrachlondeisthe second organic, liquid phase. The purpose of this paper was to combine the processes of glycoalkaloid hydrolysis to solanidine and solanidine extraction into one step, and to find the optimal liquid-liquid system for such a process.

  1. Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology

    OpenAIRE

    Brown, Leslie; Earle, Martyn J; Gilea, Manuela; Plechkova, Natalia V; Seddon, Kenneth R

    2017-01-01

    Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous char...

  2. Liquid-liquid structure transition and nucleation in undercooled Co-B eutectic alloys

    Energy Technology Data Exchange (ETDEWEB)

    He, Yixuan [Northwestern Polytechnical University, State Key Laboratory of Solidification Processing, Xi' an, Shanxi (China); Universite Grenoble Alpes, LNCMI, Grenoble (France); CNRS, LNCMI, Grenoble (France); Li, Jinshan; Wang, Jun; Kou, Hongchao [Northwestern Polytechnical University, State Key Laboratory of Solidification Processing, Xi' an, Shanxi (China); Beagunon, Eric [Universite Grenoble Alpes, LNCMI, Grenoble (France); CNRS, LNCMI, Grenoble (France)

    2017-06-15

    Cyclic superheating and cooling were carried out for the undercooled hypereutectic Co{sub 80}B{sub 20}, eutectic Co{sub 81.5}B{sub 18.5,} and hypoeutectic Co{sub 83}B{sub 17} alloys. For each alloy, there is a critical overheating temperature T{sub c}° at which there is a sharp increase of the mean undercooling, i.e., below (above) T{sub c}°, and the mean undercooling is about 80 °C (200 °C). DSC measurements show that there is a thermal absorption peak in the heating process, the peak temperature of which is nearly equal to the critical overheating temperature, indicating that the temperature-induced liquid-liquid structure transition does occur and should relate highly to nucleation in the undercooled Co-B eutectic melts. The effect of the liquid-liquid structure transition on nucleation was interpreted by the recent nucleation theory that considers the structures of overheated melts, and the composition-dependent overheating temperature was ascribed to the change of local favored structures. The present work provides further evidences for the liquid-liquid structure transition and is helpful for understanding solidification in undercooled melts. (orig.)

  3. The competition between the liquid-liquid dewetting and the liquid-solid dewetting.

    Science.gov (United States)

    Xu, Lin; Shi, Tongfei; An, Lijia

    2009-05-14

    We investigate the dewetting behavior of the bilayer of air/PS/PMMA/silanized Si wafer and find the two competing dewetting pathways in the dewetting process. The upper layer dewets on the lower layer (dewetting pathway 1, the liquid-liquid dewetting) and the two layers rupture on the solid substrate (dewetting pathway 2, the liquid-solid dewetting). To the two competing dewetting pathways, the process of forming holes and the process of hole growth, influence their competing relation. In the process of forming holes, the time of forming holes is a main factor that influences their competing relation. During the process of hole growth, the dewetting velocity is a main factor that influences their competing relation. The liquid-liquid interfacial tension, the film thickness of the polymer, and the viscosity of the polymer are important factors that influence the time of forming holes and the dewetting velocity. When the liquid-liquid dewetting pathway and the liquid-solid dewetting pathway compete in the dewetting process, the competing relation can be controlled by changing the molecular weight of the polymer, the film thickness, and the annealing temperature. In addition, it is also found that the rim growth on the solid substrate is by a rolling mechanism in the process of hole growth.

  4. Thermal properties of ionic systems near the liquid-liquid critical point.

    Science.gov (United States)

    Méndez-Castro, Pablo; Troncoso, Jacobo; Pérez-Sánchez, Germán; Peleteiro, José; Romaní, Luis

    2011-12-07

    Isobaric heat capacity per unit volume, C(p), and excess molar enthalpy, h(E), were determined in the vicinity of the critical point for a set of binary systems formed by an ionic liquid and a molecular solvent. Moreover, and, since critical composition had to be accurately determined, liquid-liquid equilibrium curves were also obtained using a calorimetric method. The systems were selected with a view on representing, near room temperature, examples from clearly solvophobic to clearly coulombic behavior, which traditionally was related with the electric permittivity of the solvent. The chosen molecular compounds are: ethanol, 1-butanol, 1-hexanol, 1,3-dichloropropane, and diethylcarbonate, whereas ionic liquids are formed by imidazolium-based cations and tetrafluoroborate or bis-(trifluromethylsulfonyl)amide anions. The results reveal that solvophobic critical behavior-systems with molecular solvents of high dielectric permittivity-is very similar to that found for molecular binary systems. However, coulombic systems-those with low permittivity molecular solvents-show strong deviations from the results usually found for these magnitudes near the liquid-liquid phase transition. They present an extremely small critical anomaly in C(p)-several orders of magnitude lower than those typically obtained for binary mixtures-and extremely low h(E)-for one system even negative, fact not observed, up to date, for any liquid-liquid transition in the nearness of an upper critical solution temperature. © 2011 American Institute of Physics

  5. Feasibility of bio-based lactate esters as extractant for biobutanol recovery: (Liquid + liquid) equilibria

    International Nuclear Information System (INIS)

    Zheng, Shaohua; Cheng, Hongye; Chen, Lifang; Qi, Zhiwen

    2016-01-01

    Highlights: • Lactate esters were studied as solvent to remove butanol from aqueous media. • (Liquid + liquid) equilibrium data were measured at T = 298.15 K and 1 atm. • Selectivity and 1-butanol partition coefficient were calculated. • COSMO-based study of separation efficiency on solvent structure was conducted. - Abstract: As bio-based solvents, lactate esters can be used as extractant for removing 1-butanol from the aqueous fermentation broths. In order to evaluate the separation efficiency of butyl lactate and 2-ethylhexyl lactate for the extraction of 1-butanol from its mixture with water, the (liquid + liquid) equilibrium for the ternary systems {water (1) + 1-butanol (2) + lactate ester (3)} were measured at T = 298.15 K. The 1-butanol partition coefficient varied in the range of 4.46 to 10.29, and the solvent selectivity within 32.12 to 108.18. For the separation of low-concentration butanol from fermentation broths, butyl lactate exhibits higher partition coefficient and lower selectivity than 2-ethylhexyl lactate. The NRTL model was employed to correlate the experimental data, and the COSMO-RS theory was utilized to predict the (liquid + liquid) equilibria and to analyze the influence of lactate esters on extraction efficiency.

  6. Removal of nitrogen compounds from Brazilian petroleum samples by oxidation followed by liquid-liquid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Conceicao, L.; Pergher, S.B.C. [Universidade Regional Integrada do Alto Uruguai e das Misses (URI), Erechim, RS (Brazil). Dept. de Quimica], E-mail: pergher@uricer.edu.br; Oliveira, J.V. [Universidade Regional Integrada do Alto Uruguai e das Misses (URI), Erechim, RS (Brazil). Dept. de Engenharia dos Alimentos; Souza, W.F. [Petroleo Brasileiro S.A. (CENPES/PETROBRAS), Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    2009-10-15

    This work reports liquid-liquid extraction of nitrogen compounds from oxidized and non-oxidized Brazilian petroleum samples. The experiments were accomplished in a laboratory-scale liquid-liquid apparatus in the temperature range of 303 K-323 K, using methanol, n-methyl-2-pyrrolidone (NMP) and N,Ndimethylformamide (DMF), and their mixtures as extraction solvents, employing solvent to sample volume ratios of 1:2, 1:1 and 2:1, exploring up to three separation stages. Results show that an increase in temperature, solvent to oil ratio, and number of equilibrium stages greatly improves the nitrogen removal from the oxidized sample (from 2600 to 200 ppm). The employed oxidation scheme is thus demonstrated to be an essential and efficient step of sample preparation for the selective liquid-liquid removal of nitrogen compounds. It is shown that the use of mixtures of DMF and NMP as well their use as co-solvents with methanol did not prove to be useful for selective nitrogen extraction since great oil losses were observed in the final process. (author)

  7. Phase stability analysis of liquid-liquid equilibrium with stochastic methods

    Directory of Open Access Journals (Sweden)

    G. Nagatani

    2008-09-01

    Full Text Available Minimization of Gibbs free energy using activity coefficient models and nonlinear equation solution techniques is commonly applied to phase stability problems. However, when conventional techniques, such as the Newton-Raphson method, are employed, serious convergence problems may arise. Due to the existence of multiple solutions, several problems can be found in modeling liquid-liquid equilibrium of multicomponent systems, which are highly dependent on the initial guess. In this work phase stability analysis of liquid-liquid equilibrium is investigated using the NRTL model. For this purpose, two distinct stochastic numerical algorithms are employed to minimize the tangent plane distance of Gibbs free energy: a subdivision algorithm that can find all roots of nonlinear equations for liquid-liquid stability analysis and the Simulated Annealing method. Results obtained in this work for the two stochastic algorithms are compared with those of the Interval Newton method from the literature. Several different binary and multicomponent systems from the literature were successfully investigated.

  8. A comparison of various modes of liquid-liquid based microextraction techniques: determination of picric acid.

    Science.gov (United States)

    Burdel, Martin; Šandrejová, Jana; Balogh, Ioseph S; Vishnikin, Andriy; Andruch, Vasil

    2013-03-01

    Three modes of liquid-liquid based microextraction techniques--namely auxiliary solvent-assisted dispersive liquid-liquid microextraction, auxiliary solvent-assisted dispersive liquid-liquid microextraction with low-solvent consumption, and ultrasound-assisted emulsification microextraction--were compared. Picric acid was used as the model analyte. The determination is based on the reaction of picric acid with Astra Phloxine reagent to produce an ion associate easily extractable by various organic solvents, followed by spectrophotometric detection at 558 nm. Each of the compared procedures has both advantages and disadvantages. The main benefit of ultrasound-assisted emulsification microextraction is that no hazardous chlorinated extraction solvents and no dispersive solvent are necessary. Therefore, this procedure was selected for validation. Under optimized experimental conditions (pH 3, 7 × 10(-5) mol/L of Astra Phloxine, and 100 μL of toluene), the calibration plot was linear in the range of 0.02-0.14 mg/L and the LOD was 7 μg/L of picric acid. The developed procedure was applied to the analysis of spiked water samples. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Liquid-liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding.

    Science.gov (United States)

    Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde

    2011-06-01

    Liquid-liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented.

  10. Liquid-liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding

    International Nuclear Information System (INIS)

    Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde

    2011-01-01

    Liquid-liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented. (orig.)

  11. Microsystems for liquid-liquid extraction of radionuclides in the analytical protocols

    International Nuclear Information System (INIS)

    Helle, Gwendolyne

    2014-01-01

    Radiochemical analyses are necessary to numerous steps for nuclear wastes management and for the control of the environment. An analytical protocol generally includes different steps of chemical separations which are lengthy, manual and complicated to implement because of their confinement in glove boxes and because of the hostile chemical and radiochemical media. Thus there is a huge importance to propose innovative and robust solutions to automate these steps but also to reduce the volumes of the radioactive and chemical wastes at the end of the analytical cycle. One solution consists in the miniaturization of the analyses through the use of lab-on-chip. The objective of this thesis work was to propose a rational approach to the conception of separative microsystems for the liquid-liquid extraction of radionuclides. To achieve this, the hydrodynamic behavior as well as the extraction performances have been investigated in one chip for three different chemical systems: Eu(III)-HNO 3 /DMDBTDMA, Eu(III)-AcO(H,Na)-HNO 3 /HDEHP and U(VI)-HCl/Aliquat336. A methodology has been developed for the implementation of the liquid-liquid extraction in micro-system for each chemical system. The influence of various geometric parameters such as channel length or specific interfacial area has been studied and the comparison of the liquid-liquid extraction performances has led to highlight the influence of the phases viscosities ratio on the flows. Thanks to the modeling of both hydrodynamics and mass transfer in micro-system, the criteria related to physical and kinetic properties of the chemical systems have been distinguished to propose a rational conception of tailor-made chips. Finally, several examples of the liquid-liquid extraction implementation in micro-system have been described for analytical applications in the nuclear field: U/Co separation by Aliquat336, Eu/Sm separation by DMDBTDMA or even the coupling between a liquid-liquid extraction chip and the system of

  12. Determination of Organic Pollutants in Small Samples of Groundwaters by Liquid-Liquid Extraction and Capillary Gas Chromatography

    DEFF Research Database (Denmark)

    Harrison, I.; Leader, R.U.; Higgo, J.J.W.

    1994-01-01

    A method is presented for the determination of 22 organic compounds in polluted groundwaters. The method includes liquid-liquid extraction of the base/neutral organics from small, alkaline groundwater samples, followed by derivatisation and liquid-liquid extraction of phenolic compounds after neu...... neutralisation. The extracts were analysed by capillary gas chromatography. Dual detection by flame Ionisation and electron capture was used to reduce analysis time....

  13. Hollow fiber-based liquid-liquid-liquid micro-extraction with osmosis: II. Application to quantification of endogenous gibberellins in rice plant.

    Science.gov (United States)

    Wu, Qian; Wu, Dapeng; Duan, Chunfeng; Shen, Zheng; Guan, Yafeng

    2012-11-23

    The phenomenon and benefits of osmosis in hollow fiber-based liquid-liquid-liquid micro-extraction (HF-LLLME) were theoretically discussed in part I of this study. In this work, HF-LLLME with osmosis was coupled with high performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-triple quadrupole MS/MS) to analyze eight gibberellins (gibberellin A(1), gibberellin A(3), gibberellin A(4), gibberellin A(7), gibberellin A(8), gibberellin A(9), gibberellin A(19) and gibberellin A(20)) in rice plant samples. According to the theory of HF-LLLME with osmosis, single factor experiments, orthogonal design experiments and mass transfer simulation of extraction process were carried out to select the optimal conditions. Cyclohexanol - n-octanol (1:3, v/v) was selected as organic membrane. Donor phase of 12 mL was adjusted to pH 2 and 20% NaCl (w/v) was added. Acceptor phase with an initial volume of 20 μL was the solution of 0.12 mol L(-1) Na(2)CO(3)-NaHCO(3) buffer (pH 9). Temperature was chosen to be 30 °C and extraction time was selected to be 90 min. Under optimized conditions, this method provided good linearity (r, 0.99552-0.99991) and low limits of detection (0.0016-0.061 ng mL(-1)). Finally, this method was applied to the analysis of endogenous gibberellins from plant extract which was obtained with traditional solvent extraction of rice plant tissues, and the relative recoveries were from 62% to 166%. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Simultaneous determination of several phytohormones in natural coconut juice by hollow fiber-based liquid-liquid-liquid microextraction-high performance liquid chromatography.

    Science.gov (United States)

    Wu, Yunli; Hu, Bin

    2009-11-06

    A simple, selective, sensitive and inexpensive method of hollow fiber-based liquid-liquid-liquid microextraction (HF-LLLME) combined with high performance liquid chromatography (HPLC)-ultraviolet (UV) detection was developed for the determination of four acidic phytohormones (salicylic acid (SA), indole-3-acetic acid (IAA), (+/-) abscisic acid (ABA) and (+/-) jasmonic acid (JA)) in natural coconut juice. To the best of our knowledge, this is the first report on the use of liquid phase microextraction (LPME) as a sample pretreatment technique for the simultaneous analysis of several phytohormones. Using phenetole to fill the pores of hollow fiber as the organic phase, 0.1molL(-1) NaOH solution in the lumen of hollow fiber as the acceptor phase and 1molL(-1) HCl as the donor phase, a simultaneous preconcentration of four target phytohormones was realized. The acceptor phase was finally withdrawn into the microsyringe and directly injected into HPLC for the separation and quantification of the target phytohormones. The factors affecting the extraction efficiency of four phytohormones by HF-LLLME were optimized with orthogonal design experiment, and the data was analyzed by Statistical Product and Service Solutions (SPSS) software. Under the optimized conditions, the enrichment factors for SA, IAA, ABA and JA were 243, 215, 52 and 48, with the detection limits (S/N=3) of 4.6, 1.3, 0.9ngmL(-1) and 8.8 microg mL(-1), respectively. The relative standard deviations (RSDs, n=7) were 7.9, 4.9, 6.8% at 50ngmL(-1) level for SA, IAA, ABA and 8.4% at 500 microg mL(-1) for JA, respectively. To evaluate the accuracy of the method, the developed method was applied for the simultaneous analysis of several phytohormones in five natural coconut juice samples, and the recoveries for the spiked samples were in the range of 88.3-119.1%.

  15. Analysis of aromatic amines in water samples by liquid-liquid-liquid microextraction with hollow fibers and high-performance liquid chromatography.

    Science.gov (United States)

    Zhao, Limian; Zhu, Lingyan; Lee, Hian Kee

    2002-07-19

    Liquid-liquid-liquid microextraction (LLLME) with hollow fibers in high-performance liquid chromatography (HPLC) has been applied as a rapid and sensitive quantitative method for the detection of four aromatic amines (3-nitroaniline, 4-chloroaniline, 4-bromoaniline and 3,4-dichloroaniline) in environmental water samples. The preconcentration procedure was induced by the pH difference inside and outside the hollow fiber. The target compounds were extracted from 4-ml aqueous sample (donor solution, pH approximately 13) through a microfilm of organic solvent (di-n-hexyl ether), immobilized in the pores of a hollow fiber (1.5 cm length x 0.6 mm I.D.), and finally into 4 microl of acid acceptor solution inside the fiber. After a prescribed period of time, the acceptor solution inside the fiber was withdrawn into the microsyringe and directly injected into the HPLC system for analysis. Factors relevant to the extraction procedure were studied. Up to 500-fold enrichment of analytes could be obtained under the optimized conditions (donor solution: 0.1 M sodium hydroxide solution with 20% sodium chloride and 2% acetone; organic phase: di-n-hexyl ether; acceptor solution: 0.5 M hydrochloric acid and 500 mM 18-crown-6 ether; extraction time of 30 min; stirring at 1,000 rev./min). The procedure also served as a sample clean-up step. The influence of humic acid on the extraction efficiency was also investigated, and more than 85% relative recoveries of the analytes at two different concentrations (20 and 100 microg/l) were achieved at various concentration of humic acid. This technique is a low cost, simple and fast approach to the analysis of polar compounds in aqueous samples.

  16. Highly precise (liquid + liquid) equilibrium and heat capacity measurements near the critical point for [Bmim][BF4] + 1H, 1H, 2H, 2H perfluoroctanol

    International Nuclear Information System (INIS)

    Pérez-Sánchez, G.; Troncoso, J.; Losada-Pérez, P.; Méndez-Castro, P.; Romaní, L.

    2013-01-01

    Highlights: • Highly precise liquid–liquid curves for [Bmim][BF 4 ] + perfluoroctanol are reported. • Critical behavior of heat capacity for the same system was also characterized. • In contrast to previous results, no coulombic/solvophobic crossover for coexistence curve diameter was found. • The system criticality shows characteristics both solvophobic and coulombic. -- Abstract: Liquid + liquid equilibrium of the system [Bmim][BF 4 ] + 1H, 1H, 2H, 2H perfluoroctanol using a highly precise methodology based on refractive index measurements was experimentally determined. In addition, isobaric heat capacity near the critical point was obtained. The performance of the new refractive index set-up was successfully checked against the coexistence curve of the system dimethyl carbonate + decane, since highly accurate data are available in the literature. The choice of [Bmim][BF 4 ] + 1H, 1H, 2H, 2H perfluoroctanol was motivated by a previous experimental work, whose results suggest that this system could present characteristics of both solvophobic and coulombic behavior, which are the two categories to which an ionic system can belong. Although this was previously observed for other ionic systems, this mixture presented a very striking feature: the diameter of the coexistence curve seemed to change its criticality in the studied temperature range, from solvophobic far away to coulombic close to the critical point. The results of this work reveal that, in fact, [Bmim][BF 4 ] + 1H, 1H, 2H, 2H perfluoroctanol presents characteristics of both solvophobic and coulombic criticality, but no evidence of the observed crossover over the experimental temperature range has been found

  17. NATO Advanced Research Workshop on Metastable Systems under Pressure: Platform for New Technologies and Environmental Applications

    CERN Document Server

    Rzoska, Sylwester; Mazur, Victor

    2010-01-01

    The fundamental insight and the technological & environmental relevance of metastable systems have given a strong impetus from the last decade development of extreme pressures experimental techniques, from the GPa region to the challenging negative pressures domain. The ultimate verification of theoretical models and reliable equations for portraying basic properties for such systems seems to be possible only when including temperature and pressure paths. This volume presents a set of papers related to novel findings on the glass transition phenomenon, phase transitions in liquid crystals, critical mixtures, bioliquids, geophysical system which can reveal surprising "secret" features only when using extreme pressures. This can be illustrated by the link between colloidal and molecular glassformers, the universal onset of the non-trivial dynamics in glasses, demistification of the secondary relaxation or novel findings associated with liquid - liquid near critical transitions in critical mixture, liquid cr...

  18. Metastable states in magnetic nanorings

    DEFF Research Database (Denmark)

    Castaño, F. J.; Ross, C. A.; Frandsen, Cathrine

    2003-01-01

    Magnetization states and hysteresis behavior of small ferromagnetic rings, of diameters 180-520 nm, have been investigated using magnetic force microscopy. In addition to the expected bi-domain ("onion") and flux-closed ("vortex") magnetization states, a metastable state has been found. This "twi......Magnetization states and hysteresis behavior of small ferromagnetic rings, of diameters 180-520 nm, have been investigated using magnetic force microscopy. In addition to the expected bi-domain ("onion") and flux-closed ("vortex") magnetization states, a metastable state has been found....... This "twisted" state contains a 360degrees domain wall which can exist over a wide range of applied fields. Four possible configurations of the twisted state are possible. Micromagnetic modeling shows that the twisted state is stabilised in small diameter, narrow rings. Additionally, more complex configurations...

  19. Instability of colliding metastable strings

    Energy Technology Data Exchange (ETDEWEB)

    Hiramatsu, Takashi [Kyoto Univ. (Japan). Yukawa Inst. for Theoretical Physics; Eto, Minoru [Yamagata Univ. (Japan). Dept. of Physics; Kamada, Kohei [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Kobayashi, Tatsuo [Kyoto Univ. (Japan). Dept. of Physics; Ookouchi, Yutaka [Kyoto Univ. (Japan). Dept. of Physics; Kyoto Univ. (Japan). The Hakubi Center for Advanced Research

    2013-04-15

    We investigate the collision dynamics of two metastable strings which can be viewed as tube-like domain walls with winding numbers interpolating a false vacuum and a true vacuum. We find that depending on the relative angle and speed of two strings, instability of strings increases and the false vacuum is filled out by rapid expansion of the strings or of a remnant of the collision.

  20. Instability of colliding metastable strings

    International Nuclear Information System (INIS)

    Hiramatsu, Takashi; Kobayashi, Tatsuo; Ookouchi, Yutaka; Kyoto Univ.

    2013-04-01

    We investigate the collision dynamics of two metastable strings which can be viewed as tube-like domain walls with winding numbers interpolating a false vacuum and a true vacuum. We find that depending on the relative angle and speed of two strings, instability of strings increases and the false vacuum is filled out by rapid expansion of the strings or of a remnant of the collision.

  1. Modeling of the (liquid + liquid) equilibrium of polydisperse hyperbranched polymer solutions by lattice-cluster theory

    International Nuclear Information System (INIS)

    Enders, Sabine; Browarzik, Dieter

    2014-01-01

    Graphical abstract: - Highlights: • Calculation of the (liquid + liquid) equilibrium of hyperbranched polymer solutions. • Description of branching effects by the lattice-cluster theory. • Consideration of self- and cross association by chemical association models. • Treatment of the molar-mass polydispersity by the use of continuous thermodynamics. • Improvement of the theoretical results by the incorporation of polydispersity. - Abstract: The (liquid + liquid) equilibrium of solutions of hyperbranched polymers of the Boltorn type is modeled in the framework of lattice-cluster theory. The association effects are described by the chemical association models CALM (for self association) and ECALM (for cross association). For the first time the molar mass polydispersity of the hyperbranched polymers is taken into account. For this purpose continuous thermodynamics is applied. Because the segment-molar excess Gibbs free energy depends on the number average of the segment number of the polymer the treatment is more general than in previous papers on continuous thermodynamics. The polydispersity is described by a generalized Schulz–Flory distribution. The calculation of the cloud-point curve reduces to two equations that have to be numerically solved. Conditions for the calculation of the spinodal curve and of the critical point are derived. The calculated results are compared to experimental data taken from the literature. For Boltorn solutions in non-polar solvents the polydispersity influence is small. In all other of the considered cases polydispersity influences the (liquid + liquid) equilibrium considerably. However, association and polydispersity influence phase equilibrium in a complex manner. Taking polydispersity into account the accuracy of the calculations is improved, especially, in the diluted region

  2. (Liquid + liquid) equilibria for benzene + cyclohexane + N,N-dimethylformamide + sodium thiocyanate

    International Nuclear Information System (INIS)

    Dong, Hongxing; Yang, Xiaoguang; Yue, Guojun; Zhang, Wei; Zhang, Jin

    2013-01-01

    Graphical abstract: On the left, the figure was phase diagram about the LLE date. On the right, the figure was about the effects of mass fraction of benzene in the raffinate phase to the selectivity(S) coefficient under different salt concentration. ■, the NaSCN and DMF in ratio of 5/95; • , the NaSCN and DMF in ratio of 10/90; ▴, the NaSCN and DMF in ratio of 15/85; ★, the NaSCN and DMF in ratio of 20/80; ▾, the NaSCN and DMF in ratio of 23/77. ♦, only DMF was used extractant (the selectivity coefficient was calculated by literature 17). w 22 , refer to the mass fraction of benzene in the raffinate phase (cyclohexane-rich phase). Highlights: • (Liquid + liquid) equilibrium for quaternary system was measured. • The components include benzene, cyclohexane, N,N-dimethylformamide, sodium thiocyanate. • The (liquid + liquid) equilibrium data can be well correlated by the NRTL model. • Separation of benzene and cyclohexane by NaSCN + DMF was discussed. -- Abstract: (Liquid + liquid) equilibrium (LLE) data for benzene + cyclohexane + N,N-dimethylformamide (DMF) + sodium thiocyanate (NaSCN) were measured experimentally at atmospheric pressure and 303.15 K. The selectivity coefficients from these LLE data were calculated and compared to those previously reported in the literature for the systems (benzene + cyclohexane + DMF) and (benzene + cyclohexane + DMF + KSCN). The NRTL equation was used to correlate the experimental data. The agreement between the predicted and experimental results was good. It was found that the selectivity coefficients of DMF + NaSCN for benzene ranged from 2.45 to 11.99. Considering the relatively high extraction capacity and selectivity for benzene, DMF + NaSCN may be used as a potential extracting solvent for the separation of benzene from cyclohexane

  3. Core-softened fluids, water-like anomalies, and the liquid-liquid critical points.

    Science.gov (United States)

    Salcedo, Evy; de Oliveira, Alan Barros; Barraz, Ney M; Chakravarty, Charusita; Barbosa, Marcia C

    2011-07-28

    Molecular dynamics simulations are used to examine the relationship between water-like anomalies and the liquid-liquid critical point in a family of model fluids with multi-Gaussian, core-softened pair interactions. The core-softened pair interactions have two length scales, such that the longer length scale associated with a shallow, attractive well is kept constant while the shorter length scale associated with the repulsive shoulder is varied from an inflection point to a minimum of progressively increasing depth. The maximum depth of the shoulder well is chosen so that the resulting potential reproduces the oxygen-oxygen radial distribution function of the ST4 model of water. As the shoulder well depth increases, the pressure required to form the high density liquid decreases and the temperature up to which the high-density liquid is stable increases, resulting in the shift of the liquid-liquid critical point to much lower pressures and higher temperatures. To understand the entropic effects associated with the changes in the interaction potential, the pair correlation entropy is computed to show that the excess entropy anomaly diminishes when the shoulder well depth increases. Excess entropy scaling of diffusivity in this class of fluids is demonstrated, showing that decreasing strength of the excess entropy anomaly with increasing shoulder depth results in the progressive loss of water-like thermodynamic, structural and transport anomalies. Instantaneous normal mode analysis was used to index the overall curvature distribution of the fluid and the fraction of imaginary frequency modes was shown to correlate well with the anomalous behavior of the diffusivity and the pair correlation entropy. The results suggest in the case of core-softened potentials, in addition to the presence of two length scales, energetic, and entropic effects associated with local minima and curvatures of the pair interaction play an important role in determining the presence of water

  4. (Liquid + liquid) equilibria of {benzene + cyclohexane + two ionic liquids} at different temperature and atmospheric pressure

    International Nuclear Information System (INIS)

    Sakal, Salem A.; Shen, Chong; Li, Chun-xi

    2012-01-01

    Highlights: ► (Liquid + liquid) equilibrium for two quaternary and two ternary systems were measured. ► The components include cyclohexane, benzene, [MIM][BF4], [MIM][ClO4] and [MMIM][DMP]. ► The (liquid + liquid) equilibrium data can be well correlated by the NRTL model. ► Separation of benzene and cyclohexane by pure ILs and their mixtures were discussed. - Abstract: (Liquid + liquid) equilibrium data of the following ternary and quaternary systems at different temperatures and mass fractions of ionic liquids (ILs) were measured at atmospheric pressure, i.e., {cyclohexane + benzene + 1,3-dimethylimidazolium dimethylphosphate ([MMIM][DMP])} at 298.2 K, {cyclohexane + benzene + 1-methylimidazolium tetrafluoroborate ([MIM][BF 4 ])} at 338.2 K, {cyclohexane + benzene + [MIM][BF 4 ] + [MMIM][DMP]} at (298.2 and 313.2) K, and {cyclohexane + benzene + 1-methylimidazolium perchlorate [MIM][ClO 4 ] + [MMIM][DMP]} at 298.2 K. The results indicate that both selectivity and distribution factor of the IL mixture for benzene are lower than that of pure IL [MMIM][DMP] at a specified condition, and decrease with the increase of the mass fraction of [MIM][BF 4 ] or [MIM][ClO 4 ] in its mixture of [MMIM][DMP] and the mole fraction of benzene. The extremely high selectivity of [MIM][BF 4 ] and [MIM][ClO 4 ] for aromatic compounds as predicted by the COSMOS-RS model is not justified by the present experimental results, and on the contrary, they show a relatively lower selectivity and extraction capacity for benzene than [MMIM][DMP].

  5. Counter current 'emulsion flow' extractor for continuous liquid-liquid extraction from suspended solutions

    International Nuclear Information System (INIS)

    Yanase, Nobuyuki; Naganawa, Hirochika; Nagano, Tetsushi; Noro, Junji

    2011-01-01

    A single current 'emulsion flow' liquid-liquid extraction apparatus has a head with a number of holes from which micrometer-sized droplets of an aqueous phase spout into an organic phase to mix the two liquid phases. For practical use, however, a fatal problem can occur when particulate components in the aqueous phase plug the holes. In the present study, we have succeeded in solving the problem by applying a counter current-type emulsion flow extractor where micrometer-sized droplets of the organic phase are generated. (author)

  6. (Liquid + liquid) equilibrium of {water + phenol + (1-butanol, or 2-butanol, or tert-butanol)} systems

    International Nuclear Information System (INIS)

    Hadlich de Oliveira, Leonardo; Aznar, Martin

    2010-01-01

    (Liquid + liquid) equilibrium (LLE) and binodal curve data were determined for the systems (water + phenol + tert-butanol) at T = 298.15 K, (water + phenol + 2-butanol) and (water + phenol + 1-butanol) at T = 298.15 K and T = 313.15 K by the combined techniques of densimetry and refractometry. Type I curve (for tert-butanol) and Type II curves (for 1- and 2-butanol) were found. The data were correlated with the NRTL model and the parameters estimated present root mean square deviations below 2% for the system with tert-butanol and lower than 0.8% for the other systems.

  7. Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.

    Science.gov (United States)

    Brown, Leslie; Earle, Martyn J; Gîlea, Manuela A; Plechkova, Natalia V; Seddon, Kenneth R

    2017-08-10

    Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

  8. On-line control of a liquid-liquid extraction column by the modal control method

    International Nuclear Information System (INIS)

    Bonnefoi, P.; Poujol, A.; Zwingelstein, G.; Dargier, C.; Rouyer, H.

    1977-02-01

    The application of modal analysis to the on-line control of a liquid-liquid extraction column is presented. This process is used in reprocessing for U purification. U in the aqueous acid phase is extracted by a solvent flowing at counter-current. The process is described by 4 nonlinear equations and gives the U and acid concentrations in the two phases. An approximative model is established adapted to the control of the column. Some results of a numerical simulation are given when a single mode is controled. They show that a single sensor allows a good control [fr

  9. (Liquid + liquid) equilibrium of (dibutyl ether + methanol + water) at different temperatures

    International Nuclear Information System (INIS)

    Arce, Alberto; Rodriguez, Hector; Rodriguez, Oscar; Soto, Ana

    2005-01-01

    (Liquid + liquid) equilibrium data for the ternary system (dibutyl ether + methanol + water) were experimentally determined at T = (298.15, 308.15, and 318.15) K. The experimental results were correlated by means of the NRTL and UNIQUAC equations, the best results being achieved with the UNIQUAC equation, both for the individual correlations at each temperature and for the overall correlation considering all the three experimental data sets. The experimental tie-lines were also compared to the values predicted by the UNIFAC method

  10. Factors influencing the thermodynamic isotope effect of lithium in polyetherlithium liquid-liquid extraction systems

    International Nuclear Information System (INIS)

    Fu Lian; Fang Shengqiang; Yao Zhongqi; Gao Zhichang; Tan Ganzhu

    1989-01-01

    The published data up to now concerning polyether-lithium liquid-liquid extraction systems, can be summarized by the equation, ε p = (α-1)/[1 + 0.46(1-P)], where α denotes the isotope separation factor; P - the ratio of the lithium concentration in the organic phase to the initial concentration of crown ethers; ε p -the enrichment coefficient as P = 100%. Based on the changes in ε p , P, α and D(distribution ratio), the functions of factors such as polyether's structure, polyether's side group, polyether's concentration, organic solvent, negative ion of lithium salt and lithium salt's concentration, are discussed and reported

  11. Liquid-liquid extraction of uranium (VI) using Cyanex 272 in kerosene from sodium salicylate medium

    International Nuclear Information System (INIS)

    Kamble, Pravin N.; Mohite, Baburao S.; Suryavanshi, Vishal J.; Salunkhe, Suresh T.

    2015-01-01

    Liquid-liquid extraction of uranium (VI) from sodium salicylate media using Cyanex 272 in kerosene has been carried out. Uranium (VI) was quantitatively extracted from 1x10 -4 M sodium salicylate with 5x10 -4 M Cyanex 272 in kerosene. It was stripped quantitatively from the organic phase with 4M HCl and determined spectrophotometrically with arsenazo(III) at 600 nm. The effects of concentrations of sodium salicylate, metal ions and strippants have been studied. Separation of uranium (VI) from other elements was achieved from binary as well as from multicomponent mixtures. The method is simple, rapid and selective with good reproducibility (approximately ±2%). (author)

  12. Application of salting-out effect equation to modelling of liquid-liquid distribution systems

    International Nuclear Information System (INIS)

    Pitsch, H.K.

    1986-03-01

    Physicochemical interpretation of salting-out is reviewed and effects of the medium on liquid-liquid distribution equilibria are described by two non-specific parameters of salting-out agents: total concentration of species in the aqueous phase and water activity. Thus extraction of a given constituent in various media can be forecasted with few data. Different uranyl and technetium (VII) extraction systems are analyzed to show the potentiality of the method. Coextraction of nitric acid and uranyl nitrate by tributyl phosphate is used to show the possibility of modelling complex distribution systems in industrial conditions [fr

  13. Electrical control of Faraday rotation at a liquid-liquid interface.

    Science.gov (United States)

    Marinescu, Monica; Kornyshev, Alexei A; Flatté, Michael E

    2015-01-01

    A theory is developed for the Faraday rotation of light from a monolayer of charged magnetic nanoparticles at an electrified liquid-liquid interface. The polarization fields of neighboring nanoparticles enhance the Faraday rotation. At such interfaces, and for realistic sizes and charges of nanoparticles, their adsorption-desorption can be controlled with a voltage variationFaraday rotation. A calculation based on the Maxwell-Garnett theory predicts that the corresponding redistribution of 40 nm nanoparticles of yttrium iron garnet can switch a cavity with a quality factor larger than 10(4) for light of wavelength 500 nm at normal incidence.

  14. Liquid-liquid extraction and separation studies of uranium(VI)

    International Nuclear Information System (INIS)

    Langade, A.D.; Shinde, V.M.

    1980-01-01

    Separation of uranium(VI) from iron(III), molybdenum(VI), vanadium(V), bismuth(III), zirconium(IV) and thorium(IV) is achieved by liquid-liquid extraction with 4-methyl-3-pentene-2-one (mesityl oxide; MeO) from sodium salicylate media (0.1M, pH 6.0). The extracted species is UO 2 (HO.C 6 H 4 COO) 2 .2MeO. A procedure for separating 50 μg of uranium from mg amounts of the other metals is described. (author)

  15. Ternary (liquid + liquid) equilibria of {bis(trifluoromethylsulfonyl)-amide based ionic liquids + butan-1-ol + water}

    International Nuclear Information System (INIS)

    Marciniak, Andrzej; Wlazło, Michał; Gawkowska, Joanna

    2016-01-01

    Highlights: • Ternary (liquid + liquid) equilibria for 3 ionic liquid + butanol + water systems. • The influence of ionic liquid structure on phase diagrams is discussed. • Influence of IL structure on S and β for butanol/water separation is discussed. - Abstract: Ternary (liquid + liquid) phase equilibria for 3 systems containing bis(trifluoromethylsulfonyl)-amide ionic liquids (1-buthyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, 1-(2-methoxyethyl)-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, {1-(2-methoxyethyl)-1-methylpyrrolidinium bis(trifluorylsulfonyl)-amide) + butan-1-ol + water} have been determined at T = 298.15 K. The selectivity and solute distribution ratio were calculated for investigated systems and compared with literature data for other systems containing ionic liquids. In each system total solubility of butan-1-ol and low solubility of water in the ionic liquid is observed. The experimental results have been correlated using NRTL model. The influence of the structure of ionic liquid on phase equilibria, selectivity and solute distribution ratio is shortly discussed.

  16. SISAK liquid-liquid extraction experiments with preseparated {sup 257}Rf

    Energy Technology Data Exchange (ETDEWEB)

    Omtvedt, Jon Petter; Alstad, J.; Breivik, H. [University of Oslo, Department of Chemistry, Oslo (NO)] (and others)

    2002-06-01

    The SISAK liquid-liquid extraction system was used to extract 4.0-s {sup 257}Rf. The {sup 257}Rf was produced in the reaction {sup 208}Pb({sup 50}Ti, 1n){sup 257}Rf with 237-MeV beam energy on target, separated in the Berkeley Gas-filled Separator (BGS) and transferred to a gas jet using the Recoil Transfer Chamber (RTC). The activity delivered by the gas jet was dissolved in 6-M HNO{sub 3} and Rf was extracted into 0.25-M dibutyl-phosphoric acid in toluene. This was the first time a transactinide, i.e., an element with Z{>=}104, was extracted and unequivocally identified by the SISAK system. Thus, this pilot experiment demonstrates that the fast liquid-liquid extraction system SISAK, in combination with liquid-scintillation detectors, can be used for investigating the chemical properties of the transactinides. The extraction result is in accordance with the behaviour shown by the Rf group IV homologues Zr and Hf. (author)

  17. Carbon nanoparticle stabilised liquid|liquid micro-interfaces for electrochemically driven ion-transfer processes

    International Nuclear Information System (INIS)

    MacDonald, Stuart M.; Fletcher, Paul D.I.; Cui Zhenggang; Opallo, Marcin; Chen Jingyuan; Marken, Frank

    2007-01-01

    Stabilised liquid|liquid interfaces between an organic 4-(3-phenylpropyl)-pyridine (PPP) phase and an aqueous electrolyte phase are obtained in the presence of suitable nanoparticles. The use of nanoparticulate stabilisers (ca. 30 nm diameter laponite or 9-18 nm diameter carbon) in 'Pickering' emulsion systems allows stable organic microdroplets to be formed and these are readily deposited onto conventional tin-doped indium oxide (ITO) electrodes. In contrast to the electrically insulating laponite nanoparticles, conducting carbon nanoparticles are shown to effectively catalyse the simultaneous electron transfer and ion transfer process at triple phase boundary junctions. Anion transfer processes between the aqueous and organic phase are driven electrochemically at the extensive triple phase junction carbon nanoparticle|4-(3-phenylpropyl)-pyridine|aqueous electrolyte. The organic phase consists of a redox active reagent 5,10,15,20-tetraphenyl-21H,23H-porphinato manganese(III) (MnTPP + ), 5,10,15,20-tetraphenyl-21H,23H-porphinato iron(III) (FeTPP + ), or proto-porphyrinato-IX iron(III) (hemin) dissolved in 4-(3-phenylpropyl)-pyridine (PPP). The composition of the aqueous electrolyte phase determines the reversible potential for the Nernstian anion transfer process. The methodology is shown to be versatile and, in future, could be applied more generally in liquid|liquid electroanalysis

  18. Liquid / liquid biphasic electrochemistry in ultra-turrax dispersed acetonitrile / aqueous electrolyte systems

    International Nuclear Information System (INIS)

    Watkins, John D.; Amemiya, Fumihiro; Atobe, Mahito; Bulman-Page, Philip C.; Marken, Frank

    2010-01-01

    Unstable acetonitrile | aqueous emulsions generated in situ with ultra-turrax agitation are investigated for applications in dual-phase electrochemistry. Three modes of operation for liquid / liquid aqueous-organic electrochemical processes are demonstrated with no intentionally added electrolyte in the organic phase based on (i) the formation of a water-soluble product in the aqueous phase in the presence of the organic phase, (ii) the formation of a product and ion transfer at the liquid / liquid-electrode triple phase boundary, and (iii) the formation of a water-insoluble product in the aqueous phase which then transfers into the organic phase. A three-electrode electrolysis cell with ultra-turrax agitator is employed and characterised for acetonitrile / aqueous 2 M NaCl two phase electrolyte. Three redox systems are employed in order to quantify the electrolysis cell performance. The one-electron reduction of Ru(NH 3 ) 6 3+ in the aqueous phase is employed to determine the rate of mass transport towards the electrode surface and the effect of the presence of the acetonitrile phase. The one-electron oxidation of n-butylferrocene in acetonitrile is employed to study triple phase boundary processes. Finally, the one-electron reduction of cobalticenium cations in the aqueous phase is employed to demonstrate the product transfer from the electrode surface into the organic phase. Potential applications in biphasic electrosynthesis are discussed.

  19. Liquid-liquid extraction from molten alkaline nitrates by using nitrogenous and organophosphorus derivatives

    International Nuclear Information System (INIS)

    Vittori, Olivier

    1971-01-01

    This research thesis reports the use of a system made of the LiNO 3 -KNO 3 eutectic at 160 deg. C and poly-phenyls in order to study the behaviour of phosphine and arsine oxides as extracting agents in a liquid-liquid process. In a first part, the author presents the studied system, its physical characteristics and its preparation, and the various analytical methods which have used. He discusses existing computation methods adapted to the separation of molten salts and organic phase, and proposes a specific method. Then, he reports the study of the behaviour of a phosphine oxide with Cobalt II and Nickel II, and discusses its application to the separation of this pair, Co II and Ni II. He highlights the different possibilities of three agents which are derivatives of phosphine and arsine in their ability to extract rare earths. A study of separation of rare earths is then addressed. The author reports the application of extraction equilibriums to the study of equilibriums in environments of molten salts with the Co II - chloride ions system. The author finally addresses the synergic phenomenon that pairs of neutral complexing agents of neighbouring structure or different donor central atom may display in liquid-liquid extraction

  20. Binary liquid-liquid equilibria of aniline-paraffin and furfural-paraffin systems

    Energy Technology Data Exchange (ETDEWEB)

    Sen, S.C.; Maity, S.; Ganguli, K.; Ray, P. (Calcutta Univ., (India))

    1991-12-01

    Liquid-liquid-equilibria (L-L-E) of hydrocarbon containing systems are of considerable commercial importance to refineries. But prediction of L-L-E of such systems is extremely difficult owing to the complex nature of the petroleum fluids. For treating such complex mixtures, a continuous component method is appropriate and for representing such liquids, a group contribution model like the UNIFAC is extremely convenient. It is, however, necessary to determine the appropriate group interaction parameters, and also to test the applicability of the UNIFAC method to these cases. Binary liquid-liquid-equilibria data for several aniline-paraffin and furfural-paraffin systems have been taken. These data along with data for other aniline-hydrocarbon and furfural-hydrocarbon systems from literature have been correlated using the UNIFAC model. The UNIFAC group interaction parameters have been found to have a linear temperature dependence. The CH{sub 2} groups in cyclo and non-cyclo paraffins require different interaction parameters. It was also found that a scaling of the combinatorial term is necessary for higher molecular weight hydrocarbons. 13 refs., 12 figs., 5 tabs.

  1. Application of liquid-liquid extraction in uranium hydrometallurgy (Paper No. : V-1)

    Energy Technology Data Exchange (ETDEWEB)

    Murthy, T K.S.; Koppiker, K S

    1979-01-01

    Uranium recovery from the ores is carried out exclusively by hydrometallurgical techniques. The initial solubilisation of uranium is achieved by either sodium carbonate or sulphuric acid leaching, the latter being more common. Further purification and upgrading of uranium from the sulphate liquors is carried out by an ion-exchange process. Solid resin type anion exchangers or liquid ion-exchangers are employed. The processing of uranium liquors is, perhaps, the first major application of liquid-liquid extraction in metal recovery. Organophosphoric acids were initially used but later the long-chain aliphatic amines have superseded them. The amine extraction system has been widely studied and several variations are now known. Chloride, nitrate, carbonate or sulphate or acid stripping can be used for getting back the uranium into the aqueous phase. Combination of ion exchange (resin type) and solvent extraction processes called Eluex processes are developed for special applications. Studies have also been made of solvent extraction of uranium from leach pulps instead of clear liquors. Tributylphosphate has found wide application in the refining of uranium concentrates to meet the stringent needs of nuclear purity. liquid-liquid extraction is, perhaps, the only successful technique for the recovery of uranium, as by-product, from wet-process phosphoric acid. This has opened up a new source of uranium.

  2. Pharmaceutical Perspective on Opalescence and Liquid-Liquid Phase Separation in Protein Solutions.

    Science.gov (United States)

    Raut, Ashlesha S; Kalonia, Devendra S

    2016-05-02

    Opalescence in protein solutions reduces aesthetic appeal of a formulation and can be an indicator of the presence of aggregates or precursor to phase separation in solution signifying reduced product stability. Liquid-liquid phase separation of a protein solution into a protein-rich and a protein-poor phase has been well-documented for globular proteins and recently observed for monoclonal antibody solutions, resulting in physical instability of the formulation. The present review discusses opalescence and liquid-liquid phase separation (LLPS) for therapeutic protein formulations. A brief discussion on theoretical concepts based on thermodynamics, kinetics, and light scattering is presented. This review also discusses theoretical concepts behind intense light scattering in the vicinity of the critical point termed as "critical opalescence". Both opalescence and LLPS are affected by the formulation factors including pH, ionic strength, protein concentration, temperature, and excipients. Literature reports for the effect of these formulation factors on attractive protein-protein interactions in solution as assessed by the second virial coefficient (B2) and the cloud-point temperature (Tcloud) measurements are also presented. The review also highlights pharmaceutical implications of LLPS in protein solutions.

  3. Liquid-liquid phase separation in internally mixed magnesium sulfate/glutaric acid particles

    Science.gov (United States)

    Wu, Feng-Min; Wang, Xiao-Wei; Jing, Bo; Zhang, Yun-Hong; Ge, Mao-Fa

    2018-04-01

    The confocal Raman microscopy is utilized to investigate the liquid-liquid phase separation (LLPS) of mixed magnesium sulfate/glutaric acid (MgSO4/GA) droplets deposited on a hydrophobic polytetrafluoroethylene (PTFE) substrate and a hydrophilic quartz substrate. Raman spectra collected from different regions of the mixed droplets provide detailed information of component distributions for MgSO4 and GA. During the dehydration process, the MgSO4/GA mixed particles show the initial liquid-liquid phase separation between 85% and 80% relative humidity (RH) on both the hydrophobic and hydrophilic substrates. For the droplets deposited on the two substrates, the inner phase of droplets is dominated by aqueous MgSO4, which is surrounded by a rich GA organic layer due to the surface tension effects. In addition, the crystallization of GA could be observed in the organic aqueous phase while it is inhibited in the inner MgSO4 phase due to the effects of gel formation of MgSO4 at low RH. The Raman spectra reveal that with decreasing RH the morphology of the mixed droplet evolves from a uniform droplet to the structure of LLPS with the GA crystallizing in the outer layer and MgSO4 gel formed in the inner phase. These findings contribute to the further understanding of the role of interactions between inorganic salts and organic acids on the morphological evolution and environmental effects of atmospheric aerosols under ambient RH conditions.

  4. Experimental evidence of a liquid-liquid transition in interfacial water

    Science.gov (United States)

    Zanotti, J.-M.; Bellissent-Funel, M.-C.; Chen, S.-H.

    2005-07-01

    At ambient pressure, bulk liquid water shows an anomalous increase of thermodynamic quantities and apparent divergences of dynamic properties on approaching a temperature Ts of 228 K. At normal pressure, supercooled water spontaneously freezes below the homogeneous nucleation temperature, TH = 235 K. Upon heating, the two forms of Amorphous Solid Water (ASW), LDA (Low Density Amorphous Ice) and HDA (High Density Amorphous Ice), crystallise above TX = 150 K. As a consequence, up to now no experiment has been able to explore the properties of liquid water in this very interesting temperature range between 150 and 235 K. We present nanosecond-time-scale measurements of local rotational and translational dynamics of interfacial, non-crystalline, water from 77 to 280 K. These experimental dynamic results are combined with calorimetric and diffraction data to show that after exhibiting a glass transition at 165 K, interfacial water experiences a first-order liquid-liquid transition at 240 K from a low-density to a high-density liquid. This is the first direct evidence of the existence of a liquid-liquid transition involving water.

  5. [Preparation and applications of a supported liquid-liquid extraction column with a composite diatomite material].

    Science.gov (United States)

    Bao, Jianmin; Ma, Zhishuang; Sun, Ying; Wang, Yongzun; Li, Youxin

    2012-08-01

    A rapid and special supported liquid-liquid extraction (SLE) column was developed with a composite diatomite material. The SLE column was evaluated by high performance liquid chromatography (HPLC) with acidic, neutral and alkaline compounds dissolved in water. Furthermore, some real complex samples were also analyzed by HPLC with the SLE method. The recoveries of benzoic acid (acidic), p-nitroaniline (alkaline) and 4-hydroxy-benzoic methyl ester (neutral) treated by the SLE column were 90.6%, 98.1% and 97.7%. However, the recoveries of the three compounds treated by traditional liquid-liquid extraction (LLE) method were 71.9%, 81.9% and 83.9%. The results showed that the SLE technique had higher recoveries than the traditional LLE method. The spiked recoveries of the complex samples, such as benzoic acid in Sprite and dexamethasone acetate, chlorphenamine maleate, indomethacin in bovine serum, were between 80% and 110% and the relative standard deviations (RSDs) were less than 15%. For biological specimen, the results could be accepted. Meantime, many disadvantages associated with traditional LLE method, such as emulsion formation, didn't occur using SLE column. The SLE column technique is a good sample preparation method with many advantages, such as rapid, simple, robust, easily automated, high recovery and high-throughput, which would be widely used in the future.

