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Sample records for multicomponent liquid mixtures

  1. Uphill diffusion in multicomponent mixtures.

    PubMed

    Krishna, Rajamani

    2015-05-21

    Molecular diffusion is an omnipresent phenomena that is important in a wide variety of contexts in chemical, physical, and biological processes. In the majority of cases, the diffusion process can be adequately described by Fick's law that postulates a linear relationship between the flux of any species and its own concentration gradient. Most commonly, a component diffuses down the concentration gradient. The major objective of this review is to highlight a very wide variety of situations that cause the uphill transport of one constituent in the mixture. Uphill diffusion may occur in multicomponent mixtures in which the diffusion flux of any species is strongly coupled to that of its partner species. Such coupling effects often arise from strong thermodynamic non-idealities. For a quantitative description we need to use chemical potential gradients as driving forces. The transport of ionic species in aqueous solutions is coupled with its partner ions because of the electro-neutrality constraints; such constraints may accelerate or decelerate a specific ion. When uphill diffusion occurs, we observe transient overshoots during equilibration; the equilibration process follows serpentine trajectories in composition space. For mixtures of liquids, alloys, ceramics and glasses the serpentine trajectories could cause entry into meta-stable composition zones; such entry could result in phenomena such as spinodal decomposition, spontaneous emulsification, and the Ouzo effect. For distillation of multicomponent mixtures that form azeotropes, uphill diffusion may allow crossing of distillation boundaries that are normally forbidden. For mixture separations with microporous adsorbents, uphill diffusion can cause supra-equilibrium loadings to be achieved during transient uptake within crystals; this allows the possibility of over-riding adsorption equilibrium for achieving difficult separations.

  2. Method for locating the vapor-liquid critical point of multicomponent fluid mixtures using a shear mode piezoelectric sensor.

    PubMed

    Ke, Jie; King, P J; George, Michael W; Poliakoff, Martyn

    2005-01-01

    A new approach to locating the critical point of fluid mixtures is reported, utilizing a shear mode piezoelectric sensor. This technique employs a single piece of quartz crystal that is installed at the bottom of a strongly stirred high-pressure vessel. The sensor response indicates whether liquid or gas is in contact with its surfaces. Thus, the sensor is able to identify vapor-liquid phase separation by registering a discontinuity in the impedance minimum of the sensor as a function of pressure. Two systems (methanol + CO2 and H2 + CO2) have been investigated using this method. The critical point data of the methanol + CO2 system were chosen to validate the approach against a wealth of literature data, and good agreement was obtained. The sensor behavior in the two-phase region, as well as the effect of stirring, is discussed. The method is general and can be used with other sensors.

  3. Development and validation of chemometrics-assisted spectrophotometry and liquid chromatography methods for the simultaneous determination of the active ingredients in two multicomponent mixtures containing chlorpheniramine maleate and phenylpropanolamine hydrochloride.

    PubMed

    Hadad, Ghada M; El-Gindy, Alaa; Mahmoud, Waleed M M

    2007-01-01

    Multivariate spectrophotometric calibration and liquid chromatography (LC) methods were used for the simultaneous determination of the active ingredients in 2 multicomponent mixtures containing chlorpheniramine maleate and phenylpropanolamine hydrochloride with ibuprofen and caffeine (mixture 1) or with propyphenazone (mixture 2). For the multivariate spectrophotometric calibration methods, principal component regression (PCR) and partial least squares (PLS-1), a calibration set of the mixtures consisting of the components of each mixture was prepared in distilled water. A leave-1-out cross-validation procedure was used to find the optimum numbers of latent variables. Analytical parameters such as sensitivity, selectivity, analytical sensitivity, limit of quantitation, and limit of detection were determined for both PLS-1 and PCR. The LC method depends on the use of a cyanopropyl column with the mobile phase acetonitrile-12 mM ammonium acetate, pH 5.0 (25 + 75, v/v), for mixture 1 or acetonitrile-10 mM potassium dihydrogen phosphate, pH 4.7 (45 + 55, v/v), for mixture 2; the UV detector was set at 212 nm. In spite of the presence of a high degree of spectral overlap of these components, they were rapidly and simultaneously determined with high accuracy and precision, with no interference from the matrix excipients. The proposed methods were successfully applied to the analysis of pharmaceutical formulations and laboratory-prepared mixtures containing the 2 multicomponent combinations.

  4. Multicomponent liquid ion exchange with chabazite zeolites

    SciTech Connect

    Robinson, S.M.; Arnold, W.D. Jr.; Byers, C.W.

    1993-10-01

    In spite of the increasing commercial use of zeolites for binary and multicomponent sorption, the understanding of the basic mass-transfer processes associated with multicomponent zeolite ion-exchange systems is quite limited. This study was undertaken to evaluate Na-Ca-Mg-Cs-Sr ion exchange from an aqueous solution using a chabazite zeolite. Mass-transfer coefficients and equilibrium equations were determined from experimental batch-reactor data for single and multicomponent systems. The Langmuir isotherm was used to represent the equilibrium relationship for binary systems, and a modified Dubinin-Polyani model was used for the multicomponent systems. The experimental data indicate that diffusion through the microporous zeolite crystals is the primary diffusional resistance. Macropore diffusion also significantly contributes to the mass-transfer resistance. Various mass-transfer models were compared to the experimental data to determine mass-transfer coefficients. Effective diffusivities were obtained which accurately predicted experimental data using a variety of models. Only the model which accounts for micropore and macropore diffusion occurring in series accurately predicted multicomponent data using single-component diffusivities. Liquid and surface diffusion both contribute to macropore diffusion. Surface and micropore diffusivities were determined to be concentration dependent.

  5. Liquid-liquid equilibria for ternary polymer mixtures

    NASA Astrophysics Data System (ADS)

    Oh, Suk Yung; Bae, Young Chan

    2011-01-01

    A molecular thermodynamic model for multicomponent systems based on a closed-packed lattice model is presented based on two contributions; entropy and energy contribution. The calculated liquid-liquid equilibria of ternary chainlike mixtures agreed with Monte Carlo simulation results. The proposed model can satisfactorily predict Types 0, 1, 2 and 3 phase separations of the Treybal classification. The model parameters obtained from the binary systems were used to directly predict real ternary systems and the calculated results correlated well with experimental data using few adjustable parameters. Specific interactions in associated binary systems were considered using a secondary lattice.

  6. Multicomponent Diffusion of Penetrant Mixtures in Rubbery Polymers: A Molecular Dynamics Study

    NASA Astrophysics Data System (ADS)

    Bringuier, Stefan; Varady, Mark; Knox, Craig; Cabalo, Jerry; Pearl, Thomas; Mantooth, Brent

    The importance of understanding transport of chemical species across liquid-solid boundaries is of particular interest in the decontamination of harmful chemicals absorbed within polymeric materials. To characterize processes associated with liquid-phase extraction of absorbed species from polymers, it is necessary to determine an appropriate physical description of species transport in multicomponent systems. The Maxwell-Stefan (M-S) formulation is a rigorous description of mass transport in multicomponent solutions, in which, mutual diffusivities determine the degree of relative motion between interacting molecules in response to a chemical potential gradient. The work presented focuses on the determination of M-S diffusivities from molecular dynamics (MD) simulations of nerve agent O-ethyl S-[2(diisopropylamino)ethyl] methylphosphonothioate (VX), water, and methanol mixtures within a poly(dimethylsiloxane) matrix. We investigate the composition dependence of M-S diffusivities and compare the results to values predicted using empirical relations for binary and ternary mixtures. Finally, we highlight the pertinent differences in molecular mechanisms associated with species transport and employ non-equilibrium MD to probe transport across the mixture-polymer interface.

  7. Isentropic Compression of Multicomponent Mixtures of Fuels and Inert Gases

    NASA Technical Reports Server (NTRS)

    Barragan, Michelle; Julien, Howard L.; Woods, Stephen S.; Wilson, D. Bruce; Saulsberry, Regor L.

    2000-01-01

    In selected aerospace applications of the fuels hydrazine and monomethythydrazine, there occur conditions which can result in the isentropic compression of a multicomponent mixture of fuel and inert gas. One such example is when a driver gas such as helium comes out of solution and mixes with the fuel vapor, which is being compressed. A second example is when product gas from an energetic device mixes with the fuel vapor which is being compressed. Thermodynamic analysis has shown that under isentropic compression, the fuels hydrazine and monomethylhydrazine must be treated as real fluids using appropriate equations of state. The appropriate equations of state are the Peng-Robinson equation of state for hydrazine and the Redlich-Kwong-Soave equation of state for monomethylhydrazine. The addition of an inert gas of variable quantity and input temperature and pressure to the fuel compounds the problem for safety design or analysis. This work provides the appropriate thermodynamic analysis of isentropic compression of the two examples cited. In addition to an entropy balance describing the change of state, an enthalpy balance is required. The presence of multicomponents in the system requires that appropriate mixing rules are identified and applied to the analysis. This analysis is not currently available.

  8. Dissolution, Cyclodextrin-Enhanced Solubilization, and Mass Removal of an Ideal Multicomponent Organic Liquid

    PubMed Central

    Carroll, Kenneth C.; Brusseau, Mark L.

    2010-01-01

    Laboratory experiments and mathematical modeling were conducted to examine the influence of a hydroxypropyl-beta-cyclodextrin (HPCD) solution on the dissolution of single- and three-component organic liquids. The results of batch experiments showed that HPCD-enhanced solubilization of the organic-liquid mixtures was ideal (describable using Raoult’s Law), and that solubilization-enhancement factors were independent of mixture composition. Addition of the HPCD solution to columns containing residual saturations of the organic liquid enhanced the dissolution and removal of all three compounds in the mixture. The results of the column experiments and multicomponent rate-limited dissolution modeling suggest that solubilization was ideal for both water and cyclodextrin flushing. Concomitantly, the mass-flux reduction versus mass removal behavior was ideal for all experiments. Mass transfer was increased for HPCD solubilization relative to the water flushing due to solubility and concentration-gradient enhancement. Organic-liquid composition did not significantly impact mass transfer coefficients, and fractional mass removal behavior during HPCD solubilization was nearly identical for each compound whether present as a single component or in a mixture. Additionally, mass transfer coefficients for aqueous and HPCD solubilization for single and multicomponent mixtures were not statistically different upon normalizing by the solubility enhancement factor. PMID:19233508

  9. Uphill diffusion and phase separation in partially miscible multicomponent mixtures

    NASA Astrophysics Data System (ADS)

    He, Ping; Raghavan, Ashwin; Ghoniem, Ahmed

    2015-11-01

    The partially miscible multicomponent mixtures, which are frequently encountered in green chemistry processes, often exhibit complicated behaviors, and are critical to the production rate, energy efficiency, and pollution controls. Recent studies have been mainly focused on phase behaviors. However, the coupled phase equilibrium and transport process, which may be the answer to phase separations observed in experiments, is not well researched. Here, we present a numerical and theoretical study on coupled mixing of heavy oil and supercritical water, and the results of our state-of-art modeling agree with experimental measurements. We find that due to the non-ideal diffusion driving force, (1) strong uphill diffusion of heavy oil fractions occurs, (2) a new heavy oil phase is separated starting from the plait point, and heavy fractions become highly concentrated, and (3) water diffusion initially overshoots in oil, and is expelled lately. Finally, we conclude our analysis applicable to different molecules and conditions. The authors thank Saudi Aramco for supporting this work (contract number 6600023444).

  10. Phase-field theory of multicomponent incompressible Cahn-Hilliard liquids

    NASA Astrophysics Data System (ADS)

    Tóth, Gyula I.; Zarifi, Mojdeh; Kvamme, Bjørn

    2016-01-01

    In this paper, a generalization of the Cahn-Hilliard theory of binary liquids is presented for multicomponent incompressible liquid mixtures. First, a thermodynamically consistent convection-diffusion-type dynamics is derived on the basis of the Lagrange multiplier formalism. Next, a generalization of the binary Cahn-Hilliard free-energy functional is presented for an arbitrary number of components, offering the utilization of independent pairwise equilibrium interfacial properties. We show that the equilibrium two-component interfaces minimize the functional, and we demonstrate that the energy penalization for multicomponent states increases strictly monotonously as a function of the number of components being present. We validate the model via equilibrium contact angle calculations in ternary and quaternary (four-component) systems. Simulations addressing liquid-flow-assisted spinodal decomposition in these systems are also presented.

  11. Influence factors of multicomponent mixtures containing reactive chemicals and their joint effects.

    PubMed

    Tian, Dayong; Lin, Zhifen; Yu, Jianqiao; Yin, Daqiang

    2012-08-01

    Organic chemicals usually coexist as a mixture in the environment, and the mixture toxicity of organic chemicals has received increased attention. However, research regarding the joint effects of reactive chemicals is lacking. In this study, we examined two kinds of reactive chemicals, cyanogenic toxicants and aldehydes and determined their joint effects on Photobacterium phosphoreum. Three factors were found to influence the joint effects of multicomponent mixtures containing reactive chemicals, including the number of components, the dominating components and the toxic ratios. With an increased number of components, the synergistic or antagonistic effects (interactions) will weaken to the additive effects (non-interactions) if the added component cannot yield a much stronger joint effect with an existing component. Contrarily, the joint effect of the mixture may become stronger instead of weaker if the added components can yield a much stronger joint effect than the existing joint effect of the multicomponent mixture. The components that yield the strongest interactions in their binary mixture can be considered the dominating components. These components contribute more to the interactions of multicomponent mixtures than other components. Moreover, the toxic ratios also influence the joint effects of the mixtures. This study provides an insight into what are the main factors and how they influence the joint effects of multicomponent mixtures containing reactive chemicals, and thus, the findings are beneficial to the study of mixture toxicology.

  12. One- and multi-component theories of mixtures

    SciTech Connect

    Ree, F.H.

    1993-07-01

    We describe one-component statistical mechanical theories and van der Waal`s effective one-component mixture model. We then show how to apply them to mixtures (containing CO{sub 2}) to extract reliable unlike-pair potential involving CO{sub 2} molecules as well as their dissociation products. A more fundamental approach will require the development of a perturbation or variational theory of mixtures based on a non-additive hard-sphere mixture reference system. Recent progresses made in this direction by means of an integral equation and computer simulations is described.

  13. Rayleigh-Benard instability in multicomponent mixtures with the Soret effect

    NASA Astrophysics Data System (ADS)

    Ryzhkov, Ilya

    2011-11-01

    Convection in multicomponent mixtures can show a variety of flow patterns due to several heat and mass transfer mechanisms: convection, heat conduction, main and cross diffusion, and the Soret effect. Convective stability of multicomponent fluids has not been widely investigated so far. The use of simplifying assumptions (e.g. the absence of cross-diffusion) may lead to the disagreement between theory and experiment. We study the stability of a plane multicomponent fluid layer heated from above/below in gravity field. In the basic state, the fluid is at rest and temperature gradient induces concentration gradients due to the Soret effect. The problem is reduced to that without cross-diffusion and Soret effect by a special transformation. Several types of boundary conditions are considered: 1) free, permeable 2) rigid, permeable 3) rigid, impermeable. The theorems, which generalize the exchange of stability principle to multicomponent fluids, are proved for boundary conditions 1 and 2. An explicit formula for critical Rayleigh numbers is obtained for boundary conditions 1. The stability problem for boundary conditions 3 was solved numerically for a ternary mixture. The stability maps are constructed in a wide range of parameters. The work is supported by the Interdisciplinary project of SB RAS N 116 and Krasnoyarsk Science Foundation.

  14. Liquid class predictor for liquid handling of complex mixtures

    SciTech Connect

    Seglke, Brent W.; Lekin, Timothy P.

    2008-12-09

    A method of establishing liquid classes of complex mixtures for liquid handling equipment. The mixtures are composed of components and the equipment has equipment parameters. The first step comprises preparing a response curve for the components. The next step comprises using the response curve to prepare a response indicator for the mixtures. The next step comprises deriving a model that relates the components and the mixtures to establish the liquid classes.

  15. Water uptake of multicomponent organic mixtures and their influence on hygroscopicity of inorganic salts.

    PubMed

    Wang, Yuanyuan; Jing, Bo; Guo, Yucong; Li, Junling; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

    2016-07-01

    The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds (WSOCs) and their effects on ammonium sulfate (AS) and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA) in the relative humidity (RH) range of 5%-90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM) and Zdanovskii-Stokes-Robinson (ZSR) method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles. When organic content was dominant in the mixture (75%), the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles.

  16. Bonding and structure in dense multi-component molecular mixtures

    SciTech Connect

    Meyer, Edmund R.; Ticknor, Christopher; Bethkenhagen, Mandy; Hamel, Sebastien; Redmer, Ronald; Kress, Joel D.; Collins, Lee A.

    2015-10-30

    We have performed finite-temperature density functional theory molecular dynamics simulations on dense methane, ammonia, and water mixtures (CH4:NH3:H2O) for various compositions and temperatures (2000 K ≤ T ≤ 10000 K) that span a set of possible conditions in the interiors of ice-giant exoplanets. The equation-of-state, pair distribution functions, and bond autocorrelation functions (BACF) were used to probe the structure and dynamics of these complex fluids. In particular, an improvement to the choice of the cutoff in the BACF was developed that allowed analysis refinements for density and temperature effects. We note the relative changes in the nature of these systems engendered by variations in the concentration ratios. As a result, a basic tenet emerges from all these comparisons that varying the relative amounts of the three heavy components (C,N,O) can effect considerable changes in the nature of the fluid and may in turn have ramifications for the structure and composition of various planetary layers.

  17. Bonding and structure in dense multi-component molecular mixtures

    DOE PAGES

    Meyer, Edmund R.; Ticknor, Christopher; Bethkenhagen, Mandy; ...

    2015-10-30

    We have performed finite-temperature density functional theory molecular dynamics simulations on dense methane, ammonia, and water mixtures (CH4:NH3:H2O) for various compositions and temperatures (2000 K ≤ T ≤ 10000 K) that span a set of possible conditions in the interiors of ice-giant exoplanets. The equation-of-state, pair distribution functions, and bond autocorrelation functions (BACF) were used to probe the structure and dynamics of these complex fluids. In particular, an improvement to the choice of the cutoff in the BACF was developed that allowed analysis refinements for density and temperature effects. We note the relative changes in the nature of these systemsmore » engendered by variations in the concentration ratios. As a result, a basic tenet emerges from all these comparisons that varying the relative amounts of the three heavy components (C,N,O) can effect considerable changes in the nature of the fluid and may in turn have ramifications for the structure and composition of various planetary layers.« less

  18. Thermodynamics of Multicomponent PAH Mixtures and Development of Tar-Like Behavior

    PubMed Central

    Rice, James W.; Fu, Jinxia; Suuberg, Eric M.

    2011-01-01

    This study explores the solid/liquid phase behavior of mixtures of polycyclic aromatic hydrocarbons (PAHs), exploring the transition from non-ideal solid mixtures to a relatively ideal liquid behavior characteristic of “tars”. PAH mixtures have been studied using differential scanning calorimetry, melting point analysis and Knudsen effusion. Mixtures of anthracene, pyrene and fluoranthene show behavior that is consistent with other binary PAH mixtures; that is, the initially solid mixture exhibits a significant melting point depression, relative to the pure components, and in a certain range of composition, solid azeotrope behavior on vaporization. As the number of distinct PAH species is increased (by adding in benzo[a]pyrene, phenanthrene, fluorene and chrysene) this behavior gradually gives way to liquid phase character at even room temperature, and the vaporization behavior approaches that crudely predictable from ideal mixture theory. PMID:21442010

  19. Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

    NASA Technical Reports Server (NTRS)

    Thompson, W. Reid; Calado, Jorge C. G.; Zollweg, John A.

    1990-01-01

    Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar.

  20. On the separation of multicomponent mixtures in a cylindrical thermogravitational column

    NASA Astrophysics Data System (ADS)

    Kozlova, Sofia V.; Ryzhkov, Ilya I.

    2016-11-01

    This work studies the stationary separation of a multicomponent mixture in a thermogravitational column (TGC). The existing theory for a flat-plate column is extended to the case of a cylindrical column. The equations of motion and heat/mass transfer are written in cylindrical coordinates to take into account the impact of the cylinders curvature and the ratio of their radii on the separation process. To characterize the impact of each component on convective motion induced by thermal diffusion, the dimensionless separation ratios are used. A multicomponent system as a whole is described by the net separation ratio. The approximation neglecting vertical diffusion in the column is employed and conditions for its validity are analyzed. The profiles of velocity, temperature, composition, and density in the column with a multicomponent mixture are found and their dependence on the separation ratios and the ratio of cylinders radii is analyzed. The vertical separation is described by the solutal Rayleigh numbers, which are proportional to the vertical concentration gradients. It is shown that the key relation of TGC theory, which relates the net solutal Rayleigh number to the net separation ratio, essentially depends on the ratio of cylinders radii. The working formulas for the thermal diffusion coefficients are derived and the importance of forgotten effect is discussed. It is found that the vertical separation in the column increases with decreasing the ratio of inner and outer cylinders radii. A detailed comparison of results with the case of a flat-plate column is performed. Example of a ternary hydrocarbon mixture is analyzed on the basis of obtained solution and numerical simulation.

  1. Analysis of aromatic constituents in multicomponent hydrocarbon mixtures by infrared spectroscopy using multiple linear regression

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.; Muradov, V. G.

    2012-09-01

    Absorption spectra of multicomponent hydrocarbon mixtures based on n-heptane and isooctane with addition of benzene (up to 1%) and toluene and o-xylene (up to 20%) were investigated experimentally in the region of the first overtones of the hydrocarbon groups (λ = 1620-1780 nm). It was shown that their concentrations could be determined separately by using a multiple linear regression method. The optimum result was obtained by including four wavelengths at 1671, 1680, 1685, and 1695 nm, which took into account absorption of CH groups in benzene, toluene, and o-xylene and CH3 groups, respectively.

  2. Flash evaporation of liquid monomer particle mixture

    DOEpatents

    Affinito, J.D.; Darab, J.G.; Gross, M.E.

    1999-05-11

    The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer. 3 figs.

  3. Flash evaporation of liquid monomer particle mixture

    DOEpatents

    Affinito, John D.; Darab, John G.; Gross, Mark E.

    1999-01-01

    The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer.

  4. Rate Limited Diffusion and Dissolution of Multicomponent Nonaqueous Phase Liquids (NAPLs) and Effects on Mass Discharge in Groundwater

    NASA Astrophysics Data System (ADS)

    Padgett, M.; Tick, G.; Carroll, K. C.

    2014-12-01

    Remediation efforts and contaminant transport predictions generally neglect the complicated dissolution and transport behavior associated with multicomponent NAPL (Non-aqueous phase liquid) sources. Therefore, it is important to understand the diffusion and dissolution processes occurring in these multicomponent systems as a function of mole fraction, molecular similarity/dissimilarity, hydraulic, or nonideal factors. A series of laboratory scale NAPL-aqueous phase dissolution experiments were conducted to assess dissolution and intra-NAPL diffusion as a function of multicomponent NAPL composition (i.e. mole fraction) for both trichloroethene and toluene. These target compounds were selected as representative contaminants as they are commonly components of NAPL mixtures and they define both classes of NAPL (dense-DNAPL and light-LNAPL). Predetermined volumes of target NAPL were mixed with an insoluble n-hexadecane NAPL to create mixtures that vary by NAPL composition. The ideality of resulting target compound dissolution was evaluated by quantifying NAPL-phase activity coefficient through Raoult's Law analysis. The results show that dissolution from the NAPL mixtures behave ideally for mole fractions above 0.2. As the target compound fraction of the NAPL mixture get smaller, the dissolution behavior becomes increasingly more nonideal (i.e. greater NAPL-phase activity coefficients). Overall, the time-series batch experiments show that dissolution rates were consistent for various mole fraction ratios, indicating that intra-NAPL diffusion is not the rate-limiting control over aqueous concentrations or is not significantly controlled by NAPL composition-dependent factors. The results of this work will improve transport predictions, remediation design, and risk assessments especially for sites contaminated by complex NAPL mixtures.

  5. Nonlinear ultrasonic nature of organic liquid and organic liquid mixture.

    PubMed

    Lu, Yi-gang; Zhang, Yang; Dong, Yan-wu

    2006-12-22

    Based on Jacobson's molecular free length theory in liquids and the relationship between ultrasonic velocity and the molecular free length in organic liquids, this paper deduces the equations for pressure coefficient and temperature coefficient of ultrasonic velocity and nonlinear acoustic parameter B/A in both of organic liquid and organic liquid binary mixtures. These nonlinear acoustic parameters are evaluated against the measured results and data from other sources. The equations reveal the connections between the nonlinear acoustic parameters and some internal structural of the medium or mixtures e.g. the sizes of molecule, several thermodynamic physical parameters and outside status e.g. condition of pressure and temperature of the liquid or liquid mixture. With the equations the nonlinear acoustic parameter B/A of organic liquid binary mixtures, which is impossible to know without the nonlinear acoustic parameter B/A of the tow components before, can be calculated based on the structural and physical parameters of organic liquid and organic liquid binary mixtures.

  6. IDENTIFICATION AND EXPERIMENTAL DATABASE FOR BINARY AND MULTICOMPONENT MIXTURES WITH POTENTIAL FOR INCREASING OVERALL CYCLE EFFICIENCY

    SciTech Connect

    Stephen M Bajorek; J. Schnelle

    2002-05-01

    This report describes an experimental investigation designed to identify binary and multicomponent mixture systems that may be for increasing the overall efficiency of a coal fired unit by extracting heat from flue gases. While ammonia-water mixtures have shown promise for increasing cycle efficiencies in a Kalina cycle, the costs and associated range of thermal conditions involved in a heat recovery system may prohibit its use in a relatively low temperature heat recovery system. This investigation considered commercially available non-azeotropic binary mixtures with a boiling range applicable to a flue gas initially at 477.6 K (400 F) and developed an experimental database of boiling heat transfer coefficients for those mixtures. In addition to their potential as working fluids for increasing cycle efficiency, cost, ease of handling, toxicity, and environmental concerns were considered in selection of the mixture systems to be examined experimentally. Based on this review, water-glycol systems were identified as good candidates. However, previous investigations of mixture boiling have focused on aqueous hydrocarbon mixtures, where water is the heaviest component. There have been few studies of water-glycol systems, and those that do exist have investigated boiling on plain surfaces only. In water-glycol systems, water is the light component, which makes these systems unique compared to those that have been previously examined. This report examines several water-glycol systems, and documents a database of experimental heat transfer coefficients for these systems. In addition, this investigation also examines the effect of an enhanced surface on pool boiling in water-glycol mixtures, by comparing boiling on a smooth surface to boiling on a Turbo IIIB. The experimental apparatus, test sections, and the experimental procedures are described. The mixture systems tested included water-propylene glycol, water-ethylene glycol, and water-diethylene glycol. All

  7. Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Jing, B.; Tong, S. R.; Liu, Q. F.; Li, K.; Wang, W. G.; Zhang, Y. H.; Ge, M. F.

    2015-08-01

    Water soluble organic compounds (WSOCs) are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, water uptake behavior of internally mixed WSOC aerosols remains limited characterization. Here, the hygroscopic properties of single component such as levoglucosan, oxalic acid, malonic acid, succinic acid and phthalic acid and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA). The coexisting hygroscopic species including levoglucosan, malonic acid and phthalic acid have strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppress its crystallization completely. The interactions between oxalic acid and levoglucosan are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM) with UNIFAC method and Zdanovskii-Stokes-Robinson (ZSR) approach increase at medium and high relative humidity (RH) assuming oxalic acid in a solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH due to positive chemical interactions between solutes. Organic mixture has more complex effect on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan accounts for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake under high RH conditions and thus affect the cloud condensation nuclei (CCN) activity, optical properties and chemical reactivity of atmospheric particles.

  8. Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Jing, Bo; Tong, Shengrui; Liu, Qifan; Li, Kun; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

    2016-03-01

    Water-soluble organic compounds (WSOCs) are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, knowledge on the water uptake behavior of internally mixed WSOC aerosols remains limited. Here, the hygroscopic properties of single components such as levoglucosan, oxalic acid, malonic acid, succinic acid, phthalic acid, and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA). The coexisting hygroscopic species including levoglucosan, malonic acid, and phthalic acid have a strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppressing its crystallization completely during the drying process. The phase behaviors of oxalic acid/levoglucosan mixed particles are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM) with the Universal Quasi-Chemical Functional Group Activity Coefficient (UNIFAC) method and Zdanovskii-Stokes-Robinson (ZSR) approach increase at medium and high relative humidity (RH) assuming oxalic acid in a crystalline solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH compared to the model predictions based on reasonable oxalic acid phase assumption. Organic mixture has more complex effects on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan account for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing the phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake

  9. Sedimentation dynamics and equilibrium profiles in multicomponent mixtures of colloidal particles.

    PubMed

    Spruijt, E; Biesheuvel, P M

    2014-02-19

    In this paper we give a general theoretical framework that describes the sedimentation of multicomponent mixtures of particles with sizes ranging from molecules to macroscopic bodies. Both equilibrium sedimentation profiles and the dynamic process of settling, or its converse, creaming, are modeled. Equilibrium profiles are found to be in perfect agreement with experiments. Our model reconciles two apparently contradicting points of view about buoyancy, thereby resolving a long-lived paradox about the correct choice of the buoyant density. On the one hand, the buoyancy force follows necessarily from the suspension density, as it relates to the hydrostatic pressure gradient. On the other hand, sedimentation profiles of colloidal suspensions can be calculated directly using the fluid density as apparent buoyant density in colloidal systems in sedimentation-diffusion equilibrium (SDE) as a result of balancing gravitational and thermodynamic forces. Surprisingly, this balance also holds in multicomponent mixtures. This analysis resolves the ongoing debate of the correct choice of buoyant density (fluid or suspension): both approaches can be used in their own domain. We present calculations of equilibrium sedimentation profiles and dynamic sedimentation that show the consequences of these insights. In bidisperse mixtures of colloids, particles with a lower mass density than the homogeneous suspension will first cream and then settle, whereas particles with a suspension-matched mass density form transient, bimodal particle distributions during sedimentation, which disappear when equilibrium is reached. In all these cases, the centers of the distributions of the particles with the lowest mass density of the two, regardless of their actual mass, will be located in equilibrium above the so-called isopycnic point, a natural consequence of their hard-sphere interactions. We include these interactions using the Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equation of

  10. Quantitative NIR Raman analysis in liquid mixtures.

    PubMed

    Sato-Berrú, R Ysacc; Medina-Valtierra, Jorge; Medina-Gutiérrez, Cirilo; Frausto-Reyes, Claudio

    2004-08-01

    The capability to obtain quantitative information of a simple way from Raman spectra is a subject of considerable interest. In this work, this is demonstrated for mixtures of ethanol with water and rhodamine-6G (R-6G) with methanol, which were analyzed directly in glass vessel. The Raman intensities and a simple mathematical model have been used and applied for the analysis of liquid samples. It is starting point to generate a general expression, from the experimental spectra, as the sum of the particular expression for each pure compound allow us to obtain an expression for the mixtures which can be used for determining concentrations, from the Raman spectrum, of the mixture.

  11. Evaporation of Liquid Hydrocarbon Mixtures on Titan

    NASA Astrophysics Data System (ADS)

    Luspay-Kuti, Adrienn; Chevrier, V. F.; Rivera-Valentin, E. G.; Singh, S.; Roe, L. A.; Wagner, A.

    2013-10-01

    Besides Earth, Titan is the only other known planetary body with proven stable liquids on its surface. The hydrological cycle of these liquid hydrocarbon mixtures is critical in understanding Titan’s atmosphere and surface features. Evaporation of liquid surface bodies has been indirectly observed as shoreline changes from measurements by Cassini ISS and RADAR (Hayes et al. 2011, Icarus 211, 655-671; Turtle et al. 2011, Science 18, 1414-1417.), but the long seasons of Saturn strongly limit the time span of these observations and their validity over the course of an entire Titan year. Using a novel Titan simulation chamber, the evaporation rate of liquid methane and dissolved nitrogen mixture under Titan surface conditions was derived (Luspay-Kuti et al. 2012, GRL 39, L23203), which is especially applicable to low latitude transient liquids. Polar lakes, though, are expected to be composed of a variety of hydrocarbons, primarily a mixture of ethane and methane (e.g. Cordier et al. 2009, ApJL 707, L128-L131). Here we performed laboratory simulations of ethane-methane mixtures with varying mole fraction under conditions suitable for the polar regions of Titan. We will discuss results specifically addressing the evaporation behavior as the solution becomes increasingly ethane dominated, providing quantitative values for the evaporation rate at every step. These laboratory results are relevant to polar lakes, such as Ontario Lacus, and can shed light on their stability.

  12. Emergence of life from multicomponent mixtures of chemicals: the case for experiments with cycling physicochemical gradients.

    PubMed

    Spitzer, Jan

    2013-04-01

    The emergence of life from planetary multicomponent mixtures of chemicals is arguably the most complicated and least understood natural phenomenon. The fact that living cells are non-equilibrium systems suggests that life can emerge only from non-equilibrium chemical systems. From an astrobiological standpoint, non-equilibrium chemical systems arise naturally when solar irradiation strikes rotating surfaces of habitable planets: the resulting cycling physicochemical gradients persistently drive planetary chemistries toward "embryonic" living systems and an eventual emergence of life. To better understand the factors that lead to the emergence of life, I argue for cycling non-equilibrium experiments with multicomponent chemical systems designed to represent the evolving chemistry of Hadean Earth ("prebiotic soups"). Specifically, I suggest experimentation with chemical engineering simulators of Hadean Earth to observe and analyze (i) the appearances and phase separations of surface active and polymeric materials as precursors of the first "cell envelopes" (membranes) and (ii) the accumulations, commingling, and co-reactivity of chemicals from atmospheric, oceanic, and terrestrial locations.

  13. Discrete velocity models for multicomponent mixtures and polyatomic molecules without nonphysical collision invariants and shock profiles

    NASA Astrophysics Data System (ADS)

    Bernhoff, Niclas

    2016-11-01

    An important aspect of constructing discrete velocity models (DVMs) for the Boltzmann equation is to obtain the right number of collision invariants. It is a well-known fact that, in difference to in the continuous case, DVMs can have extra collision invariants, so called spurious collision invariants, in plus to the physical ones. A DVM with only physical collision invariants, and so without spurious ones, is called normal. The construction of such normal DVMs has been studied a lot in the literature for single species as well as for binary mixtures. For binary mixtures also the concept of supernormal DVMs has been introduced by Bobylev and Vinerean. Supernormal DVMs are defined as normal DVMs such that both restrictions to the different species are normal as DVMs for single species. In this presentation we extend the concept of supernormal DVMs to the case of multicomponent mixtures and introduce it for polyatomic molecules. By polyatomic molecules we mean here that each molecule has one of a finite number of different internal energies, which can change, or not, during a collision. We will present some general algorithms for constructing such models, but also give some concrete examples of such constructions. The two different approaches above can be combined to obtain multicomponent mixtures with a finite number of different internal energies, and then be extended in a natural way to chemical reactions. The DVMs are constructed in such a way that we for the shock-wave problem obtain similar structures as for the classical discrete Boltzmann equation (DBE) for one species, and therefore will be able to apply previously obtained results for the DBE. In fact the DBE becomes a system of ordinary differential equations (dynamical system) and the shock profiles can be seen as heteroclinic orbits connecting two singular points (Maxwellians). The previous results for the DBE then give us the existence of shock profiles for shock speeds close to a typical speed

  14. The Godunov Method for Calculating Multidimensional Flows of a One-Velocity Multicomponent Mixture

    NASA Astrophysics Data System (ADS)

    Surov, V. S.

    2016-09-01

    Computational formulas of the Godunov method are given for the equations of a generalized-equilibrium model of a heterogeneous medium on a curvilinear grid; with the use of this method, the problems of interaction of air shock waves with bubbles of various gases are investigated. Flow of a gas-liquid mixture in a nozzle mouthpiece is considered. The Prandtl-Meyer flow of a water-air mixture is calculated and compared with a self-similar solution.

  15. Loss of thermodynamic work at the cascade stages during the separation of a multicomponent mixture of ideal gases

    NASA Astrophysics Data System (ADS)

    Chizhkov, V. P.; Boitsov, V. N.

    2016-01-01

    Formulas for estimating the thermodynamic work during the separation of components of binary and multicomponent mixtures are discussed and generalized. The difference between the work of separation determined from the separation potential and the thermodynamically estimated work during the isobaric-isothermal mixing of fractions separated at the ends of a cascade is calculated and explained.

  16. The New TLC Method for Separation and Determination of Multicomponent Mixtures of Plant Extracts

    PubMed Central

    Matysik, Elżbieta; Woźniak, Anna; Paduch, Roman; Rejdak, Robert; Polak, Beata; Donica, Helena

    2016-01-01

    The new mode of two-dimensional gradient thin layer chromatography (MGD-2D TLC) has been presented. Short distance development of sample in the first dimension leads to formation of the preconcentrated narrow zones. They are consecutively separated in the second dimension with the mobile phase gradient in several steps of development until the eluent reaches the further end of the chromatographic plate. The use of the above-mentioned technique allows isolating and then identifying the compounds of various polarity from the multicomponent mixture. The practical application of two-dimensional gradient thin layer chromatography has been performed for isolation of the two plant (Juniperus and Thymus) oils components as the examples of test mixtures. The experiments have been carried out with the use of silica gel plates as well as a normal phase condition. The results of solute separation with isocratic one-dimensional thin layer chromatography system have been compared with those of two-dimensional gradient system. It has been observed that application of the latter mode leads to almost triplicated number of zones in comparison with the former one. It is purposeful to apply the proposed mode to control the purity of the dominant component or components of the mixture. PMID:26981317

  17. Efficient Discovery of Novel Multicomponent Mixtures for Hydrogen Storage: A Combined Computational/Experimental Approach

    SciTech Connect

    Wolverton, Christopher; Ozolins, Vidvuds; Kung, Harold H.; Yang, Jun; Hwang, Sonjong; Shore, Sheldon

    2016-11-28

    The objective of the proposed program is to discover novel mixed hydrides for hydrogen storage, which enable the DOE 2010 system-level goals. Our goal is to find a material that desorbs 8.5 wt.% H2 or more at temperatures below 85°C. The research program will combine first-principles calculations of reaction thermodynamics and kinetics with material and catalyst synthesis, testing, and characterization. We will combine materials from distinct categories (e.g., chemical and complex hydrides) to form novel multicomponent reactions. Systems to be studied include mixtures of complex hydrides and chemical hydrides [e.g. LiNH2+NH3BH3] and nitrogen-hydrogen based borohydrides [e.g. Al(BH4)3(NH3)3]. The 2010 and 2015 FreedomCAR/DOE targets for hydrogen storage systems are very challenging, and cannot be met with existing materials. The vast majority of the work to date has delineated materials into various classes, e.g., complex and metal hydrides, chemical hydrides, and sorbents. However, very recent studies indicate that mixtures of storage materials, particularly mixtures between various classes, hold promise to achieve technological attributes that materials within an individual class cannot reach. Our project involves a systematic, rational approach to designing novel multicomponent mixtures of materials with fast hydrogenation/dehydrogenation kinetics and favorable thermodynamics using a combination of state-of-the-art scientific computing and experimentation. We will use the accurate predictive power of first-principles modeling to understand the thermodynamic and microscopic kinetic processes involved in hydrogen release and uptake and to design new material/catalyst systems with improved properties. Detailed characterization and atomic-scale catalysis experiments will elucidate the effect of dopants and nanoscale catalysts in achieving fast kinetics and reversibility. And

  18. UV sensors based on liquid crystals mixtures

    NASA Astrophysics Data System (ADS)

    Chanishvili, Andro; Petriashvili, Gia; Chilaya, Guram; Barberi, Riccardo; De Santo, Maria P.; Matranga, Mario A.; Ciuchi, F.

    2006-04-01

    The Erythemal Response Spectrum is a scientific expression that describes the sensitivity of the skin to the ultraviolet radiation. The skin sensitivity strongly depends on the UV wavelength: a long exposition to UV radiation causes erythema once a threshold dose has been exceeded. In the past years several devices have been developed in order to monitor the UV exposure, most of them are based on inorganic materials that are able to mimic the human skin behaviour under UV radiation. We present a new device based on liquid crystals technology. The sensor is based on a liquid crystalline mixture that absorbs photons at UV wavelength and emits them at a longer one. This system presents several innovative features: the absorption range of the mixture can be varied to be sensitive to different wavelengths, the luminescence intensity can be tuned, the system can be implemented on flexible devices.

  19. Molecular thermodiffusion (thermophoresis) in liquid mixtures.

    PubMed

    Semenov, Semen N; Schimpf, Martin E

    2005-10-01

    Thermodiffusion (thermophoresis) in liquid mixtures is theoretically examined using a hydrodynamic approach. Thermodiffusion is related to the local temperature-induced pressure gradient in the liquid layer surrounding the selected molecule and to the secondary macroscopic pressure gradient established in the system. The local pressure gradient is produced by excess pressure due to the asymmetry of interactions with surrounding molecules in a nonuniform temperature field. The secondary pressure gradient is considered an independent parameter related to the concentration gradient formed by volume forces, calculated from the generalized equations for mass transfer. Values of Soret coefficients for mixtures of toluene and -hexane are calculated using parameters in the literature. When the molecules are assumed to be similar in shape, the calculated Soret coefficients are lower than the empirical values found in the literature. However, by introducing an asymmetry parameter, which is calculated from independent measurements of component diffusion in the literature, very good agreement is obtained.

  20. Unmixing Multi-Component Magnetic Mixtures in Geologic Materials Using First Order Reversal Curve Diagrams

    NASA Astrophysics Data System (ADS)

    Lascu, I.; Harrison, R. J.; Li, Y.; Muraszko, J.; Channell, J. E. T.; Piotrowski, A. M.; Hodell, D. A.; Necula, C.; Panaiotu, C. G.

    2015-12-01

    We have developed a magnetic unmixing method based on principal component analysis (PCA) of first-order reversal curve (FORC) diagrams. PCA provides an objective and robust statistical framework for unmixing, because it represents data variability as a linear combination of a limited number of principal components that are derived purely on the basis of natural variations contained within the dataset. For PCA we have resampled FORC distributions on grids that capture diagnostic signatures of magnetic domain states. Individual FORC diagrams were then recast as linear combinations of end-member (EM) FORC diagrams, located at user-defined positions in PCA space. The EM selection is guided by constraints derived from physical modeling, and is imposed by data scatter. To test our model, we have investigated temporal variations of two EMs in bulk North Atlantic sediment cores collected from the Rockall Trough and the Iberian Continental Margin. Sediments from these sites contain a mixture of magnetosomes and granulometrically distinct detrital magnetite. We have also quantified the spatial variation of three EM components in surficial sediments along the flow path of the North Atlantic Deep Water (NADW). These samples were separated into granulometric fractions, which also assisted in constraining EM definition. The unmixing model reveals systematic variations in EM relative abundance as a function of distance along NADW flow. Finally, we have applied PCA to the combined dataset of Rockall Trough and NADW sediments, which can be recast as a four-EM mixture, providing enhanced discrimination between components. Our method forms the foundation of a general solution to the problem of unmixing multi-component magnetic mixtures, a fundamental task of rock magnetic studies.

  1. Direct numerical simulation of gaseous mixing layers laden with multicomponent-liquid drops: liquid-specific effects

    NASA Astrophysics Data System (ADS)

    Le Clercq, Patrick C.; Bellan, Josette

    2005-06-01

    A representation of multicomponent-liquid (MC-liquid) composition as a linear combination of two single-Gamma probability distribution functions (PDFs) is used to describe a large number of MC-liquid drops evaporating in a gas flow. The PDF, called the double-Gamma PDF, depends on the molar mass. The gas-phase conservation equations are written in an Eulerian frame and the drops are described in a Lagrangian frame. Gas conservation equations for mass, momentum, species and energy are combined with differential conservation equations for the first four moments of the gas-composition PDF and coupled to the perfect gas equation of state. Source terms in all conservation equations account for the gas/drop interaction. The drop governing equations encompass differential conservation statements for position, mass, momentum, energy and four moments of the liquid-composition PDF. Simulations are performed for a three-dimensional mixing layer whose lower stream is initially laden with drops colder than the surrounding gas. Initial perturbations excite the layer to promote the double pairing of its four initial spanwise vortices to an ultimate vortex. During the layer evolution, the drops heat and evaporate. The results address the layer evolution, and the state of the gas and drops when layers reach a momentum-thickness maximum past the double vortex pairing. Of interest is the influence of the liquid composition on the development of the vortical features of the flow, on the vortical state reached after the second pairing, and on the gas temperature and composition. The MC-liquid simulations are initiated with a single-Gamma PDF composition so as to explore the development of the double-Gamma PDF. Examination of equivalent simulations with n-decane, diesel and three kerosenes as the liquid, permits assessment of the single-species versus the MC-liquid aspect, and of mixture composition specific effects. Global layer growth and global rotational characteristics are

  2. Direct Numerical Simulation of Transitional Multicomponent-Species Gaseous and Multicomponent-Liquid Drop-Laden Mixing

    NASA Technical Reports Server (NTRS)

    Selle, Laurent C.; Bellan, Josette

    2006-01-01

    A model of multicomponent-liquid (MC-liquid) drop evaporation in a three-dimensional mixing layer is here exercised at larger Reynolds numbers than in a previous study, and transitional states are obtained. The gas phase is followed in an Eulerian frame and the multitude of drops is described in a Lagrangian frame. Complete coupling between phases is included with source terms in the gas conservation equations accounting for the drop/flow interaction in terms of drop drag, drop heating and species evaporation. The liquid composition, initially specified as a single-Gamma (SG) probability distribution function (PDF) depending on the molar mass is allowed to evolve into a linear combination of two SGPDFs, called the double-Gamma PDF (DGPDF). The compositions of liquid and vapor emanating from the drops are calculated through four moments of the DGPDFs, which are drop-specific and location-specific, respectively. The mixing layer is initially excited to promote the double pairing of its four initial spanwise vortices into an ultimate vortex in which small scales proliferate. Simulations are performed for four liquids of different compositions and the effect of the initial mass loading and initial free-stream gas temperature are explored. For reference, Simulations are also performed for gaseous multicomponent mixing layers for which the effect of Reynolds number is investigated. The results encompass examination of the global layer characteristics, flow visualizations and homogeneous-plane statistics at transition. Comparisons are performed with previous pre-transitional MC-liquid simulations and with transitional single-component (SC) liquid studies. It is found that MCC flows at transition, the classical energy cascade is of similar strength, but that the smallest scales contain orders of magnitude less energy than SC flows, which is confirmed by the larger viscous dissipation in the former case. Contrasting to pre-transitional MC flows, the vorticity and drop

  3. Zwanzig model of multi-component mixtures of biaxial particles: y3 theory re-visited

    NASA Astrophysics Data System (ADS)

    Sokolova, E. P.; Tumanyan, N. P.; Vlasov, A. Yu.; Masters, A. J.

    The paper considers the thermodynamic and phase ordering properties of a multi-component Zwanzig mixture of hard rectangular biaxial parallelepipeds. An equation of state (EOS) is derived based on an estimate of the number of arrangements of the particles on a three- dimensional cubic lattice. The methodology is a generalization of the Flory-DiMarzio counting scheme, but, unlike previous work, this treatment is thermodynamically consistent. The results are independent of the order in which particles are placed on the lattice. By taking the limit of zero lattice spacing, a translationally continuous variant of the model (the off-lattice variant) is obtained. The EOS is identical to that obtained previously by a wide variety of different approaches. In the off-lattice limit, it corresponds to a third-level y-expansion and, in the case of a binary mixture of square platelets, it also corresponds to the EOS obtained from fundamental measure theory. On the lattice it is identical to the EOS obtained by retaining only complete stars in the virial expansion. The off-lattice theory is used to study binary mixtures of rods (R1 - R2) and binary mixtures of platelets (P1 - P2). The particles were uniaxial, of length (thickness) L and width D. The aspect ratios Γi = Li/Di of the components were kept constant (Γ1R = 15, Γ1P = 1/15 and Γ2R = 150, Γ2P = 1/150), so the second virial coefficient of R1 was identical to P1 and similarly for R2 and P2. The volume ratio of particles 1 and 2, v1/v2, was then varied, with the constraints that viR = viP and ILM0001. Results on nematic-isotropic (N - I) phase coexistence at an infinite dilution of component 2, are qualitatively similar for rods and platelets. At small values of the ratio v1/v2, the addition of component 2 (i.e. a thin rod (e.g. a polymer) or a thin plate) results in the stabilization of the nematic phase. For larger values of v1/v2, however, this effect is reversed and the addition of component 2 destabilizes the

  4. Study on the variation rules of the joint effects for multicomponent mixtures containing cyanogenic toxicants and aldehydes based on the transition state theory.

    PubMed

    Li, Weiying; Tian, Dayong; Lin, Zhifen; Wang, Dali; Yu, Hongxia

    2014-02-28

    Although the study of the variation rules of the joint effects for multicomponent mixtures has gained increasing attention, it still remains unclear how the variation occurs and what the relationships between the joint effects of multicomponent mixtures and their corresponding binary mixtures are. To explain how the variation occurs, this study first proposes a hypothesis on the variation rules of the joint effects using the well-known transition state theory. The hypothesis concluded that the joint effect of multicomponent mixtures is among the joint effects of the corresponding binary mixtures. This hypothesis was named the fishing hypothesis because there is a similarity between the action process of the joint effects and the fishing process. Next, the hypothesis was validated by use of the experimental data by evaluating the joint effects of binary, ternary and quaternary mixtures containing cyanogenic toxicants and aldehydes on Photobacterium phosphoreum. The application of the fishing hypothesis can explain the rule as to how the joint effects of a multicomponent-mixture vary with its number of components and their ratios. This study provides a good method to predict the joint effects of multicomponent mixtures using the joint effects of their corresponding binary mixtures. An improvement in the fishing hypothesis will be needed in our future studies due to the approximate assumptions used in the deduction of the hypothesis.

  5. CONTAMINANT TRANSPORT RESULTING FROM MULTICOMPONENT NONAQUEOUS PHASE LIQUID POOL DISSOLUTION IN THREE-DIMENSIONAL SUBSURFACE FORMATIONS (R823579)

    EPA Science Inventory

    A semi-analytical method for simulating transient contaminant transport originating from the dissolution of multicomponent nonaqueous phase liquid (NAPL) pools in three-dimensional, saturated, homogeneous porous media is presented. Each dissolved component may undergo first-order...

  6. DETERMINATION AND QUANTIFICATION OF NON-AQUEOUS PHASE LIQUID MIXTURES IN ENVIRONMENTAL MEDIA

    SciTech Connect

    Rucker, G

    2006-09-22

    It is important to recognize the presence of Non-Aqueous Phase Liquids (NAPLs) in soils at a waste site in order to design and construct a successful remediation system. NAPLs often manifest as a complex, multi-component mixture of organic compounds that can occur in environmental media, such as vadose zone soil, where the mixture will partition and equilibrate with soil particles, pore vapor, and pore water. Complex organic mixtures can greatly complicate the determination and quantification of NAPL in soil due to inter-media transfer. NAPL thresholds can also change because of mixture physical properties and can disguise the presence of NAPL. A unique analytical method and copyrighted software have been developed at the Department of Energy's Savannah River Site that facilitates solution of this problem. The analytical method uses a classic chemistry approach and applies the principals of solubility limit theory, Raoult's Law, and equilibrium chemistry to derive an accurate estimation of NAPL presence and quantity. The method is unique because it calculates an exact result that is mass balanced for each physical state, chemical mixture component, and mixture characteristics. The method is also unique because the solution can be calculated on both a wet weight and dry weight basis--a factor which is often overlooked. The software includes physical parameters for 300 chemicals in a database that self-loads into the model to save time. The method accommodates up to 20 different chemicals in a multi-component mixture analysis. A robust data display is generated including important parameters of the components and mixture including: NAPL thresholds for individual chemical components within the mixture, mass distribution in soil for each physical state, molar fractions, density, vapor pressure, solubility, mass balance, media concentrations, residual saturation, and modest graphing capabilities. This method and software are power tools to simplify otherwise tedious

  7. Stable Isotope Labeling Strategy for Protein-Ligand Binding Analysis in Multi-Component Protein Mixtures

    NASA Astrophysics Data System (ADS)

    DeArmond, Patrick D.; West, Graham M.; Huang, Hai-Tsang; Fitzgerald, Michael C.

    2011-03-01

    Described here is a stable isotope labeling protocol that can be used with a chemical modification- and mass spectrometry-based protein-ligand binding assay for detecting and quantifying both the direct and indirect binding events that result from protein-ligand binding interactions. The protocol utilizes an H{2/16}O2 and H{2/18}O2 labeling strategy to evaluate the chemical denaturant dependence of methionine oxidation in proteins both in the presence and absence of a target ligand. The differential denaturant dependence to the oxidation reactions performed in the presence and absence of ligand provides a measure of the protein stability changes that occur as a result of direct interactions of proteins with the target ligand and/or as a result of indirect interactions involving other protein-ligand interactions that are either induced or disrupted by the ligand. The described protocol utilizes the 18O/16O ratio in the oxidized protein samples to quantify the ligand-induced protein stability changes. The ratio is determined using the isotopic distributions observed for the methionine-containing peptides used for protein identification in the LC-MS-based proteomics readout. The strategy is applied to a multi-component protein mixture in this proof-of-principle experiment, which was designed to evaluate the technique's ability to detect and quantify the direct binding interaction between cyclosporin A and cyclophilin A and to detect the indirect binding interaction between cyclosporin A and calcineurin (i.e., the protein-protein interaction between cyclophilin A and calcineurin that is induced by cyclosporin A binding to cyclophilin A).

  8. Dynamic thermodiffusion model for binary liquid mixtures

    NASA Astrophysics Data System (ADS)

    Eslamian, Morteza; Saghir, M. Ziad

    2009-07-01

    Following the nonequilibrium thermodynamics approach, we develop a dynamic model to emulate thermo-diffusion process and propose expressions for estimating the thermal diffusion factor in binary nonassociating liquid mixtures. Here, we correlate the net heat of transport in thermodiffusion with parameters, such as the mixture temperature and pressure, the size and shape of the molecules, and mobility of the components, because the molecules have to become activated before they can move. Based on this interpretation, the net heat of transport of each component can be somehow related to the viscosity and the activation energy of viscous flow of the same component defined in Eyring’s reaction-rate theory [S. Glasstone, K. J. Laidler, and H. Eyring, The Theory of Rate Processes: The Kinetics of Chemical Reactions, Viscosity, Diffusion and Electrochemical Phenomena (McGraw-Hill, New York, 1941)]. This modeling approach is different from that of Haase and Kempers, in which thermodiffusion is considered as a function of the thermostatic properties of the mixture such as enthalpy. In simulating thermodiffusion, by correlating the net heat of transport with the activation energy of viscous flow, effects of the above mentioned parameters are accounted for, to some extent of course. The model developed here along with Haase-Kempers and Drickamer-Firoozabadi models linked with the Peng-Robinson equation of sate are evaluated against the experimental data for several recent nonassociating binary mixtures at various temperatures, pressures, and concentrations. Although the model prediction is still not perfect, the model is simple and easy to use, physically justified, and predicts the experimental data very good and much better than the existing models.

  9. Dynamic thermodiffusion model for binary liquid mixtures.

    PubMed

    Eslamian, Morteza; Saghir, M Ziad

    2009-07-01

    Following the nonequilibrium thermodynamics approach, we develop a dynamic model to emulate thermo-diffusion process and propose expressions for estimating the thermal diffusion factor in binary nonassociating liquid mixtures. Here, we correlate the net heat of transport in thermodiffusion with parameters, such as the mixture temperature and pressure, the size and shape of the molecules, and mobility of the components, because the molecules have to become activated before they can move. Based on this interpretation, the net heat of transport of each component can be somehow related to the viscosity and the activation energy of viscous flow of the same component defined in Eyring's reaction-rate theory [S. Glasstone, K. J. Laidler, and H. Eyring, (McGraw-Hill, New York, 1941)]. This modeling approach is different from that of Haase and Kempers, in which thermodiffusion is considered as a function of the thermostatic properties of the mixture such as enthalpy. In simulating thermodiffusion, by correlating the net heat of transport with the activation energy of viscous flow, effects of the above mentioned parameters are accounted for, to some extent of course. The model developed here along with Haase-Kempers and Drickamer-Firoozabadi models linked with the Peng-Robinson equation of sate are evaluated against the experimental data for several recent nonassociating binary mixtures at various temperatures, pressures, and concentrations. Although the model prediction is still not perfect, the model is simple and easy to use, physically justified, and predicts the experimental data very good and much better than the existing models.

  10. Enantiomer-specific analysis of multi-component mixtures by correlated electron imaging–ion mass spectrometry

    PubMed Central

    Fanood, Mohammad M Rafiee; Ram, N. Bhargava; Lehmann, C. Stefan; Powis, Ivan; Janssen, Maurice H. M.