  6. Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for soybean biodiesel

    International Nuclear Information System (INIS)

    Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Lanza, Marcelo; Priamo, Wagner L.; Oliveira, J. Vladimir

    2013-01-01

    Highlights: ► (Liquid + liquid) equilibrium data for the systems of biodiesel production. ► LLE data for multicomponent FAME and FAEE from (303.15 to 333.15) K. ► Experimental data correlated using the UNIQUAC model. -- Abstract: This work reports (liquid + liquid) equilibrium (LLE) data for the systems of interest in soybean biodiesel production. Numerical data for LLE were obtained for binary, ternary and quaternary systems comprising fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) from soybean oil, water, glycerol, methanol, and ethanol at temperatures of (303.15, 318.15, and 333.15) K. Quantification of compounds in equilibrium in both phases was determined by analytical methods whereas solubility curves (binodal) were obtained by the cloud-point method. For all systems investigated, good alignments were obtained between phase compositions and the initial as well as overall compositions hence indicating low deviations from the mass balance. Experimental results were correlated using the UNIQUAC model with satisfactory agreement between experiment and theory

  7. Vacuum metastability with black holes

    Energy Technology Data Exchange (ETDEWEB)

    Burda, Philipp [Centre for Particle Theory, Durham University,South Road, Durham, DH1 3LE (United Kingdom); Gregory, Ruth [Centre for Particle Theory, Durham University,South Road, Durham, DH1 3LE (United Kingdom); Perimeter Institute, 31 Caroline Street North,Waterloo, ON, N2L 2Y5 (Canada); Moss, Ian G. annd [School of Mathematics and Statistics, Newcastle University,Newcastle Upon Tyne, NE1 7RU (United Kingdom)

    2015-08-24

    We consider the possibility that small black holes can act as nucleation seeds for the decay of a metastable vacuum, focussing particularly on the Higgs potential. Using a thin-wall bubble approximation for the nucleation process, which is possible when generic quantum gravity corrections are added to the Higgs potential, we show that primordial black holes can stimulate vacuum decay. We demonstrate that for suitable parameter ranges, the vacuum decay process dominates over the Hawking evaporation process. Finally, we comment on the application of these results to vacuum decay seeded by black holes produced in particle collisions.

  8. Vacuum metastability with black holes

    International Nuclear Information System (INIS)

    Burda, Philipp; Gregory, Ruth; Moss, Ian G. annd

    2015-01-01

    We consider the possibility that small black holes can act as nucleation seeds for the decay of a metastable vacuum, focussing particularly on the Higgs potential. Using a thin-wall bubble approximation for the nucleation process, which is possible when generic quantum gravity corrections are added to the Higgs potential, we show that primordial black holes can stimulate vacuum decay. We demonstrate that for suitable parameter ranges, the vacuum decay process dominates over the Hawking evaporation process. Finally, we comment on the application of these results to vacuum decay seeded by black holes produced in particle collisions.

  9. Geometrically induced metastability and holography

    Energy Technology Data Exchange (ETDEWEB)

    Aganagic, Mina; Aganagic, Mina; Beem, Christopher; Seo, Jihye; Vafa, Cumrun

    2006-10-23

    We construct metastable configurations of branes and anti-branes wrapping 2-spheres inside local Calabi-Yau manifolds and study their large N duals. These duals are Calabi-Yau manifolds in which the wrapped 2-spheres have been replaced by 3-spheres with flux through them, and supersymmetry is spontaneously broken. The geometry of the non-supersymmetric vacuum is exactly calculable to all orders of the't Hooft parameter, and to the leading order in 1/N. The computation utilizes the same matrix model techniques that were used in the supersymmetric context. This provides a novel mechanism for breaking supersymmetry in the context of flux compactifications.

  10. Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

    KAUST Repository

    Hellmann, Christoph

    2014-12-17

    © 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

  11. Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

    KAUST Repository

    Hellmann, Christoph; Treat, Neil D.; Scaccabarozzi, Alberto D.; Razzell Hollis, Joseph; Fleischli, Franziska D.; Bannock, James H.; de Mello, John; Michels, Jasper J.; Kim, Ji-Seon; Stingelin, Natalie

    2014-01-01

    © 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

  12. Miniaturized preconcentration methods based on liquid-liquid extraction and their application in inorganic ultratrace analysis and speciation: A review

    International Nuclear Information System (INIS)

    Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

    2009-01-01

    Liquid-liquid extraction (LLE) is widely used as a pre-treatment technique for separation and preconcentration of both organic and inorganic analytes from aqueous samples. Nevertheless, it has several drawbacks, such as emulsion formation or the use of large volumes of solvents, which makes LLE expensive and labour intensive. Therefore, miniaturization of conventional liquid-liquid extraction is needed. The search for alternatives to the conventional LLE using negligible volumes of extractant and the minimum number of steps has driven the development of three new miniaturized methodologies, i.e. single-drop microextraction (SDME), hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME). The aim of this paper is to provide an overview of these novel preconcentration approaches and their potential use in analytical labs involved in inorganic (ultra)trace analysis and speciation. Relevant applications to the determination of metal ions, metalloids, organometals and non-metals are included

  13. (Vapor + liquid + liquid) equilibrium measurements and correlation for {1,1,2,2-tetrafluoroethane (R134) + isobutane (R600a)} system

    International Nuclear Information System (INIS)

    Zhao, Yanxing; Gong, Maoqiong; Dong, Xueqiang; Guo, Hao; Wu, Jianfeng

    2014-01-01

    Highlights: • VLLE data for the (R134 + R600a) system at temperatures ranging from (235.311 to 241.720) K was measured. • The experiment was carried out using an apparatus based on the recirculation of vapor into liquid. • Correlation of VLE data was made using PR−HV−NRTL model. • A strong critical opalescence was observed. - Abstract: In this work, a study on the (vapor + liquid + liquid) equilibrium (VLLE) for the (R134 + R600a) system was carried out using an apparatus based on the recirculation of vapor into liquid at temperatures ranging from (235.311 to 241.720) K. The uncertainties of the composition, temperature, and pressure were less than ±0.005, ±5 mK and ±0.5 kPa, respectively. Thirty-eight experimental p–T–x data covering both branches of the binodal boundary and nineteen experimental p–T–y data were presented. Three numerical methods were used to obtain the second liquid phase compositions coexisting in equilibrium, and all the three methods lead to consistent results. Moreover, all of the experimental data were correlated by the Peng–Robinson equation of state (PR EoS) with the Huron–Vidal (HV) mixing rule involving the non-random two-liquid (NRTL) activity coefficient model. Then the vapor phase compositions were calculated. The results show good agreement with the experimental data, and the maximum deviation is less than 0.006

  14. (Ternary liquid + liquid) equilibria for (water + acetone + α-pinene, or β-pinene, or limonene) mixtures

    International Nuclear Information System (INIS)

    Li Xiaoli; Tamura, Kazuhiro

    2010-01-01

    (Ternary liquid + liquid) equilibria (tie-lines) of (water + acetone + α-pinene) at T = (288.15, 298.15, and 308.15) K and (water + acetone + β-pinene, or limonene) at T = 298.15 K have been measured. The experimental (ternary liquid + liquid) equilibrium data have been correlated successfully by the original UNIQUAC and modified UNIQUAC models. The modified UNIQUAC model reproduced accurately the experimental results for the (water + acetone + α-pinene) system at all the temperatures but fairly agreed with the experimental data for the (water + acetone + β-pinene, or limonene) systems.

  15. Temperature dependence on mutual solubility of binary (methanol + limonene) mixture and (liquid + liquid) equilibria of ternary (methanol + ethanol + limonene) mixture

    International Nuclear Information System (INIS)

    Tamura, Kazuhiro; Li Xiaoli; Li Hengde

    2009-01-01

    Mutual solubility data of the binary (methanol + limonene) mixture at the temperatures ranging from 288.15 K close to upper critical solution temperature, and ternary (liquid + liquid) equilibrium (tie-lines) of the (methanol + ethanol + limonene) mixture at the temperatures (288.15, 298.15, and 308.15) K have been obtained. The experimental results have been represented accurately in terms of the extended and modified UNIQUAC models with binary parameters, compared with the UNIQUAC model. The temperature dependence of binary and ternary (liquid + liquid) equilibrium for the binary (methanol + limonene) and ternary (methanol + ethanol + limonene) mixtures could be calculated successfully using the extended and modified UNIQUAC model

  16. Metastable Supersymmetry Breaking in a Cooling Universe

    International Nuclear Information System (INIS)

    Kaplunovsky, Vadim S.

    2007-01-01

    I put metastable supersymmetry breaking in a cosmological context. I argue that under reasonable assumptions, the cooling down early Universe favors metastable SUSY-breaking vacua over the stable supersymmetric vacua. To illustrate the general argument, I analyze the early-Universe history of the Intriligator-Seiberg-Shih model

  17. Desensitization and recovery of metastable intermolecular composites

    Science.gov (United States)

    Busse, James R [South Fork, CO; Dye, Robert C [Los Alamos, NM; Foley, Timothy J [Los Alamos, NM; Higa, Kelvin T [Ridgecrest, CA; Jorgensen, Betty S [Jemez Springs, NM; Sanders, Victor E [White Rock, NM; Son, Steven F [Los Alamos, NM

    2010-09-07

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  18. Pre-concentration of uranium from water samples by dispersive liquid-liquid micro-extraction

    Energy Technology Data Exchange (ETDEWEB)

    Khajeh, Mostafa; Nemch, Tabandeh Karimi [Zabol Univ. (Iran, Islamic Republic of). Dept. of Chemistry

    2014-07-01

    In this study, a simple and rapid dispersive liquid-liquid microextraction (DLLME) was developed for the determination of uranium in water samples prior to high performance liquid chromatography with diode array detection. 1-(2-pyridylazo)-2-naphthol (PAN) was used as complexing agent. The effect of various parameters on the extraction step including type and volume of extraction and dispersive solvents, pH of solution, concentration of PAN, extraction time, sample volume and ionic strength were studied and optimized. Under the optimum conditions, the limit of detection (LOD) and preconcentration factor were 0.3 μg L{sup -1} and 194, respectively. Furthermore, the relative standard deviation of the ten replicate was <2.6%. The developed procedure was then applied to the extraction and determination of uranium in the water samples.

  19. Liquid-Liquid Extraction and Determination of Trace Elements in Iron Minerals by Atomic Absorption Spectrometry

    International Nuclear Information System (INIS)

    Taseska, Milena; Stafilov, Trajche; Makreski, Petre; Jacimovic, Radojko; Jovanovski, Gligor

    2006-01-01

    Various trace elements (cadmium, chromium, cobalt, nickel, manganese) in some iron minerals were determined by flame (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). The studied minerals were chalcopyrite (CuFeS 2 ), hematite (Fe 2 O 3 ) and pyrite (FeS 2 ). To avoid the interference of iron, a method for liquid-liquid extraction of iron and determination of investigated elements in the inorganic phase was proposed. Iron was extracted by diisopropyl ether in hydrochloride acid solution and the extraction method was optimized. Some parameters were obtained to be significantly important: Fe mass in the sample should not exceed 0.3 g, the optimal concentration of HCI should be 7.8 mol 1 -1 and ratio of the inorganic and organic phase should be 1: 1. The procedure was verified by the method of standard additions and by its applications to reference standard samples. The investigated minerals originate from various mines in the Republic of Macedonia. (Author)

  20. Preparation of N-Graphdiyne Nanosheets at Liquid/Liquid Interface for Photocatalytic NADH Regeneration.

    Science.gov (United States)

    Pan, Qingyan; Liu, Hui; Zhao, Yingjie; Chen, Siqi; Xue, Bo; Kan, Xiaonan; Huang, Xiaowen; Liu, Jian; Li, Zhibo

    2018-04-16

    Two-dimensional (2D) N-graphdiyne (N-GDY) nanosheets containing different number of N were synthesized by polymerization of triazine, pyrazine, and pyridine-based monomers at liquid/liquid interface. The configurations and nanostructures of N-GDY were well-characterized. The wettability changed to more hydrophilic as the N contents increased. The collected N-GDY was further employed as metal-free photocatalyst for NADH regeneration. The catalytic performance was related with the N content in the graphdiyne. The N3-GDY demonstrated the best activity. This strategy provided a new promising platform of designing unique 2D N-GDY with tunable performance in biorelated catalysis.

  1. Liquid-liquid extraction of beryllium (II) using Cyanex 923 in kerosene from sodium acetate medium

    International Nuclear Information System (INIS)

    Kamble, Pravin N.; Madane, Namdev S.; Mohite, Baburao S.

    2013-01-01

    Liquid-liquid extraction of beryllium(II) from sodium acetate media using cyanex 923 in kerosene has been carried out. Beryllium(II) was quantitatively extracted from 1x10 -1 M sodium acetate with 1x10 -2 M cyanex 923 in kerosene. It was stripped quantitatively from the organic phase with 1M H 2 SO 4 and determined spectrophotometrically with eriochrome cyanine R at 525 nm. The effect of concentrations of sodium acetate, metal ions and strippants have been studied. Separation of beryllium(II) from other elements was achieved from binary as well as from multicomponent mixtures. The method is simple, rapid and selective with good reproducibility (approximately±2%). (author)

  2. Frontiers in poly(ionic liquid)s: syntheses and applications.

    Science.gov (United States)

    Qian, Wenjing; Texter, John; Yan, Feng

    2017-02-20

    We review recent works on the synthesis and application of poly(ionic liquid)s (PILs). Novel chemical structures, different synthetic strategies and controllable morphologies are introduced as a supplement to PIL systems already reported. The primary properties determining applications, such as ionic conductivity, aqueous solubility, thermodynamic stability and electrochemical/chemical durability, are discussed. Furthermore, the near-term applications of PILs in multiple fields, such as their use in electrochemical energy materials, stimuli-responsive materials, carbon materials, and antimicrobial materials, in catalysis, in sensors, in absorption and in separation materials, as well as several special-interest applications, are described in detail. We also discuss the limitations of PIL applications, efforts to improve PIL physics, and likely future developments.

  3. On the abundance and general nature of the liquid-liquid phase transition in molecular systems

    International Nuclear Information System (INIS)

    Kurita, Rei; Tanaka, Hajime

    2005-01-01

    Even a single-component liquid may have more than two kinds of isotropic liquid states. The transition between these different states is called a liquid-liquid transition (LLT). An LLT has been considered to be a rather rare phenomenon, in particular for molecular liquids. Very recently, however, we found an LLT in triphenyl phosphite, which may be the first experimental observation of an LLT for molecular liquids. Here we report convincing evidence of the second example of LLT for another molecular liquid, n-butanol. Despite large differences in the chemical structure and the molecular shape between triphenyl phosphite and n-butanol, the basic features of the transformation kinetics are strikingly similar. This suggests that an LLT may not be a rare phenomenon restricted to specific liquids, but may exist in various molecular liquids, which have a tendency to form long-lived locally favoured structures due to anisotropic interactions (e.g., hydrogen bonding). (letter to the editor)

  4. Association of solvent extraction and liquid-liquid flotation processes for metal recovery

    International Nuclear Information System (INIS)

    Puget, Flavia P.; Mendonca, Luciano A. de; Massarani, Giulio

    2000-01-01

    From the batch solvent extraction process, in this work it has been carried out a preliminary study aiming the determination of the optimal operating conditions for zirconium recovery (10 ppm) using alamine 336 (tricaprylylamine) as extractor. The results have shown that the extraction takes place instantaneously (5s of manual agitation) and that at pH around 2.0 the extraction efficiency is up to 98-99% for an aqueous/organic phase volumetric ratio of 10. Based on these results, it is proposed to evaluate the possibility of using of a pioneering technology for metal recovery at low concentrations, using a experimental set-up that associates standard solvent extraction process with liquid-liquid flotation process. (author)

  5. Pre-concentration of uranium from water samples by dispersive liquid-liquid micro-extraction

    International Nuclear Information System (INIS)

    Khajeh, Mostafa; Nemch, Tabandeh Karimi

    2014-01-01

    In this study, a simple and rapid dispersive liquid-liquid microextraction (DLLME) was developed for the determination of uranium in water samples prior to high performance liquid chromatography with diode array detection. 1-(2-pyridylazo)-2-naphthol (PAN) was used as complexing agent. The effect of various parameters on the extraction step including type and volume of extraction and dispersive solvents, pH of solution, concentration of PAN, extraction time, sample volume and ionic strength were studied and optimized. Under the optimum conditions, the limit of detection (LOD) and preconcentration factor were 0.3 μg L -1 and 194, respectively. Furthermore, the relative standard deviation of the ten replicate was <2.6%. The developed procedure was then applied to the extraction and determination of uranium in the water samples.

  6. Electrodeposition of Polymer Nanostructures using Three Diffuse Double Layers: Polymerization beyond the Liquid/Liquid Interfaces

    Science.gov (United States)

    Divya, Velpula; Sangaranarayanan, M. V.

    2018-04-01

    Nanostructured conducting polymers have received immense attention during the past few decades on account of their phenomenal usefulness in diverse contexts, while the interface between two immiscible liquids is of great interest in chemical and biological applications. Here we propose a novel Electrode(solid)/Electrolyte(aqueous)/Electrolyte(organic) Interfacial assembly for the synthesis of polymeric nanostructures using a novel concept of three diffuse double layers. There exist remarkable differences between the morphologies of the polymers synthesized using the conventional electrode/electrolyte method and that of the new approach. In contrast to the commonly employed electrodeposition at liquid/liquid interfaces, these polymer modified electrodes can be directly employed in diverse applications such as sensors, supercapacitors etc.

  7. Liquid-liquid phase separation and cluster formation at deposition of metals under inhomogeneous magnetic field

    Science.gov (United States)

    Gorobets, O. Yu; Gorobets, Yu I.; Rospotniuk, V. P.; Grebinaha, V. I.; Kyba, A. A.

    2017-10-01

    The formation and dynamic of expansion and deformation of the liquid-liquid interface of an electrolyte at deposition of metals at the surface of the magnetized steel ball is considered in this paper. The electrochemical processes were investigated in an external magnetic field directed at an arbitrary angle to the force of gravity. These processes are accompanied by the formation of effectively paramagnetic clusters of electrochemical products - magnions. Tyndall effect was used for detection of the presence of magnions near the magnetized steel electrode in a solution. The shape of the interface separating the regions with different concentration of magnions, i.e. different magnetic susceptibilities, was described theoretically based on the equation of hydrostatic equilibrium which takes into account magnetic, hydrostatic and osmotic pressures.

  8. Separation of phosphorous by liquid-liquid extraction for the measurement of 32P

    International Nuclear Information System (INIS)

    Lee, H.N.; Yang, S.D.

    2010-01-01

    Phosphorous containing radioisotope waste was separated and determined by liquid-liquid extraction method through liquid scintillation counter (LSC). In this process, ammonium phosphate was converted to phosphomolybdate (PMo) by the reaction of ammonium molybdate (Mo) in HCl solution (0.02 M) and maximum UV/VIS absorbance (λ max ) 218 nm was observed. The PMo solution was extracted with TOA (Tri-n-Octylamine)/xylene mixture and λ max 290 nm was found for this organic layer. Absorbance of aqueous and organic layer was linear through concentration. The impurities such as Co, Cr, Gd, etc. remain in aqueous layer by treating with Mo which was determined by ICP-AES and AAS. The quenching correction curve for 32 P was calculated using LSC results. No counting change was observed as the volume of quenchers increased. The recovery was 98% and 81% for the extraction and separation process from the test using H 3 32 PO 4 as standard tracer. (author)

  9. Liquid-liquid extraction of plutonium and americium by cekanoic acid from alkaline medium

    International Nuclear Information System (INIS)

    Venugopal Chetty, K.; Sagar, V.; Swarup, R.

    2001-01-01

    Liquid-liquid extraction studies of plutonium and americium from aqueous carbonate medium using a high molecular weight carboxylic acid namely cekanoic acid in different diluents has been carried out. The distribution ratio (D) values for Pu(IV) and Am(III) under various parameters such as concentration of extractant, Na 2 CO 3 and initial pH were obtained. Results indicated that Pu(IV) and Am(III) could be satisfactorily extracted together or individually from aqueous carbonate medium using cekanoic acid in different diluents like carbon tetrachloride, cyclohexane, toluene, n-dodecane or solvesso-100. The D values for Pu(IV) and Am(III) also indicated the possibility of their mutual separation. The back extraction of Pu and Am with different reagents was also studied. (orig.)

  10. Use of dispersive liquid-liquid microextraction for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium

    International Nuclear Information System (INIS)

    Mallah, M.H.; Atomic Energy Organization of Iran, Tehran; Shemirani, F.; Ghannadi Maragheh, M.

    2008-01-01

    A new preconcentration method of dispersive liquid-liquid microextraction (DLLME) was developed for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium. DLLME technique was successfully used as a sample preparation method. In this preconcentration method, an appropriate mixture of extraction solvent, disperser solvent was injected rapidly into an aqueous solution containing Sm, Eu, Gd and Dy after complex formation using chelating reagent of the 1-(2-pyridylazo)-2-naphthol (PAN). After phase separation, 0.5 mL of the settled phase containing enriched analytes was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The main factors affected the preconcentration of Sm, Eu, Gd and Dy were extraction and dispersive solvent type and their volume, extraction time, volume of chelating agent (PAN), centrifuge speed and drying temperature of the samples. Under the best operating condition simultaneous preconcentration factors of 80, 100, 103 and 78 were obtained for Sm, Eu, Gd and Dy, respectively. (author)

  11. Liquid liquid extraction of Th(IV) and its complexation study by Calix(4)pyrole

    International Nuclear Information System (INIS)

    Rathod, N.V.; Kamble, J.H.; Malkhede, D.D.

    2015-01-01

    Due to increased demand for carbon-free energy, accelerated growth of nuclear power is foreseen in several countries, especially in China and India. This has made the sustainable use of fuel resources such as uranium and thorium very important. Today, uranium is the main-stay of the present generation of nuclear power plants. However, the anticipated growth in nuclear energy may require introducing thorium as a fuel in future. Meso-octamethyl calix(4)pyrole is known for anion receptor however the present study evaluate the effect of cation for complexation of thorium by liquid liquid extraction technique. Calix(4)pyrole was evaluated for extraction of Th(IV), and 97% extraction efficiency was obtained. Th(IV) was determine with arsenazo(III) at 655 nm. The effect of acid molarity of 0.1 M, 1:5 metal to ligand ratio found efficient for maximum extraction. The stoichiometry ratio 1:2 between metal to ligand is established

  12. Glycerol-based deep eutectic solvents as extractants for the separation of MEK and ethanol via liquid-liquid extraction

    NARCIS (Netherlands)

    Rodriguez, N.R.; Ferré Güell, J.; Kroon, M.C.

    2016-01-01

    Four different glycerol-based deep eutectic solvents (DESs) were tested as extracting agents for the separation of the azeotropic mixture {methyl ethyl ketone + ethanol} via liquid-liquid extraction. The selected DESs for this work were: glycerol/choline chloride with molar ratios (4:1) and (2:1),

  13. Binary, ternary and quaternary liquid-liquid equilibria in 1-butanol, oleic acid, water and n-heptane mixtures

    NARCIS (Netherlands)

    Winkelman, J. G. M.; Kraai, G. N.; Heeres, H. J.

    2009-01-01

    This work reports on liquid-liquid equilibria in the system 1-butanol, oleic acid, water and n-heptane used for biphasic, lipase catalysed esterifications. The literature was studied on the mutual solubility in binary systems of water and each of the organic components. Experimental results were

  14. Advancing liquid/liquid extraction through a novel microfluidic device: Theory, instrumentation and applications in gas chromatography

    NARCIS (Netherlands)

    Peroni, D.; van Egmond, W.; Kok, W.T.; Janssen, J.G.M.

    2012-01-01

    A new chip-based liquid-liquid extraction technique for sample preparation of aqueous samples for GC was developed. Extraction is performed in a segmented flow system with additional mixing provided by an etched channel structure. The dimensions of the device are optimized to allow benefiting of the

  15. Proof of concept for continuous enantioselective liquid-liquid extraction in capillary microreactors using 1-octanol as a sustainable solvent

    NARCIS (Netherlands)

    Susanti, S.; Meinds, Tim G.; Pinxterhuis, Erik B.; Schuur, Boelo; De Vries, Johannes G.; Feringa, Ben L.; Winkelman, Jozef G.M.; Yue, Jun; Heeres, Hero J.

    2017-01-01

    The use of capillary microreactors for enantioselective liquid-liquid extraction (ELLE) was successfully demonstrated using a model system consisting of a buffered aqueous amino acid derivative (3,5-dinitrobenzoyl-(R,S)-leucine) solution (phosphate buffer, pH 6.58) and a chiral cinchona alkaloid

  16. Rapid screening of oxytetracycline residue in catfish muscle by dispersive liquid-liquid microextraction and europium-sensitized luminescence

    Science.gov (United States)

    Oxytetracycline (OTC) residue in catfish muscle was screened by dispersive liquid-liquid microextraction (DLLME) and europium-sensitized luminescence (ESL). After extraction in EDTA, HCl, and acetonitrile, cleanup was carried out by DLLME, and ESL was measured at microgram = 385 nm and wavelength = ...

  17. Liquid-Liquid Equilibrium and Excess Enthalpies in the Binary System 2-Methylpentane + N,N-Dimethylformamide

    Czech Academy of Sciences Publication Activity Database

    Bendová, Magdalena; Řehák, K.; Matouš, J.; Novák, J. P.

    2004-01-01

    Roč. 49, č. 5 (2004), s. 1318-1322 ISSN 0021-9568 Institutional research plan: CEZ:AV0Z4072921 Keywords : liquid-liquid equilibrium * excess enthalpies * thermodynamic models Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.368, year: 2004

  18. Coexistence between neighbours

    DEFF Research Database (Denmark)

    Shenge, K.C.; Mabagala, R.B.; Mortensen, C A Nieves Paulino

    2008-01-01

    Experiments were conducted under laboratory and screenhouse conditions to study the coexistence between Pseudomonas syringae pv. tomato and Xanthomonas campestris pv. vesicatoria, incitants of bacterial speck and bacterial spot diseases of tomato. Results of in vitro studies showed that when mixe...

  19. Constitutive modeling of metastable austenitic stainless steel

    NARCIS (Netherlands)

    Perdahcioglu, Emin Semih; Geijselaers, Hubertus J.M.; Huetink, Han; Khan, A.

    2010-01-01

    A physically based, macroscale constitutive model has been developed that can describe the complex mechanical behavior of metastable austenitic stainless steels. In the developed model a generalized model for the mechanically induced martensitic transformation is introduced. Mechanical tests have

  20. Consitutive modeling of metastable austenitic stainless steel

    NARCIS (Netherlands)

    Perdahcioglu, Emin Semih; Perdahcioglu, Emin Semih

    2008-01-01

    Metastable austenitic stainless steels combine high formability and high strength, which are generally opposing properties in materials. This property is a consequence of the martensitic phase transformation that takes place during deformation. This transformation is purely mechanically induced

  1. Understanding voltage-induced localization of nanoparticles at a liquid-liquid interface

    International Nuclear Information System (INIS)

    Flatte, M E; Kornyshev, A A; Urbakh, M

    2008-01-01

    Functionalization of liquid-liquid interfaces is a hot area, driven by aspirations to build self-assembled interfacial structures with unique properties, in particular accessible to light from both sides of the interface. Adsorption of nanoparticles is an example of such functionalization. Interesting new developments take place in electrochemical liquid-liquid systems, consisting of two immiscible electrolytic solutions that form an interface impermeable to ions until a sufficiently high voltage is applied across the interface. The voltage drops across a nanoscale region near the interface due to the formation of two back-to-back electrical double layers on the two sides of the interface. This highly localized voltage drop opens a new possibility for the stabilization and control of interfacial architectures. This appears to be particularly important for metal and even semiconductor nanoparticles, because they are, in turn, 'functionalized'. They are covered by surfactants with acidic groups, some of which dissociate in water. Coverage with surfactants is required to avoid particle-particle agglomeration in the bulk. An electric field can push such nanoparticles to the interface or move them away, depending on the direction of the field. This, together with the change of the free energy of solvation of nanoparticles when they move from the bulk to the surface, are the two new decisive factors affecting their adsorption and desorption. We discuss these effects together with the more familiar ones that are known to determine interfacial localization of uncharged nanoparticles. The presented critical analysis is qualitative. Although we will try to rationalize the main effects by some simplified formulae, they should not be taken literally: they pave the way towards understanding of nanoparticle localization in these systems, rather than give exact answers. These equations will, however, help us to 'visualize' how a properly applied electric field, assisted by the

  2. (Liquid + liquid) equilibrium for binary systems of N-formylmorpholine with alkanes

    International Nuclear Information System (INIS)

    Wang Zhengrong; Xia Shuqian; Ma Peisheng; Liu Tao; Han Kewei

    2012-01-01

    Highlights: ► The LLE data of four binary systems containing N-formylmorpholine were measured. ► Both NRTL and UNIQUAC models can fit the experimental data well. ► The new group interaction parameters of UNIFAC (Do) were regressed from the LLE data. ► The estimated result shows that the group interaction parameters and methods are reliable. - Abstract: (Liquid + liquid) equilibrium (LLE) data were determined for four binary systems containing N-formylmorpholine (NFM) and alkanes (3-methylpentane, heptane, nonane, and 2,2,4-trimethylpentane) over the temperature range from around 300 K to near 420 K using a set of newly designed equilibrium equipment. The compositions of both light and heavy phases were analyzed by gas chromatography. The mutual solubility increased as the temperature increased for all these systems. The binary (liquid + liquid) equilibrium data were correlated by the NRTL and UNIQUAC equations with temperature-dependent parameters. Both models correlate the experimental results well. Furthermore, the UNIFAC (Do) group contribution model was used to correlate and estimate the LLE data for NFM containing systems. Two methods of group division for NFM were used. NFM is treated as a single group: NFM group (method I) or divided into two groups: CHO and C 4 H 8 NO (method II), respectively. The group interaction parameters for CH 2 –NFM, or CH 2 –CHO and CH 2 –C 4 H 8 NO were fitted from the experimental LLE data. The UNIFAC (Do) model correlates the experimental data well. In addition, in order to develop UNIFAC (Do) group contribution model to estimate the LLE data of (NFM + cycloalkane) systems, some literature LLE data were used. The group interaction parameters for c-CH 2 –NFM, c-CH 2 –CHO and c-CH 2 –C 4 H 8 NO were correlated. Then these group interaction parameters were used to estimate the phase equilibrium data of binary systems in the literature by the UNIFAC (Do) model. The results showed that the estimated values are in

  3. Evaluation of a contact device type ejector system for liquid-liquid extraction

    International Nuclear Information System (INIS)

    Schwamback, Niomedes

    2002-04-01

    The objective of the present work was to evaluate an ejector system, operated simultaneously with two immiscible liquid phases and a gas phase, as a contact device for liquid-liquid extraction processes. The ejector, made of perspex, has a variable geometry, although this feature was not explored in the thesis. Motivated by recent uses of liquid-liquid extraction processes for the removal of traces of heavy metal from waste waters, it was decided to carry out tests with synthetic effluents. This strategy, typical of experimental work under evaluation of technical feasibility, greatly simplifies experiments, since the nature of the chemical species involved and their feed concentrations are known exactly and do not fluctuate. The extractant used was DEHPA (diethyl hexyl phosphoric acid). The metal chosen for tests was iron with oxidation number +3, because of its high extraction coefficient towards DEHPA and also for its chemical behavior similar to americium and other heavy metals. In addition to that, iron forms soluble coloured complexes adequate to spectrophotometric determination analysis, a simple, quick and very reliable analytical technique. The effects of electrolytes of interest, namely NaCl, FeSO 4 and Al(NO 3 ) 3 , upon the extraction process were investigated. The effects resulting from the introduction of a gas phase, actually air (bubbles), in the ejector upon the extraction efficiency were studied. By coupling advanced digital photographic technique and image analysis with microcomputer, the bubble mean size was measured. It was then correlated with equipment's geometrical (characteristic diameters) and operational variables (phases' flow rates and gas hold-ups). To enable scale-up procedures, data were preferably correlated by means of dimensionless groups. For the systems and conditions investigated in this thesis and under the same operational conditions, the introduction of air bubbles by means of an ejector has greatly improved the process

  4. Dispersive liquid-liquid microextraction combined with graphite furnace atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Zeini Jahromi, Elham; Bidari, Araz; Assadi, Yaghoub; Milani Hosseini, Mohammad Reza; Jamali, Mohammad Reza

    2007-01-01

    Dispersive liquid-liquid microextraction (DLLME) technique was successfully used as a sample preparation method for graphite furnace atomic absorption spectrometry (GF AAS). In this extraction method, 500 μL methanol (disperser solvent) containing 34 μL carbon tetrachloride (extraction solvent) and 0.00010 g ammonium pyrrolidine dithiocarbamate (chelating agent) was rapidly injected by syringe into the water sample containing cadmium ions (interest analyte). Thereby, a cloudy solution formed. The cloudy state resulted from the formation of fine droplets of carbon tetrachloride, which have been dispersed, in bulk aqueous sample. At this stage, cadmium reacts with ammonium pyrrolidine dithiocarbamate, and therefore, hydrophobic complex forms which is extracted into the fine droplets of carbon tetrachloride. After centrifugation (2 min at 5000 rpm), these droplets were sedimented at the bottom of the conical test tube (25 ± 1 μL). Then a 20 μL of sedimented phase containing enriched analyte was determined by GF AAS. Some effective parameters on extraction and complex formation, such as extraction and disperser solvent type and their volume, extraction time, salt effect, pH and concentration of the chelating agent have been optimized. Under the optimum conditions, the enrichment factor 125 was obtained from only 5.00 mL of water sample. The calibration graph was linear in the rage of 2-20 ng L -1 with detection limit of 0.6 ng L -1 . The relative standard deviation (R.S.D.s) for ten replicate measurements of 20 ng L -1 of cadmium was 3.5%. The relative recoveries of cadmium in tap, sea and rivers water samples at spiking level of 5 and 10 ng L -1 are 108, 95, 87 and 98%, respectively. The characteristics of the proposed method have been compared with cloud point extraction (CPE), on-line liquid-liquid extraction, single drop microextraction (SDME), on-line solid phase extraction (SPE) and co-precipitation based on bibliographic data. Therefore, DLLME combined with

  5. On a metastable vacuum burning phenomenon

    International Nuclear Information System (INIS)

    Berezin, V.A.; Tkachev, I.I.; Kuzmin, V.A.; AN SSSR, Moscow. Inst. Yadernykh Issledovanij)

    1983-02-01

    Equations of motion of an interface between two phases with arbitrary equations of state are obtained. It is found that there may take place a process of metastable vacuum burning. It is shown that under some conditions the process of the new phase bubble expansion is described by the detonation wave equations. Possible cosmological consequences of the metastable phase burning effect are briefly discussed. (author)

  6. Metastability and Rydberg states of triatomic hydrogen

    International Nuclear Information System (INIS)

    Helm, H.

    1991-01-01

    The np,nd and nf Rydberg series of H 3 have been studied by one- or two-photon excitation from the lowest metastable state of H 3 :B2p 2 A 2 ''. The lifetime of the metastable state has been measured and the influence of an external electric field on the Rydberg states has been studied under both aspects of dynamics (field-ionization and field-induced predissociation) and structure (Strak effect)

  7. HPLC/Fluorometric Detection of Carvedilol in Real Human Plasma Samples Using Liquid-Liquid Extraction.

    Science.gov (United States)

    Yilmaz, Bilal; Arslan, Sakir

    2016-03-01

    A simple, rapid and sensitive high-performance liquid chromatography (HPLC) method has been developed to quantify carvedilol in human plasma using an isocratic system with fluorescence detection. The method included a single-step liquid-liquid extraction with diethylether and ethylacetate mixture (3 : 1, v/v). HPLC separation was carried out by reversed-phase chromatography with a mobile phase composed of 20 mM phosphate buffer (pH 7)-acetonitrile (65 : 35, v/v), pumped at a flow rate of 1.0 mL/min. Fluorescence detection was performed at 240 nm (excitation) and 330 nm (emission). The calibration curve for carvedilol was linear from 10 to 250 ng/mL. Intra- and interday precision values for carvedilol in human plasma were plasma averaged out to 91.8%. The limits of detection and quantification of carvedilol were 3.0 and 10 ng/mL, respectively. Also, the method was successfully applied to three patients with hypertension who had been given an oral tablet of 25 mg carvedilol. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  8. Perfect additivity of microinterface arrays for liquid-liquid measurements: Application to cadmium ions quantification

    International Nuclear Information System (INIS)

    Mastouri, A.; Peulon, S.; Farcage, D.; Bellakhal, N.; Chaussé, A.

    2014-01-01

    Graphical abstract: - Highlights: • Confirmation of the perfect additivity of micropores independently of the geometry of arrays. • Study of assisted transfer of cadmium ions by 8-HQ at water/1,2-DCE. • Validation by cyclic and square wave voltammetry measurements for high and low concentrations. • Quantification of Cd(II) ions until 11 ppb in very simple conditions. • Highlighting of the very interesting use of arrays in a classical liquid-liquid microinterface device. - Abstract: For the first time, experimental measurements confirm the real additivity of the currents with micropore arrays, independently of the geometry (square, circular or in crosswise), from one single micropore until 256 micropores, in the case of the assisted transfer of cadmium ions by 8-hydroxyquinolinol (8-HQ). This result was obtained for measurements made by cyclic voltammetry at high concentration of cadmium ions (10 −4 M). At lower concentrations (until 10 −6 M), measurements performed by square wave voltammetry confirm also this additivity until 64 micropores. A calibration curve performed with a 64 micropores array allows us, in very simple conditions, the quantification of cadmium ions until 11 ppb (100 nM), which is lower than to the imposed limit for this specie in various fields, and in industrial effluents, in particular. The gain of sensitivity is close to 170 compared to measurements performed with one single micropore, illustrating the real interest of these arrays

  9. Liquid-liquid phase separation in particles containing secondary organic material free of inorganic salts

    Science.gov (United States)

    Song, Mijung; Liu, Pengfei; Martin, Scot T.; Bertram, Allan K.

    2017-09-01

    Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid-liquid phase separation (LLPS) occurs at high relative humidity (RH) (greater than ˜ 95 %) in α-pinene-derived SOM particles free of inorganic salts, while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS at 290 ± 1 K in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ˜ 95 % RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the oxygen-to-carbon elemental ratio (O : C) of the organic material. These results help explain the difference between the hygroscopic parameter κ of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.

  10. Spectrophotometric determination of mercury in water samples after preconcentration using dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Lemos, Valfredo Azevedo; dos Santos, Liz Oliveira; Silva, Eldevan dos Santos; Vieira, Emanuel Vitor dos Santos

    2012-01-01

    A simple method for the determination of mercury in water samples after preconcentration using dispersive liquid-liquid microextraction is described. The procedure is based on the extraction of mercury in the form of a complex and its subsequent determination by spectrophotometry. The complex is formed between Hg(II) and 2-(2-benzothiazolylazo)-p-cresol. The detection at 650 nm is performed directly in the metal-rich phase, which is spread on a triacetylcellulose membrane. The method eliminates the need to use a cuvet or large quantities of samples and reagents. The parameters that influence the preconcentration were studied, and the analytical characteristics were determined. The enrichment factor and the consumptive index for this method were 64 and 0.16 mL, respectively. The LOD (3.3 microg/L) and LOQ (11.1 microg/L) were also determined. The accuracy of the method was tested by the determination of mercury in certified reference materials BCR 397 (Human Hair) and SRM 2781 (Domestic Sludge). The method was applied to the determination of mercury in samples of drinking water, sea water, and river water.

  11. Dispersive liquid-liquid microextraction coupled with magnetic nanoparticles for extraction of zearalenone in wheat samples

    Directory of Open Access Journals (Sweden)

    Mitra Amoli-Diva

    2017-01-01

    Full Text Available A new, sensitive and fast dispersive liquid-liquid microextraction (DLLME coupled with micro-solid phase extraction (μ-SPE was developed for determination of zearalenone (ZEN in wheat samples. The DLLME was performed using acetonitrile/water (80:20 v/v as the disperser solvent and 1-octanol as the extracting solvent.  The acetonitrile/water (80:20 v/v solvent was also used to extract ZEN from solid wheat matrix, and was directly applied as the disperser solvent for DLLME process. Additionally, hydrophobic oleic-acid-modified magnetic nanoparticles were used in μ-SPE approach to retrieve the analyte from the DLLME step. So, the method uses high surface area and strong magnetism properties of these nanoparticles to avoid time-consuming column-passing processes in traditional SPE. Main parameters affecting the extraction efficiency and signal enhancement were investigated and optimized. Under the optimum conditions, the calibration curve showed a good linearity in the range of 0.1-500 μg kg−1 (R2=0.9996 with low detection limit of 83 ng g−1. The intra-day and inter-day precisions (as RSD % in the range of 2.6-4.3 % and high recoveries ranging from 91.6 to 99.1 % were obtained. The pre-concentration factor was 3. The method is simple, inexpensive, accurate and remarkably free from interference effects.

  12. Epitaxial thin film growth of LiH using a liquid-Li atomic template

    Energy Technology Data Exchange (ETDEWEB)

    Oguchi, Hiroyuki, E-mail: oguchi@nanosys.mech.tohoku.ac.jp [Department of Nanomechanics, Tohoku University, Sendai 980-8579 (Japan); Micro System Integration Center (muSIC), Tohoku University, Sendai 980-0845 (Japan); Ikeshoji, Tamio; Orimo, Shin-ichi [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980-8577 (Japan); Ohsawa, Takeo; Shiraki, Susumu; Hitosugi, Taro [Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980-8577 (Japan); Kuwano, Hiroki [Department of Nanomechanics, Tohoku University, Sendai 980-8579 (Japan)

    2014-11-24

    We report on the synthesis of lithium hydride (LiH) epitaxial thin films through the hydrogenation of a Li melt, forming abrupt LiH/MgO interface. Experimental and first-principles molecular dynamics studies reveal a comprehensive microscopic picture of the crystallization processes, which sheds light on the fundamental atomistic growth processes that have remained unknown in the vapor-liquid-solid method. We found that the periodic structure that formed, because of the liquid-Li atoms at the film/MgO-substrate interface, serves as an atomic template for the epitaxial growth of LiH crystals. In contrast, films grown on the Al{sub 2}O{sub 3} substrates indicated polycrystalline films with a LiAlO{sub 2} secondary phase. These results and the proposed growth process provide insights into the preparation of other alkaline metal hydride thin films on oxides. Further, our investigations open the way to explore fundamental physics and chemistry of metal hydrides including possible phenomena that emerge at the heterointerfaces of metal hydrides.

  13. Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

    Science.gov (United States)

    Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

    2012-01-01

    Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models – one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT. PMID:22550566

  14. Dispersive liquid-liquid microextraction of copper ions as neocuproine complex in environmental aqueous samples.

    Science.gov (United States)

    Shariati, Shahab; Golshekan, Mostafa

    2011-06-01

    In the present study, a simple and efficient extraction method based on dispersive liquid-liquid microextraction prior to UV-Vis spectrophotometry was developed for the preconcentration and determination of copper ions in environmental samples. Briefly, cupric ions (Cu II) were reduced to cuprous (Cu I) with addition of hydroxyl amine hydrochloride and formed hydrophobic chelates with neocuproine. Then, a proper mixture of acetonitrile (as dispersive solvent) and choloroform (as extraction solvent) was rapidly injected into the solution and a cloudy solution was formed. After centrifuging, choloroform was sedimented at the bottom of a conical tube and diluted with 100 µL of methanol for further UV-Vis spectrophotometry measurement. An orthogonal array design (OAD) was employed to study the effects of different parameters on the extraction efficiency. Under the optimum experimental conditions, a preconcentration factor up to 63.6 was achieved for extraction from 5.0 mL of sample solution. The limit of detection (LOD) based on S/N = 3 was 0.33 µg L-1 and the calibration curve was linear in the range of 1-200 µg L-1 with reasonable linearity (r2 > 0.997). Finally, the accuracy of the proposed method was successfully evaluated by determination of trace amounts of copper ions in different water samples and satisfactory results were obtained.

  15. Optical properties of cadmium sulfide nanocrystal film prepared by electrochemical synthesis at liquid-liquid interface

    International Nuclear Information System (INIS)

    Luan Yemei; An Maozhong; Lu Guoqi

    2006-01-01

    Dendritic nanocrystalline CdS film was deposited at liquid-liquid interface of surfactants and an electrolyte containing 4 mmol L -1 cadmium chloride (CdCl 2 ) and 16 mmol L -1 thioacetamide (CH 3 CSNH 2 ) with an initial pH value of 5 at 15 deg. C by electrochemical synthesis. The nanofilm was characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), ultraviolet visible (UV-vis) absorption spectroscopy and fluorescence spectroscopy. The surface morphology and particle size of the nanofilm were investigated by AFM, SEM and TEM, and the crystalline size was 30-50 nm. The thickness of the nanofilm calculated by optical absorption spectrum was 80 nm. The microstructure and composition of the nanofilm was investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), showing its polycrystalline structure consisting of CdS and Cd. Optical properties of the nanofilm were investigated systematically by UV-vis absorption and fluorescence spectroscopy. A λ onset blue shift compared with bulk CdS was observed in the absorption spectra. Fluorescence spectra of the nanofilm indicated that the CdS nanofilm emitted blue and green light. The nanocomposites film electrode will bring about anodic photocurrent during illumination, showing that the transfer of cavities produces photocurrent

  16. The removal of dinitrochlorobenzene from industrial residuals by liquid-liquid extraction with chemical reaction

    Directory of Open Access Journals (Sweden)

    G. C. M. Ferreira

    2007-09-01

    Full Text Available Nitrochlorobenzenes (NCBs are very important in the chemical industry since they have been used as raw material for the manufacture of crop protection products, as active ingredients in the pharmaceutical industry, as pigments and as antioxidants as well as for other uses. In industrial processes, NCBs are produced by monochlorobenzene (MCB nitration reactions and one of the main residuals formed is dinitrochlorobenzene (DNCB, which is mainly composed of the isomer 2,4DNCB. This subproduct, although of commercial interest when in its pure state, is generally incinerated due to the high costs of recovery treatment and purification. The objective of this study is to present an alternative to the treatment of industrial residuals containing DNCB. The technique consists of converting DNCB into sodium dinitrophenolate, which is very soluble in water and is also easy to reuse. For this purpose, liquid-liquid extraction with chemical reaction (alkaline hydrolysis with a rotating disc contactor (RDC is used. Experimental data on MCB nitration reactions as well as alkaline hydrolysis using a rotating disc contactor are presented.

  17. Effect of silica nanoparticles on the phase inversion of liquid-liquid dispersions

    International Nuclear Information System (INIS)

    Asadabadi, Maliheh Raji; Abolghasemi, Hossein; Nasab, Payman Davoodi; Maragheh, Mohammad Ghannadi

    2013-01-01

    The effect of silica nanoparticles on phase inversion of liquid-liquid dispersions in a stirred vessel was investigated. The studied systems were toluene dispersed in water and vice versa. In the first set of experiments, phase inversion behavior of systems without Silica nanoparticles was evaluated and subsequent experiments were conducted in the presence of the nanoparticles. For this purpose, Silica nanoparticles of different concentrations (0.01, 0.03, 0.05, 0.07 wt%) were dispersed in water. The nanofluid stability was examined using an ultraviolet-visible (UV-vis) spectrophotometer. The results indicated that increase in silica nanoparticle concentrations up to 0.07 wt% led to increase in agitation speed of phase inversion 43-53.5% and 38.5-45% in the case of O/W and W/O dispersions, respectively. Consequently, the tendency of dispersions to inversion diminished as nanoparticle concentrations increased. Finally, 0.05 wt% of silica nanoparticle was selected as the optimum on the range studied

  18. Variation in pH of Model Secondary Organic Aerosol during Liquid-Liquid Phase Separation.

    Science.gov (United States)

    Dallemagne, Magda A; Huang, Xiau Ya; Eddingsaas, Nathan C

    2016-05-12

    The majority of atmospheric aerosols consist of both organic and inorganic components. At intermediate relative humidity (RH), atmospheric aerosol can undergo liquid-liquid phase separation (LLPS) in which the organic and inorganic fractions segregate from each other. We have extended the study of LLPS to the effect that phase separation has on the pH of the overall aerosols and the pH of the individual phases. Using confocal microscopy and pH sensitive dyes, the pH of internally mixed model aerosols consisting of polyethylene glycol 400 and ammonium sulfate as well as the pH of the organic fraction during LLPS have been directly measured. During LLPS, the pH of the organic fraction was observed to increase to 4.2 ± 0.2 from 3.8 ± 0.1 under high RH when the aerosol was internally mixed. In addition, the high spatial resolution of the confocal microscope allowed us to characterize the composition of each of the phases, and we have observed that during LLPS the organic shell still contains large quantities of water and should be characterized as an aqueous organic-rich phase rather than simply an organic phase.

  19. Effect of shear-thinning behaviour on liquid-liquid plug flow in microchannels

    Science.gov (United States)

    Roumpea, Evangelia; Chinaud, Maxime; Weheliye, Weheliye Hashi; Angeli, Panagiota; Kahouadji, Lyes; Matar, Omar K.

    2016-11-01

    The present work investigates the dynamics of plug formation of shear-thinning solutions in a 200 μm microchannel using a two-colour micro-PIV system. Measurements, including phase-averaged velocity fields, have been conducted both at the T-junction inlet and the main channel to enhance understanding of non-Newtonian liquid-liquid flows. Two aqueous glycerol solutions containing xanthan gum are used as the non-Newtonian fluids while 5 cSt silicone oil is the Newtonian phase. The current experimental results revealed a pronounced impact of the xanthan gum (shear-thinning behaviour) on the flow pattern transition boundaries, and enhance the fluid flowrates where plug flow occurred. The addition of polymer resulted also in different hydrodynamic characteristics such as a bullet-shaped plug and an increased film thickness between the plug and the wall. In the present work, the technique allows to capture the velocity field of both phases simultaneously. Experimental results are compared with the numerical simulations provided by the code BLUE. Project funded under the UK Engineering and Physical Sciences Research Council (EPSRC) Programme Grant MEMPHIS.

  20. Rapid determination of octanol-water partition coefficient using vortex-assisted liquid-liquid microextraction.

    Science.gov (United States)

    Román, Iván P; Mastromichali, Anna; Tyrovola, Konstantina; Canals, Antonio; Psillakis, Elefteria

    2014-02-21

    Vortex-assisted liquid-liquid microextraction (VALLME) coupled with high-performance liquid chromatography (HPLC) is proposed here for the rapid determination of octanol-water partitioning coefficients (Kow). VALLME uses vortex agitation, a mild emulsification procedure, to disperse microvolumes of octanol in the aqueous phase thus increasing the interfacial contact area and ensuring faster partitioning rates. With VALLME, 2min were enough to achieve equilibrium conditions between the octanolic and aqueous phases. Upon equilibration, separation was achieved using centrifugation and the octanolic microdrop was collected and analyzed in a HPLC system. Six model compounds with logKow values ranging between ∼0.5 and 3.5 were used during the present investigations. The proposed method produced logKow values that were consistent with previously published values and the recorded uncertainty was well within the acceptable log unit range. Overall, the key features of the proposed Kow determination procedure comprised speed, reliability, simplicity, low cost and minimal solvent consumption. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Interfacial transport characteristics in a gas-liquid or an immiscible liquid-liquid stratified flow

    International Nuclear Information System (INIS)

    Inoue, A.; Aoki, S.; Aritomi, M.; Kozawa, Y.