    2015-01-01

    Simultaneous, enantiomer-specific identification of chiral molecules in multi-component mixtures is extremely challenging. Many established techniques for single-component analysis fail to provide selectivity in multi-component mixtures and lack sensitivity for dilute samples. Here we show how enantiomers may be differentiated by mass-selected photoelectron circular dichroism using an electron–ion coincidence imaging spectrometer. As proof of concept, vapours containing ∼1% of two chiral monoterpene molecules, limonene and camphor, are irradiated by a circularly polarized femtosecond laser, resulting in multiphoton near-threshold ionization with little molecular fragmentation. Large chiral asymmetries (2–4%) are observed in the mass-tagged photoelectron angular distributions. These asymmetries switch sign according to the handedness (R- or S-) of the enantiomer in the mixture and scale with enantiomeric excess of a component. The results demonstrate that mass spectrometric identification of mixtures of chiral molecules and quantitative determination of enantiomeric excess can be achieved in a table-top instrument. PMID:26104140

  11. Triphilic Ionic-Liquid Mixtures: Fluorinated and Non-fluorinated Aprotic Ionic-Liquid Mixtures

    PubMed Central

    Hollóczki, Oldamur; Macchiagodena, Marina; Weber, Henry; Thomas, Martin; Brehm, Martin; Stark, Annegret; Russina, Olga; Triolo, Alessandro; Kirchner, Barbara

    2015-01-01

    We present here the possibility of forming triphilic mixtures from alkyl- and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains—polar and nonpolar—three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self-associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long-range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment. PMID:26305804

  12. Percolation segregation in multi-size and multi-component particulate mixtures: Measurement, sampling, and modeling

    NASA Astrophysics Data System (ADS)

    Jha, Anjani K.

    Particulate materials are routinely handled in large quantities by industries such as, agriculture, electronic, ceramic, chemical, cosmetic, fertilizer, food, nutraceutical, pharmaceutical, power, and powder metallurgy. These industries encounter segregation due to the difference in physical and mechanical properties of particulates. The general goal of this research was to study percolation segregation in multi-size and multi-component particulate mixtures, especially measurement, sampling, and modeling. A second generation primary segregation shear cell (PSSC-II), an industrial vibrator, a true cubical triaxial tester, and two samplers (triers) were used as primary test apparatuses for quantifying segregation and flowability; furthermore, to understand and propose strategies to mitigate segregation in particulates. Toward this end, percolation segregation in binary, ternary, and quaternary size mixtures for two particulate types: urea (spherical) and potash (angular) were studied. Three coarse size ranges 3,350-4,000 mum (mean size = 3,675 mum), 2,800-3,350 mum (3,075 mum), and 2,360-2,800 mum (2,580 mum) and three fines size ranges 2,000-2,360 mum (2,180 mum), 1,700-2,000 mum (1,850 mum), and 1,400-1,700 mum (1,550 mum) for angular-shaped and spherical-shaped were selected for tests. Since the fines size 1,550 mum of urea was not available in sufficient quantity; therefore, it was not included in tests. Percolation segregation in fertilizer bags was tested also at two vibration frequencies of 5 Hz and 7Hz. The segregation and flowability of binary mixtures of urea under three equilibrium relative humidities (40%, 50%, and 60%) were also tested. Furthermore, solid fertilizer sampling was performed to compare samples obtained from triers of opening widths 12.7 mm and 19.1 mm and to determine size segregation in blend fertilizers. Based on experimental results, the normalized segregation rate (NSR) of binary mixtures was dependent on size ratio, mixing ratio

  13. Liquid-gas phase transitions in a multicomponent nuclear system with Coulomb and surface effects

    SciTech Connect

    Lee, S. J.; Mekjian, A. Z.

    2001-04-01

    The liquid-gas phase transition is studied in a multicomponent nuclear system using a local Skyrme interaction with Coulomb and surface effects. Some features are qualitatively the same as the results of Mu''ller and Serot where a relativistic mean field was used without Coulomb and surface effects. Surface tension brings the coexistence binodal surface to lower pressure. The Coulomb interaction makes the binodal surface smaller and causes another pair of binodal points at low pressure and large proton fraction with fewer protons in the liquid phase and more protons in the gas phase.

  14. Diffusion controlled evaporation of a multicomponent droplet - Theoretical studies on the importance of variable liquid properties

    NASA Astrophysics Data System (ADS)

    Kneer, R.; Schneider, M.; Noll, B.; Wittig, S.

    1993-06-01

    A well-known multicomponent droplet vaporization model, the Diffusion Limit Model, has been extended to account for property variations in the liquid phase. The model has been tested for typical conditions of modern gas turbine combustors. The results for a hexane/tetradecane droplet show that the temperature- and concentration-dependence of the liquid properties affect the vaporization process, especially with regard to a reduced diffusional resistance. Additionally, remarkable variations of the refractive index are observed yielding helpful information for the estimation of errors in optical particle sizing techniques. Regarding comprehensive spray calculations, the use of the constant property formulation is recommended with improved reference values based on variable property calculations.

  15. Investigations into complex liquid crystal mixtures

    NASA Astrophysics Data System (ADS)

    Kirchhoff, Jennifer

    Liquid crystal phases exhibit physical characteristics that lie between those of liquid and crystal phases. The many liquid crystal sub-phases are defined based on the degree of positional and orientational ordering the molecules have and the materials that make up these liquid crystal phases. This thesis presents a study of the molecular packing and physical properties of complex liquid crystal phases using dopants to better examine the stability and packing mechanisms of these phases. It also looks at the dispersion of quantum dots in liquid crystal materials, examining the electro-optical properties of the mixtures. The main goal of this thesis is to examine the effects of dopants on the properties of liquid crystal phases using optical microscopy, differential scanning calorimetry, electro-optical measurements, and X-ray scattering. For those mixtures with quantum dots fluorescence microscopy and photoluminescence measurements were also conducted. Rod-like liquid crystals are commonly used in display applications when the material is in a nematic liquid crystal phase, which is the least ordered phase exhibiting no positional ordering. The more complicated chiral smectic liquid crystal phases, which have a one dimensional layer structure, show potential for faster and tri-stable switching. A chiral rod-like liquid crystal material is doped with both chiral and achiral rod-like liquid crystals to examine the stability of one of the chiral smectic sub-phase, the SmC* FI1 phase. This phase consists of tilted molecules rotating about the cone defined by the tilt angle with a periodicity of three layers and an overall helical structure. The SmC*FI1 phase is stabilized by the competition between antiferroelectric and ferroelectric interactions, and small amounts of the achiral dopant broadens the range of this phase by almost 5°C. Higher dopant concentrations of the achiral material result in the destabilization of not just the SmC*FI1 phase but all tilted sub

  16. Sound speed measurements in liquid oxygen-liquid nitrogen mixtures

    NASA Technical Reports Server (NTRS)

    Zuckerwar, A. J.; Mazel, D. S.

    1985-01-01

    The sound speed in liquid oxygen (LOX), liquid nitrogen (LN2), and five LOX-LN2 mixtures was measured by an ultrasonic pulse-echo technique at temperatures in the vicinity of -195.8C, the boiling point of N2 at a pressure of I atm. Under these conditions, the measurements yield the following relationship between sound speed in meters per second and LN2 content M in mole percent: c = 1009.05-1.8275M+0.0026507 M squared. The second speeds of 1009.05 m/sec plus or minus 0.25 percent for pure LOX and 852.8 m/sec plus or minus 0.32 percent for pure LN2 are compared with those reported by past investigators. Measurement of sound speed should prove an effective means for monitoring the contamination of LOX by Ln2.

  17. Enhanced-Solubilization of a Multi-Component Immiscible Liquid Source Zone within an Intermediate-scale Flow Cell System

    NASA Astrophysics Data System (ADS)

    Harvell, J. R.; Tick, G. R.

    2011-12-01

    Complex multi-component immiscible liquid mixtures can significantly limit the effectiveness of groundwater remediation. The use of enhanced-flushing technologies has emerged as a promising technique for the remediation of sites contaminated with immiscible liquids. A series of two dimensional (2-D) flow cell experiments was conducted to quantify the effectiveness of two different flushing agents on the removal of a uniformly distributed multi-component immiscible liquid source zone. A 39.5 x 20.2 cm flow-cell was packed with 20/30-mesh sand and emplaced with a 15 x 3 cm rectangular source zone within the center of the flow cell. The source zone was established with a 10% NAPL saturation (Sn) consisting of equal 1:1:1 mole mixture of tetrachloroethene (PCE), trichloroethene (TCE), and cis-1,2-dichloroethene (DCE). The solubilization agents investigated included 5 wt% solution of a complexing sugar, hydroxypropyl-$betacyclodextrin (HPCD), and a 5 wt% solution of a surfactant, sodium dodecyl sulfate (SDS). The results of these experiments indicate that the addition of a chemical flushing agent greatly reduces the time needed to remove each component compared to flushing with water alone (i.e. pump and treat). Elution curve (concentration-time) analysis from both total extraction and at the down-gradient end of the source zone showed that SDS removed all three components from the source zone approximately 10 times faster than HPCD. For the extraction port SDS showed slightly more ideal removal in terms of mass flux behavior, removing more mass initially before a significant reduction in mass flux was observed. Although SDS was superior when evaluated on a recovery basis, HPCD outperformed SDS for all components when compared based on contaminant-mass to reagent-mass and moles of contaminant to moles of reagent removed for the source zone port. These findings suggest that the selection of a particular flushing agent should be evaluated carefully prior to remediation as

  18. ION-pair liquid chromatography technique for the estimation of metformin in its multicomponent dosage forms.

    PubMed

    Vasudevan, M; Ravi, J; Ravisankar, S; Suresh, B

    2001-04-01

    A simple, precise and accurate high performance liquid chromatography (HPLC) method was developed for the simultaneous estimation of metformin with gliclazide and glipizide present in multicomponent dosage forms. The method was carried out on Inertsil C(18) column. A mobile phase composed of acetonitrile-water containing camphor sulphonic acid (adjusted to pH 7 using 0.1 N sodium hydroxide; 75 mM) at a flow rate of 1 ml min(-1) was used for the separation. Detection was carried out at 225 nm. Tolbutamide was used as internal standard. Validation of the developed HPLC method was carried out.

  19. Synthesis of task specific and reusable protic ionic liquids for one-pot multicomponent syntheses

    NASA Astrophysics Data System (ADS)

    Sardar, Sabahat; Wilfred, Cecilia Devi; Marc, Leveque Jean

    2016-11-01

    Protic ionic liquids (ILs) synthesized from 1-methylimidazole with 1,3-propane sultone and 1,4-butane sultone catalyzed Mannich reaction at 25 °C to afford Mannich bases in high yield (76%) and less time duration (20 min). Ionic liquids have been used as dual reagent i.e., as catalyst as well as solvent. Simple extraction by water separated ionic liquid from reaction mixture with 4 times recycling without any significant loss in activity.

  20. A Variational Statistical-Field Theory for Polar Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Zhuang, Bilin; Wang, Zhen-Gang

    Using a variational field-theoretic approach, we derive a molecularly-based theory for polar liquid mixtures. The resulting theory consists of simple algebraic expressions for the free energy of mixing and the dielectric constant as functions of mixture composition. Using only the dielectric constants and the molar volumes of the pure liquid constituents, the theory evaluates the mixture dielectric constants in good agreement with the experimental values for a wide range of liquid mixtures, without using adjustable parameters. In addition, the theory predicts that liquids with similar dielectric constants and molar volumes dissolve well in each other, while sufficient disparity in these parameters result in phase separation. The calculated miscibility map on the dielectric constant-molar volume axes agrees well with known experimental observations for a large number of liquid pairs. Thus the theory provides a quantification for the well-known empirical ``like-dissolves-like'' rule. Bz acknowledges the A-STAR fellowship for the financial support.

  1. Phase-field modeling of isothermal quasi-incompressible multicomponent liquids

    NASA Astrophysics Data System (ADS)

    Tóth, Gyula I.

    2016-09-01

    In this paper general dynamic equations describing the time evolution of isothermal quasi-incompressible multicomponent liquids are derived in the framework of the classical Ginzburg-Landau theory of first order phase transformations. Based on the fundamental equations of continuum mechanics, a general convection-diffusion dynamics is set up first for compressible liquids. The constitutive relations for the diffusion fluxes and the capillary stress are determined in the framework of gradient theories. Next the general definition of incompressibility is given, which is taken into account in the derivation by using the Lagrange multiplier method. To validate the theory, the dynamic equations are solved numerically for the quaternary quasi-incompressible Cahn-Hilliard system. It is demonstrated that variable density (i) has no effect on equilibrium (in case of a suitably constructed free energy functional) and (ii) can influence nonequilibrium pattern formation significantly.

  2. Phase-field modeling of isothermal quasi-incompressible multicomponent liquids.

    PubMed

    Tóth, Gyula I

    2016-09-01

    In this paper general dynamic equations describing the time evolution of isothermal quasi-incompressible multicomponent liquids are derived in the framework of the classical Ginzburg-Landau theory of first order phase transformations. Based on the fundamental equations of continuum mechanics, a general convection-diffusion dynamics is set up first for compressible liquids. The constitutive relations for the diffusion fluxes and the capillary stress are determined in the framework of gradient theories. Next the general definition of incompressibility is given, which is taken into account in the derivation by using the Lagrange multiplier method. To validate the theory, the dynamic equations are solved numerically for the quaternary quasi-incompressible Cahn-Hilliard system. It is demonstrated that variable density (i) has no effect on equilibrium (in case of a suitably constructed free energy functional) and (ii) can influence nonequilibrium pattern formation significantly.

  3. Effect of Various Enhanced-Solubilization Agents on Multi-Component Immiscible Liquid Dissolution and Mass Flux in Homogeneous Porous Media

    NASA Astrophysics Data System (ADS)

    Tick, G. R.; Slavic, D.

    2010-12-01

    Complex multi-component immiscible liquid mixtures can significantly limit the effectiveness of groundwater remediation. The use of enhanced-flushing technologies has emerged as a promising technique for the remediation of sites contaminated with immiscible liquids. An important aspect for the effective remediation of these sites depends on the physical heterogeneity of the subsurface, the related distribution of immiscible liquid present within porous media, and the composition of the immiscible liquid mixture. A series of column experiments was conducted to quantify the effectiveness of four different flushing agents on the removal of a uniformly distributed multi-component immiscible liquid consisting of equal mole fractions of tetrachloroethene (PCE), trichloroethene (TCE), and cis-1,2-dichloroethene (DCE) in homogeneous quartz sand. The solubilization agents investigated included: two complexing sugars, hydroxypropyl-β-cyclodextrin (HPCD) and methyl-β-cyclodextrin (MCD); one surfactant, sodium dodecyl sulfate (SDS); and one cosolvent, ethanol (ETOH). The effectiveness of the flushing agents was evaluated by comparing elution profiles, flushing efficiencies, mass flux behavior, and dissolution ideality (i.e. Raoult’s law prediction) of each component. The results of these experiments indicate that the addition of a chemical flushing agent greatly reduces the time needed to remove each component compared to flushing with water alone (i.e. pump and treat). Although the stronger solubilization-power agents (i.e. SDS and ETOH) showed quicker removal in general, each solubilization agent exhibited unique removal limitations based upon different removal efficiency analyses. For instance, TCE and DCE exhibited relatively ideal dissolution while PCE showed significant nonideal dissolution behavior during flushing with MCD. These findings suggest that the selection of a particular flushing agent should be evaluated carefully prior to remediation as the mass flux and

  4. Multicomponent membranes

    DOEpatents

    Kulprathipanja, Santi; Kulkarni, Sudhir S.; Funk, Edward W.

    1988-01-01

    A multicomponent membrane which may be used for separating various components which are present in a fluid feed mixture comprises a mixture of a plasticizer such as a glycol and an organic polymer cast upon a porous organic polymer support. The membrane may be prepared by casting an emulsion or a solution of the plasticizer and polymer on the porous support, evaporating the solvent and recovering the membrane after curing.

  5. Equation-of-state modeling of mixtures with ionic liquids.

    PubMed

    Tsioptsias, Costas; Tsivintzelis, Ioannis; Panayiotou, Costas

    2010-05-14

    A non-electrolyte equation-of-state model was used to describe the phase behavior of binary systems containing alkyl-methyimidazolium bis(trifluoromethyl-sulfonyl)imide ionic liquids. A methodology is suggested for modeling this phase behavior by using the Non-Random Hydrogen-Bonding (NRHB) model. According to this methodology, the scaling constants of the ionic liquid are calculated using limited available experimental data on liquid densities and Hansen's solubility parameters, while all electrostatic interactions (polar, hydrogen bonding and ionic) are treated as strong specific interactions. Using the aforementioned methodology, the model is applied to describe the vapor-liquid and the liquid-liquid equilibria in mixtures of ionic liquids with various polar or quadrupolar solvents at low and high pressures. In all cases, one temperature-independent binary interaction parameter was used. Accurate correlations were obtained for the majority of the systems, both, for vapor-liquid and liquid-liquid equilibria.

  6. Multicomponent effective medium-correlated random walk theory for the diffusion of fluid mixtures through porous media.

    PubMed

    Bonilla, Mauricio R; Bhatia, Suresh K

    2012-01-10

    Molecular transport in nanoconfined spaces plays a key role in many emerging technologies for gas separation and storage, as well as in nanofluidics. The infiltration of fluid mixtures into the voids of porous frameworks having complex topologies is common place to these technologies, and optimizing their performance entails developing a deeper understanding of how the flow of these mixtures is affected by the morphology of the pore space, particularly its pore size distribution and pore connectivity. Although several techniques have been developed for the estimation of the effective diffusivity characterizing the transport of single fluids through porous materials, this is not the case for fluid mixtures, where the only alternatives rely on a time-consuming solution of the pore network equations or adaptations of the single fluid theories which are useful for a limited type of systems. In this paper, a hybrid multicomponent effective medium-correlated random walk theory for the calculation of the effective transport coefficients matrix of fluid mixtures diffusing through porous materials is developed. The theory is suitable for those systems in which component fluxes at the single pore level can be related to the potential gradients of the different species through linear flux laws and corresponds to a generalization of the classical single fluid effective medium theory for the analysis of random resistor networks. Comparison with simulation of the diffusion of binary CO(2)/H(2)S and ternary CO(2)/H(2)S/C(3)H(8) gas mixtures in membranes modeled as large networks of randomly oriented pores with both continuous and discrete pore size distributions demonstrates the power of the theory, which was tested using the well-known generalized Maxwell-Stefan model for surface diffusion at the single pore level.

  7. Multicomponent reactions and ionic liquids: a perfect synergy for eco-compatible heterocyclic synthesis.

    PubMed

    Isambert, Nicolas; Sanchez Duque, Maria del Mar; Plaquevent, Jean-Christophe; Génisson, Yves; Rodriguez, Jean; Constantieux, Thierry

    2011-03-01

    The efficiency of a chemical synthesis can be nowadays measured, not only by parameters like selectivity and overall yield, but also by its raw material, time, human resources and energy requirements, as well as the toxicity and hazard of the chemicals and the protocols involved. The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. The aim of this tutorial review is to highlight the synergistic effect of the combined use of MCRs and ILs for the development of new eco-compatible methodologies for heterocyclic chemistry.

  8. Perturbation theory for multicomponent fluids based on structural properties of hard-sphere chain mixtures

    SciTech Connect

    Hlushak, Stepan

    2015-09-28

    An analytical expression for the Laplace transform of the radial distribution function of a mixture of hard-sphere chains of arbitrary segment size and chain length is used to rigorously formulate the first-order Barker-Henderson perturbation theory for the contribution of the segment-segment dispersive interactions into thermodynamics of the Lennard-Jones chain mixtures. Based on this approximation, a simple variant of the statistical associating fluid theory is proposed and used to predict properties of several mixtures of chains of different lengths and segment sizes. The theory treats the dispersive interactions more rigorously than the conventional theories and provides means for more accurate description of dispersive interactions in the mixtures of highly asymmetric components.

  9. `Guest-host' effect in liquid crystal mixtures

    NASA Astrophysics Data System (ADS)

    Suchodolska, B.; Rudzki, A.; Ossowska-Chruściel, M. D.; Zalewski, S.; Chruściel, J.

    2015-01-01

    The most important goal of our research is to show the influence of the 'guest' (bent-core mesogen, 1,3-phenyldicarboxylatebis{4-[(4-octylbenzoyl)sulphanyl]phenyl} [IFOS8], banana-shaped liquid crystal [BLC]) on the 'host' (calamitic liquid crystal [CLC], (S)-(+)-1-methylheptyloxybiphenyl-(4-n-octylphenyl)thiobenzoate [MHOBS8]), on the stability and the destabilization of the antiferroelectric B2 and the ferroelectric smectic C* (SmC*) phases, and change of the temperature ranges of other phases in the binary liquid crystal mixtures. This work is focused on polymorphism of three new binary liquid crystal mixtures, exhibiting a 'guest-host' (guest liquid crystal-host liquid crystal [GH-LC]) effect. MHOBS8 has, among others, a ferroelectric SmC* phase, and IFOS8 assumes the B2 phase with antiferroelectric properties. The observed properties of the mixtures, such as variation of the phase transition temperatures, spontaneous polarization, tilt angle and switching time, are characteristic of a 'guest-host' mixture. The influence of BLC on the character of the interactions within the CLC host is discussed, with particular attention paid to electro-optical properties of the GH-LC mixtures.

  10. Heat capacity singularity of binary liquid mixtures at the liquid-liquid critical point.

    PubMed

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

    2013-10-01

    The critical anomaly of the isobaric molar heat capacity for the liquid-liquid phase transition in binary nonionic mixtures is explained through a theory based on the general assumption that their partition function can be exactly mapped into that of the Ising three-dimensional model. Under this approximation, it is found that the heat capacity singularity is directly linked to molar excess enthalpy. In order to check this prediction and complete the available data for such systems, isobaric molar heat capacity and molar excess enthalpy near the liquid-liquid critical point were experimentally determined for a large set of binary liquid mixtures. Agreement between theory and experimental results-both from literature and from present work-is good for most cases. This fact opens a way for explaining and predicting the heat capacity divergence at the liquid-liquid critical point through basically the same microscopic arguments as for molar excess enthalpy, widely used in the frame of solution thermodynamics.

  11. Low-melting mixtures based on choline ionic liquids.

    PubMed

    Rengstl, Doris; Fischer, Veronika; Kunz, Werner

    2014-11-07

    In this article a strategy is proposed for the design of low toxic, room temperature liquid low-melting mixtures (LMMs) which are entirely composed of natural materials. From literature it is well known that, in general, deep eutectic solvents based on choline chloride and dicarboxylic acids are LMMs, but not liquids at room temperature, with one exception: a 1 : 1 molar mixture of malonic acid and choline chloride. Therefore, the starting point of this study was the decrease of the melting point of one of the components, namely the dicarboxylic acid, which is succinic, glutaric or adipic acid. For this purpose, one of the two protons of the acidic group was exchanged by a bulky unsymmetrical choline cation. The resulting ionic liquids (ILs) were still solid at room temperature, but have a reduced melting temperature compared to the corresponding acids. In the second step, mixtures of these ILs with choline chloride were prepared. It turned out that choline glutarate-choline chloride mixtures are liquids at room temperature at compositions containing 95-98 wt% of choline glutarate. Finally, urea was added as another hydrogen bond donor. Density, conductivity and viscosity measurements were performed for all obtained mixtures. Moreover, a Walden plot was drawn which indicates that all mixtures are liquids with fully dissociated ions moving independently. Therefore, they are considered as "good" ionic liquids and, thus, for example they can be used to exchange more toxic or less biodegradable ILs in application processes. A brief outlook containing application possibilities is given. It is demonstrated that choline dodecylsulfate is readily soluble in these mixtures, forming aggregates in the LMM at temperatures exceeding 55 °C.

  12. Evaporation of multi-component mixtures and shell formation in spray dried droplets

    NASA Astrophysics Data System (ADS)

    Valente, Pedro; Duarte, Íris; Porfirio, Tiago; Temtem, Márcio

    2015-11-01

    Drug particles where the active pharmaceutical ingredient (APIs) is dispersed in a polymer matrix forming an amorphous solid dispersion (ASD) is a commonly used strategy to increase the solubility and dissolution rate of poorly water soluble APIs. However, the formation and stability of an amorphous solid dispersion depends on the polymer/API combination and process conditions to generate it. The focus of the present work is to further develop a numerical tool to predict the formation of ASDs by spray drying solutions of different polymer/API combinations. Specifically, the evaporation of a multi-component droplet is coupled with a diffusion law within the droplet that minimizes the Gibbs free energy of the polymer/API/solvents system, following the Flory-Huggins model. Prior to the shell formation, the evaporation of the solvents is modelled following the simplified approach proposed by Abramzon & Sirignano (1989) which accounts for the varying relative velocity between the droplet and the drying gas. After shell formation, the diffusion of the solvents across the porous shell starkly modifies the evaporative dynamics.

  13. Molecular-thermodynamic theory of micellization of multicomponent surfactant mixtures: 2. pH-sensitive surfactants.

    PubMed

    Goldsipe, Arthur; Blankschtein, Daniel

    2007-05-22

    In article 1 of this series, we developed a molecular-thermodynamic (MT) theory to model the micellization of mixtures containing an arbitrary number of conventional (pH-insensitive) surfactants. In this article, we extend the MT theory to model mixtures containing a pH-sensitive surfactant. The MT theory was validated by examining mixtures containing both a pH-sensitive surfactant and a conventional surfactant, which effectively behave like ternary surfactant mixtures. We first compared the predicted micellar titration data to experimental micellar titration data that we obtained for varying compositions of mixed micelles containing the pH-sensitive surfactant dodecyldimethylamine oxide (C12DAO) mixed with either a cationic surfactant (dodecyltrimethylammonium bromide, C12TAB), a nonionic surfactant (dodecyl octa(ethylene oxide), C12E8), or an anionic surfactant (sodium dodecyl sulfate, SDS) surfactant. The MT theory accurately modeled the titration behavior of C12DAO mixed with C12E8. However, C12DAO was observed to interact more favorably with SDS and with C12TAB than was predicted by the MT theory. We also compared predictions to data from the literature for mixtures of C12DAO and SDS. Although the pH values of solutions with no added acid were modeled with only qualitative accuracy, the MT theory resulted in quantitatively accurate predictions of solution pH for mixtures containing added acid. In addition, the predicted degree of counterion binding yielded a lower bound to the experimentally measured value. Finally, we predicted the critical micelle concentration (cmc) of solutions of two pH-sensitive surfactants, tetradecyldimethylamine oxide (C14DAO) and hexadecyldimethyl betaine (C16Bet), at varying solution pH and surfactant composition. However, at the pH values considered, the pH sensitivity of C16Bet could be neglected, and it was equivalently modeled as a zwitterionic surfactant. The cmc's predicted using the MT theory agreed well with the experimental

  14. Evaporation of Ethanol-Water Binary Mixture Sessile Liquid Marbles.

    PubMed

    Ooi, Chin Hong; Bormashenko, Edward; Nguyen, Anh V; Evans, Geoffrey M; Dao, Dzung V; Nguyen, Nam-Trung

    2016-06-21

    Liquid marble is a liquid droplet coated with particles. Recently, the evaporation process of a sessile liquid marble using geometric measurements has attracted great attention from the research community. However, the lack of gravimetric measurement limits further insights into the physical changes of a liquid marble during the evaporation process. Moreover, the evaporation process of a marble containing a liquid binary mixture has not been reported before. The present paper investigates the effective density and the effective surface tension of an evaporating liquid marble that contains aqueous ethanol at relatively low concentrations. The effective density of an evaporating liquid marble is determined from the concurrent measurement of instantaneous mass and volume. Density measurements combined with surface profile fitting provide the effective surface tension of the marble. We found that the density and surface tension of an evaporating marble are significantly affected by the particle coating.

  15. Liquid clathrate formation in ionic liquid-aromatic mixtures.

    PubMed

    Holbrey, John D; Reichert, W Matthew; Nieuwenhuyzen, Mark; Sheppard, Oonagh; Hardacre, Christopher; Rogers, Robin D

    2003-02-21

    1-Alkyl-3-methylimidazolium containing ionic liquids with hexafluorophosphate, bis(trifyl)imide, tetrafluoroborate, and chloride anions form liquid clathrates when mixed with aromatic hydrocarbons; in the system 1,3-dimethylimidazolium hexafluorophosphate-benzene, the aromatic solute could be trapped in the solid state forming a crystalline 2:1 inclusion compound.

  16. Viscosity of Liquid Crystal Mixtures in the Presence of Electroconvection

    NASA Astrophysics Data System (ADS)

    Nagaya, Tomoyuki; Satou, Yuki; Goto, Yoshitomo; Hidaka, Yoshiki; Orihara, Hiroshi

    2016-07-01

    We have experimentally investigated the viscosity of nematic liquid crystal mixtures of p-methoxybenzylidene-p'-n-butylaniline (MBBA) and p-ethoxybenzylidene-p'-cyanoaniline (EBCA) in the presence of electroconvection under an ac electric field with 60 Hz. Although the viscosity of the mixtures with negative dielectric anisotropy shows a characteristic decrease in the high-voltage regime, that with positive dielectric anisotropy shows a monotonic increase as the applied voltage is increased. The experimental results suggest that the decrease in viscosity observed only for the mixtures with negative dielectric anisotropy is attributed to the negative contribution of electric stress caused by the anisotropic director distribution of the turbulent state.

  17. On the ideality of binary mixtures of ionic liquids.

    PubMed

    Brüssel, Marc; Brehm, Martin; Pensado, Alfonso S; Malberg, Friedrich; Ramzan, Muhammad; Stark, Annegret; Kirchner, Barbara

    2012-10-14

    In this work, structural and dynamical properties of the binary mixture of 1-ethyl-3-methyl-imidazolium chloride and 1-ethyl-3-methyl-imidazolium thiocyanate are investigated from ab initio molecular dynamics simulations and compared to the pure ionic liquids. Furthermore, the binary mixture is simulated with two different densities to gain insight into how the selected density affects the different properties. In addition, a simple NMR experiment is carried out to investigate the changes of the chemical shifts of the hydrogen atoms due to the composition of the mixture.

  18. Dynamic thermodiffusion theory for ternary liquid mixtures

    NASA Astrophysics Data System (ADS)

    Eslamian, Morteza; Ziad Saghir, M.

    2010-04-01

    Following the non-equilibrium thermodynamics approach, we develop expressions for the calculation of the thermal diffusion coefficients in a ternary system. On the basis of some physical justifications, we approximate the net heat of transport with the activation energy of viscous flow. In parallel, we revisit the Kempers model and propose new expressions for the estimation of the thermal diffusion factors in a ternary mixture. The proposed expressions are based on a dynamic modeling approach, as they incorporate the activation energy of viscous flow, which is a fluid flow property and contains the effects of some of the parameters that govern thermodiffusion. The proposed expressions, the Kempers and Ghorayeb-Firoozabadi-Shukla models are evaluated against the experimental data. Our expression which was developed on the basis of the Kempers approach has the best performance.

  19. Dielectric constant of liquid alkanes and hydrocarbon mixtures

    NASA Technical Reports Server (NTRS)

    Sen, A. D.; Anicich, V. G.; Arakelian, T.

    1992-01-01

    The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

  20. Dielectric constant of liquid alkanes and hydrocarbon mixtures.

    PubMed

    Sen, A D; Anicich, V G; Arakelian, T

    1992-01-01

    The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

  1. Electron avalanches in liquid argon mixtures

    SciTech Connect

    Kim, J.G.; Dardin, S.M.; Kadel, R.W.; Kadyk, J.A.; Wenzel, W.B.; Peskov, V.

    2004-03-19

    We have observed stable avalanche gain in liquid argon when mixed with small amounts of xenon in the high electric field (>7 MV/cm) near the point of a chemically etched needle in a point-plane geometry. We identify two gain mechanisms, one pressure dependent, and the other independent of the applied pressure. We conclude that the pressure dependent signals are from avalanche gain in gas bubbles at the tip of the needle, while the pressure independent pulses are from avalanche gain in liquid. We measure the decay time spectra of photons from both types of avalanches. The decay times from the pressure dependent pulses decrease (increase) with the applied pressure (high voltage), while the decay times from the pressure independent pulses are approximately independent of pressure or high voltage. For our operating conditions, the collected charge distribution from avalanches is similar for 60 keV or 122 keV photon sources. With krypton additives, instead of Xe, we measure behavior consistent with only the pressure dependent pulses. Neon and TMS were also investigated as additives, and designs for practical detectors were tested.

  2. Composition dependent structural organization in trihexyl(tetradecyl)phosphonium chloride ionic liquid-methanol mixtures

    SciTech Connect

    Gupta, Aditya; Sharma, Shobha; Kashyap, Hemant K.

    2015-04-07

    This article reports results from the molecular dynamics simulations on the structural arrangement of the ions and molecules in the mixtures of trihexyl(tetradecyl)phosphonium chloride ([P{sub 666,14}{sup +}][Cl{sup −}]) ionic liquid (IL) and methanol (MeOH) over the entire composition range. Effects of composition on the charge and polarity orderings have been investigated via computation of X-ray scattering structure function, S(q), and by using a partitioning scheme proposed for such multi-component mixtures. Except for the neat methanol liquid, the total S(q) shows two peaks in its intermolecular region for all the mole-fractions. The lowest q peak is dominated primarily by anion-anion, cation-anion, and methanol-anion correlations. Our results signify that the methanol bulk structure, which predominantly has short-distance characteristic correlations and is governed by polar group of methanol, is retained for x{sub IL} ≤ 0.1. Then, the mixture goes through gradual structural changes from methanol-like to the IL-like for 0.1 < x{sub IL} ≤ 0.7. The dipolar interaction between methanol molecules weakens in this range, and the structural landscape of the mixture is steered by strong ion-ion, anion-methanol, and nonpolar interactions. The IL-like structural arrangement is virtually recovered for x{sub IL} > 0.7. At all the compositions studied, while the cation head groups are predominantly solvated by anions and subsequently by methanol molecules, the polar hydroxyl group of methanol is preferentially solvated by the anions. The radial distribution functions of selected pair of atomic species have also confirmed these observations.

  3. An investigation of vapor concentration during boiling of liquid mixtures

    SciTech Connect

    Utaka, Yoshio; Takahashi, Katsuaki; Tsuboi, Takao

    1999-07-01

    The objective of the study is to clarify experimentally the variation of the vapor concentration of binary mixture generated during nucleate boiling in a saturated pool under various boiling conditions. The generated vapor concentrations in the bulk vapor layer were measured for the binary mixtures of water-ethanol and ethanol-acetone under various liquid concentrations, the heat fluxes and the liquid layer heights from the heated thin wires at the atmospheric pressure. The main experimental apparatus for measuring concentration of bulk vapor in the boiling and condensation system is shown. Two methods of measuring concentration, i.e., the dew point method and the laser absorption method were adopted. The dew point measurement was carried out by utilizing the copper heat transfer block installed in the central part of the vapor layer in the vessel. The commencement of the condensation was observed directly for determining the dew point by controlling its temperature. The laser light having wavelength of 3.39 micron meters was used for the laser light absorption method utilizing its absorptive property against ethanol vapor. The measured results by using both methods coincided well with each other. The measured concentrations of the bulk vapor for various superheatings of heated wires, the depth of liquid mixture layer and liquid concentrations were almost independent of those parameters and were almost in equilibrium with bulk liquid conditions even under the higher surface superheating and the lower liquid heights.

  4. A simple method for the titration of multicomponent acid-base mixtures.

    PubMed

    Moisio, T; Heikonen, M

    1996-01-01

    A titration method has been developed to analyze acid mixtures, in which the pK values differed by 0.5 to 1 pH units. Instead of the use of equivalence points a buffer capacity curve is numerically derived from the titration curve resulting in a presentation similar to chromatograms and spectra. The consumption of the NaOH titrant is determined within pH intervals of 0.2-0.6 units around the pK values of the components. The buffer capacity measured is expressed as the consumption of NaOH over the pH interval. The amounts of compounds are found from these results using simple models of chemometrics. The method has been applied to a mixture of formic and acetic acids with concentrations of 0-3 mmol/20 ml with an error of 0-0.05 mmol. Furthermore a curve-fitting method based on a theoretical equation of buffer capacity can be applied with an error slightly larger than with the previous method. In this case, the pK values were also computed. For titrations beyond the pH range 4-10, the buffer capacity of water has to be subtracted from the titration results. The whole procedure requires including the computations about 3-6 min.

  5. Ultrafast photophysical studies of a multicomponent sunscreen: Oxybenzone-titanium dioxide mixtures

    NASA Astrophysics Data System (ADS)

    Baker, Lewis A.; Grosvenor, Lucy C.; Ashfold, Michael N. R.; Stavros, Vasilios G.

    2016-11-01

    Recent studies of the sunscreen constituent oxybenzone have suggested that the dominant mechanism underlying the efficient photoprotection it offers relies on an initial ultrafast enol → keto tautomerisation, followed by nonadiabatic transfer to the ground electronic state. Subsequent collisions with the solvent bath then reform the original enol-tautomer. Utilising femtosecond transient electronic absorption spectroscopy we explore the dissipation of electronic excitation energy in oxybenzone in the presence of titanium dioxide, a widely used, and complementary sunscreen component. We find the relaxation dynamics of this popular organic filter are unaltered by the presence of this favoured inorganic scatterer and the overall dynamics can be described by the additive contribution of the individual constituents. The combination of the two components provides broadband photoprotective properties justifying the widely used organic filter and inorganic scatterer mixtures in commercial sunscreen products.

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

    DOEpatents

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

    2004-03-23

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

  7. Confinement-Driven Phase Separation of Quantum Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Prisk, T. R.; Pantalei, C.; Kaiser, H.; Sokol, P. E.

    2012-08-01

    We report small-angle neutron scattering studies of liquid helium mixtures confined in Mobil Crystalline Material-41 (MCM-41), a porous silica glass with narrow cylindrical nanopores (d=3.4nm). MCM-41 is an ideal model adsorbent for fundamental studies of gas sorption in porous media because its monodisperse pores are arranged in a 2D triangular lattice. The small-angle scattering consists of a series of diffraction peaks whose intensities are determined by how the imbibed liquid fills the pores. Pure He4 adsorbed in the pores show classic, layer-by-layer film growth as a function of pore filling, leaving the long range symmetry of the system intact. In contrast, the adsorption of He3-He4 mixtures produces a structure incommensurate with the pore lattice. Neither capillary condensation nor preferential adsorption of one helium isotope to the pore walls can provide the symmetry-breaking mechanism. The scattering is consistent with the formation of randomly distributed liquid-liquid microdomains ˜2.3nm in size, providing evidence that confinement in a nanometer scale capillary can drive local phase separation in quantum liquid mixtures.

  8. The Liquid Glass Transition in Sugars and Sugar Mixtures

    NASA Astrophysics Data System (ADS)

    Seo, Jeong-Ah; Oh, Jiyoung; Kwon, Hyun-Joung; Kim, Hyung Kook; Hwang, Yoon-Hwae

    2006-05-01

    The liquid-glass transition in sugars and sugar mixtures was studied with calorimetry, Brillouin scattering, and dielectric spectroscopy. Sugars are particular interest among other glass forming materials because sugars are main constitution of the biological system and sugar glasses play an important role in preservation and protection of biological cells. We studied a number of sugars and sugar mixtures including glucose, galactose, sucrose, maltose, trehalose, glucose/sucrose, sucrose/trehalose, using calorimetry (DTA and DSC), Brillouin scattering, and dielectric spectroscopy. We found the following: (1) Brillouin scattering technique can be used to determine the glass transition temperature. (2) In sugar mixtures, the volume compression effect from the molecule size and shape played an important role in the glass transition temperature. (3) The origin of the secondary relaxation in glucose-water mixtures maybe relate to the rotation-translation coupling constant in the schematic mode coupling theory.

  9. Low Mach number fluctuating hydrodynamics of multispecies liquid mixtures

    SciTech Connect

    Donev, Aleksandar Bhattacharjee, Amit Kumar; Nonaka, Andy; Bell, John B.; Garcia, Alejandro L.

    2015-03-15

    We develop a low Mach number formulation of the hydrodynamic equations describing transport of mass and momentum in a multispecies mixture of incompressible miscible liquids at specified temperature and pressure, which generalizes our prior work on ideal mixtures of ideal gases [Balakrishnan et al., “Fluctuating hydrodynamics of multispecies nonreactive mixtures,” Phys. Rev. E 89 013017 (2014)] and binary liquid mixtures [Donev et al., “Low mach number fluctuating hydrodynamics of diffusively mixing fluids,” Commun. Appl. Math. Comput. Sci. 9(1), 47-105 (2014)]. In this formulation, we combine and extend a number of existing descriptions of multispecies transport available in the literature. The formulation applies to non-ideal mixtures of arbitrary number of species, without the need to single out a “solvent” species, and includes contributions to the diffusive mass flux due to gradients of composition, temperature, and pressure. Momentum transport and advective mass transport are handled using a low Mach number approach that eliminates fast sound waves (pressure fluctuations) from the full compressible system of equations and leads to a quasi-incompressible formulation. Thermal fluctuations are included in our fluctuating hydrodynamics description following the principles of nonequilibrium thermodynamics. We extend the semi-implicit staggered-grid finite-volume numerical method developed in our prior work on binary liquid mixtures [Nonaka et al., “Low mach number fluctuating hydrodynamics of binary liquid mixtures,” http://arxiv.org/abs/1410.2300 (2015)] and use it to study the development of giant nonequilibrium concentration fluctuations in a ternary mixture subjected to a steady concentration gradient. We also numerically study the development of diffusion-driven gravitational instabilities in a ternary mixture and compare our numerical results to recent experimental measurements [Carballido-Landeira et al., “Mixed-mode instability of a

  10. New phase equilibrium analyzer for determination of the vapor-liquid equilibrium of carbon dioxide and permanent gas mixtures for carbon capture and storage.

    PubMed

    Ke, Jie; Parrott, Andrew J; Sanchez-Vicente, Yolanda; Fields, Peter; Wilson, Richard; Drage, Trevor C; Poliakoff, Martyn; George, Michael W

    2014-08-01

    A high-pressure, phase equilibrium analyzer incorporating a fiber-optic reflectometer is described. The analyzer has been designed for measuring the vapor-liquid equilibrium data of multi-component mixtures of carbon dioxide and permanent gases, providing a novel tool to acquire of a large number of phase equilibrium data for the development of the new carbon capture and storage technologies. We demonstrate that the analyzer is suitable for determining both the bubble- and dew-point lines at temperature from 253 K and pressure up to 25 MPa using pure CO2 and two binary mixtures of CO2 + N2 and CO2 + H2.

  11. New phase equilibrium analyzer for determination of the vapor-liquid equilibrium of carbon dioxide and permanent gas mixtures for carbon capture and storage

    NASA Astrophysics Data System (ADS)

    Ke, Jie; Parrott, Andrew J.; Sanchez-Vicente, Yolanda; Fields, Peter; Wilson, Richard; Drage, Trevor C.; Poliakoff, Martyn; George, Michael W.

    2014-08-01

    A high-pressure, phase equilibrium analyzer incorporating a fiber-optic reflectometer is described. The analyzer has been designed for measuring the vapor-liquid equilibrium data of multi-component mixtures of carbon dioxide and permanent gases, providing a novel tool to acquire of a large number of phase equilibrium data for the development of the new carbon capture and storage technologies. We demonstrate that the analyzer is suitable for determining both the bubble- and dew-point lines at temperature from 253 K and pressure up to 25 MPa using pure CO2 and two binary mixtures of CO2 + N2 and CO2 + H2.

  12. Some Correlations for Saturated-Liquid Density of Refrigerant Mixtures

    NASA Astrophysics Data System (ADS)

    Maezawa, Yukishige; Sato, Haruki; Watanabe, Koichi

    Three methods to correlate and estimate the saturated-1iquid density of refrigerant mixtures are compared and evaluated on the basis of the measurements for five bibary and one ternary mixtures performed by the present authors. The first of them is a method using Peng-Robinson equation (PR-method) proposed originally by Peneloux et al. Since this method dose not require any measurements of the saturated-liquid density of mixture, it is useful for the estimation. However, the applicability of this method to various substances may be restricted. The second is the modified Rackett equation proposed by Spencer and Dannar (mR-method). The temperature functional form of this equation is quite simple, so it is useful to use it as a functional form of the fitting. Unfortunately this method can not be used for strongly non-ideal mixtures. The last one is the Hankinson-Brobst-Thomson equation (HBT-method). This method can provide the most accurate density values among the three methods with two kinds of binary parameters where these binary parameters are introduced by the present authors. In the case that many experimental saturated liquid densities of mixtures are available in the wide range of temperatures, the HBT-method is recommended for the practical use.

  13. Density measurements of compressed-liquid dimethyl ether + pentane mixtures

    PubMed Central

    Outcalt, Stephanie L.; Lemmon, Eric W.

    2016-01-01

    Compressed-liquid densities of three compositions of the binary mixture dimethyl ether (CAS No. 115-10-6) + pentane (CAS No. 109-66-0) have been measured with a vibrating U-tube densimeter. Measurements were made at temperatures from 270 K to 390 K with pressures from 1.0 MPa to 50 MPa. The overall combined uncertainty (k=2) of the density data is 0.81 kg·m−3. Data presented here have been used to improve a previously formulated Helmholtz energy based mixture model. The newly derived parameters are given. PMID:27840450

  14. Ionic liquids for separation of olefin-paraffin mixtures

    DOEpatents

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2014-07-15

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  15. Ionic liquids for separation of olefin-paraffin mixtures

    DOEpatents

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2013-09-17

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  16. Fuel compositions comprising coal-liquid fuel mixture

    SciTech Connect

    Kobayashi, T.; Niimi, H.; Nobe, T.; Wada, T.

    1981-01-20

    The invention provides: a fuel composition comprising 100 parts by weight of a coal-liquid fuel mixture and 0.02 to 1.0 part by weight of at least one additive selected from the group consisting of dibenzylidene sorbitol, ditoluylidene sorbitol, tribenzylidene sorbitol, tritoluylidene sorbitol and hydrogenated castor oil; and a fuel composition comprising 100 parts by weight of a coal-liquid fuel mixture, 0.02 to 1.0 part by weight of at least one additive selected from the group consisting of dibenzylidene sorbitol, ditoluylidene sorbitol, tribenzylidene sorbitol, tritoluylidene sorbitol and hydrogenated castor oil, and 1 to 10 parts by weight of water. The composition shows high stability over a prolonged period of time, preventing the separation into layers of the components.

  17. Improved Oral Bioavailability Using a Solid Self-Microemulsifying Drug Delivery System Containing a Multicomponent Mixture Extracted from Salvia miltiorrhiza.

    PubMed

    Bi, Xiaolin; Liu, Xuan; Di, Liuqing; Zu, Qiang

    2016-04-08

    The active ingredients of salvia (dried root of Salvia miltiorrhiza) include both lipophilic (e.g., tanshinone IIA, tanshinone I, cryptotanshinone and dihydrotanshinone I) and hydrophilic (e.g., danshensu and salvianolic acid B) constituents. The low oral bioavailability of these constituents may limit their efficacy. A solid self-microemulsifying drug delivery system (S-SMEDDS) was developed to load the various active constituents of salvia into a single drug delivery system and improve their oral bioavailability. A prototype SMEDDS was designed using solubility studies and phase diagram construction, and characterized by self-emulsification performance, stability, morphology, droplet size, polydispersity index and zeta potential. Furthermore, the S-SMEDDS was prepared by dispersing liquid SMEDDS containing liposoluble extract into a solution containing aqueous extract and hydrophilic polymer, and then freeze-drying. In vitro release of tanshinone IIA, salvianolic acid B, cryptotanshinone and danshensu from the S-SMEDDS was examined, showing approximately 60%-80% of each active component was released from the S-SMEDDS in vitro within 20 min. In vivo bioavailability of these four constituents indicated that the S-SMEDDS showed superior in vivo oral absorption to a drug suspension after oral administration in rats. It can be concluded that the novel S-SMEDDS developed in this study increased the dissolution rate and improved the oral bioavailability of both lipophilic and hydrophilic constituents of salvia. Thus, the S-SMEDDS can be regarded as a promising new method by which to deliver salvia extract, and potentially other multicomponent drugs, by the oral route.

  18. Viscosity minima in binary mixtures of ionic liquids + molecular solvents.

    PubMed

    Tariq, M; Shimizu, K; Esperança, J M S S; Canongia Lopes, J N; Rebelo, L P N

    2015-05-28

    The viscosity (η) of four binary mixtures (ionic liquids plus molecular solvents, ILs+MSs) was measured in the 283.15 < T/K < 363.15 temperature range. Different IL/MS combinations were selected in such a way that the corresponding η(T) functions exhibit crossover temperatures at which both pure components present identical viscosity values. Consequently, most of the obtained mixture isotherms, η(x), exhibit clear viscosity minima in the studied T-x range. The results are interpreted using auxiliary molecular dynamics (MD) simulation data in order to correlate the observed η(T,x) trends with the interactions in each mixture, including the balance between electrostatic forces and hydrogen bonding.

  19. Molecular thermodynamics of some highly asymmetric liquid mixtures

    NASA Astrophysics Data System (ADS)

    Wu, Jianzhong

    1998-11-01

    To advance understanding of the thermodynamic properties of complex liquid mixtures, molecular-thermodynamic attention is given to several types of asymmetric mixtures: asphaltene-containing crude oils, water- hydrocarbon mixtures with or without salt, and aqueous saline solutions of proteins and colloids. The phase behavior of these liquid mixtures is important for optimum design of industrial processes including production of petroleum and natural gas, separation of protein mixtures, and synthesis of new materials. The objective is to provide molecular-thermodynamic models for describing thermodynamic properties of these industry-oriented liquid mixtures. Our model for an asphaltene-containing crude oil represents asphaltenes by attractive hard spheres, resins by attractive hard-sphere chains, and all other components by a continuous medium that affects interactions between asphaltene-asphaltene, asphaltene- resin, and resin-resin pairs. We consider explicitly associations between asphaltene and asphaltene, and between asphaltene and resin. Thermodynamic properties are described in the McMillan-Mayer framework using the statistical-associated-fluid theory (SAFT). Our model can semi-quantitatively explain essentially all experimental observations concerning asphaltene precipitation from crude oils. This model has been applied to identify approximately the operating conditions at the onset of asphaltene precipitation, and the amount of precipitation under various petroleum-reservoir conditions. For the prevention of asphaltene precipitation, we recommend the use of amphiphiles that like both asphaltenes and the oil medium, but not the resins. For water-hydrocarbon mixtures with or without salt, we have developed theoretically-based extensions of the Peng-Robinson equation of state by including associations and electrostatic interactions. Illustrative examples show that these extensions are successful for correlating vapor-liquid equilibria for hydrocarbon

  20. Solid-liquid equilibria of binary mixtures of fluorinated ionic liquids.

    PubMed

    Teles, Ana Rita R; Correia, Helga; Maximo, Guilherme J; Rebelo, Luís P N; Freire, Mara G; Pereiro, Ana B; Coutinho, João A P

    2016-09-28

    Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid-liquid and solid-solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid-liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid-solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures.

  1. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    SciTech Connect

    Stout, R B

    2001-04-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  2. New design of fiber-optic reflectometer for determining the phase boundary of multicomponent fluid mixtures at high pressures and high temperatures

    NASA Astrophysics Data System (ADS)

    Wu, Weize; Ke, Jie; Poliakoff, Martyn

    2006-02-01

    A dynamic synthetic method based on an optic fiber sensor has been developed to measure phase boundaries of multicomponent fluid at high temperatures >300°C and pressures >30MPa. The breakthrough has been the design of the equilibrium cell containing the optic fiber, which gives highly reproducible signals for the phase transition. We demonstrate that this method can clearly distinguish between dew points and bubble points in the phase transitions of mixtures. Overall, the method is characterized by speed, simplicity, high pressures, and high temperatures.

  3. Fractionation in Gay-Berne liquid crystal mixtures.

    PubMed

    Moreno-Razo, J Antonio; Díaz-Herrera, Enrique; Klapp, Sabine H L

    2007-10-01

    We present a constant-pressure molecular dynamics simulation study of the phase behavior of binary (50:50) Gay-Berne liquid crystal mixtures consisting of elongated particles with different lengths (LA>LB) and equal diameters. We focus on systems at dense liquid-state conditions. Considering three mixtures characterized by different values of LA(B) and different length ratios q=LB/LA<1, we find complex fluid-fluid phase behavior resulting from the interplay between nematic, smectic-A-type, or smectic-B-type orientational ordering, on the one hand, and demixing into two phases of different composition (fractionation), on the other hand. The driving "forces" of demixing transitions are the temperature and the length ratio. Indeed, in the system characterized by the largest value of q (q=0.86) orientational order occurs already in mixed states, whereas full fractionation is found at q=0.71. The two resulting states are either of type smectic-B-nematic (intermediate temperatures) or smectic-B-smectic-B (low temperatures). In the intermediate case q=0.80 we observe a stepwise ordering and demixing behavior on cooling the system from high temperatures. Moreover, our results show that the stability range of (partially) nematic structures in mixtures of sufficiently small q can be significantly larger than in the pure counterparts, in qualitative agreement with experimental observations.

  4. Mathematical modeling of planar and spherical vapor-liquid phase interfaces for multicomponent fluids

    NASA Astrophysics Data System (ADS)

    Celný, David; Vinš, Václav; Planková, Barbora; Hrubý, Jan

    2016-03-01

    Development of methods for accurate modeling of phase interfaces is important for understanding various natural processes and for applications in technology such as power production and carbon dioxide separation and storage. In particular, prediction of the course of the non-equilibrium phase transition processes requires knowledge of the properties of the strongly curved phase interfaces of microscopic droplets. In our work, we focus on the spherical vapor-liquid phase interfaces for binary mixtures. We developed a robust computational method to determine the density and concentration profiles. The fundamentals of our approach lie in the Cahn-Hilliard gradient theory, allowing to transcribe the functional formulation into a system of ordinary Euler-Langrange equations. This system is then split and modified into a shape suitable for iterative computation. For this task, we combine the Newton-Raphson and the shooting methods providing a good convergence speed. For the thermodynamic roperties, the PC-SAFT equation of state is used. We determine the density and concentration profiles for spherical phase interfaces at various saturation factors for the binary mixture of CO2 and C9H20. The computed concentration profiles allow to the determine the work of formation and other characteristics of the microscopic droplets.

  5. Rheology of protic ionic liquids and their mixtures.

    PubMed

    Smith, J A; Webber, Grant B; Warr, Gregory G; Atkin, Rob

    2013-11-07

    The rheological properties of five pure protic ionic liquids (ILs), ethylammonium nitrate (EAN), propylammonium nitrate (PAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), and dimethylethylammonium formate (DMEAF), are characterized and interpreted by considering the effects of both the H-bond network and the solvophobic nanostructure of the liquids. The results demonstrate that these effects are not, however, independent or simply additive. At 20 °C, EtAN has the highest zero shear viscosity of 156.1 mPa·s, followed by PAN (89.3 mPa·s), EAN (35.9 mPa·s), EAF (23.1 mPa·s), and DMEAF (9.8 mPa·s). The primary ammonium ILs behave as Newtonian fluids at low shear rates but shear thin at high shear. Fits to the Vogel-Fulcher-Tammann model reveal that nanostructure is not affected appreciably by temperature and that all the ILs studied are of intermediate fragility. The rheology of binary mixtures of these ILs was analyzed and used to demonstrate fundamental differences in the way IL cations and anions interact. IL mixtures containing both nitrate and formate anions resist flow more strongly than the pure liquids, which is a consequence of the difference in hydrogen bonding capacity of the anions. Mixing cations can give rise to complex behavior due to the offsetting effects of hydrogen bonding and solvophobic nanostructure formation.

  6. Dielectrophoretic manipulation of the mixture of isotropic and nematic liquid

    NASA Astrophysics Data System (ADS)

    Kim, Soo-Dong; Lee, Bomi; Kang, Shin-Woong; Song, Jang-Kun

    2015-08-01

    In various applications involving liquid crystals, the manipulation of the nanoscale molecular assembly and microscale director alignment is highly useful. Here we show that a nematic-isotropic mixture, a unique bi-liquid system, has potential for the fabrication of microstructures having an ordered phase within a disordered phase, or vice versa. The volume expansion and shrinkage, migration, splitting, mergence and elongation of one phase within the other are easily accomplished via thermal treatment and dielectrophoretic manipulation. This is particularly achievable when one phase is suspended in the middle. In that case, a highly biased ordered-phase preference of surfaces, that is, the nematic-philic nature of a polyimide layer and the nematic-phobic nature of a self-assembled monolayer of chlorosilane derivatives, is used. Further, by combining this approach with photopolymerization, the patterned microstructure is solidified as a patterned polymer film having both isotropic and anisotropic molecular arrangements simultaneously, or as a template with a morphological variation.

  7. Mixing Enthalpy for Binary Mixtures Containing Ionic Liquids.

    PubMed

    Podgoršek, A; Jacquemin, J; Pádua, A A H; Costa Gomes, M F

    2016-05-25

    A complete review of the published data on the mixing enthalpies of mixtures containing ionic liquids, measured directly using calorimetric techniques, is presented in this paper. The field of ionic liquids is very active and a number of research groups in the world are dealing with different applications of these fluids in the fields of chemistry, chemical engineering, energy, gas storage and separation or materials science. In all these fields, the knowledge of the energetics of mixing is capital both to understand the interactions between these fluids and the different substrates and also to establish the energy and environmental cost of possible applications. Due to the relative novelty of the field, the published data is sometimes controversial and recent reviews are fragmentary and do not represent a set of reliable data. This fact can be attributed to different reasons: (i) difficulties in controlling the purity and stability of the ionic liquid samples; (ii) availability of accurate experimental techniques, appropriate for the measurement of viscous, charged, complex fluids; and (iii) choice of an appropriate clear thermodynamic formalism to be used by an interdisciplinary scientific community. In this paper, we address all these points and propose a critical review of the published data, advise on the most appropriate apparatus and experimental procedure to measure this type of physical-chemical data in ionic liquids as well as the way to treat the information obtained by an appropriate thermodynamic formalism.

  8. Collapse of granular-liquid mixtures over rigid, inclined beds.

    PubMed

    Berzi, D; Bossi, F C; Larcan, E

    2012-05-01

    This work deals with the propagation of granular-liquid waves over rigid beds, originated by the sudden removal of a sluice gate in a rectangular, inclined flume. In particular, we experimentally investigate the role of the initial volume ratio of granular material-monodispersed plastic cylinders-to water, the flume width, and the bed roughness on the time evolution of the granular front. Due to the presence of the interstitial liquid, we observed previously unreported types of collapse: (i) discontinuous flows, where the granular material stops after an initial spreading, and then flows again when the liquid, initially slower than the particles, reaches the front and remobilizes it; (ii) flows evolving into uniformly progressive waves at an angle of inclination of the flume well below the angle of repose of the dry granular material. We also noticed an unusual influence of the lateral confinement on the wave propagation. Indeed, the constant front velocity in the uniformly progressive state decreases when the channel width increases. We claim that the latter observation and the presence of discontinuous flows, strongly support the idea that only two-phase, stratified mathematical models can predict the behavior of unsteady, granular-liquid mixtures at high concentration, such as debris flows.

  9. Algorithms for GPU-based molecular dynamics simulations of complex fluids: Applications to water, mixtures, and liquid crystals.

    PubMed

    Kazachenko, Sergey; Giovinazzo, Mark; Hall, Kyle Wm; Cann, Natalie M

    2015-09-15

    A custom code for molecular dynamics simulations has been designed to run on CUDA-enabled NVIDIA graphics processing units (GPUs). The double-precision code simulates multicomponent fluids, with intramolecular and intermolecular forces, coarse-grained and atomistic models, holonomic constraints, Nosé-Hoover thermostats, and the generation of distribution functions. Algorithms to compute Lennard-Jones and Gay-Berne interactions, and the electrostatic force using Ewald summations, are discussed. A neighbor list is introduced to improve scaling with respect to system size. Three test systems are examined: SPC/E water; an n-hexane/2-propanol mixture; and a liquid crystal mesogen, 2-(4-butyloxyphenyl)-5-octyloxypyrimidine. Code performance is analyzed for each system. With one GPU, a 33-119 fold increase in performance is achieved compared with the serial code while the use of two GPUs leads to a 69-287 fold improvement and three GPUs yield a 101-377 fold speedup.

  10. Mutual diffusion in binary mixtures of ionic liquids and molecular liquids by dynamic light scattering (DLS).

    PubMed

    Rausch, Michael Heinrich; Lehmann, Julia; Leipertz, Alfred; Fröba, Andreas Paul

    2011-05-28

    The present study shows that dynamic light scattering (DLS) is capable of measuring mutual diffusion coefficients for binary mixtures of ionic liquids (ILs) with different molecular liquids over the complete composition range. Evidence is given that the light scattering signals are related to true molecular binary diffusion. The method stands out due to its ability to work non-invasively in macroscopic thermodynamic equilibrium with reasonable accuracy and within convenient measurement periods. Compared with other techniques, mixtures with distinctly higher viscosities can be probed. For exemplary binary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO(4)]) with acetone, acetonitrile, dichloromethane, ethanol, or water as well as of 1-ethyl-3-methylimidazolium methanesulfonate ([EMIM][MeSO(3)]) with acetone, water, or methanol, mutual diffusivity data were measured over a wide range of composition at a temperature of 293.15 K. In general, the mutual diffusivity increases with increasing mole fraction of the molecular liquid and similarities to aqueous solutions of classical inorganic salts can be found. The characteristic behavior of the mutual diffusion coefficients is influenced by the nature of the chosen molecular liquid. For IL water mixtures, low light scattering intensities were observed despite the large refractive index difference of the pure components. The reason for this behavior may be the existence of water clusters in the mixtures. Additional measurements for IL acetone mixtures at temperatures ranging from 278.15 K to 323.15 K showed that the temperature dependence of the mutual diffusivity can be represented by Arrhenius functions and is increasing for decreasing mole fractions of acetone.

  11. The Soret Effect in Liquid Mixtures - A Review

    NASA Astrophysics Data System (ADS)

    Köhler, Werner; Morozov, Konstantin I.

    2016-07-01

    The Soret effect describes diffusive motion that originates from a temperature gradient. It is observed in mixtures of gases, liquids and even solids. Although there is a formal phenomenological description based on linear nonequilibrium thermodynamics, the Soret effect is a multicause phenomenon and there is no univocal microscopic picture. After a brief historical overview and an outline of the fundamental thermodynamic concepts, this review focuses on thermodiffusion in binary and ternary liquid mixtures. The most important experimental techniques used nowadays are introduced. Then, a modern development in studying thermal diffusion, the discovery of both integral and specific additivity laws, is discussed. The former relate to the general behavior of the substances in a temperature field according to their thermophobicities, which prove to be pure component properties. The thermophobicities allow for a convenient classification of the phenomenon, a simple interpretation and a proper estimation and prediction of the thermodiffusion parameters. The specific laws relate to the additivity of the particular contributions. Among the latter, we discuss the isotopic Soret effect and the so-called chemical contribution. From the theoretical side, there are kinetic and thermodynamic theories, and the nature of the driving forces of thermodiffusion can be either of volume or surface type. Besides analytical models, computer simulations become increasingly important. Polymer solutions are special as they represent highly asymmetric molecular systems with a molar mass-independent thermophoretic mobility. Its origin is still under debate, and draining and non-draining models are presently discussed. Finally, some discussion is devoted to ternary mixtures, which only recently have been investigated in more detail.

  12. Ion Partitioning at the liquid/vapor interface of a multi-component alkali halidesolution: A model for aqueous sea salt aerosols

    SciTech Connect

    Ghosal, Sutapa; Brown, Matthew A.; Bluhm, Hendrik; Krisch, Maria J.; Salmeron, Miquel; Jungwirth, Pavel; Hemminger, John C.

    2008-12-22

    The chemistry of Br species associated with sea salt ice and aerosols has been implicated in the episodes of ozone depletion reported at Arctic sunrise. However, Br{sup -} is only a minor component in sea salt, which has a Br{sup -}/Cl{sup -} molar ratio of {approx}0.0015. Sea salt is a complex mixture of many different species, with NaCl as the primary component. In recent years experimental and theoretical studies have reported enhancement of the large, more polarizable halide ion at the liquid/vapor interface of corresponding aqueous alkali halide solutions. The proposed enhancement is likely to influence the availability of sea salt Br{sup -} for heterogeneous reactions such as those involved in the ozone depletion episodes. We report here ambient pressure x-ray photoelectron spectroscopy studies and molecular dynamics simulations showing direct evidence of Br{sup -} enhancement at the interface of an aqueous NaCl solution doped with bromide. The experiments were carried out on samples with Br{sup -}/Cl{sup -} ratios in the range 0.1% to 10%, the latter being also the ratio for which simulations were carried out. This is the first direct measurement of interfacial enhancement of Br{sup -} in a multi-component solution with particular relevance to sea salt chemistry.

  13. Thermochromic Behavior of a Novel Nematic Liquid Crystal Mixture:. Effects of Chiral Doping

    NASA Astrophysics Data System (ADS)

    Kapila, Shikha; Raina, K. K.

    Chirality was induced in a room temperature nematic liquid crystalline mixture. The phase transitions of doped samples were studied and thermochromic response of the mixture was investigated via RGB (Red-Green-Blue) and Hue measurements.

  14. Multicomponent high-performance liquid chromatography/tandem mass spectrometry analysis of ten chemotherapeutic drugs in wipe samples.

    PubMed

    Maeda, Shinichiro; Miwa, Yoshihiro

    2013-03-15

    Progress in chemotherapy leads to increased numbers and variety of chemotherapeutic drugs, and multicomponent analysis of these drugs is a necessary step. We used liquid chromatography-tandem mass spectrometry and developed a multicomponent analysis of ten drugs used in chemotherapy: vindesine, vincristine, vinblastine, doxorubicin, epirubicin, ifosfamide, cyclophosphamide, irinotecan, docetaxel, and paclitaxel. We selected five internal standards for each category of drug, because the ionization efficiencies of product ions varied widely. The total run time was 22min, applying a gradient elution of water and acetonitrile in the presence of 0.1% formic acid. The lower limit of quantification was 50ng/wipe samples for vindesine, vincristine, and vinblastine, and 5ng/wipe samples for the remaining seven drugs. Accuracy (88.6-112.9%, 85.2-111.7%) and precision (1.0-11.5%CV, 3.6-14.4%CV) in within-run and between-run assays of QC solutions were acceptable. Without outliers, in within-run and between-run assays of QC samples, accuracy was 90.6-113.9% and 91.1-130.4%, respectively, and precision was 2.2-19.0%CV and 4.8-14.9%CV, respectively. Accuracy and precision of High QC samples of irinotecan were deviated. Our analysis procedure has sufficient sensitivity and is convenient enough for regular monitoring.

  15. Qualitative Analysis of Liquid Hydrocarbon Mixtures by Absorption Spectra of Their Vapors

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.

    2016-11-01

    Absorption spectra of saturated vapors of hydrocarbons and their mixtures were studied near their first overtones. Absorption spectra of hydrocarbons in the liquid and vapor states were compared. The ability to analyze qualitatively the compositions of liquid hydrocarbon mixtures using absorption spectra of their vapors was demonstrated. Indirect evidence suggested that the nonlinear absorption as a function of concentration that was seen in liquid hydrocarbon mixtures was negligible in their vapors.

  16. Multiphase, multicomponent parameter estimation for liquid and vapor fluxes in deep arid systems using hydrologic data and natural environmental tracers

    USGS Publications Warehouse

    Kwicklis, E.M.; Wolfsberg, A.V.; Stauffer, P.H.; Walvoord, M.A.; Sully, M.J.

    2006-01-01

    Multiphase, multicomponent numerical models of long-term unsaturated-zone liquid and vapor movement were created for a thick alluvial basin at the Nevada Test Site to predict present-day liquid and vapor fluxes. The numerical models are based on recently developed conceptual models of unsaturated-zone moisture movement in thick alluvium that explain present-day water potential and tracer profiles in terms of major climate and vegetation transitions that have occurred during the past 10 000 yr or more. The numerical models were calibrated using borehole hydrologic and environmental tracer data available from a low-level radioactive waste management site located in a former nuclear weapons testing area. The environmental tracer data used in the model calibration includes tracers that migrate in both the liquid and vapor phases (??D, ??18O) and tracers that migrate solely as dissolved solutes (Cl), thus enabling the estimation of some gas-phase as well as liquid-phase transport parameters. Parameter uncertainties and correlations identified during model calibration were used to generate parameter combinations for a set of Monte Carlo simulations to more fully characterize the uncertainty in liquid and vapor fluxes. The calculated background liquid and vapor fluxes decrease as the estimated time since the transition to the present-day arid climate increases. However, on the whole, the estimated fluxes display relatively little variability because correlations among parameters tend to create parameter sets for which changes in some parameters offset the effects of others in the set. Independent estimates on the timing since the climate transition established from packrat midden data were essential for constraining the model calibration results. The study demonstrates the utility of environmental tracer data in developing numerical models of liquid- and gas-phase moisture movement and the importance of considering parameter correlations when using Monte Carlo analysis to

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

    PubMed

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

    2015-09-14

    We determine the interfacial properties of a symmetrical binary mixture of equal-sized spherical Lennard-Jones molecules, σ11 = σ22, with the same dispersive energy between like species, ϵ11 = ϵ22, 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 Janec̆ek [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 rc 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 rc 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 molecules

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

    SciTech Connect

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

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    We determine the interfacial properties of a symmetrical binary mixture of equal-sized spherical Lennard-Jones molecules, σ11 = σ22, with the same dispersive energy between like species, ɛ11 = ɛ22, 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 Janec̆ek [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 rc 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 rc 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 molecules

  20. Critical Casimir effect in classical binary liquid mixtures

    NASA Astrophysics Data System (ADS)

    Gambassi, A.; Maciołek, A.; Hertlein, C.; Nellen, U.; Helden, L.; Bechinger, C.; Dietrich, S.

    2009-12-01

    If a fluctuating medium is confined, the ensuing perturbation of its fluctuation spectrum generates Casimir-like effective forces acting on its confining surfaces. Near a continuous phase transition of such a medium the corresponding order parameter fluctuations occur on all length scales and therefore close to the critical point this effect acquires a universal character, i.e., to a large extent it is independent of the microscopic details of the actual system. Accordingly it can be calculated theoretically by studying suitable representative model systems. We report on the direct measurement of critical Casimir forces by total internal reflection microscopy with femtonewton resolution. The corresponding potentials are determined for individual colloidal particles floating above a substrate under the action of the critical thermal noise in the solvent medium, constituted by a binary liquid mixture of water and 2,6-lutidine near its lower consolute point. Depending on the relative adsorption preferences of the colloid and substrate surfaces with respect to the two components of the binary liquid mixture, we observe that, upon approaching the critical point of the solvent, attractive or repulsive forces emerge and supersede those prevailing away from it. Based on the knowledge of the critical Casimir forces acting in film geometries within the Ising universality class and with equal or opposing boundary conditions, we provide the corresponding theoretical predictions for the sphere—planar wall geometry of the experiment. The experimental data for the effective potential can be interpreted consistently in terms of these predictions and a remarkable quantitative agreement is observed.

  1. Critical Casimir effect in classical binary liquid mixtures.

    PubMed

    Gambassi, A; Maciołek, A; Hertlein, C; Nellen, U; Helden, L; Bechinger, C; Dietrich, S

    2009-12-01

    If a fluctuating medium is confined, the ensuing perturbation of its fluctuation spectrum generates Casimir-like effective forces acting on its confining surfaces. Near a continuous phase transition of such a medium the corresponding order parameter fluctuations occur on all length scales and therefore close to the critical point this effect acquires a universal character, i.e., to a large extent it is independent of the microscopic details of the actual system. Accordingly it can be calculated theoretically by studying suitable representative model systems. We report on the direct measurement of critical Casimir forces by total internal reflection microscopy with femtonewton resolution. The corresponding potentials are determined for individual colloidal particles floating above a substrate under the action of the critical thermal noise in the solvent medium, constituted by a binary liquid mixture of water and 2,6-lutidine near its lower consolute point. Depending on the relative adsorption preferences of the colloid and substrate surfaces with respect to the two components of the binary liquid mixture, we observe that, upon approaching the critical point of the solvent, attractive or repulsive forces emerge and supersede those prevailing away from it. Based on the knowledge of the critical Casimir forces acting in film geometries within the Ising universality class and with equal or opposing boundary conditions, we provide the corresponding theoretical predictions for the sphere-planar wall geometry of the experiment. The experimental data for the effective potential can be interpreted consistently in terms of these predictions and a remarkable quantitative agreement is observed.

  2. Assessment of toxic interactions of heavy metals in multi-component mixtures using sea urchin embryo-larval bioassay.

    PubMed

    Xu, Xue; Li, Yan; Wang, Yuan; Wang, Yonghua

    2011-02-01

    The toxicities of copper, lead, zinc and cadmium ions and various concentrations of mixtures of them were studied using sea urchin (Strongylocentyotus intermedius) embryo-larval bioassay. Toxic unit analysis was used to determine type of joint action for each mixture combination (binary, ternary and quaternary). For the majority of the binary combinations, the interactions were of synergistic nature, but in ternary or quaternary mixtures, the joint action was mainly concentration additive, while antagonism was only observed for two mixtures (Cu+Pb and Zn+Cd) among all the 11 combinations. Two prevailing theoretical models: the concentration addition (CA) model and the independent action (IA) model were used to predict the mixture toxicities. The weak correlation obtained (R≃0.55) indicated that the hypotheses of mode of action involved in the two models to some extent failed to describe the behavior of the mixture system. Then a novel bio-concentration factor-based model was developed and was successful to predict the toxicities of mixtures, with an obtained R of 0.92. This model indicated that in a mixture system of heavy metals, the joint toxicity was mainly determined by the combined action of bio-concentrations of metals other than the simply similar (CA) or dissimilar (IA) modes of action of the mixture components.

  3. A new developed velocity of sound measurement device for characterization of multi-component gas mixtures under elevated temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Seibel, C.; Suedmeyer, J.; Fieback, T. M.

    2014-07-01

    Inline process control by measurement of velocity of sound of fluids is a direct and comprehensive technique [J. D. N. Cheeke and Z. Wang, "Acoustic wave gas sensors," Sens. Actuators B 59, 146-153 (1999); J. W. Grate, S. J. Martin, and R. M. White, "Acoustic wave microsensors," Anal. Chem. 65, 1868 (1993)]. Depending on the varying conditions of measuring fluid(s), temperatures and pressures, it is a challenging task to find the best possible acoustic setup. Taking this background into account, a velocity of sound measurement device for temperatures up to 475 K and pressures up to 24 MPa was designed and assembled that is to be used for testing different resonator types. Two bulk acoustic wave resonators out of the commonly used lead zirconatetitanate compound (PZT) were tested at different test fluids under temperatures up to 423.15 K and pressures up to 24 MPa [S. Gebhardt, L. Seffner, F. Schlenkirch, and A. Schönecker, "PZT thick films for sensor and actuator applications," J. Eur. Ceram. Soc. 27, 4177-4180 (2007)]. Initially the pure gases methane, ethane, carbon dioxide, nitrogen, and helium were measured, followed by multi-component gas mixtures. Beside methane-based binary and ternary gas mixtures, a quaternary gas mixture comprising methane, ethane, carbon dioxide, and helium was analyzed. Results for all measurement fluids in a broad temperature and pressure range show a relative deviation to theoretical values derived from GERG-2008 smaller than 0.5%.

  4. Use of pruned computational neural networks for processing the response of oscillating chemical reactions with a view to analyzing nonlinear multicomponent mixtures.

    PubMed

    Hervás, C; Toledo, R; Silva, M

    2001-01-01

    The suitability of pruned computational neural networks (CNNs) for resolving nonlinear multicomponent systems involving synergistic effects by use of oscillating chemical reaction-based methods implemented using the analyte pulse perturbation technique is demonstrated. The CNN input data used for this purpose are estimates provided by the Levenberg-Marquardt method in the form of a three-parameter Gaussian curve associated with the singular profile obtained when the oscillating system is perturbed by an analyte mixture. The performance of the proposed method was assessed by applying it to the resolution of mixtures of pyrogallol and gallic acid based on their perturbating effect on a classical oscillating chemical system, viz. the Belousov-Zhabotinskyi reaction. A straightforward network topology (3:3:2, with 18 connections after pruning) allowed the resolution of mixtures of the two analytes in concentration ratios from 1:7 to 6:2 with a standard error of prediction for the testing set of 4.01 and 8.98% for pyrogallol and gallic acid, respectively. The reduced dimensions of the selected CNN architecture allowed a mathematical transformation of the input vector into the output one that can be easily implemented via software. Finally, the suitability of response surface analysis as an alternative to CNNs was also tested. The results were poor (relative errors were high), which confirms that properly selected pruned CNNs are effective tools for solving the analytical problem addressed in this work.

  5. A new developed velocity of sound measurement device for characterization of multi-component gas mixtures under elevated temperatures and pressures.

    PubMed

    Seibel, C; Suedmeyer, J; Fieback, T M

    2014-07-01

    Inline process control by measurement of velocity of sound of fluids is a direct and comprehensive technique [J. D. N. Cheeke and Z. Wang, "Acoustic wave gas sensors," Sens. Actuators B 59, 146-153 (1999); J. W. Grate, S. J. Martin, and R. M. White, "Acoustic wave microsensors," Anal. Chem. 65, 1868 (1993)]. Depending on the varying conditions of measuring fluid(s), temperatures and pressures, it is a challenging task to find the best possible acoustic setup. Taking this background into account, a velocity of sound measurement device for temperatures up to 475 K and pressures up to 24 MPa was designed and assembled that is to be used for testing different resonator types. Two bulk acoustic wave resonators out of the commonly used lead zirconatetitanate compound (PZT) were tested at different test fluids under temperatures up to 423.15 K and pressures up to 24 MPa [S. Gebhardt, L. Seffner, F. Schlenkirch, and A. Schönecker, "PZT thick films for sensor and actuator applications," J. Eur. Ceram. Soc. 27, 4177-4180 (2007)]. Initially the pure gases methane, ethane, carbon dioxide, nitrogen, and helium were measured, followed by multi-component gas mixtures. Beside methane-based binary and ternary gas mixtures, a quaternary gas mixture comprising methane, ethane, carbon dioxide, and helium was analyzed. Results for all measurement fluids in a broad temperature and pressure range show a relative deviation to theoretical values derived from GERG-2008 smaller than 0.5%.

  6. Combustion characteristics of nanoaluminum, liquid water, and hydrogen peroxide mixtures

    SciTech Connect

    Sabourin, J.L.; Yetter, R.A.; Risha, G.A.; Son, S.F.; Tappan, B.C.

    2008-08-15

    An experimental investigation of the combustion characteristics of nanoaluminum (nAl), liquid water (H{sub 2}O{sub (l)}), and hydrogen peroxide (H{sub 2}O{sub 2}) mixtures has been conducted. Linear and mass-burning rates as functions of pressure, equivalence ratio ({phi}), and concentration of H{sub 2}O{sub 2} in H{sub 2}O{sub (l)} oxidizing solution are reported. Steady-state burning rates were obtained at room temperature using a windowed pressure vessel over an initial pressure range of 0.24 to 12.4 MPa in argon, using average nAl particle diameters of 38 nm, {phi} from 0.5 to 1.3, and H{sub 2}O{sub 2} concentrations between 0 and 32% by mass. At a nominal pressure of 3.65 MPa, under stoichiometric conditions, mass-burning rates per unit area ranged between 6.93 g/cm{sup 2} s (0% H{sub 2}O{sub 2}) and 37.04 g/cm{sup 2} s (32% H{sub 2}O{sub 2}), which corresponded to linear burning rates of 9.58 and 58.2 cm/s, respectively. Burning rate pressure exponents of 0.44 and 0.38 were found for stoichiometric mixtures at room temperature containing 10 and 25% H{sub 2}O{sub 2}, respectively, up to 5 MPa. Burning rates are reduced above {proportional_to}5 MPa due to the pressurization of interstitial spaces of the packed reactant mixture with argon gas, diluting the fuel and oxidizer mixture. Mass burning rates were not measured above {proportional_to}32% H{sub 2}O{sub 2} due to an anomalous burning phenomena, which caused overpressurization within the quartz sample holder, leading to tube rupture. High-speed imaging displayed fingering or jetting ahead of the normal flame front. Localized pressure measurements were taken along the sample length, determining that the combustion process proceeded as a normal deflagration prior to tube rupture, without significant pressure buildup within the tube. In addition to burning rates, chemical efficiencies of the combustion reaction were determined to be within approximately 10% of the theoretical maximum under all conditions

  7. Biomass Pretreatment using Ionic Liquid and Glycerol Mixtures

    NASA Astrophysics Data System (ADS)

    Lynam, Joan Goerss

    Lignocellulosic biomass is a renewable, sustainable resource that can replace or supplement fossil fuels use for liquid fuels and chemicals. However, its recalcitrant structure including interwoven cellulose, hemicelluloses, and lignin biomacromolecules is challenging to deconstruct. Pretreating biomass so that it can be converted to useful liquids dominates process economics. Many pretreatment methods exist, but most require hazardous chemicals or processing conditions. Many ionic liquids (ILs), salts molten below 100°C, can be used to deconstruct lignocellulosic biomass and are less hazardous than the volatile organic compounds typically used. While effective, relatively safe, and recyclable, ILs are expensive. To reduce costs, dilution with other safe compounds is desirable, if there is no impact on deconstruction efficiency. Glycerol, a food additive, is inexpensive and becoming even more so since it is a by-product of the burgeoning biodiesel industry. Use of glycerol as an additive or diluent for ILs is extensively evaluated in this work. Rice hulls are an abundant biomass, with over 100 million tons produced per year, but with little practical use. The IL 1-ethyl-3-methylimidazolium formate ([C2mim][O2CH] or EMIM Form) when mixed with an equal amount of glycerol has been shown to be effective in pretreating rice hulls. Ambient pressure, a pretreatment temperature of 110°C, and a reaction time of three hours produced rice hulls that could be enzymatically hydrolyzed to give reasonably good glucose and xylose yields considering the recalcitrance of this silica-armored biomass. The IL [C2mim][O2CH] was also effective when mixed with an equal amount of glycerol to pretreat loblolly pine, a fast-growing softwood. Loblolly pine was pretreated at 140°C for three hours to produce a solid rich in cellulose and hemicelluloses, while a lignin-rich product could be precipitated from the IL. Similar products were obtained from pretreatment with a mixture of 75% 1

  8. Correlations and scaling properties of nonequilibrium fluctuations in liquid mixtures

    NASA Astrophysics Data System (ADS)

    Brogioli, Doriano; Croccolo, Fabrizio; Vailati, Alberto

    2016-08-01

    Diffusion in liquids is accompanied by nonequilibrium concentration fluctuations spanning all the length scales comprised between the microscopic scale a and the macroscopic size of the system, L . Up to now, theoretical and experimental investigations of nonequilibrium fluctuations have focused mostly on determining their mean-square amplitude as a function of the wave vector. In this work, we investigate the local properties of nonequilibrium fluctuations arising during a stationary diffusion process occurring in a binary liquid mixture in the presence of a uniform concentration gradient, ∇ c0 . We characterize the fluctuations by evaluating statistical features of the system, including the mean-square amplitude of fluctuations and the corrugation of the isoconcentration surfaces; we show that they depend on a single mesoscopic length scale l =√{a L } representing the geometric average between the microscopic and macroscopic length scales. We find that the amplitude of the fluctuations is very small in practical cases and vanishes when the macroscopic length scale increases. The isoconcentration surfaces, or fronts of diffusion, have a self-affine structure with corrugation exponent H =1 /2 . Ideally, the local fractal dimension of the fronts of diffusion would be Dl=d -H , where d is the dimensionality of the space, while the global fractal dimension would be Dg=d -1 . The transition between the local and global regimes occurs at a crossover length scale of the order of the microscopic length scale a . Therefore, notwithstanding the fact that the fronts of diffusion are corrugated, they appear flat at all the length scales probed by experiments, and they do not exhibit a fractal structure.

  9. Thermoelectric-enhanced, liquid-based cooling of a multi-component electronic system

    DOEpatents

    Chainer, Timothy J; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Schmidt, Roger R; Steinke, Mark E

    2015-11-10

    Methods are provided for facilitating cooling of an electronic component. The methods include providing: a liquid-cooled structure, a thermal conduction path coupling the electronic component and the liquid-cooled structure, a coolant loop in fluid communication with a coolant-carrying channel of the liquid-cooled structure, and an outdoor-air-cooled heat exchange unit coupled to facilitate heat transfer from the liquid-cooled structure via, at least in part, the coolant loop. The thermoelectric array facilitates transfer of heat from the electronic component to the liquid-cooled structure, and the heat exchange unit cools coolant passing through the coolant loop by dissipating heat from the coolant to outdoor ambient air. In one implementation, temperature of coolant entering the liquid-cooled structure is greater than temperature of the outdoor ambient air to which heat is dissipated.

  10. Thermoelectric-enhanced, liquid-based cooling of a multi-component electronic system

    DOEpatents

    Chainer, Timothy J; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Schmidt, Roger R; Steinke, Mark E

    2015-05-12

    Apparatus and method are provided for facilitating cooling of an electronic component. The apparatus includes a liquid-cooled structure, a thermal conduction path coupling the electronic component and the liquid-cooled structure, a coolant loop in fluid communication with a coolant-carrying channel of the liquid-cooled structure, and an outdoor-air-cooled heat exchange unit coupled to facilitate heat transfer from the liquid-cooled structure via, at least in part, the coolant loop. The thermoelectric array facilitates transfer of heat from the electronic component to the liquid-cooled structure, and the heat exchange unit cools coolant passing through the coolant loop by dissipating heat from the coolant to outdoor ambient air. In one implementation, temperature of coolant entering the liquid-cooled structure is greater than temperature of the outdoor ambient air to which heat is dissipated.

  11. Membrane permeation process for dehydration of organic liquid mixtures using sulfonated ion-exchange polyalkene membranes

    DOEpatents

    Cabasso, Israel; Korngold, Emmanuel

    1988-01-01

    A membrane permeation process for dehydrating a mixture of organic liquids, such as alcohols or close boiling, heat sensitive mixtures. The process comprises causing a component of the mixture to selectively sorb into one side of sulfonated ion-exchange polyalkene (e.g., polyethylene) membranes and selectively diffuse or flow therethrough, and then desorbing the component into a gas or liquid phase on the other side of the membranes.

  12. Liquid-liquid phase separation in atmospheric aerosol particles: dependence on organic functionalities and mixture complexity

    NASA Astrophysics Data System (ADS)

    Song, M.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Peter, T.

    2012-04-01

    In the troposphere, aerosol particles undergo phase transitions such as deliquescence and efflorescence during humidity cycles (Marcolli and Krieger, 2006). In addition, interactions between organic and inorganic compounds lead to liquid-liquid phase separation (LLPS) (Ciobanu et al., 2009). Recent studies on a limited number of model systems have shown that oxygen-to-carbon ratios (O:C) of the organic aerosol fraction might be a good predictor for LLPS in mixed organic/ammonium sulfate (AS) particles (Bertram et al., 2011; Song et al., 2011). However, in order to corroborate this hypothesis experiments with an organic fraction that consists of a higher number of components with different O:C ratios and functional groups are needed. In order to determine the influence of O:C ratio, the specific organic functionalities and the mixture complexity on LLPS, we subjected organic/AS particles deposited on a hydrophobically coated substrate to relative humidity (RH) cycles and observed phase changes using optical microscopy and micro-Raman spectroscopy. To determine the influence of mixture complexity, we mixed together up to 10 organic compounds. We also prepared mixtures that were rich in different types of functional groups like polyols, aromatics and dicarboxylic acids which were identified from field measurements. We screened for a miscibility gap by varying the organic-to-inorganic ratio from 2:1 to 1:6. AS in the investigated single particles effloresced at 27 - 50 %RH and deliquesced at 72 - 79 %RH during humidity cycles. The occurrence of LLPS is determined to a high degree by the O:C of the organics: there was no LLPS for mixtures with O:C > 0.8 and there was always LLPS for mixtures with O:C < 0.57. In the range in between, we observed a dependence on the specific functional groups: a high share of aromatic functionalities shifts the range of O:C for which LLPS occurs to lower values. A correlation was also found for the onset RH of LLPS as a function of O

  13. Metastable sound speed in gas-liquid mixtures

    NASA Technical Reports Server (NTRS)

    Bursik, J. W.; Hall, R. M.

    1979-01-01

    A new method of calculating speed of sound for two-phase flow is presented. The new equation assumes no phase change during the propagation of an acoustic disturbance and assumes that only the total entropy of the mixture remains constant during the process. The new equation predicts single-phase values for the speed of sound in the limit of all gas or all liquid and agrees with available two-phase, air-water sound speed data. Other expressions used in the two-phase flow literature for calculating two-phase, metastable sound speed are reviewed and discussed. Comparisons are made between the new expression and several of the previous expressions -- most notably a triply isentropic equation as used, a triply isentropic equation as used, among others, by Karplus and by Wallis. Appropriate differences are pointed out and a thermodynamic criterion is derived which must be satisfied in order for the triply isentropic expression to be thermodynamically consistent. This criterion is not satisfied for the cases examined, which included two-phase nitrogen, air-water, two-phase parahydrogen, and steam-water. Consequently, the new equation derived is found to be superior to the other equations reviewed.

  14. Determination of low concentrations of aromatic hydrocarbons in multicomponent mixtures with iso-octane and n-heptane

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.; Muradov, V. G.

    2011-11-01

    We have experimentally studied the absorption spectra of hydrocarbon mixtures based on n-heptane and isooctane with small (1%-2%) additions of aromatic hydrocarbons (benzene, toluene, xylene). The study was conducted in the region of the first overtones of the vibrational spectra for the hydrocarbon groups CH3, CH2, CH. We show that four-component modeling of the absorption spectrum of the hydrocarbon mixture and minimization of the deviation of the model spectrum from the experimental spectrum allow us to separately determine the content of the aromatic additives for concentrations from 1%.

  15. Online combination of reversed-phase/reversed-phase and porous graphitic carbon liquid chromatography for multicomponent separation of proteomics and glycoproteomics samples.

    PubMed

    Lam, Maggie P Y; Lau, Edward; Siu, S O; Ng, Dominic C M; Kong, Ricky P W; Chiu, Philip C N; Yeung, William S B; Lo, Clive; Chu, Ivan K

    2011-11-01

    In this paper, we describe an online combination of reversed-phase/reversed-phase (RP-RP) and porous graphitic carbon (PGC) liquid chromatography (LC) for multicomponent analysis of proteomics and glycoproteomics samples. The online RP-RP portion of this system provides comprehensive 2-D peptide separation based on sequence hydrophobicity at pH 2 and 10. Hydrophilic components (e.g. glycans, glycopeptides) that are not retained by RP are automatically diverted downstream to a PGC column for further trapping and separation. Furthermore, the RP-RP/PGC system can provide simultaneous extension of the hydropathy range and peak capacity for analysis. Using an 11-protein mixture, we found that the system could efficiently separate native peptides and released N-glycans from a single sample. We evaluated the applicability of the system to the analysis of complex biological samples using 25 μg of the lysate of a human choriocarcinoma cell line (BeWo), confidently identifying a total of 1449 proteins from a single experiment and up to 1909 distinct proteins from technical triplicates. The PGC fraction increased the sequence coverage through the inclusion of additional hydrophilic sequences that accounted for up to 6.9% of the total identified peptides from the BeWo lysate, with apparent preference for the detection of hydrophilic motifs and proteins. In addition, RP-RP/PGC is applicable to the analysis of complex glycomics samples, as demonstrated by our analysis of a concanavalin A-extracted glycoproteome from human serum; in total, 134 potentially N-glycosylated serum proteins, 151 possible N-glycosylation sites, and more than 40 possible N-glycan structures recognized by concanavalin A were simultaneously detected.

  16. A direct method for calculating thermodynamic factors for liquid mixtures using the Permuted Widom test particle insertion method

    NASA Astrophysics Data System (ADS)

    Prasaad Balaji, Sayee; Schnell, Sondre K.; McGarrity, Erin S.; Vlugt, Thijs J. H.

    2013-01-01

    Understanding mass transport in liquids by mutual diffusion is an important topic for many applications in chemical engineering. The reason for this is that diffusion is often the rate limiting step in chemical reactors and separators. In multicomponent liquid mixtures, transport diffusion can be described by both generalized Fick's law and the Maxwell-Stefan theory. The Maxwell-Stefan and Fick approaches in an n-component system are related by the so-called thermodynamic factor [R. Taylor and H.A. Kooijman, Chem. Eng. Commun, 102, 87 (1991)]. As Fick diffusivities can be measured in experiments and Maxwell-Stefan diffusivities can be obtained from molecular simulations/theory, the thermodynamic factors bridge the gap between experiments and molecular simulations/theory. It is therefore desirable to be able to compute thermodynamic factors from molecular simulations. Unfortunately, presently used simulation techniques for computing thermodynamic factors are inefficient and often require numerical differentiation of simulation results. In this work, we propose a modified version of the Widom test-particle method to compute thermodynamic factors from a single simulation. This method is found to be more efficient than the conventional Widom test particle insertion method combined with numerical differentiation of simulation results. The approach is tested for binary systems consisting of Lennard-Jones particles. The thermodynamic factors computed from the simulation and from numerically differentiating the activity coefficients obtained from the conventional Widom test particle insertion method are in excellent agreement.

  17. Simultaneous multicomponent spectrophotometric monitoring of methyl and propyl parabens using multivariate statistical methods after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction

    NASA Astrophysics Data System (ADS)

    Khani, Rouhollah; Ghasemi, Jahan B.; Shemirani, Farzaneh

    2014-03-01

    A powerful and efficient signal-preprocessing technique that combines local and multiscale properties of the wavelet prism with the global filtering capability of orthogonal signal correction (OSC) is applied for pretreatment of spectroscopic data of parabens as model compounds after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction method (IL-DLLME). In the proposed technique, a mixture of a water-immiscible ionic liquid (as extraction solvent) [Hmim][PF6] and disperser solvent is injected into an aqueous sample solution containing one of the IL's ions, NaPF6, as extraction solvent and common ion source. After preconcentration, the absorbance of the extracted compounds was measured in the wavelength range of 200-700 nm. The wavelet orthogonal signal correction with partial least squares (WOSC-PLS) method was then applied for simultaneous determination of each individual compound. Effective parameters, such as amount of IL, volume of the disperser solvent and amount of NaPF6, were inspected by central composite design to identify the most important parameters and their interactions. The effect of pH on the sensitivity and selectivity was studied according to the net analyte signal (NAS) for each component. Under optimum conditions, enrichment factors of the studied compounds were 75 for methyl paraben (MP) and 71 for propyl paraben (PP). Limits of detection for MP and PP were 4.2 and 4.8 ng mL-1, respectively. The root mean square errors of prediction for MP and PP were 0.1046 and 0.1275 μg mL-1, respectively. The practical applicability of the developed method was examined using hygienic, cosmetic, pharmaceutical and natural water samples.

  18. Simultaneous multicomponent spectrophotometric monitoring of methyl and propyl parabens using multivariate statistical methods after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction.

    PubMed

    Khani, Rouhollah; Ghasemi, Jahan B; Shemirani, Farzaneh

    2014-03-25

    A powerful and efficient signal-preprocessing technique that combines local and multiscale properties of the wavelet prism with the global filtering capability of orthogonal signal correction (OSC) is applied for pretreatment of spectroscopic data of parabens as model compounds after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction method (IL-DLLME). In the proposed technique, a mixture of a water-immiscible ionic liquid (as extraction solvent) [Hmim][PF6] and disperser solvent is injected into an aqueous sample solution containing one of the IL's ions, NaPF6, as extraction solvent and common ion source. After preconcentration, the absorbance of the extracted compounds was measured in the wavelength range of 200-700 nm. The wavelet orthogonal signal correction with partial least squares (WOSC-PLS) method was then applied for simultaneous determination of each individual compound. Effective parameters, such as amount of IL, volume of the disperser solvent and amount of NaPF6, were inspected by central composite design to identify the most important parameters and their interactions. The effect of pH on the sensitivity and selectivity was studied according to the net analyte signal (NAS) for each component. Under optimum conditions, enrichment factors of the studied compounds were 75 for methyl paraben (MP) and 71 for propyl paraben (PP). Limits of detection for MP and PP were 4.2 and 4.8 ng mL(-)(1), respectively. The root mean square errors of prediction for MP and PP were 0.1046 and 0.1275 μg mL(-)(1), respectively. The practical applicability of the developed method was examined using hygienic, cosmetic, pharmaceutical and natural water samples.

  19. Highly viscous liquid crystalline mixtures: the alternative to liquid crystalline elastomers

    NASA Astrophysics Data System (ADS)

    Shibaev, Petr; Schlesier, Cristina; Newman, Leah; McDonald, Scott

    2012-02-01

    Novel highly viscous liquid crystalline materials based on mixtures of glass forming oligomers and low molar mass liquid crystals were recently designed [1, 2] and studied. In this communication the novel data are presented, the analysis and discussion are extended. It is shown that viscoelastic properties of the materials are due to the physical entanglements between cyclic oligomers and low molar mass mesogens, not due to the chemical crosslinks between molecular moities. However, the mechanical properties of these viscoelastic materials resemble those of chemically crosslinked elastomers (elasticity and reversibility of deformations). The properties of chiral and non-chiral materials loaded with ferromagnetic nanoparticles are discussed in detail. Cholesteric materials undergo gigantic color changes in the wide spectral range under the deformation that allows distant detection of deformation and determination the anisotropy of deformation and its type. The materials doped with laser dyes become mechanically tunable lasers themselves and emit coherent light while pumped by external laser. A simple model is suggested to account for the observed effects; physical properties of the novel materials and liquid crystalline elastomers are compared and discussed. [4pt] [1] P.V. Shibaev, C. Schlesier, R. Uhrlass, S. Woodward, E. Hanelt, Liquid Crystals, 37:12, 1601-1604 [0pt] [2] P.V. Shibaev, P. Riverra, D. Teter, S. Marsico, M. Sanzari, V. Ramakrishnan, E. Hanelt, Optics Express, 16, 2965 (2008)

  20. Determination of solubility parameters of ionic liquids and ionic liquid/solvent mixtures from intrinsic viscosity.

    PubMed

    Weerachanchai, Piyarat; Wong, Yuewen; Lim, Kok Hwa; Tan, Timothy Thatt Yang; Lee, Jong-Min

    2014-11-10

    The total and partial solubility parameters (dispersion, polar and hydrogen-bonding solubility parameters) of ten ionic liquids were determined. Intrinsic viscosity approaches were used that encompassed a one-dimensional method (1D-Method), and two different three-dimensional methods (3D-Method1 and 3D-Method2). The effect of solvent type, the dimethylacetamide (DMA) fraction in the ionic liquid, and dissolution temperature on solubility parameters were also investigated. For all types of effect, both the 1D-Method and 3D-Method2 present the same trend in the total solubility parameter. The partial solubility parameters are influenced by the cation and anion of the ionic liquid. Considering the effect on partial solubility parameters of the solvent type in the ionic liquid, it was observed that in both 3D methods, the dispersion and polar parameters of a 1-ethyl-3-methylimidazolium acetate/solvent (60:40 vol %) mixture tend to increase as the total solubility parameter of the solvent increases.

  1. Understanding positive and negative deviations in polarity of ionic liquid mixtures by pseudo-solvent approach.

    PubMed

    Beniwal, Vijay; Kumar, Anil

    2016-08-24

    Physico-chemical properties of liquid mixtures in general display large deviations from linear behaviour, arising out of complex specific and non-specific intermolecular interactions. The polarity of liquid mixtures displaying large positive and negative deviations can be minimized and linear mixing can be achieved in liquids using a pseudo-solvent methodology. The work described herein is designed to investigate the influence of different physical parameters on the linear pseudo-solvent composition in ionic liquid mixtures. For this purpose, we have determined the deviations from linearity, ΔE values (defined as given by ) for binary mixtures of a variety of ionic liquids, including two molecular solvents, DMSO and formamide. Firstly, the investigations were carried out in three 1-butyl-3-methylimidazolium cation based aprotic ionic liquids and the roles of anionic structure and hydrogen bond acceptor basicities (β values) of the ionic liquids were determined. The influence of the cationic structure, i.e., the hydrogen bond donor acidity (α values) and non-associative nature of the ionic liquids, was determined using C2-methylated analogs, 1-butyl-2,3-dimethylimidazolium cation based ionic liquids. The role of the protic nature of ionic liquids was studied in two protic ionic liquids, viz., 1-methylimidazolium formate and 1-methylimidazolium acetate. The effects of the temperature, pseudo-solvent structure and solvatochromic probe structure on the ΔE values were also explored.

  2. Viscosity Difference Measurements for Normal and Para Liquid Hydrogen Mixtures

    NASA Technical Reports Server (NTRS)

    Webeler, R.; Bedard, F.

    1961-01-01

    The absence of experimental data in the literature concerning a viscosity difference for normal and equilibrium liquid hydrogen may be attributed to the limited reproducibility of "oscillating disk" measurements in a liquid-hydrogen environment. Indeed, there is disagreement over the viscosity values for equilibrium liquid hydrogen even without proton spin considerations. Measurements presented here represent the first application of the piezoelectric alpha quartz torsional oscillator technique to liquid-hydrogen viscosity measurements.

  3. On the Crystallization of Compacted and Chunky Graphite from Liquid Multicomponent Iron-Carbon-Silicon-Based Melts

    NASA Astrophysics Data System (ADS)

    Stefanescu, D. M.; Huff, R.; Alonso, G.; Larrañaga, P.; De la Fuente, E.; Suarez, R.

    2016-08-01

    Extensive SEM work was carried out on deep-etched specimens to reveal the evolution of compacted and chunky graphite in magnesium-modified multicomponent Fe-C-Si alloys during early solidification and at room temperature. The findings of this research were then integrated in the current body of knowledge to produce an understanding of the crystallization of compacted and chunky graphite. It was confirmed that growth from the liquid for both compacted and chunky graphite occurs radially from a nucleus, as foliated crystals and dendrites. The basic building blocks of the graphite aggregates are hexagonal faceted graphite platelets with nanometer height and micrometer width. Thickening of the platelets occurs through growth of additional graphene layers nucleated at the ledges of the graphite prism. Additional thickening resulting in complete joining of the platelets may occur from the recrystallization of the amorphous carbon that has diffused from the liquid through the austenite, once the graphite aggregate is enveloped in austenite. With increasing magnesium levels, the foliated graphite platelets progressively aggregate along the c-axis forming clusters. The clusters that have random orientation, eventually produce blocky graphite, as the spaces between the parallel platelets disappear. This is typical for compacted graphite irons and tadpole graphite. The chunky graphite aggregates investigated are conical sectors of graphite platelets stacked along the c-axis. The foliated dendrites that originally develop radially from a common nucleus may aggregate along the c-axis forming blocky graphite that sometimes exhibits helical growth. The large number of defects (cavities) observed in all graphite aggregates supports the mechanism of graphite growth as foliated crystals and dendrites.

  4. Investigation of simultaneous biosorption of copper(II) and chromium(VI) on dried Chlorella vulgaris from binary metal mixtures: Application of multicomponent adsorption isotherms

    SciTech Connect

    Aksu, Z.; Acikel, U.; Kutsal, T.

    1999-02-01

    Although the biosorption of single metal ions to various kinds of microorganisms has been extensively studied and the adsorption isotherms have been developed for only the single metal ion situation, very little attention has been given to the bioremoval and expression of adsorption isotherms of multimetal ions systems. In this study the simultaneous biosorption of copper(II) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single- and dual-metal ion concentrations on the equilibrium uptakes were investigated. In previous studies the optimum biosorption pH had been determined as 4.0 for copper(II) and as 2.0 for chromium(VI). Multimetal ion biosorption studies were performed at these two pH values. It was observed that the equilibrium uptakes of copper(II) or chromium(VI) ions were changed due to the biosorption pH and the presence of other metal ions. Adsorption isotherms were developed for both single- and dual-metal ions systems at these two pH values, and expressed by the mono- and multicomponent Langmuir and Freundlich adsorption models. Model parameters were estimated by nonlinear regression. It was seen that the adsorption equilibrium data fitted very well to the competitive Freundlich model in the concentration ranges studied.

  5. Study of solid surface interactions with binary liquid mixtures and liquid crystals

    NASA Astrophysics Data System (ADS)

    Polak, Robert Dale

    The adsorption profile of a binary liquid mixture against a solid substrate was studied using an optical probe. The effective surface field was controlled by partially coating one half of the glass surface with octadecyltrichlorosilane, while the other half remained bare. On the bare surface, one component of the binary liquid mixture was strongly adsorbed to the surface, and, in the one-phase region, adsorption could be observed far from the bulk transition temperature. This adsorption scales as expected by a normal surface transition in which the surface orders at a higher temperature than the bulk. On the partially coated surface, the adsorption could only be observed very near the bulk critical temperature. Over the course of the first several days of the experiment, the adsorption profile changed, but it eventually became stable. Scaling analysis of the stable surface suggests the possibility that the surface was in the crossover region between normal and ordinary (where the surface and bulk order at the same temperature) surface transitions. In a separate series of experiments, the interaction between a nematic liquid crystal and substrate was studied, in particular, the energetic cost to deviate the surface director from its preferred orientation. To accurately determine the energetic cost, denoted by the polar anchoring coefficient W, of a typical alignment layer/liquid crystal was measured using three techniques. The first is the 'high-electric-field' (HEF) technique was found to give the largest value of W. In the course of the study, the HEF technique was improved by no longer requiring the measurement of capacitance of the sample liquid crystal cell. Also, the source of the large value of W is detected, and a protocol was developed to determine the reliability of the results given by the HEF technique. Two other techniques are used to determine W: the measurement of capacitance in a magnetic field and the measurement of the Frederiks transition at

  6. Amphiphile Meets Amphiphile: Beyond the Polar-Apolar Dualism in Ionic Liquid/Alcohol Mixtures.

    PubMed

    Russina, Olga; Sferrazza, Alessio; Caminiti, Ruggero; Triolo, Alessandro

    2014-05-15

    The mesoscopic morphology of binary mixtures of ethylammonium nitrate (EAN), the protic ionic liquid par excellence, and methanol is explored using neutron/X-ray diffraction and computational techniques. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network: surprisingly, though macroscopically homogeneous, these mixtures turn out to be mesoscopically highly heterogeneous. Our study reveals that even in methanol-rich mixtures, a wide distribution of clusters exists where EAN preserves its bulk, sponge-like morphology. Accordingly methanol does not succeed in fully dissociating the ionic liquid that keeps on organizing in a bulk-like fashion. This behavior represents the premises to the more dramatic phenomenology observed with longer alcohols that eventually phase separate from EAN. These results challenge the commonly accepted polar and apolar moieties segregation in ionic liquids/molecular liquids mixtures and the current understanding of technologically relevant solvation processes.

  7. Characterizing droplet combustion of pure and multi-component liquid fuels in a microgravity environment

    NASA Technical Reports Server (NTRS)

    Jackson, Gregory S.; Avedisian, C. Thomas

    1993-01-01

    The importance of understanding the effects of fuel composition, length scales, and other parameters on the combustion of liquid fuels has motivated the examination of simple flames which have easily characterized flow fields and hence, the potential of being modeled accurately. One such flame for liquid fuel combustion is the spherically symmetric droplet flame which can be achieved in an environment with sufficiently low gravity (i.e., low buoyancy). To examine fundamental characteristics of spherically symmetric droplet combustion, a drop tower facility has been employed to provide a microgravity environment to study droplet combustion. This paper gives a brief review of results obtained over the past three years under NASA sponsorship (grant NAG3-987).

  8. Liquid-liquid equilibria of binary mixtures of a lipidic ionic liquid with hydrocarbons.

    PubMed

    Green, Blane D; Badini, Alexander J; O'Brien, Richard A; Davis, James H; West, Kevin N

    2016-01-28

    Although structurally diverse, many ionic liquids (ILs) are polar in nature due to the strong coulombic forces inherent in ionic compounds. However, the overall polarity of the IL can be tuned by incorporating significant nonpolar content into one or more of the constituent ions. In this work, the binary liquid-liquid equilibria of one such IL, 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide, with several hydrocarbons (n-hexane, n-octane, n-decane, cyclohexane, methylcyclohexane, 1-octene) is measured over the temperature range 0-70 °C at ambient pressure using a combination of cloud point and gravimetric techniques. The phase behavior of the systems are similar in that they exhibit two phases: one that is 60-90 mole% hydrocarbon and a second phase that is nearly pure hydrocarbon. Each phase exhibits a weak dependence of composition on temperature (steep curve) above ∼10 °C, likely due to swelling and restructuring of the nonpolar nano-domains of the IL being limited by energetically unfavorable restructuring in the polar nano-domains. The solubility of the n-alkanes decreases with increasing size (molar volume), a trend that continues for the cyclic alkanes, for which upper critical solution temperatures are observed below 70 °C. 1-Octene is found to be more soluble than n-octane, attributable to a combination of its lower molar volume and slightly higher polarity. The COSMO-RS model is used to predict the T-x'-x'' diagrams and gives good qualitative agreement of the observed trends. This work presents the highest known solubility of n-alkanes in an IL to date and tuning the structure of the ionic liquid to maximize the size/shape trends observed may provide the basis for enhanced separations of nonpolar species.

  9. Mixtures of protic ionic liquids and propylene carbonate as advanced electrolytes for lithium-ion batteries.

    PubMed

    Vogl, T; Menne, S; Balducci, A

    2014-12-07

    In this study we investigated the chemical-physical properties of mixtures containing the protic ionic liquid (PIL) N-butyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYRH4TFSI), propylene carbonate (PC) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in view of their use as electrolytes for lithium-ion batteries (LIBs). We showed that these electrolytic solutions might display conductivity and viscosity comparable to those of conventional electrolytes. Depending on the amount of PIL present inside the mixtures, such mixtures might also display the ability to suppress the anodic dissolution of Al. Furthermore, we showed that the coordination of lithium ions by TFSI in PIL-PC mixtures appears to be different than the one observed for mixtures of PC and aprotic ionic liquids (AILs). When used in combination with a battery electrode, e.g. lithium iron phosphate (LFP), these mixtures allow the achievement of high performance also at a very high C-rate.

  10. Nanoscale Density Fluctuations in Ionic Liquid Binary Mixtures with Nonamphiphilic Compounds: First Experimental Evidence.

    PubMed

    Mariani, Alessandro; Dattani, Rajeev; Caminiti, Ruggero; Gontrani, Lorenzo

    2016-10-04

    A complex mesoscopic organization is observed in systems containing ethylammonium nitrate (EAN) and two nonamphiphilic compounds, using wide and small angle X-ray scattering and molecular dynamics simulations. The macroscopically homogeneous mixtures exhibit a separation where an ionic liquid-rich region is percolating a molecular liquid-rich one, but no unmixing is observed. This effect was already reported in EAN-alcohol mixtures, but the models proposed so far cannot explain this behavior for a nonamphiphilic compound.

  11. Development of low anchoring strength liquid crystal mixtures for bistable nematic displays

    NASA Astrophysics Data System (ADS)

    Stoenescu, D.; Gallaire, D.; Faget, L.; Lamarque-Forget, S.; Joly, S.; Dubois, J.-C.; Martinot-Lagarde, Ph.; Dozov, I.

    2006-02-01

    The recent Bistable Nematic (BiNem (R)) LCD technology presents long term bistability, high level passive matrix multiplexing and high optical quality. The BiNem device, based on anchoring breaking, needs specific low anchoring strength materials - alignment layers and liquid crystal mixtures. We present here our approach to develop nematic mixtures with wide enough temperature range and low zenithal anchoring energy.

  12. Recent advances in liquid mixtures in electric fields

    NASA Astrophysics Data System (ADS)

    Katsir, Yael; Tsori, Yoav

    2017-02-01

    When immiscible liquids are subject to electric fields interfacial forces arise due to a difference in the permittivity or the conductance of the liquids, and these forces lead to shape change in droplets or to interfacial instabilities. In this topical review we discuss recent advances in the theory and experiments of liquids in electric fields with an emphasis on liquids which are initially miscible and demix under the influence of an external field. In purely dielectric liquids demixing occurs if the electrode geometry leads to sufficiently large field gradients. In polar liquids field gradients are prevalent due to screening by dissociated ions irrespective of the electrode geometry. We examine the conditions for these ‘electro prewetting’ transitions and highlight few possible systems where they might be important, such as in stabilization of colloids and in gating of pores in membranes.

  13. Nanostructural organization and anion effects in the optical Kerr effect spectra of binary ionic liquid mixtures.

    PubMed

    Xiao, Dong; Rajian, Justin Rajesh; Hines, Larry G; Li, Shengfu; Bartsch, Richard A; Quitevis, Edward L

    2008-10-23

    This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).

  14. Playing with ionic liquid mixtures to design engineered CO2 separation membranes.

    PubMed

    Tomé, Liliana C; Florindo, Catarina; Freire, Carmen S R; Rebelo, Luís Paulo N; Marrucho, Isabel M

    2014-08-28

    Ionic liquids have been explored as attractive alternative media for CO2 separation not only due to their low volatility but also due to their highly tuneable nature. Aiming at designing highly efficient liquid phases for flue gas separation and natural gas purification, this work focuses on the use of binary ionic liquid mixtures containing sulfate and/or cyano-functionalized anions. Several mixtures were prepared and their gas transport properties through supported ionic liquid membranes (SILMs) were investigated. The thermophysical properties of these mixtures, namely viscosity and density (data presented and discussed in ESI), were also measured so that trends between transport properties and thermophysical properties could be evaluated. The results obtained indicate that depending on the anions mixed, membranes with fine-tuned gas permeabilities, diffusivities and solubilities can be obtained. Additionally, SILMs prepared with these ionic liquid mixtures are on the upper bound of the CO2/N2 separation, or even may surpass it, indicating their potential for separating CO2 in low-pressure post-combustion processes. Overall, the use of ionic liquid mixtures combining the most selective anions with the least viscous anions is a highly promising strategy to design advanced engineered liquid phases for CO2 separation membranes.

  15. Transient Numerical Modeling of the Combustion of Bi-Component Liquid Droplets: Methanol/Water Mixture

    NASA Technical Reports Server (NTRS)

    Marchese, A. J.; Dryer, F. L.

    1994-01-01

    This study shows that liquid mixtures of methanol and water are attractive candidates for microgravity droplet combustion experiments and associated numerical modeling. The gas phase chemistry for these droplet mixtures is conceptually simple, well understood and substantially validated. In addition, the thermodynamic and transport properties of the liquid mixture have also been well characterized. Furthermore, the results obtained in this study predict that the extinction of these droplets may be observable in ground-based drop to tower experiments. Such experiments will be conducted shortly followed by space-based experiments utilizing the NASA FSDC and DCE experiments.

  16. "Zahraa", a Unani multicomponent herbal tea widely consumed in Syria: components of drug mixtures and alleged medicinal properties.