    1982-01-01

    This paper is a review for an interfacial transport characteristics of mass, momentum and energy in a gas-liquid or a immiscible liquid-liquid stratified flow with wavy interface which have been studied in our division. In the experiment, a characteristic of wave motion and its effect to the turbulence near the interface as well as overall flow characteristics like pressure drop, position of the interface were investigated in an air-water, an air-mercury and a water-liquid metal stratified flow. On the other hand, several models based on the mixing length model and a two-equation model of turbulence, with special interfacial boundary conditions in which the wavy surface was regarded as a rough surface correspond to the wavy height, a source of turbulent energy equal to the wave energy and a damped-turbulence due to the surface tension, were proposed to predict the flow characteristics and the interfacial heat transfer in a fully developed and an undeveloped stratified flow and examined by the experimental data. (author)

  2. Ligandless-dispersive liquid-liquid microextraction of trace amount of copper ions

    Energy Technology Data Exchange (ETDEWEB)

    Mohammadi, Sayed Zia, E-mail: szmohammadi@yahoo.com [Department of Chemistry, Payame Noor University (PNU), Kerman (Iran, Islamic Republic of); Afzali, Daryoush [Environment Department, Institute Research of Environmental Sciences, International Center for Science, High Technology and Environmental Sciences, Kerman (Iran, Islamic Republic of); Baghelani, Yar Mohammad [Department of Chemistry, Payame Noor University (PNU), Kerman (Iran, Islamic Republic of)

    2009-10-27

    In the present work, a new ligandless-dispersive liquid-liquid microextraction (LL-DLLME) method has been developed for preconcentration trace amounts of copper as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents, respectively. Some factors influencing on the extraction efficiency of copper and its subsequent determination were studied and optimized, such as the extraction and dispersive solvent type and volume, pH of sample solution, extraction time and salting out effect. Under the optimal conditions, the calibration curve was linear in the range of 1.0 ng mL{sup -1}-0.6 {mu}g mL{sup -1} of copper with R{sup 2} = 0.9985. Detection limit was 0.5 ng mL{sup -1} in original solution (3S{sub b}/m) and the relative standard deviation for seven replicate determination of 0.2 {mu}g mL{sup -1} copper was {+-}1.4%. The proposed method has been applied for determination of copper in standard and water samples with satisfactory results.

  3. Identification of chemical compounds in a liquid-liquid extraction system

    International Nuclear Information System (INIS)

    Ramirez C, F de M de la.

    1980-01-01

    The objective of the present work is to identify the chemical compounds that are distributed in a liquid-liquid extraction system in which the third phase is observed; for this purpose the FeCl 3 (0.12M) - HCl (8.43M) - Diisopropilic ether - system was used, for the quantitative determination of the chemical compounds, FeCl 3 solutions labelled with 59 Fe or witH 38 Cl were used; the Karl Fischer method for the determination of the water concentration at the organic phases was used, the obtained data was used for the calculations of the H + distribution in each phase. The results are that when the distribution equilibrium is reached, the aqueous phase is a 7.5M HCl solution; the light organic phase contains 2 H[FeCl 4 ].6H 2 O and the dense organic phase contains 2 H[FeCl 4 ].6H 2 O.3HCl.12H 2 O. The differences between these compounds are due to a high concentration of water and the HCl in the organic solvent. This causes a heterogeneous physic field, and then the third phase formation. (author)

  4. Liquid-liquid phase separation in aerosol particles: Imaging at the Nanometer Scale

    Energy Technology Data Exchange (ETDEWEB)

    O' Brien, Rachel; Wang, Bingbing; Kelly, Stephen T.; Lundt, Nils; You, Yuan; Bertram, Allan K.; Leone, Stephen R.; Laskin, Alexander; Gilles, Mary K.

    2015-04-21

    Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission x-ray microscopy (STXM) to investigate the LLPS of micron sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), a, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS with apparent core-shell particle morphology were observed for all samples with both techniques. Chemical imaging with STXM showed that both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH’s above the deliquescence point and that the majority of the organic component was located in the shell. The shell composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 50:50% organic to inorganic mix in the shell. These two chemical imaging techniques are well suited for in-situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.

  5. Epitaxial thin film growth of LiH using a liquid-Li atomic template

    International Nuclear Information System (INIS)

    Oguchi, Hiroyuki; Ikeshoji, Tamio; Orimo, Shin-ichi; Ohsawa, Takeo; Shiraki, Susumu; Hitosugi, Taro; Kuwano, Hiroki

    2014-01-01

    We report on the synthesis of lithium hydride (LiH) epitaxial thin films through the hydrogenation of a Li melt, forming abrupt LiH/MgO interface. Experimental and first-principles molecular dynamics studies reveal a comprehensive microscopic picture of the crystallization processes, which sheds light on the fundamental atomistic growth processes that have remained unknown in the vapor-liquid-solid method. We found that the periodic structure that formed, because of the liquid-Li atoms at the film/MgO-substrate interface, serves as an atomic template for the epitaxial growth of LiH crystals. In contrast, films grown on the Al 2 O 3 substrates indicated polycrystalline films with a LiAlO 2 secondary phase. These results and the proposed growth process provide insights into the preparation of other alkaline metal hydride thin films on oxides. Further, our investigations open the way to explore fundamental physics and chemistry of metal hydrides including possible phenomena that emerge at the heterointerfaces of metal hydrides

  6. Reactive liquid/liquid extraction of heavy metals from landfill seepage waters. Its characterisation and application

    International Nuclear Information System (INIS)

    Woller, N.

    1994-06-01

    This study demonstrates the applicability of liquid-liquid extraction by means of the commercial complexers LIX26 R and LIX84 R to heavy metal removal from waste waters. The composition of this oil-soluble complex is MeR 2 , where Me denotes Hg 2+ , Cd 2+ , Zn 2+ , Cu 2+ , and Ni 2+ , and R denotes LIX84 R . This composition makes the complex electrically neutral, and all polar groups are located inside the molecule. The extraction efficiency of the complexer LIX84 R for the various metal ions is evident in the succession Cu 2+ , Ni 2+ >> Zn 2+ > Hg 2+ > Cd 2+ . These heavy metal ions are even readily extractable at chloride concentrations of up to 1 mol/l. As the structure of the complexer is that of an oil-soluble surfactant with complexing properties, it accumulates at the phase boundary between oil and water. Measurement of interfacial tension in various solvent systems showed that the polar solvent chloroform permits only a weak accumulation of the complexer (400 nmol/m 2 ), whereas the unpolar solvent kerosine permits greater accumulation specifically on the water side of the phase boundary (1958 nmol/m 2 ). Organic solvents solvate the complexer so well, that it is even removed from the air side of the phase boundary. The differing accumulation of the complexer at the water/oil phase boundary explains the differing increase of phase separation time for polar and unpolar solvents. (orig.) [de

  7. Ligandless-dispersive liquid-liquid microextraction of trace amount of copper ions

    International Nuclear Information System (INIS)

    Mohammadi, Sayed Zia; Afzali, Daryoush; Baghelani, Yar Mohammad

    2009-01-01

    In the present work, a new ligandless-dispersive liquid-liquid microextraction (LL-DLLME) method has been developed for preconcentration trace amounts of copper as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents, respectively. Some factors influencing on the extraction efficiency of copper and its subsequent determination were studied and optimized, such as the extraction and dispersive solvent type and volume, pH of sample solution, extraction time and salting out effect. Under the optimal conditions, the calibration curve was linear in the range of 1.0 ng mL -1 -0.6 μg mL -1 of copper with R 2 = 0.9985. Detection limit was 0.5 ng mL -1 in original solution (3S b /m) and the relative standard deviation for seven replicate determination of 0.2 μg mL -1 copper was ±1.4%. The proposed method has been applied for determination of copper in standard and water samples with satisfactory results.

  8. Application of liquid-liquid extraction in separation of rare earths [Paper No. : V-6

    International Nuclear Information System (INIS)

    Deshpande, S.M.; Krishnan, N.P.K.; Murthy, T.K.S.; Swaminathan, T.V.

    1979-01-01

    The rare earths consist of fifteen elements which have very similar chemical properties and are difficult to separate from each other. Since they exist together in all naturally occurring minerals their separation is one of the important and difficult aspects of their technology. Liquid-liquid extraction has proved to be an efficient technique for their separation. The two important extraction systems that find practical and large scale application, the nitric acid + tri-n-butyl phosphate, and mineral acid (particularly hydrochloric acid) + organo phosphoric acid (like di-2-ethyl hexyl phosphoric acid), are briefly reviewed. The factors affecting the extraction and separation of rare earths in the two systems are discussed. On an industrial scale the extraction process is very often employed for an initial concentration of the desired rare earths from complex mixtures. The final purification is generally achieved by the ion exchange method. The utility of the solvent extraction process for the upgrading of selected rare earths-europium, samarium and gadolinium-from a mixed rare earth chloride, derived from monazite, is illustrated by the work carried out in this laboratory and pilot plant operation at the Alwaye plant of M/s. Indian Rare Earths Ltd. (author)

  9. Predictive thermodynamic models for liquid--liquid extraction of single, binary and ternary lanthanides and actinides

    International Nuclear Information System (INIS)

    Hoh, Y.C.

    1977-03-01

    Chemically based thermodynamic models to predict the distribution coefficients and the separation factors for the liquid--liquid extraction of lanthanides-organophosphorus compounds were developed by assuming that the quotient of the activity coefficients of each species varies slightly with its concentrations, by using aqueous lanthanide or actinide complexes stoichiometric stability constants expressed as its degrees of formation, by making use of the extraction mechanism and the equilibrium constant for the extraction reaction. For a single component system, the thermodynamic model equations which predict the distribution coefficients, are dependent on the free organic concentration, the equilibrated ligand and hydrogen ion concentrations, the degree of formation, and on the extraction mechanism. For a binary component system, the thermodynamic model equation which predicts the separation factors is the same for all cases. This model equation is dependent on the degrees of formation of each species in their binary system and can be used in a ternary component system to predict the separation factors for the solutes relative to each other

  10. Multimycotoxin LC-MS/MS Analysis in Tea Beverages after Dispersive Liquid-Liquid Microextraction (DLLME).

    Science.gov (United States)

    Pallarés, Noelia; Font, Guillermina; Mañes, Jordi; Ferrer, Emilia

    2017-11-29

    The aim of the present study was to develop a multimycotoxin liquid chromatography tandem mass spectrometry (LC-MS/MS) method with a dispersive liquid-liquid microextraction procedure (DLLME) for the analysis of AFs, 3aDON, 15aDON, NIV, HT-2, T-2, ZEA, OTA, ENNs, and BEA in tea beverages and to evaluate their mycotoxin contents. The proposed method was characterized in terms of linearity, limits of detection (LODs), limits of quantification (LOQs), recoveries, repeatability (intraday precision), reproducibility (interday precision), and matrix effects to check suitability. The results show LODs in the range of 0.05-10 μg/L, LOQs in the range of 0.2-33 μg/L, and recoveries in the range of 65-127% (RSD tea, red tea, green tea, and green mint tea. The results show that, of the analyzed mycotoxins, AFB2, AFG2, 15aDON, AFG1, and ENB were detected in the samples. AFB2 (14.4-32.2 μg/L) and 15aDON (60.5-61 μg/L) presented the highest levels. Green mint tea contained the highest concentration of mycotoxins. The risk assessment study shows that the population is not much exposed to mycotoxins through the consumption of tea beverages.

  11. A technical review of liquid/liquid and solid/liquid separation equipment in the field of nuclear-fuel reprocessing

    International Nuclear Information System (INIS)

    Vassallo, G.

    1981-01-01

    Liquid/liquid extraction is generally accepted as the preferred method in nuclear-fuel reprocessing. However, although many types of liquid/liquid contactors are available, only a few meet the stringent specifications set by the nuclear industry. This report discusses the criteria for contactor selection and then reviews the most important types, namely packed columns, pulsed columns, mixer-setters and centrifugal contactors. Finally, a short section concerned with solid/liquid separations is included because of the possible deleterious effects caused by solids in liquid/liquid contactors

  12. Ultra-trace determination of gold nanoparticles in environmental water by surfactant assisted dispersive liquid liquid microextraction coupled with electrothermal vaporization-inductively coupled plasma-mass spectrometry

    Science.gov (United States)

    Liu, Ying; He, Man; Chen, Beibei; Hu, Bin

    2016-08-01

    A new method by coupling surfactant assisted dispersive liquid liquid microextraction (SA-DLLME) with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was proposed for the analysis of gold nanoparticles (AuNPs) in environmental water samples. Effective separation of AuNPs from ionic gold species was achieved by using sodium thiosulphate as a complexing agent. Various experimental parameters affecting SA-DLLME of AuNPs, such as the organic solvent, organic solvent volume, pH of the sample, the kind of surfactant, surfactant concentration, vortex time, speed of centrifugation, centrifugation time, and different coating as well as sizes of AuNPs were investigated carefully. Furthermore, the interference of coexisting ions, dissolved organic matter (DOM) and other metal nanoparticles (NPs) were studied. Under the optimal conditions, a detection limit of 2.2 ng L- 1 and an enrichment factor of 152-fold was achieved for AuNPs, and the original morphology of the AuNPs could be maintained during the extraction process. The developed method was successfully applied for the analysis of AuNPs in environmental water samples, including tap water, the East Lake water, and the Yangtze River water, with recoveries in the range of 89.6-102%. Compared with the established methods for metal NPs analysis, the proposed method has the merits of simple and fast operation, low detection limit, high selectivity, good tolerance to the sample matrix and no digestion or dilution required. It provides an efficient quantification methodology for monitoring AuNPs' pollution in the environmental water and evaluating its toxicity.

  13. Homogeneous and Stratified Liquid-Liquid Flow Effect of a Viscosity Reducer: I. Comparison in parallel plates for heavy crude

    Directory of Open Access Journals (Sweden)

    E. J. Suarez-Dominguez

    2016-12-01

    Full Text Available Production of heavy crude oil in Mexico, and worldwide, is increasing which has led to the application of different methods to reduce viscosity or to enhance transport through stratified flow to continue using the existing infrastructures. In this context, injecting a viscosity improver that does not mix completely with the crude, establishes a liquid-liquid stratified flow. On the basis of a parallel plates model, comparing the increase of flow that occurs in the one-phase case which assumes a complete mixture between the crude and the viscosity improver against another stratified liquid-liquid (no mixing between the oil and compared improver; it was found that in both cases there is a flow increase for the same pressure drop with a maximum for the case in which the flow improver is between the plates and the crude.

  14. Liquid-liquid extraction assisted by a carbon nanoparticles interface. Electrophoretic determination of atrazine in environmental samples.

    Science.gov (United States)

    Caballero-Díaz, Encarnación; Simonet, Bartolomé; Valcárcel, Miguel

    2013-10-21

    A novel method for the determination of atrazine, using liquid-liquid extraction assisted by a nanoparticles film formed in situ and composed of organic solvent stabilized-carbon nanoparticles, is described. The presence of nanoparticles located at the liquid-liquid interface reinforced the extraction of analyte from matrix prior to capillary electrophoresis (CE) analysis. Some influential experimental variables were optimized in order to enhance the extraction efficiency. The developed procedure confirmed that carbon nanoparticles, especially multi-walled carbon nanotubes, are suitable to be used in sample treatment processes introducing new mechanisms of interaction with the analyte. The application of the proposed preconcentration method followed by CE detection enabled the determination of atrazine in spiked river water providing acceptable RSD values (11.6%) and good recoveries (about 87.0-92.0%). Additionally, a similar extraction scheme was tested in soil matrices with a view to further applications in real soil samples.

  15. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants

    International Nuclear Information System (INIS)

    Toulemonde, V.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

    1995-01-01

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author)

  16. About the Shape of the Melting Line as a Possible Precursor of a Liquid-Liquid Phase Transition

    Science.gov (United States)

    Imre, Attila R.; Rzoska, Sylwester J.

    Several simple, non-mesogenic liquids can exists in two or more different liquid forms. When the liquid-liquid line, separating two liquid forms, meets the melting line, one can expect some kind of break on the melting line, caused by the different freezing/melting behaviour of the two liquid forms. Unfortunately recently several researchers are using this vein of thinking in reverse; seeing some irregularity on the melting line, they will expect a break and the appearance of a liquid-liquid line. In this short paper, we are going to show, that in the case of the high-pressure nitrogen studied recently by Mukherjee and Boehler, the high-pressure data can be easily described by a smooth, break-free function, the modified Simon-Glatzel equation. In this way, the break, suggested by them and consequently the suggested appearance of a new liquid phase of the nitrogen might be artefacts.

  17. CONTRIBUTION TO THE DEVELOPMENT OF A SIMULATION SOFTWARE PERFORMANCE AND SHARING RATIO IN LIQUID-LIQUID EXTRACTION

    Directory of Open Access Journals (Sweden)

    A. Hadj Seyd

    2015-07-01

    Full Text Available The present work is to develop software to predict the value yield and the distribution coefficient in the process of liquid-liquid extraction of components of a mixture, from mathematical models expressing these entities, based on equations equilibrium between liquid-liquid phases, and predict the conditions under which the extraction operation is favorable, unfavorable or impossible to realize, by studying the variation of the entities cited, based on the parameters influencing the extraction, which are: initial concentrations, rate of solvent and pH, in the case of a simple extraction (extraction of neutral products or when it is reactive (extraction of complex acids or bases for one or more components.The programming language used is "Delphi" which is a very powerful oriented object programming under Windows.

  18. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air.

    Science.gov (United States)

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-04-08

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m²/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

  19. Literature Review: Crud Formation at the Liquid/Liquid Interface of TBP-Based Solvent-Extraction Processes

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Casella, Amanda J.

    2016-09-30

    This report summarizes the literature reviewed on crud formation at the liquid:liquid interface of solvent extraction processes. The review is focused both on classic PUREX extraction for industrial reprocessing, especially as practiced at the Hanford Site, and for those steps specific to plutonium purification that were used at the Plutonium Reclamation Facility (PRF) within the Plutonium Finishing Plant (PFP) at the Hanford Site.

  20. (Liquid + liquid) equilibria of four alcohol–water systems containing 1,8-cineole at T = 298.15 K

    International Nuclear Information System (INIS)

    Li, Hengde; Feng, Zhangni; Wan, Li; Huang, Cheng; Zhang, Tianfei; Fang, Yanxiong

    2016-01-01

    Graphical abstract: (Liquid + liquid) equilibria of C_1–C_4 alcohol–water systems containing 1,8-cineole are presented. Distribution ratios of alcohol in the mixtures are examined. The immiscible region of the LLE systems is evaluated and discussed. - Highlights: • Ternary (liquid + liquid) equilibria containing 1,8-cineole are presented. • Distribution ratios of C_1–C_4 alcohol in the mixtures are examined. • The LLE values were correlated using the NRTL and UNIQUAC models. - Abstract: As an eco-friendly compound from essential oils, 1,8-cineole (cineole, eucalyptol) has the potential to replace the ozone depleting industrial solvents. This paper presents experimental (liquid + liquid) equilibrium (LLE) data for four alcohol–water systems containing 1,8-cineole. To evaluate the phase equilibrium properties of 1,8-cineole in aqueous alcohol mixtures, LLE values for the ternary systems (water + methanol or ethanol or 1-propanol or 1-butanol + 1,8-cineole) were determined with a tie-line method at T = 298.15 K under atmospheric pressure. The well-known Hand, Bachman and Othmer–Tobias equations were used to test the reliability of the experimental results. The binodal curves and distribution ratios of alcohol in the mixtures are shown and discussed. The experimental LLE values were satisfactorily correlated by the NRTL and UNIQUAC models.

  1. Vortex-assisted liquid-liquid microextraction for the rapid screening of short-chain chlorinated paraffins in water.

    Science.gov (United States)

    Chang, Chia-Yu; Chung, Wu-Hsun; Ding, Wang-Hsien

    2016-01-01

    The rapid screening of trace levels of short-chain chlorinated paraffins in various aqueous samples was performed by a simple and reliable procedure based on vortex-assisted liquid-liquid microextraction combined with gas chromatography and electron capture negative ionization mass spectrometry. The optimal vortex-assisted liquid-liquid microextraction conditions for 20 mL water sample were as follows: extractant 400 μL of dichloromethane; vortex extraction time of 1 min at 2500 × g; centrifugation of 3 min at 5000 × g; and no ionic strength adjustment. Under the optimum conditions, the limit of quantitation was 0.05 μg/L. Precision, as indicated by relative standard deviations, was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was above 91%. The vortex-assisted liquid-liquid microextraction with gas chromatography and electron capture negative ionization mass spectrometry method was successfully applied to quantitatively extract short-chain chlorinated paraffins from samples of river water and the effluent of a wastewater treatment plant, and the concentrations ranged from 0.8 to 1.6 μg/L. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Rational approach to solvent system selection for liquid-liquid extraction-assisted sample pretreatment in counter-current chromatography.

    Science.gov (United States)

    Wang, Jiajia; Gu, Dongyu; Wang, Miao; Guo, Xinfeng; Li, Haoquan; Dong, Yue; Guo, Hong; Wang, Yi; Fan, Mengqi; Yang, Yi

    2017-05-15

    A rational liquid-liquid extraction approach was established to pre-treat samples for high-speed counter-current chromatography (HSCCC). n-Hexane-ethyl acetate-methanol-water (4:5:4:5, v/v) and (1:5:1:5, v/v) were selected as solvent systems for liquid-liquid extraction by systematically screening K of target compounds to remove low- and high-polarity impurities in the sample, respectively. After liquid-liquid extraction was performed, 1.4g of crude sample II was obtained from 18.5g of crude sample I which was extracted from the flowers of Robinia pseudoacacia L., and then separated with HSCCC by using a solvent system composed of n-hexane-ethyl acetate-methanol-water (1:2:1:2, v/v). As a result, 31mg of robinin and 37mg of kaempferol 7-O-α-l-rhamnopyranoside were isolated from 200mg of crude sample II in a single run of HSCCC. A scale-up separation was also performed, and 160mg of robinin with 95% purity and 188mg of kaempferol 7-O-α-l-rhamnopyranoside with 97% purity were produced from 1.2g of crude sample II. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Influence of the temperature on the (liquid + liquid) phase equilibria of (water + 1-propanl + linalool or geraniol)

    International Nuclear Information System (INIS)

    Wan, Li; Li, Hengde; Huang, Cheng; Feng, Yuqing; Chu, Guoqiang; Zheng, Yuying; Tan, Wei; Qin, Yanlin; Sun, Dalei; Fang, Yanxiong

    2017-01-01

    Highlights: • Ternary LLEs containing linalool and geraniol are presented. • Distribution ratios of 1-propanol in the mixtures are examined. • Influence of the temperature on the LLE is studied. • The LLE data were correlated using the NRTL and UNIQUAC models. - Abstract: Linalool and geraniol are the primary components of rose oil, palmarosa oil, and citronella oil and many other essential oils, and two important compounds used in the flavour and fragrance, cosmetic or pharmaceutical industries. Phase equilibria (LLE, VLE, solubility, etc.) and related thermodynamic properties of a mixture are essential in the processes design and control of mass transfer process. In this work, experimental (liquid + liquid) equilibria data of the systems (water + 1-propanl + linalool) and (water + 1-propanl + geraniol) are presented. The (liquid + liquid) equilibria of both systems were determined with a tie-line method at T = (283.15, 298.15 and 313.15) K under atmospheric pressure. The well-known Hand, Bachman and Othmer–Tobias equations were used to test the reliability of the experimental values. The influence of the temperature on the (liquid + liquid) phase equilibria of the mixtures, the binodal curves and distribution ratios of 1-propanl are shown and discussed. Moreover, the NRTL and UNIQUAC models were applied to fit the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. Furthermore, the ternary systems could be represented using the binary parameters of the thermodynamic model with a function of temperature.

  4. Modeling the liquid-liquid interface and the transfer of a solute by molecular dynamics simulation

    International Nuclear Information System (INIS)

    Hayoun, Marc

    1990-11-01

    Molecular Dynamics method and Lennard-Jones potential functions have been employed to model Liquid-Liquid Interfaces. The variation of the miscibilities between the two liquids is obtained by changing the interaction between the two atomic species. The resulting interfaces have a thickness of about three atomic diameters and are stable on the time scale of the simulation. They have been characterized by the density and pressure profiles. The interfacial tension has also been computed and is of the order of magnitude of experimental values. The diffusion process is anisotropic in the interfacial region: the transverse diffusion coefficient (parallelly to the interface) is higher than the normal one. A qualitative explanation of this behaviour is suggested by considering the pressure tensor. The second part of this work, performed by Molecular Dynamics in the canonical ensemble, is devoted to the kinetic study of the transfer of a solute through the interface. A model of a symmetric interface with an atomic solute has been used. The interaction potential between the solute and the solvents has been built in order to obtain an activation barrier to the transfer. We have computed the mean force exerted by the solvent on the solute as a function of its distance to the interface. The resulting mean force potential corresponds to a free energy difference. The height of the energy barrier involved is about 4 kT. The potential energy and entropy profiles have also been calculated and discussed. The diffusion coefficient of the solute has been computed by equilibrium and non-equilibrium methods. We deduced the friction coefficient of the solvent, which is essential to determine the Kramers transmission coefficient. This coefficient is compared to the one obtained by simulation. Finally, the solute transfer rate constant has been calculated. (author) [fr

  5. Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

    Science.gov (United States)

    Giovambattista, Nicolas

    2013-03-01

    Most liquids can form a single glass or amorphous state when cooled sufficiently fast (in order to prevent crystallization). However, there are a few substances that are relevant to scientific and technological applications which can exist in at least two different amorphous states, a property known as polyamorphism. Examples include silicon, silica, and in particular, water. In the case of water, experiments show the existence of a low-density (LDA) and high-density (HDA) amorphous ice that are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation evolves into a first-order liquid-liquid phase transition (LLPT) at temperatures above the glass transition temperature Tg. However, obtaining direct experimental evidence of the LLPT has been challenging since the LLPT occurs at conditions where water rapidly crystallizes. In this talk, I will (i) discuss the general phenomenology of polyamorphism in water and its implications, and (ii) explore the effects of a LLPT on the pressure dependence of Tg(P) for LDA and HDA. Our study is based on computer simulations of two water models - one with a LLPT (ST2 model), and one without (SPC/E model). In the absence of a LLPT, Tg(P) for all glasses nearly coincide. Instead, when there is a LLPT, different glasses exhibit dramatically different Tg(P) loci which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario that includes a LLPT (ST2 model) and hence, our results support the view that a LLPT may exist for the case of water.

  6. Pesticide extraction from table grapes and plums using ionic liquid based dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Herrera-Herrera, Antonio V; Rodríguez-Delgado, Miguel Angel

    2009-12-01

    Room temperature ionic liquids (RTILs) have been used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the determination of eight multi-class pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox, and fenazaquin) in table grapes and plums. The developed method involves the combination of DLLME and high-performance liquid chromatography with diode array detection. Samples were first homogenized and extracted with acetonitrile. After evaporation and reconstitution of the extract in water containing sodium chloride, a quick DLLME procedure that used the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) and methanol was developed. The RTIL dissolved in a very small volume of acetonitrile was directed injected in the chromatographic system. The comparison between the calibration curves obtained from standards and from spiked sample extracts (matrix-matched calibration) showed the existence of a strong matrix effect for most of the analyzed pesticides. A recovery study was also developed with five consecutive extractions of the two types of fruits spiked at three concentration levels. Mean recovery values were in the range of 72-100% for table grapes and 66-105% for plum samples (except for thiophanate-methyl and carbofuran, which were 64-75% and 58-66%, respectively). Limits of detection (LODs) were in the range 0.651-5.44 microg/kg for table grapes and 0.902-6.33 microg/kg for plums, representing LODs below the maximum residue limits (MRLs) established by the European Union in these fruits. The potential of the method was demonstrated by analyzing 12 commercial fruit samples (six of each type).

  7. Ionic liquid based dispersive liquid-liquid microextraction for the extraction of pesticides from bananas.

    Science.gov (United States)

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Asensio-Ramos, María; Rodríguez-Delgado, Miguel Angel

    2009-10-23

    This paper describes a dispersive liquid-liquid microextraction (DLLME) procedure using room temperature ionic liquids (RTILs) coupled to high-performance liquid chromatography with diode array detection capable of quantifying trace amounts of eight pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox and fenazaquin) in bananas. Fruit samples were first homogenized and extracted (1g) with acetonitrile and after suitable evaporation and reconstitution of the extract in 10 mL of water, a DLLME procedure using 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) as extraction solvent was used. Experimental conditions affecting the DLLME procedure (sample pH, sodium chloride percentage, ionic liquid amount and volume of disperser solvent) were optimized by means of an experimental design. In order to determine the presence of a matrix effect, calibration curves for standards and fortified banana extracts (matrix matched calibration) were studied. Mean recovery values of the extraction of the pesticides from banana samples were in the range of 69-97% (except for thiophanate-methyl and carbofuran, which were 53-63%) with a relative standard deviation lower than 8.7% in all cases. Limits of detection achieved (0.320-4.66 microg/kg) were below the harmonized maximum residue limits established by the European Union (EU). The proposed method, was also applied to the analysis of this group of pesticides in nine banana samples taken from the local markets of the Canary Islands (Spain). To the best of our knowledge, this is the first application of RTILs as extraction solvents for DLLME of pesticides from samples different than water.

  8. Entropy-driven metastable defects in silicon

    International Nuclear Information System (INIS)

    Hamilton, B.; Peaker, A.R.; Pantelides, S.T.

    1989-01-01

    The known metastable defects are usually describable by a configuration coordinate diagram in which two energy minima are separated by a barrier. This diagram does not change with temperature and each configuration is stable over some temperature range. Here we report the observation of a novel metastability: A configuration change occurs spontaneously and abruptly at a critical temperature, giving rise to a discontinuous DLTS (deep level transient spectroscopy) spectrum. We propose that this phenomenon is a manifestation of entropy variations in the configurational space. (author) 12 refs., 4 figs

  9. Chalcogenides Metastability and Phase Change Phenomena

    CERN Document Server

    Kolobov, Alexander V

    2012-01-01

    A state-of-the-art description of metastability observed in chalcogenide alloys is presented with the accent on the underlying physics. A comparison is made between sulphur(selenium)-based chalcogenide glasses, where numerous photo-induced phenomena take place entirely within the amorphous phase, and tellurides where a reversible crystal-to-amorphous phase-change transformation is a major effect. Applications of metastability in devices¿optical memories and nonvolatile electronic phase-change random-access memories among others are discussed, including the latest trends. Background material essential for understanding current research in the field is also provided.

  10. Memory, Conviviality and Coexistence

    DEFF Research Database (Denmark)

    Duru, Deniz Neriman

    2016-01-01

    that postulates cohesion and conflict as rooted in ethnic and religious differences. It suggests ‘conviviality’ as the production of space, by arguing that hard times, tensions as well as sensorial pleasures produce a sense of belonging in a place, through shared ways of living. While memories of ‘coexistence......The article explores the narratives and memories of past diversity and current practices of conviviality to investigate how class, lifestyle and tastes affect the daily interactions between people belonging to different ethno-religious backgrounds. This chapter critiques ‘coexistence’ as a concept......’ emphasize the fragmentation of people into ethnic and religious groups as a consequence of the homogenization process in the post-Ottoman Turkish context, bitter sweet memories of conviviality create a sense of belonging to Burgaz....

  11. Effect of mixing rule boundary conditions on high pressure (liquid + liquid) equilibrium prediction

    International Nuclear Information System (INIS)

    Hsieh, Min-Kang; Lin, Shiang-Tai

    2012-01-01

    Highlights: ► Prediction of LLE from the combined use of EOS and liquid model are examined. ► The mixing rule used affects the predicted pressure dependence of LLE. ► MHV1 mixing rule predicts decent LLE at low pressures. ► WS mixing rule predicts more accurate excess volume and LLE at high pressures. ► The hybrid of MHV1 and WS mixing rule gives overall the best predictions. - Abstract: We examine the prediction of high pressure (liquid + liquid) equilibrium (LLE) from the Peng–Robinson equation with three excess Gibbs free energy (G ex )-based mixing rules (MR): the first order modified Huron–Vidal (MHV1), the Wong–Sandler (WS), and a hybrid of these two (referred to as G ex B 2 ). These mixing rules differ by the boundary conditions used for determination of the temperature and composition dependence of parameters a and b in the PR EOS. The condition of matching the excess Gibbs free energy from the EOS at zero pressure to that from the G ex model, used in MHV1 and G ex B 2 MR, leads to a similar miscibility gap from PR EOS and the G ex model used. On the other hand, the condition of matching excess Helmholtz energy from the EOS at infinite pressure to that from the G ex model, used in the WS MR, shows remarkable deviations. The condition of quadratic composition dependence in the second virial coefficient (B 2 ), used in WS and G ex B 2 MR, allows for both positive and negative values in the molar excess volume. Depending on the mixture, either the increase or decrease of the miscibility gap with pressure can be observed when the WS or the G ex B 2 MR is used. The condition of linear combination of molecular sizes of each component used in the MHV1 MR, however, often leads to small, positive molar excess volumes. As a consequence, the predicted LLE from using the MHV1 MR are insensitive to pressure. Therefore, we find that the G ex B 2 mixing rule provides the best predictive power for the LLE over a wide range of temperature and pressure.

  12. Review of algorithms for modeling metal distribution equilibria in liquid-liquid extraction processes

    Directory of Open Access Journals (Sweden)

    Lozano, L. J.

    2005-10-01

    Full Text Available This work focuses on general guidelines to be considered for application of least-squares routines and artificial neural networks (ANN in the estimation of metal distribution equilibria in liquid-liquid extraction process. The goal of the procedure in the statistical method is to find the values of the equilibrium constants (Kj for the reactions involved in the metal extraction which minimizes the differences between experimental distribution coefficient (Dexp and theoretical distribution coefficients according to the mechanism proposed (Dtheor- In the first part of the article, results obtained with the most frequently routine reported in the bibliography are compared with those obtained using the algorithms previously discussed. In the second part, the main features of a single back-propagation neural network for the same purpose are discussed, and the results obtained are compared with those obtained with the classical methods.

    El trabajo presenta las líneas generales a considerar para la estimación del equilibrio de distribución de metales en procesos de extracción líquido-líquido, según dos métodos: algoritmo clásico de mínimos cuadrados y redes neuronales artificiales. El objetivo del procedimiento, en el caso del método estadístico, es encontrar los valores de las constantes de equilibrio (Kj para las reacciones involucradas en la extracción del metal, que minimizan las diferencias entre el coeficiente de distribución experimental y el coeficiente de distribución teórico, de acuerdo al mecanismo propuesto. En la primera parte del artículo se comparan los resultados obtenidos a partir de los algoritmos usados más habitualmente en la bibliografía, con los datos obtenidos mediante el algoritmo previamente descrito. En la segunda parte, se presentan las características fundamentales para aplicar una red neuronal sencilla con algoritmo back-propagation y los

  13. Inelastic collision rates of trapped metastable hydrogen

    NARCIS (Netherlands)

    Landhuis, D; Matos, L; Moss, SC; Steinberger, JK; Vant, K; Willmann, L; Greytak, TJ; Kleppner, D

    We report the first detailed decay studies of trapped metastable (2S) hydrogen. By two-photon excitation of ultracold H samples, we have produced clouds of at least 5x10(7) magnetically trapped 2S atoms at densities greater than 4x10(10) cm(-3) and temperatures below 100 muK. At these densities and

  14. Modelling the material behaviour of metastable stainless

    NARCIS (Netherlands)

    Datta, K.; Geijselaers, Hubertus J.M.; Post, J.; Beyer, J.; Huetink, Han; Cesar de Sa, Jose M.A.; Santos, Abel D.

    2007-01-01

    Metastable austenitic stainless steels are designed to be thermodynamically unstable such that deformation even at room temperatures can bring about a change in the phase of face centred cubic austenite to either hexagonal close packed martensite and/or to body centred cubic martensite. This solid

  15. Inflating metastable quark-gluon plasma universe

    International Nuclear Information System (INIS)

    Jenkovszky, L.L.; Kaempfer, B.; Sysoev, V.M.

    1990-01-01

    We show within the Friedmann model with the equation of state p(T)=aT 4 -AT that our universe has expanded exponentially when it was in a metastable quark-gluon plasma state. The scale factor during that epoch increased by many orders of magnitude. 13 refs.; 5 figs

  16. Metastable and bistable defects in silicon

    International Nuclear Information System (INIS)

    Mukashev, Bulat N; Abdullin, Kh A; Gorelkinskii, Yurii V

    2000-01-01

    Existing data on the properties and structure of metastable and bistable defects in silicon are analyzed. Primary radiation-induced defects (vacancies, self-interstitial atoms, and Frenkel pairs), complexes of oxygen, carbon, hydrogen, and other impurity atoms and defects with negative correlation energy are considered. (reviews of topical problems)

  17. "Liquid-liquid-solid"-type superoleophobic surfaces to pattern polymeric semiconductors towards high-quality organic field-effect transistors.

    Science.gov (United States)

    Wu, Yuchen; Su, Bin; Jiang, Lei; Heeger, Alan J

    2013-12-03

    Precisely aligned organic-liquid-soluble semiconductor microwire arrays have been fabricated by "liquid-liquid-solid" type superoleophobic surfaces directed fluid drying. Aligned organic 1D micro-architectures can be built as high-quality organic field-effect transistors with high mobilities of >10 cm(2) ·V(-1) ·s(-1) and current on/off ratio of more than 10(6) . All these studies will boost the development of 1D microstructures of organic semiconductor materials for potential application in organic electronics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. APPLICATION OF A GENERALIZED MAXIMUM LIKELIHOOD METHOD IN THE REDUCTION OF MULTICOMPONENT LIQUID-LIQUID EQUILIBRIUM DATA

    Directory of Open Access Journals (Sweden)

    L. STRAGEVITCH

    1997-03-01

    Full Text Available The equations of the method based on the maximum likelihood principle have been rewritten in a suitable generalized form to allow the use of any number of implicit constraints in the determination of model parameters from experimental data and from the associated experimental uncertainties. In addition to the use of any number of constraints, this method also allows data, with different numbers of constraints, to be reduced simultaneously. Application of the method is illustrated in the reduction of liquid-liquid equilibrium data of binary, ternary and quaternary systems simultaneously

  19. Aluminium sensitized spectrofluorimetric determination of fluoroquinolones in milk samples coupled with salting-out assisted liquid-liquid ultrasonic extraction

    Science.gov (United States)

    Xia, Qinghai; Yang, Yaling; Liu, Mousheng

    2012-10-01

    An aluminium sensitized spectrofluorimetric method coupled with salting-out assisted liquid-liquid ultrasonic extraction for the determination of four widely used fluoroquinolones (FQs) namely norfloxacin (NOR), ofloxacin (OFL), ciprofloxacin (CIP) and gatifloxacin (GAT) in bovine raw milk was described. The analytical procedure involves the fluorescence sensitization of aluminium (Al3+) by complexation with FQs, salting-out assisted liquid-liquid ultrasonic extraction (SALLUE), followed by spectrofluorometry. The influence of several parameters on the extraction (the salt species, the amount of salt, pH, temperature and phase volume ratio) was investigated. Under optimized experimental conditions, the detection limits of the method in milk varied from 0.009 μg/mL for NOR to 0.016 μg/mL for GAT (signal-to-noise ratio (S/N) = 3). The relative standard deviations (RSD) values were found to be relatively low (0.54-2.48% for four compounds). The calibration graph was linear from 0.015 to 2.25 μg/mL with coefficient of determinations not less than 0.9974. The methodology developed was applied to the determination of FQs in bovine raw milk samples. The main advantage of this method is simple, accurate and green. The method showed promising applications for analyzing polar analytes especially polar drugs in various sample matrices.

  20. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

    2011-07-01

    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  1. Quaternary (liquid + liquid) equilibrium data for the extraction of toluene from alkanes using the ionic liquid [EMim][MSO4

    International Nuclear Information System (INIS)

    Corderí, Sandra; Calvar, Noelia; Gómez, Elena; Domínguez, Ángeles

    2014-01-01

    Highlights: • EMim[MSO 4 ] was proposed as solvent for the extraction of toluene from alkanes. • The quaternary system {heptane + cyclohexane + toluene + [EMim][MSO 4 ]} was evaluated. • The extraction of toluene would be facilitated in the presence of one alkane. • Experimental LLE data were successfully correlated with the NRTL model. - Abstract: (Liquid + liquid) equilibrium (LLE) studies for the extraction of aromatics from alkanes present in the petroleum fractions are important to develop theoretical/semiempirical (liquid + liquid) equilibrium models, which are used in the design of extraction processes. In this work, the ionic liquid 1-ethyl-3-methylimidazolium methylsulfate, [EMim][MSO 4 ], was evaluated as potential solvent for the separation of toluene from heptane and cyclohexane. The LLE data for the quaternary system {heptane (1) + cyclohexane (2) + toluene (3) + [EMim][MSO 4 ] (4)} were experimentally determined at T = 298.15 K and atmospheric pressure. Moreover, the LLE data for the ternary systems {heptane or cyclohexane (1) + toluene (2) + [EMim][MSO 4 ] (3)} were also determined. Solute distribution ratios and selectivities were calculated and analysed in order to evaluate the capability of the ionic liquid to accomplish the separation target. A comparison between the solute distribution ratios and selectivities for the quaternary and the ternary systems was also made. Finally, the experimental tie-line data were correlated with the NRTL model

  2. Fabrication of Supramolecular Chirality from Achiral Molecules at the Liquid/Liquid Interface Studied by Second Harmonic Generation.

    Science.gov (United States)

    Lin, Lu; Zhang, Zhen; Guo, Yuan; Liu, Minghua

    2018-01-09

    We present the investigation into the supramolecular chirality of 5-octadecyloxy-2-(2-pyridylazo)phenol (PARC18) at water/1,2-dichloroethane interface by second harmonic generation (SHG). We observe that PARC18 molecules form supramolecular chirality through self-assembly at the liquid/liquid interface although they are achiral molecules. The bulk concentration of PARC18 in the organic phase has profound effects on the supramolecular chirality. By increasing bulk concentration, the enantiomeric excess at the interface first grows and then decreases until it eventually vanishes. Further analysis reveals that the enantiomeric excess is determined by the twist angle of PARC18 molecules at the interface rather than their orientational angle. At lower and higher bulk concentrations, the average twist angle of PARC18 molecules approaches zero, and the assemblies are achiral; whereas at medium bulk concentrations, the average twist angle is nonzero, so that the assemblies show supramolecular chirality. We also estimate the coverage of PARC18 molecules at the interface versus the bulk concentration and fit it to Langmuir adsorption model. The result indicates that PARC18 assemblies show strongest supramolecular chirality in a half-full monolayer. These findings highlight the opportunities for precise control of supramolecular chirality at liquid/liquid interfaces by manipulating the bulk concentration.

  3. Thermodynamic modeling of ternary and quaternary (liquid + liquid) systems containing water, FeCl3, HCl and diisopropyl ether

    International Nuclear Information System (INIS)

    Milosevic, Miran; Hendriks, Ilse; Smits, Ralph E.R.; Schuur, Boelo; Haan, André B. de

    2013-01-01

    Highlights: • Literature data from various sources was validated experimentally. • Ternary and quaternary (liquid + liquid) systems were successfully described with the NRTL model. • Some deflection at higher HCl concentrations between model and data. • Additional data verification proved correctness of the literature data. -- Abstract: Liquid–liquid extraction using ethers as solvents is a potentially energy saving alternative for the concentration of aqueous ferric chloride solutions. Adequate thermodynamic models that describe the behavior of the resulting quaternary systems (FeCl 3 , ether, acid and water) are not available in the literature. In this paper, the development of an equilibrium description applying the NRTL-model is presented, including experimental validation and fitting of the NRTL-parameters on the validated data. Equilibrium experiments were performed for the ternary systems (water + HCl + DiPE) and (water + FeCl 3 + DiPE) and the obtained data is in good agreement with the results from Maljkovic et al.[37] and Cambell et al.[39]. Experimental data of the quaternary system is taken from Maljkovic et al.[37]. The obtained binary interaction parameters to describe the (liquid + liquid) quaternary system (water + FeCl 3 + HCl + DiPE) and the constituting ternaries by the NRTL model are presented. Model predictions are in good agreement with the experimental data

  4. Studies of extractant molecules in solution and at liquid-liquid interfaces: structural and mechanistic aspects of synergy effects

    International Nuclear Information System (INIS)

    Baaden, Marc

    2000-01-01

    Molecular dynamics simulations reported herein provide new important insights into cation recognition and complexation in solution as well as liquid-liquid extraction, with a particular focus on the microscopic events taking place at the interface between two immiscible liquids. Preliminary studies concerned the representation of the trivalent rare earth cations La 3+ , Eu 3+ and Yb 3+ in force field simulations, probing structural and energetic features on an experimentally characterized model system based on substituted pyridine dicarboxamide ligands. Complexation of such cations by a novel calixarene derivative was investigated showing unexpected features, such as the position of the cation in the complex. Independent experimental studies published subsequently support these findings. Another part of the work is related to industrial liquid-liquid extraction systems using tri-n-butyl phosphate (TBP) as co-solvent, extractant, surfactant and synergist. We investigate 1) concentration effects simulating up to 60 TBP at a water/chloroform interface, 2) acidity using a neutral and ionic model of HNO 3 and 3) synergistic aspects of mixed TBP/calixarene extraction systems. These simulations provide the first microscopic insights into such issues. We finally addressed the topic of solute transfer across the water/chloroform interface. The potential of mean force for such a process has been calculated by both standard methods and novel approaches [fr

  5. Metastable states in amorphous chalcogenide semiconductors

    CERN Document Server

    Mikla, Victor I

    2009-01-01

    This book addresses an interesting and technologically important class of materials, the amorphous chalcogenide semiconductors. Experimental results on the structural and electronic metastable states in Se-rich chalcogenides are presented. Special attention is paid to the states in the mobility gap and their sensitivity to various factors such as irradiation, annealing and composition. Photoinduced changes of structure and physical properties are also considered and structural transformation at photocrystallization is studied in detail. Finally, the authors discuss potential applications of th

  6. A Note on Scenarios of Metastable Water

    Czech Academy of Sciences Publication Activity Database

    Jirsák, Jan; Nezbeda, Ivo

    2010-01-01

    Roč. 75, č. 5 (2010), s. 593-605 ISSN 0010-0765 R&D Projects: GA AV ČR IAA400720802; GA AV ČR IAA200760905; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : metastable water * spinodal * scenarios Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.853, year: 2010

  7. Metastability in Field Theory and Statistical Mechanics

    International Nuclear Information System (INIS)

    Carvalho, C.A. de.

    1984-01-01

    After a phase transition analysis which can occur in the framework of a scalar field theory, at finite temperature and in presence of a external field, possibles metastable situations are studied and also how is their relationship with the transitions. In both cases it is used a semiclassical approximation to the theory which, in Statistical Mechanics, corresponds to the droplet-bubble model. (L.C.) [pt

  8. Investigation of metastable ions by mass spectrometry

    International Nuclear Information System (INIS)

    Szilagyi, Z.

    1998-01-01

    Metastable decompositions of ions was studied by various methods. The results are summarized in three chapters in this thesis. The development of a method can be used for evaluation of experimental data is described in the first chapter; the second one presents an example for the application of the developed method; and the laser power dependence of MALDI-TOF PSD (matrix-assisted laser desorption/ionization time-of-flight post-source decay) spectra is discussed in chapter three. (author)

  9. Metastability of Queuing Networks with Mobile Servers

    Science.gov (United States)

    Baccelli, F.; Rybko, A.; Shlosman, S.; Vladimirov, A.

    2018-04-01

    We study symmetric queuing networks with moving servers and FIFO service discipline. The mean-field limit dynamics demonstrates unexpected behavior which we attribute to the metastability phenomenon. Large enough finite symmetric networks on regular graphs are proved to be transient for arbitrarily small inflow rates. However, the limiting non-linear Markov process possesses at least two stationary solutions. The proof of transience is based on martingale techniques.

  10. Detonation of Meta-stable Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Kuhl, Allen; Kuhl, Allen L.; Fried, Laurence E.; Howard, W. Michael; Seizew, Michael R.; Bell, John B.; Beckner, Vincent; Grcar, Joseph F.

    2008-05-31

    We consider the energy accumulation in meta-stable clusters. This energy can be much larger than the typical chemical bond energy (~;;1 ev/atom). For example, polymeric nitrogen can accumulate 4 ev/atom in the N8 (fcc) structure, while helium can accumulate 9 ev/atom in the excited triplet state He2* . They release their energy by cluster fission: N8 -> 4N2 and He2* -> 2He. We study the locus of states in thermodynamic state space for the detonation of such meta-stable clusters. In particular, the equilibrium isentrope, starting at the Chapman-Jouguet state, and expanding down to 1 atmosphere was calculated with the Cheetah code. Large detonation pressures (3 and 16 Mbar), temperatures (12 and 34 kilo-K) and velocities (20 and 43 km/s) are a consequence of the large heats of detonation (6.6 and 50 kilo-cal/g) for nitrogen and helium clusters respectively. If such meta-stable clusters could be synthesized, they offer the potential for large increases in the energy density of materials.

  11. Metastable State Diamond Growth and its Applications to Electronic Devices.

    Science.gov (United States)

    Jeng, David Guang-Kai

    Diamond which consists of a dense array of carbon atoms joined by strong covalent bonds and formed into a tetrahedral crystal structure has remarkable mechanical, thermal, optical and electrical properties suitable for many industrial applications. With a proper type of doping, diamond is also an ideal semiconductor for high performance electronic devices. Unfortunately, natural diamond is rare and limited by its size and cost, it is not surprising that people continuously look for a synthetic replacement. It was believed for long time that graphite, another form of carbon, may be converted into diamond under high pressure and temperature. However, the exact condition of conversion was not clear. In 1939, O. I. Leipunsky developed an equilibrium phase diagram between graphite and diamond based on thermodynamic considerations. In the phase diagram, there is a low temperature (below 1000^ circC) and low pressure (below 1 atm) region in which diamond is metastable and graphite is stable, therefore establishes the conditions for the coexistence of the two species. Leipunsky's pioneer work opened the door for diamond synthesis. In 1955, the General Electric company (GE) was able to produce artificial diamond at 55k atm pressure and a temperature of 2000^ circC. Contrary to GE, B. Derjaguin and B. V. Spitzyn in Soviet Union, developed a method of growing diamonds at 1000^circC and at a much lower pressure in 1956. Since then, researchers, particularly in Soviet Union, are continuously looking for methods to grow diamond and diamond film at lower temperatures and pressures with slow but steady progress. It was only in the early 80's that the importance of growing diamond films had attracted the attentions of researchers in the Western world and in Japan. Recent progress in plasma physics and chemical vapor deposition techniques in integrated electronics technology have pushed the diamond growth in its metastable states into a new era. In this research, a microwave plasma

  12. Competitive intransitivity promotes species coexistence.

    Science.gov (United States)

    Laird, Robert A; Schamp, Brandon S

    2006-08-01

    Using a spatially explicit cellular automaton model with local competition, we investigate the potential for varied levels of competitive intransitivity (i.e., nonhierarchical competition) to promote species coexistence. As predicted, on average, increased levels of intransitivity result in more sustained coexistence within simulated communities, although the outcome of competition also becomes increasingly unpredictable. Interestingly, even a moderate degree of intransitivity within a community can promote coexistence, in terms of both the length of time until the first competitive exclusion and the number of species remaining in the community after 500 simulated generations. These results suggest that modest levels of intransitivity in nature, such as those that are thought to be characteristic of plant communities, can contribute to coexistence and, therefore, community-scale biodiversity. We explore a potential connection between competitive intransitivity and neutral theory, whereby competitive intransitivity may represent an important mechanism for "ecological equivalence."