    PubMed

    Carmona, M D; Llorach, R; Obon, C; Rivera, D

    2005-12-01

    In Unani system of medicine, drugs consist of complex formulae with more than three components, for which, literature analysing these mixtures as they are sold in the market is scarce. In this paper, the main botanical components of the herbal tea known as "Zahraa" in Damascus, which contains between 6 and 14 species components is elucidated: Alcea damascena (Mout.) Mout. (Malvaceae), Aloysia triphylla (L'Herit.) Britt. (Malvaceae), Astragalus cf. amalecitanus Boiss., Cercis siliquastrum L. subsp. hebecarpa (Bornm.) Yalt. and subsp. siliquastrum. (Leguminosae), Colutea cilicica Boiss. et Bal. in Boiss. (Leguminosae), Crataegus aronia (L.) Bosc. ex DC. (Rosaceae), Cytisopsis pseudocytisus (Boiss.) Fertig. (Leguminosae), Eleagnus angustifolia L. (Eleagnaceae), Equisetum telmateia Ehrh. (Equisetaceae), Helichrysum stoechas (L.) Moench. subsp. barrelieri (Ten.) Nyman. (Compositae), Matricaria recutita L. (Compositae), Mentha longifolia L. subsp. noeana (Boiss. ex. Briq.) Briq. (Labiatae), Mentha spicata L. subsp. condensata (Briq.) Greuter and Burdet (Labiatae), Micromeria myrtifolia Boiss. and Hohen. in Boiss. (Labiatae), Paronychia argentea Lam. (Caryophyllaceae), Phlomis syriaca Boiss. (Labiatae), Rosa damascena Mill. (Rosaceae), Salvia fruticosa Mill. (Labiatae), Sambucus nigra L. (Caprifoliaceae), Spartium junceum L. (Leguminosae), Zea mays L. (Gramineae).

  17. Effect of water-table fluctuation on dissolution and biodegradation of a multi-component, light nonaqueous-phase liquid.

    PubMed

    Dobson, Richard; Schroth, Martin H; Zeyer, Josef

    2007-12-07

    Light nonaqueous-phase liquids (LNAPLs) such as gasoline and diesel fuel are among the most common causes of soil and groundwater contamination. Dissolution and subsequent advective transport of LNAPL components can negatively impact water supplies, while biodegradation is thought to be an important sink for this class of contaminants. We present a laboratory investigation of the effect of a water-table fluctuation on dissolution and biodegradation of a multi-component LNAPL (85% hexadecane, 5% toluene, 5% ethylbenzene, and 5% 2-methylnapthalene on a molar basis) in a pair of similar model aquifers (80 cm x 50 cm x 3 cm), one of which was subjected to a water-table fluctuation. Water-table fluctuation resulted in LNAPL and air entrapment below the water table, an increase in the vertical extent of the LNAPL source zone (by factor 6.7), and an increase in the volume of water passing through the source zone (by factor ~18). Effluent concentrations of dissolved LNAPL components were substantially higher and those of dissolved nitrate lower in the model aquifer where a fluctuation had been induced. Thus, water-table fluctuation led to enhanced biodegradation activity (28.3 mmol of nitrate consumed compared to 16.3 mmol in the model without fluctuation) as well as enhanced dissolution of LNAPL components. Despite the increased biodegradation, fluctuation led to increased elution of dissolved LNAPL components from the system (by factors 10-20). Hence, water-table fluctuations in LNAPL-contaminated aquifers might be expected to result in increased exposure of downgradient receptors to LNAPL components. Accordingly, water-table fluctuations in contaminated aquifers are probably undesirable unless the LNAPL is of minimal solubility or the dissolved-phase plume is not expected to reach a receptor due to distance or the presence of some form of containment.

  18. Reversible and non-reactive cellulose separations from ionic liquid mixtures with compressed carbon dioxide.

    PubMed

    Minnick, David L; Scurto, Aaron M

    2015-08-14

    A novel physical (non-reactive) separation of cellulose from an ionic liquid (IL)/cosolvent mixture by compressed carbon dioxide is presented. The precipitation is completely reversible and rapid within small changes of pressure i.e. liquid phase CO2 composition. High pressure phase equilibrium, high pressure NMR, and solid state NMR have been utilized to understand the separation phenomena.

  19. Reversible and Non-Reactive Cellulose Separations from Ionic Liquid Mixtures with Compressed Carbon Dioxide

    PubMed Central

    Minnick, David L.; Scurto, Aaron M.

    2016-01-01

    A novel physical (non-reactive) separation of cellulose from an ionic liquid (IL) / cosolvent mixture by compressed carbon dioxide is presented. The precipitation is completely reversible and rapid within small changes of pressure i.e. liquid phase CO2 composition. High pressure phase equilibrium, high pressure NMR, and solid state NMR have been utilized to understand the separation phenomena. PMID:26159829

  20. Exposure of Mammalian Cells to Air-Pollutant Mixtures at the Air-Liquid Interface

    EPA Science Inventory

    It has been widely accepted that exposure of mammalian cells to air-pollutant mixtures at the air-liquid interface is a more realistic approach than exposing cell under submerged conditions. The VITROCELL systems, are commercially available systems for air-liquid interface expo...

  1. Fine tuning the ionic liquid-vacuum outer atomic surface using ion mixtures.

    PubMed

    Villar-Garcia, Ignacio J; Fearn, Sarah; Ismail, Nur L; McIntosh, Alastair J S; Lovelock, Kevin R J

    2015-03-28

    Ionic liquid-vacuum outer atomic surfaces can be created that are remarkably different from the bulk composition. In this communication we demonstrate, using low-energy ion scattering (LEIS), that for ionic liquid mixtures the outer atomic surface shows significantly more atoms from anions with weaker cation-anion interactions (and vice versa).

  2. Intermolecular forces in acetonitrile + ethanol binary liquid mixtures

    NASA Astrophysics Data System (ADS)

    Elangovan, A.; Shanmugam, R.; Arivazhagan, G.; Mahendraprabu, A.; Karthick, N. K.

    2015-10-01

    FTIR spectral measurements have been carried out on the binary mixtures of acetonitrile with ethanol at 1:0 (acetonitrile:ethanol), 1:1, 1:2, 1:3 and 0:1 at room temperature. DFT and isosurface calculations have been performed. The acetonitrile + ethanol binary mixtures consist of 1:1, 1:2, 1:3 and 1:4 complexes formed through both the red and blue shifting H-bonds. Inter as well as intra molecular forces are found to exist in 1:3 and 1:4 complexes.

  3. Nano bubbles in liquid of a noble-gas mixture.

    PubMed

    Yamamoto, Takenori; Ohnishi, Shuhei

    2010-02-07

    Large-scale molecular dynamics (MD) simulations with over one million atoms are used to investigate nano bubbles in Ar-Ne liquid. The simulations demonstrate cavitations in the stretched liquid, and bubble creation and collapse. We find that a small cavity created in the stretched liquid spontaneously transforms into a nano bubble with the homogeneous vapor region. The equilibrium spherical bubble of 11.4 nm in radius is obtained after the long-time MD run. The surface tension of the nano bubble is found to be larger than that of the flat surface.

  4. Formation of Multicomponent Star Structures at the Liquid/Solid Interface.

    PubMed

    Tahara, Kazukuni; Kaneko, Kyohei; Katayama, Keisuke; Itano, Shintaro; Nguyen, Chi Huan; Amorim, Deborah D D; De Feyter, Steven; Tobe, Yoshito

    2015-06-30

    To demonstrate key roles of multiple interactions between multiple components and multiple phases in the formation of an uncommon self-assembling pattern, we present here the construction of a porous hexagonal star (h-star) structure using a trigonal molecular building block at the liquid/solid interface. For this purpose, self-assembly of hexaalkoxy-substituted dehydrobenzo[12]annulene derivatives DBA-OCns was investigated at the tetradecane/graphite interface by means of scanning tunneling microscopy (STM). Monolayer structures were significantly influenced by coadsorbed tetradecane molecules depending on the alkyl chains length (C13-C16) of DBA-OCn. However, none of DBA-OCn molecules formed the expected trigonal complexes, indicating that an additional driving force is necessary for the formation of the trigonal complex and its assembly into the h-star structure. As a first approach, we employed the "guest induced structural change" for the formation of the h-star structure. In the presence of two guest molecules, nonsubstituted DBA and hexakis(phenylethynyl)benzene which fit the respective pores, an h-star structure was formed by DBA-OC15 at the tetradecane/graphite interface. Moreover, a tetradecane molecule was coadsorbed between a pair of alkyl chains of DBA-OC15, thereby blocking the interdigitation of the alkyl chain pairs. Therefore, the h-star structure results from the self-assembly of the four molecular components including the solvent molecule. The second approach is based on aggregation of perfluoroalkyl chains via fluorophilicity of DBA-F, in which the perfluoroalkyl groups are substituted at the end of three alkyl chains of DBA-OCn via p-phenylene linkers. A trigonal complex consisting of DBA-F and three tetradecane molecules formed an h-star structure, in which the perfluoroalkyl groups that orient into the alkane solution phase aggregated at the hexagonal pore via fluorophilicity. The present result provides useful insight into the design and

  5. Shock Hugoniot equations of state for binary water-alcohol liquid mixtures

    NASA Astrophysics Data System (ADS)

    Moore, David; Bolme, Cynthia; Brown, Kathryn; McGrane, Shawn; Schulze, Peter

    2015-06-01

    Shock Hugoniot data were obtained using laser generated shock and ultrafast dynamic ellipsometry (UDE) methods for several non-ideal water-alcohol liquid mixtures, using methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol (a.k.a., 2-methyl-2-propanol or tert-butanol). The sound speeds of the mixtures were obtained using Brillouin scattering when not available in the literature. The shock and particle velocities obtained from the UDE data were compared to expectations of the universal liquid Hugoniot (ULH) and to literature shock (plate impact) data where available. The shock Hugoniot trends for all these mixtures, represented as deviations from predictions of the ULH, versus fraction of alcohol are quite similar to each other and suggest that complex hydrogen bonding networks in water-alcohol mixtures alter the compressibility of the mixtures. Data and trends will be presented. LA-UR-15-20328.

  6. Phase equilibria in ionic liquid-aromatic compound mixtures, including benzene fluorination effects.

    PubMed

    Blesic, Marijana; Lopes, José N Canongia; Pádua, Agílio A H; Shimizu, Karina; Gomes, Margarida F Costa; Rebelo, Luís Paulo N

    2009-05-28

    This work extends the scope of previous studies on the phase behavior of mixtures of ionic liquids with benzenes or its derivatives by determining the solid-liquid and liquid-liquid phase diagrams of mixtures containing an ionic liquid and a fluorinated benzene. The systems studied include 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide plus hexafluorobenzene or 1,3,5-trifluorobenzene and 1-ethyl-3-methylimidazolium triflate or N-ethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide plus benzene. The phase diagrams exhibit different kinds of solid-liquid behavior: the (usual) occurrence of eutectic points; the (not-so-usual) presence of congruent melting points and the corresponding formation of inclusion crystals; or the observation of different ionic liquid crystalline phases (polymorphism). These different types of behavior can be controlled by temperature annealing during crystallization or by the nature of the aromatic compound and can be interpreted, at a molecular level, taking into account the structure of the crystals or liquid mixtures, together with the unique characteristics of ionic liquids, namely the dual nature of their interactions with aromatic compounds.

  7. Structure of molecular liquids: hard rod-disk mixtures.

    PubMed

    Cheung, David L; Anton, Lucian; Allen, Michael P; Masters, Andrew J

    2008-01-01

    The structure of hard rod-disk mixtures is studied using Monte Carlo simulations and integral equation theory, for a range of densities in the isotropic phase. By extension of methods used in single component fluids, the pair correlation functions of the molecules are calculated and comparisons between simulation and integral equation theory, using a number of different closure relations, are made. Comparison is also made for thermodynamic data and phase behavior.

  8. Synergistic effects and correlating polarity parameters in binary mixtures of ionic liquids.

    PubMed

    Beniwal, Vijay; Kumar, Anil

    2015-04-07

    Understanding how a chemical reaction proceeds in solution requires precise knowledge of solute-solvent interactions. Certain issues involved in ionic liquid binary mixtures are still not clearly understood, including: 1) the effects of hydrogen-bond-acceptor basicity (β) of solvents on the "synergistic effects" found in ionic liquid-alcohol mixtures, 2) the interrelation between the polarity parameters in binary mixtures, and 3) the application of a model for the description of normalised electronic transition energy for all the binary mixtures. Here, a detailed analysis of polarity parameters in both hydrophilic and hydrophobic ionic liquids has been carried out. A three-parameter model developed by Roses et al. [J. Chem. Soc. Perkin Trans. 2 1997, 1341-1348] was found to be applicable to all the binary mixtures, and synergistic effects are generated as a result of high β values of alcohols compared with those of the ionic liquids. A strong correlation was observed in the β values and hydrophobicities of pure ionic liquids, suggesting that β values can play a role in describing synergism.

  9. Solid–liquid equilibria of binary mixtures of fluorinated ionic liquids†

    PubMed Central

    Teles, Ana Rita R.; Correia, Helga; Maximo, Guilherme J.; Rebelo, Luís P. N.; Freire, Mara G.; Pereiro, Ana B.; Coutinho, João A. P.

    2016-01-01

    Within ionic liquids, fluorinated ionic liquids (FILs) present unique physico-chemical properties and potential applications in several fields. However, the melting point of these neoteric compounds is usually higher due to the presence of fluorine atoms. This drawback may be resolved by, for instance, mixing different FILs to create eutectic mixtures. In this work, binary mixtures of fluoro-containing and fluorinated ionic liquids were considered with the aim of decreasing their melting temperatures as well as understanding and characterizing these mixtures and their phase transitions. Five FILs were selected, allowing the investigation of four binary mixtures, each of them with a common ion. Their solid–liquid and solid–solid equilibria were studied by differential scanning calorimetry and the non-ideality of the mixtures was investigated. Overall, a variety of solid–liquid equilibria with systems exhibiting eutectic behavior, polymorphs with solid–solid phase transitions, and the formation of intermediate compounds and solid solutions were surprisingly found. In addition to these intriguing behaviours, novel FILs with lower melting temperatures were obtained by the formation of binary systems, thus enlarging the application range of FILs at lower temperatures. PMID:27603428

  10. Symmetry energy in the liquid-gas mixture

    NASA Astrophysics Data System (ADS)

    López, J. A.; Terrazas Porras, S.

    2017-01-01

    Results from classical molecular dynamics simulations of infinite nuclear systems with varying density, temperature and isospin content are used to calculate the symmetry energy at low densities. The results show an excellent agreement with the experimental data and corroborate the claim that the formation of clusters has a strong influence on the symmetry energy in the liquid-gas coexistence region.

  11. Bubble nucleation in a Lennard-Jones binary liquid mixture

    NASA Astrophysics Data System (ADS)

    Baidakov, Vladimir G.; Protsenko, Sergey P.; Bryukhanov, Vasiliy M.

    2016-10-01

    We report a molecular dynamics (MD) study of homogeneous bubble nucleation in a stretched Lennard-Jones binary mixture at a temperature close to the solvent triple point. The pressure of the limiting stretching pn corresponding to a fixed value of the nucleation rate has been determined. The values of pn achieved in MD simulation are lower than those calculated from classical nucleation theory (CNT). The discrepancy between the data of MD simulation and CNT may be connected with the neglect in the latter of the size dependence of the surface tension of critical bubbles.

  12. Combustion Characteristics of Nanoaluminum, Liquid Water, and Hydrogen Peroxide Mixtures

    DTIC Science & Technology

    2008-01-01

    test peroxide ( HTP , 85% H2O2) as the oxidizer [22– 26]. Problems with the use of H2O2 systems include its sensitivity to shock and its tendency to...reported that the mix- ture would not self-deflagrate without the addition of the thickening agent into the mixture. At their maximum test pressure, 7...A pycnometer test determined particle density to be 3.205 g/cm3, which is inclusive of the oxide passiva- tion layer (∼3.97 g/cm3), which explains

  13. Hazards Induced by Breach of Liquid Rocket Fuel Tanks: Conditions and Risks of Cryogenic Liquid Hydrogen-Oxygen Mixture Explosions

    NASA Technical Reports Server (NTRS)

    Osipov, Viatcheslav; Muratov, Cyrill; Hafiychuk, Halyna; Ponizovskya-Devine, Ekaterina; Smelyanskiy, Vadim; Mathias, Donovan; Lawrence, Scott; Werkheiser, Mary

    2011-01-01

    We analyze the data of purposeful rupture experiments with LOx and LH2 tanks, the Hydrogen-Oxygen Vertical Impact (HOVI) tests that were performed to clarify the ignition mechanisms, the explosive power of cryogenic H2/Ox mixtures under different conditions, and to elucidate the puzzling source of the initial formation of flames near the intertank section during the Challenger disaster. We carry out a physics-based analysis of general explosions scenarios for cryogenic gaseous H2/Ox mixtures and determine their realizability conditions, using the well-established simplified models from the detonation and deflagration theory. We study the features of aerosol H2/Ox mixture combustion and show, in particular, that aerosols intensify the deflagration flames and can induce detonation for any ignition mechanism. We propose a cavitation-induced mechanism of self-ignition of cryogenic H2/Ox mixtures that may be realized when gaseous H2 and Ox flows are mixed with a liquid Ox turbulent stream, as occurred in all HOVI tests. We present an overview of the HOVI tests to make conclusion on the risk of strong explosions in possible liquid rocket incidents and provide a semi-quantitative interpretation of the HOVI data based on aerosol combustion. We uncover the most dangerous situations and discuss the foreseeable risks which can arise in space missions and lead to tragic outcomes. Our analysis relates to only unconfined mixtures that are likely to arise as a result of liquid propellant space vehicle incidents.

  14. Elastic Waves in Binary Solid Liquid Mixtures, Similarities at Macro and Nono Scales

    NASA Astrophysics Data System (ADS)

    Tavossi, Hasson M.

    2007-04-01

    Stress wave propagation in solid liquid mixtures at ultrasonic frequencies, in some cases, resembles wave propagation behaviors of materials at nanometer or atomic scales. For instance, it can be shown that wave; dispersion, attenuation, and cutoff-frequency effects depend on the same structural parameters as those observed at nano or atomic levels and can have similar interpretations at both scales. It follows that, to investigate theoretical models of wave and matter interactions at nano scale it is more convenient to use, as experimental tools, the readily analyzable models of propagation at macro-scales. Experimental findings on elastic wave propagation in the mixtures of liquid and solid particles will be presented and discussed. Results of wave dispersion, attenuation, band-pass, and cutoff frequency measured for ultrasonic waves in inhomogeneous mixtures of solid and liquid will be presented showing these similarities at the radically different scales.

  15. Phase diagrams of mixtures of a polymer and a cholesteric liquid crystal under an external field

    SciTech Connect

    Matsuyama, Akihiko

    2014-11-14

    We present a mean field theory to describe phase behaviors in mixtures of a polymer and a cholesteric liquid crystal under an external magnetic or electric field. Taking into account a chiral coupling between a polymer and a liquid crystal under the external field, we examine twist-untwist phase transitions and phase separations in the mixtures. It is found that a cholesteric-nematic phase transition can be induced by not only the external field but also concentration and temperature. Depending on the strength of the external field, we predict cholesteric-paranematic (Ch+pN), nematic-paranematic (N+pN), cholesteric-nematic (Ch+N) phase separations, etc., on the temperature-concentration plane. We also discuss mixtures of a non-chiral nematic liquid crystal and a chiral dopant.

  16. Velocity of large bubble in liquid-solid mixture in a vertical tube

    SciTech Connect

    Hamaguchi, H.; Sakaguchi, T.

    1995-09-01

    The upward movement of a large bubble in a stationary mixture of liquid and solid is one of the most fundamental phenomena of gas-liquid-solid three phase slug flow in a vertical tube. The purpose of this study is to make clear the characteristic of the rising velocity of this fundamental flow experimentally. The rising velocity of a large bubble V in a liquid-solid mixture was measured and compared with the velocity V{sub o} in a liquid (without solid). The experimental results were correlated using a non-dimensional velocity V{sup *}(=V/V{sub o}), and the following results were obtained. It was found that the characteristic of the rising velocity differs according to the tube diameter and the liquid viscosity, or the Galileo number in the non-dimensional expression. It can be classified into two regimes. (i) When the liquid viscosity is large (or the tube diameter is small), V{sup *} decreases linearly against the volumetric solid fraction {epsilon} of the mixture. (ii) When the viscosity is small, on the other hand, the relation between V{sup *} and {epsilon} is not linear. This classification can be explained by the results in the previous papers by the authors dealing with a large bubble in a liquid.

  17. A non-equilibrium state diagram for liquid/fluid/particle mixtures.

    PubMed

    Velankar, Sachin S

    2015-11-21

    The equilibrium structures of ternary oil/water/surfactant systems are often represented within a triangular composition diagram with various regions of the triangle corresponding to different equilibrium states. We transplant this idea to ternary liquid/fluid/particle systems that are far from equilibrium. Liquid/liquid/particle mixtures or liquid/gas/particle mixtures yield a wide diversity of morphologies including Pickering emulsions, bijels, pendular aggregates, spherical agglomerates, capillary suspensions, liquid marbles, powdered liquids, and particle-stabilized foams. This paper argues that such ternary liquid/fluid/particle mixtures can be unified into a non-equilibrium state diagram. What is common among all these systems is that the morphology results from an interplay between the preferential wettability of the particles, capillarity, and viscous forces encountered during mixing. Therefore all such systems share certain universal features, regardless of the details of the particles or fluids used. These features guide the construction of a non-equilibrium state diagram which takes the form of a triangular prism, where each triangular cross-section of the prism corresponds to a different relative affinity of the particles towards the two fluids. We classify the prism into regions in which the various morphologies appear and also emphasize the major difference between systems in which the particles are fully-wetted by one of the fluids vs. partially-wetted by both fluids. We also discuss how the state diagram may change with mixing intensity or with interparticle attractions.

  18. Dissociation of equimolar mixtures of aqueous carboxylic acids in ionic liquids: role of specific interactions.

    PubMed

    Shukla, Shashi Kant; Kumar, Anil

    2015-04-30

    Hammett acidity function observes the effect of protonation/deprotonation on the optical density/absorbance of spectrophotometric indicator. In this work, the Hammett acidity, H0, of equimolar mixtures of aqueous HCOOH, CH3COOH, and CH3CH2COOH was measured in 1-methylimidazolium-, 1-methylpyrrolidinium-, and 1-methylpiperidinium-based protic ionic liquids (PILs) and 1-butyl-3-methylimidazolium-based aprotic ionic liquid (AIL) with formate (HCOO(-)) anion. Higher H0 values were observed for the equimolar mixtures of aqueous carboxylic acids in protic ionic liquids compared with those of the aprotic ionic liquid because of the involvement of the stronger specific interactions between the conjugate acid of ionic liquid and conjugate base of carboxylic acids as suggested by the hard-soft acid base (HSAB) theory. The different H0 values for the equimolar mixtures of aqueous carboxylic acids in protic and aprotic ionic liquids were noted to depend on the activation energy of proton transfer (Ea,H(+)). The higher activation energy of proton transfer was obtained in AIL, indicating lower ability to form specific interactions with solute than that of PILs. Thermodynamic parameters determined by the "indicator overlapping method" further confirmed the involvement of the secondary interactions in the dissociation of carboxylic acids. On the basis of the thermodynamic parameter values, the potential of different ionic liquids in the dissociation of carboxylic acids was observed to depend on the hydrogen bond donor acidity (α) and hydrogen bond acceptor basicity (β), characteristics of specific interactions.

  19. Induced stabilization of columnar phases in binary mixtures of discotic liquid crystals.

    PubMed

    Cienega-Cacerez, Octavio; García-Alcántara, Consuelo; Moreno-Razo, José Antonio; Díaz-Herrera, Enrique; Sambriski, Edward John

    2016-01-28

    Three discotic liquid-crystalline binary mixtures, characterized by their extent of bidispersity in molecular thickness, were investigated with molecular dynamics simulations. Each equimolar mixture contained A-type (thin) and B-type (thick) discogens. The temperature-dependence of the orientational order parameter reveals that A-type liquid samples produce ordered phases more readily, with the (hexagonal) columnar phase being the most structured variant. Moderately and strongly bidisperse mixtures produce globally-segregated samples for temperatures corresponding to ordered phases; the weakly bidisperse mixture displays microheterogeneities. Ordered phases in the B-type liquid are induced partially by the presence of the A-type fluid. In the moderately bidisperse mixture, order is induced through orientational frustration: a mixed prenematic-like phase precedes global segregation to yield nematic and columnar mesophases upon further cooling. In the strongly bidisperse mixture, order is induced less efficiently through a paranematic-like mechanism: a highly-ordered A-type fluid imparts order to B-type discogens found at the interface of a fully-segregated sample. This ordering effect permeates into the disordered B-type domain until nematic and columnar phases emerge upon further cooling. At sufficiently low temperatures, all samples investigated exhibit the (hexagonal) columnar mesophase.

  20. [Analysis of psychotropic drug mixtures using high-pressure liquid chromatography in acute poisoning cases].

    PubMed

    Kazlauskiene, Daiva; Vainauskas, Paulius; Kazlauskas, Saulius

    2002-01-01

    The qualitative and quantitative method of determination of amitryptilin, codeine and fluoxetine in the mixture using high-pressure liquid chromatography is described in this paper. Chromatogram is presented which shows, that preparations are fully separated and do not interfere each others analysis. Tables with chromatographical separation characteristics are also presented. Proposed calibration curves of quantitative analysis and calculated medium relative error of quantitative ascertainment for every preparation of the mixture are shown. Final conclusion: method is applicable for qualitative and quantitative analysis of amitryptiline, fluoxetine and codeine in the mixture in hasty poisoning cases.

  1. Binary mixtures of ionic liquids: a joint approach to investigate their properties and catalytic ability.

    PubMed

    D'Anna, Francesca; Marullo, Salvatore; Vitale, Paola; Noto, Renato

    2012-05-14

    The growing interest in the properties and applications of ionic liquids has recently led to research into the possibility of using their binary mixtures. This work reports on the effects of binary mixtures of ionic liquids on the outcome of organic reactions such as the mononuclear rearrangement of heterocycles and the solvatochromic behavior of Nile Red. Binary mixtures formed by ionic liquids differing in the structure of the cation and the anion are taken into account. In particular, ionic liquids such as 1-benzyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(2,3,4,5,6-pentafluorobenzyl)-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, and 1-benzyl-3-butylimidazolium tetrafluoroborate, are studied. To achieve a deep understanding of the properties of ionic-liquid binary mixtures, their three-dimensional organization was analyzed by a combination of resonance light scattering, UV/Vis spectroscopy, and (1)H and (19)F NMR spectroscopy. Data collected herein evidence that the most significant changes in the ionic lattice structure, and consequently the most pronounced effects exerted as solvent media, occur when the studied system involves a blend of different anions.

  2. Molecular dynamics simulations of the structural and thermodynamic properties of imidazolium-based ionic liquid mixtures.

    PubMed

    Méndez-Morales, T; Carrete, J; Cabeza, O; Gallego, L J; Varela, L M

    2011-09-29

    In this work, extensive molecular dynamics simulations of mixtures of alcohols of several chain lengths (methanol and ethanol) with the ionic liquids (ILs) composed of the cation 1-hexyl-3-methylimidazolium and several anions of different hydrophobicity degrees (Cl(-), BF(4)(-), PF(6)(-)) are reported. We analyze the influence of the nature of the anion, the length of the molecular chain of the alcohol, and the alcohol concentration on the thermodynamic and structural properties of the mixtures. Densities, excess molar volumes, total and partial radial distribution functions, coordination numbers, and hydrogen bond degrees are reported and analyzed for mixtures of the ILs with methanol and ethanol. The aggregation process is shown to be highly dependent on the nature of the anion and the size of the alcohol, since alcohol molecules tend to interact predominantly with the anionic part of the IL, especially in mixtures of the halogenated IL with methanol. Particularly, our results suggest that the formation of an apolar network similar to that previously reported in mixtures of ILs with water does not take place in mixtures with alcohol when the chloride anion is present, the alcohol molecules being instead homogeneously distributed in the polar network of IL. Moreover, the alcohol clusters formed in mixtures of [HMIM][PF(6)] with alcohol were found to have a smaller size than in mixtures with water. Additionally, we provide a semiquantitative analysis of the dependence of the hydrogen bonding degree of the mixtures on the alcohol concentration.

  3. Protonic Ammonium Nitrate Ionic Liquids and Their Mixtures: Insights into Their Thermophysical Behavior.

    PubMed

    Canongia Lopes, José N; Esperança, José M S S; de Ferro, André Mão; Pereiro, Ana B; Plechkova, Natalia V; Rebelo, Luis P N; Seddon, Kenneth R; Vázquez-Fernández, Isabel

    2016-03-10

    This study is centered on the thermophysical characterization of different families of alkylammonium nitrate ionic liquids and their binary mixtures, namely the determination at atmospheric pressure of densities, electric conductivities and viscosities in the 288.15 < T/K < 353.15 range. First, measurements focusing on ethylammonium, propylammonium and butylammonium nitrate systems, and their binary mixtures, were determined. These were followed by studies involving binary mixtures composed of ethylammonium nitrate (with three hydrogen bond donor groups) and different homologous ionic liquids with differing numbers of hydrogen bond donor groups: diethylammonium nitrate (two hydrogen bond donors), triethylammonium nitrate (one hydrogen bond donor) and tetraethylammonium nitrate (no hydrogen bond donors). Finally, the behavior of mixtures with different numbers of equivalent carbon atoms in the alkylammonium cations was analyzed. The results show a quasi-ideal behavior for all monoalkylammonium nitrate mixtures. In contrast, the other mixtures show deviations from ideality, namely when the difference in the number of carbon atoms present in the cations increases or the number of hydrogen bond donors present in the cation decreases. Overall, the results clearly show that, besides the length and distribution of alkyl chains present in a cation such as alkylammonium, there are other structural and interaction parameters that influence the thermophysical properties of both pure compounds and their mixtures.

  4. Prediction of acute toxicity of chemicals in mixtures: worms Tubifex tubifex and gas/liquid distribution.

    PubMed

    Tichý, M; Borek-Dohalský, V; Matousová, D; Rucki, M; Feltl, L; Roth, Z

    2002-03-01

    The aim of this contribution is to support our proposal of the procedure for predicting acute toxicity of binary mixtures by QSAR analysis techniques. The changes of a mixture composition are described by molar ratio R and visualized in the R-plot (QCAR--quantitative composition-activity relationships). The approach was inspired by Rault and Dalton's laws, their positive and negative deviations in the behavior of a mixture of real gases, by Loewe and Muischnek isoboles and by the Finney test of additivity. Acute toxicity was determined by the laboratory test with woms Tubifex tubifex. The additivity of the acute toxicity in the binary mixture benzene + nitrobenzene was confirmed and a new interaction is described: "mixed interaction" with the binary mixture aniline + ethanol. The "mixed interaction" means that depending on mixture composition, both potentiation and inhibition can occur. As the first physicochemical descriptor of the changes caused by the changing composition of binary mixtures, the gas/liquid equilibrium was studied and a composition of the gaseous phase was determined by a gas chromatographic method. The method for determination of concentrations in the gaseous phase was described. The gaseous phase composition of benzene + nitrobenzene. benzene + ethanol, benzene + aniline and ethanol + aniline mixtures was analyzed. It was found that if the concentrations of the mixture's components in the gaseous phase behave nonideally (they are not additive), the acute toxicity of the same mixture is not additive as well. Another descriptor to distinguish between potentiation and inhibition will be, however, necessary. The properties, both gaseous phase composition and the acute toxicity, of the benzene + nitrobenzene mixture are additive. In mixtures with the mixed interaction, the R-plot of the composition of the gaseous phase is complex with a large variation of results.

  5. Molecular dynamics simulations of mixtures of protic and aprotic ionic liquids.

    PubMed

    Docampo-Álvarez, Borja; Gómez-González, Víctor; Méndez-Morales, Trinidad; Rodríguez, Julio R; López-Lago, Elena; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M

    2016-09-14

    Molecular dynamics simulations of mixtures of the protic ionic liquid ethylammonium nitrate (EAN) and the aprotic 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) are reported and the results are compared with experimental density and electrical conductivity measurements. Essentially ideal mixing of the ionic liquids is seen to take place by means of experimental and simulated excess molar volumes, whose very low values suggest a gradual transition between the structures of the two end constituents of the mixture. A weak dominance of the structure of the protic ionic liquid is nevertheless registered, due to a slight preferential formation of the network of hydrogen bonds, as reflected in the coordination number and the number of hydrogen bonds in the mixture. A novel conductivity curve showing pronounced deviations from the simple ideal mixing rule is reported, with three different regions defined by a local maximum - reflecting enhanced translational dynamics relative to ideal mixture behaviour - and a global minimum at intermediate concentrations. The physical origin of this behaviour is discussed along with the structure and single-particle dynamics of the mixture, and it is seen that these regions are defined by the onset of the formation of the EAN hydrogen bonded network (xEAN = 0.2) and the virtual disappearance of the structure of the aprotic ionic liquid at xEAN = 0.7. It is concluded that the delicate interplay between both networks has a deep effect on the placement and mobility of [EMIM](+) cations in the mixture all throughout the different stages of the structural transition, which seems to be the driving force behind the reported transport properties of the mixture at intermediate to high EAN concentrations.

  6. Use of neural networks for prediction of vapor/liquid equilibrium K values for light-hydrocarbon mixtures

    SciTech Connect

    Habiballah, W.A.; Startzman, R.A.; Barrufet, M.A.

    1996-05-01

    Equilibrium ratios play a fundamental role in the understanding of phase behavior of hydrocarbon mixtures. They are important in predicting compositional changes under varying temperature and pressure in reservoirs, surface separators, and production and transportation facilities. In particular, they are critical for reliable and successful compositional reservoir simulation. This paper presents a new approach for predicting K values with neural networks (NN`s). The method is applied to binary and multicomponent mixtures, and K-value prediction accuracy is on the order of the traditional methods. However, computing speed is significantly faster.

  7. Mixing Enthalpies of TbBr3-MBr Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Rycerz, L.; Gaune-Escard, M.

    2001-12-01

    The molar enthalpies of mixing, Δmix Hm in the binary liquid systems TbBr3-MBr (M = Li, Na, K, Rb, Cs) have been m easured with a Calvet-type high-tem perature microcalorimeter over the entire composition range with an accuracy of about 6 %. Mixing of the two liquid components was achieved by using the "break-off am poule" technique. All the investigated systems show negative enthalpies of mixing with a minim um value of approxim ately -1.25, - 8 .3 , -17.0, - 2 0 . 0 and -22.5 kJ mol -1, for M = Li, Na, K, Rb and Cs, respectively. The mixing enthalpy in the TbBr3- LiBr system is positive in the TbBr3-rich region. For all the systems, the enthalpy minimum occurs at mole fraction xTbBr3 ≈ 0.3 - 0.4. The molar enthalpies of form ation Δ formHm (3MBr, TbBr3, 1) for M = Li, Na, K, Rb and Cs at 1113 K (arising from the reaction 3M Br(1) +TbBr3(1) = (3MBr, TbBr3) (1)) are found to be -4 .8 , -31.3, -63.3, -70.3 and -8 1 .2 kJ mol-1 , respectively. The leastsquares coefficients A, B, C, D and E in the equation λ (kJ mol-1) = A + B x + C x2 + Dx3 + Ex4, where A is an interaction param eter and x = xTbBr , are also reported.

  8. Liquid-liquid transition without macroscopic phase separation in a water-glycerol mixture

    NASA Astrophysics Data System (ADS)

    Murata, Ken-Ichiro; Tanaka, Hajime

    2012-05-01

    The existence of more than two liquid states in a single-component substance and the ensuing liquid-liquid transitions (LLTs) has attracted considerable attention because of its counterintuitive nature and its importance in the fundamental understanding of the liquid state. Here we report direct experimental evidence for a genuine (isocompositional) LLT without macroscopic phase separation in an aqueous solution of glycerol. We show that liquid I transforms into liquid II by way of two types of kinetics: nucleation and growth, and spinodal decomposition. Although liquid II is metastable against crystallization, we could access both its static and dynamical properties experimentally. We find that liquids I and II differ in density, refractive index, structure, hydrogen bonding state, glass transition temperature and fragility, and that the transition between the two liquids is mainly driven by the local structuring of water rather than of glycerol, suggesting a link to a plausible LLT inpure water.

  9. Dissolution of carbon from alumina-carbon mixtures into liquid iron: Influence of carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Khanna, Rita; Sahajwalla, Veena; Rodgers, Brenton; McCarthy, Fiona

    2006-08-01

    Due to their excellent thermal shock and wear resistance at high temperatures, alumina-carbon based refractories are used extensively in the steel industry. A clear understanding of factors affecting the dissolution of carbon from refractories is of crucial importance, as carbon depletion from the refractory can significantly deteriorate refractory performance and metal quality. Atomistic simulations on the alumina-graphite/liquid iron system have shown that nonwetting between alumina and liquid iron is an important factor inhibiting the penetration of liquid metal in the refractory matrix and limiting carbon dissolution. This study investigates the role played by the carbonaceous material in the dissolution of carbon from the refractory composite. Two carbonaceous materials, namely, petroleum coke and natural graphite, respectively, containing 0.35 and 5.26 pct ash, were used in this study. Substrates were prepared from mixtures of alumina and carbon over a wide concentration range. Using a sessile drop arrangement, carbon pickup by liquid iron from alumina-carbon mixtures was measured at 1550 °C and was compared with the carbon pickup from alumina-synthetic graphite mixtures. These studies were supplemented with wettability measurements and microscopic investigations on the interfacial region. For high alumina concentrations (>40 wt pct), carbon dissolution from refractory mixtures was found to be negligible for all carbonaceous materials under investigation. Significant differences however were observed at lower alumina concentrations. Carbon dissolution from alumina-petroleum coke mixtures was much lower than the corresponding dissolution from alumina synthetic graphite-mixtures and was attributed to poor wettability of petroleum coke with liquid iron, its structural disorder, and the presence of sulfur. Very high levels of carbon dissolution, however, were observed from alumina-natural graphite mixtures, with carbon pickup by liquid iron from mixtures with up

  10. Switching the Structural Force in Ionic Liquid-Solvent Mixtures by Varying Composition.

    PubMed

    Smith, Alexander M; Lee, Alpha A; Perkin, Susan

    2017-03-03

    The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.

  11. Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

    NASA Technical Reports Server (NTRS)

    Elliott, D. G.; Hays, L. G.

    1976-01-01

    A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

  12. Switching the Structural Force in Ionic Liquid-Solvent Mixtures by Varying Composition

    NASA Astrophysics Data System (ADS)

    Smith, Alexander M.; Lee, Alpha A.; Perkin, Susan

    2017-03-01

    The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.

  13. Nonaqueous Phase Liquid Dissolution in Porous Media: Multi-Scale Effects of Multi-Component Dissolution Kinetics on Cleanup Time

    SciTech Connect

    McNab, W; Ezzedine, S; Detwiler, R

    2007-02-26

    Industrial organic solvents such as trichloroethylene (TCE) and tetrachloroethylene (PCE) constitute a principal class of groundwater contaminants. Cleanup of groundwater plume source areas associated with these compounds is problematic, in part, because the compounds often exist in the subsurface as dense nonaqueous phase liquids (DNAPLs). Ganglia (or 'blobs') of DNAPL serve as persistent sources of contaminants that are difficult to locate and remediate (e.g. Fenwick and Blunt, 1998). Current understanding of the physical and chemical processes associated with dissolution of DNAPLs in the subsurface is incomplete and yet is critical for evaluating long-term behavior of contaminant migration, groundwater cleanup, and the efficacy of source area cleanup technologies. As such, a goal of this project has been to contribute to this critical understanding by investigating the multi-phase, multi-component physics of DNAPL dissolution using state-of-the-art experimental and computational techniques. Through this research, we have explored efficient and accurate conceptual and numerical models for source area contaminant transport that can be used to better inform the modeling of source area contaminants, including those at the LLNL Superfund sites, to re-evaluate existing remediation technologies, and to inspire or develop new remediation strategies. The problem of DNAPL dissolution in natural porous media must be viewed in the context of several scales (Khachikian and Harmon, 2000), including the microscopic level at which capillary forces, viscous forces, and gravity/buoyancy forces are manifested at the scale of individual pores (Wilson and Conrad, 1984; Chatzis et al., 1988), the mesoscale where dissolution rates are strongly influenced by the local hydrodynamics, and the field-scale. Historically, the physico-chemical processes associated with DNAPL dissolution have been addressed through the use of lumped mass transfer coefficients which attempt to quantify the

  14. Influence of organic solvent on the separation of an ionic liquid from a lignin-ionic liquid mixture.

    PubMed

    Weerachanchai, Piyarat; Lim, Kok Hwa; Lee, Jong-Min

    2014-03-01

    Sixteen solvents added in lignin-ionic liquid mixture provide four types of solubility characteristics. The distinct characteristics can be classified by considering solubility parameters including ET Scale, Kamlet-Taft parameters and solubility parameters. Group 1 solvent shows promising solvents for lignin-ionic liquid separation, contributing full dissolution of ionic liquid with lignin precipitation. Isopropanol, the most potential solvent has solubility properties as following normalized molar electronic transition energies (ET(N))=0.57, hydrogen-bond acidity (α)=0.76 and Hildebrand solubility parameter (δT)=23.58. This study examines potential solvents for ionic recovery, provides simple method of separation and leads to the feasibility of using ionic liquids in industrial applications.

  15. Mixtures of protic ionic liquids and molecular cosolvents: a molecular dynamics simulation.

    PubMed

    Docampo-Álvarez, Borja; Gómez-González, Víctor; Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

    2014-06-07

    In this work, the effect of molecular cosolvents (water, ethanol, and methanol) on the structure of mixtures of these compounds with a protic ionic liquid (ethylammonium nitrate) is analyzed by means of classical molecular dynamics simulations. Included are as-yet-unreported measurements of the densities of these mixtures, used to test our parameterized potential. The evolution of the structure of the mixtures throughout the concentration range is reported by means of the calculation of coordination numbers and the fraction of hydrogen bonds in the system, together with radial and spatial distribution functions for the various molecular species and molecular ions in the mixture. The overall picture indicates a homogeneous mixing process of added cosolvent molecules, which progressively accommodate themselves in the network of hydrogen bonds of the protic ionic liquid, contrarily to what has been reported for their aprotic counterparts. Moreover, no water clustering similar to that in aprotic mixtures is detected in protic aqueous mixtures, but a somehow abrupt replacing of [NO3](-) anions in the first hydration shell of the polar heads of the ionic liquid cations is registered around 60% water molar concentration. The spatial distribution functions of water and alcohols differ in the coordination type, since water coordinates with [NO3](-) in a bidentate fashion in the equatorial plane of the anion, while alcohols do it in a monodentate fashion, competing for the oxygen atoms of the anion. Finally, the collision times of the different cosolvent molecules are also reported by calculating their velocity autocorrelation functions, and a caging effect is observed for water molecules but not in alcohol mixtures.

  16. Mixtures of protic ionic liquids and molecular cosolvents: A molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Docampo-Álvarez, Borja; Gómez-González, Víctor; Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R.; Cabeza, Óscar; Gallego, Luis J.; Varela, Luis M.

    2014-06-01

    In this work, the effect of molecular cosolvents (water, ethanol, and methanol) on the structure of mixtures of these compounds with a protic ionic liquid (ethylammonium nitrate) is analyzed by means of classical molecular dynamics simulations. Included are as-yet-unreported measurements of the densities of these mixtures, used to test our parameterized potential. The evolution of the structure of the mixtures throughout the concentration range is reported by means of the calculation of coordination numbers and the fraction of hydrogen bonds in the system, together with radial and spatial distribution functions for the various molecular species and molecular ions in the mixture. The overall picture indicates a homogeneous mixing process of added cosolvent molecules, which progressively accommodate themselves in the network of hydrogen bonds of the protic ionic liquid, contrarily to what has been reported for their aprotic counterparts. Moreover, no water clustering similar to that in aprotic mixtures is detected in protic aqueous mixtures, but a somehow abrupt replacing of [NO3]- anions in the first hydration shell of the polar heads of the ionic liquid cations is registered around 60% water molar concentration. The spatial distribution functions of water and alcohols differ in the coordination type, since water coordinates with [NO3]- in a bidentate fashion in the equatorial plane of the anion, while alcohols do it in a monodentate fashion, competing for the oxygen atoms of the anion. Finally, the collision times of the different cosolvent molecules are also reported by calculating their velocity autocorrelation functions, and a caging effect is observed for water molecules but not in alcohol mixtures.

  17. Porous silicon optical template for determination of chromatic dispersion of transparent liquid mixture

    NASA Astrophysics Data System (ADS)

    Cafe, Arven I.; Lopez, Joybelle; Lopez, Lorenzo; Faustino, Maria Angela; Mabilangan, Arvin; Salvador, Arnel; Somintac, Armando

    2017-03-01

    Porous silicon was fabricated through electrochemical etching and is used as an optical template for liquid sensing application. Using reflectance spectroscopy, change in optical properties such as refractive index and reflectivity upon liquid introduction were obtained. Chromatic dispersion of porous silicon upon detection of transparent liquids such as absolute ethanol, methanol, 2-propanol and distilled water were determined for spectral range 450nm to 1100nm. Mixture of the organic transparent liquid and water was also tested. In this study, porosity and liquid's concentration were varied to establish the sensitivity of detection. Expected ideal values were also simulated for comparison and correction factor computation. Results provide calibration basis for water quality assessment, environmental monitoring, and diagnostic application.

  18. Ionic liquids and deep eutectic solvents in natural products research: mixtures of solids as extraction solvents.

    PubMed

    Dai, Yuntao; van Spronsen, Jaap; Witkamp, Geert-Jan; Verpoorte, Robert; Choi, Young Hae

    2013-11-22

    Mixtures of solid chemicals may become liquid under certain conditions. These liquids are characterized by the formation of strong ionic (ionic liquids) or hydrogen bonds (deep eutectic solvents). Due to their extremely low vapor pressure, they are now widely used in polymer chemistry and synthetic organic chemistry, yet little attention has been paid to their use as extraction solvents of natural products. This review summarizes the preparation of ionic liquids and deep eutectic solvents with natural product components and recent progress in their applications to the extraction and analysis of natural products as well as the recovery of extracted compounds from their extracts. Additionally, various factors affecting extraction features of ionic liquids and deep eutectic solvents, as well as potential useful technologies including microwave and ultrasound to increase the extraction efficiency, are discussed.

  19. Phase equilibrium calculations of ternary liquid mixtures with binary interaction parameters and molecular size parameters determined from molecular dynamics.

    PubMed

    Oh, Suk Yung; Bae, Young Chan

    2010-07-15

    The method presented in this paper was developed to predict liquid-liquid equilibria in ternary liquid mixtures by using a combination of a thermodynamic model and molecular dynamics simulations. In general, common classical thermodynamic models have many parameters which are determined by fitting a model with experimental data. This proposed method, however, provides a simple procedure for calculating liquid-liquid equilibria utilizing binary interaction parameters and molecular size parameters determined from molecular dynamics simulations. This method was applied to mixtures containing water, hydrocarbons, alcohols, chlorides, ketones, acids, and other organic liquids over various temperature ranges. The predicted results agree well with the experimental data without the use of adjustable parameters.

  20. Adsorption of hydrophobin/β-casein mixtures at the solid-liquid interface.

    PubMed

    Tucker, I M; Petkov, J T; Penfold, J; Thomas, R K; Cox, A R; Hedges, N

    2016-09-15

    The adsorption behaviour of mixtures of the proteins β-casein and hydrophobin at the hydrophilic solid-liquid surface have been studied by neutron reflectivity. The results of measurements from sequential adsorption and co-adsorption from solution are contrasted. The adsorption properties of protein mixtures are important for a wide range of applications. Because of competing factors the adsorption behaviour of protein mixtures at interfaces is often difficult to predict. This is particularly true for mixtures containing hydrophobin as hydrophobin possesses some unusual surface properties. At β-casein concentrations ⩾0.1wt% β-casein largely displaces a pre-adsorbed layer of hydrophobin at the interface, similar to that observed in hydrophobin-surfactant mixtures. In the composition and concentration range studied here for the co-adsorption of β-casein-hydrophobin mixtures the adsorption is dominated by the β-casein adsorption. The results provide an important insight into how the competitive adsorption in protein mixtures of hydrophobin and β-casein can impact upon the modification of solid surface properties and the potential for a wide range of colloid stabilisation applications.

  1. Chromonic liquid crystalline nematic phase exhibited in binary mixture of two liquid crystals

    SciTech Connect

    Govindaiah, T. N. Sreepad, H. R.; Sridhar, K. N.; Sridhara, G. R.; Nagaraja, N.

    2015-06-24

    A binary mixture of abietic acid and orthophosphoric acid (H{sub 3}PO{sub 4}) exhibits co-existence of biphasic region of Nematic+Isotropic (N+I), lyotropic Nematic (ND) and Smectic-G (SmG) phases. The mixture exhibits N+I, N and SmG phases at different concentrations and at different temperatures. Mixtures with all concentrations of abietic acid exhibit I→N+I→N→SmG phases sequentially when the specimen is cooled from its isotropic melt. These phases have been characterized by using differential scanning calorimetric, X-ray diffraction, and optical texture studies.

  2. Water-in-ionic liquid microemulsion formation in solvent mixture of aprotic and protic imidazolium-based ionic liquids.

    PubMed

    Kusano, Takumi; Fujii, Kenta; Hashimoto, Kei; Shibayama, Mitsuhiro

    2014-10-14

    We report that water-in-ionic liquid microemulsions (MEs) are stably formed in an organic solvent-free system, i.e., a mixture of aprotic (aIL) and protic (pIL) imidazolium-based ionic liquids (ILs) containing the anionic surfactant dioctyl sulfosuccinate sodium salt (AOT). Structural investigations using dynamic light, small-angle X-ray, and small-angle neutron scatterings were performed for MEs formed in mixtures of aprotic 1-octyl-3-methylimidazolium ([C8mIm(+)]) and protic 1-alkylimidazolium ([CnImH(+)], n = 4 or 8) IL with a common anion, bis(trifluoromethanesulfonyl)amide ([TFSA(-)]). It was found that the ME structure strongly depends on the mixing composition of the aIL/pIL in the medium. The ME size appreciably increases with increasing pIL content in both [C8mIm(+)][TFSA(-)]/[C8ImH(+)][TFSA(-)] and [C8mIm(+)][TFSA(-)]/[C4ImH(+)][TFSA(-)] mixtures. The size is larger for the n = 8 system than that for the n = 4 system. These results indicate that the shell part of MEs is composed of both AOT and pIL cation, and the ME size can be tuned by pIL content in the aIL/pIL mixtures.

  3. Synergistic conversion of glucose into 5-hydroxymethylfurfural in ionic liquid-water mixtures.

    PubMed

    Qi, Xinhua; Watanabe, Masaru; Aida, Taku M; Smith, Richard L

    2012-04-01

    A method for converting glucose into 5-hydroxymethylfurfural (5-HMF) without using chromium-containing catalysts was developed. The method uses ionic liquid-water mixtures with a ZrO(2) catalyst. Addition of a certain amount of water (10-50 wt.%) into the 1,3-dialkylimidazolium chloride ionic liquid promoted the formation of 5-HMF from glucose compared with that in either pure water or in the pure ionic liquid. A 5-HMF yield of 53% was obtained within 10 min at 200 °C in a 50:50 w/w% 1-hexyl-3-methyl imidazolium chloride-water mixture in the presence of ZrO(2). The 1,3-dialkylimidazolium ionic liquids having Cl(-) or HSO(4)(-) anions were effective for promoting 5-HMF formation. Addition of protic solvents such as methanol and ethanol to the ionic liquid had a similar synergistic effect as water and promoted fructose and 5-HMF formation. The results reported in this work can be extended to other fields, where the ratio of ionic liquid and protic solvent can be adjusted to promote the desired reactions.

  4. Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Minnick, David L.

    Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

  5. Shock Hugoniot equations of state for binary water-alcohol liquid mixtures

    NASA Astrophysics Data System (ADS)

    Schulze, Peter A.; Ivanov, Trevor W.; Bolme, Cynthia A.; Brown, Kathryn E.; McGrane, Shawn D.; Moore, David S.

    2014-01-01

    Shock Hugoniot data were obtained using laser generated shock and ultrafast dynamic ellipsometry (UDE) methods for several non-ideal water-alcohol liquid mixtures, with the alcohols being methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol (a.k.a., 2-methyl-2-propanol or tert-butanol). The sound speeds of the mixtures were obtained using Brillouin scattering when not available in the literature. The shock and particle velocities obtained from the UDE data were compared to expectations of the universal liquid Hugoniot (ULH) and to literature shock (plate impact) data where available. The ethanol/water data were presented in a previous publication [Schulze et al., J. Phys. Chem. A 117, 6158-6163 (2013)]. The shock Hugoniot trends for all these mixtures, here represented as deviations from predictions of the ULH, versus fraction of alcohol are quite similar to each other and suggest that complex hydrogen bonding networks in alcohol-water mixtures alter the compressibility of the mixtures.

  6. Enhanced self-assembly for the solubilization of cholesterol in molecular solvent/ionic liquid mixtures.

    PubMed

    Jin, Wenbin; Ke, Yuqi; Liu, Xianxian; Yang, Qiwei; Bao, Zongbi; Su, Baogen; Ren, Qilong; Yang, Yiwen; Xing, Huabin

    2017-04-07

    The development of new solvents combining greatly enhanced solubility for sparingly soluble compounds and good kinetic properties is challenging. In this study, we constructed a family of new molecular solvent/ionic liquid (IL) mixtures with amphiphilic, anionic functional long-chain carboxylate ionic liquids (LCC-ILs) as a key component for the solubilization of sparingly soluble compounds, using cholesterol as a model solute. Polarized optical microscopy (POM), wide angle X-ray diffraction (WAXD), Fourier-transform infrared (FTIR) spectra and (1)H NMR showed that ordered mesoscopic structures, such as liquid crystals (LCs), were formed when cholesterol was dissolved in the mixtures, presenting a self-assembly induced dissolution mechanism driven by H-bond interaction and van der Waals forces in the mixtures. A synergistic effect between the molecular solvents and LCC-ILs was revealed, which contributed to enhanced solute-solvent self-assembly in dissolution over pure LCC-ILs and thus elevated solubility. Additionally, the effect of IL concentration, solvent type and anionic alkyl-chain length on self-assembly and solubility was investigated. These mixtures showed unparalleled solubilities for cholesterol, while maintaining a low viscosity. The quantitative solubilities (g g(-1)) of cholesterol were as high as 0.70, 0.84 and 0.82, respectively, at 25 °C in ethyl acetate/[P4444][C15H31COO] (50 wt%), n-heptane/[P4444][C15H31COO] (40 wt%) and ethyl acetate/[P4444][C17H35COO] (50 wt%) mixtures, which were the highest solubilities of cholesterol ever reported, six- to 980-fold higher than traditional molecular solvents and even one- to seven-fold higher compared to pure LCC-ILs. These results demonstrated the considerable potential of molecular solvent/LCC-ILs mixtures as promising solvents for solubilization and advanced separation processes.

  7. Communication: Unusual structure and transport in ionic liquid-hexane mixtures

    DOE PAGES

    Liang, Min; Khatun, Sufia; Castner, Edward W.

    2015-03-28

    Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C6D14 with this ionic liquid. High- energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C6D14. NMR self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C6D14 is on average a factor of 21more » times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

  8. Communication: Unusual structure and transport in ionic liquid-hexane mixtures

    SciTech Connect

    Liang, Min; Khatun, Sufia; Castner, Edward W.

    2015-03-28

    Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C6D14 with this ionic liquid. High- energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C6D14. NMR self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C6D14 is on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.

  9. Communication: Unusual structure and transport in ionic liquid-hexane mixtures

    SciTech Connect

    Liang, Min; Khatun, Sufia; Castner, Edward W.

    2015-03-28

    Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C{sub 6}D{sub 14} with this ionic liquid. High-energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C{sub 6}D{sub 14}. Nuclear magnetic resonance self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C{sub 6}D{sub 14} is on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.

  10. A molecular dynamics simulation study of dynamic process and mesoscopic structure in liquid mixture systems

    NASA Astrophysics Data System (ADS)

    Yang, Peng

    The focus of this dissertation is the Molecular Dynamics (MD) simulation study of two different systems. In thefirst system, we study the dynamic process of graphene exfoliation, particularly graphene dispersion using ionic surfactants (Chapter 2). In the second system, we investigate the mesoscopic structure of binary solute/ionic liquid (IL) mixtures through the comparison between simulations and corresponding experiments (Chapter 3 and 4). In the graphene exfoliation study, we consider two separation mechanisms: changing the interlayer distance and sliding away the relative distance of two single-layer graphene sheets. By calculating the energy barrier as a function of separation (interlayer or sliding-away) distance and performing sodium dodecyl sulfate (SDS) structure analysis around graphene surface in SDS surfactant/water + bilayer graphene mixture systems, we find that the sliding-away mechanism is the dominant, feasible separation process. In this process, the SDS-graphene interaction gradually replaces the graphene-graphene Van der Waals (VdW) interaction, and decreases the energy barrier until almost zero at critical SDS concentration. In solute/IL study, we investigate nonpolar (CS2) and dipolar (CH 3CN) solute/IL mixture systems. MD simulation shows that at low concentrations, IL is nanosegregated into an ionic network and nonpolar domain. It is also found that CS2 molecules tend to be localized into the nonpolar domain, while CH3CN interacts with nonpolar domain as well as with the charged head groups in the ionic network because of its amphiphilicity. At high concentrations, CH3CN molecules eventually disrupt the nanostructural organization. This dissertation is organized in four chapters: (1) introduction to graphene, ionic liquids and the methodology of MD; (2) MD simulation of graphene exfoliation; (3) Nanostructural organization in acetonitrile/IL mixtures; (4) Nanostructural organization in carbon disulfide/IL mixtures; (5) Conclusions. Results

  11. Mesomorphic and physicochemical properties of liquid crystal mixture composed of chiral molecules with perfluorinated terminal chains

    NASA Astrophysics Data System (ADS)

    Tomczyk, Wojciech; Marzec, Monika; Juszyńska-Gałązka, Ewa; Węgłowska, Dorota

    2017-02-01

    New binary mixture of thermotropic liquid crystalline compounds, possessing both ferro- and antiferroelectric smectic C* phases, has been studied by complementary methods: calorimetric, X-ray powder diffractometry and electro-optic. Additionally, quantum-chemical model based on the density functional theory was also applied. It was found that mixture studied did not exhibit antiferroelectric phase at any rate of heating or cooling in contradiction to its ingredients. On the other hand it has a wide temperature range of ferroelectric smectic C* phase, which is invariant with respect to different heating and cooling rates within the range of thermal hysteresis. Furthermore, temperature dependence of switching time and spontaneous polarization were measured.

  12. Monolayer and bilayer structures in ionic liquids and their mixtures confined to nano-films.

    PubMed

    Smith, Alexander M; Lovelock, Kevin R J; Perkin, Susan

    2013-01-01

    The confinement of liquids to thin films can lead to dramatic changes in their structural arrangement and dynamic properties. Ionic liquids display nano-structures in the bulk of the liquid, consisting of polar and non-polar domains, whereas a solid surface can induce layered structures in the near-surface liquid. Here we compare and contrast the layer structures in a series of imidazolium and pyrrolidinium-based ionic liquids upon confinement of the liquids to films of approximately 0-20 nm between two negatively charged mica surfaces. Using a surface force balance (SFB) we measured the force between the two atomically smooth mica surfaces with ionic liquid between, directly revealing the ion packing and dimensions of layered structures for each liquid. The ionic liquids with shorter alkyl chain substituents form alternating cation-anion monolayer structures on confinement, whilst a longer alkyl chain leads to alignment of the cations in bilayer formation. The crossover from monolayers to bilayers, however, occurs at different alkyl chain lengths for imidazolium- and pyrrolidinium-based ionic liquids with a common anion. In addition, we find that imidazolium cation bilayers are arranged in toe-to-toe orientation, whereas pyrrolidinium cations form bilayers consisting of fully interdigitated alkyl chains. Results for a mixture of monolayer-preferring (i.e. short alkyl chain) and bilayer-preferring (i.e. long alkyl chain) liquids indicate alkyl chain segregation and bilayer-like structures. We discuss the driving forces for these self-assembly effects, and the contrasting behaviour of the imidazolium and pyrrolidinium-type ionic liquids.

  13. CRYSTALLIZATION IN MULTICOMPONENT GLASSES

    SciTech Connect

    KRUGER AA; HRMA PR

    2009-10-08

    In glass processing situations involving glass crystallization, various crystalline forms nucleate, grow, and dissolve, typically in a nonuniform temperature field of molten glass subjected to convection. Nuclear waste glasses are remarkable examples of multicomponent vitrified mixtures involving partial crystallization. In the glass melter, crystals form and dissolve during batch-to-glass conversion, melter processing, and product cooling. Crystals often agglomerate and sink, and they may settle at the melter bottom. Within the body of cooling glass, multiple phases crystallize in a non-uniform time-dependent temperature field. Self-organizing periodic distribution (the Liesegnang effect) is common. Various crystallization phenomena that occur in glass making are reviewed.

  14. Magnetization of multicomponent ferrofluids.

    PubMed

    Szalai, I; Dietrich, S

    2011-08-17

    The solution of the mean spherical approximation (MSA) integral equation for isotropic multicomponent dipolar hard sphere fluids without external fields is used to construct a density functional theory (DFT), which includes external fields, in order to obtain an analytical expression for the external field dependence of the magnetization of ferrofluidic mixtures. This DFT is based on a second-order Taylor series expansion of the free energy density functional of the anisotropic system around the corresponding isotropic MSA reference system. The ensuing results for the magnetic properties are in quantitative agreement with our canonical ensemble Monte Carlo simulation data presented here.

  15. Maxwell-Stefan diffusivities in binary mixtures of ionic liquids with dimethyl sulfoxide (DMSO) and H2O.

    PubMed

    Liu, Xin; Vlugt, Thijs J H; Bardow, André

    2011-07-07

    Ionic liquids (ILs) are promising solvents for applications ranging from CO2 capture to the pretreatment of biomass. However, slow diffusion often restricts their applicability. A thorough understanding of diffusion in ILs is therefore highly desirable. Previous research largely focused on self-diffusion in ILs. For practical applications, mutual diffusion is by far more important than self-diffusion. For describing mutual diffusion in multicomponent systems, the Maxwell-Stefan (MS) approach is commonly used. Unfortunately, it is difficult to obtain MS diffusivities from experiments, but they can be directly extracted from molecular dynamics (MD) simulations. In this work, MS diffusivities were computed in binary systems containing 1-alkyl-3-methylimidazolium chloride (C(n)mimCl, n = 2, 4, 8), water, and/or dimethyl sulfoxide (DMSO) using MD. The dependence of self- and MS diffusivities on mixture composition was investigated. Our results show the following: (1) For solutions of ILs in water and DMSO, self-diffusivities decrease strongly with increasing IL concentration. For DMSO-IL, a single exponential decay is observed. (2) In both water-IL and DMSO-IL, MS diffusivities vary by a factor of 10 within the concentration range which is, however, still significantly smaller than the variation of the self-diffusion coefficients. (3) The MS diffusivities of the IL are almost independent of the alkyl chain length. (4) ILs stay in a form of isolated ions in C(n)mimCl-H2O mixtures; however, dissociation into ions is much less observed in C(n)mimCl-DMSO systems. This has a large effect on the concentration dependence of MS diffusivities. (5) Recently, we proposed a new model for predicting the MS diffusivity at infinite dilution, that is, Đ(ij)(x(k-->)1) (Ind. Eng. Chem. Res. 2011, 50, 4776-4782). This quantity describes the friction between components i and j when both are infinitely diluted in component k. In contrast to earlier empirical models, our model is based on

  16. Gas-liquid-liquid equilibria in mixtures of water, light gases, and hydrocarbons

    SciTech Connect

    Chao, K.C.

    1990-01-01

    Phase equilibrium in mixtures of water + light gases and water + heavy hydrocarbons has been investigated with the development of new local composition theory, new equations of state, and new experimental data. The preferential segregation and orientation of molecules due to different energies of molecular interaction has been simulated with square well molecules. Extensive simulation has been made for pure square well fluids and mixtures to find the local composition at wide ranges of states. A theory of local composition has been developed and an equation of state has been obtained for square well fluids. The new local composition theory has been embedded in several equations of state. The pressure of water is decoupled into a polar pressure and non-polar pressure according to the molecular model of water of Jorgensen et al. The polar pressure of water is combined with the BACK equation for the general description of polar fluids and their mixtures. Being derived from the steam table, the Augmented BACK equation is particularly suited for mixtures of water + non-polar substances such as the hydrocarbons. The hydrophobic character of the hydrocarbons had made their mixtures with water a special challenge. A new group contribution equation of state is developed to describe phase equilibrium and volumetric behavior of fluids while requiring only to know the molecular structure of the components. 15 refs., 1 fig.

  17. Ideal gas solubilities and solubility selectivities in a binary mixture of room-temperature ionic liquids

    SciTech Connect

    Finotello Alexia; Bara Jason E.; Narayan Suguna; Campder Dean; Noble Richard D.

    2008-07-01

    This study focuses on the solubility behaviors of CO{sub 2}, CH{sub 4}, and N{sub 2} gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide ((C{sub 2}mim)(Tf{sub 2}N)) and l-ethyl-3-methylimidazolium tetrafluoroborate ((C{sub 2}mim)(BF{sub 4})) at 40{sup o}C and low pressures (about 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % (C{sub 2}mim)(BF{sub 4}) in (C{sub 2}-mim)(Tf2{sub N}). Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO{sub 2} with N{sub 2} or CH{sub 4} in pure (C{sub 2}mim)(BF4) can be enhanced by adding 5 mol% (C{sub 2}-mim)(Tf{sub 2}N).

  18. Ethanol, acetic acid, and water adsorption from binary and ternary liquid mixtures on high-silica zeolites.

    PubMed

    Bowen, Travis C; Vane, Leland M

    2006-04-11

    Adsorption isotherms were measured for ethanol, acetic acid, and water adsorbed on high-silica ZSM-5 zeolite powder from binary and ternary liquid mixtures at room temperature. Ethanol and water adsorption on two high-silica ZSM-5 zeolites with different aluminum contents and a high-silica beta zeolite were also compared. The amounts adsorbed were measured using a recently developed technique that accurately measures the changes in adsorbent/liquid mixture density and liquid concentration. This technique allows the adsorption of each compound in a liquid mixture to be measured. Adsorption data for binary mixtures were fit with the dual-site extended Langmuir model, and the parameters were used to predict ternary adsorption isotherms for each compound with reasonable accuracy. In ternary mixtures, acetic acid competed with ethanol and water for adsorption sites and reduced ethanol adsorption more than it reduced water adsorption.

  19. Combustion and micro-explosion of multicomponent droplets

    SciTech Connect

    Wang, C.H.

    1983-01-01

    An experimental investigation of the gasification, combustion, and micro-explosion of droplets of miscible multicomponent fuel mixtures and water/oil emulsions in hot, oxidizing, pressurized environments is described. The experiment involves generating a stream of droplets of uniform and controllable size, spacing, and velocity by the ink-jet printing technique, injecting them into the continuously flowing combustion environment produced by a flat-flame burner, and examining the subsequent combustion processes using high-speed photography. Results show that the gasification mechanism of miscible multicomponent droplets consist of an initial phase of transient adjustment of the droplet surface layer such that it becomes more concentrated with the less volatile component, and a second phase of liquid-phase-diffusion-limited steady-state combustion with the fractional gasification rate of the constituents being equal to their respective initial mass fractions in the mixture. Micro-explosion of miscible multicomponent droplets is found to be favored with an unstable droplet generation mode, with increasing the system pressure, and with light alcohol addition. The internal bubble growth process is a relatively slow one, occupying about 10% of the droplet lifetime. Micro-explosion of water/oil emulsion droplets occurs under both normal and high pressure environments. Results also show that prior to the onset of micro-explosion in the nominally opaque droplet becomes transparent, indicating deterioration of the emulsion structure. Results and insights on the ignition, extinction, and soot formation characteristics are also documented.

  20. Analytical performances of two liquid crystals and their mixture as stationary phases in capillary gas chromatography.

    PubMed

    Bélaïdi, D; Sebih, S; Boudah, S; Guermouche, M H; Bayle, J P

    2005-09-16

    Comparative gas chromatographic applications of two new liquid crystals called LCa and LCb and their equimolar mixture LC(a+b) were investigated. The thermal properties of LCa, LCb and LC(a+b) were established with differential scanning calorimetry (DSC) and polarizing microscopy. Differential scanning calorimetry of LC(a+b) showed that the melting or clearing temperature was intermediate between the corresponding temperatures of the pure compounds. Polarizing microscopy showed that the liquid crystal phase of A + B was nematic. The chromatographic separation abilities LCa, LCb and LC(a+b) were studied using fused silica capillary columns. Interesting analytical performances were obtained: isomeric separation of aromatics, polyaromatics, phenols.

  1. Tunable structures of mixtures of magnetic particles in liquid-crystalline matrices.

    PubMed

    Peroukidis, Stavros D; Lichtner, Ken; Klapp, Sabine H L

    2015-08-14

    We investigate the self-organization of a binary mixture of similar sized rods and dipolar soft spheres by means of Monte-Carlo simulations. We model interparticle interactions by employing anisotropic Gay-Berne, dipolar and soft-sphere interactions. In the limit of vanishing magnetic moments we obtain a variety of fully miscible liquid crystalline phases including nematic, smectic and lamellar phases. For the magnetic mixture, we find that the liquid crystalline matrix supports the formation of orientationally ordered ferromagnetic chains. Depending on the relative size of the species the chains align parallel or perpendicular to the director of the rods forming uniaxial or biaxial nematic, smectic and lamellar phases. As an exemplary external perturbation we apply a homogeneous magnetic field causing uniaxial or biaxial ordering to an otherwise isotropic state.

  2. Microcantilever sensors for monitoring the evaporation of microdrops of pure liquids and mixtures.

    PubMed

    Liu, Chuanjun; Bonaccurso, Elmar

    2010-01-01

    We describe in detail a nonimaging technique that allows the measurement of the mass, the radius, and the contact angle of evaporating sessile microdrops of pure liquids and binary mixtures. The microdrops were deposited onto hydrophobized silicon microcantilevers whose bending and resonance frequency were monitored during drop evaporation. We verify the laws of evaporation kinetics for microdrops with diameters from 80 down to 10 microm. The evaporation of mixtures of water/ethanol drops confirmed previous results with millimeter sized drops. N,N-dimethylformamide drops undergo a transformation from an initial spherical shape to a thin film. Flattening of the drop causes a slowdown of the evaporation kinetics at the end. Two concurring factors are at its origin: the rising disjoining pressure stabilizes the thin liquid film and the increasing radius of curvature of the drop reduces the vapor pressure.

  3. Microcantilever sensors for monitoring the evaporation of microdrops of pure liquids and mixtures

    NASA Astrophysics Data System (ADS)

    Liu, Chuanjun; Bonaccurso, Elmar

    2010-01-01

    We describe in detail a nonimaging technique that allows the measurement of the mass, the radius, and the contact angle of evaporating sessile microdrops of pure liquids and binary mixtures. The microdrops were deposited onto hydrophobized silicon microcantilevers whose bending and resonance frequency were monitored during drop evaporation. We verify the laws of evaporation kinetics for microdrops with diameters from 80 down to 10 μm. The evaporation of mixtures of water/ethanol drops confirmed previous results with millimeter sized drops. N,N-dimethylformamide drops undergo a transformation from an initial spherical shape to a thin film. Flattening of the drop causes a slowdown of the evaporation kinetics at the end. Two concurring factors are at its origin: the rising disjoining pressure stabilizes the thin liquid film and the increasing radius of curvature of the drop reduces the vapor pressure.

  4. Topological and spatial structure in the liquid-water-acetonitrile mixture

    NASA Astrophysics Data System (ADS)

    Bergman, Dan L.; Laaksonen, Aatto

    1998-10-01

    We have studied the structure of the liquid-water-acetonitrile mixture using molecular configurations obtained by molecular dynamics simulation. Spatial distribution functions have been used to analyze the local structures surrounding the molecules. The effective hydrogen-bond definition has been used to study basic hydrogen-bond properties and topological properties of the hydrogen-bond network. The topology of the network depends on the acetonitrile concentration. Up to a critical concentration, there is an infinite network of hydrogen-bonded water molecules. At higher concentrations, the network cannot be supported, and finite water clusters form. In order to characterize the networks and clusters, we have calculated some properties of loops and chains of water molecules. The patterns of hydrogen bonds surrounding the molecules and the size distribution of the clusters have also been calculated. We suggest that this approach can be useful when studying the structure of other liquid mixtures where hydrogen bonds are an important mode of interaction.

  5. Understanding lignin treatment in dialkylimidazolium-based ionic liquid-water mixtures.

    PubMed

    Yan, Bing; Li, Kunlan; Wei, Ligang; Ma, Yingchong; Shao, Guolin; Zhao, Deyang; Wan, Wenying; Song, Lili

    2015-11-01

    The treatment of enzymatically hydrolyzed lignin (EHL) in dialkylimidazolium-based ionic liquid (IL)-water mixtures (50-100wt% IL content) was investigated at 150°C for 3h. pH, IL type, and IL content were found to greatly influence the degradation of lignin and the structure of regenerated lignin. 1-Butyl-3-methylimidazolium methylsulfonate-water mixtures with low pH facilitated lignin depolymerization but destroyed the regenerated lignin substructure. Regenerated lignin with low molecular weight and narrow polydispersity index (2.2-7.7) was obtained using a 1-butyl-3-methylimidazolium acetate-based system. Water addition inhibited lignin depolymerization at 50-100wt% IL content, except for 70wt% 1-butyl-3-methylimidazolium chloride-water mixture. Compared with pure IL treatment, obvious differences were observed in the breakdown of inter-unit linkages and ratio of syringyl to guaiacyl units in regenerated lignin with IL-water treatment.

  6. Numerical Analysis of Multicomponent Suspension Droplets in High-Velocity Flame Spray Process

    NASA Astrophysics Data System (ADS)

    Gozali, Ebrahim; Mahrukh, Mahrukh; Gu, Sai; Kamnis, Spyros

    2014-08-01

    The liquid feedstock or suspension as a different mixture of liquid fuel ethanol and water is numerically studied in high-velocity suspension flame spray (HVSFS) process, and the results are compared for homogenous liquid feedstock of ethanol and water. The effects of mixture on droplet aerodynamic breakup, evaporation, combustion, and gas dynamics of HVSFS process are thoroughly investigated. The exact location where the particle heating is initiated (above the carrier liquid boiling point) can be controlled by increasing the water content in the mixture. In this way, the particle inflight time in the high-temperature gas regions can be adjusted avoiding adverse effects from surface chemical transformations. The mixture is modeled as a multicomponent droplet, and a convection/diffusion model, which takes into account the convective flow of evaporating material from droplet surface, is used to simulate the suspension evaporation. The model consists of several sub-models that include premixed combustion of propane-oxygen, non-premixed ethanol-oxygen combustion, modeling of multicomponent droplet breakup and evaporation, as well as heat and mass transfer between liquid droplets and gas phase.

  7. Superconducting cable cooling system by helium gas and a mixture of gas and liquid helium

    DOEpatents

    Dean, John W.

    1977-01-01

    Thermally contacting, oppositely streaming cryogenic fluid streams in the same enclosure in a closed cycle that changes from a cool high pressure helium gas to a cooler reduced pressure helium fluid comprised of a mixture of gas and boiling liquid so as to be near the same temperature but at different pressures respectively in go and return legs that are in thermal contact with each other and in thermal contact with a longitudinally extending superconducting transmission line enclosed in the same cable enclosure that insulates the line from the ambient at a temperature T.sub.1. By first circulating the fluid in a go leg from a refrigerator at one end of the line as a high pressure helium gas near the normal boiling temperature of helium; then circulating the gas through an expander at the other end of the line where the gas becomes a mixture of reduced pressure gas and boiling liquid at its boiling temperature; then by circulating the mixture in a return leg that is separated from but in thermal contact with the gas in the go leg and in the same enclosure therewith; and finally returning the resulting low pressure gas to the refrigerator for compression into a high pressure gas at T.sub.2 is a closed cycle, where T.sub.1 >T.sub.2, the temperature distribution is such that the line temperature is nearly constant along its length from the refrigerator to the expander due to the boiling of the liquid in the mixture. A heat exchanger between the go and return lines removes the gas from the liquid in the return leg while cooling the go leg.

  8. Molecular dynamics study of polysaccharides in binary solvent mixtures of an ionic liquid and water.

    PubMed

    Liu, Hanbin; Sale, Kenneth L; Simmons, Blake A; Singh, Seema

    2011-09-01

    Some ionic liquids (ILs) have great promise as effective solvents for biomass pretreatment, and there are several that have been reported that can dissolve large amounts of cellulose. The solubilized cellulose can then be recovered by addition of antisolvents, such as water or ethanol, and this regeneration process plays an important role in the subsequent enzymatic saccharification reactions and in the recovery of the ionic liquid. To date, little is known about the fundamental intermolecular interactions that drive the dissolution and subsequent regeneration of cellulose in complex mixtures of ionic liquids, water, and cellulose. To investigate these interactions, in this work, molecular dynamics (MD) simulations were carried out to study binary and ternary mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) with water and a cellulose oligomer. Simulations of a cellulose oligomer dissolved in three concentrations of binary mixtures of [C2mim][OAc] and water were used to represent the ternary system in the dissolution phase (high [C2mim][OAc] concentration) and present during the initial phase of the regeneration step (intermediate and low [C2mim][OAc] concentrations). The MD analysis of the structure and dynamics that exist in these binary and ternary mixtures provides information on the key intermolecular interactions between cellulose and [C2mim][OAc] that lead to dissolution of cellulose and the key intermolecular interactions in the intermediate states of cellulose precipitation as a function of water content in the cellulose/IL/water system. The analysis of this intermediate state provides new insight into the molecular driving forces present in this ternary system.

  9. Reaction of singlet oxygen with thioanisole in ionic liquid-acetonitrile binary mixtures.

    PubMed

    Baciocchi, Enrico; Chiappe, Cinzia; Fasciani, Chiara; Lanzalunga, Osvaldo; Lapi, Andrea

    2010-11-19

    A study of the reaction of thioanisole with singlet oxygen in different ionic liquid-acetonitrile binary mixtures has shown that ILs are able to accelerate the thioanisole sulfoxidation when used as additives. With imidazolium ILs, the maximum efficiency is reached at x(IL) ∼ 0.1-0.2, whereas for the pyrrolidinium IL a plateau is reached. These results are discussed in terms of the ILs' tendency to form ionic aggregates and of differences in sulfoxidation reaction mechanism.

  10. Divergent trend in density versus viscosity of ionic liquid/water mixtures: a molecular view from guanidinium ionic liquids.

    PubMed

    Singh, Akhil Pratap; Gardas, Ramesh L; Senapati, Sanjib

    2015-10-14

    Ionic liquids (ILs) have shown great potential in the dissolution and stability of biomolecules when a low-to-moderate quantity of water is added. Hence, determining the thermophysical properties and understanding these novel mixtures at the molecular level are of both fundamental and practical importance. In this context, here we report the synthesis of two nontoxic guanidinium cation based ILs, tetramethylguanidinium benzoate [TMG][BEN] and tetramethylguanidinium salicylate [TMG][SAL], and present a detailed comparison of their thermophysical properties in the presence of water. The results show that the [TMG][SAL]/water mixtures have higher density and higher apparent molar volume, but a lower viscosity and higher compressibility than the [TNG][BEN]/water mixtures. The measured viscosity and compressibility data are explained from ab initio quantum mechanical calculations and liquid-phase molecular dynamics simulations, where salicylate anions of denser [TMG][SAL]/water were found to exist as isolated ions due to intramolecular H-bonding. On the contrary, intermolecular H-bonding among the benzoate anions and their strong tendency to form an extended H-bonding network with water made [TMG][BEN]/water solutions more viscous and less compressible. This study shows the importance of probing these emerging solvents at the molecular-to-atomic level, which could be helpful in their optimal usage for task-specific applications.

  11. The suitability of concentration addition for predicting the effects of multi-component mixtures of up to 17 anti-androgens with varied structural features in an in vitro AR antagonist assay

    SciTech Connect

    Ermler, Sibylle; Scholze, Martin; Kortenkamp, Andreas

    2011-12-15

    The risks associated with human exposures to chemicals capable of antagonising the effects of endogenous androgens have attracted considerable recent interest. Exposure is typically to large numbers of chemicals with androgen receptor (AR) antagonist activity, yet there is limited evidence of the combined effects of multi-component mixtures of these chemicals. A few in vitro studies with mixtures of up to six AR antagonists suggest that the concept of concentration addition (CA) provides good approximations of experimentally observed mixture effects, but studies with larger numbers of anti-androgens, and with more varied structural features, are missing. Here we show that the mixture effects of up to 17 AR antagonists, comprising compounds as diverse as UV-filter substances, parabens, perfluorinated compounds, bisphenol-A, benzo({alpha})pyrene, synthetic musks, antioxidants and polybrominated biphenyls, can be predicted well on the basis of the anti-androgenicity of the single components using the concept of CA. We tested these mixtures in an in vitro AR-dependent luciferase reporter gene assay, based on MDA-kb2 cells. The effects of further mixtures, composed of four and six anti-androgens, could be predicted accurately by CA. However, there was a shortfall from expected additivity with a ten-component mixture at two different mixture ratios, but attempts to attribute these deviations to differential expression of hormone-metabolising CYP isoforms did not produce conclusive results. CA provides good approximations of in vitro mixture effects of anti-androgens with varying structural features. -- Highlights: Black-Right-Pointing-Pointer Humans are exposed to a large number of androgen receptor antagonists. Black-Right-Pointing-Pointer There is limited evidence of the combined effects of anti-androgenic chemicals. Black-Right-Pointing-Pointer We modelled the predictability of combined effects of up to 17 anti-androgens. Black-Right-Pointing-Pointer We tested the

  12. Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures

    SciTech Connect

    Lian, C.; Liu, K.; Van Aken, Katherine L.; Gogotsi, Yury G.; Wesolowski, David J.; Liu, Honglai; Jiang, D. E.; Wu, Jianzhong

    2016-04-18

    Formulating room-temperature ionic liquid (RTIL) mixed electrolytes was recently proposed as an effective and convenient strategy to increase the capacitive performance of electrochemical capacitors. In this paper, we investigate the electrical double-layer (EDL) structure and the capacitance of two RTILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF4), and their mixtures with onion-like carbon electrodes using experiment and classical density functional theory. The principal difference between these ionic liquids is the smaller diameter of the BF4 anion relative to the TFSI anion and the EMI+ cation. A volcano-shaped trend is identified for the capacitance versus the composition of the RTIL mixture. The mixture effect, which makes more counterions pack on and more co-ions leave from the electrode surface, leads to an increase of the counterion density within the EDL and thus a larger capacitance. Finally, these theoretical predictions are in good agreement with our experimental observations and offer guidance for designing RTIL mixtures for EDL supercapacitors.

  13. Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures

    DOE PAGES

    Lian, C.; Liu, K.; Van Aken, Katherine L.; ...

    2016-04-18

    Formulating room-temperature ionic liquid (RTIL) mixed electrolytes was recently proposed as an effective and convenient strategy to increase the capacitive performance of electrochemical capacitors. In this paper, we investigate the electrical double-layer (EDL) structure and the capacitance of two RTILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF4), and their mixtures with onion-like carbon electrodes using experiment and classical density functional theory. The principal difference between these ionic liquids is the smaller diameter of the BF4– anion relative to the TFSI– anion and the EMI+ cation. A volcano-shaped trend is identified for the capacitance versus the composition of the RTIL mixture.more » The mixture effect, which makes more counterions pack on and more co-ions leave from the electrode surface, leads to an increase of the counterion density within the EDL and thus a larger capacitance. Finally, these theoretical predictions are in good agreement with our experimental observations and offer guidance for designing RTIL mixtures for EDL supercapacitors.« less

  14. True molecular solutions of natural cellulose in the binary ionic liquid-containing solvent mixtures.

    PubMed

    Rein, Dmitry M; Khalfin, Rafail; Szekely, Noemi; Cohen, Yachin

    2014-11-04

    Evidence is presented for the first time of true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with ionic liquid. Cryogenic transmission electron microscopy, small-angle neutron-, X-ray- and static light scattering were used to investigate the structure of cellulose solutions in mixture of dimethyl formamide and 1-ethyl-3-methylimidazolium acetate. Structural information on the dissolved chains (average molecular weight ∼ 5 × 10(4)g/mol; gyration radius ∼ 36 nm, persistence length ∼ 4.5 nm), indicate the absence of significant aggregation of the dissolved chains and the calculated value of the second virial coefficient ∼ 2.45 × 10(-2)mol ml/g(2) indicates that this solvent system is a good solvent for cellulose. More facile dissolution of cellulose could be achieved in solvent mixtures that exhibit the highest electrical conductivity. Highly concentrated cellulose solution in pure ionic liquid (27 wt.%) prepared according to novel method, utilizing the rapid evaporation of a volatile co-solvent in binary solvent mixtures at superheated conditions, shows insignificant cellulose molecular aggregation.

  15. Effect of the oxygen balance on ignition and detonation properties of liquid explosive mixtures

    NASA Astrophysics Data System (ADS)

    Genetier, Marc; Osmont, Antoine; Baudin, Gerard

    2013-06-01

    The objective is to compare ignition and detonation properties of various liquid high explosives having negative up to positive oxygen balance (OB): nitromethane (OB < 0), saccharose and hydrogen peroxide based mixture (quasi nil OB), hydrogen peroxide with more than 90% purity (OB > 0). The decomposition kinetic rates and the equations of state (EOS) for the liquid mixtures and detonation products (DP) are the input data for a detonation model. EOS are theoretically determined using the Woolfolk et al universal liquid polar shock law and thermochemical computations for DP. The decomposition kinetic rate laws are determined to reproduce the shock to detonation transition for the mixtures submitted to planar plate impacts. Such a model is not sufficient to compute open field explosions. The aerial overpressure is well reproduced in the first microseconds, however, after it becomes worse at large expansion of the fireball and the impulse is underestimated. The problem of the DP EOS alone is that it takes into account only the detonation, the secondary combustion DP - air being not considered. To solve this problem a secondary combustion model has been developed to take into account the OB effect. The detonation model has been validated on planar plate impact experiments. The secondary combustion parameters were deduced from thermochemical computations. The whole model has been used to predict the effects of the oxygen balance on open air blast effects of spherical charges.

  16. Effect of the oxygen balance on ignition and detonation properties of liquid explosive mixtures

    NASA Astrophysics Data System (ADS)

    Genetier, M.; Osmont, A.; Baudin, G.

    2014-05-01

    The objective is to compare the ignition and detonation properties of various liquid high explosives having negative up to positive oxygen balance (OB): nitromethane (OB < 0), saccharose and hydrogen peroxide based mixture (quasi nil OB), hydrogen peroxide with more than 90% purity (OB > 0). The decomposition kinetic rates and the equations of state (EOS) for the liquid mixtures and detonation products (DP) are the input data for a detonation model. EOS are theoretically determined using the Woolfolk et al. universal liquid polar shock law and thermochemical computations for DP. The decomposition kinetic rate laws are determined to reproduce the shock to detonation transition for the mixtures submitted to planar plate impacts. Such a model is not sufficient to compute open field explosions. The aerial overpressure is well reproduced in the first few microseconds, however, after it becomes worse at large expansion of the fireball and the impulse is underestimated. The problem of the DP EOS alone is that it takes only the detonation into account, the secondary combustion DP - air is not considered. To solve this problem a secondary combustion model has been developed to take the OB effect into account. The detonation model has been validated on planar plate impact experiments. The secondary combustion parameters were deduced from thermochemical computations. The whole model has been used to predict the effects of the oxygen balance on open air blast effects of spherical charges.

  17. Phase behaviour, interactions, and structural studies of (amines+ionic liquids) binary mixtures.

    PubMed

    Jacquemin, Johan; Bendová, Magdalena; Sedláková, Zuzana; Blesic, Marijana; Holbrey, John D; Mullan, Claire L; Youngs, Tristan G A; Pison, Laure; Wagner, Zdeněk; Aim, Karel; Costa Gomes, Margarida F; Hardacre, Christopher

    2012-05-14

    We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [C(n)mim] [NTf(2)] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory-Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C(2)mim] [NTf(2)]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C(2)mim][NTf(2)]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents.

  18. Mutual diffusion of binary liquid mixtures containing methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride.

    PubMed

    Guevara-Carrion, Gabriela; Janzen, Tatjana; Muñoz-Muñoz, Y Mauricio; Vrabec, Jadran

    2016-03-28

    Mutual diffusion coefficients of all 20 binary liquid mixtures that can be formed out of methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride without a miscibility gap are studied at ambient conditions of temperature and pressure in the entire composition range. The considered mixtures show a varying mixing behavior from almost ideal to strongly non-ideal. Predictive molecular dynamics simulations employing the Green-Kubo formalism are carried out. Radial distribution functions are analyzed to gain an understanding of the liquid structure influencing the diffusion processes. It is shown that cluster formation in mixtures containing one alcoholic component has a significant impact on the diffusion process. The estimation of the thermodynamic factor from experimental vapor-liquid equilibrium data is investigated, considering three excess Gibbs energy models, i.e., Wilson, NRTL, and UNIQUAC. It is found that the Wilson model yields the thermodynamic factor that best suits the simulation results for the prediction of the Fick diffusion coefficient. Four semi-empirical methods for the prediction of the self-diffusion coefficients and nine predictive equations for the Fick diffusion coefficient are assessed and it is found that methods based on local composition models are more reliable. Finally, the shear viscosity and thermal conductivity are predicted and in most cases favorably compared with experimental literature values.

  19. Multiphase, multicomponent phase behavior prediction

    NASA Astrophysics Data System (ADS)

    Dadmohammadi, Younas

    Accurate prediction of phase behavior of fluid mixtures in the chemical industry is essential for designing and operating a multitude of processes. Reliable generalized predictions of phase equilibrium properties, such as pressure, temperature, and phase compositions offer an attractive alternative to costly and time consuming experimental measurements. The main purpose of this work was to assess the efficacy of recently generalized activity coefficient models based on binary experimental data to (a) predict binary and ternary vapor-liquid equilibrium systems, and (b) characterize liquid-liquid equilibrium systems. These studies were completed using a diverse binary VLE database consisting of 916 binary and 86 ternary systems involving 140 compounds belonging to 31 chemical classes. Specifically the following tasks were undertaken: First, a comprehensive assessment of the two common approaches (gamma-phi (gamma-ϕ) and phi-phi (ϕ-ϕ)) used for determining the phase behavior of vapor-liquid equilibrium systems is presented. Both the representation and predictive capabilities of these two approaches were examined, as delineated form internal and external consistency tests of 916 binary systems. For the purpose, the universal quasi-chemical (UNIQUAC) model and the Peng-Robinson (PR) equation of state (EOS) were used in this assessment. Second, the efficacy of recently developed generalized UNIQUAC and the nonrandom two-liquid (NRTL) for predicting multicomponent VLE systems were investigated. Third, the abilities of recently modified NRTL model (mNRTL2 and mNRTL1) to characterize liquid-liquid equilibria (LLE) phase conditions and attributes, including phase stability, miscibility, and consolute point coordinates, were assessed. The results of this work indicate that the ϕ-ϕ approach represents the binary VLE systems considered within three times the error of the gamma-ϕ approach. A similar trend was observed for the for the generalized model predictions using

  20. How do liquid mixtures solubilize insoluble gelators? Self-assembly properties of pyrenyl-linker-glucono gelators in tetrahydrofuran-water mixtures.

    PubMed

    Yan, Ni; Xu, Zhiyan; Diehn, Kevin K; Raghavan, Srinivasa R; Fang, Yu; Weiss, Richard G

    2013-06-19

    The self-assembly behavior of a series of glucono-appended 1-pyrenesulfonyl derivatives containing α,ω-diaminoalkane spacers (Pn, where n, the number of methylene units separating the amino groups, is 2, 3, 4, 6, 7, and 8) in v:v tetrahydrofuran (THF):water mixtures is examined at room temperature. The Pn at 2 w/v % concentrations do not dissolve in either THF or water at room temperature. However, the Pn can be dissolved in some THF:water mixtures, and they form gels spontaneously in other compositions without dissolving completely. The self-assembly of the Pn in the liquid mixtures has been investigated using a variety of techniques. The particle sizes of the Pn in their solutions/sols, critical gelation concentrations, microstructures, thermal and mechanical stabilities of the gels, and molecular packing modes of Pn molecules in their gel networks are found to be very dependent on the composition of the liquid mixtures. Correlations between the self-assembly behavior of the Pn and the polarity of the liquid mixtures, as probed by E(T)(30) and Hansen solubility parameters, yield both qualitative and quantitative insights into why self-assembly of the Pn can or cannot be achieved in different liquid compositions. As revealed by UV-vis and fluorescence spectroscopy studies, π-π stacking of the pyrenyl groups occurs as part of the aggregation process. Correlations between the rheological properties of the gels and the Hansen solubility parameters of the Pn and the solvent mixtures indicate that hydrogen-bonding interactions are a major contributor to the mechanical stability. Overall, the results of this study offer a new strategy to investigate the balance between dissolution and aggregation of molecular gelators. To the best of our knowledge, this is the first example of the spontaneous formation of molecular gels without heating by placing gelators in mixtures of liquids in which they are insoluble in the neat components.

  1. Stokes shift dynamics in (ionic liquid + polar solvent) binary mixtures: composition dependence.

    PubMed

    Daschakraborty, Snehasis; Ranjit, Biswas

    2011-04-14

    An approximate semimolecular theory has been developed to investigate the composition dependence of Stokes shift dynamics of a fluorescent dye molecule dissolved in binary mixtures of an ionic liquid (IL) with a conventional polar solvent at different mole fractions. The theory expresses the dynamic Stokes shift as a sum of contributions from the dye-IL and the dye-polar solvent interactions and suggests substantial solute-cation dipole-dipole interaction contribution to the solvation energy relaxation. The theory, when applied to aqueous mixtures of 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF(6)]) and tetrafluoroborate ([Bmim][BF(4)]), and binary mixtures of ([Bmim][BF(4)] + acetonitrile), predicts reduction of Stokes shift but acceleration of the dynamics upon increasing the polar solvent concentration for the most part of the mixture composition. The decrease in dynamic Stokes shift values has been found to occur due to decrease of the dye-IL interaction in the presence of the added polar solvent. For aqueous binary mixtures of IL, the predicted results are in semiquantitative agreement with the available experimental results. However, the calculated dynamics suggest much weaker composition dependence than that observed in experiments. In addition, the theory predicts a turn around for dynamic Stokes shift in its composition dependence for ([Bmim][BF(4)] + acetonitrile) mixtures at higher dilutions of the IL. Interestingly, effective dipolar medium calculations for Stokes shift dynamics in ([Bmim][BF(4)] + dichloromethane) binary mixtures predict a very weak or even nonexistent nonlinear composition dependence. These predictions should be reexamined in experiments.

  2. TMVOC-MP: a parallel numerical simulator for Three-PhaseNon-isothermal Flows of Multicomponent Hydrocarbon Mixtures inporous/fractured media

    SciTech Connect

    Zhang, Keni; Yamamoto, Hajime; Pruess, Karsten

    2008-02-15

    TMVOC-MP is a massively parallel version of the TMVOC code (Pruess and Battistelli, 2002), a numerical simulator for three-phase non-isothermal flow of water, gas, and a multicomponent mixture of volatile organic chemicals (VOCs) in multidimensional heterogeneous porous/fractured media. TMVOC-MP was developed by introducing massively parallel computing techniques into TMVOC. It retains the physical process model of TMVOC, designed for applications to contamination problems that involve hydrocarbon fuels or organic solvents in saturated and unsaturated zones. TMVOC-MP can model contaminant behavior under 'natural' environmental conditions, as well as for engineered systems, such as soil vapor extraction, groundwater pumping, or steam-assisted source remediation. With its sophisticated parallel computing techniques, TMVOC-MP can handle much larger problems than TMVOC, and can be much more computationally efficient. TMVOC-MP models multiphase fluid systems containing variable proportions of water, non-condensible gases (NCGs), and water-soluble volatile organic chemicals (VOCs). The user can specify the number and nature of NCGs and VOCs. There are no intrinsic limitations to the number of NCGs or VOCs, although the arrays for fluid components are currently dimensioned as 20, accommodating water plus 19 components that may be either NCGs or VOCs. Among them, NCG arrays are dimensioned as 10. The user may select NCGs from a data bank provided in the software. The currently available choices include O{sub 2}, N{sub 2}, CO{sub 2}, CH{sub 4}, ethane, ethylene, acetylene, and air (a pseudo-component treated with properties averaged from N{sub 2} and O{sub 2}). Thermophysical property data of VOCs can be selected from a chemical data bank, included with TMVOC-MP, that provides parameters for 26 commonly encountered chemicals. Users also can input their own data for other fluids. The fluid components may partition (volatilize and/or dissolve) among gas, aqueous, and NAPL

  3. CHROMATOGRAPHIC ALTERATION OF A NONIONIC SURFACTANT MIXTURE DURING TRANSPORT IN DENSE NONAQUEOUS PHASE LIQUID CONTAMINATED SEDIMENT (R826650)

    EPA Science Inventory

    Chromatographic alteration of a nonionic surfactant mixture during transport through DNAPL-contaminated aquifer sediment may occur due to differential loss of oligomers to sediment and to dense nonaqueous phase liquid (DNAPL). These losses may significantly alter the solubilizing...

  4. Another glimpse over the salting-out assisted liquid-liquid extraction in acetonitrile/water mixtures.

    PubMed

    Valente, Inês Maria; Gonçalves, Luís Moreira; Rodrigues, José António

    2013-09-20

    The use of the salting-out effect in analytical chemistry is very diverse and can be applied to increase the volatility of the analytes in headspace extractions, to cause the precipitation of proteins in biological samples or to improve the recoveries in liquid-liquid extractions. In the latter, the salting-out process can be used to create a phase separation between water-miscible organic solvents and water. Salting-out assisted liquid-liquid extraction (SALLE) is an advantageous sample preparation technique aiming HPLC-UV analysis when developing analytical methodologies. In fact, some new extraction methodologies like QuEChERS include the SALLE concept. This manuscript discusses another point of view over SALLE with particular emphasis over acetonitrile-water mixtures for HPLC-UV analysis; the influence of the salting-out agents, their concentration and the water-acetonitrile volume ratios were the studied parameters. α-dicarbonyl compounds and beer were used as test analytes and test samples, respectively. The influence of the studied parameters was characterized by the obtained phase separation volume ratio and the fraction of α-dicarbonyls extracted to the acetonitrile phase. Results allowed the distribution of salts within three groups according to the phase separation and their extractability: (1) chlorides and acetates, (2) carbonates and sulfates and (3) magnesium sulfate; of all tested salts, sodium chloride had the highest influence on the α-dicarbonyls fraction extracted.

  5. Viscosity of liquid mixtures: The Vesovic-Wakeham method for chain molecules

    NASA Astrophysics Data System (ADS)

    de Wijn, Astrid S.; Riesco, Nicolas; Jackson, George; Martin Trusler, J. P.; Vesovic, Velisa

    2012-02-01

    New expressions for the viscosity of liquid mixtures, consisting of chain-like molecules, are derived by means of Enskog-type analysis. The molecules of the fluid are modelled as chains of equally sized, tangentially joined, and rigid spheres. It is assumed that the collision dynamics in such a fluid can be approximated by instantaneous collisions. We determine the molecular size parameters from the viscosity of each pure species and show how the different effective parameters can be evaluated by extending the Vesovic-Wakeham (VW) method. We propose and implement a number of thermodynamically consistent mixing rules, taking advantage of SAFT-type analysis, in order to develop the VW method for chain molecules. The predictions of the VW-chain model have been compared in the first instance with experimental viscosity data for octane-dodecane and methane-decane mixtures, thus, illustrating that the resulting VW-chain model is capable of accurately representing the viscosity of real liquid mixtures.

  6. Phase behavior of chromonic liquid crystal mixtures of Sunset Yellow and Disodium Cromoglycate

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Akihiro; Smith, Gregory; Yi, Youngwoo; Xu, Charles; Biffi, Silvia; Serra, Francesca; Bellini, Tommaso; Clark, Noel

    2014-03-01

    Chromonic liquid crystals (CLCs) are formed when planar molecules dissolved in water stack into rod-like aggregates that can order as liquid crystals. Isotropic, nematic, and M-phases can be observed depending on the degree of molecular orientational and positional order by variation of the CLC concentration. We focused on mixtures of two well-known CLCs, Sunset Yellow, a food dye, and disodium cromoglycate (DSCG), an asthma medication. In order to study the phase behaviors of these mixtures, we observed their textures in glass cells and capillaries using polarized light microscopy. We report here a ternary phase diagram describing the complete phase behavior of the CLC mixtures. We observed a variety of phase behaviors depending on species ratio and concentration. In the isotropic phase, no clear phase separation of the two dyes was observed, while separation did occur in many nematic and M-phase combinations. We will also describe phase observations made using a light spectroscopy and bulk centrifugal partitioning. Grant support: NSF DMR 1207606 and NSF MRSEC DMR-0820579.

  7. Ultrasonic and IR study of intermolecular association through hydrogen bonding in ternary liquid mixtures.

    PubMed

    Awasthi, Aashees; Shukla, J P

    2003-08-01

    Complex formation in ternary liquid mixtures of dimethylsulfoxide (DMSO) with phenol and o-cresol in carbontetrachloride has been studied by measuring ultrasonic velocity at 2 MHz, in the concentration range of 0.019-0.162 (in mole fraction of DMSO) at varying temperatures of 20, 30 and 40 degrees C. Using measured values of ultrasonic velocity, other parameters such as adiabatic compressibility, intermolecular free length, molar sound velocity, molar compressibility, specific acoustic impedance and molar volume have been evaluated. These parameters have been utilized to study the solute-solute interactions in these systems. The ultrasonic velocity shows a maxima and adiabatic compressibility a corresponding minima as a function of concentration for these mixtures. The results indicate the occurrence of complex formation between unlike molecules through intermolecular hydrogen bonding between oxygen atom of DMSO molecule and hydrogen atom of phenol and o-cresol molecules. The excess values of adiabatic compressibility and intermolecular free length have also been evaluated. The variation of both these parameters with concentration also indicates the possibility of the complex formation in these systems. Further, to investigate the presence of O-HO bond complexes and the strength of molecular association with concentrations, the infrared spectra of both the systems, DMSO-phenol and DMSO-o-cresol, have been recorded for various concentrations at room temperature (20 degrees C). The results obtained using infrared spectroscopy for both the systems also support the occurrence of complex formation through intermolecular hydrogen bonding in these ternary liquid mixtures.

  8. Structural properties of geminal dicationic ionic liquid/water mixtures: a theoretical and experimental insight.

    PubMed

    Serva, Alessandra; Migliorati, Valentina; Lapi, Andrea; Aquilanti, Giuliana; Arcovito, Alessandro; D'Angelo, Paola

    2016-06-28

    The structural behavior of geminal dicationic ionic liquid 1,n-bis[3-methylimidazolium-1-yl] alkane bromide ([Cn(mim)2]Br2)/water mixtures has been studied using extended X-ray absorption fine structure (EXAFS) spectroscopy in combination with molecular dynamics (MD) simulations. The properties of the mixtures are investigated as a function of both water concentration and alkyl-bridge chain length. The very good agreement between the EXAFS experimental data and the theoretical curves calculated from the MD structural results has proven the validity of the theoretical framework used for all of the investigated systems. In all the solutions the water molecules are preferentially coordinated with the Br(-) ion, even if a complex network of interactions among dications, anions and water molecules takes place. The local molecular arrangement around the bromide ion is found to change with increasing water content, as more and more water molecules are accomodated in the Br(-) first coordination shell. Moreover, with the decrease of the alkyl-bridge chain length, the interactions between dications and anions increase, with Br(-) forming a bridge between the two imidazolium rings of the same dication. On the other hand, in [Cn(mim)2]Br2/water mixtures with long alkyl-bridge chains peculiar internal arrangements of the dications are found, leading to different structural features of geminal dicationic ionic liquids as compared to their monocationic counterparts.

  9. Ultrafast molecular dynamics of liquid aromatic molecules and the mixtures with CCl4

    NASA Astrophysics Data System (ADS)

    Shirota, Hideaki

    2005-01-01

    The ultrafast molecular dynamics of liquid aromatic molecules, benzene, toluene, ethylbenzene, cumene, and 1,3-diphenylpropane, and the mixtures with CCl4 have been investigated by means of femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The picosecond Kerr transients of benzene, toluene, ethylbenzene, and cumene and the mixtures with CCl4 show a biexponential feature. 1,3-Diphenylpropane and the mixtures with CCl4 show triexponential picosecond Kerr transients. The slow relaxation time constants of the aromatic molecules and the mixtures with CCl4 are qualitatively described by the Stoke-Einstein-Debye hydrodynamic model. The ultrafast dynamics have been discussed based on the Kerr spectra in the frequency range of 0-800 cm-1 obtained by the Fourier transform analysis of the Kerr transients. The line shapes of the low-frequency intermolecular spectra located at 0-180 cm-1 frequency range have been analyzed by two Brownian oscillators (˜11 cm-1 and ˜45 cm-1 peaks) and an antisymmetric Gaussian function (˜65 cm-1 peak). The spectrum shape of 1,3-diphenylpropane is quite different from the spectrum shapes of the other aromatic molecules for the low magnitude of the low-frequency mode of 1,3-diphenylpropane and/or an intramolecular vibration. Although the concentration dependences of the low- and intermediate-frequency intermolecular modes (Brownian oscillators) do not show a significant trend, the width of high-frequency intermolecular mode (antisymmetric Gaussian) becomes narrower with the higher CCl4 concentration for all the aromatics mixtures with CCl4. The result indicates that the inhomogeneity of the intermolecular vibrational mode in aromatics/CCl4 mixtures is decreasing with the lower concentration of aromatics. The intramolecular vibrational modes of the aromatic molecules observed in the Kerr spectra are also shown with the calculation results based on the density functional theory.

  10. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes

    NASA Astrophysics Data System (ADS)

    Reis, Martina Costa; Wang, Yongqi

    2016-12-01

    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  11. Coarse-Grained Molecular Monte Carlo Simulations of Liquid Crystal-Nanoparticle Mixtures

    NASA Astrophysics Data System (ADS)

    Neufeld, Ryan; Kimaev, Grigoriy; Fu, Fred; Abukhdeir, Nasser M.

    Coarse-grained intermolecular potentials have proven capable of capturing essential details of interactions between complex molecules, while substantially reducing the number of degrees of freedom of the system under study. In the domain of liquid crystals, the Gay-Berne (GB) potential has been successfully used to model the behavior of rod-like and disk-like mesogens. However, only ellipsoid-like interaction potentials can be described with GB, making it a poor fit for many real-world mesogens. In this work, the results of Monte Carlo simulations of liquid crystal domains using the Zewdie-Corner (ZC) potential are presented. The ZC potential is constructed from an orthogonal series of basis functions, allowing for potentials of essentially arbitrary shapes to be modeled. We also present simulations of mixtures of liquid crystalline mesogens with nanoparticles. Experimentally these mixtures have been observed to exhibit microphase separation and formation of long-range networks under some conditions. This highlights the need for a coarse-grained approach which can capture salient details on the molecular scale while simulating sufficiently large domains to observe these phenomena. We compare the phase behavior of our simulations with that of a recently presented continuum theory. This work was made possible by the Natural Sciences and Engineering Research Council of Canada and Compute Ontario.

  12. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes

    NASA Astrophysics Data System (ADS)

    Reis, Martina Costa; Wang, Yongqi

    2017-03-01

    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  13. Bubble curves and saturated liquid molar volumes for chlorofluorohydrocarbon-hydrocarbon mixtures: Experimental data and modeling

    SciTech Connect

    Laugier, S. ); Richon, D.; Renon, H. . Lab. de Thermodynamique)

    1994-01-01

    Vapor-liquid equilibria and liquid densities were obtained using a static apparatus fitted with a variable-volume cell which was described in detail by Valtz et al. (1). Results are given at four temperatures for the binary systems butane--1,2,2-trichlorotrifluoroethane, pentane--1,2-dichloro-1,1,2,2-tetrafluoroethane, hexane--1,2-dichloro-1,1,2,2-tetrafluoroethane, heptane--1,12-trichloro-1,2,2-trifluoromethane, heptane--1,2-dichloro-1,1,2,2-tetrafluoroethane, and benzene--1,2-dichloro-1,1,2,2-tetrafluoroethane and the ternary system 1,2-dichloro-1,1,2,2-tetrafluoroethane--1,1,2-trichloro-1,2,2-trifluoromethane--heptane. The best simultaneous representation of pressures and saturated liquid molar volumes at a given temperature and liquid composition for these mixtures is obtained using either the Patel-Teja or Trebble-Bishnoi-Salim equation of state (TBS EOS) in either their standard or generalized form (maximum deviation 0.7% in pressure and 3.1% in saturated liquid molar volume with the TBS EOS).

  14. Two-step switching in dual-frequency nematic liquid crystal mixtures

    NASA Astrophysics Data System (ADS)

    Mrukiewicz, M.; Perkowski, P.; Piecek, W.; Mazur, R.; Chojnowska, O.; Garbat, K.

    2015-11-01

    The so-called dual-frequency nematic mixtures are very promising components for applications in fast operating devices. Compared with classical nematics, they exhibit positive or negative anisotropy of the electric permittivity depending on the applied frequencies of an external electric field. Owing to this property, an overall switching process from planar to homeotropic orientations, and vice versa, can be shortened by using the electric field with two different frequencies. Electro-optical switching characteristics of transmission versus time as a function of applied voltage were obtained for two different dual-frequency mixtures in twisted nematic cells. For one of the investigated mixtures, unusual decrease in the light transmission at switching from the homeotropic to planar orientation at threshold voltage was observed. The switching process apparently occurs in two steps. The mechanism of the two-step switching at twisted dual-frequency nematic structures was discussed. The explanation of the switching mechanism takes into account the influence of the electric field with different frequencies on molecules with transverse and longitudinal dipole moments. Moreover, molecular structure of compounds constituting the mixtures was analyzed. Additionally, response times of the switching driven with low and high frequency pulses were shown. This work helps to understand the molecular interaction and electro-optical switching in the dual-frequency nematic liquid crystals.

  15. Dynamical properties of alcohol + 1-hexyl-3-methylimidazolium ionic liquid mixtures: a computer simulation study.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; García, Manuel; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M

    2011-12-29

    In this work, extensive molecular dynamics simulations of the dynamics of mixtures of ionic liquids (ILs) composed of the cation 1-hexyl-3-methylimidazolium and several anions of different hydrophobicity degrees (Cl(-), BF(4)(-), PF(6)(-)) with alcohols of different chain lengths (methanol and ethanol) are reported. We evaluated the influence of the nature of the anion, the length of the molecular chain of the alcohol, and the alcohol concentration on some dynamical properties of the mixtures, such as self-diffusion coefficients of all the species, mean square displacements (with an analysis of both ballistic and diffusive regimes), and velocity autocorrelation functions of alcohol molecules. The diffusivity of the mixtures was found to be highly dependent on the nature of the anion since the interaction between chloride and alcohols is greater than that with fluorinated anions and leads to slower dynamics. Additionally, our results show that self-diffusion coefficients increase with alcohol concentration. On the other hand, a subdiffusive regime over thousands of picoseconds was detected at intermediate times through analysis of the center-of-mass mean square displacements of alcohol molecules, a region that becomes narrower as alcohol concentration increases. Finally, the study of the role of the anion and of solvent concentration on velocity autocorrelation functions reflects an increase in mean collision times as the amount of alcohol increases until the value of pure alcohols is reached. These collision times are smaller in mixtures with halogenated ILs.

  16. Optical studies of a binary liquid crystal mixture exhibiting induced smectic A phase

    NASA Astrophysics Data System (ADS)

    Thingujam, Kiranmala; Bhattacharjee, Ayon; Choudhury, Basana; Sarkar, S. D.

    2016-08-01

    A binary liquid crystalline mixture of a monotropic polar compound 4-cyanophenyl 4'- n-pentyl benzoate (CPPB) and an enantiotropic non-polar compound 4- n-hexyl phenyl 4- n'-pentyloxy benzoate (ME5O.6) shows the presence of an induced smectic A phase in the region 0.1 ≤ x CPPB ≤ 0.82, where x CPPB is the mole fraction of CPPB. The results of texture study, density study and refractive index measurements of the eutectic mixture along with those of the pure samples are reported in this paper. The density values of the eutectic mixture are found to be much higher than that of the pure samples. The determination of order parameters of the pure samples and eutectic mixture has been carried out. In order to determine the order parameters of the samples, we have used different methods, Vuks', Neugebauer's, modified Vuks' and direct extrapolation method. The results of order parameters obtained from the different approaches are compared and analysed in detail.

  17. Serpentine diffusion trajectories and the Ouzo effect in partially miscible ternary liquid mixtures.

    PubMed

    Krishna, Rajamani

    2015-11-07

    This work investigates the transient equilibration process when partially miscible ternary liquid mixtures of two different compositions are brought into contact with each other. Diffusional coupling effects are shown to become increasingly significant as the mixture compositions approach the meta-stable regions of the phase equilibrium diagrams. The proper modelling of coupled diffusion phenomena requires the use of a Fick diffusivity matrix [D], with inclusion of non-zero off-diagonal elements. The primary objective of this article is to develop a simple, robust, procedure for the estimation of the matrix [D], using the Maxwell-Stefan (M-S) formulation as a convenient starting point. In the developed simplified approach, the Fick diffusivity matrix [D] is expressed as the product of a scalar diffusivity and the matrix of thermodynamic correction factors [Γ]. By detailed examination of experimental data for the matrix [D] in a wide variety of ternary mixtures, it is deduced that the major contribution of diffusional coupling arises from the contributions of non-ideal solution thermodynamics, quantified by the matrix of thermodynamic correction factors [Γ]. An important consequence of strong thermodynamic coupling is that equilibration trajectories are serpentine in shape and may exhibit incursions into meta-stable zones opening up the possibility of spontaneous emulsification and the Ouzo effect. If diffusional coupling effects are ignored, the equilibration trajectory is linear in composition space. For a wide variety of partially miscible ternary mixtures, it is demonstrated that the corresponding linear equilibration trajectories do not anticipate the possibility of emulsification.