  13. Determination of ten pyrethroids in various fruit juices: comparison of dispersive liquid-liquid microextraction sample preparation and QuEChERS method combined with dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Zhang, Yaohai; Zhang, Xuelian; Jiao, Bining

    2014-09-15

    Dispersive liquid-liquid microextraction (DLLME) sample preparation and the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with DLLME were developed and compared for the analysis of ten pyrethroids in various fruit juices using gas chromatography-electron capture detection (GC-ECD). QuEChERS-DLLME method has found its widespread applications to all the fruit juices including those samples with more complex matrices (orange, lemon, kiwi and mango) while DLLME was confined to the fruit juices with simpler matrices (apple, pear, grape and peach). The two methods provided acceptable recoveries and repeatability. In addition, the applicabilities of two methods were demonstrated with the real samples and further confirmed by gas chromatography-mass spectrometry (GC-MS). Copyright © 2014. Published by Elsevier Ltd.

  14. Liquid-liquid critical point in a simple analytical model of water

    Science.gov (United States)

    Urbic, Tomaz

    2016-10-01

    A statistical model for a simple three-dimensional Mercedes-Benz model of water was used to study phase diagrams. This model on a simple level describes the thermal and volumetric properties of waterlike molecules. A molecule is presented as a soft sphere with four directions in which hydrogen bonds can be formed. Two neighboring waters can interact through a van der Waals interaction or an orientation-dependent hydrogen-bonding interaction. For pure water, we explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility and found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations. The model exhibits also two critical points for liquid-gas transition and transition between low-density and high-density fluid. Coexistence curves and a Widom line for the maximum and minimum in thermal expansion coefficient divides the phase space of the model into three parts: in one part we have gas region, in the second a high-density liquid, and the third region contains low-density liquid.

  15. Fluctuations in an Inorganic Glass Forming System Capable of Liquid-Liquid Phase Separation

    Science.gov (United States)

    Bogdanov, V.; Maksimov, L.; Anan'ev, A.; Nemilov, S.; Rusan, V.

    2012-08-01

    Rayleigh and Mandel'shtam-Brillouin scattering (RMBS) spectroscopy and high temperature ultrasonic study (HTUS) are applied to PbO-Al2O3-B2O3 glass forming system characterized by over liquidus miscibility gap. Temperature dependences of ultrasonic velocity of glass melts were measured in 600-1200°C range. "Frozen-in" density fluctuations in two phase glasses were estimated from HTUS data by Macedo-Shroeder formulation. Landau-Placzek ratios were found from RMBS spectra of single phase glasses at room temperature. Results of RMBS and HTUS were compared with well-known SAXS data. It was found that contribution of "frozen-in" density fluctuations into light scattering by two-phase glasses is much smaller than the scattering on particles of the second glassy phase causing opalescence of the glasses. Abnormal "water-like" growth of ultrasonic velocity with melt temperature can be explained by coexistence of two types of packaging of structural elements.

  16. Trace analysis of three antihistamines in human urine by on-line single drop liquid-liquid-liquid microextraction coupled to sweeping micellar electrokinetic chromatography and its application to pharmacokinetic study.

    Science.gov (United States)

    Gao, Wenhua; Chen, Yunsheng; Chen, Gaopan; Xi, Jing; Chen, Yaowen; Yang, Jianying; Xu, Ning

    2012-09-01

    A rapid and efficient dual preconcentration method of on-line single drop liquid-liquid-liquid microextraction (SD-LLLME) coupled to sweeping micellar electrokinetic chromatography (MEKC) was developed for trace analysis of three antihistamines (mizolastine, chlorpheniramine and pheniramine) in human urine. Three analytes were firstly extracted from donor phase (4 mL urine sample) adjusted to alkaline condition (0.5 M NaOH). The unionized analytes were subsequently extracted into a drop of n-octanol layered over the urine sample, and then into a microdrop of acceptor phase (100 mM H(3)PO(4)) suspended from a capillary inlet. The enriched acceptor phase was on-line injected into capillary with a height difference and then analyzed directly by sweeping MEKC. Good linear relationships were obtained for all analytes in a range of 6.25 × 10(-6) to 2.5 × 10(-4)g/L with correlation coefficients (r) higher than 0.987. The proposed method achieved limits of detections (LOD) varied from 1.2 × 10(-7) to 9.5 × 10(-7)g/L based on a signal-to-noise of 3 (S/N=3) with 751- to 1372-fold increases in detection sensitivity for analytes, and it was successfully applied to the pharmacokinetic study of three antihistamines in human urine after an oral administration. The results demonstrated that this method was a promising combination for the rapid trace analysis of antihistamines in human urine with the advantages of operation simplicity, high enrichment factor and little solvent consumption. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. A Liquid-Liquid Thermoelectric Heat Exchanger as a Heat Pump for Testing Phase Change Material Heat Exchangers

    Science.gov (United States)

    Sheth, Rubik B.; Makinen, Janice; Le, Hung V.

    2016-01-01

    The primary objective of the Phase Change HX payload on the International Space Station (ISS) is to test and demonstrate the viability and performance of Phase Change Material Heat Exchangers (PCM HX). The system was required to pump a working fluid through a PCM HX to promote the phase change material to freeze and thaw as expected on Orion's Multipurpose Crew Vehicle. Due to limitations on ISS's Internal Thermal Control System, a heat pump was needed on the Phase Change HX payload to help with reducing the working fluid's temperature to below 0degC (32degF). This paper will review the design and development of a TEC based liquid-liquid heat exchanger as a way to vary to fluid temperature for the freeze and thaw phase of the PCM HX. Specifically, the paper will review the design of custom coldplates and sizing for the required heat removal of the HX.

  18. Prediction of liquid-liquid equilibria for polyethylene glycol based aqueous two-phase system by ASOG and UNIFAC method

    Directory of Open Access Journals (Sweden)

    M. Perumalsamy

    2009-03-01

    Full Text Available Liquid-Liquid equilibrium data were obtained for the polyethylene glycol2000(PEG2000-sodium citrate-water system at 298.15, 308.15 and 318.15 K. The effect of temperature on binodal and tie line data was studied and published in a previous article (Murugesan and Perumalsamy, 2005. The interaction parameters of ASOG and UNIFAC models were estimated using the LLE data of PEG2000-sodium citrate-water system and are used to predict the LLE data for PEG6000-sodium citrate-water system at 298.15, 308.15 and 318.15 K (literature data. The predicted LLE data by both ASOG and UNIFAC models showed good agreement with the experimental and literature data.

  19. SYNTHESE D’EXTRACTANTS ACIDES HEXADECYL- ET DECYLAMINOBIMETHYLENEDIPHOSPHONIQUES APPLICATION A L’EXTRACTION LIQUIDE-LIQUIDE DE Ni (II

    Directory of Open Access Journals (Sweden)

    M.A DIDI

    2007-06-01

    Après purification puis caractérisation des produits, nous avons réalisé divers tests d’extraction liquide - liquide de Ni (II en milieu sulfaté. Le temps d’équilibre déterminé par étude cinétique a été fixé à 40 minutes. Les paramètres changeant tels la température ( T = 20°C, 30°C et 50°C, le rapport du nombre de moles (n extractant / n métal (Q =1 à 6 et le rapport des volumes (Vaq / Vorg= 1, 2, 3 et 4 ont permis de maximiser le rendement d’extraction qui est de 46% avec le HABMP et de 44% pour le DADMP et ceci pour des extractions à un seul plateau.

  20. MEASUREMENT AND CORRELATION OF THE MASS TRANSFER COEFFICIENT FOR A LIQUID-LIQUID SYSTEM WITH HIGH DENSITY DIFFERENCE

    Directory of Open Access Journals (Sweden)

    Zhixian Huang

    Full Text Available Abstract To investigate the mass transfer behavior of a liquid-liquid system with high density difference (∆ρ≈500 kg/m3, single drop experiments were performed by using the ternary chloroform-ethanol-water system. The mass transfer direction was from the dispersed phase to the continuous phase, while the aqueous phase was dispersed in chloroform to generate drops. The influences of drop diameter, initial solute concentration and temperature on the mass transfer were investigated. The effects of the drop diameter and initial solute concentration on interfacial instability of droplets hanging in the continuous phase were also observed. For the purpose of correlation, a mass transfer enhancement factor F was introduced and then correlated as a function of dimensionless variables. The modified correlation from the mass transfer coefficient model was found to fit well with the experimental values.

  1. Liquid-liquid extraction of uranium(VI) using Cyanex 272 in toluene from sodium salicylate medium

    International Nuclear Information System (INIS)

    Madane, Namdev S.; Nikam, Gurunath H.; Jadhav, Deepali V.; Mohite, Baburao S.

    2011-01-01

    Liquid-liquid extraction of U(VI) from sodium salicylate media using Cyanex 272 in toluene has been carried out. Uranium(VI) was quantitatively extracted from 1 x 10 -3 M sodium salicylate with 5 x 10 -4 M Cyanex 272 in toluene. It was stripped quantitatively from the organic phase with 1M HCl and determined spectrophotometrically with arsenazo(III) at 660 nm. The effect of concentrations of sodium salicylate, extractant, diluents, metal ion and strippants have been studied. Separation of uranium(VI) from other elements was achieved from binary as well as from multicomponent mixtures. The method was extended to determination of uranium(VI) in geological samples. The method is simple, rapid and selective with good reproducibility (approximately ± 2%). (author)

  2. Separation of aromatic precipitates from simulated high level radioactive waste by hydrolysis, evaporation and liquid-liquid extraction

    International Nuclear Information System (INIS)

    Young, S.R.; Shah, H.B.; Carter, J.T.

    1991-01-01

    The Defense Waste Processing Facility (DWPF) at the SRS will be the United States' first facility to process High Level radioactive Waste (HLW) into a borosilicate glass matrix. The removal of aromatic precipitates by hydrolysis, evaporation and liquid-liquid extraction will be a key step in the processing of the HLW. This step, titled the Precipitate Hydrolysis Process, has been demonstrated by the Savannah River Laboratory with the Precipitate Hydrolysis Experimental Facility (PHEF). The mission of the PHEF is to demonstrate processing of simulated high level radioactive waste which contains tetraphenylborate precipitates and nitrite. Reduction of nitrite by hydroxylamine nitrate and hydrolysis of the tetraphenylborate by formic acid is discussed. Gaseous production, which is primarily benzene, nitrous oxide and carbon dioxide, has been quantified. Production of high-boiling organic compounds and the accumulation of these organic compounds within the process are addressed

  3. Determination of trace amount of lead in industrial and municipal effluent water samples based on dispersive liquid-liquid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Shirkhanloo, H. [Iranian Petroleum Industry Health Research Institute, Occupational and Environmental Health Research Center, Tehran (Iran, Islamic Republic of); Sedighi, K.; Mousavi, H. Z., E-mail: hzmousavi@semnan.ac.ir [Semnan University, College of Science, Department of Chemistry, Semnan (Iran, Islamic Republic of)

    2014-10-01

    In this study, a simple, sensitive and accurate method was developed for the determination of lead ion by combining ionic liquid dispersive liquid-liquid extraction (Il-DLL E) with flame atomic absorption spectrometry. Tetraethyl thiuram disulfide (Tetd), acetone and 1-octyl-3m ethylimidazolium hexafluorophosphate [(C{sub 8}MIM) (PF{sub 6})] were used as the chelating agent, dispersive and extraction solvent, respectively. Under the optimal conditions, the calibration graph was linear in the range of 5-190 μg L{sup -1} of lead and the detection limit was 0.8 μg L{sup -1} with a sample volume of 200 ml. The proposed method was validated by the analysis of one certified reference material and applied successfully to the determination of lead in real water samples. (Author)

  4. Trace recovery of uranium and rare earth contained in phosphates by liquid-liquid extraction in sulfuric attack liquor

    International Nuclear Information System (INIS)

    Bousquet, F.; Foraison, D.; Leveque, A.; Sabot, J.L.

    1980-06-01

    Uranium and rare earths can be recovered in sedimentary phosphates during the wet processing of the ore by sulfuric acid giving raw phosphoric acid at 30 per cent of P 2 O 5 . Practically all the uranium contained and only part of rare earths are put into solution in this treatment. Separation of these elements in the phosphoric solution is obtained by liquid-liquid extraction with alkylphosphoric acids and especially with their mono and di esters. Partition isotherms are determined and counter-current tests are effected. Uranium and rare earths reextraction from these solvents can be simultaneous or separate with aqueous solutions alkaline or containing HF or by antisynergism. Pros and cons of each reextraction process are discussed. In conclusion HDEHP or OPPA are recommended because of availability, stability and hydrodynamic, OPPA less selective with rare earths allows the recovery with uranium of ceric earths, yttrium and yttric earths [fr

  5. Liquid-liquid extraction of ion-association complexes of cobalt(II-4-(2-pyridylazoresorcinol with ditetrazolium salts

    Directory of Open Access Journals (Sweden)

    Divarova Vidka V.

    2015-01-01

    Full Text Available The formation and liquid-liquid extraction of ion-association complexes between Co(II-4-(2-Pyridylazoresorcinol (PAR anionic chelates and cations of three ditetrazolium chlorides were studied: Blue Tetrazolium chloride (BTC, Neotetrazolium chloride (NTC and Nitro Blue Tetrazolium chloride (NBT. The optimum conditions for the formation and solvent extraction of the ion-association comlpex chelates were determined. It has been found that in the systems of Co(II-PAR-DTS, the reactants are reacted in molar ratios 1:2:1 and the general formula of complexes was suggested. The extraction equilibria were investigated and quantitatively characterized by the equilibrium constants and the recovery factors. The analytical characteristics of the complexes were calculated.

  6. Use of Dispersive Liquid-Liquid Microextraction and UV-Vis Spectrophotometry for the Determination of Cadmium in Water Samples

    Directory of Open Access Journals (Sweden)

    J. Pérez-Outeiral

    2014-01-01

    Full Text Available A simple and inexpensive method for cadmium determination in water using dispersive liquid-liquid microextraction and ultraviolet-visible spectrophotometry was developed. In order to obtain the best experimental conditions, experimental design was applied. Calibration was made in the range of 10–100 μg/L, obtaining good linearity (R2 = 0.9947. The obtained limit of detection based on calibration curve was 8.5 μg/L. Intra- and interday repeatability were checked at two levels, obtaining relative standard deviation values from 9.0 to 13.3%. The enrichment factor had a value of 73. Metal interferences were also checked and tolerable limits were evaluated. Finally, the method was applied to cadmium determination in real spiked water samples. Therefore, the method showed potential applicability for cadmium determination in highly contaminated liquid samples.

  7. A microfluidic platform for the rapid determination of distribution coefficients by gravity assisted droplet-based liquid-liquid extraction

    DEFF Research Database (Denmark)

    Poulsen, Carl Esben; Wootton, Robert C. R.; Wolff, Anders

    2015-01-01

    The determination of pharmacokinetic properties of drugs, such as the distribution coefficient, D, is a crucial measurement in pharmaceutical research. Surprisingly, the conventional (gold standard) technique used for D measurements, the shake-flask method, is antiquated and unsuitable...... for the testing of valuable and scarce drug candidates. Herein we present a simple micro fluidic platform for the determination of distribution coefficients using droplet-based liquid-liquid extraction. For simplicity, this platform makes use of gravity to enable phase separation for analysis and is 48 times...... the apparent acid dissociation constant, pK', as a proxy for inter-system comparison. Our platform determines a pK' value of 7.24 ± 0.15, compared to 7.25 ± 0.58 for the shake-flask method in our hands and 7.21 for the shake-flask method in literature. Devices are fabricated using injection moulding, the batch...

  8. Effect of temperature on the (liquid + liquid) equilibrium for aqueous solution of nonionic surfactant and salt: Experimental and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Foroutan, Masumeh [Physical Chemistry Department, School of Chemistry, College of Science, University of Tehran, 14155-6455 Enghelab Avenue, Tehran (Iran, Islamic Republic of)], E-mail: foroutan@khayam.ut.ac.ir; Heidari, Nosrat; Mohammadlou, Maryam [Chemistry Department, Faculty of Science, Uremia University, Uremia (Iran, Islamic Republic of); Sojahrood, Amin Jafari [Physics Department, Faculty of Science, Uremia University, Uremia (Iran, Islamic Republic of)

    2008-07-15

    The effect of temperature on the (liquid + liquid) equilibrium of the aqueous solution of surfactant polyoxyethylene cetylether (with abbreviation name Brij 58) and diammonium hydrogen phosphate has been investigated at T = (303.15, 313.15, 323.15, and 333.15) K. The Flory-Huggins equation with two electrostatic terms (Debye-Huckle and Pitzer-Debye-Huckle equations) was used to correlate the phase behavior of this system. Good agreement has been found between experimental and calculated data from both models. The results indicated that the enlargement of the two-phase region upon increasing the temperature. Additionally temperature dependency of the parameters of the Flory-Huggins model has been calculated.

  9. The effect of heat exchanger parameters on performance predictions for nonazeotropic refrigerant mixtures in liquid-liquid heat pumps

    International Nuclear Information System (INIS)

    Stanger, S.; Den Braven, K.R.; Owre, T.A.S.

    1990-01-01

    The effects of constant heat exchanger area on the coefficient of performance (COP) for liquid-liquid heat pumps were analyzed for systems which use nonazeotropic mixtures as the working fluid. For this analysis, two different computer models were compared. In the first, the log mean temperature differences (LMTDs) through the heat exchangers were specified, and were held constant for all refrigerant compositions. The second method was constructed so that the heat exchanger UA product was held constant, thus approximating constant heat exchanger area over a range of refrigerant compositions. Results from these models show only a one percent difference in COP prediction between holding LMTD constant and holding UA constant over the range of mixture composition. This paper reports the models compared using mixtures of R-22/R-11 and R-22/R-114. It is also shown that changes in glide and lift temperatures have little influence on the differences between the two models

  10. Determination of trace amount of lead in industrial and municipal effluent water samples based on dispersive liquid-liquid extraction

    International Nuclear Information System (INIS)

    Shirkhanloo, H.; Sedighi, K.; Mousavi, H. Z.

    2014-01-01

    In this study, a simple, sensitive and accurate method was developed for the determination of lead ion by combining ionic liquid dispersive liquid-liquid extraction (Il-DLL E) with flame atomic absorption spectrometry. Tetraethyl thiuram disulfide (Tetd), acetone and 1-octyl-3m ethylimidazolium hexafluorophosphate [(C 8 MIM) (PF 6 )] were used as the chelating agent, dispersive and extraction solvent, respectively. Under the optimal conditions, the calibration graph was linear in the range of 5-190 μg L -1 of lead and the detection limit was 0.8 μg L -1 with a sample volume of 200 ml. The proposed method was validated by the analysis of one certified reference material and applied successfully to the determination of lead in real water samples. (Author)

  11. The status of research on CFD-PBM simulation of liquid-liquid two-phase flow in extraction columns

    International Nuclear Information System (INIS)

    Li Shaowei; Jing Shan; Wu Qiulin; Zhang Qi

    2012-01-01

    Computational fluid dynamics (CFD) simulation has gained more and more interest in the chemical engineering researchers and is becoming a useful tool for the chemical engineering research. The research on liquid-liquid two-phase flow CFD simulation in extraction columns is now in its initial stage. There is much work to do for the developing of this research field. The purpose of this article is to review the CFD simulation methods for two-phase flow in extraction column. The population balance model (PBM) is detailedly described in this article because it is the main method used in the two-phase flow CFD simulation currently. Then some examples for the two-phase flow simulation in extraction columns are briefly introduced. The strategy for the research on CFD simulation of two-phase flow in extraction columns is suggested at last. (authors)

  12. Separation of thorium and uranium by liquid-liquid extraction from mixed aqueous nitric acidic-methanolic solutions

    International Nuclear Information System (INIS)

    Schmid, E.R.; Kenndler, E.

    1976-01-01

    A method is described for the separation of Th and U from each other and from other elements, usually occuring in minerals, by liquid-liquid extraction with Aliquat Nitrate (tricaprylmethyl ammoniumnitrate, 6 vol%) in benzene from a mixed solution of 2.5 M HNO 3 and methanol (1:1 volume ratio). Permissible upper concentration ratios of interfering elements, such as Li, Na, K, Mg, Ca, Al, Cu, Co(II), Fe(III), Mn(II), Ti(IV), La(III), U(VI), Cl - , ClO 4 - , SO 4 2- , PO 4 3- , have been determined. Following the separation, Th has been determined by spectrophotometry using Thorin, and U by fluorometry. Results for yield under varying conditions, together with elemental concentrations in the ppm range for U and Th in minerals, are given. (B.T.)

  13. Determination of Zinc Ions in Environmental Samples by Dispersive Liquid- Liquid Micro Extraction and Atomic Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    F. Arabi

    2012-11-01

    Full Text Available In this work preconcentration of the Zn ions was investigated in water sample by Dispersive liquid- liquid micro extraction (DLLME using chloroform as an extraction solvent, methanol as a disperser solvent and 8-Hydroxyquinoline as a chelating agent. The determination of extracted ions was done by graphite furnace atomic absorption spectrometry. The influence of various analytical parameters including pH, extraction and disperser solvent type and volume and concentration of the chelating agent on the extraction efficiency of analyses was investigated. After extraction, the enrichment factor was 26 and the detection limit of the method was 0.0033 µg l-1 and the relative standard deviations (R.S.D for five determinations of 1 ng/ml Zn were 7.41%. 

  14. Coexisting diseases of moyamoya vasculopathy.

    Science.gov (United States)

    Wei, Yi-Chia; Liu, Chi-Hung; Chang, Ting-Yu; Chin, Shy-Chyi; Chang, Chien-Hung; Huang, Kuo-Lun; Chang, Yeu-Jhy; Peng, Tsung-I; Lee, Tsong-Hai

    2014-07-01

    Several coexisting diseases have been reported in patients with moyamoya vasculopathy (MMV), but studies of quasi-moyamoya disease (quasi-MMD) are rare. This study aims to investigate the frequency of known coexisting diseases in patients with quasi-MMD and to compare quasi-MMD with moyamoya disease (MMD). Between 2000 and 2011, we retrospectively screened patients with International Classification of Diseases, Ninth Revision, code of 4375 (MMD) in the Health Information System of our hospital. The vascular images of each patient were confirmed by 2 neurologists and 1 neuroradiologist based on the diagnostic criteria of Japan Ministry of Health and Welfare. We excluded the patients with missing images and erroneous diagnosis. Demographics, coexisting diseases, laboratory data, treatment, and recurrent strokes were recorded. The eligible patients were divided into quasi-MMD and MMD groups according to the presence or absence of coexisting diseases. MMV was found in 90 patients including 37 (41.1%) quasi-MMD and 53 (58.9%) MMD. Atherosclerosis (32.4%) and thyroid disease (29.7%) were the leading coexisting diseases in quasi-MMD. Patients with MMD became symptomatic in a bimodal age distribution, whereas patients with quasi-MMD became symptomatic in a single-peak distribution. The prognosis of recurrent strokes was similar between quasi-MMD and MMD based on Kaplan-Meier analysis. A bimodal distribution of onset age was noted in MMD, whereas a single-peak distribution was found in quasi-MMD. Coexisting diseases were usually underevaluated but were more common than expected in patients with MMV. Atherosclerosis and thyroid diseases were the leading coexisting diseases in different preferential age. Copyright © 2014 National Stroke Association. Published by Elsevier Inc. All rights reserved.

  15. Electrochemical ion transfer across liquid/liquid interfaces confined within solid-state micropore arrays--simulations and experiments.

    Science.gov (United States)

    Strutwolf, Jörg; Scanlon, Micheál D; Arrigan, Damien W M

    2009-01-01

    Miniaturised liquid/liquid interfaces provide benefits for bioanalytical detection with electrochemical methods. In this work, microporous silicon membranes which can be used for interface miniaturisation were characterized by simulations and experiments. The microporous membranes possessed hexagonal arrays of pores with radii between 10 and 25 microm, a pore depth of 100 microm and pore centre-to-centre separations between 99 and 986 microm. Cyclic voltammetry was used to monitor ion transfer across arrays of micro-interfaces between two immiscible electrolyte solutions (microITIES) formed at these membranes, with the organic phase present as an organogel. The results were compared to computational simulations taking into account mass transport by diffusion and encompassing diffusion to recessed interfaces and overlapped diffusion zones. The simulation and experimental data were both consistent with the situation where the location of the liquid/liquid (l/l) interface was on the aqueous side of the silicon membrane and the pores were filled with the organic phase. While the current for the forward potential scan (transfer of the ion from the aqueous phase to the organic phase) was strongly dependent on the location of the l/l interface, the current peak during the reverse scan (transfer of the ion from the organic phase to the aqueous phase) was influenced by the ratio of the transferring ion's diffusion coefficients in both phases. The diffusion coefficient of the transferring ion in the gelified organic phase was ca. nine times smaller than in the aqueous phase. Asymmetric cyclic voltammogram shapes were caused by the combined effect of non-symmetrical diffusion (spherical and linear) and by the inequality of the diffusion coefficient in both phases. Overlapping diffusion zones were responsible for the observation of current peaks instead of steady-state currents during the forward scan. The characterisation of the diffusion behaviour is an important requirement

  16. Simulations of electrolytes at the liquid-liquid interface and of lanthanide cations complexes in gas phase

    International Nuclear Information System (INIS)

    Berny, F.

    2000-01-01

    Two processes related to liquid/liquid extraction of ions by extractant molecules were studied: the ion approach at the interface and the ion complexation by ligands. In the first part, the behaviour of salts at the chloroform/water interface was simulated by molecular dynamics. The aim was to understand the way these salts ions approach the interface in order to be extracted. Some ions are repelled by the interface (K + , Cl - , UO 2 2+ , Na + , NO 3 - ) whereas others adsorb (amphiphilic molecules and also ClO 4 - , SCN - , guanidinium Gu + and picrate Pic - ). The surface-active counter-ions make the ion approach at the interface easier. In a perfectly homogeneous mixture of the two solvents (water and chloroform) de-mixing, the ions seem to influence the phases separation rate. Nitric acid which is known to favour liquid/liquid extraction reveals strong adsorption at the interface in its neutral form and a smaller one in its ionic form (H 3 O + /NO 3 - ). HNO 3 and H 3 O + display particular orientations at the interface: hydrogen atoms are pointing in the direction of the water slab. The nature of the organic phase can also influence the ion approach at the interface. For example, Gu + and Pic - adsorb much less at the supercritical CO 2 /water interface than at the chloroform/water interface. In the second part, complexes of La 3+ , Eu 3+ and Yb 3+ with ligands such as amide, urea, thio-amide, thiourea were studied by quantum mechanics. Our calculations show that cation-ligand interactions depend on the nature of substituents on ligands, on the presence of counter-ions or on the number of ligands in the complex. Sulfur compounds seem to less interact with cations than oxygen compounds. Ureas interact as much as amides and are potentially good ligands. (author)

  17. Measurements and correlation of liquid-liquid equilibrium data for the ternary (3-heptanone + phenol + water) system

    International Nuclear Information System (INIS)

    Xu, Gaojie; Yang, Deling; Ning, Pengge; Wang, Qingjie; Gong, Fuchun; Cao, Hongbin

    2017-01-01

    Highlights: • The liquid-liquid equilibrium data for 3-heptanone + phenol + water were measured. • The distribution coefficient of phenol and selectivity for solvent extraction efficiency were calculated. • The NRTL model (two regression methods) and UNIQUAC model were used to correlate the experimental data with good results. • The physical meaning of the regressed binary parameters was explained by intermolecular attractive energy. • The activity coefficient of phenol and enthalpy change in extraction process were investigated. - Abstract: Liquid-liquid equilibrium (LLE) for the ternary (3-heptanone + phenol + water) system has been determined under atmospheric pressure at 298.15 K, 303.15 K, 318.15 K and 323.15 K. The NRTL and UNIQUAC models were used to correlate the experimental results. The corresponding binary parameters were obtained and their physical meaning is explained by intermolecular attractive energy. The results from the two models agree well with experimental values. The NRTL model was more accurate than that of the UNIQUAC model. Meanwhile, the NRTL model was used to regress all the experimental values at different temperatures simultaneously, which is defined as total-regression. Compared with the individual regression by the NRTL model, the total regression by the NRTL model has fewer parameters and covers a wider interpolated range from 298.15 K to 323.15 K. The distribution coefficient for phenol changes with temperature. The phenol concentration can be expressed as a function of activity coefficient of phenol in both phases. The effect of temperature on the extraction performance of 3-heptanone was also investigated. The phenol extraction process by 3-heptanone is exothermic. The increase of temperature is not a benefit to phenol extraction.

  18. Synergistic effect of dicarbollide anions in liquid-liquid extraction: a molecular dynamics study at the octanol-water interface.

    Science.gov (United States)

    Chevrot, G; Schurhammer, R; Wipff, G

    2007-04-28

    We report a molecular dynamics study of chlorinated cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)Cl(3))(2)Co](-)"CCD(-)" in octanol and at the octanol-water interface, with the main aim to understand why these hydrophobic species act as strong synergists in assisted liquid-liquid cation extraction. Neat octanol is quite heterogeneous and is found to display dual solvation properties, allowing to well solubilize CCD(-), Cs(+) salts in the form of diluted pairs or oligomers, without displaying aggregation. At the aqueous interface, octanol behaves as an amphiphile, forming either monolayers or bilayers, depending on the initial state and confinement conditions. In biphasic octanol-water systems, CCD(-) anions are found to mainly partition to the organic phase, thus attracting Cs(+) or even more hydrophilic counterions like Eu(3+) into that phase. The remaining CCD(-) anions adsorb at the interface, but are less surface active than at the chloroform interface. Finally, we compare the interfacial behavior of the Eu(BTP)(3)(3+) complex in the absence and in the presence of CCD(-) anions and extractant molecules. It is found that when the CCD(-)'s are concentrated enough, the complex is extracted to the octanol phase. Otherwise, it is trapped at the interface, attracted by water. These results are compared to those obtained with chloroform as organic phase and discussed in the context of synergistic effect of CCD(-) in liquid-liquid extraction, pointing to the importance of dual solvation properties of octanol and of the hydrophobic character of CCD(-) for synergistic extraction of cations.

  19. Quantitation of tetrabromobisphenol-A from dust sampled on consumer electronics by dispersed liquid-liquid microextraction

    International Nuclear Information System (INIS)

    Di Napoli-Davis, Gina; Owens, Janel E.

    2013-01-01

    Tetrabromobisphenol-A (TBBPA) is a brominated flame retardant used worldwide. Despite its widespread use, there are few data concerning environmental concentrations of TBBPA. Thus, the objective of this work was to optimize an ultrasound-assisted dispersed liquid-liquid microextraction (DLLME) method to analyze swabbed surfaces of consumer electronics to determine TBBPA concentrations. Upon sample preparation with DLLME, TBBPA was derivatized with acetic anhydride and then analyzed by gas chromatography–mass spectrometry (GC/MS). Using a 13 C 12 -TBBPA internal standard to improve precision and quantitation, a recovery study was performed. At concentrations of 250–1000 ng/mL, recoveries were 104–106%. Sample preparation with solid phase extraction had comparable recoveries, although overall, improved analyte recovery and precision were achieved with DLLME. In a small survey study, TBBPA concentrations in dust collected from 100 cm 2 areas on electronic surfaces (monitor, microwave, refrigerator, and TV) were determined to range from less than the LOQ to 523 ng/mL. -- Highlights: •Tetrabromobisphenol-A (TBBPA) concentrations in dust samples were determined. •Dust samples were collected from surfaces of consumer electronics. •Dispersed liquid-liquid microextraction was used to prepare samples for GC/MS. •A 13 C 12 -labeled internal standard was used to improve precision and quantitation. •TBBPA was found in dust samples at levels below LOQ to 523 ng/mL. -- This work describes the analysis of the brominated flame retardant, tetrabromobisphenol-A (TBBPA), from dust sampled on surfaces of consumer electronics

  20. Transient cognitive dynamics, metastability, and decision making.

    Directory of Open Access Journals (Sweden)

    Mikhail I Rabinovich

    2008-05-01

    Full Text Available The idea that cognitive activity can be understood using nonlinear dynamics has been intensively discussed at length for the last 15 years. One of the popular points of view is that metastable states play a key role in the execution of cognitive functions. Experimental and modeling studies suggest that most of these functions are the result of transient activity of large-scale brain networks in the presence of noise. Such transients may consist of a sequential switching between different metastable cognitive states. The main problem faced when using dynamical theory to describe transient cognitive processes is the fundamental contradiction between reproducibility and flexibility of transient behavior. In this paper, we propose a theoretical description of transient cognitive dynamics based on the interaction of functionally dependent metastable cognitive states. The mathematical image of such transient activity is a stable heteroclinic channel, i.e., a set of trajectories in the vicinity of a heteroclinic skeleton that consists of saddles and unstable separatrices that connect their surroundings. We suggest a basic mathematical model, a strongly dissipative dynamical system, and formulate the conditions for the robustness and reproducibility of cognitive transients that satisfy the competing requirements for stability and flexibility. Based on this approach, we describe here an effective solution for the problem of sequential decision making, represented as a fixed time game: a player takes sequential actions in a changing noisy environment so as to maximize a cumulative reward. As we predict and verify in computer simulations, noise plays an important role in optimizing the gain.

  1. Interaction of rare gas metastable atoms

    International Nuclear Information System (INIS)

    Wang, A.Z.F.

    1977-11-01

    The physical and chemical properties of metastable rare gas atoms are discussed and summarized. This is followed by a detailed examination of the various possible pathways whereby the metastable's excess electronic energy can be dissipated. The phenomenon of chemi-ionization is given special emphasis, and a theoretical treatment based on the use of complex (optical) potential is presented. This is followed by a discussion on the unique advantages offered by elastic differential cross section measurements in the apprehension of the fundamental forces governing the ionization process. The methodology generally adopted to extract information about the interaction potential for scattering data is also systematically outlined. Two widely studied chemi-ionization systems are then closely examined in the light of accurate differential cross section measurements obtained in this work. The first system is He(2 3 S) + Ar for which one can obtain an interaction potential which is in good harmony with the experimental results of other investigators. The validity of using the first-order semiclassical approximation for the phase shifts calculation in the presence of significant opacities is also discussed. The second reaction studied is He*+D 2 for which measurements were made on both spin states of the metastable helium. A self-consistent interaction potential is obtained for the triplet system, and reasons are given for not being able to do likewise for the singlet system. The anomalous hump proposed by a number of laboratories is analyzed. Total elastic and ionization cross sections as well as rate constants are calculated for the triplet case. Good agreement with experimental data is found. Finally, the construction and operation of a high power repetitively pulsed nitrogen laser pumped dye laser system is described in great details. Details for the construction and operation of a flashlamp pumped dye laser are likewise given

  2. Collisional interaction between metastable neon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Drunen, Wouter Johannes van

    2008-07-07

    In this thesis, the study of cold gases of neon atoms in different metastable states is described. It contains measurements of the collisional parameters for both the 3s[3/2]{sub 2} and the 3s'[1/2]{sub 0} metastable state and the dependence of the inelastic loss on external fields. Furthermore, the investigation of frequency dependent laser-induced collisions, and the possibility to excite photoassociation resonances is presented. For the measurements described here, neon atoms have been confined in a magnetooptical trap, in a magnetostatic trap, or in an optical dipole trap, respectively. By laser cooling inside the magnetic trap, atomic samples with more than 95 percent occupation of the magnetic substate m{sub J} = +2 could be prepared. They have a typical temperature of 0.5 mK, central densities up to 10{sup 11} cm{sup -3}, and a central phase-space density of up to 2.2.10{sup -7}. After loading the optical dipole trap from the magnetic trap, 2.5.10{sup 6} atoms with typical temperatures of 0.1 mK, and central densities up to 5.10{sup 10} cm{sup -3} were trapped. By evaporative cooling of the atoms in the magnetic trap we could increase the phase-space density by a factor of 200 to 5.10{sup -5}. Investigating the frequency dependence of laser-induced collisions did not reveal an experimental signature for the excitation of photoassociation resonances. For the {sup 3}D{sub 3} line a frequency dependence of laser enhanced Penning ionization was observed. Measurement of the two-body loss coefficient as function of the magnetic field showed a field dependence of the inelastic loss. These losses increase towards both small and large offset fields. The implementation of an optical dipole trap allowed us to trap the {sup 3}P{sub 0} metastable state. From the trap loss measurements we determined the two-body loss coefficient of the {sup 3}P{sub 0} metastable state for both bosonic isotopes {sup 20}Ne and {sup 22}Ne. For {sup 20}Ne we obtained {beta}=6{sup +5}{sub

  3. Collisional interaction between metastable neon atoms

    International Nuclear Information System (INIS)

    Drunen, Wouter Johannes van

    2008-01-01

    In this thesis, the study of cold gases of neon atoms in different metastable states is described. It contains measurements of the collisional parameters for both the 3s[3/2] 2 and the 3s'[1/2] 0 metastable state and the dependence of the inelastic loss on external fields. Furthermore, the investigation of frequency dependent laser-induced collisions, and the possibility to excite photoassociation resonances is presented. For the measurements described here, neon atoms have been confined in a magnetooptical trap, in a magnetostatic trap, or in an optical dipole trap, respectively. By laser cooling inside the magnetic trap, atomic samples with more than 95 percent occupation of the magnetic substate m J = +2 could be prepared. They have a typical temperature of 0.5 mK, central densities up to 10 11 cm -3 , and a central phase-space density of up to 2.2.10 -7 . After loading the optical dipole trap from the magnetic trap, 2.5.10 6 atoms with typical temperatures of 0.1 mK, and central densities up to 5.10 10 cm -3 were trapped. By evaporative cooling of the atoms in the magnetic trap we could increase the phase-space density by a factor of 200 to 5.10 -5 . Investigating the frequency dependence of laser-induced collisions did not reveal an experimental signature for the excitation of photoassociation resonances. For the 3 D 3 line a frequency dependence of laser enhanced Penning ionization was observed. Measurement of the two-body loss coefficient as function of the magnetic field showed a field dependence of the inelastic loss. These losses increase towards both small and large offset fields. The implementation of an optical dipole trap allowed us to trap the 3 P 0 metastable state. From the trap loss measurements we determined the two-body loss coefficient of the 3 P 0 metastable state for both bosonic isotopes 20 Ne and 22 Ne. For 20 Ne we obtained β=6 +5 -4 .10 -10 cm 3 /s and for 22 Ne β = 11 +7 -6 .10 -10 cm 3 /s. (orig.)

  4. Metastable structure formation during high velocity grinding

    International Nuclear Information System (INIS)

    Samarin, A.N.; Klyuev, M.M.

    1984-01-01

    Metastable structures in surface layers of samples are; investigated during force high-velocity abrasive grinding. Samples of martensitic (40Kh13), austenitic (12Kh18N10T), ferritic (05Kh23Yu5) steels and some alloys, in particular KhN77TYuR (EhI437B), were grinded for one pass at treatment depth from 0.17 up to 2.6 mm. It is established that processes of homogenizing, recrystallization and coagulation are; developed during force high-velocity grinding along with polymorphic transformations in the zone of thermomechanical effect, that leads to changes of physical and mechanical properties of the surface

  5. Bitopic Ligands and Metastable Binding Sites

    DEFF Research Database (Denmark)

    Fronik, Philipp; Gaiser, Birgit I; Sejer Pedersen, Daniel

    2017-01-01

    of orthosteric binding sites. Bitopic ligands have been employed to address the selectivity problem by combining (linking) an orthosteric ligand with an allosteric modulator, theoretically leading to high-affinity subtype selective ligands. However, it remains a challenge to identify suitable allosteric binding...... that have been reported to date, this type of bitopic ligands would be composed of two identical pharmacophores. Herein, we outline the concept of bitopic ligands, review metastable binding sites, and discuss their potential as a new source of allosteric binding sites....

  6. Ternary and quaternary (liquid + liquid) equilibria for (water + ethanol + α-pinene, +β-pinene, or +limonene) and (water + ethanol + α-pinene + limonene) at the temperature 298.15 K

    International Nuclear Information System (INIS)

    Li Hengde; Tamura, Kazuhiro

    2006-01-01

    (Liquid + liquid) equilibria and tie-lines for the ternary (water + ethanol + α-pinene, or β-pinene or limonene) and quaternary (water + ethanol + α-pinene + limonene) mixtures have been measured at T = 298.15 K. The experimental multicomponent (liquid + liquid) equilibrium data have been successfully represented in terms of the modified UNIQUAC model with binary parameters

  7. Determination of methylphenidate in Calliphorid larvae by liquid-liquid extraction and liquid chromatography mass spectrometry - Forensic entomotoxicology using an in vivo rat brain model

    DEFF Research Database (Denmark)

    Bushby, Sarah K.; Thomas, Nicky; Priemel, Petra A.

    2012-01-01

    and Calliphorid larvae) by liquid-liquid extraction with recovery of >80%, and quantified using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The LC-MS/MS assay was validated for entomotoxicological use and initially applied to male Sprague-Dawley rats (n=6) that were dosed with MPH (20mg/kg) ante...

  8. Calculation of liquid-liquid phase separation in a ternary system of a polymer in a mixture of a solvent and a nonsolvent

    NARCIS (Netherlands)

    Altena, Frank W.; Smolders, C.A.

    1982-01-01

    A numerical method for the calculation of the binodal of liquid-liquid phase separation in a ternary system is described. The Flory-Huggins theory for three-component systems is used. Binodals are calculated for polymer/solvent/nonsolvent systems which are used in the preparation of asymmetric

  9. Process intensification of catalytic liquid-liquid solid processes : Continuous biodiesel production using an immobilized lipase in a centrifugal contactor separator

    NARCIS (Netherlands)

    Ilmi, M.; Kloekhorst, A.; Winkelman, J. G. M.; Euverink, G. J. W.; Hidayat, C.; Heeres, H. J.

    Biodiesel or fatty acid methyl ester (FAME) synthesis from sunflower oil and methanol using an immobilized lipase, an example of a liquid-liquid solid reaction, was studied in batch and various continuous reactor set-ups including the use of a centrifugal contactor separator (CCCS). The latter is an

  10. Liquid chromatography-tandem mass spectrometric assay for the quantitative determination of the tyrosine kinase inhibitor quizartinib in mouse plasma using salting-out liquid-liquid extraction

    NARCIS (Netherlands)

    Retmana, Irene A; Wang, Jing; Schinkel, Alfred H; Schellens, Jan H M; Beijnen, Jos H; Sparidans, Rolf W

    2017-01-01

    A bioanalytical assay for quizartinib -a potent, and selective FLT3 tyrosine kinase inhibitor- in mouse plasma was developed and validated. Salting-out assisted liquid-liquid extraction (SALLE), using acetonitrile and magnesium sulfate, was selected as sample pretreatment with deuterated quizartinib

  11. Shape coexistence in selenium isotopes

    International Nuclear Information System (INIS)

    Liu Ying; Cao Zhongbin; Xu Furong

    2010-01-01

    Nuclear shape change and shape coexistence in the Selenium isotopes have been investigated by Total-Routhian-Surface (TRS) calculations. It is found that nuclear shapes vary significantly with increasing neutron number. The TRS calculations for the ground states of 66,72,92,94 Se isotopes show that both neutron-deficient and neutron-dripline Selenium isotopes have oblate and prolate shape coexistence. The cranking shell-model calculations for 72,94 Se give that prolate and oblate shape coexistence in low rotational frequency. However, oblate rotational bands disappear and prolate rotational bands become yrast bands with increasing rotational frequency, which is due to the intrusion of the g 9/2 orbitals. (authors)

  12. A study on metastable superconducting magnets

    International Nuclear Information System (INIS)

    Koyama, Kenichi

    1976-01-01

    It is important to construct superconducting magnets as cheap as possible. One of the methods to achieve such a purpose is to save the superconducting material and operate the magnets at a high current density. Therefore it is useful to investigate the requirements for the operation of metastable superconducting magnets which can work at a current higher than the recovery current. Using the theory of flux jump, we introduce a ''stable current'' below which no flux jump can occur. On a rough approximation, it is given by I sub(s) =√A P sub(i) H sub(e) T sub(o) f(x)/rho where A : cross-section of the composite conductor. P sub(i) : total perimeter of all the superconducting cores. h sub(e) : effective heat transfer coefficient to the liquid helium through the stabilizer. T sub(o) : a characteristic temperature of the superconducting cores. f(x) : a characteristic function for the relative core radius x. rho : effective resistivity of the composite. Then it is shown that superconducting magnets can operate without unexpected normal transitions in the region enclosed by the two curves of I sub(s) and I sub(c). Next, we discuss the characteristics of our saddle shaped superconducting magnet for an one-KW MHD generator. We found that, 1) the magnet does safely operate in the metastable state; 2) the characteristics of the magnet are consistent with our theoretical results. (auth.)

  13. Metastable beta limit in DIII-D

    International Nuclear Information System (INIS)

    La Haye, R.J.; Callen, J.D.; Gianakon, T.A.

    1997-06-01

    The long-pulse, slowly evolving single-null divertor (SND) discharges in DIII-D with H-mode, ELMs, and sawteeth are found to be limited significantly below (factor of 2) the predicted ideal limit β N = 4l i by the onset of tearing modes. The tearing modes are metastable in that they are explained by the neoclassical bootstrap current (high β θ ) destabilization of a seed island which occurs even if Δ' θ , there is a region of the modified Rutherford equation such that dw/dt > 0 for w larger than a threshold value; the plasma is metastable, awaiting the critical perturbation which is then amplified to the much larger saturated island. Experimental results from a large number of tokamaks indicate that the high beta operational envelope of the tokamak is well defined by ideal magnetohydrodynamic (MHD) theory. The highest beta values achieved have historically been obtained in fairly short pulse discharges, often <1-2 sawteeth periods and < 1-2 energy replacement times. The maximum operational beta in single-null divertor (SND), long-pulse discharges in DIII-D with a cross-sectional shape similar to the proposed ITER tokamak is found to be limited significantly below the threshold for ideal instabilities by the onset of resistive MHD instabilities

  14. Explosive synchronization coexists with classical synchronization in the Kuramoto model

    Energy Technology Data Exchange (ETDEWEB)

    Danziger, Michael M., E-mail: michael.danziger@biu.ac.il; Havlin, Shlomo [Department of Physics, Bar-Ilan University, Ramat Gan (Israel); Moskalenko, Olga I.; Kurkin, Semen A. [Faculty of Nonlinear Processes, Saratov State University, Astrakhanskaya, 83, Saratov 410012 (Russian Federation); Saratov State Technical University, Politehnicheskaya, 77, Saratov 410054 (Russian Federation); Zhang, Xiyun [Department of Physics, East China Normal University, Shanghai 200062 (China); Boccaletti, Stefano [CNR-Institute of Complex Systems, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence (Italy); The Italian Embassy in Israel, 25 Hamered Street, 68125 Tel Aviv (Israel)

    2016-06-15

    Explosive synchronization has recently been reported in a system of adaptively coupled Kuramoto oscillators, without any conditions on the frequency or degree of the nodes. Here, we find that, in fact, the explosive phase coexists with the standard phase of the Kuramoto oscillators. We determine this by extending the mean-field theory of adaptively coupled oscillators with full coupling to the case with partial coupling of a fraction f. This analysis shows that a metastable region exists for all finite values of f > 0, and therefore explosive synchronization is expected for any perturbation of adaptively coupling added to the standard Kuramoto model. We verify this theory with GPU-accelerated simulations on very large networks (N ∼ 10{sup 6}) and find that, in fact, an explosive transition with hysteresis is observed for all finite couplings. By demonstrating that explosive transitions coexist with standard transitions in the limit of f → 0, we show that this behavior is far more likely to occur naturally than was previously believed.

  15. Thermodynamic equilibrium model to predict the cobalt distribution coefficient in the CoCl2--HCl--H2O--TBP liquid--liquid extraction system

    International Nuclear Information System (INIS)

    Nevarez, M.; Bautista, R.G.

    1976-01-01

    The development of a thermodynamic equilibrium model to predict the cobalt distribution coefficient in the CoCl 2 -HCl-H 2 O-TBP system is described. The model makes use of the various aqueous phase cobaltous chloride complexes stoichiometric stability constants expressed as their degree of formation, their mechanism of extraction into the organic phase, and the equilibrium constant for the extraction reaction. The model was verified by the good agreement between the calculated cobalt distribution coefficients and those obtained experimentally both in the present study and published by other investigators. The optimum extraction of cobalt by the TBP occurred at an HCl equilibrium aqueous place concentration between 8.5 and 9.5M. The development of efficient procedures for the separation and concentration of important industrial metals from their aqueous solutions by liquid-liquid extraction has recently been given impetus by the realization of an impending shortage of energy and mineral resources. Liquid-liquid extraction is one of the few methods by which it is possible to quantitatively separate elements which are similar in properties. The use of liquid-liquid extraction to separate cobalt and nickel, which very frequently occur in nature together, is an important separation problem in nonferrous metallurgy. There is some fundamental information available in the chemical literature regarding the mechanism and equilibrium thermodynamic properties of selected liquid-liquid extraction systems. This research effort shows how this available information can be utilized to improve existing separation and concentration theory and technique. The development and application of a thermodynamic equilibrium model for describing the liquid-liquid extraction of cobaltous chloride from aqueous HCl solutions by tributyl phosphate (TBP) using experimental data obtained in this investigation and from the literature are presented

  16. Critical behaviour of binary mixture of {xC6H5CN + (1 - x)CH3(CH2)7CH3}: Measurements of coexistence curves, light scattering, and heat capacity

    International Nuclear Information System (INIS)

    Lei Yuntao; Chen Zhiyun; Wang Nong; Mao Chunfeng; An Xueqin; Shen Weiguo

    2010-01-01

    Liquid + liquid coexistence, light scattering, and isobaric heat capacity per unit volume for the critical solutions of (benzonitrile + n-nonane) have been measured. The critical exponents relating to the coexistence curve β, the osmotic compressibility γ, the correlation length ν, and the heat capacity α have been deduced and the values are consistent with the 3D-Ising values in the range close to the critical point. The experimental results of the liquid + liquid coexistence were analyzed to examine the Wegner correction terms and the behaviour of the diameter of the coexistence curves. The light scattering data were well described by the crossover model proposed by Anisimov and Sengers, and showed a tendency of monotonic crossover of the critical exponents γ and ν from the 3D-Ising values to the mean-field values as the temperature departures from the critical point. From calorimetric measurements, the amplitude A ± and the critical background B cr of the heat capacity in the critical region have been deduced and some universal ratios are tested.

  17. Development of a new extraction method based on counter current salting-out homogenous liquid-liquid extraction followed by dispersive liquid-liquid microextraction: Application for the extraction and preconcentration of widely used pesticides from fruit juices.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Feriduni, Behruz; Mogaddam, Mohammad Reza Afshar

    2016-01-01

    In this paper, a new extraction method based on counter current salting-out homogenous liquid-liquid extraction (CCSHLLE) followed by dispersive liquid-liquid microextraction (DLLME) has been developed for the extraction and preconcentration of widely used pesticides in fruit juice samples prior to their analysis by gas chromatography-flame ionization detection (GC-FID). In this method, initially, sodium chloride as a separation reagent is filled into a small column and a mixture of water (or fruit juice) and acetonitrile is passed through the column. By passing the mixture sodium chloride is dissolved and the fine droplets of acetonitrile are formed due to salting-out effect. The produced droplets go up through the remained mixture and collect as a separated layer. Then, the collected organic phase (acetonitrile) is removed with a syringe and mixed with 1,1,2,2-tetrachloroethane (extraction solvent at µL level). In the second step, for further enrichment of the analytes the above mixture is injected into 5 mL de-ionized water placed in a test tube with conical bottom in order to dissolve acetonitrile into water and to achieve a sedimented phase at µL-level volume containing the enriched analytes. Under the optimal extraction conditions (extraction solvent, 1.5 mL acetonitrile; pH, 7; flow rate, 0.5 mL min(-1); preconcentration solvent, 20 µL 1,1,2,2-tetrachloroethane; NaCl concentration; 5%, w/w; and centrifugation rate and time, 5000 rpm and 5 min, respectively), the extraction recoveries and enrichment factors ranged from 87% to 96% and 544 to 600, respectively. Repeatability of the proposed method, expressed as relative standard deviations, ranged from 2% to 6% for intra-day (n=6, C=250 or 500 µg L(-1)) and inter-days (n=4, C=250 or 500 µg L(-1)) precisions. Limits of detection are obtained between 2 and 12 µg L(-1). Finally, the proposed method is applied for the determination of the target pesticide residues in the juice samples. Copyright © 2015

  18. Simulations of electrolytes at the liquid-liquid interface and of lanthanide cations complexes in gas phase; Simulations d'electrolytes a l'interface liquide/liquide et de complexes de cations lanthanides en phase gazeuse

    Energy Technology Data Exchange (ETDEWEB)

    Berny, F

    2000-07-01

    Two processes related to liquid/liquid extraction of ions by extractant molecules were studied: the ion approach at the interface and the ion complexation by ligands. In the first part, the behaviour of salts at the chloroform/water interface was simulated by molecular dynamics. The aim was to understand the way these salts ions approach the interface in order to be extracted. Some ions are repelled by the interface (K{sup +}, Cl{sup -}, UO{sub 2}{sup 2+}, Na{sup +}, NO{sub 3}{sup -}) whereas others adsorb (amphiphilic molecules and also ClO{sub 4}{sup -}, SCN{sup -}, guanidinium Gu{sup +} and picrate Pic{sup -}). The surface-active counter-ions make the ion approach at the interface easier. In a perfectly homogeneous mixture of the two solvents (water and chloroform) de-mixing, the ions seem to influence the phases separation rate. Nitric acid which is known to favour liquid/liquid extraction reveals strong adsorption at the interface in its neutral form and a smaller one in its ionic form (H{sub 3}O{sup +}/NO{sub 3}{sup -}). HNO{sub 3} and H{sub 3}O{sup +} display particular orientations at the interface: hydrogen atoms are pointing in the direction of the water slab. The nature of the organic phase can also influence the ion approach at the interface. For example, Gu{sup +} and Pic{sup -} adsorb much less at the supercritical CO{sub 2}/water interface than at the chloroform/water interface. In the second part, complexes of La{sup 3+}, Eu{sup 3+} and Yb{sup 3+} with ligands such as amide, urea, thio-amide, thiourea were studied by quantum mechanics. Our calculations show that cation-ligand interactions depend on the nature of substituents on ligands, on the presence of counter-ions or on the number of ligands in the complex. Sulfur compounds seem to less interact with cations than oxygen compounds. Ureas interact as much as amides and are potentially good ligands. (author)

  19. Experimental study of the spin density of metastable fcc ferromagnetic Fe-Cu alloys

    International Nuclear Information System (INIS)

    Bove, L. E.; Petrillo, C.; Sacchetti, F.; Mazzone, G.

    2000-01-01

    Magnetization density measurements on metastable Fe x Cu 1-x alloys at four compositions (x=20, 40, 50, and 60 at. %) and at 5 K temperature were carried out by means of polarized neutron diffraction. The samples were produced by high-energy ball milling and characterized by x-ray diffraction and fluorescence measurements. Additional bulk magnetization measurements were carried out on the two samples at high Fe concentration. Over the present concentration region, the Fe-Cu system is ferromagnetic and the four samples were found to be in the fcc phase. Fe-Cu is therefore a very suitable system to investigate the magnetic state of Fe in an fcc environment. Other than confirming that the Fe-Cu system is not a simple dilution alloy, the present results were compatible with a two-state model for fcc Fe--that is, two different coexisting electronic states associated with different magnetic moments and form factors

  20. Crystal-liquid-gas phase transitions and thermodynamic similarity

    CERN Document Server

    Skripov, Vladimir P; Schmelzer, Jurn W P

    2006-01-01

    Professor Skripov obtained worldwide recognition with his monograph ""Metastable liquids"", published in English by Wiley & Sons. Based upon this work and another monograph published only in Russia, this book investigates the behavior of melting line and the properties of the coexisting crystal and liquid phase of simple substances across a wide range of pressures, including metastable states of the coexisting phases. The authors derive new relations for the thermodynamic similarity for liquid-vapour phase transition, as well as describing solid-liquid, liquid-vapor and liquid-liquid phase tra

  1. Local coexistance of different phases

    International Nuclear Information System (INIS)

    Narnhofer, H.

    1982-01-01

    Under intuitively reasonable assumptions it is shown that in two dimensions different phases cannot exist locally. In three dimensions we discuss the possibility of local coexistance of districts with different magnetization for the Heisenberg ferromagnet and show that an interaction that breaks rotational invariance is necessary for this phenomenon. (Author)

  2. Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

    Directory of Open Access Journals (Sweden)

    A. Zuend

    2012-05-01

    Full Text Available The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA. Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH, as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality and EVAPORATION (for pure compound vapor pressures with oxidation product information from the Master Chemical Mechanism (MCM for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of α-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH. Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1 non-ideality in the condensed phase needs to be considered and (2 liquid-liquid phase separation is a consequence of considerable deviations

  3. In line digital holography measurement for liquid-liquid flow: application to the characterization of emulsions produced in pulsed column

    International Nuclear Information System (INIS)

    Lamadie, F.

    2013-01-01

    Several processes used in research and industry are based on liquid-liquid extraction, a method designed for selective separation of products in a mixture. In liquid-liquid extraction, two immiscible liquids are contacted: an aqueous phase and an organic phase, one of which generally contains an extractant molecule capable of transferring the desired elements to the other phase. The transfer occurs at the contact surface between the two phases. After transfer, both phases are separated by settling. In practice, these operations are performed in industrial apparatus. In order to optimize the operation of these devices, it's important to determine the fundamental characteristics of the emulsion. These include parameters related to the fluid flow velocity as well as parameters related to fluid mixing such as the interfacial area, hold-up, and size distribution of the droplets population. Numerous imaging techniques can be used to measure these parameters. One of them, digital holography, is well-known for allowing complete reconstruction of information about a 3D flow in a single shot. This PhD work deals with a direct application of digital in line holography to droplets rising in a continuous liquid phase. The droplet size imposes a regime of intermediate-field diffraction hardly explored to date. Acquired diffraction patterns show that the usual dark disk model is not valid and that good agreement is obtained with a mixed model coupling thin lens with opaque disk. Hologram focusing is nevertheless performed with a dedicated automated method. A literature review has been conducted to identify the sharpest auto-focus function for our application. In a second step, in order to measure high retention rates, an inverse problem approach is applied on all the outliers and missing droplets. This hologram restitution treatment has been applied to experimental results with a comparison to independent measurements. The main results obtained with calibrated droplets are

  4. Bulk and interfacial molecular structure near liquid-liquid critical points

    Energy Technology Data Exchange (ETDEWEB)

    Manzanares-Papayanopoulos, Emilio

    2000-09-01

    Critical behaviour occurs when two coexisting phases merge identity without abrupt change in physical properties. The detail of this behaviour is nowadays considered universal, being dominated by the divergence of the correlation length {xi}. Following this universality, the detailed behaviour can be studied experimentally using any convenient system. For that reason, the study of fluids, and in particular fluid mixtures, offers a useful platform since critical behaviour in such systems can often be studied at convenient temperatures and pressures. Although criticality is a consequence of the divergence of {xi}, and so in a sense is a large-scale phenomenon, nevertheless it has an influence on events at molecular level. This aspect of criticality has received relatively little study compared to the enormous effort expended over the past thirty years in elucidating the macroscopic or phenomenological aspects of criticality. The signature of criticality at molecular level is the central theme running through this research.The aim of the work described in this thesis was to investigate the surface and transport properties of near-critical binary liquid mixtures. The surface properties mainly concerned the adsorption and wetting behaviour at the vapour-liquid and liquid-solid interfaces. The transport property studied was the shear viscosity at bulk or macroscopic level and the corresponding property at molecular or microscopic level, the micro viscosity. The work presented in this thesis comprises the experimental measurements and the theoretical interpretations drawn from the results. The experimental work was varied, using both classical and modern techniques. The theoretical interpretation was used as directed towards validating and comparing the results of the experimental programme with the predictions of the current classical critical-state theories. The systems investigated have been mostly alkane + perfluoroalkane mixtures or mixtures with very similar

  5. Salting-out homogenous extraction followed by ionic liquid/ionic liquid liquid-liquid micro-extraction for determination of sulfonamides in blood by high performance liquid chromatography.

    Science.gov (United States)

    Liu, Zhongling; Yu, Wei; Zhang, Hanqi; Gu, Fanbin; Jin, Xiangqun

    2016-12-01

    Salting-out homogenous extraction followed by ionic liquid/ionic liquid dispersive liquid-liquid micro-extraction system was developed and applied to the extraction of sulfonamides in blood. High-performance liquid chromatography was applied to the determination of the analytes. The blood sample was centrifuged to obtain the serum. After the proteins in the serum were removed in the presence of acetonitrile, ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, dipotassium hydrogen phosphate, ionic liquid 1-Hexyl-3-methylimidazolium hexafluorophosphate were added into the resulting solution. After the resulting mixture was ultrasonically shaken and centrifuged, the precipitate was separated. The acetonitrile was added in the precipitate and the analytes were extracted into the acetonitrile phase. The parameters affecting the extraction efficiency, such as volume of ionic liquid, amount of dipotassium hydrogen phosphate, volume of dispersant, extraction time and temperature were investigated. The limits of detection of sulfamethizole (STZ), sulfachlorpyridazine (SCP), sulfamethoxazole (SMX) and Sulfisoxazole (SSZ) were 4.78, 3.99, 5.21 and 3.77μgL -1 , respectively. When the present method was applied to the analysis of real blood samples, the recoveries of analytes ranged from 90.0% to 113.0% and relative standard deviations were lower than 7.2%. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. From materials control to astrophysics: metastable superconductors

    International Nuclear Information System (INIS)

    Waysand, G.

    1984-01-01

    The basic properties of metastable superconducting materials are reviewed: superheated domain, size of the granules, reading of the change of state. In the case of superheating, the phase transition can occur following two paths: a) increase of temperature (thermal nucleation) which allows an analysis of the calorimetric behavior for particle detection; b) increase of the applied magnetic field which allows the evaluation of surface defects promoting the nucleation of the normal state, and, more generally, the study of the superheated material as a disordered system. The thermal nucleation is useful for X-ray detection in non-destructive control as well as for the solar neutrino detection in real time. The magnetic nucleation is the basis for a proposal of detection of magnetic monopoles by induction [fr

  7. Metastable electroweak vacuum. Implications for inflation

    Energy Technology Data Exchange (ETDEWEB)

    Lebedev, Oleg; Westphal, Alexander [DESY Theory Group, Hamburg (Germany)

    2012-10-15

    Within the Standard Model, the current Higgs and top quark data favor metastability of the electroweak vacuum, although the uncertainties are still significant. The true vacuum is many orders of magnitude deeper than ours and the barrier separating the two is tiny compared to the depth of the well. This raises a cosmological question: how did the Higgs field get trapped in the shallow minimum and why did it stay there during inflation? The Higgs initial conditions before inflation must be fine-tuned to about one part in 10{sup 8} in order for the Higgs field to end up in the right vacuum. In this note, we show that these problems can be resolved if there is a small positive coupling between the Higgs and the inflaton.

  8. Transition Manifolds of Complex Metastable Systems

    Science.gov (United States)

    Bittracher, Andreas; Koltai, Péter; Klus, Stefan; Banisch, Ralf; Dellnitz, Michael; Schütte, Christof

    2018-04-01

    We consider complex dynamical systems showing metastable behavior, but no local separation of fast and slow time scales. The article raises the question of whether such systems exhibit a low-dimensional manifold supporting its effective dynamics. For answering this question, we aim at finding nonlinear coordinates, called reaction coordinates, such that the projection of the dynamics onto these coordinates preserves the dominant time scales of the dynamics. We show that, based on a specific reducibility property, the existence of good low-dimensional reaction coordinates preserving the dominant time scales is guaranteed. Based on this theoretical framework, we develop and test a novel numerical approach for computing good reaction coordinates. The proposed algorithmic approach is fully local and thus not prone to the curse of dimension with respect to the state space of the dynamics. Hence, it is a promising method for data-based model reduction of complex dynamical systems such as molecular dynamics.

  9. Metastable cosmic strings in realistic models

    International Nuclear Information System (INIS)

    Holman, R.

    1992-01-01

    The stability of the electroweak Z-string is investigated at high temperatures. The results show that, while finite temperature corrections can improve the stability of the Z-string, their effect is not strong enough to stabilize the Z-string in the standard electroweak model. Consequently, the Z-string will be unstable even under the conditions present during the electroweak phase transition. Phenomenologically viable models based on the gauge group SU(2) L x SU(2) R x U(1) B-L are then considered, and it is shown that metastable strings exist and are stable to small perturbations for a large region of the parameter space for these models. It is also shown that these strings are superconducting with bosonic charge carriers. The string superconductivity may be able to stabilize segments and loops against dynamical contraction. Possible implications of these strings for cosmology are discussed

  10. Metastable electroweak vacuum. Implications for inflation

    International Nuclear Information System (INIS)

    Lebedev, Oleg; Westphal, Alexander

    2012-10-01

    Within the Standard Model, the current Higgs and top quark data favor metastability of the electroweak vacuum, although the uncertainties are still significant. The true vacuum is many orders of magnitude deeper than ours and the barrier separating the two is tiny compared to the depth of the well. This raises a cosmological question: how did the Higgs field get trapped in the shallow minimum and why did it stay there during inflation? The Higgs initial conditions before inflation must be fine-tuned to about one part in 10 8 in order for the Higgs field to end up in the right vacuum. In this note, we show that these problems can be resolved if there is a small positive coupling between the Higgs and the inflaton.

  11. Path lumping: An efficient algorithm to identify metastable path channels for conformational dynamics of multi-body systems

    Science.gov (United States)

    Meng, Luming; Sheong, Fu Kit; Zeng, Xiangze; Zhu, Lizhe; Huang, Xuhui

    2017-07-01

    Constructing Markov state models from large-scale molecular dynamics simulation trajectories is a promising approach to dissect the kinetic mechanisms of complex chemical and biological processes. Combined with transition path theory, Markov state models can be applied to identify all pathways connecting any conformational states of interest. However, the identified pathways can be too complex to comprehend, especially for multi-body processes where numerous parallel pathways with comparable flux probability often coexist. Here, we have developed a path lumping method to group these parallel pathways into metastable path channels for analysis. We define the similarity between two pathways as the intercrossing flux between them and then apply the spectral clustering algorithm to lump these pathways into groups. We demonstrate the power of our method by applying it to two systems: a 2D-potential consisting of four metastable energy channels and the hydrophobic collapse process of two hydrophobic molecules. In both cases, our algorithm successfully reveals the metastable path channels. We expect this path lumping algorithm to be a promising tool for revealing unprecedented insights into the kinetic mechanisms of complex multi-body processes.

  12. Determination of Levetiracetam in Human Plasma by Dispersive Liquid-Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry

    Science.gov (United States)

    2016-01-01

    Levetiracetam (LEV) is an antiepileptic drug that is clinically effective in generalized and partial epilepsy syndromes. The use of this drug has been increasing in clinical practice and intra- or -interindividual variability has been exhibited for special population. For this reason, bioanalytical methods are required for drug monitoring in biological matrices. So this work presents a dispersive liquid-liquid microextraction method followed by gas chromatography-mass spectrometry (DLLME-GC-MS) for LEV quantification in human plasma. However, due to the matrix complexity a previous purification step is required. Unlike other pretreatment techniques presented in the literature, for the first time, a procedure employing ultrafiltration tubes Amicon® (10 kDa porous size) without organic solvent consumption was developed. GC-MS analyses were carried out using a linear temperature program, capillary fused silica column, and helium as the carrier gas. DLLME optimized parameters were type and volume of extraction and dispersing solvents, salt addition, and vortex agitation time. Under chosen parameters (extraction solvent: chloroform, 130 μL; dispersing solvent: isopropyl alcohol, 400 μL; no salt addition and no vortex agitation time), the method was completely validated and all parameters were in agreement with the literature recommendations. LEV was quantified in patient's plasma sample using less than 550 μL of organic solvent. PMID:27830105

  13. Complex Formation in a Liquid-Liquid Extraction System Containing Cobalt(II, 4-(2-Pyridylazoresorcinol, and Nitron

    Directory of Open Access Journals (Sweden)

    Petya Vassileva Racheva

    2013-01-01

    Full Text Available Complex formation and liquid-liquid extraction were studied in a system containing cobalt(II, 4-(2-pyridylazoresorcinol (PAR, 1,4-diphenyl-3-(phenylamino-1H-1,2,4-triazole (Nitron, Nt, water, and chloroform. The effect of some experimental parameters (pH, shaking time, concentration of PAR, and concentration of Nt was systematically investigated, and the optimum conditions for cobalt extraction as an ion-association complex, (NtH+[Co3+(PAR2], were found. The following key equilibrium constants were calculated: constant of association (Log β=4.77±0.06, constant of distribution (LogKD=1.34±0.01, and constant of extraction (LogKex=6.11±0.07. Beer’s law was obeyed for Co concentrations up to 1.7 μg mL−1 with a molar absorptivity of 6.0×104 L mol−1 cm−1 at λmax=520 nm. Some additional characteristics, such as limit of detection, limit of quantification, and Sandell’s sensitivity, were estimated as well.

  14. Measurements and modeling of quaternary (liquid + liquid) equilibria for mixtures of (methanol or ethanol + water + toluene + n-dodecane)

    International Nuclear Information System (INIS)

    Mohammad Doulabi, F.S.; Mohsen-Nia, M.; Modarress, H.

    2006-01-01

    The extraction of aromatic compound toluene from alkane, dodecane, by mixed solvents (water + methanol) (water + ethanol) and (methanol + ethanol) have been studied by (liquid + liquid) equilibrium (LLE) measurements at three temperatures (298.15, 303.15, and 313.15) K and ambient pressure. The compositions of liquid phases at equilibrium were determined by gas liquid chromatography. The experimental tie-line data for three quaternary mixtures of {(water + methanol) + toluene + dodecane}, {(water + ethanol) + toluene + dodecane}, and {(methanol + ethanol) + toluene + dodecane} are presented. The experimental quaternary LLE data have been satisfactorily correlated by using the UNIQUAC and NRTL activity coefficient models. The parameters of the models have been evaluated and presented. The tie-line data of the studied quaternary mixtures also were correlated using the Hand method. The partition coefficients and the selectivity factor of solvent are calculated and compared for the three mixed solvents. The comparisons indicate that the selectivity factor for mixed solvent (methanol + ethanol) is higher than the other two mixed solvents at the three studied temperatures. However, considering the temperature variations of partition coefficients of toluene in two liquid phases at equilibrium, an optimum temperature may be obtained for an efficient extraction of toluene from dodecane by the mixed solvents

  15. Feasibility of corona discharge ion mobility spectrometry for direct analysis of samples extracted by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Jafari, Mohammad T; Riahi, Farhad

    2014-05-23

    The capability of corona discharge ionization ion mobility spectrometry (CD-IMS) for direct analysis of the samples extracted by dispersive liquid-liquid microextraction (DLLME) was investigated and evaluated, for the first time. To that end, an appropriate new injection port was designed and constructed, resulting in possibility of direct injection of the known sample volume, without tedious sample preparation steps (e.g. derivatization, solvent evaporation, and re-solving in another solvent…). Malathion as a test compound was extracted from different matrices by a rapid and convenient DLLME method. The positive ion mobility spectra of the extracted malathion were obtained after direct injection of carbon tetrachloride or methanol solutions. The analyte responses were compared and the statistical results revealed the feasibility of direct analysis of the extracted samples in carbon tetrachloride, resulting in a convenient methodology. The coupled method of DLLME-CD-IMS was exhaustively validated in terms of sensitivity, dynamic range, recovery, and enrichment factor. Finally, various real samples of apple, river and underground water were analyzed, all verifying the feasibility and success of the proposed method for the easy extraction of the analyte using DLLME separation before the direct analysis by CD-IMS. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Numerical investigation on liquid sheets interaction characteristics of liquid-liquid coaxial swirling jets in bipropellant thruster

    International Nuclear Information System (INIS)

    Ding, Jia-Wei; Li, Guo-Xiu; Yu, Yu-Song

    2016-01-01

    Highlights: • A LES-VOF model is conducted to simulate atomization of coaxial swirling jets. • Structure and flow field of coaxial swirling jets are investigated. • Merging process occurs at the nozzle exit and generates additional perturbation. • The Rayleigh mode instability dominates the breakup of ligaments. - Abstract: Spray atomization process of a liquid-liquid coaxial swirl injector in bipropellant thruster has been investigated using volume of fluid (VOF) method coupled with large eddy simulation methodology. With fine grid resolution, detailed flow field of interacted liquid sheet has been captured and analyzed. For coaxial swirling jet, static pressure drop in the region between the liquid sheets makes two liquid sheets to approach each other and merge. A strong pressure, velocity and turbulent fluctuations are calculated near the contact position of two coaxial jets. Simulation results indicate that additional perturbations are generated due to strong radial and axial shear effects between coaxial jets. Observation of droplet formation process reveals that the Rayleigh mode instability dominates the breakup of the ligament. Droplet diameter and distribution have been investigated quantitatively. The mean diameter of the coaxial jets is between that of the inner and the outer jets. Compared with the individual swirling jets, wider size distributions of droplets are produced in the coaxial jets.

  17. Determination of thiobencarb in water samples by gas chromatography using a homogeneous liquid-liquid microextraction via flotation assistance procedure

    Directory of Open Access Journals (Sweden)

    H.A. Mashayekhi

    2013-09-01

    Full Text Available Homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA coupled with gas chromatography-flame ionization detection (GC-FID was applied for the extraction and determination of thiobencarb in water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added into the extraction cell which contained an appropriate mixture of toluene (as an extraction solvent and acetone (as a homogeneous solvent. By using air flotation, the organic solvent was collected at the conical part of the designed cell. The effect of the different parameters on the efficiency of extraction such as type and volume of extraction and homogeneous solvents, ionic strength and extraction time were studied and optimized. Under the optimal conditions, linearity of the method was in the range of 1.0-200 µg L-1. The relative standard deviations in the real samples varied from 7.8-11.7 % (n = 3. The proposed method was successfully applied to analysis of thiobencarb in the water samples and satisfactory results were obtained.DOI: http://dx.doi.org/10.4314/bcse.v27i3.4

  18. Fully-automated in-syringe dispersive liquid-liquid microextraction for the determination of caffeine in coffee beverages.

    Science.gov (United States)

    Frizzarin, Rejane M; Maya, Fernando; Estela, José M; Cerdà, Víctor

    2016-12-01

    A novel fully-automated magnetic stirring-assisted lab-in-syringe analytical procedure has been developed for the fast and efficient dispersive liquid-liquid microextraction (DLLME) of caffeine in coffee beverages. The procedure is based on the microextraction of caffeine with a minute amount of dichloromethane, isolating caffeine from the sample matrix with no further sample pretreatment. Selection of the relevant extraction parameters such as the dispersive solvent, proportion of aqueous/organic phase, pH and flow rates have been carefully evaluated. Caffeine quantification was linear from 2 to 75mgL(-1), with detection and quantification limits of 0.46mgL(-1) and 1.54mgL(-1), respectively. A coefficient of variation (n=8; 5mgL(-1)) of a 2.1% and a sampling rate of 16h(-1), were obtained. The procedure was satisfactorily applied to the determination of caffeine in brewed, instant and decaf coffee samples, being the results for the sample analysis validated using high-performance liquid chromatography. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Preparation of high purification and food grade phosphoric acid from technical grade phosphoric acid by liquid-liquid detraction method

    International Nuclear Information System (INIS)

    Alimoradi, M.; Borji, F.; Kishani, A.

    2002-01-01

    Pay attention to increasing consumption of high purification and food grade phosphoric acid in various industries and food industries and on in on hand and lack of preparation between production and distribution of this products its purification is so vital. In this article of liquid-liquid extraction method with normal hexane-mixture of ammonia and acetone-diisopropyl alcohol and normal butanol solvents and these determination of distribution coefficient each one with ph-me try titration we can evaluate effectiveness and sufficiency each one. Because of proper coefficient distribution and its local production of normal butanol solvent and low price is the best solvent. To phosphoric acid modifying coefficient distribution for extraction of phosphoric acid we can add a little value sulfuric acid to the mixture and to remove flouride impurity we add a little Na 2 O. After extraction stage extracted phosphoric acid in the normal strips by evaluating with distilled water and then by passing the carbon active bed and following passes of cationic resine column and concentrated with vacuum distillation. Conclusion of this article is produce of phosphoric acid 85% w/w and food grade from impure phosphoric acid 52% w/w with technical grade

  20. Detection of Organophosphorus Pesticides in Wheat by Ionic Liquid-Based Dispersive Liquid-Liquid Microextraction Combined with HPLC

    Directory of Open Access Journals (Sweden)

    Wei Liu

    2018-01-01

    Full Text Available Food safety issues closely related to human health have always received widespread attention from the world society. As a basic food source, wheat is the fundamental support of human survival; therefore, the detection of pesticide residues in wheat is very necessary. In this work, the ultrasonic-assisted ionic liquid-dispersive liquid-liquid microextraction (DLLME method was firstly proposed, and the extraction and analysis of three organophosphorus pesticides were carried out by combining high-performance liquid chromatography (HPLC. The extraction efficiencies of three ionic liquids with bis(trifluoromethylsulfonylimide (Tf2N anion were compared by extracting organophosphorus in wheat samples. It was found that the use of 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([OMIM][Tf2N] had both high enrichment efficiency and appropriate extraction recovery. Finally, the method was used for the determination of three wheat samples, and the recoveries of them were 74.8–112.5%, 71.8–104.5%, and 83.8–115.5%, respectively. The results show that the method proposed is simple, fast, and efficient, which can be applied to the extraction of organic matters in wheat samples.

  1. Enhanced electrocatalytic activity of reduced graphene oxide-Os nanoparticle hybrid films obtained at a liquid/liquid interface

    Science.gov (United States)

    Bramhaiah, K.; Pandey, Indu; Singh, Vidya N.; Kavitha, C.; John, Neena S.

    2018-03-01

    Hybrid films of reduced graphene oxide-osmium nanoparticles (rGO-Os NPs) synthesized at a liquid/liquid interface are explored for their electrocatalytic activity towards the oxidation of rhodamine B (RhB), a popular colourant found in textile industry effluents and a non-permitted food colour. The free-standing nature of the films enables them to be lifted directly on to electrodes without the aid of any binders. The films consist of aggregates of ultra-small Os NPs interspersed with rGO layers. The hybrid film exhibits enhanced RhB oxidation when compared to its constituents arising from the synergic effect between rGO and Os NPs, Os contributing to electrocatalysis and rGO contributing to high surface area and conductance as well as stabilization of Os nanoparticles. The electrochemical sensor based on rGO-Os NP hybrid film on pencil graphite electrode shows a remarkable performance for the quantitative detection of RhB with a linear variation in a wide range of concentrations, 4-1300 ppb (8.3 nM-2.71 μM). The modified electrode presents good stability over more than 6 months, reproducibility and anti-interference capability. The use of developed sensor for adequate detection of RhB in real samples such as food samples and pen markers is also demonstrated.

  2. Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function

    International Nuclear Information System (INIS)

    Toulemonde, V.

    1995-01-01

    Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.)

  3. Determination of Levetiracetam in Human Plasma by Dispersive Liquid-Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Greyce Kelly Steinhorst Alcantara

    2016-01-01

    Full Text Available Levetiracetam (LEV is an antiepileptic drug that is clinically effective in generalized and partial epilepsy syndromes. The use of this drug has been increasing in clinical practice and intra- or -interindividual variability has been exhibited for special population. For this reason, bioanalytical methods are required for drug monitoring in biological matrices. So this work presents a dispersive liquid-liquid microextraction method followed by gas chromatography-mass spectrometry (DLLME-GC-MS for LEV quantification in human plasma. However, due to the matrix complexity a previous purification step is required. Unlike other pretreatment techniques presented in the literature, for the first time, a procedure employing ultrafiltration tubes Amicon® (10 kDa porous size without organic solvent consumption was developed. GC-MS analyses were carried out using a linear temperature program, capillary fused silica column, and helium as the carrier gas. DLLME optimized parameters were type and volume of extraction and dispersing solvents, salt addition, and vortex agitation time. Under chosen parameters (extraction solvent: chloroform, 130 μL; dispersing solvent: isopropyl alcohol, 400 μL; no salt addition and no vortex agitation time, the method was completely validated and all parameters were in agreement with the literature recommendations. LEV was quantified in patient’s plasma sample using less than 550 μL of organic solvent.

  4. Synthesis and application of magnetic deep eutectic solvents: Novel solvents for ultrasound assisted liquid-liquid microextraction of thiophene.

    Science.gov (United States)

    Khezeli, Tahere; Daneshfar, Ali

    2017-09-01

    Two novel magnetic deep eutectic solvents (MDESs), comprised of cheap and simple components named [choline chloride/phenol] [FeCl 4 ] and [choline chloride/ethylene glycol] [FeCl 4 ] were prepared and characterized by CHN elemental analysis, proton nuclear magnetic resonance ( 1 H NMR), vibrating sample magnetometery (VSM), Raman, Fourier transform-infrared (FT-IR) and UV-Vis spectrometery. The extraction efficiency of the prepared MDESs has been investigated in ultrasound assisted liquid-liquid microextraction based MDES (UALLME-MDES). Briefly, MDESs were added to n-heptan containing thiophene. Then, MDESs were dispersed in n-heptane by sonication. After that, microdroplets of MDESs were collected by a magnet and the remained concentration of thiophene in n-heptane phase was analyzed by GC-FID. The results indicated that [choline chloride/phenol] [FeCl 4 ] has higher extraction efficiency than [choline chloride/ethylene glycol] [FeCl 4 ]. This work opens a new way to the application of MDESs. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Analysis of ecstasy in oral fluid by ion mobility spectrometry and infrared spectroscopy after liquid-liquid extraction.

    Science.gov (United States)

    Armenta, Sergio; Garrigues, Salvador; de la Guardia, Miguel; Brassier, Judit; Alcalà, Manel; Blanco, Marcelo

    2015-03-06

    We developed and evaluated two different strategies for determining abuse drugs based on (i) the analysis of saliva by ion mobility spectrometry (IMS) after thermal desorption and (ii) the joint use of IMS and infrared (IR) spectroscopy after liquid-liquid microextraction (LLME) to enable the sensitivity-enhanced detection and double confirmation of ecstasy (MDMA) abuse. Both strategies proved effective for the intended purpose. Analysing saliva by IMS after thermal desorption, which provides a limit of detection (LOD) of 160μgL(-1), requires adding 0.2M acetic acid to the sample and using the truncated negative second derivative of the ion mobility spectrum. The joint use of IMS and IR spectroscopy after LLME provides an LOD of 11μgL(-1) with the former technique and 800μgL(-1) with the latter, in addition to a limit of confirmation (LOC) of 1.5mgL(-1). Using IMS after thermal desorption simplifies the operational procedure, and using it jointly with IR spectroscopy after LLME allows double confirmation of MDMA abuse with two techniques based on different principles (viz., IMS drift times and IR spectra). Also, it affords on-site analyses, albeit at a lower throughput. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Highly pressurized partially miscible liquid-liquid flow in a micro-T-junction. II. Theoretical justifications and modeling

    Science.gov (United States)

    Qin, Ning; Wen, John Z.; Ren, Carolyn L.

    2017-04-01

    This is the second part of a two-part study on a partially miscible liquid-liquid flow (carbon dioxide and deionized water) that is highly pressurized and confined in a microfluidic T-junction. In the first part of this study, we reported experimental observations of the development of flow regimes under various flow conditions and the quantitative characteristics of the drop flow including the drop length, after-generation drop speed, and periodic spacing development between an emerging drop and the newly produced one. Here in part II we provide theoretical justifications to our quantitative studies on the drop flow by considering (1) C O2 hydration at the interface with water, (2) the diffusion-controlled dissolution of C O2 molecules in water, and (3) the diffusion distance of the dissolved C O2 molecules. Our analyses show that (1) the C O2 hydration at the interface is overall negligible, (2) a saturation scenario of the dissolved C O2 molecules in the vicinity of the interface will not be reached within the contact time between the two fluids, and (3) molecular diffusion does play a role in transferring the dissolved molecules, but the diffusion distance is very limited compared with the channel geometry. In addition, mathematical models for the drop length and the drop spacing are developed based on the observations in part I, and their predictions are compared to our experimental results.

  7. (Surfactant + polymer) interaction parameter studied by (liquid + liquid) equilibrium data of quaternary aqueous solution containing surfactant, polymer, and salt

    Energy Technology Data Exchange (ETDEWEB)

    Foroutan, Masumeh [Physical Chemistry Department, School of Chemistry, College of Science, University of Tehran, 14155-6455 Tehran (Iran, Islamic Republic of)], E-mail: foroutan@khayam.ut.ac.ir; Heidari, Nosrat; Mohammadlou, Maryam [Chemistry Department, Faculty of Science, Uremia University, Uremia (Iran, Islamic Republic of); Sojahrood, Amin Jafari [Physics Department, Faculty of Science, Uremia University, Uremia (Iran, Islamic Republic of)

    2009-02-15

    (Liquid + liquid) equilibrium (LLE) data of quaternary aqueous system containing polyoxyethylene (20) cetyl ether (with abbreviation name Brij 58, non-ionic surfactant), diammonium hydrogen phosphate, and poly ethylene glycol (PEG) with three molar masses {l_brace}M{sub W} = (1000, 6000, and 35,000) g . mol{sup -1}{r_brace} have been determined experimentally at T = 313.15 K. Furthermore, the Flory-Huggins theory with two electrostatic terms (Debye-Hueckel and Pitzer-Debye-Hueckel equations) have been used to calculate the phase behavior of the quaternary systems and (surfactant + polymer) interaction parameter as well as interaction parameters between other species. Temperature dependency of the parameters of the Flory-Huggins theory has been obtained. Also an effort have been done to show that addition of PEG as well as increasing the temperature can shift the binodal curves of the ternary aqueous system containing surfactant and salt to lower mole fraction of salt. Also the effect of polymer molar mass on the binodal diagram displacement has been discussed.

  8. Synthesis of hexavalent molybdenum formo- and aceto-hydroxamates and deferoxamine via liquid-liquid metal partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Breshears, Andrew T.; Brown, M. Alex; Bloom, Ira; Barnes, Charles L.; Gelis, Artem V.

    2018-03-01

    We report a new method of crystal growth and synthesis based on liquid-liquid partitioning that allows for isolation and in-depth characterization of molybdenyl bis(formohydroxamate), Mo-FHA, molybdenyl bis(acetohydroxamate), Mo-AHA, and molybdenyl deferoxamine, Mo-DFO, for the first time. This novel approach affords shorter crystal growth time (hourly timeframe) without sacrificing crystal size or integrity when other methods of crystallization were unsuccessful. All three Mo complexes are characterized in solution via FTIR, NMR, UV-vis, and EXAFS spectroscopy. Mo-AHA and Mo-FHA structures are resolved by single crystal X-ray diffraction. Using the molybdenyl hydroxamate structural information, the speciation of Mo in a siderophore complex (Mo-DFO) is determined via complimentary spectroscopic methods and confirmed by DFT calculations. ESI-MS verifies that a complex of 1:1 molybdenum to deferoxamine is present in solution. Additionally, the Mo solution speciation in the precursor organic phase, MoO2(NO3)2HEH[EHP]2 (where HEH[EHP] is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), is characterized by FTIR and EXAFS spectroscopy as well as DFT calculations.

  9. Separation of tungsten from molybdenum by liquid-liquid extraction and extraction chromatography using thiocyanate and a quarternary ammonium salt

    International Nuclear Information System (INIS)

    Yonezawa, C.; Onishi, H.

    1977-01-01

    Methods were developed for the separation of tungsten from molybdenum by liquid-liquid extraction and extraction chromatography using thiocyanate and a quaternary ammonium salt, Zephiramine. Tungsten was extracted into chloroform as an ion associate of tungsten(V)-thiocyanate complex and Zephiramine cation was retained on a column of Teflon powder coated with Zephiramine, but molybdenum(III) was neither extracted nor retained. The extraction chromatographic method was succesfully applied to the determination of trace amounts of tungsten in molybdenum by neutron activation analysis. The γ-ray spectrum, observed with the Ge(Li) detector, of tungsten fraction separated from irradiated molybdenum are shown. The peaks of 99 Mo, sup(99m)Tc, and sup(99m)Nb (produced by 92 Mo(n,p)sup(99m)Nb) were seen, but these nuclides did nit interfere with the determination of tungsten using a NaI(Tl) detector. The results of the neutron activation analysis of a sample of ammonium molybdate agreed quite well with that of the spectrophotometric determination after extraction chromatographic separation. (T.G.)

  10. Photoinduced Electron Transfer of PAMAM Dendrimer-Zinc(II) Porphyrin Associates at Polarized Liquid|Liquid Interfaces.

    Science.gov (United States)

    Nagatani, Hirohisa; Sakae, Hiroki; Torikai, Taishi; Sagara, Takamasa; Imura, Hisanori

    2015-06-09

    The heterogeneous photoinduced electron-transfer reaction of the ion associates between NH2-terminated polyamidoamine (PAMAM) dendrimers and 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinato zinc(II) (ZnTPPS(4-)) was studied at the polarized water|1,2-dichloroethane (DCE) interface. The positive photocurrent arising from the photoreduction of ZnTPPS(4-) by a lipophilic quencher, decamethylferrocene, in the interfacial region was significantly enhanced by the ion association with the PAMAM dendrimers. The photocurrent response of the dendrimer-ZnTPPS(4-) associates was dependent on the pH condition and on the generation of dendrimer. A few cationic additives such as polyallylamine and n-octyltrimethyammonium were also examined as alternatives to the PAMAM dendrimer, but the magnitude of the photocurrent enhancement was rather small. The high photoreactivity of the dendrimer-ZnTPPS(4-) associates was interpreted mainly as a result of the high interfacial concentration of photoreactive porphyrin units associated stably with the dendrimer which was preferably adsorbed at the polarized water|DCE interface. The photochemical data observed in the second and fourth generation PAMAM dendrimer systems demonstrated that the higher generation dendrimer which can incorporate a porphyrin molecule more completely in the interior is less efficient for the photocurrent enhancement at the interface. These results indicated that the photoreactivity of ionic reactant at a polarized liquid|liquid interface can readily be modified via ion association with the charged dendrimer.

  11. In-syringe dispersive liquid-liquid microextraction with liquid chromatographic determination of synthetic pyrethroids in surface water

    Directory of Open Access Journals (Sweden)

    Saeed S. Albaseer

    2012-03-01

    Full Text Available An indigenously fabricated in laboratory glass syringe was used for in-syringe dispersive liquid-liquid microextraction (is-DLLME and preconcentration of synthetic pyrethroids (SPs from surface waters suitable for their determination by high performance liquid chromatography. In contrast to classical DLLME, is-DLLME allows the use of lighter-than-water organic solvents and the analysis of environmental contaminants’ samples without prior filtration, which is of great importance due to the high affinity of pyrethroids to adsorb to solid particulates present in environmental samples. The effects of various parameters on the extraction efficiency were evaluated and optimized systemically using one-factor-at-a-time method (OFAT and statistically using full factorial design (24. Three SPs (viz.; cypermethrin, resmethrin and permethrin were analyzed. The method showed good accuracy with RSD% in the range of of 4.8–6.9%. The method detection limits of the three pesticides ranged from 0.14 to 0.16 ng mL-1. The proposed method was applied for the determination of synthetic pyrethroids in lake water

  12. Sol-Gel synthesis of MgO-SiO2 glass compositions having stable liquid-liquid immiscibility

    Science.gov (United States)

    Bansal, Narottam P.

    1987-01-01

    MgO-SiO2 glasses containing up to 15 mol % MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol % MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol % MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol %) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

  13. Removal of actinide elements from liquid scintillation cocktail wastes using liquid-liquid extraction and demulsification techniques

    International Nuclear Information System (INIS)

    Foltz, K.; Landsberger, S.; Srinivasan, B.; Vandegrift, G.F.

    1994-01-01

    For many years liquid scintillation cocktail (LSC) wastes have been generated and stored at Argonne National Laboratory (ANL). These wastes are stored in thousands of 10--20 m scintillation vials, many of which contain elements with Z > 88. Because storage space is limited, disposal of this waste is pressing. These wastes could be commercially incinerated if the radionuclides with Z>88 are reduced to sufficiently low levels. However, there is currently no deminimus level for these radionuclides, and separation techniques are still being tested. The University of Illinois is conducting experiments to separate radionuclides with Z > 88 from simulated LSC wastes by using liquid-liquid extraction (LLX) and demulsification techniques. The actinide elements are removed from the LSC by extraction into an aqueous phase after the cocktail has been demulsified. The aqueous and organic phases are separated and the organic phase, now free from radionuclides with Z > 88, can be sent to a commercial incineration facility. The aqueous phase may be treated and disposed of using existing techniques. The LLX separation techniques used solutions of sodium oxalate, aluminum nitrate, and tetrasodium EDTA at varying concentrations. These extractants were mixed with the simulated waste in a 1:1 volume ratio. Using 1.0M Na 4 EDTA salt solutions, decontamination ratios as high as 230 were achieved

  14. Overcoming the challenges of conventional dispersive liquid-liquid microextraction: analysis of THMs in chlorinated swimming pools.

    Science.gov (United States)

    Faraji, Hakim; Helalizadeh, Masoumeh; Kordi, Mohammad Reza

    2018-01-01

    A rapid, simple, and sensitive approach to the analysis of trihalomethanes (THMs) in swimming pool water samples has been developed. The main goal of this study was to overcome or to improve the shortcomings of conventional dispersive liquid-liquid microextraction (DLLME) and to maximize the realization of green analytical chemistry principles. The method involves a simple vortex-assisted microextraction step, in the absence of the dispersive solvent, followed by salting-out effect for the elimination of the centrifugation step. A bell-shaped device and a solidifiable solvent were used to simplify the extraction solvent collection after phase separation. Optimization of the independent variables was performed by using chemometric methods in three steps. The method was statistically validated based on authentic guidance documents. The completion time for extraction was less than 8 min, and the limits of detection were in the range between 4 and 72 ng L -1 . Using this method, good linearity and precision were achieved. The results of THMs determination in different real samples showed that in some cases the concentration of total THMs was more than threshold values of THMs determined by accredited healthcare organizations. This method indicated satisfactory analytical figures of merit. Graphical Abstract A novel green microextraction technique for overcoming the challenges of conventional DLLME. The proposed procedure complies with the principles of green/sustainable analytical chemistry, comprising decreasing the sample size, making easy automation of the process, reducing organic waste, diminishing energy consumption, replacing toxic reagents with safer reagents, and enhancing operator safety.

  15. Development of a dispersive liquid-liquid microextraction method for the determination of polychlorinated biphenyls in water

    International Nuclear Information System (INIS)

    Rezaei, Fatemeh; Bidari, Araz; Birjandi, Afsoon Pajand; Milani Hosseini, Mohammad Reza; Assadi, Yaghoub

    2008-01-01

    A very simple and powerful microextraction procedure, the dispersive liquid-liquid microextraction (DLLME), was used for the determination of the content of 10 polychlorinated biphenyls (PCBs) in water samples, using gas chromatography coupled with electron-capture detection (GC-ECD). The appropriate amount of acetone (disperser solvent) and chlorobenzene (extraction solvent) at the microlevel volume was used for this procedure. The conditions for the microextraction performance were investigated and optimized. The optimized method exhibited a good linearity (R 2 > 0.996) over the studied range (0.005-2 μg L -1 ), illustrating a satisfactory precision level with R.S.D. values between 4.1% and 11.0%. The values of the detection limit (S/N = 3) were found to be lower than 0.002 μg L -1 . Furthermore, a large enrichment factor for the analytes (up to a 540-fold) was achieved in a very short time for only a 5.00-mL water sample. The effectiveness of the method towards real samples was tested by analyzing well, river and seawater samples. The relative recoveries of the well, river and seawater samples, which had been spiked with different levels of PCBs were equal to 92.0-114.0%, 97.0-102.0% and 96.0-103.0%, respectively. The attained results demonstrated that DLLME combined with GC-ECD was a fast and inexpensive technique for the PCBs determination in water samples

  16. Surfactant-enhanced liquid-liquid microextraction coupled to micro-solid phase extraction onto highly hydrophobic magnetic nanoparticles

    International Nuclear Information System (INIS)

    Giannoulis, Kiriakos M.; Giokas, Dimosthenis L.; Tsogas, George Z.; Vlessidis, Athanasios G.; Zhu, Qing; Pan, Qinmin

    2013-01-01

    We are presenting a simplified alternative method for dispersive liquid-liquid microextraction (DLLME) by resorting to the use of surfactants as emulsifiers and micro solid-phase extraction (μ-SPE). In this combined procedure, DLLME of hydrophobic components is initially accomplished in a mixed micellar/microemulsion extractant phase that is prepared by rapidly mixing a non-ionic surfactant and 1-octanol in aqueous medium. Then, and in contrast to classic DLLME, the extractant phase is collected by highly hydrophobic polysiloxane-coated core-shell Fe 2 O 3 (at)C magnetic nanoparticles. Hence, the sample components are the target analyte in the DLLME which, in turn, becomes the target analyte of the μ-SPE step. This 2-step approach represents a new and simple DLLME procedure that lacks tedious steps such as centrifugation, thawing, or delicate collection of the extractant phase. As a result, the analytical process is accelerated and the volume of the collected phase does not depend on the volume of the extraction solvent. The method was applied to extract cadmium in the form of its pyrrolidine dithiocarbamate chelate from spiked water samples prior to its determination by FAAS. Detection limits were brought down to the low μg L −1 levels by preconcentrating 10 mL samples with satisfactory recoveries (96.0–108.0 %). (author)

  17. Modified Dispersive Liquid-Liquid Micro Extraction Using Green Solvent for Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Vegetable Samples

    International Nuclear Information System (INIS)

    Kin, C.M.; Shing, W.L.

    2016-01-01

    According to International Agency for Research on Cancer (IARC), most of Polycyclic Aromatic Hydrocarbons (PAHs) known as genotoxic human carcinogen and mutagenic. PAHs represent as poorly degradable pollutants that exist in soils, sediments, surface water and atmosphere. A simple, rapid and sensitive extraction method termed modified Dispersive Liquid-Liquid Micro extraction (DLLME) using green solvent was developed to determine PAHs in vegetable samples namely radish, cabbage and cucumber prior to Gas Chromatography Flame Ionization Detection (GC-FID). The extraction method is based on replacing chlorinated organic extraction solvent in the conventional DLLME with low toxic solvent, 1-bromo-3-methylbutane without using dispersive solvent. Several experimental factors such as type and volume of extraction solvents, extraction time, confirmation of 12 PAHs by GC-MS, recovery percentages on vegetable samples and the comparative analysis with conventional DLLME were carried out. Both DLLME were successfully extracted 12 types of PAHs. In modified DLLME, the recoveries of the analytes obtained were in a range of 72.72 - 88.07 % with RSD value below 7.5 % which is comparable to the conventional DLLME. The use of microliter of low toxic extraction solvent without addition of dispersive solvent caused the method is economic and environmental friendly which is fulfill the current requirement, green chemistry based analytical method. (author)

  18. Optimization and application of homogeneous liquid-liquid extraction in preconcentration of copper (II) in a ternary solvent system

    Energy Technology Data Exchange (ETDEWEB)

    Farajzadeh, Mir Ali [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of)], E-mail: farajzade@yahoo.com; Bahram, Morteza [Department of Chemistry, Faculty of Science, Urmia University, Urmia (Iran, Islamic Republic of); Zorita, Saioa [Department of Analytical Chemistry, University of Lund, P.O. Box 124, 221 00 Lund (Sweden); Mehr, Behzad Ghorbani [Department of Chemistry, Faculty of Science, Urmia University, Urmia (Iran, Islamic Republic of)

    2009-01-30

    In this study a homogeneous liquid-liquid extraction based on the Ph-dependent phase-separation process was investigated using a ternary solvent system (water-acetic acid-chloroform) for the preconcentration of Cu{sup 2+} ions. 8-Hydroxy quinoline was used as the chelating agent prior to its extraction. Flame atomic absorption spectrophotometry using acetylene-air flame was used for the quantitation of analyte after preconcentration. The effect of various experimental parameters in extraction step was investigated using two optimization methods, one variable at a time and central composite design. The experimental design was done at five levels of operating parameters. Nearly the same optimized results were obtained using both methods: sample size, 5 mL; volume of NaOH 10 M, 2 mL; chloroform volume, 300 {mu}L; 8-hydroxy quinoline concentration more than 0.01 M and salt amount did not affect the extraction significantly. Under the optimum conditions the calibration graph was linear over the range 10-2000 {mu}g L{sup -1}. The relative standard deviation was 7.6% for six repeated determinations (C = 500 {mu}g L{sup -1}). Furthermore, the limit of detection (S/N = 3) and limit of quantification (S/N = 10) of the method were obtained as 1.74 and 6 {mu}g L{sup -1}, respectively.

  19. Analysis of chlorpheniramine in human urine samples using dispersive liquid-liquid microextraction combined with high-performance liquid chromatography

    Directory of Open Access Journals (Sweden)

    Mehdi Maham

    2014-09-01

    Full Text Available A simple and environmentally friendly microextraction technique was used for determination of chlorpheniramine (CPM, an antihistamine drug, in human urine samples using dispersive liquid-liquid microextraction (DLLME followed by high performance liquid chromatography with diode array detection (HPLC-DAD. In this extraction technique, an appropriate mixture of acetonitrile (disperser solvent and carbon tetrachloride (extraction solvent was rapidly injected into the urine sample containing the target analyte. Tiny droplets of extractant were formed and dispersed into the sample solution and then sedimented at the bottom of the conical test tube by centrifugation. Under optimal conditions, the calibration curve was linear in the range of 0.055-5.5 µg mL-1, with a detection limit of 16.5 ng mL-1. This proposed method was successfully applied to the analysis of real urine samples. Low consumption of toxic organic solvents, simplicity of operation, low cost and acceptable figures of merit are the main advantages of the proposed technique.

  20. Can magnetism and superconductivity coexist

    International Nuclear Information System (INIS)

    Ishikawa, M.

    1982-01-01

    Recent syntheses of rare earth (RE) ternary superconductors such as (RE)Mo 6 X 8 (X=S or Se) and (RE)Rh 4 B 4 have provided the first opportunity to explore the interaction between magnetism and superconductivity in detail owing to their particular crystal structure. The regular sublattice of the rare-earth ions in these new ternary compounds undergoes a ferro- or antiferromagnetic phase transition in the superconducting state. If the transition is antiferromagnetic, the superconductivity is preserved so that true coexistence results. If it is ferromagnetic, on the other hand, the superconductivity eventually gives way to uniform ferromagnetism at low temperatures. However, recent theories predict several possible states of coexistence even in ferromagnetic superconductors. This article reviews aspects of these new phase transitions in ternary superconductors. (author)

  1. Shape coexistence in 153Ho

    Science.gov (United States)

    Pramanik, Dibyadyuti; Sarkar, S.; Saha Sarkar, M.; Bisoi, Abhijit; Ray, Sudatta; Dasgupta, Shinjinee; Chakraborty, A.; Krishichayan, Kshetri, Ritesh; Ray, Indrani; Ganguly, S.; Pradhan, M. K.; Ray Basu, M.; Raut, R.; Ganguly, G.; Ghugre, S. S.; Sinha, A. K.; Basu, S. K.; Bhattacharya, S.; Mukherjee, A.; Banerjee, P.; Goswami, A.