  18. Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

    PubMed Central

    2015-01-01

    Kirkwood-Buff or Fluctuation Solution Theory can be used to provide experimental pair fluctuations, and/or integrals over the pair distribution functions, from experimental thermodynamic data on liquid mixtures. Here, this type of approach is used to provide triplet and quadruplet fluctuations, and the corresponding integrals over the triplet and quadruplet distribution functions, in a purely thermodynamic manner that avoids the use of structure factors. The approach is then applied to binary mixtures of water + methanol and benzene + methanol over the full composition range under ambient conditions. The observed correlations between the different species vary significantly with composition. The magnitude of the fluctuations and integrals appears to increase as the number of the most polar molecule involved in the fluctuation or integral also increases. A simple physical picture of the fluctuations is provided to help rationalize some of these variations. PMID:25747091

  19. Direct Conversion of Mono- and Polysaccharides into 5-Hydroxymethylfurfural Using Ionic-Liquid Mixtures.

    PubMed

    Siankevich, Sviatlana; Fei, Zhaofu; Scopelliti, Rosario; Jessop, Philip G; Zhang, Jiaguang; Yan, Ning; Dyson, Paul J

    2016-08-23

    Platform chemicals are usually derived from petrochemical feedstocks. A sustainable alternative commences with lignocellulosic biomass, a renewable feedstock, but one that is highly challenging to process. Ionic liquids (ILs) are able to solubilize biomass and, in the presence of catalysts, convert the biomass into useful platform chemicals. Herein, we demonstrate that mixtures of ILs are powerful systems for the selective catalytic transformation of cellulose into 5-hydroxymethylfurfural (HMF). Combining ILs with continuous HMF extraction into methyl-isobutyl ketone or 1,2-dimethoxyethane, which form a biphase with the IL mixture, allows the online separation of HMF in high yield. This one-step process is operated under relatively mild conditions and represents a significant step forward towards sustainable HMF production.

  20. Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

    SciTech Connect

    Ploetz, Elizabeth A.; Smith, Paul E.

    2015-03-07

    Kirkwood-Buff or Fluctuation Solution Theory can be used to provide experimental pair fluctuations, and/or integrals over the pair distribution functions, from experimental thermodynamic data on liquid mixtures. Here, this type of approach is used to provide triplet and quadruplet fluctuations, and the corresponding integrals over the triplet and quadruplet distribution functions, in a purely thermodynamic manner that avoids the use of structure factors. The approach is then applied to binary mixtures of water + methanol and benzene + methanol over the full composition range under ambient conditions. The observed correlations between the different species vary significantly with composition. The magnitude of the fluctuations and integrals appears to increase as the number of the most polar molecule involved in the fluctuation or integral also increases. A simple physical picture of the fluctuations is provided to help rationalize some of these variations.

  1. Surface segregation in binary mixtures of imidazolium-based ionic liquids

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2010-09-01

    Surface composition of binary mixtures of room-temperature ionic liquids has been investigated using time-of-flight secondary ion mass spectrometry at room temperature over a wide composition range. The imidazolium cations with longer aliphatic groups tend to segregate to the surface, and a bis(trifluoromethanesulfonyl)imide anion (Tf 2N -) is enriched at the surface relative to hexafluorophosphate (PF 6-). The surface of an equimolar mixture of Li[Tf 2N] and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6]) has a nominal composition of [bmim][Tf 2N] because of surface segregation and ligand exchange. The surface segregation of cations and anions is likely to result from alignment of specific ligand-exchanged molecules at the topmost surface layer to exclude more hydrophobic part of the molecules.

  2. Formation of smectic phases in binary liquid crystal mixtures with a huge length ratio

    PubMed Central

    Knecht, Friederike; Hartley, C Scott; Roberts, Jeffrey C; Lemieux, Robert P; Giesselmann, Frank

    2012-01-01

    Summary A system of two liquid-crystalline phenylpyrimidines differing strongly in molecular length was studied. The phase diagram of these two chemically similar mesogens, with a length ratio of 2, was investigated, and detailed X-ray diffraction and electrooptical measurements were performed. The phase diagram revealed a destabilization of the nematic phase, which is present in the pure short compound, while the smectic state was stabilized. The short compound forms smectic A and smectic C phases, whereas the longer compound forms a broad smectic C phase and a narrow higher-ordered smectic phase. Nevertheless, in the mixtures, the smectic C phase is destabilized and disappears rapidly, whereas smectic A is the only stable phase observed over a broad concentration range. In addition, the smectic translational order parameters as well as the tilt angles of the mixtures are reduced. The higher-ordered smectic phase of the longer mesogen was identified as a smectic F phase. PMID:23019439

  3. Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture

    DOEpatents

    Rao, V. Udaya S.; Gormley, Robert J.

    1987-01-01

    Synthesis gas containing CO and H.sub.2 is converted to a high-octane hydrocarbon liquid in the gasoline boiling point range by bringing the gas into contact with a heterogeneous catalyst including, in physical mixture, a zeolite molecular sieve, cobalt at 6-20% by weight, and thoria at 0.5-3.9% by weight. The contacting occurs at a temperature of 250.degree.-300.degree. C., and a pressure of 10-30 atmospheres. The conditions can be selected to form a major portion of the hydrocarbon product in the gasoline boiling range with a research octane of more than 80 and less than 10% by weight aromatics.

  4. Thermophysical Properties of Energetic Ionic Liquids/Nitric Acid Mixtures: Insights from Molecular Dynamics Simulations

    DTIC Science & Technology

    2013-01-01

    W L. Physical properties of concentrated nitric acid . UNT Digital Library. http://digital.library.unt.edu/ark:/67531/metadc56640/.) 23 M. Engelmann... Nitric Acid Mixtures: Insights from Molecular Dynamics Simulations 5a. CONTRACT NUMBER FA9300-11-C-3012 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER...Rev. 8-98) Prescribed by ANSI Std. 239.18 1     Thermophysical  Properties  of  Energetic  Ionic  Liquids/ Nitric   Acid

  5. Theoretical Rocket Performance of Liquid Methane with Several Fluorine-Oxygen Mixtures Assuming Frozen Composition

    NASA Technical Reports Server (NTRS)

    Gordon, Sanford; Kastner, Michael E

    1958-01-01

    Theoretical rocket performance for frozen composition during expansion was calculated for liquid methane with several fluorine-oxygen mixtures for a range of pressure ratios and oxidant-fuel ratios. The parameters included are specific impulse, combustion-chamber temperature, nozzle-exit temperature molecular weight, characteristic velocity, coefficient of thrust, ratio of nozzle-exit area to throat area, specific heat at constant pressure, isentropic exponent, viscosity, and thermal conductivity. The maximum calculated value of specific impulse for a chamber pressure of 600 pounds per square inch absolute (40.827atm) and an exit pressure of 1 atmosphere is 315.3 for 79.67 percent fluorine in the oxidant.

  6. Vapor-Liquid Equilibrium of the Mixture H2O + H2O2 (LB3902, EVLM 1112)

    NASA Astrophysics Data System (ADS)

    Wichterle, I.; Linek, J.; Wagner, Z.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A2 `Binary Liquid Systems of Nonelectrolytes, Part 2' of Volume 13 `Vapor-Liquid Equilibrium in Mixtures and Solutions' of Landolt-Börnstein Group IV `Physical Chemistry'. It corresponds to the entry LB3902 of the Print Version and the ELBT Database, respectively.

  7. Impact of Liquid-Vapor to Liquid-Liquid-Vapor Phase Transitions on Asphaltene-Rich Nanoaggregate Behavior in Athabasca Vacuum Residue + Pentane Mixtures

    SciTech Connect

    Long, Bingwen; Chodakowski, Martin; Shaw, John M.

    2013-06-05

    The bulk phase behavior of heavy oil + alkane mixtures and the behavior of the asphaltenes that they contain are topics of importance for the design and optimization of processes for petroleum production, transport, and refining and for performing routine saturates, aromatics, resins, and asphaltenes (SARA) analyses. In prior studies, partial phase diagrams and phase behavior models for Athabasca vacuum residue (AVR) comprising 32 wt % pentane asphaltenes + n-alkanes were reported. For mixtures with pentane, observed phase behaviors included single-phase liquid as well as liquid–liquid, liquid–liquid–vapor, and liquid–liquid–liquid–vapor regions. Dispersed solids were detected under some conditions as well but not quantified. In this work, small-angle X-ray scattering (SAXS) is used to study nanostructured materials in liquid phases present in AVR + n-pentane mixtures from 50 to 170 °C at mixture bubble pressure. The investigation focuses on the impact of the transition from a single AVR-rich liquid to co-existing pentane-rich and AVR-rich liquids on the nanostructure and the nanostructures most resistant to aggregation as the pentane composition axis is approached. Background scattering subtraction was performed using global mixture composition. The robustness of this assumption with respect to values obtained for coefficients appearing in a two level Beaucage unified equation fit is demonstrated. The nanostructured material is shown to arise at two length scales from 1 to 100 wt % AVR. Smaller nanostructures possess mean radii less than 50 Å, while the larger nanostructures possess mean radii greater than 250 Å. The addition of pentane to the AVR causes an increasingly large fraction of the large and small nanostructures to grow in size. Only nanostructures resistant to aggregation remain in the pentane-rich phase as the 0 wt % AVR axis is approached. Step changes in aggregation identified from changes in average radius of gyration, scattering

  8. Excess enthalpy of monoethanolamine + ionic liquid mixtures: how good are COSMO-RS predictions?

    PubMed

    Gonzalez-Miquel, Maria; Massel, Marjorie; DeSilva, Aruni; Palomar, Jose; Rodriguez, Francisco; Brennecke, Joan F

    2014-10-02

    Mixtures of ionic liquids (ILs) and molecular amines have been suggested for CO2 capture applications. The basic idea is to replace water, which volatilizes in the amine regeneration step and increases the parasitic energy load, with a nonvolatile ionic liquid solvent. To fully understand the thermodynamics of these systems, here experimental excess enthalpies for binary mixtures of monoethanolamine (MEA) and two ILs: 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [hmim][NTf2], and 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [OHemim][NTf2], were obtained by calorimetry, using a Setaram C80 calorimeter, over the whole range of compositions at 313.15 K. Since it is the temperature derivative of the Gibbs energy, enthalpy is a sensitive measure of intermolecular interactions. MEA + [hmim][NTf2] is endothermic and MEA + [OHemim][NTf2] is exothermic. The reliability of COSMO-RS to predict the excess enthalpy of the (MEA+IL) systems was tested based on the implementation of two different molecular models to define the structure of the IL: the IL as separate cation and anion [C+A] and the IL as a bonded single specie [CA]. Quantum-chemical calculations were performed to gain additional insight into the intermolecular interactions between the components of the mixture. For MEA + [hmim][NTf2] both the [C+A] and [CA] models predict endothermic behavior, but the [CA] model is in better agreement with the experimental results. For MEA + [OHemim][NTf2] the [C+A] model provides the best match to the experimental exothermic results. However, what is really surprising is that two different conformations of the cation-anion pair with nearly identical energies in the [CA] model result in completely different (exothermic vs endothermic) predictions of the excess enthalpy. Nonetheless, the results do show that the influence of the structure of the IL on the thermodynamic behavior of the mixture (endothermic vs exothermic) can be attributed

  9. Effect of electric field on reentrance transition in a binary mixture of liquid crystals

    NASA Astrophysics Data System (ADS)

    Kumari, Sunita; Singh, S.

    2015-12-01

    Employing a phenomenological mean field theory, we analyze the effect of an electric field on the N - SmA phase transition for pure liquid crystal and on the reentrant nematic phase in a binary mixture of liquid crystals exhibiting the phase sequence I - N - SmA - NR on cooling. The basic idea of the work is to explain the phase transition behavior of the system by assuming that certain Landau coefficients associated with the order parameters coupling terms of the free-energy density expansion are field dependent. These parameters play a crucial role and show a rapid variation at the SmA - NR transition as compared to the SmA - N transition.

  10. Solid-liquid equilibria for binary mixtures composed of acenaphthene, dibenzofuran, fluorene, phenanthrene, and diphenylmethane

    SciTech Connect

    Lee, M.J.; Chen, C.H.; Lin, H.

    1999-09-01

    The liquidus lines were determined with a solid-disappearance method for binary mixtures composed of acenaphthene, dibenzofuran, fluorene, phenanthrene, and diphenylmethane. While the first four substances are model compounds of wash oil, which has widely been used as a solvent to remove aromatics from coal oven gas, diphenylmethane is a high-boiling and low-melting compound that is a potential additive to modify the performance of wash oil. Each of the seven binaries appears to be a simple eutectic system, as evidenced by the experimental results. The Wilson and the NRTL models were employed to correlate the solid-liquid equilibrium data. Both activity coefficient models were found to represent accurately the nonideality of the liquid-phase for the investigated systems.

  11. Comparative study of acoustic relaxation time of cholesteric liquid crystal and mixtures

    NASA Astrophysics Data System (ADS)

    Bhave, Manisha G.; Gharde, Rita; Radha, S.

    2016-09-01

    The present study focuses on the relaxation processes in Cholesteric Liquid Crystal and mixtures. We have dispersed two different monomers in CLC to form Polymer dispersed liquid crystals (PDCLCs). PDLC films have a remarkable electro-optical behavior since they can be switched from highly light scattering state (OFF) to transparent state (ON) simply by application of an electric field. We have also doped ferroelectric nano - powder (NP) in CLC. The phase transitions occurred at temperatures lower than those exhibited by the mesogenic component before doping. The viscosity, ultrasonic velocity and density show variation with change in the material as well as temperature. The acoustic relaxation time and ultrasonic attenuation decrease with increase in temperature for CLC and CLC+NP. The parameters of PDCLC2 in comparison with PDCLC1 are more linear in isotropic and anisotropic regions. For PDCLC2 the values reach maximum value at the Cholesteric-isotropic transition.

  12. Combinatorial approach for the rapid determination of thermochromic behavior of binary and ternary cholesteric liquid crystalline mixtures.

    PubMed

    van der Werff, Louise C; Robinson, Andrea J; Kyratzis, Ilias L

    2012-11-12

    A combinatorial approach was developed for the rapid determination of thermochromic behavior of a large number of binary and ternary sterol based thermochromic liquid crystalline formulations. A binary mixture containing cholesteryl oleyl carbonate and cholesteryl nonanoate, and ternary mixtures also containing a third component, either cholesteryl oleate, cholesteryl benzoate, cholesteryl 2,4-dichlorobenzoate or cholesteryl propionate, were formulated via solvent deposition into a black Teflon coated aluminum 96 well plate. The temperature of the well plate was then varied, and the color appearance of the deposited mixture in each well was recorded. This approach allowed expedient examination of the thermochromic behavior for a large range of liquid crystal formulations. The accuracy of the rapid combinatorial technique was validated on selected thermochromic liquid crystal mixture compositions by comparing well thermochromic output with that observed using UV-vis spectroscopy on material produced in gram quantities.

  13. Coarsening in Solid-Liquid Mixtures Studied on the Space Shuttle

    NASA Technical Reports Server (NTRS)

    Caruso, John J.

    1999-01-01

    Ostwald ripening, or coarsening, is a process in which large particles in a two-phase mixture grow at the expense of small particles. It is a ubiquitous natural phenomena occurring in the late stages of virtually all phase separation processes. In addition, a large number of commercially important alloys undergo coarsening because they are composed of particles embedded in a matrix. Many of them, such as high-temperature superalloys used for turbine blade materials and low-temperature aluminum alloys, coarsen in the solid state. In addition, many alloys, such as the tungsten-heavy metal systems, coarsen in the solid-liquid state during liquid phase sintering. Numerous theories have been proposed that predict the rate at which the coarsening process occurs and the shape of the particle size distribution. Unfortunately, these theories have never been tested using a system that satisfies all the assumptions of the theory. In an effort to test these theories, NASA studied the coarsening process in a solid-liquid mixture composed of solid tin particles in a liquid lead-tin matrix. On Earth, the solid tin particles float to the surface of the sample, like ice in water. In contrast, in a microgravity environment this does not occur. The microstructures in the ground- and space-processed samples (see the photos) show clearly the effects of gravity on the coarsening process. The STS-83-processed sample (right image) shows nearly spherical uniformly dispersed solid tin particles. In contrast, the identically processed, ground-based sample (left image) shows significant density-driven, nonspherical particles, and because of the higher effective solid volume fraction, a larger particle size after the same coarsening time. The "Coarsening in Solid-Liquid Mixtures" (CSLM) experiment was conducted in the Middeck Glovebox facility (MGBX) flown aboard the shuttle in the Microgravity Science Laboratory (MSL-1/1R) on STS-83/94. The primary objective of CSLM is to measure the temporal

  14. Preparation of ibuprofen-loaded liquid suppository using eutectic mixture system with menthol.

    PubMed

    Yong, Chul Soon; Oh, Yu-Kyoung; Jung, Se Hyun; Rhee, Jong-Dal; Kim, Ho-Dong; Kim, Chong-Kook; Choi, Han-Gon

    2004-12-01

    To prepare an ibuprofen-loaded liquid suppository using eutectic mixture with menthol, the effects of menthol and poloxamer 188 (P 188) on the aqueous solubility of ibuprofen were investigated. The physicochemical properties such as gelation temperature, gel strength and bioadhesive force of various formulations composed of ibuprofen, menthol and P 188 were investigated. Then, the pharmacokinetic study of ibuprofen delivered by the liquid suppositories composed of P 188 and menthol were then performed. In the absence of P 188, the solubility of ibuprofen increased until the ratio of menthol to ibuprofen increased from 0:10 to 4:6 followed by an abrupt decrease in solubility above the ratio of 4:6, indicating that four parts of ibuprofen formed eutectic mixture with six parts of menthol. In the presence of P 188, the solutions with the same ratio showed abrupt increase in the solubility of ibuprofen. Furthermore, the solution with ratio of 4:6 showed more than 2.5- and 6-fold increase in the solubility of ibuprofen compared with that without additives and that without menthol, respectively. The poloxamer gel with menthol/ibuprofen ratio of 1:9 and higher than 15% poloxamer 188 showed the maximum solubility of ibuprofen, 1.2mg/ml. Ibuprofen increased the gelation temperature and weakened the gel strength and bioadhesive force of liquid suppositories. However, menthol did the opposite due to forming the eutectic mixture with ibuprofen. The ibuprofen-loaded liquid suppository [P 188/menthol/ibuprofen (15/0.25/2.5%)] with the maximum ibuprofen solubility of 1.2mg/ml was administered easily to the anus and to remain at the administered site without leakage after the dose. Furthermore, it gave significantly higher initial plasma concentrations, Cmax and AUC of ibuprofen than did solid suppository, indicating that the drug from poloxamer gel could be more absorbed than that from solid one in rats. Thus, the liquid suppository system with P 188 and menthol, a more

  15. Surface freezing and molecular miscibility of binary alkane-alkane and fluoroalkane-alkane liquid mixtures.

    PubMed

    Takiue, Takanori; Shimasaki, Mayuko; Tsuura, Miyako; Sakamoto, Hiroyasu; Matsubara, Hiroki; Aratono, Makoto

    2014-02-13

    The surface freezing (SF) of liquid n-heptadecane (C17)-n-octadecane (C18) and 1-perfluorooctyl decane (F8H10)-C18 mixtures were studied by surface tension and external reflection absorption FTIR (ERA-FTIR) measurements. The surface tension versus temperature curves of all pure liquids show a sharp break point at Ts corresponding to a surface liquid (SL)-SF transition. The entropy of surface formation is very negative, indicating a well-ordered structure of the SF layer. The ERA-FTIR spectra in the SF state suggested that the C18 molecules are densely packed in the solid state, while the packing of the hydrocarbon (HC) part of F8H10 is a little looser than the fluorocarbon (FC) part because of the difference in the cross-sectional area. In the C17-C18 mixture, the SL-SF transition was found at all bulk compositions. The estimation of the surface composition suggested that two components are miscible both in SL and SF states. The excess entropy of the surface is almost zero in both states, and thus, it was concluded that the two components are mixed almost ideally at the surface. In the case of the F8H10-C18 system, on the other hand, the SL layer is enriched in F8H10 with lower surface tension than C18 compared to bulk liquid. The surface composition in the SF state is almost zero or unity, indicating that F8H10 and C18 molecules are practically immiscible mainly due to the weak interaction between different components. Furthermore, the negative excess entropy in the SL layer suggests domain formation of F8H10 molecules at the surface.

  16. Predicting the Virial coefficients and thermodynamic properties of a multicomponent mixture with application to the ternary mixture of CH{sub 2}F{sub 2} + CF{sub 3}CHF{sub 2} + CF{sub 3}CH{sub 2}F

    SciTech Connect

    Weber, L.A.

    1997-01-01

    A model for estimating second and third virial coefficients, which has been used successfully to represent the behavior of pure gases and binary mixtures, was applied to a ternary mixture. An estimate for the ternary third virial coefficient, C{sub 123}, was added to the model. Three experimentally determined binary interaction parameters were also used. The model has been applied to the ternary mixture CH{sub 2}F{sub 2} + CF{sub 3}CHF{sub 2} + CF{sub 3}CH{sub 2}F (R32 + R125 + R134a). The results are useful for calculating gas-phase densities, thermodynamic properties, and fugacities for phase equilibrium calculations. The use of such models leads to a considerable economy of effort in the case of multicomponent mixtures. Examples of the thermodynamic properties are given for the equimolar ternary mixture in the range from the dew-point temperature to 400 K at pressures of 0.5, 1, and 2 MPa. Calculated densities and speeds of sound are compared with new experimental values for a near-equimolar composition.

  17. Nanostructure of mixtures of protic ionic liquids and lithium salts: effect of alkyl chain length.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R; Cabeza, Óscar; Gallego, Luis J; Russina, Olga; Varela, Luis M

    2015-02-21

    The bulk structure of mixtures of two protic ionic liquids, propylammonium nitrate and butylammonium nitrate, with a salt with a common anion, is analyzed at room temperature by means of small angle X-ray scattering and classical molecular dynamics simulations. The study of several structural properties, such as density, radial distribution functions, spatial distribution functions, hydrogen bonds, coordination numbers and velocity autocorrelation functions, demonstrates that increasing the alkyl chain length of the alkylammonium cation results in more segregated, better defined polar and apolar domains, the latter having a larger size. This increase, ascribed to the erosion of the H-bond network in the ionic liquid polar regions as salt is added, is confirmed by means of small angle X-ray scattering measurements, which show a clear linear increase of the characteristic spatial sizes of the studied protic ionic liquids with salt concentration, similar to that previously reported for ethylammonium nitrate (J. Phys. Chem. B, 2014, 118, 761-770). In addition, larger ionic liquid cations lead to a lower degree of hydrogen bonding and to more sparsely packed three-dimensional structures, which are more easily perturbed by the addition of lithium salts.

  18. Pressure drop in fully developed, duct flow of dispersed liquid-vapor mixture at zero gravity

    NASA Technical Reports Server (NTRS)

    Sridhar, K. R.; Chao, B. T.; Soo, S. L.

    1990-01-01

    The dynamics of steady, fully developed dispersed liquid-vapor flow in a straight duct at 0-g is simulated by flowing water containing n-butyl benzoate droplets. Water and benzoate are immiscible and have identical density at room temperature. The theoretical basis of the simulation is given. Experiments showed that, for a fixed combined flow rate of water and benzoate, the frictional pressure drop is unaffected by large changes in the volume fraction of benzoate drops and their size distribution. Measured power spectra of the static wall pressure fluctuations induced by the turbulent water-benzoate flow also revealed that their dynamics is essentially unaltered by the presence of the droplets. These experimental findings, together with the theoretical analysis, led to the conclusion that the pressure drop in fully developed, dispersed liquid-vapor flow in straight ducts of constant cross section at 0-g is identical to that due to liquid flowing alone at the same total volumetric flow rate of the liquid-vapor mixture and, therefore, can be readily determined.

  19. Research and Design of Thermophysical Gas-Liquid Mixture Parameters in Product Pipelines

    NASA Astrophysics Data System (ADS)

    Dudin, S. M.; Zemenkov, Yu D.; Maier, A. V.; Shabarov, A. B.

    2016-10-01

    Operational problems are hard to overcome because of the temperature and pressure conditions of the hydrocarbon flow in the pipe, as well as the composition of the hydrocarbon system and the geometry of the pipeline. It is known that energy costs to pump a unit mass of RH in the form of gas 2-3 times exceed energy costs to pump a unit mass of RH in the form of liquid. As far as energy conservation during RH transportation is concerned, an important task is development and application of a method to calculate the gas-liquid hydrocarbons flow, and heat and mass transfer in process and trunk pipelines during their design and operation. The authors have developed a calculation method which is used to analyze the hydrodynamic state and composition of the hydrocarbon mixture in each ith section of the pipeline when temperature-pressure and hydraulic conditions change. The developed technique was tested on the hydrocarbon mixture of de-ethanized condensate and oil transported from northern oil and gas condensate fields via the main gas condensate line to the refinery.

  20. Estimates of Liquid Species Diffusivities in N-Propanol/Glycerol Mixture Droplets Burning in Reduced Gravity

    NASA Astrophysics Data System (ADS)

    Vang, C. L.; Shaw, B. D.

    2015-07-01

    Results from International Space Station experiments on combustion of n-propanol/glycerol droplets are reported. The initial n-propanol mass fraction was 0.95 and droplets had initial diameters in the 2 - 5 mm range. Some droplets were fiber supported while others were free floating, and the environment was either an oxygen/nitrogen mixture at 1 atm or an oxygen/helium mixture at pressures of 1 and 3 atm. The droplets burned in a multi-stage manner where n-propanol was preferentially evaporated during the early stages of combustion. The resulting buildup of glycerol in the liquid at the droplet surface led to sudden droplet heating and flame contraction. The experimental data are evaluated to provide burning rates, radiometer outputs, and droplet diameters as functions of time. These data are used to calculate effective liquid species diffusivities, D, using asymptotic theory. The D values can be substantially larger than molecular diffusivities in some cases, indicative of the presence of strong convective mixing. It was found that support fibers can decrease D values and that high burning rates can substantially increase D. These variations are attributed to changes in droplet internal flow patterns.

  1. A Sustainable Approach to the Stereoselective Synthesis of Diazaheptacyclic Cage Systems Based on a Multicomponent Strategy in an Ionic Liquid.

    PubMed

    Suresh Kumar, Raju; Almansour, Abdulrahman I; Arumugam, Natarajan; Altaf, Mohammad; Menéndez, José Carlos; Kumar, Raju Ranjith; Osman, Hasnah

    2016-01-29

    The microwave-assisted three-component reactions of 3,5-bis(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones, acenaphthenequinone and cyclic α-amino acids in an ionic liquid, 1-butyl-3-methylimidazolium bromide, occurred through a domino sequence affording structurally intriguing diazaheptacyclic cage-like compounds in excellent yields.

  2. Hydrogen bonding in a mixture of protic ionic liquids: a molecular dynamics simulation study.

    PubMed

    Paschek, Dietmar; Golub, Benjamin; Ludwig, Ralf

    2015-04-07

    We report results of molecular dynamics (MD) simulations characterising the hydrogen bonding in mixtures of two different protic ionic liquids sharing the same cation: triethylammonium-methylsulfonate (TEAMS) and triethylammonium-triflate (TEATF). The triethylammonium-cation acts as a hydrogen-bond donor, being able to donate a single hydrogen-bond. Both, the methylsulfonate- and the triflate-anions can act as hydrogen-bond acceptors, which can accept multiple hydrogen bonds via their respective SO3-groups. In addition, replacing a methyl-group in the methylsulfonate by a trifluoromethyl-group in the triflate significantly weakens the strength of a hydrogen bond from an adjacent triethylammonium cation to the oxygen-site in the SO3-group of the anion. Our MD simulations show that these subtle differences in hydrogen bond strength significantly affect the formation of differently-sized hydrogen-bonded aggregates in these mixtures as a function of the mixture-composition. Moreover, the reported hydrogen-bonded cluster sizes can be predicted and explained by a simple combinatorial lattice model, based on the approximate coordination number of the ions, and using statistical weights that mostly account for the fact that each anion can only accept three hydrogen bonds.

  3. Pressure in the Landau-Ginzburg functional: Pascal's law, nucleation in fluid mixtures, a meanfield theory of amphiphilic action, and interface wetting in glassy liquids.

    PubMed

    Chan, Ho Yin; Lubchenko, Vassiliy

    2015-09-28

    We set up the problem of finding the transition state for phase nucleation in multi-component fluid mixtures, within the Landau-Ginzburg density functional. We establish an expression for the coordinate-dependent local pressure that applies to mixtures, arbitrary geometries, and certain non-equilibrium configurations. The expression allows one to explicitly evaluate the pressure in spherical geometry, à la van der Waals. Pascal's law is recovered within the Landau-Ginzburg density functional theory, formally analogously to how conservation of energy is recovered in the Lagrangian formulation of mechanics. We establish proper boundary conditions for certain singular functional forms of the bulk free energy density that allow one to obtain droplet solutions with thick walls in essentially closed form. The hydrodynamic modes responsible for mixing near the interface are explicitly identified in the treatment; the composition at the interface is found to depend only weakly on the droplet size. Next we develop a Landau-Ginzburg treatment of the effects of amphiphiles on the surface tension; the amphiphilic action is seen as a violation of Pascal's law. We explicitly obtain the binding potential for the detergent at the interface and the dependence of the down-renormalization of the surface tension on the activity of the detergent. Finally, we argue that the renormalization of the activation barrier for escape from long-lived structures in glassy liquids can be viewed as an action of uniformly seeded, randomly oriented amphiphilic molecules on the interface separating two dissimilar aperiodic structures. This renormalization is also considered as a "wetting" of the interface. The resulting conclusions are consistent with the random first order transition theory.

  4. Pressure in the Landau-Ginzburg functional: Pascal's law, nucleation in fluid mixtures, a meanfield theory of amphiphilic action, and interface wetting in glassy liquids

    NASA Astrophysics Data System (ADS)

    Chan, Ho Yin; Lubchenko, Vassiliy

    2015-09-01

    We set up the problem of finding the transition state for phase nucleation in multi-component fluid mixtures, within the Landau-Ginzburg density functional. We establish an expression for the coordinate-dependent local pressure that applies to mixtures, arbitrary geometries, and certain non-equilibrium configurations. The expression allows one to explicitly evaluate the pressure in spherical geometry, à la van der Waals. Pascal's law is recovered within the Landau-Ginzburg density functional theory, formally analogously to how conservation of energy is recovered in the Lagrangian formulation of mechanics. We establish proper boundary conditions for certain singular functional forms of the bulk free energy density that allow one to obtain droplet solutions with thick walls in essentially closed form. The hydrodynamic modes responsible for mixing near the interface are explicitly identified in the treatment; the composition at the interface is found to depend only weakly on the droplet size. Next we develop a Landau-Ginzburg treatment of the effects of amphiphiles on the surface tension; the amphiphilic action is seen as a violation of Pascal's law. We explicitly obtain the binding potential for the detergent at the interface and the dependence of the down-renormalization of the surface tension on the activity of the detergent. Finally, we argue that the renormalization of the activation barrier for escape from long-lived structures in glassy liquids can be viewed as an action of uniformly seeded, randomly oriented amphiphilic molecules on the interface separating two dissimilar aperiodic structures. This renormalization is also considered as a "wetting" of the interface. The resulting conclusions are consistent with the random first order transition theory.

  5. Accurate schemes for calculation of thermodynamic properties of liquid mixtures from molecular dynamics simulations.

    PubMed

    Caro, Miguel A; Laurila, Tomi; Lopez-Acevedo, Olga

    2016-12-28

    We explore different schemes for improved accuracy of entropy calculations in aqueous liquid mixtures from molecular dynamics (MD) simulations. We build upon the two-phase thermodynamic (2PT) model of Lin et al. [J. Chem. Phys. 119, 11792 (2003)] and explore new ways to obtain the partition between the gas-like and solid-like parts of the density of states, as well as the effect of the chosen ideal "combinatorial" entropy of mixing, both of which have a large impact on the results. We also propose a first-order correction to the issue of kinetic energy transfer between degrees of freedom (DoF). This problem arises when the effective temperatures of translational, rotational, and vibrational DoF are not equal, either due to poor equilibration or reduced system size/time sampling, which are typical problems for ab initio MD. The new scheme enables improved convergence of the results with respect to configurational sampling, by up to one order of magnitude, for short MD runs. To ensure a meaningful assessment, we perform MD simulations of liquid mixtures of water with several other molecules of varying sizes: methanol, acetonitrile, N, N-dimethylformamide, and n-butanol. Our analysis shows that results in excellent agreement with experiment can be obtained with little computational effort for some systems. However, the ability of the 2PT method to succeed in these calculations is strongly influenced by the choice of force field, the fluidicity (hard-sphere) formalism employed to obtain the solid/gas partition, and the assumed combinatorial entropy of mixing. We tested two popular force fields, GAFF and OPLS with SPC/E water. For the mixtures studied, the GAFF force field seems to perform as a slightly better "all-around" force field when compared to OPLS+SPC/E.

  6. Calculation of multicomponent chemical equilibria in gas-solid- liquid systems: calculation methods, thermochemical data, and applications to studies of high-temperature volcanic gases with examples from Mount St. Helens

    USGS Publications Warehouse

    Symonds, R.B.; Reed, M.H.

    1993-01-01

    This paper documents the numerical formulations, thermochemical data base, and possible applications of computer programs, SOLVGAS and GASWORKS, for calculating multicomponent chemical equilibria in gas-solid-liquid systems. SOLVGAS and GASWORKS compute simultaneous equilibria by solving simultaneously a set of mass balance and mass action equations written for all gas species and for all gas-solid or gas-liquid equilibria. Examples of gas-evaporation-from-magma and precipitation-with-cooling calculations for volcanic gases collected from Mount St. Helens are shown. -from Authors

  7. Effect of salt of various concentrations on liquid limit, and hydraulic conductivity of different soil-bentonite mixtures

    NASA Astrophysics Data System (ADS)

    Mishra, Anil Kumar; Ohtsubo, Masami; Li, Loretta Y.; Higashi, Takahiro; Park, Junboum

    2009-05-01

    Effect of the various concentrations of NaCl and CaCl2 on the four different soil-bentonite mixtures has been evaluated. The results show that the liquid limit of the mixtures decreases with an increase in the salt concentration. Liquid limit decreased significantly with an increase in CaCl2 concentration from 0 to 0.1 N. However, a further increase in the concentration did not produce any significant decrease in liquid limit. A quite opposite trend was observed for the NaCl solution. An increase in NaCl concentration from 0 to 0.1 N did not produce any major decrease in the liquid limit, but a further increase in concentration from 0.1 to 1 N decreased the liquid limit significantly. Consolidation tests were carried out on the mixtures to evaluate the effect of mineralogical composition of the bentonite on the hydraulic conductivity ( k) of the mixture in the presence of various salts concentrations. The k for any mixtures was found to be decreasing with decrease in the salt concentration. At relatively low concentration, Ca2+ had more effect on the k in comparison to the same concentration of Na+. However, at 1 N of NaCl and CaCl2 almost an equal value of k was observed. A comparison of the performance of four bentonites showed that the mixture with bentonite having highest exchangeable sodium percentage (ESP) exhibited the lowest k when permeated with de-ionized (DI) water, however, k increased with an increase in the salt concentration. Similarly, mixture with a bentonite of lower ESP exhibited a higher k with DI water but with the increase in the salt concentration alteration in the k, compared to all other mixtures, was relatively less.

  8. Multicomponent fuel vaporization at high pressures.

    SciTech Connect

    Torres, D. J.; O'Rourke, P. J.

    2002-01-01

    We extend our multicomponent fuel model to high pressures using a Peng-Robinson equation of state, and implement the model into KIVA-3V. Phase equilibrium is achieved by equating liquid and vapor fugacities. The latent heat of vaporization and fuel enthalpies are also corrected for at high pressures. Numerical simulations of multicomponent evaporation are performed for single droplets for a diesel fuel surrogate at different pressures.

  9. Density functional theory of gas-liquid phase separation in dilute binary mixtures

    NASA Astrophysics Data System (ADS)

    Okamoto, Ryuichi; Onuki, Akira

    2016-06-01

    We examine statics and dynamics of phase-separated states of dilute binary mixtures using density functional theory. In our systems, the difference of the solvation chemical potential between liquid and gas Δ {μ\\text{s}} (the Gibbs energy of transfer) is considerably larger than the thermal energy {{k}\\text{B}}T for each solute particle and the attractive interaction among the solute particles is weaker than that among the solvent particles. In these conditions, the saturated vapor pressure increases by {{k}\\text{B}}Tn2\\ell\\exp ≤ft(Δ {μ\\text{s}}/{{k}\\text{B}}T\\right) , where n2\\ell is the solute density added in liquid. For \\exp ≤ft(Δ {μ\\text{s}}/{{k}\\text{B}}T\\right)\\gg 1 , phase separation is induced at low solute densities in liquid and the new phase remains in gaseous states, even when the liquid pressure is outside the coexistence curve of the solvent. This explains the widely observed formation of stable nanobubbles in ambient water with a dissolved gas. We calculate the density and stress profiles across planar and spherical interfaces, where the surface tension decreases with increasing interfacial solute adsorption. We realize stable solute-rich bubbles with radius about 30 nm, which minimize the free energy functional. We then study dynamics around such a bubble after a decompression of the surrounding liquid, where the bubble undergoes a damped oscillation. In addition, we present some exact and approximate expressions for the surface tension and the interfacial stress tensor.

  10. Selective Single-Step Separation of a Mixture of Three Metal Ions by a Triphasic Ionic-Liquid-Water-Ionic-Liquid Solvent Extraction System.

    PubMed

    Vander Hoogerstraete, Tom; Blockx, Jonas; De Coster, Hendrik; Binnemans, Koen

    2015-08-10

    In a conventional solvent extraction system, metal ions are distributed between two immiscible phases, typically an aqueous and an organic phase. In this paper, the proof-of-principle is given for the distribution of metal ions between three immiscible phases, two ionic liquid phases with an aqueous phase in between them. Three-liquid-phase solvent extraction allows separation of a mixture of three metal ions in a single step, whereas at least two steps are required to separate three metals in the case of two-liquid-phase solvent extraction. In the triphasic system, the lower organic phase is comprised of the ionic liquid betainium- or choline bis(trifluoromethylsulfonyl)imide, whereas the upper organic phase is comprised of the ionic liquid trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide. The triphasic system was used for the separation of a mixture of tin(II), yttrium(III), and scandium(III) ions.

  11. Stokes shift dynamics in (non-dipolar ionic liquid + dipolar solvent) binary mixtures: a semi-molecular theory.

    PubMed

    Pal, Tamisra; Biswas, Ranjit

    2014-10-28

    A semi-molecular theory for studying composition dependent Stokes shift dynamics of a dipolar solute in binary mixtures of (non-dipolar ionic liquid + common dipolar solvent) is developed here. The theory provides microscopic expressions for solvation response functions in terms of static and dynamic structure factors of the mixture components and solute-solvent static correlations. In addition, the theory provides a framework for examining the interrelationship between the time dependent solvation response in and frequency dependent dielectric relaxation of a binary mixture containing electrolyte. Subsequently, the theory has been applied to predict ionic liquid (IL) mole fraction dependent dynamic Stokes shift magnitude and solvation energy relaxation for a dipolar solute, C153, in binary mixtures of an ionic liquid, trihexyltetradecylphosphonium chloride ([P(14,666)][Cl]) with a common dipolar solvent, methanol (MeOH). In the absence of suitable experimental data, necessary input parameters have been obtained from approximate methods. Dynamic shifts calculated for these mixtures exhibit a linear increase with IL mole fraction for the most part of the mixture composition, stressing the importance of solute-IL dipole-ion interaction. Average solvation rates, on the other hand, show a nonlinear IL mole fraction dependence which is qualitatively similar to what has been observed for such binary mixtures with imidazolium (dipolar) ILs. These predictions should be re-examined in suitable experiments.

  12. Delineating solute-solvent interactions in binary mixtures of ionic liquids in molecular solvents and preferential solvation approach.

    PubMed

    Khupse, Nageshwar D; Kumar, Anil

    2011-02-03

    The effect of solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators in binary mixtures of ionic liquids with molecular solvents has been investigated. The binary mixtures of the pyridinium-based ionic liquids 1-butylpyridinium tetrafluoroborate ([BP][BF4]), 1-butyl-3-methylpyridinium tetrafluoroborate ([3-MBP][BF4]), and 1-butyl-4-methylpyridinium tetrafluoroborate ([4-MBP][BF4]) with molecular solvents like water, methanol, and dichloromethane have been selected for this investigation. The effect of addition of ionic liquids to molecular solvents on the polarity parameters E(T)(N), Kamlet-Taft parameters, hydrogen bond donor ability (HBD) (α), hydrogen bond acceptor ability (HBA) (β), and polarizability (π*) was obtained. The polarity parameters of the mixture display nonideality on addition of ionic liquids to water and dichloromethane. On the other hand, strong synergetic effects were seen in the ionic liquid-methanol binary mixtures. The preferential solvation models have been employed to analyze the collected data in order to achieve information on solute-solvent interactions in these binary mixtures.

  13. Liquid Disordered-Liquid Ordered Phase Coexistence in Lipid/Cholesterol Mixtures: A Deuterium 2D NMR Exchange Study.

    PubMed

    Schmidt, Miranda L; Davis, James H

    2017-02-28

    Model membranes composed of two types of long chain phospholipids, one unsaturated and one saturated, along with cholesterol can exhibit two coexisting fluid phases (liquid disordered ([Formula: see text]) and liquid ordered ([Formula: see text])) at various temperatures and compositions. Here we used 1D and 2D (2)H NMR to compare the behavior of multilamellar dispersions, magnetically oriented bicelles, and mechanically aligned bilayers on glass plates, all of which contain the same proportions of dipalmitoleoylphosphatidylcholine (DPoPC), dimyristoylphosphatidylcholine (DMPC), and cholesterol. We found that multilamellar dispersions and bilayers aligned on glass plates behave very similarly. These samples were close to a critical composition and exhibit exchange of the lipids between the two fluid phases at temperatures near the [Formula: see text] to [Formula: see text]-[Formula: see text] phase boundary. On the other hand, when a short chain lipid is added to the ternary long chain lipid/cholesterol mixture to form bicelles, the phase behavior is changed significantly and the [Formula: see text] phase occurs at a higher than expected temperature. In addition, there was no evidence of exchange of lipids between the [Formula: see text] and [Formula: see text] phases or critical fluctuations at the temperature where the bulk of the sample enters the two-phase region for these bicelles. It appears that the addition of the short chain lipid results in these samples no longer being near a critical composition.

  14. Abundance estimation of solid and liquid mixtures in hyperspectral imagery with albedo-based and kernel-based methods

    NASA Astrophysics Data System (ADS)

    Rand, Robert S.; Resmini, Ronald G.; Allen, David W.

    2016-09-01

    This study investigates methods for characterizing materials that are mixtures of granular solids, or mixtures of liquids, which may be linear or non-linear. Linear mixtures of materials in a scene are often the result of areal mixing, where the pixel size of a sensor is relatively large so they contain patches of different materials within them. Non-linear mixtures are likely to occur with microscopic mixtures of solids, such as mixtures of powders, or mixtures of liquids, or wherever complex scattering of light occurs. This study considers two approaches for use as generalized methods for un-mixing pixels in a scene that may be linear or non-linear. One method is based on earlier studies that indicate non-linear mixtures in reflectance space are approximately linear in albedo space. This method converts reflectance to single-scattering albedo (SSA) according to Hapke theory assuming bidirectional scattering at nadir look angles and uses a constrained linear model on the computed albedo values. The other method is motivated by the same idea, but uses a kernel that seeks to capture the linear behavior of albedo in non-linear mixtures of materials. The behavior of the kernel method can be highly dependent on the value of a parameter, gamma, which provides flexibility for the kernel method to respond to both linear and non-linear phenomena. Our study pays particular attention to this parameter for responding to linear and non-linear mixtures. Laboratory experiments on both granular solids and liquid solutions are performed with scenes of hyperspectral data.

  15. Self-aggregation of cationic dimeric surfactants in water-ionic liquid binary mixtures.

    PubMed

    Martín, Victoria Isabel; Rodríguez, Amalia; Laschewsky, André; Moyá, María Luisa

    2014-09-15

    The micellization of four dimeric cationic surfactants ("gemini surfactants") derived from N-dodecyl-N,N,N-trimethylammonium chloride was studied in pure water and in water-ionic liquid (IL) solutions by a wide range of techniques. The dimeric surfactants are distinguished by their rigid spacer groups separating the two surfactant motifs, which range from C3 to C5 in length. In order to minimize organic ion pairing effects as well as the role of the ionic liquids as potential co-surfactants, ILs with inorganic hydrophilic anions and organic cations of limited hydrophobicity were chosen, namely ethyl, butyl, and hexyl-3-imidazolium chlorides. (1)H NMR two-dimensional, 2D, rotating frame nuclear Overhauser effect spectroscopy measurements, ROESY, supported this premise. The spacer nature hardly affects the micellization process, neither in water nor in water-IL solutions. However, it does influence the tendency of the dimeric surfactants to form elongated micelles when surfactant concentration increases. In order to have a better understanding of the ternary water-IL surfactant systems, the micellization of the surfactants was also studied in aqueous NaCl solutions, in water-ethylene glycol and in water-formamide binary mixtures. The combined results show that the ionic liquids play a double role in the mixed systems, operating simultaneously as background electrolytes and as polar organic solvents. The IL role as organic co-solvent becomes more dominant when its concentration increases, and when the IL alkyl chain length augments.

  16. Bubbles in liquids with phase transition—part 2: on balance laws for mixture theories of disperse vapor bubbles in liquid with phase change

    NASA Astrophysics Data System (ADS)

    Dreyer, Wolfgang; Hantke, Maren; Warnecke, Gerald

    2014-07-01

    We study averaging methods for the derivation of mixture equations for disperse vapor bubbles in liquids. The carrier liquid is modeled as a continuum, whereas simplified assumptions are made for the disperse bubble phase. An approach due to Petrov and Voinov is extended to derive mixture equations for the case that there is a phase transition between the carrier liquid and the vapor bubbles in water. We end up with a system of balance laws for a multi-phase mixture, which is completely in divergence form. Additional non-differential source terms describe the exchange of mass, momentum and energy between the phases. The sources depend explicitly on evolution laws for the total mass, the radius and the temperature of single bubbles. These evolution laws are derived in a prior article (Dreyer et al. in Cont Mech Thermodyn. doi:10.1007/s00161-0225-6, 2011) and are used to close the system. Finally, numerical examples are presented.

  17. Efficient capture of SO2 by a binary mixture of caprolactam tetrabutyl ammonium bromide ionic liquid and water.

    PubMed

    Duan, Erhong; Guo, Bin; Zhang, Miaomiao; Guan, Yanan; Sun, Hua; Han, Jing

    2011-10-30

    The solubility of SO(2) in a binary mixture of water and caprolactam tetrabutyl ammonium bromide ionic liquid (CPL-TBAB IL) was investigated. Though the ionic liquid and water were fully miscible, a phase separation occurred when SO(2) was introduced into the mixture. The SO(2) concentrated in the lower layer, and it could be released by heating the solution under reduced pressure (382.2K, 10.1 kPa). After desorption, the mixture could be reused to absorb SO(2). It was found that SO(2) acts as a switch to cause the water and CPL-TBAB IL to phase separate, and the mechanics of this phase separation process was studied by gas chromatography-mass spectrometry, fourier transform-infrared spectroscopy and Karl-Fisher titration. The absorption and desorption of SO(2) in the CPL-TBAB/water mixtures were reversible.

  18. CHARACTERIZATION AND REMEDIATION TECHNOLOGIES FOR LIGHT NONAQUEOUS PHASE LIQUIDS

    EPA Science Inventory

    Light nonaqueous phase liquids (LNAPLs), principally petroleum products, affect ground-water quality at numerous sites across this country and throughout the world. Petroleum products are typically multi-component organic mixtures composed of chemicals with a wide range of solubi...

  19. Density and molar volumes of imidazolium-based ionic liquid mixtures and prediction by the Jouyban-Acree model

    NASA Astrophysics Data System (ADS)

    Ghani, Noraini Abd; Sairi, Nor Asrina; Mat, Ahmad Nazeer Che; Khoubnasabjafari, Mehry; Jouyban, Abolghasem

    2016-11-01

    The density of imidazolium-based ionic liquid, 1-ethyl-3-methylimidazolium diethylphosphate with sulfolane were measured at atmospheric pressure. The experiments were performed at T= (293 - 343) K over the complete mole fractions. Physical and thermodynamic properties such as molar volumes, V0, and excess molar volumes, VE for this binary mixtures were derived from the experimental density data. The Jouyban-Acree model was exploited to correlate the physicochemical properties (PCPs) of binary mixtures at various mole fractions and temperatures.

  20. Segregation of ions at the interface: molecular dynamics studies of the bulk and liquid-vapor interface structure of equimolar binary mixtures of ionic liquids.

    PubMed

    Palchowdhury, Sourav; Bhargava, B L

    2015-08-14

    The structures of three different equimolar binary ionic liquid mixtures and their liquid-vapor interface have been studied using atomistic molecular dynamics simulations. Two of these binary mixtures were composed of a common cation 1-n-butyl-3-methylimidazolium and varying anions (chloride and hexafluorophosphate in one of the mixtures and chloride and trifluoromethanesulfonate in the other) and the third binary mixture was composed of a common anion, trifluoromethanesulfonate and two imidazolium cations with ethyl and octyl side chains. Binary mixtures with common cations are found to be homogeneous. The anions are preferentially located near the ring hydrogen atoms due to H-bonding interactions. Segregation of ions is observed at the interface with an enrichment of the liquid-vapor interface layer by longer alkyl chains and bigger anions with a distributed charge. The surface composition is drastically different from that of the bulk composition, with the longer alkyl tail groups and bigger anions populating the outermost layer of the interface. The longer alkyl chains of the cations and trifluoromethanesulfonate anions with a smaller charge density show orientational ordering at the liquid-vapor interface.

  1. Atomistic Insight into Tetraalkylphosphonium Bis(oxalato)borate Ionic Liquid/Water Mixtures. 2. Volumetric and Dynamic Properties.

    PubMed

    Wang, Yong-Lei; Shimpi, Manishkumar R; Sarman, Sten; Antzutkin, Oleg N; Glavatskih, Sergei; Kloo, Lars; Laaksonen, Aatto

    2016-08-04

    Atomistic molecular dynamics simulations have been performed to investigate volumetric quantities and dynamic properties of binary trihexyltetradecylphosphonium bis(oxalato)borate ([P6,6,6,14][BOB]) ionic liquid (IL)/water mixtures with different water concentrations. The predicted liquid densities for typical [P6,6,6,14][BOB] IL/water mixtures are consistent with available experimental data with a relative discrepancy of less than 3%. The liquid densities and excess molar volumes of all studied [P6,6,6,14][BOB] IL/water mixtures are characterized by concave and convex features, respectively, within full water concentration range. The dynamic properties of [P6,6,6,14] cations, [BOB] anions, and water molecules are particularly analyzed through calculation of velocity autocorrelation functions, diffusion coefficients, and reorientational autocorrelation functions and correlation times. The translational and reorientational mobilities of three species become faster upon increasing water concentration in [P6,6,6,14][BOB] IL/water mixtures and present complex dynamical characteristics arising from three distinct microscopic diffusion features within the full water concentration range. The obtained striking volumetric quantities and particular dynamic properties are well correlated to microscopic liquid structural organization and distinct local ionic environment of all studied [P6,6,6,14][BOB] IL/water mixtures.

  2. Binary Solvent Organization at Silica/Liquid Interfaces: Preferential Ordering in Acetonitrile-Methanol Mixtures.

    PubMed

    Gobrogge, Eric A; Walker, Robert A

    2014-08-07

    Nonlinear vibrational spectroscopy experiments examined solvent organization at the silica/binary solvent interface where the binary solvent consisted of methanol and acetonitrile in varying mole fractions. Data were compared with surface vibrational spectra acquired from silica surfaces exposed to a vapor phase saturated with the same binary solvent mixtures. Changes in vibrational band intensities suggest that methanol ideally adsorbs to the silica/vapor interface but acetonitrile accumulates in excess relative to vapor-phase composition. At the silica/liquid interface, acetonitrile's signal increases until a solution phase mole fraction of ∼0.85. At higher acetonitrile concentrations, acetonitrile's signal decreases dramatically until only a weak signature persists with the neat solvent. This behavior is ascribed to dipole-paired acetonitrile forming a bilayer with the first sublayer associating with surface silanol groups and a second sublayer consisting of weakly associating, antiparallel partners. On the basis of recent simulations, we propose that the second sublayer accumulates in excess.

  3. Non-ideal mixing behaviour of hydrogen bonding in mixtures of protic ionic liquids.

    PubMed

    Fumino, Koichi; Bonsa, Anne-Marie; Golub, Benjamin; Paschek, Dietmar; Ludwig, Ralf

    2015-02-02

    Ionic liquids (ILs) attract interest in science and technology as a result of their unique properties. Binary and ternary mixtures of ILs significantly increase the number of possible cation/anion combinations, resulting in targeted physical and chemical properties. In this work, we study the mixing behaviour of two protic ILs: triethyl ammonium methylsulfonate [Et3 NH][CH3 SO3 ] and triethylammonium triflate [Et3 NH][CF3 SO3 ]. We find a characteristic deviation from ideal mixing by means of low-frequency infrared spectroscopy. By using molecular dynamics simulations, we explain this behaviour as being the result of different strengths of anion/cation hydrogen bonding. This non-ideality of non-random H-bond mixing is also reflected in macroscopic properties such as the viscosity. Mixing suitable ILs may, thus, result in new ILs with targeted physical properties.

  4. Structure and dynamics of binary liquid mixtures near their continuous demixing transitions

    NASA Astrophysics Data System (ADS)

    Roy, Sutapa; Dietrich, S.; Höfling, Felix

    2016-10-01

    The dynamic and static critical behavior of a family of binary Lennard-Jones liquid mixtures, close to their continuous demixing points (belonging to the so-called model H' dynamic universality class), are studied computationally by combining semi-grand canonical Monte Carlo simulations and large-scale molecular dynamics (MD) simulations, accelerated by graphic processing units (GPU). The symmetric binary liquid mixtures considered cover a variety of densities, a wide range of compressibilities, and various interactions between the unlike particles. The static quantities studied here encompass the bulk phase diagram (including both the binodal and the λ-line), the correlation length, and the concentration susceptibility, of the finite-sized systems above the bulk critical temperature Tc, the compressibility and the pressure at Tc. Concerning the collective transport properties, we focus on the Onsager coefficient and the shear viscosity. The critical power-law singularities of these quantities are analyzed in the mixed phase (above Tc) and non-universal critical amplitudes are extracted. Two universal amplitude ratios are calculated. The first one involves static amplitudes only and agrees well with the expectations for the three-dimensional Ising universality class. The second ratio includes also dynamic critical amplitudes and is related to the Einstein-Kawasaki relation for the interdiffusion constant. Precise estimates of this amplitude ratio are difficult to obtain from MD simulations, but within the error bars our results are compatible with theoretical predictions and experimental values for model H'. Evidence is reported for an inverse proportionality of the pressure and the isothermal compressibility at the demixing transition, upon varying either the number density or the repulsion strength between unlike particles.

  5. Mathematical methods for restricted domain ternary liquid mixture free energy determination using light scattering.

    PubMed

    Wahle, Chris W; Ross, David S; Thurston, George M

    2013-09-28

    We extend methods of solution of a light scattering partial differential equation for the free energy of mixing to apply to connected, isotropic ternary liquid composition domains that do not touch all three binary axes. To do so we mathematically analyze the problem of inferring needed Dirichlet boundary data, and solving for the free energy, with use of hypothetical static light scattering measurements that correspond to dielectric composition gradient vectors that have distinct directions. The physical idea behind the technique is that contrasting absorption properties of mixture components can result in such distinctly directed dielectric composition gradient vectors, due to their differing wavelength dependences of dielectric response. At suitably chosen wavelengths, contrasting light scattering efficiency patterns in the ternary composition triangle can then correspond to the same underlying free energy, and enlarge the scope of available information about the free energy, as shown here. We show how to use distinctly directed dielectric gradients to measure the free energy on both straight lines and curves within the ternary composition triangle, so as to provide needed Dirichlet conditions for light scattering partial differential equation solution. With use of Monte Carlo simulations of noisy light scattering data, we provide estimates of the overall system measurement time and sample spacing needed to determine the free energy to a desired degree of accuracy, for various angles between the assumed dielectric gradient vectors, and indicate how the measurement time depends on instrumental throughput parameters. The present analysis methods provide a way to use static light scattering to measure, directly, mixing free energies of many systems that contain such restricted liquid domains, including aqueous solutions of biological macromolecules, micellar mixtures and microemulsions, and many small molecule systems that are important in separation technology.

  6. Mathematical methods for restricted domain ternary liquid mixture free energy determination using light scattering

    NASA Astrophysics Data System (ADS)

    Wahle, Chris W.; Ross, David S.; Thurston, George M.