    2016-08-01

    The high-spin states in 153Ho have been studied by the La57(20Ne139,6 n ) reaction at a projectile energy of 139 MeV at the Variable Energy Cyclotron Centre (VECC), Kolkata, India, utilizing an earlier campaign of the Indian National Gamma Array (INGA) setup. Data from γ -γ coincidence, directional correlation, and polarization measurements have been analyzed to assign and confirm the spins and parities of the levels. We have suggested a few additions and revisions of the reported level scheme of 153Ho. The RF-γ time difference spectra have been useful to confirm the half-life of an isomer in this nucleus. From the comparison of experimental and theoretical results, it is found that there are definite indications of shape coexistence in this nucleus. The experimental and calculated lifetimes of several isomers have been compared to follow the coexistence and evolution of shape with increasing spin.

  2. Isobaric (vapour + liquid + liquid) equilibrium data for (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) systems at 100 kPa

    International Nuclear Information System (INIS)

    Lladosa, Estela; Monton, Juan B.; Burguet, MaCruz; Torre, Javier de la

    2008-01-01

    Isobaric (vapour + liquid + liquid) equilibria were measured for the (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) system at 100 kPa. The apparatus used for the determination of (vapour + liquid + liquid) equilibrium data was an all-glass dynamic recirculating still with an ultrasonic homogenizer couple to the boiling flask. The experimental data demonstrated the existence of a heterogeneous ternary azeotrope for both ternary systems. The (vapour + liquid + liquid) equilibria data were found to be thermodynamically consistent for both systems. The experimental data were compared with the estimation using UNIQUAC and NRTL models and the prediction of UNIFAC model

  3. The liquid metastable miscibility gap in Cu-based systems

    DEFF Research Database (Denmark)

    Curiotto, S.; Greco, R.; Pryds, Nini

    2007-01-01

    Some Cu-based alloys, like Cu–Co, Cu–Fe and Cu–Co–Fe, display a liquid metastable miscibility gap. When the melt is undercooled below a certain temperature depending on the alloy composition, they present a separation in two liquid phases, followed by coagulation before dendritic solidification....... In order to predict the phase equilibria and the mechanisms of microstructure formation, a determination of the metastable monotectics in the phase diagrams is essential. This paper focuses on the up-to-date findings on the Cu–Co, Cu–Fe and Cu–Co–Fe metastable miscibility gap in the liquid phase...

  4. Calculation of liquid-liquid equilibrium of aqueous two-phase systems using a chemical-theory-based excess Gibbs energy model

    Directory of Open Access Journals (Sweden)

    Pessôa Filho P. A.

    2004-01-01

    Full Text Available Mixtures containing compounds that undergo hydrogen bonding show large deviations from ideal behavior. These deviations can be accounted for through chemical theory, according to which the formation of a hydrogen bond can be treated as a chemical reaction. This chemical equilibrium needs to be taken into account when applying stability criteria and carrying out phase equilibrium calculations. In this work, we illustrate the application of the stability criteria to establish the conditions under which a liquid-phase split may occur and the subsequent calculation of liquid-liquid equilibrium using a chemical-theory-modified Flory-Huggins equation to describe the non ideality of aqueous two-phase systems composed of poly(ethylene glycol and dextran. The model was found to be able to correlate ternary liquid-liquid diagrams reasonably well by simple adjustment of the polymer-polymer binary interaction parameter.

  5. Tar removal from biosyngas in the biomass gasification process. (Liquid + liquid) equilibrium {water + solvent (paraxylene and methyl hexadecanoate) + model molecules of tar (benzene, toluene, phenol)}

    International Nuclear Information System (INIS)

    Bassil, Georgio; Mokbel, Ilham; Abou Naccoul, Ramy; Stephan, Juliette; Jose, Jacques; Goutaudier, Christelle

    2012-01-01

    Highlights: ► (Liquid + liquid) equilibria at atmospheric pressure. ► Solubility of benzene (or toluene or phenol) in paraxylene at (303 to 343) K. ► Solubility of benzene (or toluene or phenol) in methyl palmitate or methyl hexadecanoate at (303 to 343) K. ► Correlation of LLE using NRTL model. - Abstract: Tar is generated in the process by the condensation of the gas resulting from biomass gasification. The objective of this work is a contribution to the database on thermodynamic quantity which will be useful at the operation of tar removal from aqueous medium. With this aim, (liquid + liquid) equilibrium of {water + solvent (paraxylene and methyl hexadecanoate) + model molecules of tar (benzene, toluene, phenol)} was studied at temperatures (303.2, 323.2, and 343.2) K. The data obtained were correlated with the non-random two-liquid (NRTL) model.

  6. Liquid-liquid equilibrium of water + PEG 8000 + magnesium sulfate or sodium sulfate aqueous two-phase systems at 35°C: experimental determination and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    B. D. Castro

    2005-09-01

    Full Text Available Liquid-liquid extraction using aqueous two-phase systems is a highly efficient technique for separation and purification of biomolecules due to the mild properties of both liquid phases. Reliable data on the phase behavior of these systems are essential for the design and operation of new separation processes; several authors reported phase diagrams for polymer-polymer systems, but data on polymer-salt systems are still relatively scarce. In this work, experimental liquid-liquid equilibrium data on water + polyethylene glycol 8000 + magnesium sulfate and water + polyethylene glycol 8000 + sodium sulfate aqueous two-phase systems were obtained at 35°C. Both equilibrium phases were analyzed by lyophilization and ashing. Experimental results were correlated with a mass-fraction-based NRTL activity coefficient model. New interaction parameters were estimated with the Simplex method. The mean deviations between the experimental and calculated compositions in both equilibrium phases is about 2%.

  7. (Liquid + liquid) equilibria of (water + linalool + limonene) ternary system at T = (298.15, 308.15, and 318.15) K

    International Nuclear Information System (INIS)

    Gramajo de Doz, Monica B.; Cases, Alicia M.; Solimo, Horacio N.

    2008-01-01

    (Liquid + liquid) equilibrium (LLE) data for {water (1) + linalool (2) + limonene (3)} ternary system at T = (298.15, 308.15, and 318.15 ± 0.05) K are reported. The organic chemicals were quantified by gas chromatography using a flame ionisation detector while water was quantified using a thermal conductivity detector. The effect of the temperature on (liquid + liquid) equilibrium is determined and discussed. Experimental data for the ternary mixture are compared with values calculated by the NRTL and UNIQUAC equations, and predicted by means of the UNIFAC group contribution method. It is found that the UNIQUAC and NRTL models provide a good correlation of the solubility curve at these three temperatures, while comparing the calculated values with the experimental ones, the best fit is obtained with the NRTL model. Finally, the UNIFAC model provides poor results, since it predicts a greater heterogeneous region than experimentally observed

  8. Liquid-liquid equilibria for binary and ternary systems containing glycols, aromatic hydrocarbons, and water: Experimental measurements and modeling with the CPA EoS

    DEFF Research Database (Denmark)

    Folas, Georgios; Kontogeorgis, Georgios; Michelsen, Michael Locht

    2006-01-01

    Liquid-liquid equilibrium data of four binary glycol + aromatic hydrocarbon systems and three ternary systems containing water have been measured at atmospheric pressure. The measured systems are monoethylene glycol (MEG) + benzene or toluene, triethylene glycol (TEG) + benzene or toluene, MEG...... + water + benzene, MEG + water + toluene, and TEG + water + toluene. The binary systems are correlated with the Cubic-Plus-Association (CPA) equation of state while the ternary systems are predicted from interaction parameters obtained from the binary systems. Very satisfactory liquid-liquid equilibrium...... correlations are obtained for the binary systems using temperature-independent interaction parameters, while adequate predictions are achieved for multicomponent water + glycol + aromatic hydrocarbons systems when accounting for the solvation between the aromatic hydrocarbons and glycols or water....

  9. Thermodynamic Description of Liquid-Liquid Equilibria in Systems 1-Ethyl-3-methylimidazolium Ethylsulfate + C7-Hydrocarbons by Polymer-Solution Models

    Czech Academy of Sciences Publication Activity Database

    Bendová, Magdalena; Wagner, Zdeněk

    2009-01-01

    Roč. 284, č. 2 (2009), s. 80-85 ISSN 0378-3812 R&D Projects: GA ČR GA104/07/0444; GA ČR GP104/06/P066; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : liquid-liquid equilibrium * ionic liquids * thermodynamic model Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.857, year: 2009

  10. Studies on the liquid-liquid phase distribution equilibria of selenium and its measurement in water using extraction plant with a pulsation column

    International Nuclear Information System (INIS)

    Iskanderani, F.; Sobhi, K.M.; Ejaz, M.

    1989-01-01

    Normal heptane, xylene and a 0.01 molar solution of 4-(5-nonyl)pyridine in toluene were investigated as extractants for selenium(IV) from nitric acid media in potassium iodide. Various parameters affecting the distribution of the element are investigated. Extraction at high aqueous to organic phase volume ratio was studied, using a liquid-liquid extraction plant with a pulsation column. The results were employed to measure selenium in spiked water samples. (author) 24 refs.; 8 figs

  11. Screening and quantitative determination of twelve acidic and neutral pharmaceuticals in whole blood by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry

    DEFF Research Database (Denmark)

    Simonsen, Kirsten Wiese; Steentoft, Anni; Buck, Maike

    2010-01-01

    . The method was fully validated for salicylic acid, paracetamol, phenobarbital, carisoprodol, meprobamate, topiramate, etodolac, chlorzoxazone, furosemide, ibuprofen, warfarin, and salicylamide. The method also tentatively includes thiopental, theophylline, piroxicam, naproxen, diclophenac, and modafinil......We describe a multi-method for simultaneous identification and quantification of 12 acidic and neutral compounds in whole blood. The method involves a simple liquid-liquid extraction, and the identification and quantification are performed using liquid chromatography-tandem mass spectrometry...

  12. In situ derivatization-liquid liquid extraction as a sample preparation strategy for the determination of urinary biomarker prolyl-4-hydroxyproline by liquid chromatography-tandem mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Cimlová, Jana; Kružberská, Pavla; Švagera, Z.; Hušek, Petr; Šimek, Petr

    2012-01-01

    Roč. 47, č. 3 (2012), s. 294-302 ISSN 1076-5174 R&D Projects: GA ČR GA203/09/2014; GA MZd NS9755; GA MŠk 7F09028 Institutional research plan: CEZ:AV0Z50070508 Keywords : alkyl chloroformate derivatization * liquid liquid extraction * urine Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.214, year: 2012 http://onlinelibrary.wiley.com/doi/10.1002/jms.2952/full

  13. Determination of diflubenzuron and chlorbenzuron in fruits by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by high-performance liquid chromatography.

    Science.gov (United States)

    Ruan, Chunqiang; Zhao, Xiang; Liu, Chenglan

    2015-09-01

    In this study, a simple and low-organic-solvent-consuming method combining an acetonitrile-partitioning extraction procedure followed by "quick, easy, cheap, effective, rugged and safe" cleanup with ionic-liquid-based dispersive liquid-liquid microextraction and high-performance liquid chromatography with diode array detection was developed for the determination of diflubenzuron and chlorbenzuron in grapes and pears. Ionic-liquid-based dispersive liquid-liquid microextraction was performed using the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate as the extractive solvent and acetonitrile extract as the dispersive solvent. The main factors influencing the efficiency of the dispersive liquid-liquid microextraction were evaluated, including the extractive solvent type and volume and the dispersive solvent volume. The validation parameters indicated the suitability of the method for routine analyses of benzoylurea insecticides in a large number of samples. The relative recoveries at three spiked levels ranged between 98.6 and 109.3% with relative standard deviations of less than 5.2%. The limit of detection was 0.005 mg/kg for the two insecticides. The proposed method was successfully used for the rapid determination of diflubenzuron and chlorbenzuron residues in real fruit samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. (Liquid + liquid) equilibrium data for the ternary systems (cycloalkane + ethylbenzene + 1-ethyl-3-methylimidazolim ethylsulfate) at T = 298.15 K and atmospheric pressure

    International Nuclear Information System (INIS)

    Gonzalez, Emilio J.; Calvar, Noelia; Dominguez, Irene; Dominguez, Angeles

    2011-01-01

    Research highlights: → [EMim][ESO 4 ] was studied as solvent to extract ethylbenzene from cycloalkanes. → (Liquid + liquid) equilibrium data were measured at 298.15K and atmospheric pressure. → Selectivity and solute distribution ratio were obtained and compared with literature. → Experimental data were satisfactorily correlated using NRTL and UNIQUAC models. → [EMim][ESO 4 ] can be used as solvent for the studied (liquid + liquid) extraction. - Abstract: In this paper, (liquid + liquid) equilibrium (LLE) data for the ternary systems (cyclohexane, or cyclooctane, or methylcyclohexane + ethylbenzene + 1-ethyl-3-methylimidazolium ethylsulfate) have been determined experimentally at T = 298.15 K and atmospheric pressure. The solubility curves and the tie-line compositions of the conjugate phases were obtained by means of density. The degree of consistency of the tie-lines was tested using the Othmer-Tobias equation, and the Non-Random Two-Liquid (NRTL) and the Universal Quasi-Chemical (UNIQUAC) models were used to correlate the phase equilibrium in the systems. Selectivity and solute distribution ratio were evaluated for the immiscible region.

  15. Experimental investigation of liquid-liquid system drop size distribution in Taylor-Couette flow and its application in the CFD simulation

    Science.gov (United States)

    Farzad, Reza; Puttinger, Stefan; Pirker, Stefan; Schneiderbauer, Simon

    Liquid-liquid systems are widely used in the several industries such as food, pharmaceutical, cosmetic, chemical and petroleum. Drop size distribution (DSD) plays a key role as it strongly affects the overall mass and heat transfer in the liquid-liquid systems. To understand the underlying mechanisms single drop breakup experiments have been done by several researchers in the Taylor-Couette flow; however, most of those studies concentrate on the laminar flow regime and therefore, there is no sufficient amount of data in the case of in turbulent flows. The well-defined pattern of the Taylor-Couette flow enables the possibility to investigate DSD as a function of the local fluid dynamic properties, such as shear rate, which is in contrast to more complex devices such as stirred tank reactors. This paper deals with the experimental investigation of liquid-liquid DSD in Taylor-Couette flow. From high speed camera images we found a simple correlation for the Sauter mean diameter as a function of the local shear employing image processing. It is shown that this correlation holds for different oil-in-water emulsions. Finally, this empirical correlation for the DSD is used as an input data for a CFD simulation to compute the local breakup of individual droplets in a stirred tank reactor.

  16. Quantum mechanical metastability: When and why?

    International Nuclear Information System (INIS)

    Boyanovsky, D.; Willey, R.; Holman, R.

    1992-01-01

    We study quantum mechanical metastability with an eye towards false vacuum decay. We point out some technical and conceptual problems with the familiar bounce treatment of this process. We illustrate with simple quantum mechanical examples that the bounce formalism fails to account for the correct boundary conditions. It is also shown, that the bounce approach overestimates the time scales for tunneling of localized packets in typical (slightly) biased double well potentials. We present a thorough WKB analysis with particular attention to semiclassical trajectories corresponding to complex saddle points. We point out that the boundary conditions determine the proper choice of saddle points and the bounce approach fails to account for semiclassical trajectories in many physically relevant cases. We recognize that these saddle points account for the matching conditions of the WKB wave functions beyond the barriers and restore unitarity and reality of eigenvalues for self-adjoint boundary conditions. We provide a novel approach to the semiclassical analysis of out of equilibrium decay in real time in quantum statistical mechanics. (orig.)

  17. Constitutive modeling of metastable austenitic stainless steel (CD-rom)

    NARCIS (Netherlands)

    Perdahcioglu, Emin Semih; Geijselaers, Hubertus J.M.; Huetink, Han; Boisse, P.

    2008-01-01

    A stress-update algorithm is developed for austenitic metastable steels which undergo phase evolution during deformation. The material initially comprises only the soft and ductile austenite phase which due to the phenomenon of mechanically induced martensitic transformation, transforms completely

  18. Modeling of metastable phase formation diagrams for sputtered thin films.

    Science.gov (United States)

    Chang, Keke; Music, Denis; To Baben, Moritz; Lange, Dennis; Bolvardi, Hamid; Schneider, Jochen M

    2016-01-01

    A method to model the metastable phase formation in the Cu-W system based on the critical surface diffusion distance has been developed. The driver for the formation of a second phase is the critical diffusion distance which is dependent on the solubility of W in Cu and on the solubility of Cu in W. Based on comparative theoretical and experimental data, we can describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation. Metastable phase formation diagrams for Cu-W and Cu-V thin films are predicted and validated by combinatorial magnetron sputtering experiments. The correlative experimental and theoretical research strategy adopted here enables us to efficiently describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation during magnetron sputtering.

  19. Investigation of systematic errors of metastable "atomic pair" number

    CERN Document Server

    Yazkov, V

    2015-01-01

    Sources of systematic errors in analysis of data, collected in 2012, are analysed. Esti- mations of systematic errors in a number of “atomic pairs” fr om metastable π + π − atoms are presented.

  20. Determination of five antiarrhythmic drugs in human plasma by dispersive liquid-liquid microextraction and high-performance liquid chromatography.

    Science.gov (United States)

    Jouyban, Abolghasem; Sorouraddin, Mohammad Hossein; Farajzadeh, Mir Ali; Somi, Mohammad Hossein; Fazeli-Bakhtiyari, Rana

    2015-03-01

    A fast and sensitive high-performance liquid chromatography (HPLC) method with ultraviolet (UV) detection was developed and validated for the simultaneous quantitation of five antiarrhythmic drugs (metoprolol, propranolol, carvedilol, diltiazem, and verapamil) in human plasma samples. It involves dispersive liquid-liquid microextraction (DLLME) of the desired drugs from 660 µL plasma and separation using isocratic elution with UV detection at 200 nm. The complete separation of all analytes was achieved within 7 min. Acetonitrile (as disperser solvent) resulting from the protein precipitation procedure was mixed with 100 µL dichloromethane (as an extraction solvent) and rapidly injected into 5 mL aqueous solution (pH 11.5) containing 1% (w/v), NaCl. After centrifugation, the sedimented phase containing enriched analytes was collected and evaporated to dryness. The residue was re-dissolved in 50 µL de-ionized water (acidified to pH 3) and injected into the HPLC system for analysis. Under the optimal conditions, the enrichment factors and extraction recoveries ranged between 4.4-10.8 and 33-82%, respectively. The suggested method was linear (r(2) ≥0.997) over a dynamic range of 0.02-0.80 µg mL(-1) in plasma. The intra- and inter-days relative standard deviation (RSD%) and relative error (RE%) values of the method were below 20%, which shows good precision and accuracy. Finally, this method was applied to the analysis of real plasma samples obtained from the patients treated with these drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Analysis of drugs of abuse in human plasma by dispersive liquid-liquid microextraction and high-performance liquid chromatography.

    Science.gov (United States)

    Fernández, P; Regenjo, M; Bermejo, A M; Fernández, A M; Lorenzo, R A; Carro, A M

    2015-04-01

    Opioids and cocaine are widely used at present, both for recreational purposes and as drugs of abuse. This raises the need to develop new analytical methods specifically designed for the simultaneous detection of several drugs of abuse in biological samples. In this work, dispersive liquid-liquid microextraction (DLLME) was assessed as a new sample treatment for the simultaneous extraction of morphine (MOR), 6-acetylmorphine (6AM), cocaine (COC), benzoylecgonine (BZE) and methadone (MET) from human plasma. Preliminary assays were done before developing an experimental design based on a Uniform Network Doehlert which allowed the optimum extraction conditions to be identified, namely: a volume of extractant solvent (chloroform) and dispersant solvent (acetonitrile) of 220 µl and 3.2 ml, respectively; 0.2 g of NaCl as a salting-out additive; pH 10.6 and ultrasound stirring for 3.5 min. The resulting extracts were analyzed by high-performance liquid chromatography with photodiode array detection (HPLC-PDA), using an XBridge® RP18 column (250 × 4.6 mm i.d., 5 µm particle size). Calibration graphs were linear over the concentration range 0.1-10 µg ml⁻¹, and detection limits ranged from 13.9 to 28.5 ng ml⁻¹. Precision calculated at three different concentration levels in plasma was included in the range 0.1-6.8% RSD. Recoveries of the five drugs were all higher than 84% on average. Finally the proposed method was successfully applied to 22 plasma samples from heroin, cocaine and/or methadone users, and the most frequently detected drug was benzoylecgonine, followed by methadone, cocaine and morphine. Copyright © 2014 John Wiley & Sons, Ltd.

  2. Determination of suvorexant in human plasma using 96-well liquid-liquid extraction and HPLC with tandem mass spectrometric detection.

    Science.gov (United States)

    Breidinger, S A; Simpson, R C; Mangin, E; Woolf, E J

    2015-10-01

    A method, using liquid chromatography with tandem mass spectrometric detection (LC-MS/MS), was developed for the determination of suvorexant (MK-4305, Belsomra(®)), a selective dual orexin receptor antagonist for the treatment insomnia, in human plasma over the concentration range of 1-1000ng/mL. Stable isotope labeled (13)C(2)H3-suvorexant was used as an internal standard. The sample preparation procedure utilized liquid-liquid extraction, in the 96-well format, of a 100μL plasma sample with methyl t-butyl ether. The compounds were chromatographed under isocratic conditions on a Waters dC18 (50×2.1mm, 3μm) column with a mobile phase consisting of 30/70 (v/v %) 10mM ammonium formate, pH3/acetonitrile at a flow rate of 0.3mL/min. Multiple reaction monitoring of the precursor-to-product ion pairs for suvorexant (m/z 451→186) and (13)C(2)H3-suvorexant (m/z 455→190) on an Applied Biosystems API 4000 tandem mass spectrometer was used for quantitation. Intraday assay precision, assessed in six different lots of control plasma, was within 10% CV at all concentrations, while assay accuracy ranged from 95.6 to 105.0% of nominal. Quality control (QC) samples in plasma were stored at -20°C. Initial within day analysis of QCs after one freeze-thaw cycle showed accuracy within 9.5% of nominal with precision (CV) of 6.7% or less. The plasma QC samples were demonstrated to be stable for up to 25 months at -20°C. The method described has been used to support clinical studies during Phase I through III of clinical development. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Recovery of Acetic Acid from An Ethanol Fermentation Broth by Liquid-Liquid Extraction (LLE) Using Various Solvents

    International Nuclear Information System (INIS)

    Pham, Thi Thu Huong; Kim, Tae Hyun; Um, Byung Hwan

    2015-01-01

    Liquid-liquid extraction (LLE) using various solvents was studied for recovery of acetic acid from a synthetic ethanol fermentation broth. The microbial fermentation of sugars presented in hydrolyzate gives rise to acetic acid as a byproduct. In order to obtain pure ethanol for use as a biofuel, fermentation broth should be subjected to acetic acid removal step and the recovered acetic acid can be put to industrial use. Herein, batch LLE experiments were carried out at 25°C using a synthetic fermentation broth comprising 20.0 g l -1 acetic acid and 5.0 g l -1 ethanol. Ethyl acetate (EtOAc), tri-n-octylphosphine oxide (TOPO), tri-n-octylamine (TOA), and tri-n-alkylphosphine oxide (TAPO) were utilized as solvents, and the extraction potential of each solvent was evaluated by varying the organic phase-to-aqueous phase ratios as 0.2, 0.5, 1.0, 2.0, and 4.0. The highest acetic acid extraction yield was achieved with TAPO; however, the lowest ethanol-to-acetic acid extraction ratio was obtained using TOPO. In a single-stage batch extraction, 97.0 % and 92.4 % of acetic acid could be extracted using TAPO and TOPO when the ratio of organic-to-aqueous phases is 4:1 respectively. A higher solvent-to-feed ratio resulted in an increase in the ethanol-to-acetic acid ratio, which decreased both acetic acid purity and acetic acid extraction yield.

  4. Determination of organophosphorus pesticides by dispersive liquid-liquid micro extraction coupled with gas chromatography-electron capture detection

    International Nuclear Information System (INIS)

    Mohd Marsin Sanagi; Siti Umairah Mokhtar; Mazidatul Akmam Miskam; Wan Aini Wan Ibrahim

    2011-01-01

    A simple, rapid and sensitive method termed as dispersive liquid-liquid micro extraction (DLLME) combined with gas chromatography-electron capture detector (GC-ECD) was developed for the determination of selected organophosphorus pesticides (OPPs) namely chloropyrifos, dimethoate and diazinon in water sample. In this method, a mixture of carbon disulfide, CS 2 (extraction solvent) and methanol (disperser solvent) was rapidly injected using syringe into the 5.00 mL water sample to form a cloudy solution where the OPPs were extracted into the fine droplets of extraction solvent. Upon centrifugation for 3 min at 3500 rpm, the fine droplets were sedimented at the bottom of the centrifuge tube. Sedimented phase (1 μL) was injected into the GC-ECD for separation and determination of OPPs. Important extraction parameters, such as type of disperser solvent, volume of extraction solvent and volume of disperser solvent were investigated. The optimized conditions for DLLME of the selected OPPs were methanol as disperser solvent, 30 μL of extraction solvent (CS 2 ) and 1.0 mL of disperser solvent (methanol). Under the optimum extraction conditions, the method showed good linearity in the range of 0.1 to 1.0 μg/ mL with correlation coefficient (r 2 ), in the range of 0.9976 to 0.9994 and low limits of detection (LOD) between 0.047 and 0.201 μg/ mL. The proposed method provided acceptable recoveries (72.67- 144 %) with good RSDs ranging from 2.74 % to 7.48 %. This method was successfully applied to the determination of OPPs in water samples obtained from a golf course and chloropyrifos and diazinon were detected at concentration 0.18 μg/ mL and 0.07 μg/ mL, respectively. (author)

  5. Magnetomotive room temperature dicationic ionic liquid: a new concept toward centrifuge-less dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Beiraghi, Asadollah; Shokri, Masood; Seidi, Shahram; Godajdar, Bijan Mombani

    2015-01-09

    A new centrifuge-less dispersive liquid-liquid microextraction technique based on application of magnetomotive room temperature dicationic ionic liquid followed by electrothermal atomic absorption spectrometry (ETAAS) was developed for preconcentration and determination of trace amount of gold and silver in water and ore samples, for the first time. Magnetic ionic liquids not only have the excellent properties of ionic liquids but also exhibit strong response to an external magnetic field. These properties provide more advantages and potential application prospects for magnetic ionic liquids than conventional ones in the fields of extraction processes. In this work, thio-Michler's ketone (TMK) was used as chelating agent to form Ag/Au-TMK complexes. Several important factors affecting extraction efficiency including extraction time, rate of vortex agitator, pH of sample solution, concentration of the chelating agent, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) were 3.2 and 7.3ngL(-1) with the preconcentration factors of 245 and 240 for Au and Ag, respectively. The precision values (RSD%, n=7) were 5.3% and 5.8% at the concentration level of 0.05μgL(-1) for Au and Ag, respectively. The relative recoveries for the spiked samples were in the acceptable range of 96-104.5%. The results demonstrated that except Hg(2+), no remarkable interferences are created by other various ions in the determination of Au and Ag, so that the tolerance limits (WIon/WAu or Ag) of major cations and anions were in the range of 250-1000. The validated method was successfully applied for the analysis of Au and Ag in some water and ore samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Selective extraction of emerging contaminants from water samples by dispersive liquid-liquid microextraction using functionalized ionic liquids.

    Science.gov (United States)

    Yao, Cong; Li, Tianhao; Twu, Pamela; Pitner, William R; Anderson, Jared L

    2011-03-25

    Functionalized ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion were used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the extraction of 14 emerging contaminants from water samples. The extraction efficiencies and selectivities were compared to those of an in situ IL DLLME method which uses an in situ metathesis reaction to exchange 1-butyl-3-methylimidazolium chloride (BMIM-Cl) to 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMIM-NTf(2)). Compounds containing tertiary amine functionality were extracted with high selectivity and sensitivity by the 1-(6-amino-hexyl)-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (HNH(2)MPL-FAP) IL compared to other FAP-based ILs and the BMIM-NTf(2) IL. On the other hand, polar or acidic compounds without amine groups exhibited higher enrichment factors using the BMIM-NTf(2) IL. The detection limits for the studied analytes varied from 0.1 to 55.1 μg/L using the traditional IL DLLME method with the HNH(2)MPL-FAP IL as extraction solvent, and from 0.1 to 55.8 μg/L using in situ IL DLLME method with BMIM-Cl+LiNTf(2) as extraction solvent. A 93-fold decrease in the detection limit of caffeine was observed when using the HNH(2)MPL-FAP IL compared to that obtained using in situ IL DLLME method. Real water samples including tap water and creek water were analyzed with both IL DLLME methods and yielded recoveries ranging from 91% to 110%. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Non-porous membrane-assisted liquid-liquid extraction of UV filter compounds from water samples.

    Science.gov (United States)

    Rodil, Rosario; Schrader, Steffi; Moeder, Monika

    2009-06-12

    A method for the determination of nine UV filter compounds [benzophenone-3 (BP-3), isoamyl methoxycinnamate, 4-methylbenzylidene camphor, octocrylene (OC), butyl methoxydibenzoylmethane, ethylhexyl dimethyl p-aminobenzoate (OD-PABA), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate and homosalate] in water samples was developed and evaluated. The procedure includes non-porous membrane-assisted liquid-liquid extraction (MALLE) and LC-atmospheric pressure photoionization (APPI)-MS/MS. Membrane bags made of different polymeric materials were examined to enable a fast and simple extraction of the target analytes. Among the polymeric materials tested, low- and high-density polyethylene membranes proved to be well suited to adsorb the analytes from water samples. Finally, 2 cm length tailor-made membrane bags were prepared from low-density polyethylene in order to accommodate 100 microL of propanol. The fully optimised protocol provides recoveries from 76% to 101% and limits of detection (LOD) between 0.4 ng L(-1) (OD-PABA) and 16 ng L(-1) (EHMC). The interday repeatability of the whole protocol was below 18%. The effective separation of matrix molecules was proved by only marginal matrix influence during the APPI-MS analysis since no ion suppression effects were observed. During the extraction step, the influence of the matrix was only significant when non-treated wastewater was analysed. The analysis of lake water indicated the presence of seven UV filter compounds included in this study at concentrations between 40 ng L(-1) (BP-3) and 4381 ng L(-1) (OC). In non-treated wastewater several UV filters were also detected at concentration levels as high as 5322 ng L(-1) (OC).

  8. Extractive liquid-liquid spectrophotometric procedure for the determination of thiocyanate ions employing the ion pair reagent amiloride monohydrochloride

    International Nuclear Information System (INIS)

    Bashammakh, A.S.; Bahaffi, S.O.; Al-Sibaai, A.A.; Al-Wael, H.O.; El-Shahawi, M.S.

    2007-01-01

    An accurate, inexpensive and less laborious liquid-liquid extractive spectrophotometric procedure for the determination of thiocyanate ions in aqueous media has been developed. The method has been based upon the formation of a yellow colored complex ion associate of the ion-pairing reagent 1-(3, 5-diamino-6-chloropyrazinecarboxyl) guanidine hydrochloride monohydrate, namely amiloride hydrochloride, DPG + .Cl - and the thiocyanate ions in aqueous media containing HNO 3 (0.5 mol L -1 ) and subsequent extraction with 4-methyl-2-pentanone. The absorption electronic spectrum of the ion associate showed one well-defined peak at λ max 366 nm. The stoichiometric mole ratio of DPG + .Cl - to the thiocyanate ions is 1:1.The effective molar absorptivity (ε) of the ion associate at λ max 366 nm is 1.1 ± 0.1 x 10 4 L mol -1 cm -1 . The extraction constants (K d , K ex , and β) enabled a simple and convenient use of the developed binary ion associate for the extractive spectrophotometric determination of traces of thiocyanate ions in the aqueous media. Beer's law and Ringbom's plots are obeyed in the concentration range 0.05-10 and 0.1-7 μg mL -1 of the thiocyanate ions, respectively with a relative standard deviation of ±2.3%. The calculated lower limits of detection (LOD) and quantitation (LOQ) of the developed procedure for the thiocyanate ions were found equal to 0.02 and 0.066 μg mL -1 , respectively. The developed method has been applied for the determination of trace amounts of thicyanate ions in tap-, waste- and natural water samples and compared successfully with the reported methods at the 95% confidence level. The proposed method was also applied successfully for the determination of thiocyanate ions in saliva samples

  9. Highly pressurized partially miscible liquid-liquid flow in a micro-T-junction. I. Experimental observations

    Science.gov (United States)

    Qin, Ning; Wen, John Z.; Ren, Carolyn L.

    2017-04-01

    This is the first part of a two-part study on a partially miscible liquid-liquid flow (liquid carbon dioxide and deionized water) which is highly pressurized and confined in a microfluidic T-junction. Our main focuses are to understand the flow regimes as a result of varying flow conditions and investigate the characteristics of drop flow distinct from coflow, with a capillary number, C ac , that is calculated based on the continuous liquid, ranging from 10-3 to 10-2 (10-4 for coflow). Here in part I, we present our experimental observation of drop formation cycle by tracking drop length, spacing, frequency, and after-generation speed using high-speed video and image analysis. The drop flow is chronologically composed of a stagnating and filling stage, an elongating and squeezing stage, and a truncating stage. The common "necking" time during the elongating and squeezing stage (with C ac˜10-3 ) for the truncation of the dispersed liquid stream is extended, and the truncation point is subsequently shifted downstream from the T-junction corner. This temporal postponement effect modifies the scaling function reported in the literature for droplet formation with two immiscible fluids. Our experimental measurements also demonstrate the drop speed immediately following their generations can be approximated by the mean velocity from averaging the total flow rate over the channel cross section. Further justifications of the quantitative analysis by considering the mass transfer at the interface of the two partially miscible fluids are provided in part II.

  10. Liquid-liquid extraction of uranium from nitric acid solution using di-n-butylsulfoxide in petroleum ether as extractant

    Energy Technology Data Exchange (ETDEWEB)

    Khan, M.H.; Shahida, S. [Dept. of Chemistry, Univ. of Azad Jammu and Kashmir, Muzaffarabad (Pakistan); Ali, A. [Nuclear Chemistry Div., Pakistan Inst. of Nuclear Science and Technology, Nilore, Islamabad (Pakistan)

    2008-07-01

    A simple, efficient and economical liquid-liquid extraction method has been developed for quantitative extraction of uranium from 2 M HNO{sub 3} using di-n-butyl sulfoxide in petroleum ether. The dependence of the partition reaction of U(VI) on the concentration of HNO{sub 3}, extractant and temperature was studied. The reaction was found to be inversely dependent upon the temperature and the values for related thermodynamics functions ({delta}H, {delta}S, {delta}G) for extraction equilibrium were determined to be -33.6 kJ/mol, -1.29 kJ/mol/degree and -0.11 kJ/mol/degree, respectively. The effect of Al(NO{sub 3}){sub 3} as salting-out agent and diverse ions on the extraction was examined. The salting-out agent slightly enhanced the extraction. All cations studied have showed negligible effect on the extraction, whereas phosphate and fluoride interfered seriously. Among others, oxalate, citrate and sulphide ions affect the extraction to a lesser extent. Uranium was successfully extracted from a synthetic mixture of Ti{sup +4}, Zr{sup +4}, Hf{sup +4} and Th{sup +4} using EDTA as masking agent. Among strippants, deionized water was found most suitable, and the recovery of uranium was noted to be {>=} 96%. The stoichiometric composition of the extracted species was found to be UO{sub 2}(NO{sub 3}){sub 2} . 2DBSO. The extraction mechanism is discussed on the basis of the results obtained. The extractant has high loading as well as recycling capacity without any degradation. The method was also applied to the Standard Reference Material (NBL-49) and the measured value was found to be in agreement with the reported value within {+-}2% deviation. (orig.)

  11. In-vial liquid-liquid microextraction-capillary electrophoresis method for the determination of phenolic acids in vegetable oils.

    Science.gov (United States)

    Abu Bakar, Nur Bahiyah; Makahleh, Ahmad; Saad, Bahruddin

    2012-09-12

    An in-vial liquid-liquid microextraction method was developed for the selective extraction of the phenolic acids (caffeic, gallic, cinnamic, ferulic, chlorogenic, syringic, vanillic, benzoic, p-hydroxybenzoic, 2,4-dihydroxybenzoic, o-coumaric, m-coumaric and p-coumaric) in vegetable oil samples. The optimised extraction conditions for 20 g sample were: volume of diluent (n-hexane), 2 mL; extractant, methanol: 5 mM sodium hydroxide (60:40; v/v); volume of extractant, 300 μL (twice); vortex, 1 min; centrifugation, 5 min. Recoveries for the studied phenolic acids were 80.1-119.5%. The simultaneous determination of the phenolic acid extracts was investigated by capillary electrophoresis (CE). Separations were carried out on a bare fused-silica capillary (50 μm i.d.× 40 cm length) involving 25 mM sodium tetraborate (pH 9.15) and 5% methanol as CE background electrolyte in the normal polarity mode, voltage of 30 kV, temperature of 25°C, injection time of 4s (50 mbar) and electropherograms were recorded at 200 nm. The phenolic acids were successfully separated in less than 10 min. The validated in-vial LLME-CE method was applied to the determination of phenolic acids in vegetable oil samples (extra virgin olive oil, virgin olive oil, pure olive oil, walnut oil and grapeseed oil). The developed method shows significant advantages over the current methods as lengthy evaporation step is not required. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Determination of statin drugs in hospital effluent with dispersive liquid-liquid microextraction and quantification by liquid chromatography.

    Science.gov (United States)

    Martins, Ayrton F; Frank, Carla da S; Altissimo, Joseline; de Oliveira, Júlia A; da Silva, Daiane S; Reichert, Jaqueline F; Souza, Darliana M

    2017-08-24

    Statins are classified as being amongst the most prescribed agents for treating hypercholesterolaemia and preventing vascular diseases. In this study, a rapid and effective liquid chromatography method, assisted by diode array detection, was designed and validated for the simultaneous quantification of atorvastatin (ATO) and simvastatin (SIM) in hospital effluent samples. The solid phase extraction (SPE) of the analytes was optimized regarding sorbent material and pH, and the dispersive liquid-liquid microextraction (DLLME), in terms of pH, ionic strength, type and volume of extractor/dispersor solvents. The performance of both extraction procedures was evaluated in terms of linearity, quantification limits, accuracy (recovery %), precision and matrix effects for each analyte. The methods proved to be linear in the concentration range considered; the quantification limits were 0.45 µg L -1 for ATO and 0.75 µg L -1 for SIM; the matrix effect was almost absent in both methods and the average recoveries remained between 81.5-90.0%; and the RSD values were <20%. The validated methods were applied to the quantification of the statins in real samples of hospital effluent; the concentrations ranged from 18.8 µg L -1 to 35.3 µg L -1 for ATO, and from 30.3 µg L -1 to 38.5 µg L -1 for SIM. Since the calculated risk quotient was ≤192, the occurrence of ATO and SIM in hospital effluent poses a potential serious risk to human health and the aquatic ecosystem.

  13. Separation of americium by liquid-liquid extraction using diglycol-amides water-soluble complexing agents

    Energy Technology Data Exchange (ETDEWEB)

    Chapron, S.; Marie, C.; Pacary, V.; Duchesne, M.T.; Miguirditchian, M. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Processses Departement, 30207 Bagnols-sur-Ceze (France); Arrachart, G.; Pellet-Rostaing, S. [Institut de Chimie Separative de Marcoule, LTSM, Bat 426, F-30207 Bagnols-sur- Ceze (France)

    2016-07-01

    Recycling americium (Am) alone from spent nuclear fuels is an important option studied for the future nuclear cycle (Generation IV systems) since Am belongs to the main contributors of the long-term radiotoxicity and heat power of final waste. Since 2008, a liquid-liquid extraction process called EXAm has been developed by the CEA to allow the recovery of Am alone from a PUREX raffinate (a dissolution solution already cleared from U, Np and Pu). A mixture of DMDOHEMA (N,N'-dimethyl-N,N'-dioctyl-2-(2-(hexyloxy)ethyl)-malonamide) and HDEHP (di-2-ethylhexylphosphoric acid) in TPH is used as the solvent and the Am/Cm selectivity is improved using TEDGA (N,N,N',N'-tetraethyl-diglycolamide) as a selective complexing agent to maintain Cm and heavier lanthanides in the acidic aqueous phase (5 M HNO{sub 3}). Americium is then stripped selectively from light lanthanides at low acidity (pH=3) with a poly-aminocarboxylic acid. The feasibility of sole Am recovery was already demonstrated during hot tests in ATALANTE facility and the EXAm process was adapted to a concentrated raffinate to optimize the process compactness. The speciation of TEDGA complexes formed in the aqueous phase with Am, Cm and lanthanides was studied to better understand and model the behavior of TEDGA in the process. Some Ln-TEDGA species are extracted into the organic phase and this specific chemistry might play a role in the Am/Cm selectivity improvement. Hence the hydrophilicity-lipophilicity balance of the complexing agent is an important parameter. In this comprehensive study, new analogues of TEDGA were synthesized and tested in the EXAm process conditions to understand the relationship between their structure and selectivity. New derivatives of TEDGA with different N-alkyl chain lengths and ramifications were synthesized. The impact of lipophilicity on ligand partitioning and Am/Cm selectivity was investigated. (authors)

  14. Identification of fermentation inhibitors in wood hydrolyzates and removal of inhibitors by ion exchange and liquid-liquid extraction

    Science.gov (United States)

    Luo, Caidian

    1998-12-01

    Common methods employed in the ethanol production from biomass consist of chemical or enzymatic degradation of biomass into sugars and then fermentation of sugars into ethanol or other chemicals. However, some degradation products severely inhibit the fermentation processes and substantially reduce the efficiency of ethanol production. How to remove inhibitors from the reaction product mixture and increase the production efficiency are critical in the commercialization of any processes of energy from biomass. The present study has investigated anion exchange and liquid-liquid extraction as potential methods for inhibitor removal. An analytical method has been developed to identify the fermentation inhibitors in a hydrolyzate. The majority of inhibitors present in hybrid poplar hydrolyzate have positively been identified. Ion exchange with weak basic Dowex-MWA-1 resin has been proved to be an effective mean to remove fermentation inhibitors from hybrid poplar hydrolyzate and significantly increase the fermentation productivity. Extraction with n-butanol might be a preferred way to remove inhibitors from wood hydrolyzates and improve the fermentability of sugars in the hydrolyzates. n-Butanol also removes some glucose, mannose and xylose from the hydrolyzate. Inhibitor identification reveals that lignin and sugar degradation compounds including both aromatic and aliphatic aldehydes and carboxylic acids formed in hydrolysis, plus fatty acids and other components from wood extractives are major fermentation inhibitors in Sacchromyces cerevisiae fermentation. There are 35 components identified as fermentation inhibitors. Among them, 4-hydroxy benzoic acid, 3,4-dihydroxy benzoic acid, syringic acid, syringaldehyde, and ferulic acid are among the most abundant aromatic inhibitors in hybrid poplar hydrolyzate. The conversion of aldehyde groups into carboxylic acid groups in the nitric acid catalyzed hydrolysis reduces the toxicity of the hydrolyzate. A wide spectrum of

  15. A new chiral residue analysis method for triazole fungicides in water using dispersive liquid-liquid microextraction (DLLME).

    Science.gov (United States)

    Luo, Mai; Liu, Donghui; Zhou, Zhiqiang; Wang, Peng

    2013-09-01

    A rapid, simple, reliable, and environment-friendly method for the residue analysis of the enantiomers of four chiral fungicides including hexaconazole, triadimefon, tebuconazole, and penconazole in water samples was developed by dispersive liquid-liquid microextraction (DLLME) pretreatment followed by chiral high-performance liquid chromatography (HPLC)-DAD detection. The enantiomers were separated on a Chiralpak IC column by HPLC applying n-hexane or petroleum ether as mobile phase and ethanol or isopropanol as modifier. The influences of mobile phase composition and temperature on the resolution were investigated and most of the enantiomers could be completely separated in 20 min under optimized conditions. The thermodynamic parameters indicated that the separation was enthalpy-driven. The elution orders were detected by both circular dichroism detector (CD) and optical rotatory dispersion detector (ORD). Parameters affecting the DLLME performance for pretreatment of the chiral fungicides residue in water samples, such as the extraction and dispersive solvents and their volume, were studied and optimized. Under the optimum microextraction condition the enrichment factors were over 121 and the linearities were 30-1500 µg L(-1) with the correlation coefficients (R(2)) over 0.9988 and the recoveries were between 88.7% and 103.7% at the spiking levels of 0.5, 0.25, and 0.05 mg L(-1) (for each enantiomer) with relative standard deviations varying from 1.38% to 6.70% (n = 6) The limits of detection (LODs) ranged from 8.5 to 29.0 µg L(-1) (S/N = 3). © 2013 Wiley Periodicals, Inc.

  16. Rapid determination of 226Ra in drinking water samples using dispersive liquid-liquid microextraction coupled with liquid scintillation counting

    International Nuclear Information System (INIS)

    Sadi, B.K.; Chunsheng Li; Kramer, G.H.; Johnson, C.L.; Queenie Ko; Lai, E.P.C.

    2011-01-01

    A new radioanalytical method was developed for rapid determination of 226 Ra in drinking water samples. The method is based on extraction and preconcentration of 226 Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by radiometric measurement using liquid scintillation counting. In DLLME for 226 Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion, 226 Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing 226 Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency of 226 Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands for 226 Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions, the accuracy (expressed as relative bias, B r ) and method repeatability (expressed as relative precision, S B ) were determined by spiking 226 Ra at the maximum acceptable concentration level (0.5 Bq L -1 ) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than -5% (B r ) and less than 6% (S B ), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround time for determination of 226 Ra was 33 mBq L -1 and less than 3 h, respectively. The DLLME technique is selective for extraction of 226 Ra from its decay progenies. (author)

  17. Determination of benzimidazoles in meat samples by capillary zone electrophoresis tandem mass spectrometry following dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Tejada-Casado, Carmen; Moreno-González, David; Lara, Francisco J; García-Campaña, Ana M; Del Olmo-Iruela, Monsalud

    2017-03-24

    A novel method based on capillary zone electrophoresis-tandem mass spectrometry has been proposed and validated for the identification and simultaneous quantification of twelve benzimidazoles in meat samples. Electrophoretic separation was carried out using 500mM formic acid (pH 2.2) as background electrolyte and applying a voltage of 25kV at 25°C. In order to improve the sensitivity, stacking mode injection was applied, using as injection solvent a mixture of 30:70 acetonitrile/water at 50mbar for 75s. Sensitivity enhancement factors from 74 to 317 were obtained under these conditions. Detection using an ion trap as analyzer, operating in multiple reactions monitoring mode was employed. The main MS/MS parameters as well as the composition of the sheath liquid and other electrospray variables were optimized in order to obtain the highest sensitivity and precision in conjunction with an unequivocal identification. The method was applied to poultry and pork muscle samples. The deproteinization of samples and extraction of benzimidazoles was carried out with acetonitrile. MgSO 4 and NaCl were added as salting-out agents. Subsequently, dispersive liquid-liquid microextraction was applied as clean up procedure. The organic layer (acetonitrile, used as dispersant) containing the benzimidazoles was mixed with the extractant (chloroform) and both were injected in water, producing a cloudy solution. Recoveries for fortified samples were higher than 70%, with relative standard deviations lower than 16% were obtained in all cases. The limits of detection were below 3μgkg -1 , demonstrating the applicability of this fast, simple, and environmentally friendly method. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Extension of equilibrium formation criteria to metastable microalloys

    International Nuclear Information System (INIS)

    Kaufmann, E.N.; Vianden, R.; Chelikowsky, J.R.; Phillips, J.C.

    1977-01-01

    Metastable microalloys of 25 metallic elements with beryllium have been prepared by ion implantation. The injected atoms have been found to occupy one of three sites available in the solvent lattice. A modified Laudau-Ginsburg expansion using bulk alloy variables proposed by Miedema is completely successful in predicting the observed metastable-site preferences and indicates a broader applicability of these variables than was heretofore anticipated

  19. High Cycle Fatigue of Metastable Austenitic Stainless Steels

    OpenAIRE

    Fargas Ribas, Gemma; Zapata Dederle, Ana Cristina; Anglada Gomila, Marcos Juan; Mateo García, Antonio Manuel

    2009-01-01

    Metastable austenitic stainless steels are currently used in applications where severe forming operations are required, such as automotive bodies, due to its excellent ductility. They are also gaining interest for its combination of high strength and formability after forming. The biggest disadvantage is the difficulty to predict the mechanical response, which depends heavily on the amount of martensite formed. The martensitic transformation in metastable stainless steels can b...

  20. PVP存在下液液界面生长法制备硒纳米线%Preparation of Selenium Nanowires by Liquid-liquid Interface Growth in the Presence of Polyvinylpyrrolidone

    Institute of Scientific and Technical Information of China (English)

    张胜义; 张娟; 刘明珠; 朱俊杰; 陈洪渊

    2005-01-01

    Nanowires of trigonal selenium were synthesized in large-scale by two step processes: reaction in homogeneous solution and growth at liquid-liquid interface. Polyvinylpyrrolidone was used as a soft template in the synthesis.

  1. Metastable enhancement of C+ and O+ capture reactions

    International Nuclear Information System (INIS)

    Thomas, E.W.

    1992-01-01

    The project is devoted to the study of charge transfer neutralization of Carbon and oxygen ions in H and H 2 gases at energies from 10 to 500 eV. A major motivation was to provide cross section data to support analysis of edge plasmas in Tokamak Fusion devices. The first objective was to measure cross sections for metastable excited singly charged ions separately from the cross sections for ground state ions. Previously published values are confusing because the beams used included unknown fractions of metastables and these metastables have cross sections greatly different from the ground states. The program was fully accomplished, metastable cross sections were found to be over an order of magnitude greater than ones for the ground state and existing discrepancies in the literature were resolved. Considerable effort was devoted to the design and operation of ion source configurations were the metastable content of the ion beam was known. Subsequently study progressed to the neutralization of multiply charged C and 0 ions in the same targets. First there has been a need to develop ion sources which can produce useful beams of multiply charged species. This has now been accomplished. The intent is to use these sources for the measurement of cross sections with again an attempt to differentiate between the behavior of ground and metastably excited species

  2. On the long wavelength thermodynamic limit of a neutron diffraction experiment in the vicinity of a liquid-liquid critical point. Application to the concentration fluctuations in the Li-ND3 system

    International Nuclear Information System (INIS)

    Chieux, P.; Damay, P.

    1978-01-01

    A quantitative comparison is made between the thermodynamics as obtained from the long wavelength limit of a small angle neutron scattering experiment in the vicinity of a liquid-liquid critical point for the Li-ND 3 system and the data obtained from vapour pressure measurements. The agreement is fair. It is shown how the comparison always implies an underlying model of the interacting species leading to the liquid-liquid phase separation. (Auth.)

  3. Chemi-ionization in the metastable neon--metastable argon system

    International Nuclear Information System (INIS)

    Neynaber, R.N.; Tang, S.Y.

    1980-01-01

    Studies were made by a merging-beams technique of the associative ionization (AI) reaction (1) Ne/sup asterisk/+Ar/sup asterisk/→NeAr + +e and the Penning ionization (PI) reactions (2) Ne/sup asterisk/+Ar/sup asterisk/→Ne+Ar + +e and (3) Ne/sup asterisk/+Ar/sup asterisk/→Ne + +Ar+e. The relative kinetic energy of the reactants was varied from 0.01 to 10 eV. The Ne/sup asterisk/ and Ar/sup asterisk/ each represents a composite of the metastable 0 P/sub 2,0/ states. There is a complication in the present investigation which arises because AI and PI occur in collisions of Ne/sup asterisk/ with ground-state Ar. Since the reactant beams consist of metastable as well as ground-state species, the measurements are composites of chemi-ionization in both the Ne/sup asterisk/--Ar/sup asterisk/ and Ne/sup asterisk/--Ar systems. Information on AI and PI for the Ne/sup asterisk/--Ar/sup asterisk/ system is obtained by subtracting from these composite measurements known contributions of the Ne/sup asterisk/--Ar system. From such information it appears that the molecular states of the reactants are different for reactions (2) and

  4. Extended Neural Metastability in an Embodied Model of Sensorimotor Coupling

    Directory of Open Access Journals (Sweden)

    Miguel Aguilera

    2016-09-01

    Full Text Available The hypothesis that brain organization is based on mechanisms of metastable synchronization in neural assemblies has been popularized during the last decades of neuroscientific research. Nevertheless, the role of body and environment for understanding the functioning of metastable assemblies is frequently dismissed. The main goal of this paper is to investigate the contribution of sensorimotor coupling to neural and behavioural metastability using a minimal computational model of plastic neural ensembles embedded in a robotic agent in a behavioural preference task. Our hypothesis is that, under some conditions, the metastability of the system is not restricted to the brain but extends to the system composed by the interaction of brain, body and environment. We test this idea, comparing an agent in continuous interaction with its environment in a task demanding behavioural flexibility with an equivalent model from the point of view of 'internalist neuroscience'. A statistical characterization of our model and tools from information theory allows us to show how (1 the bidirectional coupling between agent and environment brings the system closer to a regime of criticality and triggers the emergence of additional metastable states which are not found in the brain in isolation but extended to the whole system of sensorimotor interaction, (2 the synaptic plasticity of the agent is fundamental to sustain open structures in the neural controller of the agent flexibly engaging and disengaging different behavioural patterns that sustain sensorimotor metastable states, and (3 these extended metastable states emerge when the agent generates an asymmetrical circular loop of causal interaction with its environment, in which the agent responds to variability of the environment at fast timescales while acting over the environment at slow timescales, suggesting the constitution of the agent as an autonomous entity actively modulating its sensorimotor coupling

  5. Extended Neural Metastability in an Embodied Model of Sensorimotor Coupling.

    Science.gov (United States)

    Aguilera, Miguel; Bedia, Manuel G; Barandiaran, Xabier E

    2016-01-01

    The hypothesis that brain organization is based on mechanisms of metastable synchronization in neural assemblies has been popularized during the last decades of neuroscientific research. Nevertheless, the role of body and environment for understanding the functioning of metastable assemblies is frequently dismissed. The main goal of this paper is to investigate the contribution of sensorimotor coupling to neural and behavioral metastability using a minimal computational model of plastic neural ensembles embedded in a robotic agent in a behavioral preference task. Our hypothesis is that, under some conditions, the metastability of the system is not restricted to the brain but extends to the system composed by the interaction of brain, body and environment. We test this idea, comparing an agent in continuous interaction with its environment in a task demanding behavioral flexibility with an equivalent model from the point of view of "internalist neuroscience." A statistical characterization of our model and tools from information theory allow us to show how (1) the bidirectional coupling between agent and environment brings the system closer to a regime of criticality and triggers the emergence of additional metastable states which are not found in the brain in isolation but extended to the whole system of sensorimotor interaction, (2) the synaptic plasticity of the agent is fundamental to sustain open structures in the neural controller of the agent flexibly engaging and disengaging different behavioral patterns that sustain sensorimotor metastable states, and (3) these extended metastable states emerge when the agent generates an asymmetrical circular loop of causal interaction with its environment, in which the agent responds to variability of the environment at fast timescales while acting over the environment at slow timescales, suggesting the constitution of the agent as an autonomous entity actively modulating its sensorimotor coupling with the world. We

  6. An unusual coexistence of Addison's disease and ...

    African Journals Online (AJOL)

    2013-07-17

    Jul 17, 2013 ... Case Study: An unusual coexistence of Addison's disease and phaeochromocytoma. 164 ... strongly positive. ... Department of Endocrinology and Metabolism, Ondokuz Mayis University Medical School, Samsun, Turkey.

  7. Phase Coexistence in Insect Swarms

    Science.gov (United States)

    Sinhuber, Michael; Ouellette, Nicholas T.

    2017-10-01

    Animal aggregations are visually striking, and as such are popular examples of collective behavior in the natural world. Quantitatively demonstrating the collective nature of such groups, however, remains surprisingly difficult. Inspired by thermodynamics, we applied topological data analysis to laboratory insect swarms and found evidence for emergent, material-like states. We show that the swarms consist of a core "condensed" phase surrounded by a dilute "vapor" phase. These two phases coexist in equilibrium, and maintain their distinct macroscopic properties even though individual insects pass freely between them. We further define a pressure and chemical potential to describe these phases, extending theories of active matter to aggregations of macroscopic animals and laying the groundwork for a thermodynamic description of collective animal groups.

  8. A few proofs for nonexistence of the metastable states

    International Nuclear Information System (INIS)

    Blazjevski, Atanas

    2007-01-01

    This paper is the bigger part of one until now unpublished author's work, whose title is 'A few proofs for nonexistence of the metastable states'. Because of a big volume of the work, the problems of supersaturated (metastable) steam which appears at the following of slightly, superheated, saturated or wet steam in the convergent and Laval nozzles will be discussed in the main. This steam is mentioned in the literature as one between of the strongest proofs for existence of metastable states in the substances. In this work the steam is not one -phase gaseous metastable steam, as it was thought until now, but yat it is nonequilibrium wet steam in which during the expanding process in the nozzles extreme small particles condensate, consisted of two, three or only few agglomerated molecules are formed which stay in heat, mechanical and internal nonequilibrium with the rest of the expanding gaseous phase of the steam. It means, that this steam, which is called a supersaturated or metastable steam, in fact does not exist in reality because it is nothing else but only nonequilibrium wet steam consisted of tho phases: the expanding gaseous phase of the steam in the nozzle and the mentioned small and nonequilibrium particles condensate which are formed there...

  9. A metastable liquid melted from a crystalline solid under decompression

    Science.gov (United States)

    Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

    2017-01-01

    A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid-solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure-temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.

  10. Deterpenation of eucalyptus essential oil by liquid + liquid extraction: Phase equilibrium and physical properties for model systems at T = 298.2 K

    International Nuclear Information System (INIS)

    Gonçalves, Daniel; Koshima, Cristina Chiyoda; Nakamoto, Karina Thiemi; Umeda, Thayla Karla; Aracava, Keila Kazue; Gonçalves, Cintia Bernardo; Rodrigues, Christianne Elisabete da Costa

    2014-01-01

    Highlights: • Fractionation of essential oil compounds. • Liquid + liquid equilibria of limonene, citronellal, ethanol and water were studied. • Distribution coefficients of limonene and citronellal were evaluated. • Densities and viscosities of the phases were experimentally determined. • Solvent selectivities and physical properties were dependent on citronellal and water mass fractions. -- Abstract: As the principal source in Brazil of eucalyptus essential oil extracts, Eucalyptus citriodora contains citronellal, an oxygenated compound responsible for the flavour characteristics. Deterpenation processes, consisting of the removal of terpenic hydrocarbons with the subsequent concentration of the oxygenated compounds, can be used to improve the aromatic characteristics of this essential oil. The purpose of this work was to perform a study of the technical feasibility of using a liquid + liquid extraction process to deterpenate eucalyptus essential oil. Model systems with various mixtures of limonene and citronellal (representing eucalyptus essential oil) as well as solvent (ethanol with various water mass fractions) were used to obtain liquid + liquid equilibrium data. The raffinate and extract phases were also analyzed to characterize the physical properties (density and viscosity). The equilibrium data were used to adjust the NRTL and UNIQUAC parameters. Two empirical models, the simple mixing rule and the Grunberg–Nissan model, were evaluated for use in the descriptions of the densities and viscosities, respectively, of the samples. Increasing the water content in the solvent resulted in decreases in the limonene and citronellal distribution coefficients, with consequential increases in the solvent selectivity values. Increasing values of the densities and viscosities, especially for the solvent-rich phases, were associated with systems using high amounts of hydrated ethanolic solvents

  11. Complex Formation in a Liquid-Liquid Extraction System Containing Cobalt(II), 4-(2-Pyridylazo)resorcinol, and Nitron

    OpenAIRE

    Racheva, Petya Vassileva; Gavazov, Kiril Blazhev; Lekova, Vanya Dimitrova; Dimitrov, Atanas Nikolov

    2013-01-01

    Complex formation and liquid-liquid extraction were studied in a system containing cobalt(II), 4-(2-pyridylazo)resorcinol (PAR), 1,4-diphenyl-3-(phenylamino)-1H-1,2,4-triazole (Nitron, Nt), water, and chloroform. The effect of some experimental parameters (pH, shaking time, concentration of PAR, and concentration of Nt) was systematically investigated, and the optimum conditions for cobalt extraction as an ion-association complex, (NtH+)[Co3+(PAR)2], were found. The following key equilibrium ...

  12. Niobium, tantalum and titanium extraction from natural and technogenic raw materials of the Kola Peninsula by liquid-liquid extraction methods

    International Nuclear Information System (INIS)

    Kassikova, N.I.; Kassikov, A.G.; Balabanov, Yu.I.; Petrov, V.B.; Kalinnikov, V.T.

    2003-01-01

    Such rare metals as niobium and tantalum are important strategic materials underlying many of the modern advanced technologies. Since the extraction and processing of rare metal concentrates from own deposits has diminished abruptly in recent years, it is essential to look into the possibility of extracting these elements from various production wastes. This work discusses liquid-liquid extraction and purification of niobium, tantalum and titanium from process solutions of loparite, perovskite and sphene concentrate decomposition with sulphuric and hydrochloric acids; niobium from lithium niobate production wastes decomposed by hydrochloric acid; and tantalum from tantalum capacitor and heat-resistant alloy wastes. (Original)

  13. (Liquid + liquid) equilibrium of {l_brace}water + phenol + (1-butanol, or 2-butanol, or tert-butanol){r_brace} systems

    Energy Technology Data Exchange (ETDEWEB)

    Hadlich de Oliveira, Leonardo [School of Chemical Engineering, State University of Campinas, UNICAMP, P.O. Box 6066, 13083-970 Campinas-SP (Brazil); Aznar, Martin, E-mail: maznar@feq.unicamp.b [School of Chemical Engineering, State University of Campinas, UNICAMP, P.O. Box 6066, 13083-970 Campinas-SP (Brazil)

    2010-11-15

    (Liquid + liquid) equilibrium (LLE) and binodal curve data were determined for the systems (water + phenol + tert-butanol) at T = 298.15 K, (water + phenol + 2-butanol) and (water + phenol + 1-butanol) at T = 298.15 K and T = 313.15 K by the combined techniques of densimetry and refractometry. Type I curve (for tert-butanol) and Type II curves (for 1- and 2-butanol) were found. The data were correlated with the NRTL model and the parameters estimated present root mean square deviations below 2% for the system with tert-butanol and lower than 0.8% for the other systems.

  14. Unique self-assembly behavior of a triblock copolymer and fabrication of catalytically active gold nanoparticle/polymer thin films at the liquid/liquid interface

    International Nuclear Information System (INIS)

    Shang, Ke; Geng, Yuanyuan; Xu, Xingtao; Wang, Changwei; Lee, Yong-Ill; Hao, Jingcheng; Liu, Hong-Guo

    2014-01-01

    Gold nanoparticle-doped poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) thin films were prepared at the planar liquid/liquid interface between the chloroform solution of the polymer and aqueous solution of HAuCl 4 . Transmission electron microscopic (TEM) investigations revealed that foam films composed of microcapsules as well as one-dimensional belts were formed, and numerous Au nanoparticles were incorporated in the walls of the microcapsules and the nanobelts. The walls and the belts have layered structure. The formation mechanism of the foams and the belts was attributed to adsorption of the polymer molecules, combination of the polymer molecules with AuCl 4 − ions, microphase separation and self-assembly of the composite molecules at the interface. This microstructure is different apparently from those formed in solutions, in casting or spin-coating thin films and at the air/water interface of this triblock copolymer, reflecting unique self-assembly behavior at the liquid/liquid interface. This microstructure is also different from those formed by homo-P2VP and P4VP-b-PS-b-P4VP at the liquid/liquid interface, indicating the effects of molecular structures on the self-assembly behaviors of the polymers. After further treatment by UV-light irradiation and KBH 4 aqueous solution, the gold species were reduced completely, as indicated by UV–vis spectra and X-ray photoelectron spectra (XPS). Thermogravimetric analysis indicated that the composite films have high thermal stability, and the content of gold was estimated to be about 9.1%. These composite films exhibited high catalytic activity for the reduction of 4-nitrophenol by KBH 4 in aqueous solutions. - Highlights: • P2VP-b-PS-b-P2VP formed microcapsules and nanobelts at the liquid/liquid interface. • Its self-assembly behavior differs from P4VP-b-PS-b-P4VP at the interface. • This behavior also differs from those in solution, in film and at air/water interface

  15. Liquid-liquid extraction and separation of VIII group elements, especially ruthenium, by synergic combinations or aromatic polyimines and micellar cationic exchangers

    International Nuclear Information System (INIS)

    Vitart, X.

    1991-01-01

    This thesis aims to characterize and to quantify the chemical equilibria involved in d-elements liquid-liquid extraction systems, especially elements belonging to the VIII group (Fe, Ni, Co, Ru, Rh, Pd, Pt). These systems are composed of synergic combination of aromatic polyimines and micellar cationic exchangers. Substitutions are first performed in aqueous acidic media by aromatic polyimines; then extractions are operated using micellic canionic exchangers. Chemical equilibria, selectivity effects, especially those due to ion-pair formations, kinetics, extractant behaviour are analysed and quantified [fr

  16. Unique self-assembly behavior of a triblock copolymer and fabrication of catalytically active gold nanoparticle/polymer thin films at the liquid/liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Ke; Geng, Yuanyuan; Xu, Xingtao [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China); Wang, Changwei [Environmental Monitoring Center of Shandong Province, Jinan 250013 (China); Lee, Yong-Ill [Anastro Laboratory, Department of Chemistry, Changwon National University, Changwon 641-773 (Korea, Republic of); Hao, Jingcheng [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China); Liu, Hong-Guo, E-mail: hgliu@sdu.edu.cn [Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100 (China)

    2014-07-01

    Gold nanoparticle-doped poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) thin films were prepared at the planar liquid/liquid interface between the chloroform solution of the polymer and aqueous solution of HAuCl{sub 4}. Transmission electron microscopic (TEM) investigations revealed that foam films composed of microcapsules as well as one-dimensional belts were formed, and numerous Au nanoparticles were incorporated in the walls of the microcapsules and the nanobelts. The walls and the belts have layered structure. The formation mechanism of the foams and the belts was attributed to adsorption of the polymer molecules, combination of the polymer molecules with AuCl{sub 4}{sup −} ions, microphase separation and self-assembly of the composite molecules at the interface. This microstructure is different apparently from those formed in solutions, in casting or spin-coating thin films and at the air/water interface of this triblock copolymer, reflecting unique self-assembly behavior at the liquid/liquid interface. This microstructure is also different from those formed by homo-P2VP and P4VP-b-PS-b-P4VP at the liquid/liquid interface, indicating the effects of molecular structures on the self-assembly behaviors of the polymers. After further treatment by UV-light irradiation and KBH{sub 4} aqueous solution, the gold species were reduced completely, as indicated by UV–vis spectra and X-ray photoelectron spectra (XPS). Thermogravimetric analysis indicated that the composite films have high thermal stability, and the content of gold was estimated to be about 9.1%. These composite films exhibited high catalytic activity for the reduction of 4-nitrophenol by KBH{sub 4} in aqueous solutions. - Highlights: • P2VP-b-PS-b-P2VP formed microcapsules and nanobelts at the liquid/liquid interface. • Its self-assembly behavior differs from P4VP-b-PS-b-P4VP at the interface. • This behavior also differs from those in solution, in film and

  17. LIQUID-LIQUID EQUILIBRIA OF THE TERNARY SYSTEMS PROPIONIC ACID - WATER - SOLVENT (n-AMYL ALCOHOL AND n-AMYL ACETATE

    Directory of Open Access Journals (Sweden)

    Dilek ÖZMEN

    2005-02-01

    Full Text Available The experimental liquid-liquid equilibrium (LLE data have been obtained at 25 oC for ternary systems propionic acid-water-n-amyl alcohol and propionic acid-water-n-amyl acetate. The reliability of the experimental tie line data are checked using the methods of Othmer-Tobias and Hand. The distribution coefficients and separation factors were obtained from experimental results and are also reported. The predicted tie line data obtained by UNIFAC method are compared with experimental data. It is concluded that n-amyl alcohol and n-amyl acetate are suitable separating agents for dilute aqueous propionic acid solutions.

  18. Injection molded lab-on-a-disc platform for screening of genetically modified E. coli using liquid-liquid extraction and surface enhanced Raman scattering

    DEFF Research Database (Denmark)

    Morelli, Lidia; Serioli, Laura; Centorbi, Francesca Alessandra

    2018-01-01

    We present the development of an automated centrifugal microfluidic platform with integrated sample pre-treatment (filtration and liquid-liquid extraction) and detection (SERS-based sensing). The platform consists of eight calibration and four assay modules, fabricated with polypropylene using...... injection molding and bonded with ultrasonic welding. The platform was used for detection of a secondary bacterial metabolite (p-coumaric acid) from bacterial supernatant. The obtained extraction efficiency was comparable to values obtained in batch experiments and the SERS-based sensing showed a good...

  19. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V [CEA Centre d` Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France); [CEA Centre d` Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d` Exploitation du Retraitement et de Demantelement

    1995-12-20

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

  20. Classification of knotted tori in 2-metastable dimension

    KAUST Repository

    Cencelj, Matija

    2012-11-30

    This paper is devoted to the classical Knotting Problem: for a given manifold N and number m describe the set of isotopy classes of embeddings N → Sm. We study the specific case of knotted tori, that is, the embeddings Sp × Sq → Sm. The classification of knotted tori up to isotopy in the metastable dimension range m > p + 3 2 q + 2, p 6 q, was given by Haefliger, Zeeman and A. Skopenkov. We consider the dimensions below the metastable range and give an explicit criterion for the finiteness of this set of isotopy classes in the 2-metastable dimension: Theorem. Assume that p+ 4 3 q +2 < mp+ 3 2 q +2 and m > 2p+q +2. Then the set of isotopy classes of smooth embeddings Sp × Sq → Sm is infinite if and only if either q + 1 or p + q + 1 is divisible by 4. © 2012 RAS(DoM) and LMS.

  1. Classification of knotted tori in 2-metastable dimension

    KAUST Repository

    Cencelj, Matija; Repovš, Dušan; Skopenkov, Mikhail

    2012-01-01

    This paper is devoted to the classical Knotting Problem: for a given manifold N and number m describe the set of isotopy classes of embeddings N → Sm. We study the specific case of knotted tori, that is, the embeddings Sp × Sq → Sm. The classification of knotted tori up to isotopy in the metastable dimension range m > p + 3 2 q + 2, p 6 q, was given by Haefliger, Zeeman and A. Skopenkov. We consider the dimensions below the metastable range and give an explicit criterion for the finiteness of this set of isotopy classes in the 2-metastable dimension: Theorem. Assume that p+ 4 3 q +2 < mp+ 3 2 q +2 and m > 2p+q +2. Then the set of isotopy classes of smooth embeddings Sp × Sq → Sm is infinite if and only if either q + 1 or p + q + 1 is divisible by 4. © 2012 RAS(DoM) and LMS.

  2. Metastable enhancement of C+ and O+ capture reactions

    International Nuclear Information System (INIS)

    Thomas, E.W.; Moran, T.F.

    1990-09-01

    Single electron capture by 10- to 500-eV singly charged C and O ions traversing targets of H 2 and H was studied with emphasis on comparing cross sections for metastable species with those for the ground state. For an H 2 target cross sections are of the order 10 Angstrom and 20 to 30 times larger than for ground state species. Electron impact ion sources typically produce 5 to 30% of their output in the metastable state. Previous published work has largely ignored (or failed to detect) the presence of metastables and is incorrect by as much as an order of magnitude. Discrepancies between data sets have been resolved, and a reliable data set is provided for energies from 10 to 10 5 eV. Similar experiments for an atomic H target are underway. It is proposed to extend the program to similar studies with multiply charged projectile species

  3. Dynamical SUSY breaking in meta-stable vacua

    International Nuclear Information System (INIS)

    Intriligator, Kenneth; Seiberg, Nathan; Shih, David

    2006-01-01

    Dynamical supersymmetry breaking in a long-lived meta-stable vacuum is a phenomenologically viable possibility. This relatively unexplored avenue leads to many new models of dynamical supersymmetry breaking. Here, we present a surprisingly simple class of models with meta-stable dynamical supersymmetry breaking: N = 1 supersymmetric QCD, with massive flavors. Though these theories are strongly coupled, we definitively demonstrate the existence of meta-stable vacua by using the free-magnetic dual. Model building challenges, such as large flavor symmetries and the absence of an R-symmetry, are easily accommodated in these theories. Their simplicity also suggests that broken supersymmetry is generic in supersymmetric field theory and in the landscape of string vacua

  4. Sequences by Metastable Attractors: Interweaving Dynamical Systems and Experimental Data

    Directory of Open Access Journals (Sweden)

    Axel Hutt

    2017-05-01

    Full Text Available Metastable attractors and heteroclinic orbits are present in the dynamics of various complex systems. Although their occurrence is well-known, their identification and modeling is a challenging task. The present work reviews briefly the literature and proposes a novel combination of their identification in experimental data and their modeling by dynamical systems. This combination applies recurrence structure analysis permitting the derivation of an optimal symbolic representation of metastable states and their dynamical transitions. To derive heteroclinic sequences of metastable attractors in various experimental conditions, the work introduces a Hausdorff clustering algorithm for symbolic dynamics. The application to brain signals (event-related potentials utilizing neural field models illustrates the methodology.

  5. Metastability at the Yield-Stress Transition in Soft Glasses

    Science.gov (United States)

    Lulli, Matteo; Benzi, Roberto; Sbragaglia, Mauro

    2018-04-01

    We study the solid-to-liquid transition in a two-dimensional fully periodic soft-glassy model with an imposed spatially heterogeneous stress. The model we consider consists of droplets of a dispersed phase jammed together in a continuous phase. When the peak value of the stress gets close to the yield stress of the material, we find that the whole system intermittently tunnels to a metastable "fluidized" state, which relaxes back to a metastable "solid" state by means of an elastic-wave dissipation. This macroscopic scenario is studied through the microscopic displacement field of the droplets, whose time statistics displays a remarkable bimodality. Metastability is rooted in the existence, in a given stress range, of two distinct stable rheological branches, as well as long-range correlations (e.g., large dynamic heterogeneity) developed in the system. Finally, we show that a similar behavior holds for a pressure-driven flow, thus suggesting possible experimental tests.

  6. Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity.

    Science.gov (United States)

    Sun, Geng; Sautet, Philippe

    2018-02-28

    Reactivity studies on catalytic transition metal clusters are usually performed on a single global minimum structure. With the example of a Pt 13 cluster under a pressure of hydrogen, we show from first-principle calculations that low energy metastable structures of the cluster can play a major role for catalytic reactivity and that hence consideration of the global minimum structure alone can severely underestimate the activity. The catalyst is fluxional with an ensemble of metastable structures energetically accessible at reaction conditions. A modified genetic algorithm is proposed to comprehensively search for the low energy metastable ensemble (LEME) structures instead of merely the global minimum structure. In order to reduce the computational cost of density functional calculations, a high dimensional neural network potential is employed to accelerate the exploration. The presence and influence of LEME structures during catalysis is discussed by the example of H covered Pt 13 clusters for two reactions of major importance: hydrogen evolution reaction and methane activation. The results demonstrate that although the number of accessible metastable structures is reduced under reaction condition for Pt 13 clusters, these metastable structures can exhibit high activity and dominate the observed activity due to their unique electronic or structural properties. This underlines the necessity of thoroughly exploring the LEME structures in catalysis simulations. The approach enables one to systematically address the impact of isomers in catalysis studies, taking into account the high adsorbate coverage induced by reaction conditions.

  7. Multiple critical points and liquid-liquid equilibria from the van der Waals like equations of state

    International Nuclear Information System (INIS)

    Artemenko, Sergey; Lozovsky, Taras; Mazur, Victor

    2008-01-01

    The principal aim of this work is a comprehensive analysis of the phase diagram of water via the van der Waals like equations of state (EoSs) which are considered as superpositions of repulsive and attractive forces. We test more extensively the modified van der Waals EoS (MVDW) proposed by Skibinski et al (2004 Phys. Rev. E 69 061206) and refine this model by introducing instead of the classical van der Waals repulsive term a very accurate hard sphere EoS over the entire stable and metastable regions (Liu 2006 Preprint cond-mat/0605392). It was detected that the simplest form of MVDW EoS displays a complex phase behavior, including three critical points, and identifies four fluid phases (gas, low density liquid (LDL), high density liquid (HDL), and very high density liquid (VHDL)). Moreover the experimentally observed (Mallamace et al 2007 Proc. Natl Acad. Sci. USA 104 18387) anomalous behavior of the density of water in the deeply supercooled region (a density minimum) is reproduced by the MWDW EoS. An improvement of the repulsive part does not change the topological picture of the phase behavior of water in the wide range of thermodynamic variables. The new parameters set for second and third critical points are recognized by thorough analysis of experimental data for the loci of thermodynamic response function extrema

  8. Energetic Metastable Oxygen and Nitrogen Atoms in the Terrestrial Atmosphere

    Science.gov (United States)

    Kharchenko, Vasili; Dalgarno, A.

    2005-01-01

    This report summarizes our research performed under NASA Grant NAG5-11857. The three-year grant have been supported by the Geospace Sciences SR&T program. We have investigated the energetic metastable oxygen and nitrogen atoms in the terrestrial stratosphere, mesosphere and thermosphere. Hot atoms in the atmosphere are produced by solar radiation, the solar wind and various ionic reactions. Nascent hot atoms arise in ground and excited electronic states, and their translational energies are larger by two - three orders of magnitude than the thermal energies of the ambient gas. The relaxation kinetics of hot atoms determines the rate of atmospheric heating, the intensities of aeronomic reactions, and the rate of atom escape from the planet. Modeling of the non-Maxwellian energy distributions of metastable oxygen and nitrogen atoms have been focused on the determination of their impact on the energetics and chemistry of the terrestrial atmosphere between 25 and 250 km . At this altitudes, we have calculated the energy distribution functions of metastable O and N atoms and computed non-equilibrium rates of important aeronomic reactions, such as destruction of the water molecules by O(1D) atoms and production of highly excited nitric oxide molecules. In the upper atmosphere, the metastable O(lD) and N(2D) play important role in formation of the upward atomic fluxes. We have computed the upward fluxes of the metastable and ground state oxygen atoms in the upper atmosphere above 250 km. The accurate distributions of the metastable atoms have been evaluated for the day and night-time conditions.

  9. Stabilization of metastable tetragonal zirconia nanocrystallites by surface modification

    DEFF Research Database (Denmark)

    Nielsen, Mette Skovgaard; Almdal, Kristoffer; Lelieveld, A. van

    2011-01-01

    Metastable tetragonal zirconia nanocrystallites were studied in humid air and in water at room temperature (RT). A stabilizing effect of different surfactants on the tetragonal phase was observed. Furthermore, the phase stability of silanized metastable tetragonal zirconia nanocrystallites was te...... exposure to humidity. Only silanes and phosphate esters of these were able to stabilize the tetragonal phase in water. Even as small amounts of silanes as 0.25 silane molecule per nm2 are able to stabilize the tetragonal phase in water at RT. Aminopropyl trimethoxy silane and γ...

  10. Metastable states of plasma particles close to a charged surface

    Energy Technology Data Exchange (ETDEWEB)

    Shavlov, A. V., E-mail: shavlov@ikz.ru [The Institute of the Earth Cryosphere, RAS Siberian branch, 625000, P.O. 1230, Tyumen (Russian Federation); Tyumen State Oil and Gas University, 38, Volodarskogo St., 625000, Tyumen (Russian Federation); Dzhumandzhi, V. A. [The Institute of the Earth Cryosphere, RAS Siberian branch, 625000, P.O. 1230, Tyumen (Russian Federation)

    2015-09-15

    The free energy of the plasma particles and the charged surface that form an electroneutral system is calculated on the basis of the Poisson-Boltzmann equation. It is shown that, owing to correlation of light plasma particles near the charged surface and close to heavy particles of high charge, there can be metastable states in plasma. The corresponding phase charts of metastable states of the separate components of plasma, and plasma as a whole, are constructed. These charts depend on temperature, the charge magnitude, the size of the particles, and the share of the charge of the light carriers out of the total charge of the plasma particles.

  11. Decay of atomic metastable states in a plasma

    International Nuclear Information System (INIS)

    Kleiman, E.B.

    1985-01-01

    This paper discusses the influence of polarization plasma effects on the lifetime of metastable atomic levels. It is shown that plasma effects can also be important in the case when the distance between the metastable level and the closest emitting level exceeds the Langmuir frequency. The lifetime of the 2S level of a hydrogen atom in a rarefied plasma connected with the action of a longitudinal fluctuation field on the atom is estimated. It is found that this mechanism can determine the lifetime of the 2S level in a rarefied cosmic plasma

  12. Spatial Complementarity and the Coexistence of Species

    Science.gov (United States)

    Velázquez, Jorge; Garrahan, Juan P.; Eichhorn, Markus P.

    2014-01-01

    Coexistence of apparently similar species remains an enduring paradox in ecology. Spatial structure has been predicted to enable coexistence even when population-level models predict competitive exclusion if it causes each species to limit its own population more than that of its competitor. Nevertheless, existing hypotheses conflict with regard to whether clustering favours or precludes coexistence. The spatial segregation hypothesis predicts that in clustered populations the frequency of intra-specific interactions will be increased, causing each species to be self-limiting. Alternatively, individuals of the same species might compete over greater distances, known as heteromyopia, breaking down clusters and opening space for a second species to invade. In this study we create an individual-based model in homogeneous two-dimensional space for two putative sessile species differing only in their demographic rates and the range and strength of their competitive interactions. We fully characterise the parameter space within which coexistence occurs beyond population-level predictions, thereby revealing a region of coexistence generated by a previously-unrecognised process which we term the triadic mechanism. Here coexistence occurs due to the ability of a second generation of offspring of the rarer species to escape competition from their ancestors. We diagnose the conditions under which each of three spatial coexistence mechanisms operates and their characteristic spatial signatures. Deriving insights from a novel metric — ecological pressure — we demonstrate that coexistence is not solely determined by features of the numerically-dominant species. This results in a common framework for predicting, given any pair of species and knowledge of the relevant parameters, whether they will coexist, the mechanism by which they will do so, and the resultant spatial pattern of the community. Spatial coexistence arises from complementary combinations of traits in each

  13. Research on the fundamental process of thermal-hydraulic behaviors in severe accident. Heat transfer on the liquid-liquid interface between molten core pool and coolant. JAERI's nuclear research promotion program, H10-027-6. Contract research

    International Nuclear Information System (INIS)

    Mishima, Kaichiro; Saito, Yasushi

    2002-03-01

    Heat transfer experiments under steady and transient conditions were performed using molten Wood's metal and distilled water to study heat transfer on the liquid-liquid interface between molten fuel pool and coolant under severe accident conditions. In the steady state experiment, boiling curve was measured over the range from natural convection region to film boiling region. The boiling behavior was observed using a high-speed video camera. In the transient experiment, distilled water was poured onto the hot molten metal surface, and the boiling curve was obtained in the cooling process. Comparing the measured boiling curve with existing correlations and experimental data for solid-liquid and liquid-liquid systems, the following conclusions were drawn: (a) When the interface surge is negligible and oxide layer is formed on the interface, the boiling curve at the liquid-liquid surface could be approximately reproduced by the heat transfer correlations for nucleate boiling and film boiling regions and the critical heat flux correlation for a liquid-solid system. (b) When no oxide layer is formed on the interface, the boiling curve at the liquid-liquid surface moved towards higher wall superheat than that at the liquid-solid surface, as Novakovic et al. observed in their experiment using mercury. (c) Transient heat transfer coefficient for film boiling at the liquid-liquid surface was about 100% higher than that predicted by the heat transfer correlation for a solid-liquid system. (author)

  14. Physical property, phase equilibrium, distillation. Measurement and prediction of vapor-liquid and liquid-liquid equilibria; Bussei / heiko / joryu. Kieki, ekieki heiko no sokutei to suisan

    Energy Technology Data Exchange (ETDEWEB)

    Tochigi, K. [Nihon Univ., Tokyo (Japan)

    1998-08-05

    The data on vapor-liquid equilibrium are basic data indispensable to the designing of a distillation process. The stage required for separation depends greatly upon the x-y curve, and the existence/nonexistence of an azeotropic point is also an important item to be checked. This paper describes the measurement of vapor-liquid equilibrium and liquid-liquid equilibrium, and then introduces reliable data on vapor-liquid equilibrium and parameters of an activity coefficient formula. For the prediction of vapor-liquid equilibrium, the ASOG, UNIFAC, and modified NIFAC, all being group contributive methods are utilized. The differences between these group contributive methods are based on the differences between the contributive items based on the differences in size of molecules influencing the activity coefficients and the expression of the group activity coefficient formula. The applicable number of groups of the ASOG is 43, while that of groups of the UNIFAC is 50. The modified UNIFAC covers 43 groups. The prediction of liquid-liquid equilibrium by using a group contributive method has little progressed since the of the results of the study of Magnussen et al. using the UNIFAC. 12 refs., 8 figs., 1 tab.

  15. Liquid-liquid phase separation and solidification behavior of Al55Bi36Cu9 monotectic alloy with different cooling rates

    Science.gov (United States)

    Bo, Lin; Li, Shanshan; Wang, Lin; Wu, Di; Zuo, Min; Zhao, Degang

    2018-03-01

    The cooling rate has a significant effect on the solidification behavior and microstructure of monotectic alloy. In this study, different cooling rate was designed through casting in the copper mold with different bore diameters. The effects of different cooling rate on the solidification behavior of Al55Bi36Cu9 (at.%) immiscible alloy have been investigated. The liquid-liquid phase separation of Al55Bi36Cu9 immiscible alloy melt was investigated by resistivity test. The solidification microstructure and phase analysis of Al55Bi36Cu9 immiscible alloy were performed by the SEM and XRD, respectively. The results showed that the liquid-liquid phase separation occurred in the solidification of Al55Bi36Cu9 monotectic melt from 917 °C to 653 °C. The monotectic temperature, liquid phase separation temperature and immiscibility zone of Al55Bi36Cu9 monotectic alloy was lower than those of Al-Bi binary monotectic alloy. The solidification morphology of Al55Bi36Cu9 monotectic alloy was very sensitive to the cooling rate. The Al/Bi core-shell structure formed when Al55Bi36Cu9 melt was cast in the copper mold with a 8 mm bore diameter.

  16. (Liquid + liquid) equilibria for the ternary mixtures (alkane + toluene + ionic liquid) at T = 298.15 K: Influence of the anion on the phase equilibria

    International Nuclear Information System (INIS)

    Seoane, Raquel G.; Gómez, Elena; González, Emilio J.; Domínguez, Ángeles

    2012-01-01

    Highlights: ► [BMpyr][NTF 2 ] and [BMpyr][TFO] were studied as solvents to extract aromatics from alkanes. ► (Liquid + liquid) equilibrium data were measured at 298.15 K for six ternary systems. ► Selectivity and solute distribution ratio were calculated and compared. ► The influence of the structure of anion of the ionic liquid was analyzed. ► Experimental data were satisfactorily correlated using NRTL model. - Abstract: (Liquid + liquid) equilibrium data for the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMpyr][NTf 2 ], and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, [BMpyr][TFO], with toluene, and heptane or cyclohexane were determined at T = 298.15 K and atmospheric pressure. In order to check if these ILs can be used as potential solvents for the extraction of toluene from aliphatic compounds, the ability of the ILs as solvents was evaluated in terms of selectivity and solute distribution ratio. The experimental data were correlated accurately with the Non Random Two-Liquid model.

  17. Preconcentration and determination of ceftazidime in real samples using dispersive liquid-liquid microextraction and high-performance liquid chromatography with the aid of experimental design.

    Science.gov (United States)

    Razmi, Rasoul; Shahpari, Behrouz; Pourbasheer, Eslam; Boustanifar, Mohammad Hasan; Azari, Zhila; Ebadi, Amin

    2016-11-01

    A rapid and simple method for the extraction and preconcentration of ceftazidime in aqueous samples has been developed using dispersive liquid-liquid microextraction followed by high-performance liquid chromatography analysis. The extraction parameters, such as the volume of extraction solvent and disperser solvent, salt effect, sample volume, centrifuge rate, centrifuge time, extraction time, and temperature in the dispersive liquid-liquid microextraction process, were studied and optimized with the experimental design methods. Firstly, for the preliminary screening of the parameters the taguchi design was used and then, the fractional factorial design was used for significant factors optimization. At the optimum conditions, the calibration curves for ceftazidime indicated good linearity over the range of 0.001-10 μg/mL with correlation coefficients higher than the 0.98, and the limits of detection were 0.13 and 0.17 ng/mL, for water and urine samples, respectively. The proposed method successfully employed to determine ceftazidime in water and urine samples and good agreement between the experimental data and predictive values has been achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. [Determination of fatty acid esters of chloropropanediols in diet samples by gas chromatography-mass spectrometry coupled with solid-supported liquid-liquid extraction].

    Science.gov (United States)

    Gao, Jie; Liu, Qing; Han, Feng; Miao, Hong; Zhao, Yunfeng; Wu, Yongning

    2014-05-01

    To establish a method for the determination of fatty acid esters of 3-monochloropropane-1, 2-diol (3-MCPD) and 2-monochloropropane-1, 3-diol (2-MCPD) in diet samples by gas chromatography-mass spectrometry (GC-MS) with solid-supported liquid-liquid extraction (SLE). Diet samples were ultrasonically extracted by hexane, followed by ester cleavage reaction with sodium methylate in methanol, and then purified by solid-supported liquid-liquid extraction. (SLE) using diatomaceous earth as the sorbent. After derivatization with heptafluorobutyrylimidazole, the analytes were detected by GC-MS and quantified by the deuterated internal standards. The limits of detection (LODs) of 3-MCPD esters and 2-MCPD esters in different diet samples were 0.002 - 0.005 mg/kg and 0.002 - 0.006 mg/kg. The average recoveries of 3-MCPD esters and 2-MCPD esters at the spiking levels of 0.05 and 0.1 mg/kg in the diet samples were in the range of 65.9% - 104.2% and 75.4% - 118.0%, respectively, with the relative standard deviations in the range of 2.2% - 14.2% and 0.8% - .13.9%. The method is simple, accurate and rugged for the determination of fatty acid esters of 3-MCPD and 2-MCPD in diet samples.

  19. Rapid determination of some psychotropic drugs in complex matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

    Science.gov (United States)

    Asghari, Alireza; Fahimi, Ebrahim; Bazregar, Mohammad; Rajabi, Maryam; Boutorabi, Leila

    2017-05-01

    Simple and rapid determinations of some psychotropic drugs in some pharmaceutical wastewater and human plasma samples were successfully accomplished via the tandem dispersive liquid-liquid microextraction combined with high performance liquid chromatography-ultraviolet detection (TDLLME-HPLC-UV). TDLLME of the three psychotropic drugs clozapine, chlorpromazine, and thioridazine was easily performed through two consecutive dispersive liquid-liquid microextractions. By performing this convenient method, proper sample preconcentrations and clean-ups were achieved in just about 7min. In order to achieve the best extraction efficiency, the effective parameters involved were optimized. The optimal experimental conditions consisted of 100μL of CCl 4 (as the extraction organic solvent), and the pH values of 13 and 2 for the donor and acceptor phases, respectively. Under these optimum experimental conditions, the proposed TDLLME-HPLC-UV technique provided a good linearity in the range of 5-3000ngmL -1 for the three psychotropic drugs with the correlation of determinations (R 2 s) higher than 0.996. The limits of quantification (LOQs) and limits of detection (LODs) obtained were 5.0ngmL -1 and 1.0-1.5ngmL -1 , respectively. Also the proper enrichment factors (EFs) of 96, 99, and 88 for clozapine, chlorpromazine, and thioridazine, respectively, and good extraction repeatabilities (relative standard deviations below 9.3%, n=5) were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Extraction of toluene from aliphatic compounds using an ionic liquid as solvent: Influence of the alkane on the (liquid + liquid) equilibrium

    International Nuclear Information System (INIS)

    Gonzalez, Emilio J.; Calvar, Noelia; Dominguez, Irene; Dominguez, Angeles

    2011-01-01

    Research highlights: → An ionic liquid was analyzed as solvent for extraction of toluene from alkanes. → Liquid-liquid equilibrium data were measured at 298.15 K and atmospheric pressure. → Selectivity and solute distribution ratio were obtained and compared with literature. → The Othmer-Tobias equation was used to ascertain the experimental LLE data. → Experimental data were correlated using NRTL and UNIQUAC models. - Abstract: In this paper, the feasibility of using 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid, [EMim][ESO 4 ], as solvent for the extraction of toluene from aliphatic compounds (hexane, heptane, octane, or nonane) was analyzed. (Liquid + liquid) equilibrium (LLE) data for the ternary systems {alkane (1) + toluene (2) + [EMim][ESO 4 ] (3)} were measured at T = 298.15 K and atmospheric pressure. Selectivity and solute distribution ratio were calculated from the experimental LLE data, and the obtained values were compared to those previously reported using other ionic liquids and sulfolane. The degree of consistency of the experimental LLE data was ascertained using the Othmer-Tobias equation. Finally, the experimental LLE data were satisfactorily correlated with NRTL and UNIQUAC models.

  1. Metastable defect response in CZTSSe from admittance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Koeper, Mark J.; Hages, Charles J.; Li, Jian V.; Levi, Dean; Agrawal, Rakesh

    2017-10-02

    Admittance spectroscopy is a useful tool used to study defects in semiconductor materials. However, metastable defect responses in non-ideal semiconductors can greatly impact the measurement and therefore the interpretation of results. Here, admittance spectroscopy was performed on Cu2ZnSn(S,Se)4 where metastable defect response is illustrated due to the trapping of injected carriers into a deep defect state. To investigate the metastable response, admittance measurements were performed under electrically and optically relaxed conditions in comparison to a device following a low level carrier-injection pretreatment. The relaxed measurement demonstrates a single capacitance signature while two capacitance signatures are observed for the device measured following carrier-injection. The deeper level signature, typically reported for kesterites, is activated by charge trapping following carrier injection. Both signatures are attributed to bulk level defects. The significant metastable response observed on kesterites due to charge trapping obscures accurate interpretation of defect levels from admittance spectroscopy and indicates that great care must be taken when performing and interpreting this measurement on non-ideal devices.

  2. Metastable Behavior in Uniaxial Ferroelectrics TGS and TGSe near TC

    NARCIS (Netherlands)

    Fernández del Castillo, J.R.; Przeslawski, J.; Iglesias, T.; Noheda, B.; Gonzalo, J.A.

    1998-01-01

    High resolution hysteresis loops measurements in triglycine sulfate (ordinary critical point) and in triglycine selenate (tricritical point) allow the approximate characterization of the behavior in the metastable region (E < 0, P > 0, or vice versa) at T ≤ TC. The coercive field may be assumed to

  3. Metastability of Reversible Random Walks in Potential Fields

    Science.gov (United States)

    Landim, C.; Misturini, R.; Tsunoda, K.

    2015-09-01

    Let be an open and bounded subset of , and let be a twice continuously differentiable function. Denote by the discretization of , , and denote by the continuous-time, nearest-neighbor, random walk on which jumps from to at rate . We examine in this article the metastable behavior of among the wells of the potential F.

  4. Atom diffraction with a 'natural' metastable atom nozzle beam

    International Nuclear Information System (INIS)

    Karam, J-C; Wipf, N; Grucker, J; Perales, F; Boustimi, M; Vassilev, G; Bocvarski, V; Mainos, C; Baudon, J; Robert, J

    2005-01-01

    The resonant metastability-exchange process is used to obtain a metastable atom beam with intrinsic properties close to those of a ground-state atom nozzle beam (small angular aperture, narrow velocity distribution). The estimated effective source diameter (15 μm) is small enough to provide at a distance of 597 mm a transverse coherence radius of about 873 nm for argon, 1236 nm for neon and 1660 nm for helium. It is demonstrated both by experiment and numerical calculations with He*, Ne* and Ar* metastable atoms, that this beam gives rise to diffraction effects on the transmitted angular pattern of a silicon-nitride nano-slit grating (period 100 nm). Observed patterns are in good agreement with previous measurements with He* and Ne* metastable atoms. For argon, a calculation taking into account the angular aperture of the beam (0.35 mrad) and the effect of the van der Waals interaction-the van der Waals constant C 3 1.83 +0.1 -0.15 au being derived from spectroscopic data-leads to a good agreement with experiment

  5. Cyclic cosmology, conformal symmetry and the metastability of the Higgs

    Energy Technology Data Exchange (ETDEWEB)

    Bars, Itzhak [Department of Physics and Astronomy, University of Southern California, Los Angeles, CA 90089-0484 (United States); Steinhardt, Paul J., E-mail: steinh@princeton.edu [California Institute of Technology, Pasadena, CA 91125 (United States); Department of Physics and Princeton Center for Theoretical Physics, Princeton University, Princeton, NJ 08544 (United States); Turok, Neil [Perimeter Institute for Theoretical Physics, Waterloo, ON N2L 2Y5 (Canada)

    2013-10-07

    Recent measurements at the LHC suggest that the current Higgs vacuum could be metastable with a modest barrier (height (10{sup 10–12} GeV){sup 4}) separating it from a ground state with negative vacuum density of order the Planck scale. We note that metastability is problematic for standard bang cosmology but is essential for cyclic cosmology in order to end one cycle, bounce, and begin the next. In this Letter, motivated by the approximate scaling symmetry of the standard model of particle physics and the primordial large-scale structure of the universe, we use our recent formulation of the Weyl-invariant version of the standard model coupled to gravity to track the evolution of the Higgs in a regularly bouncing cosmology. We find a band of solutions in which the Higgs field escapes from the metastable phase during each big crunch, passes through the bang into an expanding phase, and returns to the metastable vacuum, cycle after cycle after cycle. We show that, due to the effect of the Higgs, the infinitely cycling universe is geodesically complete, in contrast to inflation.

  6. Cyclic cosmology, conformal symmetry and the metastability of the Higgs

    Science.gov (United States)

    Bars, Itzhak; Steinhardt, Paul J.; Turok, Neil

    2013-10-01

    Recent measurements at the LHC suggest that the current Higgs vacuum could be metastable with a modest barrier (height ( GeV)4) separating it from a ground state with negative vacuum density of order the Planck scale. We note that metastability is problematic for standard bang cosmology but is essential for cyclic cosmology in order to end one cycle, bounce, and begin the next. In this Letter, motivated by the approximate scaling symmetry of the standard model of particle physics and the primordial large-scale structure of the universe, we use our recent formulation of the Weyl-invariant version of the standard model coupled to gravity to track the evolution of the Higgs in a regularly bouncing cosmology. We find a band of solutions in which the Higgs field escapes from the metastable phase during each big crunch, passes through the bang into an expanding phase, and returns to the metastable vacuum, cycle after cycle after cycle. We show that, due to the effect of the Higgs, the infinitely cycling universe is geodesically complete, in contrast to inflation.

  7. Cyclic cosmology, conformal symmetry and the metastability of the Higgs

    International Nuclear Information System (INIS)

    Bars, Itzhak; Steinhardt, Paul J.; Turok, Neil

    2013-01-01

    Recent measurements at the LHC suggest that the current Higgs vacuum could be metastable with a modest barrier (height (10 10–12 GeV) 4 ) separating it from a ground state with negative vacuum density of order the Planck scale. We note that metastability is problematic for standard bang cosmology but is essential for cyclic cosmology in order to end one cycle, bounce, and begin the next. In this Letter, motivated by the approximate scaling symmetry of the standard model of particle physics and the primordial large-scale structure of the universe, we use our recent formulation of the Weyl-invariant version of the standard model coupled to gravity to track the evolution of the Higgs in a regularly bouncing cosmology. We find a band of solutions in which the Higgs field escapes from the metastable phase during each big crunch, passes through the bang into an expanding phase, and returns to the metastable vacuum, cycle after cycle after cycle. We show that, due to the effect of the Higgs, the infinitely cycling universe is geodesically complete, in contrast to inflation

  8. Tumor ocular metastásico Metastatic ocular tumor

    Directory of Open Access Journals (Sweden)

    Martha G Domínguez Expósito

    2004-06-01

    Full Text Available El carcinoma metastásico del ojo es considerado la neoplasia maligna que más frecuente se encuentra de forma intraocular. Solo cerca del 10 % de las personas que tienen una o más lesiones metastásicas intraoculares son detectadas clínicamente antes de la muerte. A menudo, el carcinoma metastásico ocular es diagnosticado por el oftalmólogo ante la presencia de síntomas oculares. Las lesiones están localizadas con preferencia en coroides. Nos motivo a realizar la presentación de este caso la presencia de lesiones intraoculares múltiples tumorales metastásicos en un paciente cuyo síntoma de presentación fue la disminución de la agudeza visualThe eye metastatic carcinoma is considered the most frequently found intraocular malignant neoplasia. Only 10 % of the persons with one or more metastatic intraocular injuries are clinically detected before death. The metastatic ocular carcinoma is often diagnosed by the ophthalmologist in the presence of ocular symptoms. The injuries are preferably located in the choroid. The appearance of multiple metastatic intraaocular tumoral injuries in a patient whose chief complaint was the reduction of visual acuity motivated us to presente this case

  9. Colour chemistry - a study of metastable multiquark molecules

    International Nuclear Information System (INIS)

    Chan, H.-M.; Fukugita, M.; Hansson, T.H.; Hoffman, H.J.; Konishi, K.; Hoegaasen, H.; Tsou, S.T.

    1978-03-01

    A framework is proposed for treating metastable multiquark states in general, borrowing some of the chemist's concepts and terminology. Lists of 'ions' and 'bonds' are are compiled which allow one in principle to construct models of complex 'molecules' and to predict their masses and decays. (author)

  10. 235U isotope enrichment in the metastable levels of UI

    International Nuclear Information System (INIS)

    Gagne, J.M.; Demers, Y.; Dreze, C.; Pianarosa, P.

    1983-01-01

    We have used optical pumping to produce a substantial 235 U enrichment in the metastable levels of UI in the discharge afterglow of a hollow-cathode vapor generator. The measured isotope-enrichment factor for the level at 3800 cm -1 is approximately 20

  11. Magneto-optical trap for metastable helium at 389 nm

    NARCIS (Netherlands)

    Koelemeij, J.C.J.; Stas, R.J.W.; Hogervorst, W.; Vassen, W.