    2013-09-01

    We extend methods of solution of a light scattering partial differential equation for the free energy of mixing to apply to connected, isotropic ternary liquid composition domains that do not touch all three binary axes. To do so we mathematically analyze the problem of inferring needed Dirichlet boundary data, and solving for the free energy, with use of hypothetical static light scattering measurements that correspond to dielectric composition gradient vectors that have distinct directions. The physical idea behind the technique is that contrasting absorption properties of mixture components can result in such distinctly directed dielectric composition gradient vectors, due to their differing wavelength dependences of dielectric response. At suitably chosen wavelengths, contrasting light scattering efficiency patterns in the ternary composition triangle can then correspond to the same underlying free energy, and enlarge the scope of available information about the free energy, as shown here. We show how to use distinctly directed dielectric gradients to measure the free energy on both straight lines and curves within the ternary composition triangle, so as to provide needed Dirichlet conditions for light scattering partial differential equation solution. With use of Monte Carlo simulations of noisy light scattering data, we provide estimates of the overall system measurement time and sample spacing needed to determine the free energy to a desired degree of accuracy, for various angles between the assumed dielectric gradient vectors, and indicate how the measurement time depends on instrumental throughput parameters. The present analysis methods provide a way to use static light scattering to measure, directly, mixing free energies of many systems that contain such restricted liquid domains, including aqueous solutions of biological macromolecules, micellar mixtures and microemulsions, and many small molecule systems that are important in separation technology.

  7. Density and Viscosity of Binary Mixtures of Thiocyanate Ionic Liquids + Water as a Function of Temperature.

    PubMed

    Domańska, U; Królikowska, M

    2012-09-01

    Densities and viscosities have been determined for binary mixtures of the ionic liquids (ILs) 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or 1-butyl-4-methylpyridinium thiocyanate [BMPy][SCN], or 1-butyl-1-methylpyrrolidinium thiocyanate [BMPYR][SCN], or 1-butyl-1-methylpiperidinium thiocyanate [BMPIP][SCN] with water over wide range of temperatures (298.15-348.15) K and ambient pressure. The thermal properties of [BMPy][SCN], i.e. glass transition temperature and the heat capacity at glass transition, have been measured using a differential scanning microcalorimetry, DSC. The decomposition of [BMPy][SCN] was detected. The density and viscosity correlations for these systems have been made using an empirical second-order polynomial and by the Vogel-Fulcher-Tammann equation, respectively. The concentration dependences have been described by polynomials. The excess molar volumes and deviations in viscosity have been calculated from the experimental values and were correlated by Redlich-Kister polynomial expansions. The variations of these parameters, with compositions of the mixtures and temperature, have been discussed in terms of molecular interactions. A qualitative analysis of the trend of properties with composition and temperature was performed. Further, the excess partial molar volumes, [Formula: see text] and [Formula: see text], were calculated and discussed. The isobaric expansivities (coefficient of thermal expansion), α, and the excess isobaric expansivities, α(E), were determined for four ILs and their mixtures with water. The results indicate that the interactions of thiocyanate ILs with water is not as strong as with alcohols, which is shown by the positive/slightly negative excess molar volumes in these binary systems. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s10953-012-9875-7) contains supplementary material, which is available to authorized users.

  8. Volumetric, Viscometric, and Ultrasonic Properties of Liquid Mixtures of Cyclohexane with Alkanols at Different Temperatures

    NASA Astrophysics Data System (ADS)

    Ali, Anwar; Tasneem, Shadma; Nabi, Firdosa

    2010-09-01

    The densities (ρ), viscosities (η), and ultrasonic speeds (u) of pure cyclohexane, 1-butanol, 2- butanol, and those of their binary mixtures, with cyclohexane as common component, covering the whole composition range have been measured at 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15 K. From the experimental data the excess molar volume (VE), deviations in isentropic compressibility (Δks), deviations in viscosity (Δη), deviations in ultrasonic speed (Δu), deviations in acoustic impedance (ΔZ), deviations in internal pressure (ΔPi), excess Gibbs free energy of activation (ΔG*E), entropies (ΔS*), and enthalpies (ΔH*) of activation of viscous flow have been determined. The sign and magnitude of these parameters were found to be sensitive towards interactions prevailing in the studied systems. Partial molar volumes (V0φ,2) and partial molar compressibilities (K0φ,2) of 1-butanol and 2-butanol in cyclohexane have also been evaluated. Moreover, VE values were theoretically predicted by using Flory's statistical theory. The variations of derived parameters mentioned above with composition offer a convenient method to study the nature and extent of interactions between the component molecules of the liquid mixtures, not easily obtained by other means

  9. Coarsening in Solid-Liquid Mixtures-2: A Materials Science Experiment for the ISS

    NASA Technical Reports Server (NTRS)

    Hickman, J. Mark; Voorhees, Peter W.; Kwon, Yongwoo; Lorik, Tibor

    2004-01-01

    A materials science experiment has been developed and readied for operation aboard the International Space Station (ISS). Components of this experiment are onboard ISS and area awaiting the flight of science samples. The goal of the experiment is to understand the dynamics of Ostwald ripening, also known as coarsening, a process that occurs in nearly any two-phase mixture found in nature. Attempts to obtain experimental data in ground-based laboratories are hindered due to the presence of gravity, which introduces material transport modes other than that of the coarsening phenomenon. This introduces adjustable parameters in the formulation of theory. The original Coarsening in Solid-Liquid Mixtures (CSLM) mission, which flew on the Space Shuttle in 1997, produced data from a coarsened eutectic alloy. Unfortunately, both the science matrix and the hardware, while nominally functional, did not account adequately for operations in microgravity. A significantly redesigned follow-on experiment, CSLM-2 has been developed to redress the inadequacies of the original experiment. This paper reviews the CSLM-2 project: its history, science goals, flight hardware implementation, and planned operations and analysis

  10. Detection of a new 'nematic-like' phase in liquid crystal-amphiphile mixture by differential scanning calorimetry

    SciTech Connect

    Dan, Kaustabh Roy, Madhusudan Datta, Alokmay

    2014-04-24

    Differential Scanning Calorimetry (DSC) studies on phase transitions of the pure liquid crystalline material N-4-methoxybenzylidene-4-butylaniline (MBBA) and mixtures of MBBA and the amphiphile Stearic Acid (StA) show significant changes in the behavior of mixture from pure MBBA, as regards the nematic-isotropic (N-I) transition temperature (T{sub c}) and other thermodynamic parameters like enthalpy, specific heat and activation energy with concentration of StA. In particular, the convexity of the Arrhenius plot in pure MBBA vanishes with StA concentration pointing to the formation of a new, perhaps 'nematic-like', phase in the mixtures.

  11. Hydrogen self-dynamics in liquid H2-D2 mixtures studied through inelastic neutron scattering

    NASA Astrophysics Data System (ADS)

    Colognesi, Daniele; Bafile, Ubaldo; Celli, Milva; Neumann, Martin; Orecchini, Andrea

    2015-07-01

    We have measured the dynamic structure factor of liquid para-hydrogen mixed with normal deuterium (T =20 K ) at two different concentration levels using incoherent inelastic neutron scattering. This choice has been made since the presence of D2 modifies the self-dynamics of H2 in a highly nontrivial way, acting both on its pseudophononic and its diffusive parts in a tunable way. After an accurate data reduction, recorded neutron spectra were studied through the modified Young and Koppel model and the H2 center-of-mass self-dynamics structure factor was finally extracted for the two mixtures. Some physical quantities (i.e., self-diffusion coefficient and mean kinetic energy) were determined and compared with accurate quantum calculations, which, in addition, also provided estimates of the velocity autocorrelation function for the H2 centers of mass. These estimates, in conjunction with the Gaussian approximation, were used to simulate the H2 center-of-mass self-dynamics structure factor in the same range as the experimental one. The agreement between measured and calculated spectra was globally good, but some discrepancies proved the unquestionable breakdown of the Gaussian approximation in these semiquantum systems at a level comparable to that already observed in pure liquid para-hydrogen.

  12. Ionic liquid crystalline phases in 3-hexadecylimidazolium bromide and binary mixtures with 1-decanol.

    PubMed

    Li, Cuihua; He, Jinhua; Chen, Jiahui; Liu, Jianhong; Zhang, Qianling; Yu, Zhenqiang

    2011-07-15

    3-Hexadecylimidazolium bromide was synthesized and characterized showing formation of thermotropic smectic liquid crystals at temperatures above its melting point from 48.5 to 150.9°C. With decreasing temperature, the peak intensities in XRD patterns increase and full widths at half-maximum decrease, suggesting structural order increases with decreasing temperature. Compared with 1,2-dimethyl-3-hexadecyl-imidazolium bromide and hexafluorophosphate, the IL shows a lower melting point and less degree of chain interdigitation. The main reason is due to a more symmetrical structure and denser assembly of the IL molecules, which results in more steric resistance for the alkyl chain to interdigitate. The self-assembly behavior of the hydrophobic IL in an organic solvent was investigated showing SmA(2) lyotropic liquid crystalline phases. The first-order scattering peak shifts to lower q values with increasing IL content, which is opposite to the shift directions of the binary mixtures of the soluble imidazolium IL and water, indicating a different packing behavior of the hydrophobic IL in 1-decanol.

  13. Coarsening in Solid-liquid Mixtures: Overview of Experiments on Shuttle and ISS

    NASA Technical Reports Server (NTRS)

    Duval, Walter M. B.; Hawersaat, Robert W.; Lorik, T.; Thompson, J.; Gulsoy, B.; Voorhees, P. W.

    2013-01-01

    The microgravity environment on the Shuttle and the International Space Station (ISS) provides the ideal condition to perform experiments on Coarsening in Solid-Liquid Mixtures (CSLM) as deleterious effects such as particle sedimentation and buoyancy-induced convection are suppressed. For an ideal system such as Lead-Tin in which all the thermophysical properties are known, the initial condition in microgravity of randomly dispersed particles with local clustering of solid Tin in eutectic liquid Lead-Tin matrix, permitted kinetic studies of competitive particle growth for a range of volume fractions. Verification that the quenching phase of the experiment had negligible effect of the spatial distribution of particles is shown through the computational solution of the dynamical equations of motion, thus insuring quench-free effects from the coarsened microstructure measurements. The low volume fraction experiments conducted on the Shuttle showed agreement with transient Ostwald ripening theory, and the steady-state requirement of LSW theory was not achieved. More recent experiments conducted on ISS with higher volume fractions have achieved steady-state condition and show that the kinetics follows the classical diffusion limited particle coarsening prediction and the measured 3D particle size distribution becomes broader as predicted from theory.

  14. Liquid crystalline phases and their dispersions in aqueous mixtures of glycerol monooleate and glyceryl monooleyl ether.

    PubMed

    Popescu, Georgeta; Barauskas, Justas; Nylander, Tommy; Tiberg, Fredrik

    2007-01-16

    The aqueous phase behavior of mixtures of 1-glycerol monooleate (GMO) and its ether analogue, 1-glyceryl monooleyl ether (GME) has been investigated by a combination of polarized microscopy, X-ray diffraction, and NMR techniques. Three phase diagrams of the ternary GMO/GME/water system have been constructed at 25, 40, and 55 degrees C. The results demonstrate that the increasing amount of GME favors the formation of the reversed phases, evidenced by the transformation of the lamellar and bicontinuous cubic liquid crystalline phases of the binary GMO/water system into reversed micellar or reversed hexagonal phases. For a particular liquid crystalline phase, increasing the GME content has no effect on the structural characteristics and hydration properties, thus suggesting ideal mixing with GMO. Investigations of dispersed nanoparticle samples using shear and a polymeric stabilizer, Pluronic F127, show the possibility of forming two different kinds of bicontinuous cubic phase nanoparticles by simply changing the GMO/GME ratio. Also NMR self-diffusion measurements confirm that the block copolymer, Pluronic F127, used to facilitate dispersion formation, is associated with nanoparticles and provides steric stabilization.

  15. Interactions of Aqueous Imidazolium-Based Ionic Liquid Mixtures with Solid-Supported Phospholipid Vesicles

    PubMed Central

    Losada-Pérez, Patricia; Khorshid, Mehran; Renner, Frank Uwe

    2016-01-01

    Despite the environmentally friendly reputation of ionic liquids (ILs), their safety has been recently questioned given their potential as cytotoxic agents. The fundamental mechanisms underlying the interactions between ILs and cells are less studied and by far not completely understood. Biomimetic films are here important biophysical model systems to elucidate fundamental aspects and mechanisms relevant for a large range of biological interaction ranging from signaling to drug reception or toxicity. Here we use dissipative quartz crystal microbalance QCM-D to examine the effect of aqueous imidazolium-based ionic liquid mixtures on solid-supported biomimetic membranes. Specifically, we assess in real time the effect of the cation chain length and the anion nature on a supported vesicle layer of the model phospholipid DMPC. Results indicate that interactions are mainly driven by the hydrophobic components of the IL, which significantly distort the layer and promote vesicle rupture. Our analyses evidence the gradual decrease of the main phase transition temperature upon increasing IL concentration, reflecting increased disorder by weakening of lipid chain interactions. The degree of rupture is significant for ILs with long hydrophobic cation chains and large hydrophobic anions whose behavior is reminiscent of that of antimicrobial peptides. PMID:27684947

  16. Vapor-Liquid Equilibrium in the Mixture Trichloromethane CHCl3 + C6H10O Cyclohexanone (EVLM1111, LB5654_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture Trichloromethane CHCl3 + C6H10O Cyclohexanone (EVLM1111, LB5654_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  17. ETHANOL, ACETIC ACID, AND WATER ADSORPTION FROM BINARY AND TERNARY LIQUID MIXTURES ON HIGH-SILICA ZEOLITES

    EPA Science Inventory

    Adsorption isotherms were measured for ethanol, acetic acid, and water adsorbed on high-silica ZSM-5 zeolite powder from binary and ternary liquid mixtures at room temperature. Ethanol and water adsorption on two high-silica ZSM-5 zeolites with different aluminum contents and a h...

  18. Understanding the Effect of Solvent Structure on Organic Reaction Outcomes When Using Ionic Liquid/Acetonitrile Mixtures.

    PubMed

    Keaveney, Sinead T; Greaves, Tamar L; Kennedy, Danielle F; Harper, Jason B

    2016-12-15

    The rate constant for the reaction between hexan-1-amine and 4-methoxybenzaldehyde was determined in ionic liquids containing an imidazolium cation. The effect on the rate constant of increasing the length of the alkyl substituent on the cation was examined in a number of ionic liquid/acetonitrile mixtures. In general it was found that there was no significant effect of changing the alkyl substituent on the rate constant of this process, suggesting that any nanodomains in these mixtures do not have a significant effect on the outcome of this process. A series of small-angle X-ray scattering and wide-angle X-ray scattering experiments were performed on mixtures of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][N(CF3SO2)2]) and acetonitrile; this work indicated that the main structural changes in the mixtures occur by about a 0.2 mole fraction of ionic liquid in the mixture (χIL). This region at which the main changes in the solvent structuring occurs corresponds to the region at which the main changes in the rate constant and activation parameters occur for SN2 and condensation reactions examined previously; this is the first time that such a correlation has been observed. To examine the ordering of the solvent about the nucleophile hexan-1-amine, WAXS experiments were performed on a number of [Bmim][N(CF3SO2)2]/acetonitrile/hexan-1-amine mixtures, where it was found that some of the patterns featured asymmetric peaks as well as additional peaks not observed in the [Bmim][N(CF3SO2)2]/acetonitrile mixtures; this suggests that the addition of hexan-1-amine to the mixture affects the bulk structure of the liquid. The SAXS/WAXS patterns of mixtures of 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ([Bm2im][N(CF3SO2)2]) and acetonitrile were also determined, with the results suggesting that [Bm2im][N(CF3SO2)2] is more ordered than [Bmim][N(CF3SO2)2] due to an enhancement in the short-range interactions.

  19. Mixtures of the 1-ethyl-3-methylimidazolium acetate ionic liquid with different inorganic salts: insights into their interactions.

    PubMed

    Oliveira, Filipe S; Cabrita, Eurico J; Todorovic, Smilja; Bernardes, Carlos E S; Lopes, José N Canongia; Hodgson, Jennifer L; MacFarlane, Douglas R; Rebelo, Luís P N; Marrucho, Isabel M

    2016-01-28

    In this work, we explore the interactions between the ionic liquid 1-ethyl-3-methylimidazolim acetate and different inorganic salts belonging to two different cation families, those based on ammonium and others based on sodium. NMR and Raman spectroscopy are used to screen for changes in the molecular environment of the ions in the ionic liquid + inorganic salt mixtures as compared to pure ionic liquid. The ion self-diffusion coefficients are determined from NMR data, allowing the discussion of the ionicity values of the ionic liquid + inorganic salt mixtures calculated using different methods. Our data reveal that preferential interactions are established between the ionic liquid and ammonium-based salts, as opposed to sodium-based salts. Computational calculations show the formation of aggregates between the ionic liquid and the inorganic salt, which is consistent with the spectroscopic data, and indicate that the acetate anion of the ionic liquid establishes preferential interactions with the ammonium cation of the inorganic salts, leaving the imidazolium cation less engaged in the media.

  20. Understanding liquid mixture phase miscibility via pair energy parameter behaviors with respect to temperatures determined from molecular simulations.

    PubMed

    Oh, Suk Yung; Bae, Young Chan

    2011-05-19

    The miscibility behaviors of binary liquid mixtures were studied by a combination of molecular simulations and thermodynamic theories. Pairwise interaction parameters were obtained from molecular simulations that accounted for the effect of temperature. From a thermodynamic perspective, different types of liquid-liquid equilibrium (LLE) and different degrees of miscibility can be expressed in terms of energy behaviors with respect to temperature. Our simulation results proved this viewpoint by showing a correspondence between the simulation results and experimental observations. To describe phase diagrams, thermodynamic modeling is presented using the energy parameters obtained from the simulations. Correlations are needed to correct size mismatches between the simulations and the thermodynamic model. Using this method, not only the upper critical solution temperature (UCST) but also the closed-loop miscibility phase diagrams could be calculated without requiring additional parameters for specific interactions. The utility of this method is demonstrated for mixtures containing water, hydrocarbon, alcohols, aldehydes, ketones, chlorides, amines, nitriles, sulfides, and other organic liquids in various temperature ranges. The method presented in this paper can facilitate the understanding of the miscibilities in binary liquid mixtures from the viewpoint of thermal energy behaviors.

  1. Working process study of a novel scroll type multiphase pump for the transportation of gas-liquid mixtures

    NASA Astrophysics Data System (ADS)

    Wang, J.; Zha, H. B.; Zhang, X. H.; Zhang, D. H.

    2012-11-01

    A novel scroll type multiphase pump was proposed to transport gas-liquid two-phase mixture. There is a pressure unloading gap from compression chambers to the discharge port by constructing scroll wrap profile with variational meshing clearance in this scroll multiphase pump. In the working process when the volume of working chamber decreases, the pressure of gas-liquid mixtures increases gradually, at the same time small amounts of gas-liquid mixture are pushed to the discharge port from compression chambers through the pressure unloading gap. Therefore, this multiphase pump has an advantage of unloading pressure method automatically, and the frequently problem of liquid impacting in volume multiphase pump is solved. The safety and reliability of volumetric multiphase pump are improved, and the scope of multiphase pump of the gas-liquid ratio is expanded. The working process and the performance characteristics of scroll multiphase pump were analyzed too, and the generation method of scroll wrap profile with variational meshing clearance was investigated. The equations of the profile were obtained, and the changing principle of the working volume and the meshing clearance were analyzed. The geometric theory of scroll multiphase pump was formed. All of that lay the theoretical foundation for engineering design of this novel scroll.

  2. TMVOC, A Numerical Simulator for Three-Phase Non-isothermal Flowsof Multicomponent Hydrocarbon Mixtures in Variably SaturatedHeterogeneous Media

    SciTech Connect

    Pruess, Karsten; Battistelli, Alfredo

    2005-08-20

    TMVOC is designed for studying subsurface contamination by volatile organic compounds (VOCs), such as hydrocarbon fuels and industrial solvents. It can model the one-, two-, or three-dimensional migration of non-aqueous phase liquids (NAPLs) through the unsaturated and saturated zones, the formation of an oil lens on the water table, the dissolution and subsequent transport of VOCs in groundwater, as well as the vaporization and migration of VOCs in the interstitial air of the unsaturated zone, and the reversible sorption of VOCs on the rock matrix of a porous medium. TMVOC accounts for differences in aqueous solubility and volatility of different VOCs that may be present in a NAPL. Thermal remediation treatments such as steam injection or electric resistance heating and associated phase change and flow effects can also be modeled. A simple half-life model for biodegradation is included as well.

  3. Lubrication of starch in ionic liquid-water mixtures: Soluble carbohydrate polymers form a boundary film on hydrophobic surfaces.

    PubMed

    Yakubov, Gleb E; Zhong, Lei; Li, Ming; Boehm, Michael W; Xie, Fengwei; Beattie, David A; Halley, Peter J; Stokes, Jason R

    2015-11-20

    Soluble starch polymers are shown to enhance the lubrication of ionic liquid-water solvent mixtures in low-pressure tribological contacts between hydrophobic substrates. A fraction of starch polymers become highly soluble in 1-ethyl-3-methylimidazolium acetate (EMIMAc)-water solvents with ionic liquid fraction ≥60wt%. In 65wt% EMIMAc, a small amount of soluble starch (0.33wt%) reduces the boundary friction coefficient by up to a third in comparison to that of the solvent. This low-friction is associated with a nanometre thick film (ca. 2nm) formed from the amylose fraction of the starch. In addition, under conditions where there is a mixture of insoluble starch particles and solubilised starch polymers, it is found that the presence of dissolved amylose enhances the lubrication of starch suspensions between roughened substrates. These findings open up the possibility of utilising starch biopolymers, as well as other hydrocolloids, for enhancing the performance of ionic liquid lubricants.

  4. Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory

    NASA Astrophysics Data System (ADS)

    Daschakraborty, Snehasis; Biswas, Ranjit

    2016-03-01

    A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (xIL). At higher IL concentrations (xIL > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with xIL, deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the xIL dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume ( Vmol dip ) for the rotating dipolar moiety in the present theory and suggests that only a fraction of Vmol dip is involved at high xIL. Expectedly, nice agreement between theory and experiments appears when experimental

  5. Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory.

    PubMed

    Daschakraborty, Snehasis; Biswas, Ranjit

    2016-03-14

    A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (x(IL)). At higher IL concentrations (x(IL) > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with x(IL), deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the x(IL) dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume (V(mol)(dip)) for the rotating dipolar moiety in the present theory and suggests that only a fraction of V(mol)(dip) is involved at high x(IL). Expectedly, nice agreement between theory and experiments appears when

  6. Infrared spectroscopy of acetone-water liquid mixtures. I. Factor analysis

    NASA Astrophysics Data System (ADS)

    Max, Jean-Joseph; Chapados, Camille

    2003-09-01

    Acetone and water mixtures covering the whole solubility range were measured by Fourier transform infrared attenuated total reflectance spectroscopy. In this system, only water can supply the hydrogen atoms necessary for hydrogen bonding. Using spectral windowing with factor analysis (FA), 10 principal factors were retrieved, five water and five acetone. Hydrogen bonding is observed on the carbonyl stretch band as water is introduced in the solution, redshifting the band further from its gas position than that observed in pure liquid acetone. This indicates that the hydrogen bonding is stronger than the acetone dipole-dipole interactions because it overrides them. A water molecule isolated in acetone is twice H bonded through its two H atoms; although both OH groups are H-bond donors, the OH stretch band is less redshifted (˜138 cm-1) than that of pure liquid water (˜401 cm-1). This is attributable to the two lone electron pairs remaining on the oxygen atom that sustain a large part of the OH valence bond strength. Hydrogen bonds on the water oxygen weaken both its OH valence bonds and modify the OH stretch band when water is added to the solution. The oxygen atoms of both water and acetone can accept 0, 1, and 2 H bonds given by water to yield three water and three acetone situations. Since these six situations are far less than the 10 principal factors retrieved by FA, other perturbations must be present to account for the difference. Although acetone and water are intermingled through H bonds, hydrates in the sense of an acetone molecule sequestering a number of water molecules or altering the H-bonding water network are not present because the principal factors evolve independently.

  7. Molecular dynamics simulation of nanostructural organization in ionic liquid/water mixtures.

    PubMed

    Jiang, Wei; Wang, Yanting; Voth, Gregory A

    2007-05-10

    Molecular dynamics simulations have been carried out to investigate nanostructural organization in mixtures of 1-octyl-3-methylimidazolium nitrate ionic liquid and water at multiple water concentrations. Evolution of the polar network, water network, and micelle structures is visualized and analyzed via partial radial distribution functions. The calculated static partial structure factors show that within the range of water contents examined, polar networks, water networks, and micelles possess an approximately invariant characteristic length at around 20 A. Furthermore, the above calculations point out that, as the amount of water increases, the polar network is continuously broken up (screened) by the intruding water, while the structural organization of the water network and the micelle exhibits a turnover. At the turnover point, the most ordered micelle (cation-cation) structure and water (water-anion-water) network are formed. Thereafter, the structural organization abates drastically, and only loose micelle structure exists due to the dominant water-water interactions. The simulated turnover of structural organization agrees with the sharpest peak in the experimentally obtained structure factor in aqueous solutions of similar ionic liquids; the simulated water structure reveals that water can form liquidlike associated aggregates due to the planar symmetry and strong basicity of NO(3)-, in agreement with experiment. The turnover of structural organization of micelles results from the persistent competition between the hydrophobic interactions of the nonpolar groups and the breakup of the charged polar network with increasing water content, whereas the turnover of the water network results from the competition between the water-water and water-anion interactions.

  8. Unusual solvatochromic absorbance probe behaviour within mixtures of poly(ethylene glycol)-400 + ionic liquid, [bmim][Tf2N

    NASA Astrophysics Data System (ADS)

    Ali, Anwar; Ali, Maroof; Malik, Nisar Ahmad; Uzair, Sahar

    2014-03-01

    The potentially green solvents made up of ionic liquids (ILs) and poly(ethylene glycols) may have wide range of the applications in many chemical and biochemical fields. In the present work, solvatochromic absorbance probe behaviour is used to assess the physicochemical properties of the mixtures composed of PEG-400 + IL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][Tf2N]. Lowest energy intramolecular charge-transfer absorbance maxima of a betaine dye, i.e., ETN , indicates the dipolarity/polarizability and/or hydrogen-bond donating (HBD) acidity of the [bmim][Tf2N] + PEG-400 mixtures to be even higher than that of neat [bmim][Tf2N], the solution component with higher dipolarity/polarizability and/or HBD acidity. Dipolarity/polarizability (π∗) obtained separately from the electronic absorbance response of probe N,N-diethyl-4-nitroaniline, and the HBD acidity (α) of PEG-400 + [bmim][Tf2N] mixtures are also observed to be anomalously high. A comparative study of the PEG + IL mixtures has also been done with PEG-400 + molecular organic solvents (protic polar [methanol], aprotic polar [N,N-dimethylformamide], and non polar, [benzene]) mixtures, but these mixtures do not show this type of unusual behaviour. A four-parameter simplified combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation is shown to satisfactorily predict the solvatochromic parameters within PEG-400 + different solvent mixtures.

  9. Phase conversion and interface growth in phase-separated 3He - 4He liquid mixtures

    NASA Astrophysics Data System (ADS)

    Abe, Haruka; Satoh, Takeo; Burmistrov, Serguei N.

    2005-10-01

    We have developed a method for measuring the transmission coefficient of a sound propagating through the interface in phase-separated He3-He4 liquid mixtures. The method and the results are described with discussions by examining the phase-conversion process of He3 quasiparticles driven to flow across the interface. From the data, we have determined the kinetic growth coefficient of the interface, ξ(T,P,ω) , as a function of temperature, pressure, and frequency. The temperature range of the present investigation is about 2-100mK at the pressure mainly around 1bar with sound frequency 9.64, 14.4, and 32.4MHz . The main specific features observed for the kinetic growth coefficient are, as follows: (i) there is a maximum at some temperature Tm(ω) depending on the frequency, (ii) above Tm(ω) , ξ decreases with the increase of temperature as ∝ω5/2T-3 , and (iii) below Tm(ω) , ξ becomes frequency independent and diminishes as a cube of temperature, T3 .

  10. A Method for Microscale Combustion of Near Stoichiometric Energy Dense Liquid Fuel Mixtures

    NASA Astrophysics Data System (ADS)

    Tolmachoff, E. D.; Allmon, W. R.; Waits, C. M.

    2013-12-01

    This paper reports on the potential of a heterogeneous/homogeneous (HH) reactor for use as a fuel-flexible heat source, meeting the needs of the next generation of high temperature thermal-to-electric (TEC) portable power converters. In this class of reactor, low activation energy catalytic reactions provide a means to stabilize high activation energy homogeneous reactions. Diffusion limited surface reactions play a critical role in HH reactor operation. Surface conversion must be sufficiently fast to generate the high temperatures (~1000 K) necessary to initiate gas phase reactions. Therefore, fuel diffusivity and the reactor dimension are important parameters in governing HH reactor operation. We examine the performance of an HH reactor fuelled by propane and n-dodecane, representing two extremes of liquid hydrocarbon diffusivity, as a function of confining reactor dimension. Unburned fuel/air mixtures are close to stoichiometric, which is an important factor in minimizing the amount of excess air and, therefore, balance of plant energy costs. At moderate levels of confinement, the reactor is capable producing high, uniform temperatures for both fuels.

  11. Adsorption from n-heptane/benzene liquid mixture on acid leached bentonite powders

    NASA Astrophysics Data System (ADS)

    Sarıkaya, Yüksel; Baykal, Mehmet; Önal, Müşerref; Yener, Nilgün

    2013-10-01

    In this study, adsorption excess isotherms of n-heptane/benzene liquid mixture on hydrochloric acid leached bentonite powders were determined. Adsorptions were conducted at 25 °C for 48 h. Experimental results were evaluated with both Schay-Nagy (SN) and Everett (E) methods. Specific surface areas (SSN and SE) of the powders were calculated regarding monolayer adsorption capacity of the preferentially adsorbed benzene. Adsorption equilibrium constants (K ≫ 1) were obtained by the E-method. The SE and SSN values are closed to each other. SE-values were found much lower than the corresponding Brunauer, Emmett and Teller (BET)-values. This difference was discussed with respect to the interaction of adsorbed molecules with solid surface, their collision diameter, molar cross sectional surface area and orientation in dense monolayer. Even the maximum for the SE was not associated with the maxima for K and nanopore volume (V), their values changed approximately parallel to each other with respect to the HCl% by the leaching.

  12. Studies on the tosylation of cellulose in mixtures of ionic liquids and a co-solvent.

    PubMed

    Gericke, Martin; Schaller, Jens; Liebert, Tim; Fardim, Pedro; Meister, Frank; Heinze, Thomas

    2012-06-20

    The tosylation of cellulose in ionic liquids (ILs) was studied. Due to the beneficial effect of different co-solvents, the reaction could be performed at 25°C without the need of heating (in order to reduce viscosity) or cooling (in order to prevent side reactions). The effects of reaction parameters, such as time, molar ratio, and type of base, on the degree of substitution (DS) with tosyl- and chloro-deoxy groups as well as on the molecular weight were evaluated. Products with a DStosyl≤1.14 and DSCl≤0.16 were obtained and characterized by means of NMR- and FT-IR spectroscopy in order to evaluate their purity and distribution of functional groups within the modified anhydroglucose unit (AGU). Tosylation of cellulose in mixtures of IL and a co-solvent was found to result in predominant substitution at the primary hydroxyl group. Size exclusion chromatography (SEC) revealed only a moderate degradation of the polymer backbone at a reaction time of 4-8h. Finally, the nucleophilic displacement (SN) of tosyl- and chloro-deoxy groups by azide as well as recycling of the ILs was studied.

  13. Method of extracting iodine from liquid mixtures of iodine, water and hydrogen iodide

    DOEpatents

    Mysels, Karol J.

    1979-01-01

    The components of a liquid mixture consisting essentially of HI, water and at least about 50 w/o iodine are separated in a countercurrent extraction zone by treating with phosphoric acid containing at least about 90 w/o H.sub.3 PO.sub.4. The bottom stream from the extraction zone is substantially completely molten iodine, and the overhead stream contains water, HI, H.sub.3 PO.sub.4 and a small fraction of the amount of original iodine. When the water and HI are present in near-azeotropic proportions, there is particular advantage in feeding the overhead stream to an extractive distillation zone wherein it is treated with additional concentrated phosphoric acid to create an anhydrous HI vapor stream and bottoms which contain at least about 85 w/o H.sub.3 PO.sub.4. Concentration of these bottoms provides phosphoric acid infeed for both the countercurrent extraction zone and for the extractive distillation zone.

  14. Highly selective GC stationary phases consisting of binary mixtures of polymeric ionic liquids.

    PubMed

    Zhao, Qichao; Anderson, Jared L

    2010-01-01

    GC stationary phases composed of binary mixtures of two polymeric ionic liquids (PILs), namely, poly(1-vinyl-3-hexylimidazolium) bis[(trifluoromethyl)sulfonyl]imide (poly(ViHIm-NTf(2)))/poly(1-vinyl-3-hexylimidazolium) chloride (poly(ViHIm-Cl)) and poly(1-vinyl-3-hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl]imide (poly(ViHDIm-NTf(2)))/poly(1-vinyl-3-hexadecylimidazolium) chloride (poly(ViHDIm-Cl)), were evaluated in terms of their on-set bleed temperature and separation selectivity. A total of six neat or binary PIL stationary phases were characterized using the solvation parameter model to investigate the effects of the polymeric cation and anion and PIL composition on the system constants of the resulting stationary phases. The hydrogen bond basicity of the mixed poly(ViHIm-NTf(2))/poly(ViHIm-Cl) stationary phases was enriched linearly with the increase in the poly(ViHIm-Cl) content. Results revealed that tuning the composition of the stationary phase allowed for fine control of the retention factors and separation selectivity for alcohols and carboxylic acids as well as selected ketones, aldehydes, and aromatic compounds. A reversal of elution order was observed for particular classes of analytes when the weight percentage of the chloride-based PIL was increased.

  15. Modeling and dynamic properties of dual-chamber solid and liquid mixture vibration isolator

    NASA Astrophysics Data System (ADS)

    Li, F. S.; Chen, Q.; Zhou, J. H.

    2016-07-01

    The dual-chamber solid and liquid mixture (SALiM) vibration isolator, mainly proposed for vibration isolation of heavy machines with low frequency, consists of four principle parts: SALiM working media including elastic elements and incompressible oil, multi-layers bellows container, rigid reservoir and the oil tube connecting the two vessels. The isolation system under study is governed by a two-degrees-of-freedom (2-DOF) nonlinear equation including quadratic damping. Simplifying the nonlinear damping into viscous damping, the equivalent stiffness and damping model is derived from the equation for the response amplitude. Theoretical analysis and numerical simulation reveal that the isolator's stiffness and damping have multiple properties with different parameters, among which the effects of exciting frequency, vibrating amplitude, quadratic damping coefficient and equivalent stiffness of the two chambers on the isolator's dynamics are discussed in depth. Based on the boundary characteristics of stiffness and damping and the main causes for stiffness hardening effect, improvement strategies are proposed to obtain better dynamic properties. At last, experiments were implemented and the test results were generally consistent with the theoretical ones, which verified the reliability of the nonlinear dynamic model.

  16. DETERMINATION OF SOLID-LIQUID EQUILIBRIA DATA FOR MIXTURES OF HEAVY HYDROCARBONS IN A LIGHT SOLVENT

    SciTech Connect

    F.V. Hanson; J.V. Fletcher; Karthik R.

    2003-06-01

    A methodology was developed using an FT-IR spectroscopic technique to obtain solid-liquid equilibria (SLE) data for mixtures of heavy hydrocarbons in significantly lighter hydrocarbon diluents. SLE was examined in multiple Model Oils that were assembled to simulate waxes. The various Model oils were comprised of C-30 to C-44 hydrocarbons in decane. The FT-IR technique was used to identify the wax precipitation temperature (WPT). The DSC technique was also used in the identification of the onset of the two-phase equilibrium in this work. An additional Model oil made up of C-20 to C-30 hydrocarbons in decane was studied using the DSC experiment. The weight percent solid below the WPT was calculated using the FT-IR experimental results. The WPT and the weight percent solid below the WPT were predicted using an activity coefficient based thermodynamic model. The FT-IR spectroscopy method is found to successfully provide SLE data and also has several advantages over other laboratory-based methods.

  17. Morphology and Ionic Conductivity of Oriented Block Copolymer/Ionic Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Winey, Karen I.

    2015-03-01

    Ion-containing block copolymers with increased continuity and long-range order of ion-containing microdomains were prepared to probe the impact of grain boundaries and microdomain orientation on ion transport. We studied poly(styrene- b-methyl methacrylate) diblock copolymers swollen with 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonylimide) (SbMMA/IL), and characterized the thermal transitions, morphologies, and ionic conductivities by differential scanning calorimetry, small-angle X-ray scattering, and electrochemical impedance spectroscopy over a range of compositions. Two glass transition temperatures (Tgs) are observed, corresponding to PS and PMMA/IL microdomains, and Tg,PMMA/IL is modeled well by the Gordon-Taylor expression. SbMMA/IL films prepared by solvent evaporation exhibit strongly microphase-separated lamellar morphology with long-range order. Slower rates of solvent evaporation produce films with lamellae preferentially oriented to be in the plane. In-plane conductivities increase with both increasing ionic liquid content and with better parallel alignment of lamellae. The Sax and Ottino model will be used to compare the conductivity of SbMMA/IL with the homopolymer/IL mixture, PMMA/IL, and to discuss the ion transport mechanism.

  18. Effects of variation in chain length on ternary polymer electrolyte - Ionic liquid mixture - A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Raju, S. G.; Hariharan, Krishnan S.; Park, Da-Hye; Kang, HyoRang; Kolake, Subramanya Mayya

    2015-10-01

    Molecular dynamics (MD) simulations of ternary polymer electrolyte - ionic liquid mixtures are conducted using an all-atom model. N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CnMPy][TFSI], n = 1, 3, 6, 9) and polyethylene oxide (PEO) are used. Microscopic structure, energetics and dynamics of ionic liquid (IL) in these ternary mixtures are studied. Properties of these four pure IL are also calculated and compared to that in ternary mixtures. Interaction between pyrrolidinium cation and TFSI is stronger and there is larger propensity of ion-pair formation in ternary mixtures. Unlike the case in imidazolium IL, near neighbor structural correlation between TFSI reduces with increase in chain length on cation in both pure IL and ternary mixtures. Using spatial density maps, regions where PEO and TFSI interact with pyrrolidinium cation are identified. Oxygens of PEO are above and below the pyrrolidinium ring and away from the bulky alkyl groups whereas TFSI is present close to nitrogen atom of CnMPy. In pure IL, diffusion coefficient (D) of C3MPy is larger than of TFSI but D of C9MPy and C6MPy are larger than that of TFSI. The reasons for alkyl chain dependent phenomena are explored.

  19. The Amphiphilic Character of Cellulose Molecules in True Solution in Solvent Mixtures Containing Ionic Liquid and its Utilization in Emulsification

    NASA Astrophysics Data System (ADS)

    Napso, Sofia; Cohen, Yachin; Rein, Dmitry; Khalfin, Rafail; Szekely, Noemi

    2015-03-01

    Cellulose is the most abundant renewable material in nature that is utilized as a raw material for fabrication of synthetic products. Although it is not soluble in common solvents, there is significant interest in the use of solvent mixtures containing ionic liquids (IL) and polar organic solvents for cellulose dissolution. We present evidence for true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with an ionic liquid, using cryogenic transmission electron microscopy, small-angle neutron-, x-ray- and static light scattering. In particular, the measured low values of the molecular, gyration radius and persistence length indicate the absence of significant aggregation of the dissolved chains. We conjecture that the dissolved cellulose chains are amphiphilic. This can be inferred from the facile fabrication of cellulose-encapsulated colloidal oil-in-water or water-in-oil dispersions. This may be done by mixing water, oil and cellulose solution in an ionic liquid. A more practical alternative is to form first a hydrogel from the cellulose/ionic liquid solution by coagulation with water and applying it to sonicated water/oil or oil/water mixtures. Apparently the dissolution/ regeneration process affords higher mobility to the cellulose molecules so an encapsulation coating can be formed at the water-oil interface.

  20. New insight into phase equilibria involving imidazolium bistriflamide ionic liquids and their mixtures with alcohols and water.

    PubMed

    Pereiro, Ana B; Deive, Francisco J; Rodríguez, Ana; Ruivo, Diana; Canongia Lopes, José N; Esperança, José M S S; Rebelo, Luís P N

    2010-07-15

    The fluid phase equilibria (liquid-liquid demixing behavior (LLE)) of mixtures of ionic liquids of the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide family, [C(n)mim][NTf(2)], with 2-methylpropanol or n-octanol were investigated. Binary mixtures of [C(4)mim][NTf(2)] + alcohol and [C(6)mim][NTf(2)] + alcohol were compared to pseudobinary mixtures of (0.5[C(2)mim] + 0.5[C(6)mim])[NTf(2)] + alcohol and (0.5[C(2)mim] + 0.5[C(10)mim])[NTf(2)] + alcohol, respectively. Additionally, the presence of water in the studied alcohols or as a third component in the system was analyzed in order to check any possible deviation from the LLE observed for the anhydrous systems. Systems containing small fractions of ionic liquid show similar LLE between the corresponding binary and pseudobinary systems; however, large differences are observed in the presence of water when the IL mass fraction is increased.

  1. Excess Volumes and Excess Isentropic Compressibilities of Binary Liquid Mixtures of Trichloroethylene with Esters at 303.15 K

    NASA Astrophysics Data System (ADS)

    Ramanaiah, S.; Rao, C. Narasimha; Nagaraja, P.; Venkateswarlu, P.

    2015-11-01

    Exces volumes, VE, and excess isentropic compressibilities, κSE, have been reported as a function of composition for binary liquid mixtures of trichloroethylene with ethyl acetate, n-propyl acetate, and n-butyl acetate at 303.15 K. Isentropic compressibilities are calculated using measured sound speeds and density data for pure components and for binary mixtures. Excess volumes and excess isentropic compressibilities are found to be negative for the three systems studied over the entire composition range at 303.15 K, whereas these values become more negative with an increase of carbon chain length. The results are discussed in terms of intermolecular interactions between unlike molecules.

  2. CONDENSED MATTER: STRUCTURE, THERMAL AND MECHANICAL PROPERTIES: Rotational viscosity of a liquid crystal mixture: a fully atomistic molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Zhang, Ran; Peng, Zeng-Hui; Liu, Yong-Gang; Zheng, Zhi-Gang; Xuan, Li

    2009-10-01

    Fully atomistic molecular dynamics (MD) simulations at 293, 303 and 313 K have been performed for the four-component liquid crystal mixture, E7, using the software package Material Studio. Order parameters and orientational time correlation functions (TCFs) were calculated from MD trajectories. The rotational viscosity coefficients (RVCs) of the mixture were calculated using the Nemtsov-Zakharov and Fialkowski methods based on statistical-mechanical approaches. Temperature dependences of RVC and density were discussed in detail. Reasonable agreement between the simulated and experimental values was found.

  3. A theoretical and experimental chemist's joint view on hydrogen bonding in ionic liquids and their binary mixtures.

    PubMed

    Stark, Annegret; Brehm, Martin; Brüssel, Marc; Lehmann, Sebastian B C; Pensado, Alfonso S; Schöppke, Matthias; Kirchner, Barbara

    2014-01-01

    A combined experimental and theoretical approach including quantum chemistry tools and computational simulation techniques can provide a holistic description of the nature of the interactions present in ionic liquid media. The nature of hydrogen bonding in ionic liquids is an especially intriguing aspect, and it is affected by all types of interactions occurring in this media. Overall, these interactions represent a delicate balance of forces that influence the structure and dynamics, and hence the properties of ionic liquids. An understanding of the fundamental principles can be achieved only by a combination of computations and experimental work. In this contribution we show recent results shedding light on the nature of hydrogen bonding, for certain cases the formation of a three-dimensional network of hydrogen bonding, and its dynamics by comparing 1-ethyl-3-methylimidazolium based acetate, chloride and thiocyanate ionic liquids.A particularly interesting case to study hydrogen bonding and other interactions is the investigation of binary mixtures of ionic liquids of the type [cation1][anion1]/[cation1][anion2]. In these mixtures, competing interactions are to be expected. We present both a thorough property meta-analysis of the literature and new data covering a wide range of anions, i.e., mixtures of 1-ethyl-3-methylimidazolium acetate with either trifluoroacetate, tetrafluoroborate, methanesulfonate, or bis(trifluoromethanesulfonyl)imide. In most cases, ideal mixing behavior is found, a surprising result considering the multitude of interactions present. However, ideal mixing behavior allows for the prediction of properties such as density, refractive index, surface tension, and, in most cases, viscosity as function of molar composition. Furthermore, we show that the prediction of properties such as the density of binary ionic liquid mixtures is possible by making use of group contribution methods which were originally developed for less complex non

  4. New methods for determination of cinnarizine in mixture with piracetam by spectrodensitometry, spectrophotometry, and liquid chromatography.

    PubMed

    Metwally, Fadia H; Elzeany, B A; Darwish, H W

    2005-01-01

    Four new methods were developed and validated for the determination of cinnarizine HCl in its binary mixture with piracetam in pure and pharmaceutical preparations. The first one was a densitometric analysis that provides a simple and rapid method for the separation and quantification of cinnarizine HCI. The method depends on the quantitative densitometric evaluation of thin-layer chromatograms of cinnarizine HCI at 252 nm over concentration range of 1-6 microg/spot, with a mean accuracy of 100.05 +/- 0.91%. The second method was determination of the drug using a colorimetric method that utilizes the reaction of 3-methyl-benzothiazolin-2-one in the presence of FeCl3 as an oxidant. The green color of the resulting product was measured at 630 nm over concentration range 10-40 microg/mL, with a mean accuracy of 100.10 +/- 1.13%. The third method was a direct spectrophotometric determination of cinnarizine HCI at 252 nm over the concentration range 7-20 microg/mL, while piracetam was determined by derivative ratio spectrophotometry at 221.6 nm over concentration range 5-30 microg/mL, with a mean accuracy of 100.14 +/- 0.79 and 100.26 +/- 1.24% for cinnarizine HCI and piracetam, respectively. The last method was a liquid chromatography analysis of both cinnarizine HCI and piracetam, depending on quantitative evaluation of chromatograms of cinnarizine HCI and piracetam at 252 and 212 nm, respectively, over the concentration range 10-200 microg/mL for cinnarizine HCI and 20-500 microg/mL for piracetam, with a mean accuracy of 100.03 +/- 0.89 and 100.40 +/- 0.94% for cinnarizine HCI and piracetam, respectively. The proposed procedures were checked using laboratory-prepared mixtures and successfully applied for the analysis of their pharmaceutical preparations. The validity of the proposed procedures was further assessed by applying the standard addition technique. Recoveries were quantitative, and the results obtained agreed with those obtained by other reported methods.

  5. Photoinduced Multicomponent Reactions.

    PubMed

    Garbarino, Silvia; Ravelli, Davide; Protti, Stefano; Basso, Andrea

    2016-12-12

    The combination of multicomponent approaches with light-driven processes opens up new scenarios in the area of synthetic organic chemistry, where the need for sustainable, atom- and energy-efficient reactions is increasingly urgent. Photoinduced multicomponent reactions are still in their infancy, but significant developments in this area are expected in the near future.

  6. Multicomponent Syntheses of Macrocycles

    NASA Astrophysics Data System (ADS)

    Masson, Géraldine; Neuville, Luc; Bughin, Carine; Fayol, Aude; Zhu, Jieping

    How to access efficiently the macrocyclic structure remained to be a challenging synthetic topic. Although many elegant approaches/reactions have been developed, construction of diverse collection of macrocycles is still elusive. This chapter summarized the recently emerged research area dealing with multicomponent synthesis of macrocycles, with particular emphasis on the approach named "multiple multicomponent reaction using two bifunctional building blocks".

  7. An investigation of solute-solvent interactions in binary liquid mixtures of 3'-methoxyacetophenone: using Raman spectroscopy and DFT calculations.

    PubMed

    Yamini, D; Ramakrishnan, V

    2013-07-01

    Raman spectral measurements have been carried out for neat 3'-methoxy acetophenone (3'-MAP) and binary liquid mixtures of 3'-MAP in three solvents of different polarity. Also Density Functional Theory (DFT) geometry optimization and vibrational wavenumber calculation have been performed on monomer and dimer structures of 3'-MAP to analyze the experimentally observed Raman spectrum. Mulliken charge analysis has also been made on optimized geometries of 3'-MAP with solvents. The changes associated with the observed peak position, intensity and linewidth in the carbonyl stretching mode of 3'-MAP are explained as a consequence of intermolecular interactions between solute-solute and solute-solvent molecules. This analysis reports that the solute-solvent interaction is dominant in the case of binary liquid mixtures of 3'-MAP with ethanol compared to DMF and benzene.

  8. Shock Hugoniot equations of state for binary ideal (toluene/fluorobenzene) and nonideal (ethanol/water) liquid mixtures.

    PubMed

    Schulze, Peter A; Dang, Nhan C; Bolme, Cynthia A; Brown, Kathryn E; McGrane, Shawn D; Moore, David S

    2013-07-25

    Laser shock Hugoniot data were obtained using ultrafast dynamic ellipsometry (UDE) for both nonideal (ethanol/water solutions with mole percent χ(ethanol) = 0%, 3.4%, 5.4%, 7.5%, 9.7%, 11%, 18%, 33%, 56%, 100%) and ideal liquid mixtures (toluene/fluorobenzene solutions with mole percent χ(toluene) = 0%, 26.0%, 49.1%, 74.9%, 100%). The shock and particle velocities obtained from the UDE data were compared to the universal liquid Hugoniot (ULH) and to literature shock (plate impact) data where available. It was found that the water UDE data fit to a ULH-form equation suggests an intercept of 1.32 km/s, lower than the literature ambient sound speed in water of 1.495 km/s (Mijakovic et al. J. Mol. Liq. 2011, 164, 66-73). Similarly, the ethanol UDE data fit to a ULH-form equation suggests an intercept of 1.45 km/s, which lies above the literature ambient sound speed in ethanol of 1.14 km/s. Both the literature plate impact and UDE Hugoniot data lie below the ULH for water. Likewise, the literature plate impact and UDE Hugoniot data lie above the ULH for ethanol. The UDE Hugoniot data for the mixtures of water and ethanol cross the predictions of the ULH near the same concentration where the sound speed reaches a maximum. In contrast, the UDE data from the ideal liquids and their mixtures are well behaved and agree with ULH predictions across the concentration range. The deviations of the nonideal ethanol/water data from the ULH suggest that complex hydrogen bonding networks in ethanol/water mixtures alter the compressibility of the mixture.

  9. Atomistic Insight into Tetraalkylphosphonium-Bis(oxalato)borate Ionic Liquid/Water Mixtures. I. Local Microscopic Structure.

    PubMed

    Wang, Yong-Lei; Sarman, Sten; Glavatskih, Sergei; Antzutkin, Oleg N; Rutland, Mark W; Laaksonen, Aatto

    2015-04-23

    Atomistic simulations have been performed to investigate the microscopic structural organization of aqueous solutions of trihexyltetradecylphosphonium bis(oxalato)borate ([P6,6,6,14][BOB]) ionic liquid (IL). The evolution of the microscopic liquid structure and the local ionic organization of IL/water mixtures as a function of the water concentration is visualized and systematically analyzed via radial and spatial distribution functions, coordination numbers, hydrogen bond network, and water clustering analysis. The microscopic liquid structure in neat IL is characterized by a connected apolar network composed of the alkyl chains of [P6,6,6,14] cations and isolated polar domains consisting of the central segments of [P6,6,6,14] cations and [BOB] anions, and the corresponding local ionic environment is described by direct contact ion pairs. In IL/water mixtures with lower water mole fractions, the added water molecules are dispersed and embedded in cavities between neighboring ionic species and the local ionic structure is characterized by solvent-shared ion pairs through cation-water-anion triple complexes. With a gradual increase in the water concentration in IL/water mixtures, the added water molecules tend to aggregate and form small clusters, intermediate chain-like structures, large aggregates, and eventually a water network in water concentrated simulation systems. A further progressive dilution of IL/water mixtures leads to the formation of self-organized micelle-like aggregates characterized by a hydrophobic core and hydrophilic shell consisting of the central polar segments in [P6,6,6,14] cations and [BOB] anions in a highly branched water network. The striking structural evolution of the [P6,6,6,14][BOB] IL/water mixtures is rationalized by the competition between favorable hydrogen bonded interactions and strong electrostatic interactions between the polar segments in ionic species and the dispersion interactions between the hydrophobic alkyl chains in

  10. Molecular dynamics of a binary mixture of twist-bend nematic liquid crystal dimers studied by dielectric spectroscopy.

    PubMed

    Robles-Hernández, Beatriz; Sebastián, Nerea; Salud, Josep; Diez-Berart, Sergio; Dunmur, David A; Luckhurst, Geoffrey R; López, David O; de la Fuente, M Rosario

    2016-06-01

    We report a comprehensive dielectric characterization of a liquid crystalline binary mixture composed of the symmetric mesogenic dimer CB7CB and the nonsymmetric mesogenic dimer FFO9OCB. In addition to the high-temperature nematic phase, such a binary mixture shows a twist-bend nematic phase at room temperature which readily vitrifies on slow cooling. Changes in the conformational distribution of the dimers are reflected in the dielectric permittivity and successfully analyzed by means of an appropriate theoretical model. It is shown that the dielectric spectra of the mixture reflect the different molecular dipole properties of the components, resembling in the present case the characteristic dielectric spectra of nonsymmetric dimers. Comparison of the nematic and twist-bend nematic phases reveals that molecular dynamics are similar despite the difference in the molecular environment.

  11. Equation of state modeling of the phase equilibria of ionic liquid mixtures at low and high pressure.

    PubMed

    Karakatsani, Eirini K; Economou, Ioannis G; Kroon, Maaike C; Bermejo, Maria D; Peters, Cor J; Witkamp, Geert-Jan

    2008-10-28

    Accurate design of processes based on ionic liquids (ILs) requires knowledge of the phase behavior of the systems involved. In this work, the truncated perturbed chain polar statistical associating fluid theory (tPC-PSAFT) is used to correlate the phase behavior of binary and ternary IL mixtures. Both non-polar and polar solvents are examined, while methyl imidazolium ILs are used in all cases. tPC-PSAFT accounts explicitly for weak dispersion interactions, highly directive polar interactions between permanent dipolar and quadrupolar molecules and association between hydrogen bonding molecules. For mixtures of non-polar solvents, tPC-PSAFT predicts accurately the binary mixture data. For the case of polar solvents, a binary interaction parameter is fitted to the experimental data and the agreement between experiment and correlation is very good in all cases.

  12. Comparative Study of the Intermolecular Dynamics of Benzene/Ionic Liquid Mixtures and Benzyl Functionalized Ionic Liquids: Femtosecond OKE Spectroscopic Measurements

    NASA Astrophysics Data System (ADS)

    Quitevis, Edward; Xue, Lianjie; Tamas, George

    2014-03-01

    Ionic liquids (ILs) are salts with melting points below 100 °C that are comprised of an organic cation and an inorganic or organic anion. There is great interest in obtaining a molecular level understanding of their unique physical and chemical properties, of which one of them is their ability, despite being inherently polar liquids, to dissolve large quantities of nonpolar aromatic compounds. In order to understand further the solvation of aromatic molecules in ILs, we have performed optical effect (OKE) spectroscopic measurements on 1-benzyl-3-methylimidazolum bistriflate, 1,3-dibenzylimidazolum bistriflate and the corresponding 1:1 and 2:1 benzene/1,3-dimethylimazolium bistrifate (C6H6/C1C1) mixtures. In contrast to being free in benzene/IL mixtures, the benzene rings are tethered to the imidazolium ring via methylene linkages in the case of first two ILs. The intermolecular Kerr spectra indicate that the motion of the benzene rings becomes increasingly more restricted in going from neat benzene to benzene dissolved in 1,3-dimethylimazolium bistrifate to benzene rings tethered to the imidazolium ring. This restriction causes the Kerr spectra effectively to shift to higher frequency in going from neat liquid benzene to C6H6/C1C1 mixtures to benzylimidazolium ILs. This work was supported by NSF Grant CHE-1153077.

  13. Surface tension of binary liquid-vapor mixtures: A comparison of mean-field and scaling theories

    NASA Astrophysics Data System (ADS)

    Sahimi, Muhammad; Taylor, Byron N.

    1991-11-01

    We use two different methods to estimate surface tension of binary liquid-vapor mixtures of CO2 and a hydrocarbon near a critical point. The first method is based on the gradient theory, which is essentially a mean-field approximation to the problem that reduces the determination of the interface's structure and the surface tension to a boundary value problem. The theory's input is an equation of state of homogeneous fluid and the influence parameters of inhomogeneous fluid. The Peng-Robinson equation and a modification of it are used as the equation of state of homogeneous fluid. The second method is based on the concept of two-scale-factor universality which can predict the surface tension from the singularity in the thermodynamic properties of the bulk fluid. The inputs of the method are an equation of state and certain universal amplitude ratios near the critical point. As the equation of state, we use a modification of a model first proposed by Leung and Griffiths, and further developed by Moldover, Rainwater, and co-workers. We use the two models to examine in detail CO2+n -butane and CO2+n -decane mixtures. While both models provide accurate estimates of surface tension of CO2+n -butane mixtures, only the gradient theory can predict accurately surface tension of CO2+n -decane mixtures. Moreover, while the gradient theory and the Peng-Robinson equation of state use very few adjustable parameters (at most three parameters), calculation of surface tension based on two-scale-factor universality and the corresponding equation of state requires many adjustable parameters whose number has to be increased dramatically as the fluid mixture becomes more complex. We then use the gradient theory to predict surface tension of binary liquid-vapor mixtures of CO2 and benzene, cyclohexane, and n-hexadecane. In all cases, the predictions of the gradient theory are in good agreement with the available experimental data.