    2003-01-01

    We have constructed a magneto-optical trap (MOT) for metastable triplet helium atoms utilizing the 2 S-3(1)-->3 P-3(2) line at 389 nm as the trapping and cooling transition. The far-red-detuned MOT (detuning Delta=-41 MHz) typically contains few times 10(7) atoms at a relatively high (similar

  12. Metastability Thresholds for Anisotropic Bootstrap Percolation in Three Dimensions

    NARCIS (Netherlands)

    Enter, Aernout C.D. van; Fey, Anne

    In this paper we analyze several anisotropic bootstrap percolation models in three dimensions. We present the order of magnitude for the metastability thresholds for a fairly general class of models. In our proofs, we use an adaptation of the technique of dimensional reduction. We find that the

  13. Shape coexistence in N = 28 isotones

    International Nuclear Information System (INIS)

    Saxena, G.; Kaushik, M.; Kumawat, M.; Jain, S.K.

    2016-01-01

    Shape coexistence is one of the important nuclear phenomenon which appears throughout the periodic chart from light mass nuclei to superheavy nuclei. The evolution of ground-state shapes in an isotopic or isotonic chain is governed by changes of the shell structure of single-nucleon orbitals. In recent past, evolution of shell structure guiding shape coexistence, has been observed in the N = 20 and N = 28 isotones around proton drip line. In this paper we have investigated shape coexistence phenomenon for N = 28 isotones in the vicinity of proton drip line using Relativistic Mean Field plus BCS approach

  14. Shape coexistence in N = 40 isotones

    International Nuclear Information System (INIS)

    Saxena, G.; Kumawat, M.; Kaushik, M.; Jain, S.K.; Aggarwal, Mamta

    2017-01-01

    Recently, shape coexistence in 72 Ge is investigated using projectile multistep Coulomb excitation with GRETINA and CHICO-2 and shape coexistence in the Ge and Se isotopes are studied within the interacting boson model (IBM) with the microscopic input from the self-consistent meanfield calculation based on the Gogny-D1M energy density functional. We investigated the phenomenon of shape coexistence in N = 40 isotones using Relativistic Mean-Field (RMF) plus BCS approach with TMA parameter and Nilson Strutinsky (NS) method that includes triaxial shapes also

  15. A metastable helium trap for atomic collision physics

    International Nuclear Information System (INIS)

    Colla, M.; Gulley, R.; Uhlmann, L.; Hoogerland, M.D.; Baldwin, K.G.H.; Buckman, S.J.

    1999-01-01

    Full text: Metastable helium in the 2 3 S state is an important species for atom optics and atomic collision physics. Because of its large internal energy (20eV), long lifetime (∼8000s) and large collision cross section for a range of processes, metastable helium plays an important role in atmospheric physics, plasma discharges and gas laser physics. We have embarked on a program of studies on atom-atom and electron-atom collision processes involving cold metastable helium. We confine metastable helium atoms in a magneto-optic trap (MOT), which is loaded by a transversely collimated, slowed and 2-D focussed atomic beam. We employ diode laser tuned to the 1083 nm (2 3 S 1 - 2 3 P2 1 ) transition to generate laser cooling forces in both the loading beam and the trap. Approximately 10 million helium atoms are trapped at temperatures of ∼ 1mK. We use phase modulation spectroscopy to measure the trapped atomic density. The cold, trapped atoms can collide to produce either atomic He + or molecular He 2 + ions by Penning Ionisation (PI) or Associative Ionisation (AI). The rate of formation of these ions is dependant upon the detuning of the trapping laser from resonance. A further laser can be used to connect the 2 3 S 1 state to another higher lying excited state, and variation of the probe laser detuning used to measure interatomic collision potential. Electron-atom collision processes are studied using a monochromatic electron beam with a well defined spatial current distribution. The total trap loss due to electron collisions is measured as a function of electron energy. Results will be presented for these atomic collision physics measurements involving cold, trapped metastable helium atoms. Copyright (1999) Australian Optical Society

  16. Nucleation of metastable aragonite CaCO3 in seawater.

    Science.gov (United States)

    Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

    2015-03-17

    Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

  17. Constraints representing a meta-stable régime facilitate exploration during practice and transfer of learning in a complex multi-articular task.

    Science.gov (United States)

    Orth, Dominic; Davids, Keith; Seifert, Ludovic

    2018-02-01

    Previous investigations have shown that inducing meta-stability in behavior can be achieved by overlapping affordances through constraint manipulation, allowing cooperative and competitive tendencies to functionally coexist. The purpose of this paper was to test a number of conditions applying these design principles on performance during skills practice and transfer. Of additional interest, was whether the existing skill level interacted with the environmental properties of the experimental tasks (varying indoor climbing routes). Two skill groups practised on three routes per session over four separate sessions. At the end of the final session, climbers undertook a transfer test. Routes, matched for difficulty, were manipulated in terms of hand-hold design. Route-1 and Route-2 were designed with holds with a single graspable edge, aligned entirely parallel or perpendicular to the ground plane respectively. Route-3 had at each hold, two graspable edges (one parallel and one perpendicular to the ground plane). Behavioral exploration at the hip and hands were largest under the metastable condition (Route-3). Skill level also interacted with route properties during practice and influenced transfer. Data suggest meta-stability induces exploratory behaviors. Less skilled individuals explore both hand and hip levels, whereas, more experienced climbers explore at the hip level. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Coexistence of competing stage-structured populations.

    KAUST Repository

    Fujiwara, Masami; Pfeiffer, Georgia; Boggess, May; Day, Sarah; Walton, Jay

    2011-01-01

    -use overlap. The former ratio, which we define as fitness, can be equalized by adjusting organisms' life history strategies, thereby promoting coexistence. We conclude that in addition to niche differentiation among populations, the life history strategies

  19. Gas–liquid nucleation at large metastability: unusual features and a new formalism

    International Nuclear Information System (INIS)

    Santra, Mantu; Singh, Rakesh S; Bagchi, Biman

    2011-01-01

    Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order

  20. Gas-liquid nucleation at large metastability: unusual features and a new formalism

    Science.gov (United States)

    Santra, Mantu; Singh, Rakesh S.; Bagchi, Biman

    2011-03-01

    Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order

  1. Public Spaces - Coexistence and Participation

    Science.gov (United States)

    Stasiak, Anna; Wojtowicz-Jankowska, Dorota

    2017-10-01

    question: who nowadays is a citizen and how to assist in the creation of civil society with a system of public spaces with thoughtful application program. Currently the city, through its scale, deepens the alienation of residents, therefore appears a need for treatments favouring social interaction. The aforementioned spatial actions motivate people to go out and find themselves in the public space. Coexistence is the first necessary step to produce community. This relationship and the specifics of this co-presence may encourage citizens to return to the public space.

  2. Coexistence and sport: the Israeli case

    OpenAIRE

    Yair Galily; Michael Leitner; Pini Shimon

    2013-01-01

    Utilizing sports and other recreational activities to foster peaceful relations and coexistence is an idea that has gained popularity in recent years, particularly in Israel. The aim of the current research is to fill a gap in the research literature on the subject of coexistence programming. The Mifalot organization conducts a program called “Get to Know Your Neighbor” in which Palestinian, Jordanian, and Israeli youth play soccer together. The program, based mainly on the participants’ love...

  3. Toxicological evaluation of liquids proposed for use in direct contact liquid--liquid heat exchangers for solar heated and cooled buildings

    Energy Technology Data Exchange (ETDEWEB)

    Buchan, R.M.; Majestic, J.R.; Billau, R.

    1976-09-01

    This report contains the results of the toxicological evaluation part of the project entitled, ''Direct Contact Liquid-Liquid Heat Exchangers for Solar Heated and Cooled Buildings.'' Obviously any liquid otherwise suitable for use in such a device should be subjected to a toxicological evaluation. 34 liquids (24 denser than water, 10 less dense) have physical and chemical properties that would make them suitable for use in such a device. In addition to the complexity involved in selecting the most promising liquids from the standpoint of their chemical and physical properties is added the additional difficulty of also considering their toxicological properties. Some of the physical and chemical properties of these liquids are listed. The liquids are listed in alphabetical order within groups, the denser than water liquids are listed first followed by those liquids less dense than water.

  4. (Liquid + liquid) equilibrium in binary systems of isomeric C8 aliphatic monoethers with acetonitrile and its interpretation by the COSMO-SAC model

    International Nuclear Information System (INIS)

    Reda, Mateusz; Ruszczyński, Łukasz; Gliński, Marek; Hofman, Tadeusz

    2015-01-01

    The (liquid + liquid) solubility curves have been determined by a synthetic method for six binary mixtures of [acetonitrile + {heptyl methyl ether CH 3 O n C 7 H 15 , or ethyl hexyl ether C 2 H 5 O n C 6 H 13 , or pentyl propyl ether n C 3 H 7 O n C 5 H 11 , or isopentyl propyl ether n C 3 H 7 O i C 5 H 11 , or dibutyl ether n C 4 H 9 O n C 4 H 9 , or butyl isobutyl ether n C 4 H 9 O i C 4 H 9 }]. The possibility of the COSMO-SAC model to account for the thermodynamic differences between these systems has been tested and the discussion on the influence of screening charge of ethers on the system properties was undertaken

  5. Low Density Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Synthetic Antioxidants in Beverages by High-Performance Liquid Chromatography

    Science.gov (United States)

    Çabuk, Hasan; Köktürk, Mustafa

    2013-01-01

    A simple and efficient method was established for the determination of synthetic antioxidants in beverages by using dispersive liquid-liquid microextraction combined with high-performance liquid chromatography with ultraviolet detection. Butylated hydroxy toluene, butylated hydroxy anisole, and tert-butylhydroquinone were the antioxidants evaluated. Experimental parameters including extraction solvent, dispersive solvent, pH of sample solution, salt concentration, and extraction time were optimized. Under optimal conditions, the extraction recoveries ranged from 53 to 96%. Good linearity was observed by the square of correlation coefficients ranging from 0.9975 to 0.9997. The relative standard deviations ranged from 1.0 to 5.2% for all of the analytes. Limits of detection ranged from 0.85 to 2.73 ng mL−1. The method was successfully applied for determination of synthetic antioxidants in undiluted beverage samples with satisfactory recoveries. PMID:23853535

  6. Liquid-liquid and solid-phase extractions of phenols from virgin olive oil and their separation by chromatographic and electrophoretic methods.

    Science.gov (United States)

    Bendini, Alessandra; Bonoli, Matteo; Cerretani, Lorenzo; Biguzzi, Barbara; Lercker, Giovanni; Toschi, Tullia Gallina

    2003-01-24

    The high oxidative stability of virgin olive oil is related to its high monounsaturated/polyunsaturated ratio and to the presence of antioxidant compounds, such as tocopherols and phenols. In this paper, the isolation of phenolic compounds from virgin olive oil, by different methods, was tested and discussed. Particularly liquid-liquid and solid-phase extraction methods were compared, assaying, for the latter, three stationary phases (C8, C18 and Diol) and several elution mixtures. Quantification of phenolic and o-diphenolic substances in the extracts was performed by the traditional Folin-Ciocalteau method and the sodium molybdate reaction, respectively. Furthermore, the quantification of phenolic compounds in the extracts and in a standard mixture was carried out both with diode array and mass spectrometric detection and capillary zone electrophoresis.

  7. Modified dispersive liquid-liquid microextraction for pre-concentration of benzene, toluene, ethylbenzene and xylenes prior to their determination by GC

    International Nuclear Information System (INIS)

    Faraji, Hakim; Feizbakhsh, Alireza; Helalizadeh, Masoumeh

    2013-01-01

    We have developed a modified method for the extraction and preconcentration of benzene, toluene, ethylbenzene and xylenes (BTEX) in aqueous samples. It based on dispersive liquid-liquid microextraction along with solidification of floating organic microdrops. The dispersion of microvolumes of an extracting solvent into the aqueous occurs without dispersive solvent. Various parameters have been optimized. BTEX were quantified via GC with FID detection. Under optimized conditions, the preconcentration factors range from 301 to 514, extraction efficiencies from 60 to 103 %, repeatabilities from 2.2 to 4.1 %, and intermediate precisions from 3.5 to 7.0 %. The relative recovery for each analyte in water samples at three spiking levels is >85.6 %, with a relative standard deviation of <7.4 %. (author)

  8. Low Density Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Synthetic Antioxidants in Beverages by High-Performance Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Hasan Çabuk

    2013-01-01

    Full Text Available A simple and efficient method was established for the determination of synthetic antioxidants in beverages by using dispersive liquid-liquid microextraction combined with high-performance liquid chromatography with ultraviolet detection. Butylated hydroxy toluene, butylated hydroxy anisole, and tert-butylhydroquinone were the antioxidants evaluated. Experimental parameters including extraction solvent, dispersive solvent, pH of sample solution, salt concentration, and extraction time were optimized. Under optimal conditions, the extraction recoveries ranged from 53 to 96%. Good linearity was observed by the square of correlation coefficients ranging from 0.9975 to 0.9997. The relative standard deviations ranged from 1.0 to 5.2% for all of the analytes. Limits of detection ranged from 0.85 to 2.73 ng mL−1. The method was successfully applied for determination of synthetic antioxidants in undiluted beverage samples with satisfactory recoveries.

  9. Dispersive liquid-liquid microextraction for metals enrichment: a useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis.

    Science.gov (United States)

    Aguirre, M A; Selva, E J; Hidalgo, M; Canals, A

    2015-01-01

    A rapid and efficient Dispersive Liquid-Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a multivariate approach. Under optimum DLLME conditions, DLLME-LIBS method was found to be of about 4.0-5.5 times more sensitive than LIBS, achieving limits of detection of about 3.7-5.6 times lower. To assess accuracy of the proposed DLLME-LIBS procedure, a certified reference material of estuarine water was analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Preconcentration procedure using vortex-assisted liquid-liquid microextraction for the fast determination of trace levels of thorium in water samples

    International Nuclear Information System (INIS)

    Ehsan Zolfonoun; Maryam Salahinejad

    2013-01-01

    A new simple and rapid vortex-assisted liquid-liquid microextraction method was applied for the determination of thorium in water samples. In this method, chloroform used as extraction solvent was directly injected into the water sample solution. The extraction solvent was dispersed into the aqueous phase under vigorously shaking with the vortex. After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom centrifuge tube. The effect of different experimental parameters on the performance of the method were studied and discussed. Under the optimum conditions, the detection limit for Th(IV) was 7.5 ng mL -1 . The precision of the method, evaluated as the relative standard deviation obtained by analyzing of 10 replicates, was 2.8 %. The practical applicability of the developed method was examined using natural water and monazite sand samples. (author)

  11. Headspace solid-phase microextraction (HS-SPME) and liquid-liquid extraction (LLE): comparison of the performance in classification of ecstasy tablets. Part 2.

    Science.gov (United States)

    Bonadio, Federica; Margot, Pierre; Delémont, Olivier; Esseiva, Pierre

    2008-11-20

    Headspace solid-phase microextraction (HS-SPME) is assessed as an alternative to liquid-liquid extraction (LLE) currently used for 3,4-methylenedioxymethampethamine (MDMA) profiling. Both methods were compared evaluating their performance in discriminating and classifying samples. For this purpose 62 different seizures were analysed using both extraction techniques followed by gas chromatography-mass spectroscopy (GC-MS). A previously validated method provided data for HS-SPME, whereas LLE data were collected applying a harmonized methodology developed and used in the European project CHAMP. After suitable pre-treatment, similarities between sample pairs were studied using the Pearson correlation. Both methods enable to distinguish between samples coming from the same pre-tabletting batches and samples coming from different pre-tabletting batches. This finding emphasizes the use of HS-SPME as an effective alternative to LLE, with additional advantages such as sample preparation and a solvent-free process.

  12. In situ liquid-liquid extraction as a sample preparation method for matrix-assisted laser desorption/ionization MS analysis of polypeptide mixtures

    DEFF Research Database (Denmark)

    Kjellström, Sven; Jensen, Ole Nørregaard

    2003-01-01

    A novel liquid-liquid extraction (LLE) procedure was investigated for preparation of peptide and protein samples for matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). LLE using ethyl acetate as the water-immiscible organic solvent enabled segregation of hydrophobic...... matrix to the organic solvent enhanced the efficiency of the LLE-MALDI MS method for analysis of hydrophobic peptides and proteins. LLE-MALDI MS enabled the detection of the hydrophobic membrane protein bacteriorhodopsin as a component in a simple protein mixture. Peptide mixtures containing...... phosphorylated, glycosylated, or acylated peptides were successfully separated and analyzed by the in situ LLE-MALDI MS technique and demonstrate the potential of this method for enhanced separation and structural analysis of posttranslationally modified peptides in proteomics research....

  13. Separation of {sup 195(m,g),197m}Hg from bulk gold target by liquid-liquid extraction using hydrophobic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Kaustab; Lahiri, Susanta [Saha Institute of Nuclear Physics, Kolkata (India). Chemical Sciences Div.; Maiti, Moumita [Indian Institute of Technology Roorkee, Roorkee (India). Dept. of Physics

    2017-07-01

    The {sup 195(m,g),197m}Hg radionuclides were produced in accelerator when natural Au foil was irradiated with 23 MeV protons. The no-carrier-added (NCA) Hg radioisotopes were separated from the bulk Au target by liquid-liquid extraction (LLX) employing hydrophobic RTILs 1-butyl-3-methylimidazolium hexafluorophosphate([C{sub 4}mim][PF{sub 6}]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([bmim][Tf{sub 2}N]) as extractant with HNO{sub 3} and HCl. In each case, bulk Au was extracted into the RTIL phase leaving NCA Hg-radionuclides in the aqueous phase. The RTILs were recovered by washing with 1 M K{sub 2}S{sub 2}O{sub 5} and freshly prepared 1 M FeSO{sub 4}. The reported separation methods follow green chemistry approach as it does not involve any volatile reagents.

  14. Effect of Injector Geometry on Atomization of a Liquid-Liquid Double Swirl Coaxial Injector Using Non-invasive Laser, Optical and X-ray Techniques

    Science.gov (United States)

    Radke, C. R.; Meyer, T. R.

    2014-01-01

    The spray characteristics of a liquid-liquid double swirl coaxial injector were studied using non-invasive optical, laser, and X-ray diagnostics. A parametric study of injector exit geometry demonstrated that spray breakup time, breakup type and sheet stability could be controlled with exit geometry. Phase Doppler interferometry was used to characterize droplet statistics and non-dimensional droplet parameters over a range of inlet conditions and for various fluids allowing for a study on the role of specific fluid properties in atomization. Further, X-ray radiography allowed for investigation of sheet thickness and breakup length to be quantified for different recess exit diameters and inlet pressures. Finally, computed tomography scans revealed that the spray cone was distinctively non-uniform and comprised of several pockets of increased mass flux.

  15. Liquid-liquid reductive extraction in molten fluoride salt/liquid aluminium as a core of process for the An/Ln group separation

    International Nuclear Information System (INIS)

    Conocar, O.

    2007-06-01

    This report concerns a pyrochemical process based on liquid-liquid extraction in a molten fluoride/liquid aluminium system as a core process for actinide (An)/lanthanide (Ln) group separation, studied at CEA. The basic and demonstrative experiments have established the feasibility of the An/Ln group separation in the molten fluoride/liquid aluminium system (U, Pu, Np, Am, Cm traces from Nd, Ce, Eu, Sm, Eu, La - An/Ln separation factors over 1000 - An recovery yield over 98 % in one batch). The main experimental efforts must now be targeted on the recovery of actinides from the Al matrix. A thermodynamic and bibliographical survey has been done. It shows that back-extraction in a molten chloride melt could be a promising technique for this purpose

  16. Dispersive liquid-liquid microextraction (DLLME combined with graphite furnace atomic absorption spectrometry (GFAAS for determination of trace Cu and Zn in water Samples

    Directory of Open Access Journals (Sweden)

    Ghorbani A.

    2014-07-01

    Full Text Available Dispersive liquid-liquid microextraction (DLLME combined with graphite furnace atomic absorption spectrometry (GFAAS was proposed for the determination of trace amounts of Copper and Zinc ions using 8-hydroxyquinoline (8-HQ as chelating agent. Several factors influencing the microextraction efficiency of Cu and Zn and their subsequent determinations, such as pH, extraction and disperser solvent type and their volume, concentration of the chelating agent and extraction time were studied, and the optimized experimental conditions were established. After extraction, the enrichment factors were 25 and 26 for Cu and Zn, respectively. The detection limits of the method were 0.025 and 0.0033 μg/L for Cu and Zn, and the relative standard deviations (R.S.D for five determinations of 1 ng/ml Cu and Zn were 8.51% and 7.41%, respectively.

  17. Molecular dynamics simulations of hydrophobous ions at the liquid-liquid interfaces: case of dicarbollide anions as synergy agents and of ionic liquids as extracting medium

    International Nuclear Information System (INIS)

    Chevrot, G.

    2008-01-01

    Based on molecular dynamics simulations, we first describe the distribution of dicarbollide salts (CCD - , Mn + ) in concentrated monophasic solutions (water, chloroform, octanol, nitrobenzene) and in the corresponding biphasic 'oil' - water solutions. We point to the importance of surface activity of the CCD - s and of their self-aggregation in water, with marked counterions effects, and we explain the synergistic effect of CCD - s in the Eu 3+ extraction by BTP ligands. In the second part of the thesis we report exploratory simulations on the extraction of Sr 2+ by 18-crown-6 to an hydrophobic ionic liquid ([BMI][PF6]), focusing on the liquid - liquid interface. Analogies and differences with a classical aqueous interface are outlined. (author)

  18. Quaternary isobaric (vapor + liquid + liquid) equilibrium and (vapor + liquid) equilibrium for the system (water + ethanol + cyclohexane + heptane) at 101.3 kPa

    International Nuclear Information System (INIS)

    Pequenin, Ana; Asensi, Juan Carlos; Gomis, Vicente

    2011-01-01

    Highlights: → Water-ethanol-cyclohexane-heptane and water-cyclohexane-heptane isobaric VLLE. → Isobaric experimental data were determined at 101.3 kPa. → A dynamic recirculating still with an ultrasonic homogenizer was used. → The quaternary system does not present quaternary azeotropes. - Abstract: Experimental isobaric (vapor + liquid + liquid) and (vapor + liquid) equilibrium data for the ternary system {water (1) + cyclohexane (2) + heptane (3)} and the quaternary system {water (1) + ethanol (2) + cyclohexane (3) + heptane (4)} were measured at 101.3 kPa. An all-glass, dynamic recirculating still equipped with an ultrasonic homogenizer was used to determine the VLLE. The results obtained show that the system does not present quaternary azeotropes. The point-by-point method by Wisniak for testing the thermodynamic consistency of isobaric measurements was used to test the equilibrium data.

  19. Prediction of vapour-liquid and vapour-liquid-liquid equilibria of nitrogen-hydrocarbon mixtures used in J-T refrigerators

    Science.gov (United States)

    Narayanan, Vineed; Venkatarathnam, G.

    2018-03-01

    Nitrogen-hydrocarbon mixtures are widely used as refrigerants in J-T refrigerators operating with mixtures, as well as in natural gas liquefiers. The Peng-Robinson equation of state has traditionally been used to simulate the above cryogenic process. Multi parameter Helmholtz energy equations are now preferred for determining the properties of natural gas. They have, however, been used only to predict vapour-liquid equilibria, and not vapour-liquid-liquid equilibria that can occur in mixtures used in cryogenic mixed refrigerant processes. In this paper the vapour-liquid equilibrium of binary mixtures of nitrogen-methane, nitrogen-ethane, nitrogen-propane, nitrogen-isobutane and three component mixtures of nitrogen-methane-ethane and nitrogen-methane-propane have been studied with the Peng-Robinson and the Helmholtz energy equations of state of NIST REFPROP and compared with experimental data available in the literature.

  20. Liquid-liquid reductive extraction in molten fluoride salt/liquid aluminium as a core of process for the An/Ln group separation

    Energy Technology Data Exchange (ETDEWEB)

    Conocar, O

    2007-06-15

    This report concerns a pyrochemical process based on liquid-liquid extraction in a molten fluoride/liquid aluminium system as a core process for actinide (An)/lanthanide (Ln) group separation, studied at CEA. The basic and demonstrative experiments have established the feasibility of the An/Ln group separation in the molten fluoride/liquid aluminium system (U, Pu, Np, Am, Cm traces from Nd, Ce, Eu, Sm, Eu, La - An/Ln separation factors over 1000 - An recovery yield over 98 % in one batch). The main experimental efforts must now be targeted on the recovery of actinides from the Al matrix. A thermodynamic and bibliographical survey has been done. It shows that back-extraction in a molten chloride melt could be a promising technique for this purpose.

  1. Contribution to the study of liquid-liquid extraction dynamics in the case of fast transfers. Extractions of uranium, plutonium and neptunium in a laboratory centrifugal extractor

    International Nuclear Information System (INIS)

    Bergeonneau, Philippe

    1978-01-01

    The liquid-liquid extraction (also named solvent-based extraction) is a very important technique for the reprocessing of irradiated nuclear fuels. This research thesis is based on the use of a laboratory centrifugal extractor which allows interesting conditions to be achieved: fast transfer due to an intense solution mixing, very short duration of contact between solutions. Thus, after a report of a bibliographical study on chemical mechanisms of extraction, on the composition of extracted species, on extraction kinetics, and on centrifugal extractors, this thesis reports the design, fabrication and use of a centrifugal extractor: presentation of fundamental principles, description and characteristics (materials, hydrodynamic operation test and problems, prototype). It reports studies of fast transfer kinetics: mathematical processing, result interpretation, results and discussions of extraction kinetics for nitric acid, uranium VI and IV, plutonium IV, neptunium IV, and comparison of the different extraction kinetics

  2. Optimization of two different dispersive liquid-liquid microextraction methods followed by gas chromatography-mass spectrometry determination for polycyclic aromatic hydrocarbons (PAHs) analysis in water.

    Science.gov (United States)

    Tseng, Wan-Chi; Chen, Pai-Shan; Huang, Shang-Da

    2014-03-01

    Novel sample preparation methods termed "up-and-down shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME)" and "water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquid-liquid microextraction (WLSEME)" coupled with gas chromatography-mass spectrometry (GC-MS) have been developed for the analysis of 11 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. For UDSA-DLLME, an up-and-down shaker-assisted emulsification was employed. Extraction was complete in 3min. Only 14 μL of 1-heptanol was required, without a dispersive solvent. Under the optimum conditions, the linear range was 0.08-100 µg L(-1), and the LODs were in the range 0.022-0.060 µg L(-1). The enrichment factors (EFs) ranged from 392 to 766. Relative recoveries were between 84% and 113% for river, lake, and field water. In WLSEME, 9 μL of 1-nonanol as extraction solvent and 240 μL of 1 mg L(-1) Triton X-100 as surfactant were mixed in a microsyringe to form a cloudy emulsified solution, which was then injected into the samples. Compared with other surfactant-assisted emulsion methods, WLSEME uses much less surfactant. The linear range was 0.08-100 µg L(-1), and the LODs were 0.022-0.13 µg L(-1). The EFs ranged from 388 to 649. The relative recoveries were 86-114% for all three water specimens. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Phase transitions on (liquid + liquid) equilibria for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems at T = (563, 573, and 583) K

    International Nuclear Information System (INIS)

    Togo, Masaki; Inamori, Yoshiki; Shimoyama, Yusuke

    2012-01-01

    Highlights: ► Mixtures of (water + 1-methylnaphthalene + light aromatic hydrocarbon) are focused. ► Phase transition pressures on (liquid + liquid) equilibria were measured. ► Effects of aromatic hydrocarbons on phase transition pressure are investigated. ► Phase transition pressures are discussed using dielectric constants of hydrocarbons. - Abstract: Phase transitions for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems are observed at their (liquid + liquid) equilibria at T = (563, 573, and 583) K and (8.6 to 25.0) MPa. The phase transition pressures at T = (563, 573, and 583) K were measured for the five species of light aromatic hydrocarbons, o-, m-, p-xylenes, ethylbenzene, and mesitylene. The measurements of the phase transition pressures were carried out by changing the feed mole fraction of water and 1-methylnaphthalene in water free, respectively. Effects of the feed mole fraction of water on the phase transition pressures are very small. Increasing the feed mole fraction of 1-methylnaphthalene results in decreasing the phase transition pressures at constant temperature. The slopes depending on the feed mole fraction for 1-methylnaphthalene at the phase transition pressures are decreased with increasing temperature for (water + 1-methylnaphthalene + p-xylene), (water + 1-methylnaphthalene + o-xylene), and (water + 1-methylnaphthalene + mesitylene) systems. For xylene isomers, the highest and lowest of the phase transition pressures are obtained in the case of p- and o-xylenes, respectively. The phase transition pressures for ethylbenzene are lower than those in the case of p-xylene. The similar phase transition pressures are given for p-xylene and mesitylene.

  4. Ionic liquid ultrasound assisted dispersive liquid-liquid microextraction method for preconcentration of trace amounts of rhodium prior to flame atomic absorption spectrometry determination

    Energy Technology Data Exchange (ETDEWEB)

    Molaakbari, Elaheh [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Young Research Society, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Mostafavi, Ali, E-mail: mostafavi.ali@gmail.com [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Afzali, Daryoush [Environment and Nanochemistry Department, Research Institute of Environmental Science, International Center for Science, High Technology and Environmental Science, Kerman (Iran, Islamic Republic of); Mineral Industries Research Center, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of)

    2011-01-30

    In this article, we consider ionic liquid based ultrasound-assisted dispersive liquid-liquid microextraction of trace amounts of rhodium from aqueous samples and show that this is a fast and reliable sample pre-treatment for the determination of rhodium ions by flame atomic absorption spectrometry. The Rh(III) was transferred into its complex with 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol as a chelating agent, and an ultrasonic bath with the ionic liquid, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide at room temperature was used to extract the analyte. The centrifuged rhodium complex was then enriched in the form of ionic liquid droplets and prior to its analysis by flame atomic absorption spectrometry, 300 {mu}L ethanol was added to the ionic liquid-rich phase. Finally, the influence of various parameters on the recovery of Rh(III) was optimized. Under optimum conditions, the calibration graph was linear in the range of 4.0-500.0 ng mL{sup -1}, the detection limit was 0.37 ng mL{sup -1} (3S{sub b}/m, n = 7) and the relative standard deviation was {+-}1.63% (n = 7, C = 200 ng mL{sup -1}). The results show that ionic liquid based ultrasound assisted dispersive liquid-liquid microextraction, combined with flame atomic absorption spectrometry, is a rapid, simple, sensitive and efficient analytical method for the separation and determination of trace amounts of Rh(III) ions with minimum organic solvent consumption.

  5. Experimental (liquid + liquid) equilibrium data for ternary and quaternary mixtures of fatty acid methyl and ethyl esters (FAME/FAEE) from soybean oil

    International Nuclear Information System (INIS)

    Beneti, Stéphani C.; Lanza, Marcelo; Mazutti, Marcio A.; Kunita, Marcos Hiroiuqui; Cardozo-Filho, Lúcio; Vladimir Oliveira, J.

    2014-01-01

    Highlights: • Innovative technique for quantification of compounds involved in the biodiesel production. • Easy and quick determination from NIR combined with multivariate calibration. • Reliable LLE correlation and predictions can be attained from the technique. -- Abstract: This work is aimed at providing an easy and quick determination of the biodiesel products using near infrared spectroscopy (NIR) by combination with the multivariate calibration in the analysis of (liquid + liquid) equilibrium (LLE) data for ternary and quaternary mixtures containing soybean fatty acid methyl (FAME) and ethyl (FAEE) esters, glycerol, ethanol, methanol and water, at various temperatures. The mass balance for the compositions obtained for each phase was carried out so as to demonstrate the reliability of the models generated by the multivariate calibration. Two distinct phases are observed, a glycerol-rich and the other ester-rich, while ethanol is dissolved among the phases hence reducing the partial mutual miscibility between glycerol and ester. Through (liquid + liquid) equilibrium (LLE) results, systems containing FAEE at T = 318.15 K and 303.15 K (calibration using data obtained at temperature of 318.15 K), a good agreement is verified among the values determined using conventional and NIR technique for alcoholic phase (AP) or aqueous phase (WP) and biodiesel phase (BP). Likewise in the systems containing FAME at 318.15 K, 303.15 K and 333.15 K (calibration using data obtained at temperature of 318.15 K), the LLE results were reproduced at the upper and lower temperature to the tests of the reproducibility of the models generated by the multivariate calibration

  6. Ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet for determination of three antifungal drugs in water and biological samples.

    Science.gov (United States)

    Ezoddin, Maryam; Shojaie, Mehran; Abdi, Khosrou; Karimi, Mohammad Ali

    2017-03-01

    A novel ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet (UAAD-LLM-SFO) followed by HPLC-UV detection was developed for the analysis of three antifungal drugs in water and biological samples. In this method, 1-dodecanol was used as the extraction solvent. The emulsion was rapidly formed by pulling in and pushing out the mixture of sample solution and extraction solvent for 5 times repeatedly using a 10-mL glass syringe while sonication was performed. Therefore, an organic dispersive solvent required in common microextraction methods was not used in the proposed method. After dispersing, an aliquot of acetonitrile was introduced as a demulsifier solvent into the sample solution to separate two phases. Therefore, some additional steps, such as the centrifugation, ultrasonication, or agitation of the sample solution, are not needed. Parameters influencing the extraction recovery were investigated. The proposed method showed a good linearity for the three antifungal drugs studied with the correlation coefficients (R 2  > 0.9995). The limits of detection (LODs) and the limits of the quantification (LOQs) were between 0.01-0.03 μg L -1 and 0.03-0.08 μg L -1 , respectively. The preconcentration factors (PFs) were in the range of 107-116, respectively. The precisions, as the relative standard deviations (RSDs) (n = 5), for inter-day and intra-day analysis were in the range of 2.1-4.5% and 6.5-8.5%, respectively. This method was successfully applied to determine the three antifungal drugs in tap water and biological samples. The recoveries of antifungal drugs in these samples were 92.4-98.5%. Graphical abstract Ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet for the analysis of three antifungal drugs prior HPLC-UV.

  7. Air-assisted liquid-liquid microextraction using floating organic droplet solidification for simultaneous extraction and spectrophotometric determination of some drugs in biological samples through chemometrics methods

    Science.gov (United States)

    Farahmand, Farnaz; Ghasemzadeh, Bahar; Naseri, Abdolhossein

    2018-01-01

    An air assisted liquid-liquid microextraction by applying the solidification of a floating organic droplet method (AALLME-SFOD) coupled with a multivariate calibration method, namely partial least squares (PLS), was introduced for the fast and easy determination of Atenolol (ATE), Propanolol (PRO) and Carvedilol (CAR) in biological samples via a spectrophotometric approach. The analytes would be extracted from neutral aqueous solution into 1-dodecanol as an organic solvent, using AALLME. In this approach a low-density solvent with a melting point close to room temperature was applied as the extraction solvent. The emulsion was immediately formed by repeatedly pulling in and pushing out the aqueous sample solution and extraction solvent mixture via a 10-mL glass syringe for ten times. After centrifugation, the extractant droplet could be simply collected from the aqueous samples by solidifying the emulsion at a lower than the melting point temperature. In the next step, analytes were back extracted simultaneously into the acidic aqueous solution. Derringer and Suich multi-response optimization were utilized for simultaneous optimizing the parameters of three analytes. This method incorporates the benefits of AALLME and dispersive liquid-liquid microextraction considering the solidification of floating organic droplets (DLLME-SFOD). Calibration graphs under optimized conditions were linear in the range of 0.30-6.00, 0.32-2.00 and 0.30-1.40 μg mL- 1 for ATE, CAR and PRO, respectively. Other analytical parameters were obtained as follows: enrichment factors (EFs) were found to be 11.24, 16.55 and 14.90, and limits of detection (LODs) were determined to be 0.09, 0.10 and 0.08 μg mL- 1 for ATE, CAR and PRO, respectively. The proposed method will require neither a highly toxic chlorinated solvent for extraction nor an organic dispersive solvent in the application process; hence, it is more environmentally friendly.

  8. (Liquid + liquid) equilibria measurements for ternary systems (sulfolane + a carboxylic acid + n-heptane) at T = 303.15 K and at 0.1 MPa

    International Nuclear Information System (INIS)

    Cele, N.P.; Bahadur, I.; Redhi, G.G.; Ebenso, E.E.

    2016-01-01

    Highlights: • The (liquid + liquid) equilibrium for (sulfolane + a carboxylic acid + heptane) was measured. • Selectivity values for solvent separation efficiency were calculated. • Separation of carboxylic acids from heptane is feasible by extraction. • Three parameter equations have been fitted to the binodal curve data. • The NRTL and UNIQUAC models were used to correlate the experimental data. - Abstract: In the present work, new (liquid + liquid) equilibrium (LLE) values are reported for ternary systems {sulfolane(1) + acetic acid, or propanoic acid, or butanoic acid, or 2-methylpropanoic acid, or pentanoic acid, or 3-methylbutanoic acid (2) + n-heptane (3)} at T = 303.15 K and at p = 0.1 MPa. The mutual solubility of carboxylic acid in sulfolane is dependent on the length and structure of the alkyl chain of the carboxylic acid; it progressively increases with an increase in the alkyl chain of the carboxylic acid. The single phase homogenous region increases as the alkyl chain of the carboxylic acid increases. The n-heptane is most soluble in the carboxylic acid mixtures with long alkyl chain, that is, (3-methylbutanoic acid + sulfolane) and (pentanoic acid + sulfolane) systems and least soluble in the carboxylic acid with short alkyl chain (acetic acid + sulfolane) system. Carboxylic acid together with many other oxygenates and hydrocarbons are produced by SASOL Company in South Africa using the Fischer–Tropsch process. The details about this process are given in introduction section. The NRTL and UNIQUAC models were used to correlate the experimental tie-lines and to calculate the phase compositions of the ternary systems. It was found that the NRTL model fits the experimental values significantly better than the UNIQUAC model.

  9. Binary Solvents Dispersive Liquid-Liquid Microextraction (BS-DLLME) Method for Determination of Tramadol in Urine Using High-Performance Liquid Chromatography.

    Science.gov (United States)

    Kiarostami, Vahid; Rouini, Mohamad-Reza; Mohammadian, Razieh; Lavasani, Hoda; Ghazaghi, Mehri

    2014-02-03

    Tramadol is an opioid, synthetic analog of codeine and has been used for the treatment of acute or chronic pain may be abused. In this work, a developed Dispersive liquid liquid microextraction (DLLME) as binary solvents-based dispersive liquid-liquid microextraction (BS-DLLME) combined with high performance liquid chromatography (HPLC) with fluorescence detection (FD) was employed for determination of tramadol in the urine samples. This procedure involves the use of an appropriate mixture of binary extraction solvents (70 μL CHCl3 and 30 μL ethyl acetate) and disperser solvent (600 μL acetone) for the formation of cloudy solution in 5 ml urine sample comprising tramadol and NaCl (7.5%, w/v). After centrifuging, the small droplets of extraction solvents were precipitated. In the final step, the HPLC with fluorescence detection was used for determination of tramadol in the precipitated phase. Various factors on the efficiency of the proposed procedure were investigated and optimized. The detection limit (S/N = 3) and quantification limit (S/N = 10) were found 0.2 and 0.9 μg/L, respectively. The relative standard deviations (RSD) for the extraction of 30 μg L of tramadol was found 4.1% (n = 6). The relative recoveries of tramadol from urine samples at spiking levels of 10, 30 and 60 μg/L were in the range of 95.6 - 99.6%. Compared with other methods, this method provides good figures of merit such as good repeatability, high extraction efficiency, short analysis time, simple procedure and can be used as microextraction technique for routine analysis in clinical laboratories.

  10. Rapid determination of some beta-blockers in complicated matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

    Science.gov (United States)

    Hemmati, Maryam; Asghari, Alireza; Bazregar, Mohammad; Rajabi, Maryam

    2016-11-01

    In this research work, an efficient tandem dispersive liquid-liquid microextraction (TDLLME) procedure coupled with high performance liquid chromatography-ultraviolet detection (HPLC-UV) was successfully applied for the determination of beta-blockers in human plasma and pharmaceutical wastewater samples. High clean-up and preconcentration factor are easily and rapidly feasible via this novel, cheap, and safe microextraction method, leading to high quality experimental data. It consists of two sequential dispersive liquid-liquid microextraction methods, accomplished via air/ultrasonic agitation and air agitation, respectively. In order to enrich the optimal values for the mentioned procedures, the Box-Behnken design (BBD) combined with the desirability function (DF) was used. The optimum values were found to be 11.0 % (w/v) of the salt amount, an initial pH value of 12.0, 103 μL of organic extractant phase, and 45 μL of aqueous extractant phase with pH value of 2.0, resulted in reasonable recovery percentages with a logical desirability. Under optimal experimental conditions, good linear ranges (3-2000 ng mL -1 for metoprolol and 2.5-2500 ng mL -1 for propranolol with the correlation of determinations (R 2 s) higher than 0.99) and low limits of detection (0.8 and 1.0 ng mL -1 for propranolol and metoprolol, respectively) were obtainable. Also, TDLLME-HPLC-UV provided good proper repeatabilities (relative standard deviations (RSDs) below 5.7 %, n = 3) and high enrichment factors (EFs) of 75-100. Graphical abstract TDLLME of beta-blockers from complicated matrices.

  11. Glyoxal and methylglyoxal as urinary markers of diabetes. Determination using a dispersive liquid-liquid microextraction procedure combined with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Pastor-Belda, M; Fernández-García, A J; Campillo, N; Pérez-Cárceles, M D; Motas, M; Hernández-Córdoba, M; Viñas, P

    2017-08-04

    Glyoxal (GO) and methylglyoxal (MGO) are α-oxoaldehydes that can be used as urinary diabetes markers. In this study, their levels were measured using a sample preparation procedure based on salting-out assisted liquid-liquid extraction (SALLE) and dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography-mass spectrometry (GC-MS). The effect of the derivatization reaction with 2,3-diaminonaphthalene, the addition of acetonitrile and sodium chloride to urine, and the DLLME step using the acetonitrile extract as dispersant solvent and carbon tetrachloride as extractant solvent were carefully optimized. Quantification was performed by the internal standard method, using 5-bromo-2-chloroanisole. The intraday and interday precisions were lower than 6%. Limits of detection were 0.12 and 0.06ngmL -1 , and enrichment factors 140 and 130 for GO and MGO, respectively. The concentrations of these α-oxoaldehydes in urine were between 0.9 and 35.8ngg -1 levels (creatinine adjusted). A statistical comparison of the analyte contents of urine samples from non-diabetic and diabetic patients pointed to significant differences (P=0.046, 24 subjects investigated), particularly regarding MGO, which was higher in diabetic patients. The novelty of this study compared with previous procedures lies in the treatment of the urine sample by SALLE based on the addition of acetonitrile and sodium chloride to the urine. The DLLME procedure is performed with a sedimented drop of the extractant solvent, without a surfactant reagent, and using acetonitrile as dispersant solvent. Separation of the analytes was performed using GC-MS detection, being the analytes unequivocal identified. The proposed procedure is the first microextraction method applied to the analysis of urine samples from diabetic and non-diabetic patients that allows a clear differentiation between both groups using a simple analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Metastable Amyloid Phases and their Conversion to Mature Fibrils

    Science.gov (United States)

    Muschol, Martin; Miti, Tatiana; Mulaj, Mentor; Schmit, Jeremy

    Self-assembly of proteins into amyloid fibrils plays a key role in both functional biological responses and pathogenic disorders which include Alzheimer's disease and type II diabetes. Amyloid fibril assembly frequently generates compact oligomeric and curvilinear polymeric intermediates which are implicated to be toxic to cells. Yet, the relation between these early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. Our measurements indicate that lysozyme amyloid oligomers and their curvilinear fibrils only form after crossing a salt and protein concentration dependent threshold. These oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. Our experimental transition boundaries match well with colloidal model predictions accounting for salt-modulated charge repulsion. We also report our preliminary findings on the mechanism by which these metastable oligomeric phases are converted into stable amyloid fibrils.

  13. Metastability in spin polarised Fermi gases and quasiparticle decays

    DEFF Research Database (Denmark)

    Sadeghzadeh, Kayvan; Bruun, Georg; Lobo, Carlos

    2011-01-01

    We investigate the metastability associated with the first order transition from normal to superfluid phases in the phase diagram of two-component polarised Fermi gases.We begin by detailing the dominant decay processes of single quasiparticles.Having determined the momentum thresholds of each...... the interaction strength at which a polarised phase of molecules becomes the groundstate, to the one at which the single quasiparticle groundstate changes character from polaronic to molecular. Our argument in terms of a Fermi sea of polarons naturally suggests their use as an experimental probe. We propose...... experiments to observe the threshold of the predicted region of metastability, the interaction strength at which the quasiparticle groundstate changes character, and the decay rate of polarons....

  14. Stabilizing effect of driving and dissipation on quantum metastable states

    Science.gov (United States)

    Valenti, Davide; Carollo, Angelo; Spagnolo, Bernardo

    2018-04-01

    We investigate how the combined effects of strong Ohmic dissipation and monochromatic driving affect the stability of a quantum system with a metastable state. We find that, by increasing the coupling with the environment, the escape time makes a transition from a regime in which it is substantially controlled by the driving, displaying resonant peaks and dips, to a regime of frequency-independent escape time with a peak followed by a steep falloff. The escape time from the metastable state has a nonmonotonic behavior as a function of the thermal-bath coupling, the temperature, and the frequency of the driving. The quantum noise-enhanced stability phenomenon is observed in the investigated system.

  15. Cooperative photoinduced metastable phase control in strained manganite films

    Science.gov (United States)

    Zhang, Jingdi; Tan, Xuelian; Liu, Mengkun; Teitelbaum, S. W.; Post, K. W.; Jin, Feng; Nelson, K. A.; Basov, D. N.; Wu, Wenbin; Averitt, R. D.

    2016-09-01

    A major challenge in condensed-matter physics is active control of quantum phases. Dynamic control with pulsed electromagnetic fields can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. Here we demonstrate strain-engineered tuning of La2/3Ca1/3MnO3 into an emergent charge-ordered insulating phase with extreme photo-susceptibility, where even a single optical pulse can initiate a transition to a long-lived metastable hidden metallic phase. Comprehensive single-shot pulsed excitation measurements demonstrate that the transition is cooperative and ultrafast, requiring a critical absorbed photon density to activate local charge excitations that mediate magnetic-lattice coupling that, in turn, stabilize the metallic phase. These results reveal that strain engineering can tune emergent functionality towards proximal macroscopic states to enable dynamic ultrafast optical phase switching and control.

  16. Fast production of Bose-Einstein condensates of metastable helium

    Science.gov (United States)

    Bouton, Q.; Chang, R.; Hoendervanger, A. L.; Nogrette, F.; Aspect, A.; Westbrook, C. I.; Clément, D.

    2015-06-01

    We report on the Bose-Einstein condensation of metastable 4He atoms using a hybrid approach, consisting of a magnetic quadrupole and an optical dipole trap. In our setup we cross the phase transition with 2 ×106 atoms, and we obtain pure condensates of 5 ×105 atoms in the optical trap. This approach to cooling 4He provides enhanced cycle stability, large optical access to the atoms and results in the production of a condensate every 6 s—a factor 2 faster than the state of the art. This speed-up will significantly reduce the data acquisition time needed for the measurement of many particle correlations, made possible by the ability of metastable helium atoms to be detected individually.

  17. Dependence of stability of metastable superconductors on copper fraction

    International Nuclear Information System (INIS)

    Elrod, S.A.; Lue, J.W.; Miller, J.R.; Dresner, L.

    1980-12-01

    The stability of composite superconductors operating in the metastable regime depends upon such factors as matrix resistivity, cooled surface dimensions, fraction of critical current, and volume fraction of stabilizer. By assuming constant thermophysical properties, we developed analytic expressions for the energy and voltage of the minimum propagating zone (MPZ). With other factors held constant, these expressions have been used to predict composite superconductor stability as a function of copper fraction: lower copper fractions lead to higher MPZ energies. MPZ voltages have been measured for three NbTi/Cu composites having different copper fractions and different critical current densities for several magnetic fields and transport currents. Experimental MPZ voltages have been used to calculate an effective heat transfer coefficient, which is subsequently used to calculate the MPZ energy. The experimental MPZ energies support the theoretical expectation that lower copper fractions lead to higher stability in the metastable regime

  18. Planktic foraminifera form their shells via metastable carbonate phases.

    Science.gov (United States)

    Jacob, D E; Wirth, R; Agbaje, O B A; Branson, O; Eggins, S M

    2017-11-02

    The calcium carbonate shells of planktic foraminifera provide our most valuable geochemical archive of ocean surface conditions and climate spanning the last 100 million years, and play an important role in the ocean carbon cycle. These shells are preserved in marine sediments as calcite, the stable polymorph of calcium carbonate. Here, we show that shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei originally form from the unstable calcium carbonate polymorph vaterite, implying a non-classical crystallisation pathway involving metastable phases that transform ultimately to calcite. The current understanding of how planktic foraminifer shells record climate, and how they will fare in a future high-CO 2 world is underpinned by analogy to the precipitation and dissolution of inorganic calcite. Our findings require a re-evaluation of this paradigm to consider the formation and transformation of metastable phases, which could exert an influence on the geochemistry and solubility of the biomineral calcite.

  19. Decadal variability and metastability in the Southern Hemisphere

    Science.gov (United States)

    O'Kane, Terence; Risbey, James; Franzke, Christian; Horenko, Illia; Monselesan, Didier

    2014-05-01

    An examination of systematic changes in the metastability of the southern hemisphere 500hPa circulation is performed using both cluster analysis techniques and split flow blocking indices. The cluster methodology is a purely data-driven approach for parametrisation whereby a multi-scale approximation to non-stationary dynamical processes is achieved through optimal sequences of locally stationary fast Vector Auto-Regressive Factor (VARX) processes and some slow (or persistent) hidden process switching between them. Comparison is made with blocking indices commonly used in weather forecasting and climate analysis to identify dynamically relevant metastable regimes in the 500hPa circulation in both reanalysis and AMIP model data sets. Our analysis characterises the metastable regime in both reanalysis and model data sets prior to 1978 as positive and negative phases of a hemispheric mid-latitude blocking state with the Southern Annular Mode (SAM) associated with a transition state. Post 1978, SAM emerges as a true metastable state replacing the negative phase of the hemispheric blocking pattern. The hidden state frequency of occurrences exhibits strong trends. The blocking pattern dominates in the early 1980s then gradually decreases. There is a corresponding increase in the SAM frequency of occurrence. This trend is largely evident in the reanalysis summer and spring but was not evident in the AMIP data set. Non-stationary cluster analysis was then further used to identify the Southern Oceans response to the systematic changes in the mid-latitude atmospheric circulation and identify dynamical regimes associated with subsurface thermocline anomalies which were found to teleconnect the Pacific and Atlantic regions of the Antarctic Circumpolar Current (ACC).

  20. flu, a metastable gene controlling surface properties of Escherichia coli.

    OpenAIRE

    Diderichsen, B

    1980-01-01

    flu, a gene of Escherichia coli K-12, was discovered and mapped between his and shiA. It is shown that flu is a metastable gene that changes frequently between the flu+ and flu states. flu+ variants give stable homogeneous suspensions, are piliated, and form glossy colonies. flu variants aggregate, fluff and sediment from suspensions, are nonpiliated, and form frizzy colonies. flu+ and flu variants can be isolated from most strains. Implications of these observations are discussed, and it is ...