  14. Phase behaviors of binary mixtures composed of electron-rich and electron-poor triphenylene discotic liquid crystals

    NASA Astrophysics Data System (ADS)

    An, Lingling; Jing, Min; Xiao, Bo; Bai, Xiao-Yan; Zeng, Qing-Dao; Zhao, Ke-Qing

    2016-09-01

    Disk-like liquid crystals (DLCs) can self-assemble to ordered columnar mesophases and are intriguing one-dimensional organic semiconductors with high charge carrier mobility. To improve their applicable property of mesomorphic temperature ranges, we exploit the binary mixtures of electronic donor-acceptor DLC materials. The electron-rich 2,3,6,7,10,11-hexakis(alkoxy)triphenylenes (C4, C6, C8, C10, C12) and an electron-deficient tetrapentyl triphenylene-2,3,6,10-tetracarboxylate have been prepared and their binary mixtures have been investigated. The mesomorphism of the 1:1 (molar ratio) mixtures has been characterized by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and small angel x-ray scattering (SAXS). The self-assembled monolayer structure of a discogen on a solid-liquid interface has been imaged by the high resolution scanning tunneling microscopy (STM). The match of peripheral chain length has important influence on the mesomorphism of the binary mixtures. Project supported by the National Natural Science Foundation of China (Grant Nos. 51273133 and 51443004).

  15. Column performance study of different variants of liquid chromatographic technique: an application on pharmaceutical ternary mixtures containing tetryzoline.

    PubMed

    Salem, Hesham; Hassan, Nagiba Y; Lotfy, Hayam M; Saleh, Sarah S

    2015-01-01

    High-performance liquid chromatography (HPLC), ultra-performance liquid chromatography (UPLC) and rapid resolution liquid chromatographic (RRLC) methods have been developed and validated for the separation and quantitation of both or either of two ternary mixtures present in ophthalmic solutions. The first mixture contains chloramphenicol, dexamethasone sodium phosphate and tetryzoline HCl (TZH); while the second one contains ofloxacin, prednisolone acetate and TZH. Both preparations contain benzalkonium chloride as a preservative. The columns used were a HPLC column (C18 5 µm particle size), a RRLC column (C18 2.6 µm particle size) and a UPLC column (C18 1.7 µm particle size). A comparative study was conducted to illustrate the effect of the change in column particle size and dimensions on the other chromatographic conditions, backpressure and the separation of both ternary mixtures. The methods were validated as per ICH guidelines where accuracy, repeatability, interday precision and robustness were found to be within the acceptable limits. The RRLC column provided shorter run time and better resolution than HPLC, while the UPLC column gave the shortest run time for all columns. The RRLC column resulted in minimum backpressure, so it could be used with any HPLC instrument, which makes the method more practical and economic. The results obtained from the proposed methods were statistically compared with official ones where no significant difference was observed.

  16. Phase equilibrium of liquid mixtures: Experimental and modeled data using statistical associating fluid theory for potential of variable range approach

    NASA Astrophysics Data System (ADS)

    Giner, Beatriz; Bandrés, Isabel; Carmen López, M.; Lafuente, Carlos; Galindo, Amparo

    2007-10-01

    A study of the phase equilibrium (experimental and modeled) of mixtures formed by a cyclic ether and haloalkanes has been derived. Experimental data for the isothermal vapor liquid equilibrium of mixtures formed by tetrahydrofuran and tetrahydropyran and isomeric chlorobutanes at temperatures of 298.15, 313.15, and 328.15K are presented. Experimental results have been discussed in terms of both molecular characteristics of pure compounds and potential intermolecular interaction between them using thermodynamic information of the mixtures obtained earlier. The statistical associating fluid theory for potential of variable range (SAFT-VR) approach together with standard combining rules without adjustable parameters has been used to model the phase equilibrium. Good agreement between experiment and the prediction is found with such a model. Mean absolute deviations for pressures are of the order of 1kPa, while less than 0.013mole fraction for vapor phase compositions. In order to improve the results obtained, a new modeling has been carried out by introducing a unique transferable parameter kij, which modifies the strength of the dispersion interaction between unlike components in the mixtures, and is valid for all the studied mixtures being not temperature or pressure dependent. This parameter together with the SAFT-VR approach provides a description of the vapor-liquid equilibrium of the mixtures that is in excellent agreement with the experimental data for most cases. The absolute deviations are of the order of 0.005mole fraction for vapor phase compositions and less than 0.3kPa for pressure, excepting for mixtures containing 2-chloro-2-methylpropane which deviations for pressure are larger. Results obtained in this work in the modeling of the phase equilibrium with the SAFT-VR equation of state have been compared to the ones obtained in a previous study when the approach was used to model similar mixtures with clear differences in the thermodynamic behavior. We

  17. Diffusion Of Mass In Evaporating Multicomponent Drops

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Harstad, Kenneth G.

    1992-01-01

    Report summarizes study of diffusion of mass and related phenomena occurring in evaporation of dense and dilute clusters of drops of multicomponent liquids intended to represent fuels as oil, kerosene, and gasoline. Cluster represented by simplified mathematical model, including global conservation equations for entire cluster and conditions on boundary between cluster and ambient gas. Differential equations of model integrated numerically. One of series of reports by same authors discussing evaporation and combustion of sprayed liquid fuels.

  18. Vapor-liquid equilibria of binary mixtures of alkanols with alkanes from atmospheric pressure to the critical point

    NASA Astrophysics Data System (ADS)

    Orbey, H.; Sandier, S. I.

    1995-05-01

    A reformulated version of the Wong-Sandler mixing rule and the Peng-Robinson equation of state are used for the correlation and prediction of the vapor-liquid equilibrium of several alkanol + alkane binary systems. The description of these mixtures provides a stringent test since cubic equations of state with conventional mixing rules usually predict false liquid-liquid splits for such systems. For all systems, the model parameters used were fit to data on the lowest-temperature isotherm and then higher-temperature isotherms were successfully predicted with those parameters. False phase splitting was avoided by using a constrained parameter fit. For highly asymmetric (in size) alkanol+alkane binaries four parameters were necessary for an accurate representation of the data, while for less asymmetric alkanol + alkane binaries only two parameters were used.

  19. Surface excess isotherms of organic solvent mixtures in a system made of liquid carbon dioxide and a silicagel surface.

    PubMed

    Vajda, Péter; Guiochon, Georges

    2013-09-20

    The surface excess isotherms of methanol, ethanol, 2-propanol and acetonitrile from liquid carbon dioxide on a silica adsorbent were measured, using the minor disturbance method. The minor disturbance peaks - or system peaks - of each organic modifier were recorded using UV-detection in the whole composition range of the organic/liquid carbon dioxide mixtures, the whole composition range was completed by injecting the modifiers into pure liquid carbon dioxide as well. The excess isotherms were calculated based on the retention of the organic solvent signals. Our results show an enrichment of the organic modifier at the adsorbent surface. The alcohols show multilayer adsorption with an extremely high retention on the silica surface while acetonitrile shows weaker interactions and only a slight trend toward the formation of a multilayer above the surface.

  20. Enzymatic catalysis in heterogenous mixtures of substrates: The role of the liquid phase and the effects of "Adjuvants".

    PubMed

    López-Fandiño, R; Gill, I; Vulfson, E N

    1994-05-01

    The physicochemical mechanism of protease-catalyzed peptide synthesis in heterogenous etuectic mixtures of substrates has been examined by a combination of microscopic techniques. Using a number of model reactions of dipeptide amide synthesis, it was determined that liquid phase catalysis was mostly, if not exclusively, responsible for the observed conversion of substrates. Furthermore, the formation of liquid or semiliquid eutectics was an important requirement for the occurrence of those reactions where both substrates were solids in the pure state. The addition of small quantities of hydrophilic solvents (adjuvants) often resulted in significat improvements in the rates and yields of the reactions. This was due to the ability of these adjuvants to promote the formation of eutectics, thereby increasing the proportion, as well as affecting the composition the properties, as well as affecting the composition and properties of the liquid phase. (c) 1994 John Wiley & Sons, Inc.

  1. Modeling the evaporation of sessile multi-component droplets.

    PubMed

    Diddens, C; Kuerten, J G M; van der Geld, C W M; Wijshoff, H M A

    2017-02-01

    We extended a mathematical model for the drying of sessile droplets, based on the lubrication approximation, to binary mixture droplets. This extension is relevant for e.g. inkjet printing applications, where ink consisting of several components are used. The extension involves the generalization of an established vapor diffusion-limited evaporation model to multi-component mixtures. The different volatilities of the liquid components generate a composition gradient at the liquid-air interface. The model takes the composition-dependence of the mass density, viscosity, surface tension, mutual diffusion coefficient and thermodynamic activities into account. This leads to a variety of effects ranging from solutal Marangoni flow over deviations from the typical spherical cap shape to an entrapped residual amount of the more volatile component at later stages of the drying. These aspects are discussed in detail on the basis of the numerical results for water-glycerol and water-ethanol droplets. The results show good agreement with experimental findings. Finally, the accuracy of the lubrication approximation is assessed by comparison with a finite element method.

  2. Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

  3. Vapor-Liquid Equilibrium in the Mixture Cyclohexanone C6H10O + C6H12O Cyclohexanol (EVLM1111, LB5657_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture Cyclohexanone C6H10O + C6H12O Cyclohexanol (EVLM1111, LB5657_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  4. Vapor-Liquid Equilibrium in the Mixture 1-Chlorobutane C4H9Cl + C6H10O Cyclohexanone (EVLM1111, LB5637_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1-Chlorobutane C4H9Cl + C6H10O Cyclohexanone (EVLM1111, LB5637_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  5. Vapor-Liquid Equilibrium in the Mixture 1,2-Dichloroethane C2H4Cl2 + C6H10O Cyclohexanone (EVLM1111, LB5653_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,2-Dichloroethane C2H4Cl2 + C6H10O Cyclohexanone (EVLM1111, LB5653_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  6. Flow pattern changes influenced by variation of viscosities of a heterogeneous gas-liquid mixture flow in a vertical channel

    SciTech Connect

    Keska, Jerry K.; Hincapie, Juan; Jones, Richard

    2011-02-15

    In the steady-state flow of a heterogeneous mixture such as an air-liquid mixture, the velocity and void fraction are space- and time-dependent parameters. These parameters are the most fundamental in the analysis and description of a multiphase flow. The determination of flow patterns in an objective way is extremely critical, since this is directly related to sudden changes in spatial and temporal changes of the random like characteristic of concentration. Flow patterns can be described by concentration signals in time, amplitude, and frequency domains. Despite the vital importance and countless attempts to solve or incorporate the flow pattern phenomena into multiphase models, it has still been a very challenging topic in the scientific community since the 1940's and has not yet reached a satisfactory solution. This paper reports the experimental results of the impact of fluid viscosity on flow patterns for two-phase flow. Two-phase flow was created in laboratory equipment using air and liquid as phase medium. The liquid properties were changed by using variable concentrations of glycerol in water mixture which generated a wide-range of dynamic viscosities ranging from 1 to 1060 MPa s. The in situ spatial concentration vs. liquid viscosity and airflow velocity of two-phase flow in a vertical ID=50.8 mm pipe were measured using two concomitant computer-aided measurement systems. After acquiring data, the in situ special concentration signals were analyzed in time (spatial concentration and RMS of spatial concentration vs. time), amplitude (PDF and CPDF), and frequency (PSD and CPSD) domains that documented broad flow pattern changes caused by the fluid viscosity and air velocity changes. (author)

  7. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    NASA Astrophysics Data System (ADS)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Cabeza, Oscar; Fedorov, Maxim; Lynden-Bell, Ruth M.; Gallego, Luis J.; Varela, Luis M.

    2015-09-01

    We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF6]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO3]- and [PF6]- anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca2+ cations. No qualitative difference with

  8. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    SciTech Connect

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.; Varela, Luis M.; Lynden-Bell, Ruth M.

    2015-09-28

    We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2

  9. Spatially resolved multicomponent gels

    NASA Astrophysics Data System (ADS)

    Draper, Emily R.; Eden, Edward G. B.; McDonald, Tom O.; Adams, Dave J.

    2015-10-01

    Multicomponent supramolecular systems could be used to prepare exciting new functional materials, but it is often challenging to control the assembly across multiple length scales. Here we report a simple approach to forming patterned, spatially resolved multicomponent supramolecular hydrogels. A multicomponent gel is first formed from two low-molecular-weight gelators and consists of two types of fibre, each formed by only one gelator. One type of fibre in this ‘self-sorted network’ is then removed selectively by a light-triggered gel-to-sol transition. We show that the remaining network has the same mechanical properties as it would have done if it initially formed alone. The selective irradiation of sections of the gel through a mask leads to the formation of patterned multicomponent networks, in which either one or two networks can be present at a particular position with a high degree of spatial control.

  10. BEHAVIOR OF SURFACTANT MIXTURES AT SOLID/LIQUID AND OIL/LIQUID INTERFACES IN CHEMICAL FLOODING SYSTEMS

    SciTech Connect

    Prof. P. Somasundaran

    2002-09-30

    The aim of the project is to develop and evaluate efficient novel surfactant mixtures for enhanced oil recovery. Surfactant loss by adsorption or precipitation depends to a great extent on the type of surfactant complexes and aggregates formed. Such information as well as techniques to generate the information is lacking currently particularly for surfactant mixtures and surfactant/polymer systems. A novel analytical centrifuge application is explored during the last period to generate information on structures-performance relationship for different surfactant aggregates in solution and, in turn, at interfaces. To use analytical untracentrifuge for surfactant mixtures, information on partial specific volumes of single surfactants and their mixtures is required. Towards this purpose, surface tension and density measurements were performed to determine critical micellar concentrations (cmc), partial specific volumes of n-dodecyl-{beta}-Dmaltoside (DM), nonyl phenol ethoxylated decyl ether (NP-10) and their 1:1 mixtures at 25 C. Durchschlag's theoretical calculation method was adopted to calculate the partial specific volumes. Effects of temperature and mixing, as well as methods used for estimation on micellization and partial specific volumes were studied during the current period. Surface tension results revealed no interaction between the two surfactants in mixed micelles. Partial specific volume measurements also indicated no interaction in mixed micelles. Maximum adsorption density, area per molecule and free energy of micellization were also calculated. Partial specific volumes were estimated by two experimental methods: d{sub {rho}}/dc and V{sub {sigma}}. The difference between the results of using the two methods is within 0.5% deviation. It was found that the partial specific volume is concentration dependent and sensitive to changes in temperature. The information generated in this study will be used for the study of surfactant aggregate mass distribution

  11. Surface structures of equimolar mixtures of imidazolium-based ionic liquids using high-resolution Rutherford backscattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakajima, Kaoru; Oshima, Shinichi; Suzuki, Motofumi; Kimura, Kenji

    2012-11-01

    Surface structures of equimolar mixtures of imidazolium-based ionic liquids (ILs) having a common cation (1-butyl-3-methylimidazolium ([C4MIM]) or 1-hexyl-3-methylimidazolium ([C6MIM])) and different anions (bis(trifluoromethanesulfonyl)imide ([TFSI]), hexafluorophosphate ([PF6]) or chlorine) are studied using high-resolution Rutherford backscattering spectroscopy (HRBS). Both cations and anions have the same preferential orientations at the surface as in the pure ILs. In the mixture, the larger anion is located shallower than the smaller anion. The [TFSI] anion is slightly enriched at the surface relative to [PF6] with coverage of ~ 60% for the equimolar mixtures of [C4(6)MIM] [TFSI] and [C4(6)MIM] [PF6]. No surface segregation is observed for [C6MIM] [TFSI]0.5[Cl]0.5 and [C6MIM] [PF6]0.5[Cl]0.5. These results are different from the recent TOF-SIMS measurement where very strong surface segregation of [TFSI] was concluded for the mixture of [C4MIM] [TFSI] and [C4MIM] [PF6].

  12. Features of liquid mixtures separation in large-scale distillation columns with structured packing. New ideas and approaches

    NASA Astrophysics Data System (ADS)

    Pavlenko, A. N.; Zhukov, V. E.; Pecherkin, N. I.; Li, X.; Sui, H.

    2016-10-01

    Negative vapor stratification along the height of distillation column caused by different density of vapor mixture components and higher temperature at the column bottom, leads to formation of large-scale maldistribution of temperature and mixture composition over the column cross-section even at uniform irrigation of the structured packing. Experimental results concerning the dynamic effect of packing irrigation on separation efficiency of the two-component mixture of R-21 and R-114 are presented in this paper. The structured packing Zulser 350Y was installed in the distillation column with the diameter of 0.9 m. Experiments were carried out on the 10- and 19-layer packing with an overall height of 2.1 and 4 m, respectively. The liquid distributor with independently controlled 126 valves for each irrigation point, developed by the authors, was used for packing irrigation. The experiments showed that the periodic impact of the irrigation system on the large-scale non-uniformity of mixture composition, formed in the packing, could significantly affect the distribution of flow parameters over the cross-section and height of the mass transfer unit. Essentially nonuniform periodic irrigation of the packing can improve the separation efficiency of the column within 20%, if the switching periods are comparable with the times of formation of large-scale non-uniformity.

  13. Time-derivative preconditioning method for multicomponent flow

    NASA Astrophysics Data System (ADS)

    Housman, Jeffrey Allen

    A time-derivative preconditioned system of equations suitable for the numerical simulation of single component and multicomponent inviscid flows at all speeds is formulated. The system is shown to be hyperbolic in time and remain well-posed at low Mach numbers, allowing an efficient time marching solution strategy to be utilized from transonic to incompressible flow speeds. For multicomponent flow at low speed, a preconditioned nonconservative discretization scheme is described which preserves pressure and velocity equilibrium across fluid interfaces, handles sharp liquid/gas interfaces with large density ratios, while remaining well-conditioned for time marching methods. The method is then extended to transonic and supersonic flows using a hybrid conservative/nonconservative formulation which retains the pressure/velocity equilibrium property and converges to the correct weak solution when shocks are present. In order to apply the proposed model to complex flow applications, the overset grid methodology is used where the equations are transformed to a nonorthogonal curvilinear coordinate system and discretized on structured body-fitted curvilinear grids. The multicomponent model and its extension to homogeneous multiphase mixtures is discussed and the hyperbolicity of the governing equations is demonstrated. Low Mach number perturbation analysis is then performed on the system of equations and a local time-derivative preconditioning matrix is derived allowing time marching numerical methods to remain efficient at low speeds. Next, a particular time marching numerical method is presented along with three discretization schemes for the convective terms. These include a conservative preconditioned Roe type method, a nonconservative preconditioned Split Coefficient Matrix (SCM) method, and hybrid formulation which combines the conservative and nonconservative schemes using a simple switching function. A characteristic boundary treatment which includes time

  14. Molecular dynamics simulation of the structure and dynamics of water-1-alkyl-3-methylimidazolium ionic liquid mixtures.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M

    2011-06-02

    We have performed extensive molecular dynamic simulations to analyze the influence of cation and anion natures, and of water concentration, on the structure and dynamics of water-1-alkyl-3-methylimidazolium ionic liquid mixtures. The dependence on water concentration of the radial distribution functions, coordination numbers, and hydrogen bonding degree between the different species has been systematically analyzed for different lengths of the cation alkyl chain (alkyl = ethyl, butyl, hexyl, and octyl) and several counterions. These include two halogens of different sizes and positions in Hoffmeister series, Cl(-) and Br(-), and the highly hydrophobic inorganic anion PF(6)(-) throughout its whole solubility regime. The formation of water clusters in the mixture has been verified, and the influences of both anion hydrophobicity and cation chain length on the structure and size of these clusters have been analyzed. The water cluster size is shown to be relatively independent of the cation chain length, but strongly dependent on the hydrophobicity of the anion, which also determines critically the network formation of water and therefore the miscibility of the ionic liquid. The greater influence of the anion relative to the cation one is seen to be reflected in all the analyzed physical properties. Finally, single-particle dynamics in IL-water mixtures is considered, obtaining the self-diffusion coefficients and the velocity autocorrelation functions of water molecules in the mixture, and analyzing the effect of cation, anion, and water concentration on the duration of the ballistic regime and on the time of transition to the diffusive regime. Complex non-Markovian behavior was detected at intermediate times within an interval progressively shorter as water concentration increases.

  15. Digital holographic microscopy of phase separation in multicomponent lipid membranes

    NASA Astrophysics Data System (ADS)

    Farzam Rad, Vahideh; Moradi, Ali-Reza; Darudi, Ahmad; Tayebi, Lobat

    2016-12-01

    Lateral in-homogeneities in lipid compositions cause microdomains formation and change in the physical properties of biological membranes. With the presence of cholesterol and mixed species of lipids, phospholipid membranes segregate into lateral domains of liquid-ordered and liquid-disordered phases. Coupling of two-dimensional intralayer phase separations and interlayer liquid-crystalline ordering in multicomponent membranes has been previously demonstrated. By the use of digital holographic microscopy (DHMicroscopy), we quantitatively analyzed the volumetric dynamical behavior of such membranes. The specimens are lipid mixtures composed of sphingomyelin, cholesterol, and unsaturated phospholipid, 1,2-dioleoyl-sn-glycero-3-phosphocholine. DHMicroscopy in a transmission mode is an effective tool for quantitative visualization of phase objects. By deriving the associated phase changes, three-dimensional information on the morphology variation of lipid stacks at arbitrary time scales is obtained. Moreover, the thickness distribution of the object at demanded axial planes can be obtained by numerical focusing. Our results show that the volume evolution of lipid domains follows approximately the same universal growth law of previously reported area evolution. However, the thickness of the domains does not alter significantly by time; therefore, the volume evolution is mostly attributed to the changes in area dynamics. These results might be useful in the field of membrane-based functional materials.

  16. Improved electrolytes for Li-ion batteries: Mixtures of ionic liquid and organic electrolyte with enhanced safety and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Guerfi, A.; Dontigny, M.; Charest, P.; Petitclerc, M.; Lagacé, M.; Vijh, A.; Zaghib, K.

    Physical and electrochemical characteristics of Li-ion battery systems based on LiFePO 4 cathodes and graphite anodes with mixture electrolytes were investigated. The mixed electrolytes are based on an ionic liquid (IL), and organic solvents used in commercial batteries. We investigated a range of compositions to determine an optimum conductivity and non-flammability of the mixed electrolyte. This led us to examine mixtures of ILs with the organic electrolyte usually employed in commercial Li-ion batteries, i.e., ethylene carbonate (EC) and diethylene carbonate (DEC). The IL electrolyte consisted of (trifluoromethyl sulfonylimide) (TFSI) as anion and 1-ethyl-3-methyleimidazolium (EMI) as the cation. The physical and electrochemical properties of some of these mixtures showed an improvement characteristics compared to the constituents alone. The safety was improved with electrolyte mixtures; when IL content in the mixture is ≥40%, no flammability is observed. A stable SEI layer was obtained on the MCMB graphite anode in these mixed electrolytes, which is not obtained with IL containing the TFSI-anion. The high-rate capability of LiFePO 4 is similar in the organic electrolyte and the mixture with a composition of 1:1. The interface resistance of the LiFePO 4 cathode is stabilized when the IL is added to the electrolyte. A reversible capacity of 155 mAh g -1 at C/12 is obtained with cells having at least some organic electrolyte compared to only 124 mAh g -1 with pure IL. With increasing discharge rate, the capacity is maintained close to that in the organic solvent up to 2 C rate. At higher rates, the results with mixture electrolytes start to deviate from the pure organic electrolyte cell. The evaluation of the Li-ion cells; LiFePO 4//Li 4Ti 5O 12 with organic and, 40% mixture electrolytes showed good 1st CE at 98.7 and 93.0%, respectively. The power performance of both cell configurations is comparable up to 2 C rate. This study indicates that safety and

  17. Surface tension of binary mixtures of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids: experimental measurements and soft-SAFT modeling.

    PubMed

    Oliveira, M B; Domínguez-Pérez, M; Freire, M G; Llovell, F; Cabeza, O; Lopes-da-Silva, J A; Vega, L F; Coutinho, J A P

    2012-10-11

    Ionic liquids have attracted a large amount of interest in the past few years. One approach to better understand their peculiar nature and characteristics is through the analysis of their surface properties. Some research has provided novel information on the organization of pure ionic liquids at the vapor-liquid interface; yet, a systematic study on the surface properties of mixtures of ionic liquids and their organization at the surface has not previously been carried out in the literature. This work reports, for the first time, a comprehensive analysis of the surface organization of mixtures of ionic liquids constituted by 1-alkyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ionic liquids, [C(n)mim][NTf(2)]. The surface tension of mixtures composed of [C(4)mim][NTf(2)] + [C(n)mim][NTf(2)] (n = 1, 2, 5, 6, 8, and 10) was experimentally determined, at 298.2 K and atmospheric pressure, in the whole composition range. From the experimental data, the surface tension deviations and the relative Gibbs adsorption isotherms were estimated showing how the surface composition of an ionic liquid mixture differs from that of the liquid bulk and that the surface is enriched by the ionic liquid with the longest alkyl chain length. Finally, the soft-SAFT equation of state coupled with the density gradient theory (DGT) was used, for the first time, to successfully reproduce the surface tension experimental data of binary mixtures of ionic liquids using a molecular-based approach. In addition, the DGT was used to compute the density profiles of the two components across the interface, confirming the experimental results for the components distribution at the bulk and at the vapor-liquid interface.

  18. Stability of vortex lines in liquid {sup 3}He-{sup 4}He mixtures at zero temperature

    SciTech Connect

    Jezek, D.M.; Guilleumas, M.; Pi, M.; Barranco, M.

    1997-05-01

    At low temperatures and {sup 3}He concentrations below {approximately}6.6{percent}, there is experimental evidence about the existence in liquid helium mixtures of stable vortices with {sup 3}He-rich cores. When the system is either supersaturated or submitted to a tensile strength, vortices lose stability becoming metastable and eventually completely unstable, so that their cores freely expand. Within a density functional approach, we have determined the pressure-{sup 3}He concentration curve along which this instability appears at zero temperature. {copyright} {ital 1997} {ital The American Physical Society}

  19. Experimental determination and prediction of (solid+liquid) phase equilibria for binary mixtures of heavy alkanes and fatty acids

    NASA Astrophysics Data System (ADS)

    Benziane, Mokhtar; Khimeche, Kamel; Dahmani, Abdellah; Nezar, Sawsen; Trache, Djalal

    2012-06-01

    Solid-liquid equilibria for three binary mixtures, n-Eicosane (1) + Lauric acid (2), n-Tetracosane (1) + Stearic acid (2), and n-Octacosane (1) + Palmitic acid (2), were measured using a differential scanning calorimeter. Simple eutectic behaviour was observed for these systems. The experimental results were correlated by means of the modified UNIFAC (Larsen and Gmehling versions), UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.26 to 3.15 K and depend on the particular model used. The best solubility correlation was obtained with the UNIQUAC model.

  20. Effect of three-body interactions on the vapor-liquid phase equilibria of binary fluid mixtures.

    PubMed

    Wang, Liping; Sadus, Richard J

    2006-08-21

    Gibbs-Duhem Monte Carlo simulations are reported for the vapor-liquid phase coexistence of binary argon+krypton mixtures at different temperatures. The calculations employ accurate two-body potentials in addition to contributions from three-body dispersion interactions resulting from third-order triple-dipole interactions. A comparison is made with experiment that illustrates the role of three-body interactions on the phase envelope. In all cases the simulations represent genuine predictions with input parameters obtained independently from sources other than phase equilibria data. Two-body interactions alone are insufficient to adequately describe vapor-liquid coexistence. In contrast, the addition of three-body interactions results in very good agreement with experiment. In addition to the exact calculation of three-body interactions, calculations are reported with an approximate formula for three-body interactions, which also yields good results.

  1. Molecular dynamics simulation of the behaviour of water in nano-confined ionic liquid-water mixtures

    NASA Astrophysics Data System (ADS)

    Docampo-Álvarez, B.; Gómez-González, V.; Montes-Campos, H.; Otero-Mato, J. M.; Méndez-Morales, T.; Cabeza, O.; Gallego, L. J.; Lynden-Bell, R. M.; Ivaništšev, V. B.; Fedorov, M. V.; Varela, L. M.

    2016-11-01

    This work describes the behaviour of water molecules in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid under nanoconfinement, between graphene sheets. By means of molecular dynamics simulations, the adsorption of water molecules at the graphene surface is studied. A depletion of water molecules in the vicinity of the neutral and negatively charged graphene surfaces, and their adsorption at the positively charged surface are observed in line with the preferential hydration of the ionic liquid anions. The findings are appropriately described using a two-level statistical model. The confinement effect on the structure and dynamics of the mixtures is thoroughly analyzed using the density and the potential of mean force profiles, as well as by the vibrational densities of the states of water molecules near the graphene surface. The orientation of water molecules and the water-induced structural transitions in the layer closest to the graphene surface are also discussed.

  2. Thermodynamical and structural properties of binary mixtures of imidazolium chloride ionic liquids and alcohols from molecular simulation

    NASA Astrophysics Data System (ADS)

    Raabe, Gabriele; Köhler, Jürgen

    2008-10-01

    We have performed molecular dynamics simulations to determine the densities, excess energies of mixing, and structural properties of binary mixtures of the 1-alkyl-3-methylimidazolium chloride ionic liquids (ILs) [amim][Cl] and ethanol and 1-propanol in the temperature range from 298.15to363.15K. As in our previous work [J. Chem. Phys. 128, 154509 (2008)], our simulation studies are based on a united atom model from Liu et al. [Phys. Chem. Chem. Phys. 8, 1096 (2006)] for the 1-ethyl- and 1-butyl-3-methylimidazolium cations [emim+] and [bmim+], which we have extended to the 1-hexyl-3-methylimidazolium [hmim+] cation and combined with parameters of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] for the chloride anion [Cl-] and the force field by Khare et al. for the alcohols [J. Phys. Chem. B 108, 10071 (2004)]. With this, we provide both prediction for the densities of the mixtures that have mostly not been investigated experimentally yet and a molecular picture of the interactions between the alcohol molecules and the ions. The negative excess energies of all mixtures indicate an energetically favorable mixing of [amim][Cl] ILs and alcohols. To gain insight into the nonideality of the mixtures on the molecular level, we analyzed their local structures by radial and spatial distribution functions. These analyses show that the local ordering in these mixtures is determined by strong hydrogen-bond interactions between the chloride anion and the hydroxyls of the alcohols, enhanced interactions between the anion and the charged domain of the cation, and an increasing aggregation of the nonpolar alkyl tails of the alcohols and the cations with increasing cation size, which results in a segregation of polar and nonpolar domains.

  3. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols.

    PubMed

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K

    2017-02-14

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  4. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols

    NASA Astrophysics Data System (ADS)

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K.

    2017-02-01

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  5. Large-scale inhomogeneities in solutions of low molar mass compounds and mixtures of liquids: supramolecular structures or nanobubbles?

    PubMed

    Sedlák, Marián; Rak, Dmytro

    2013-02-28

    In textbooks, undersaturated solutions of low molar mass compounds and mixtures of freely miscible liquids are considered as homogeneous at larger length scales exceeding appreciably dimensions of individual molecules. However, growing experimental evidence reveals that it is not the case. Large-scale structures with sizes on the order of 100 nm are present in solutions and mixtures used in everyday life and research practice, especially in aqueous systems. These mesoscale inhomogeneities are long-lived, and (relatively slow) kinetics of their formation can be monitored upon mixing the components. Nevertheless, the nature of these structures and mechanisms behind their formation are not clear yet. Since it was previously suggested that these can be nanobubbles stabilized by adsorbed solute at the gas/solvent interface, we devote the current study to addressing this question. Static and dynamic light scattering was used to investigate solutions and mixtures prepared at ordinary conditions (equilibrated with air at 1 atm), prepared with degassed solvent, and solutions and mixtures degassed after formation of large structures. The behavior of large structures in strong gravitational centrifugal fields was also investigated. Systems from various categories were chosen for this study: aqueous solutions of an inorganic ionic compound (MgSO4), organic ionic compound (citric acid), uncharged organic compound (urea), and a mixture of water with organic solvent freely miscible with water (tert-butyl alcohol). Obtained results show that these structures are not nanobubbles in all cases. Visualization of large-scale structures via nanoparticle tracking analysis is presented. NTA results confirm conclusions from our previous light scattering work.

  6. Electrical signatures of ethanol-liquid mixtures: implications for monitoring biofuels migration in the subsurface

    USGS Publications Warehouse

    Personna, Yves Robert; Slater, Lee; Ntarlagiannis, Dimitrios; Werkema, Dale; Szabo, Zoltan

    2013-01-01

    Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH–water mixtures (0 to 0.97 v/v EtOH) and EtOH–salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1–1000 Hz). A Lichtenecker–Rother (L–R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L–R model fitted the experimental data at concentration ≤ 0.4 v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH–water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH–EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water–water, EtOH–water, and EtOH–EtOH) occurring simultaneously in EtOH–water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH–water and EtOH–water–mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.

  7. Electrical signatures of ethanol-liquid mixtures: implications for monitoring biofuels migration in the subsurface.

    PubMed

    Personna, Yves Robert; Slater, Lee; Ntarlagiannis, Dimitrios; Werkema, Dale; Szabo, Zoltan

    2013-01-01

    Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH-water mixtures (0 to 0.97 v/v EtOH) and EtOH-salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1-1000 Hz). A Lichtenecker-Rother (L-R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L-R model fitted the experimental data at concentration ≤0.4v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH-water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH-EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water-water, EtOH-water, and EtOH-EtOH) occurring simultaneously in EtOH-water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH-water and EtOH-water-mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.

  8. Electrical signatures of ethanol-liquid mixtures: Implications for monitoring biofuels migration in the subsurface

    NASA Astrophysics Data System (ADS)

    Personna, Yves Robert; Slater, Lee; Ntarlagiannis, Dimitrios; Werkema, Dale; Szabo, Zoltan

    2013-01-01

    Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH-water mixtures (0 to 0.97 v/v EtOH) and EtOH-salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1-1000 Hz). A Lichtenecker-Rother (L-R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L-R model fitted the experimental data at concentration ≤ 0.4 v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH-water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH-EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water-water, EtOH-water, and EtOH-EtOH) occurring simultaneously in EtOH-water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH-water and EtOH-water-mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.

  9. BEHAVIOR OF SURFACTANT MIXTURES AT SOLID/LIQUID AND OIL/LIQUID INTERFACES IN CHEMICAL FLOODING SYSTEMS

    SciTech Connect

    Prof. P. Somasundaran

    2003-03-31

    The aim of the project is to develop a knowledge base to help with the design of enhanced process for mobilizing and extracting untrapped oil. We emphasize on evaluating novel surfactant mixtures and on obtaining optimum combinations of the surfactants in chemical flooding EOR process. An understanding of the micellar shape and size is crucial since these physical properties directly determine the crude oil removal efficiency. Analytical ultracentrifugation experiments were used to test the multi-micelle model proposed earlier and formulate the relationships between mixed micelle formation and the surfactant structure. Information on partial specific volume of surfactants and their mixtures is required to treat analytical ultracentrifuge data. In the last report, it was noted that the partial specific volumes of the sugar-based surfactants obtained experimentally did not agree with those from theoretical calculations. A scrutiny of partial specific volumes of the four sugar-based surfactants revealed that conformational changes upon micelle formation are responsible for the large deviation. From sedimentation equilibrium experiments, two types of micelles were identified for the nonionic polyethylene surfactant and its mixtures with the sugar-based surfactant, dodecyl maltoside. The average aggregation numbers of n-dodecyl-{beta}-D-maltoside and nonyl phenol ethoxylated decyl ether agreed with those reported in literature using other techniques. Our study displayed, for the first time, that small micelles might coexist with large micelles at high concentrations due to unique structures of the surfactant although classical thermodynamic theory supports only one type of micelle. Initial dynamic light scattering results support the results for the same mixed surfactant system from analytical ultracentrifuge equilibrium technique. The implication of this finding lies in the fact that efficiency of oil recovery will be improved due to the large micellar size, its

  10. Viscosity and Liquid Density of Asymmetric n-Alkane Mixtures: Measurement and Modeling

    NASA Astrophysics Data System (ADS)

    Queimada, A. J.; Marrucho, I. M.; Coutinho, J. A. P.; Stenby, E. H.

    2005-01-01

    Viscosity and liquid density measurements were performed, at atmospheric pressure, in pure and mixed n-decane, n-eicosane, n-docosane, and n-tetracosane from 293.15 K (or above the melting point) up to 343.15 K. The viscosity was determined with a rolling ball viscometer and liquid densities with a vibrating U-tube densimeter. Pure component results agreed, on average, with literature values within 0.2% for liquid density and 3% for viscosity. The measured data were used to evaluate the performance of two models for their predictions: the friction theory coupled with the Peng-Robinson equation of state and a corresponding states model recently proposed for surface tension, viscosity, vapor pressure, and liquid densities of the series of n-alkanes. Advantages and shortcoming of these models are discussed.

  11. Vapor-liquid equilibria of binary and ternary mixtures of cyclohexane, 3-methyl-2-butanone, and octane at 101.3 kPa

    SciTech Connect

    Chen, C.C.; Tang, M.; Chen, Y.P.

    1996-05-01

    Vapor-liquid equilibria were measured at 101.3 kPa for the three binary and one ternary mixtures of cyclohexane, 3-methyl-2-butanone, and octane. The isobaric T-x-y data were reported, including an azeotropic point for the binary mixture cyclohexane + 3-methyl-2-butanone. The virial equation of state truncated after the second coefficient was used to calculate the vapor-phase fugacity coefficients. The Tsonopoulos correlation equation was applied to determine the second virial coefficients. Various activity coefficient models of the Wilson, the NRTL, and the UNIQUAC equations were used to correlate the binary experimental vapor-liquid equilibrium results. Optimally-fitted binary parameters of the activity coefficient models were obtained and those parameters of the NRTL model were employed to predict the ternary vapor-liquid equilibria. Satisfactory results were presented for the correlation and prediction of the vapor-liquid equilibrium data on binary and ternary mixtures.

  12. Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

    PubMed Central

    Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

    2016-01-01

    We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

  13. Isobaric vapor-liquid equilibria of methanol + 1-octanol and ethanol + 1-octanol mixtures

    SciTech Connect

    Arce, A.; Blanco, A.; Soto, A.; Tojo, J.

    1995-07-01

    Isobaric vapor-liquid equilibrium data for methanol + 1-octanol and ethanol + 1-octanol have been measured at 101.325 kPa. The results were checked for thermodynamic consistency using Fredenslund et al.`s test, correlated using Wilson, NRTL, and UNIQUAC equations for the liquid phase activity coefficients, and compared with the predictions of the ASOG, UNIFAC, and modified UNIFAC group contribution methods.

  14. Dielectric relaxation and solvation dynamics in a prototypical ionic liquid + dipolar protic liquid mixture: 1-butyl-3-methylimidazolium tetrafluoroborate + water.

    PubMed

    Zhang, Xin-Xing; Liang, Min; Hunger, Johannes; Buchner, Richard; Maroncelli, Mark

    2013-12-12

    Dielectric and solvation data on mixtures of 1-butyl-3-methylimidazilium tetrafluoroborate ([Im41][BF4]) + water are reported and used to examine the utility of dielectric solvation models. Dielectric permittivity and loss spectra (25 °C) were recorded over the frequency range 200 MHz to 89 GHz at 17 compositions and fit to a 4-Debye form. Dynamic Stokes shift measurements on the solute coumarin 153 (C153), made by combining fluorescence upconversion (80 fs resolution) and time-correlated single photon counting data (20 ns range), were used to determine the solvation response at 7 compositions (20.5 °C). All properties measured here were found to depend upon mixture composition in a simple continuous manner, especially when viewed in terms of volume fraction. Solvation response functions predicted by a simple dielectric continuum model are similar to but ∼7-fold faster than the spectral response functions measured with C153. The solvation data are in better agreement with the recently published predictions of a semimolecular model of Biswas and co-workers [J. Phys. Chem. B 2011, 115, 4011], but these latter predictions are systematically slow by a factor of ∼3.

  15. Perturbation theory of structure in classical liquid mixtures: Application to metallic systems near phase separation. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Henderson, R. L.

    1974-01-01

    The partial structure factors of classical simple liquid mixtures near phase separation are dicussed. The theory is developed for particles interacting through pair potentials, and is thus appropriate both to insulating fluids, and also to metallic systems if these may be described by an effective ion-ion pair interaction. The motivation arose from consideration of metallic liquid mixtures, in which resistive anomalies have been observed near phase separation. A mean field theory correction appropriate to 3 pair potential for the effects of correlated motions in the reference fluid is studied. The work is cast in terms of functions which are closely related to the direct correlation functions of Ornstein and Zernike. The results are qualitatively in accord with physical expectations. Quantitative agreement with experiment seems to turn on the selection of the hard core reference potential in terms of the metallic effective pair potential. It is suggested that the present effective pair potentials are perhaps not properly used to calculate the metallic structure factors at long wavelength.

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

    PubMed

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

    2013-03-21

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

  17. Docosahexaenoic acid promotes micron scale liquid-ordered domains. A comparison study of docosahexaenoic versus oleic acid containing phosphatidylcholine in raft-like mixtures.

    PubMed

    Georgieva, R; Chachaty, C; Hazarosova, R; Tessier, C; Nuss, P; Momchilova, A; Staneva, G

    2015-06-01

    The understanding of the functional role of the lipid diversity in biological membranes is a major challenge. Lipid models have been developed to address this issue by using lipid mixtures generating liquid-ordered (Lo)/liquid-disordered (Ld) immiscibility. The present study examined mixtures comprising Egg sphingomyelin (SM), cholesterol (chol) and phosphatidylcholine (PC) either containing docosahexaenoic (PDPC) or oleic acid (POPC). The mixtures were examined in terms of their capability to induce phase separation at the micron- and nano-scales. Fluorescence microscopy, electron spin resonance (ESR), X-ray diffraction (XRD) and calorimetry methods were used to analyze the lateral organization of the mixtures. Fluorescence microscopy of giant vesicles could show that the temperature of the micron-scale Lo/Ld miscibility is higher for PDPC than for POPC ternary mixtures. At 37°C, no micron-scale Lo/Ld phase separation could be identified in the POPC containing mixtures while it was evident for PDPC. In contrast, a phase separation was distinguished for both PC mixtures by ESR and XRD, indicative that PDPC and POPC mixtures differed in micron vs nano domain organization. Compared to POPC, the higher line tension of the Lo domains observed in PDPC mixtures is assumed to result from the higher difference in Lo/Ld order parameter rather than hydrophobic mismatch.

  18. Molecular Dynamics Simulations of the Ionic Liquid 1-n-Butyl-3-Methylimidazolium Chloride and Its Binary Mixtures with Ethanol.

    PubMed

    Chen, Mo; Pendrill, Robert; Widmalm, Göran; Brady, John W; Wohlert, Jakob

    2014-10-14

    Room temperature ionic liquids (ILs) of the imidazolium family have attracted much attention during the past decade for their capability to dissolve biomass. Besides experimental work, numerous compuational studies have been concerned with the physical properties of both neat ILs and their interactions with different solutes, in particular, carbohydrates. Many classical force fields designed specifically for ILs have been found to yield viscosities that are too high for the liquid state, which has been attributed to the fact that the effective charge densities are too high due to the lack of electronic polarizability. One solution to this problem has been uniform scaling of the partial charges by a scale factor in the range 0.6-0.9, depending on model. This procedure has been shown to improve the viscosity of the models, and also to positively affect other properties, such as diffusion constants and ionic conductivity. However, less attention has been paid to how this affects the overall thermodynamics of the system, and the problems it might create when the IL models are combined with other force fields (e.g., for solutes). In the present work, we employ three widely used IL force fields to simulate 1-n-butyl-3-methyl-imidazolium chloride in both the crystal and the liquid state, as well as its binary mixture with ethanol. Two approaches are used: one in which the ionic charge is retained at its full integer value and one in which the partial charges are uniformly reduced to 85%. We investigate and calculate crystal and liquid structures, molar heat capacities, heats of fusion, self-diffusion constants, ionic conductivity, and viscosity for the neat IL, and ethanol activity as a function of ethanol concentration for the binary mixture. We show that properties of the crystal are less affected by charge scaling compared to the liquid. In the liquid state, transport properties of the neat IL are generally improved by scaling, whereas values for the heat of fusion are

  19. BEHAVIOR OF SURFACTANT MIXTURES AT SOLID/LIQUID AND OIL/LIQUID INTERFACES IN CHEMICAL FLOODING SYSTEMS

    SciTech Connect

    P. Somasundaran

    2004-11-20

    The aim of the project is to develop a knowledge base to help the design of enhanced processes for mobilizing and extracting untrapped oil. We emphasize evaluation of novel surfactant mixtures and obtaining optimum combinations of the surfactants for efficient chemical flooding EOR processes. In this regard, an understanding of the aggregate shape, size and structure is crucial since these properties govern the crude oil removal efficiency. During the three-year period, the adsorption and aggregation behavior of sugar-based surfactants and their mixtures with other types of surfactants have been studied. Sugar-based surfactants are made from renewable resources, nontoxic and biodegradable. They are miscible with water and oil. These environmentally benign surfactants feature high surface activity, good salinity, calcium and temperature tolerance, and unique adsorption behavior. They possess the characteristics required for oil flooding surfactants and have the potential for replacing currently used surfactants in oil recovery. A novel analytical ultracentrifugation technique has been successfully employed for the first time, to characterize the aggregate species present in mixed micellar solution due to its powerful ability to separate particles based on their size and shape and monitor them simultaneously. Analytical ultracentrifugation offers an unprecedented opportunity to obtain important information on mixed micelles, structure-performance relationship for different surfactant aggregates in solution and their role in interfacial processes. Initial sedimentation velocity investigations were conducted using nonyl phenol ethoxylated decyl ether (NP-10) to choose the best analytical protocol, calculate the partial specific volume and obtain information on sedimentation coefficient, aggregation mass of micelles. Four softwares: OptimaTM XL-A/XL-I data analysis software, DCDT+, Svedberg and SEDFIT, were compared for the analysis of sedimentation velocity

  20. BEHAVIOR OF SURFACTANT MIXTURE AT SOLID/LIQUID AND OIL/LIQUID INTERFACE IN CHEMICAL FLOODING SYSTEMS

    SciTech Connect

    Prof. P. Somasundaran

    2002-03-01

    The aim of the project is to develop and evaluate efficient novel surfactant mixtures for enhanced oil recovery. Preliminary ultra-filtration tests suggest that two kinds of micelles may exist in binary surfactant mixtures at different concentrations. Due to the important role played in interfacial processes by micelles as determined by their structures, focus of the current work is on the delineation of the relationship between such aggregate structures and chemical compositions of the surfactants. A novel analytical centrifuge application is explored to generate information on structures of different surfactants aggregates. In this report, optical systems, typical output of the analytical ultracentrifuge results and four basic experiments are discussed. Initial sedimentation velocity investigations were conducted using nonyl phenol ethoxylated decyl ether (NP-10) to choose the best analytical protocol, calculate the partial specific volume and obtain information on sedimentation coefficient, aggregation mass of micelles. The partial specific volume was calculated to be 0.920. Four softwares: Optima{trademark} XL-A/XL-I data analysis software, DCDT+, Svedberg and SEDFIT, were compared for the analysis of sedimentation velocity experimental data. The sedimentation coefficient and aggregation number of NP-10 micelles obtained using the first three softwares at 25 C are 209, 127, and 111, respectively. The last one is closest to the result from Light Scattering. The reason for the differences in numbers obtained using the three softwares is discussed. Based on these tests, Svedberg and SEDFIT analysis are chosen for further studies. This approach using the analytical ultracentrifugation offers an unprecedented opportunity now to obtain important information on mixed micelles and their role in interfacial processes.

  1. A comparative study of room temperature ionic liquids and their organic solvent mixtures near charged electrodes

    NASA Astrophysics Data System (ADS)

    Vatamanu, Jenel; Vatamanu, Mihaela; Borodin, Oleg; Bedrov, Dmitry

    2016-11-01

    The structural properties of electrolytes consisting of solutions of ionic liquids in a polar solvent at charged electrode surfaces are investigated using classical atomistic simulations. The studied electrolytes consisted of tetraethylammonium tetrafluoroborate (NEt4-BF4), 1-ethyl-3-methylimidazolium tetrafluoroborate (c2mim-BF4) and 1-octyl-3-methylimidazolium tetrafluoroborate (c8mim-BF4) salts dissolved in acetonitrile solvent. We discuss the influence of electrolyte concentration, chemical structure of the ionic salt, temperature, conducting versus semiconducting nature of the electrode, electrode geometry and surface roughness on the electric double layer structure and capacitance and compare these properties with those obtained for pure room temperature ionic liquids. We show that electrolytes consisting of solutions of ions can behave quite differently from pure ionic liquid electrolytes.

  2. Non-invasive determination of ethanol, propylene glycol and water in a multi-component pharmaceutical oral liquid by direct measurement through amber plastic bottles using Fourier transform near-infrared spectroscopy.

    PubMed

    Broad, N W; Jee, R D; Moffat, A C; Eaves, M J; Mann, W C; Dziki, W

    2000-11-01

    Fourier transform near-infrared (FT-NIR) spectroscopy was used to quantify rapidly the ethanol (34-49% v/v), propylene glycol (20-35% v/v) and water (11-20% m/m) contents within a multi-component pharmaceutical oral liquid by measurement directly through the amber plastic bottle packaging. Spectra were collected in the range 7302-12,000 cm-1 and calibration models set-up using partial least-squares regression (PLSR) and multiple linear regression. Reference values for the three components were measured using capillary gas chromatography (ethanol and propylene glycol) and Karl Fischer (water) assay procedures. The calibration and test sets consisted of production as well as laboratory batches that were made to extend the concentration ranges beyond the natural production variation. The PLSR models developed gave standard errors of prediction (SEP) of 1.1% v/v for ethanol, 0.9% v/v for propylene glycol and 0.3% m/m for water. For each component the calibration model was validated in terms of: linearity, repeatability, intermediate precision and robustness. All the methods produced statistically favourable outcomes. Ten production batches independent of the calibration and test sets were also challenged against the PLSR models, giving SEP values of 1.3% v/v (ethanol), 1.0% v/v (propylene glycol) and 0.2% m/m (water). NIR transmission spectroscopy allowed all three liquid constituents to be non-invasively measured in under 1 min.

  3. Monte Carlo simulations of the solid-liquid transition in hard spheres and colloid-polymer mixtures.

    PubMed

    Zykova-Timan, T; Horbach, J; Binder, K

    2010-07-07

    Monte Carlo simulations at constant pressure are performed to study coexistence and interfacial properties of the liquid-solid transition in hard spheres and in colloid-polymer mixtures. The latter system is described as a one-component Asakura-Oosawa (AO) model where the polymer's degrees of freedom are incorporated via an attractive part in the effective potential for the colloid-colloid interactions. For the considered AO model, the polymer reservoir packing fraction is eta(p) (r)=0.1 and the colloid-polymer size ratio is q[triple bond]sigma(p)/sigma=0.15 (with sigma(p) and sigma as the diameter of polymers and colloids, respectively). Inhomogeneous solid-liquid systems are prepared by placing the solid fcc phase in the middle of a rectangular simulation box, creating two interfaces with the adjoined bulk liquid. By analyzing the growth of the crystalline region at various pressures and for different system sizes, the coexistence pressure p(co) is obtained, yielding p(co)=11.576 k(B)T/sigma(3) for the hard-sphere system and p(co)=8.00 k(B)T/sigma(3) for the AO model (with k(B) as the Boltzmann constant and T as the temperature). Several order parameters are introduced to distinguish between solid and liquid phases and to describe the interfacial properties. From the capillary-wave broadening of the solid-liquid interface, the interfacial stiffness is obtained for the (100) crystalline plane, giving the values gamma approximately 0.49 k(B)T/sigma(2) for the hard-sphere system and gamma approximately 0.95 k(B)T/sigma(2) for the AO model.

  4. Monte Carlo simulations of the solid-liquid transition in hard spheres and colloid-polymer mixtures

    NASA Astrophysics Data System (ADS)

    Zykova-Timan, T.; Horbach, J.; Binder, K.

    2010-07-01

    Monte Carlo simulations at constant pressure are performed to study coexistence and interfacial properties of the liquid-solid transition in hard spheres and in colloid-polymer mixtures. The latter system is described as a one-component Asakura-Oosawa (AO) model where the polymer's degrees of freedom are incorporated via an attractive part in the effective potential for the colloid-colloid interactions. For the considered AO model, the polymer reservoir packing fraction is ηpr=0.1 and the colloid-polymer size ratio is q ≡σp/σ=0.15 (with σp and σ as the diameter of polymers and colloids, respectively). Inhomogeneous solid-liquid systems are prepared by placing the solid fcc phase in the middle of a rectangular simulation box, creating two interfaces with the adjoined bulk liquid. By analyzing the growth of the crystalline region at various pressures and for different system sizes, the coexistence pressure pco is obtained, yielding pco=11.576 kBT/σ3 for the hard-sphere system and pco=8.00 kBT/σ3 for the AO model (with kB as the Boltzmann constant and T as the temperature). Several order parameters are introduced to distinguish between solid and liquid phases and to describe the interfacial properties. From the capillary-wave broadening of the solid-liquid interface, the interfacial stiffness is obtained for the (100) crystalline plane, giving the values γ˜≈0.49 kBT/σ2 for the hard-sphere system and γ˜≈0.95 kBT/σ2 for the AO model.

  5. Infrared spectroscopy of methanol-hexane liquid mixtures. II. The strength of hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Max, Jean-Joseph; Chapados, Camille

    2009-03-01

    The study by Fourier transform infrared attenuated total reflectance spectroscopy at 27 °C of methanol (MeOH) and hexane mixtures is presented. In the 0-0.25 and 0.75-1.00 molar fractions, the mixtures form homogeneous solutions, whereas from 0.25 to 0.75, the mixtures are inhomogeneous forming two phases. These mixtures have the near 3300 cm-1 OH stretch band only slightly displaced throughout the whole concentration range indicating very little variation in the H-bonding condition. This result is very different from that of MeOH in CCl4 where the OH stretch bands are scattered in a wide frequency range. Factor analysis applied to the MeOH/hexane spectra gave seven principal factors (one hexane and six methanol factors) and retrieved their principal spectra and abundances. In the inhomogeneous region, the two phase volumes changed inversely with concentration, but their factor compositions are invariable at 1:3 and 3:1 molar ratios. Five of the six principal methanol factors have the O-H and the C-O stretch bands situated near, respectively, 3310 and 1025 cm-1 with little displacement in the whole concentration range. The sixth factor observed at 3654 cm-1 (full width at half height<40 cm-1) was assigned to free methanol OH by Max and Chapados [J. Chem. Phys. 128, 224512 (2008)]. This species concentration is very low but constant at around 0.01M in the methanol range of 0.5-2.5M. The main OH stretch bands (˜3300 cm-1) were simulated with six Gaussian components that were assigned to different hydrogen-bonding situations. These form reverse micelles at low methanol concentrations and micelles at high concentrations that persist in pure methanol. A very different state of affairs exists in MeOH in CCl4 where free OH groups are formed in almost all mixtures except in pure MeOH. Since hexane is a better model of a lipidic milieu than CCl4, the results for MeOH/hexane give a better representation of the fate of alcoholic OH groups in such a milieu.

  6. Self-assembly of imidazolium-based surfactants in magnetic room-temperature ionic liquids: binary mixtures.

    PubMed

    Klee, Andreas; Prevost, Sylvain; Gradzielski, Michael

    2014-12-15

    The phase behaviour of binary mixtures of ionic surfactants (1-alkyl-3-imidazolium chloride, C(n)mimCl with n=14, 16 and 18) and imidazolium-based ionic liquids (1-alkyl-3-methylimidazolium tetrachloroferrate, C(n)mimFeCl4, with n=2 and 4) over a broad temperature range and the complete range of compositions is described. By using many complementary methods including differential scanning calorimetry (DSC), polarised microscopy, small-angle neutron and X-ray scattering (SANS/SAXS), and surface tension, the ability of this model system to support self-assembly is described quantitatively and this behaviour is compared with common water systems. The existence of micelles swollen by the solvent can be deduced from SANS experiments and represent a possible model for aggregates, which has barely been considered for ionic-liquid systems until now, and can be ascribed to the rather low solvophobicity of the surfactants. Our investigation shows that, in general, C(n)mimCl is a rather weak amphiphile in these ionic liquids. The amphiphilic strength increases systematically with the length of the alkyl chain, as seen from the phase behaviour, the critical micelle concentration, and also the level of definition of the aggregates formed.

  7. Induced liquid-crystalline ordering in solutions of stiff and flexible amphiphilic macromolecules: Effect of mixture composition

    NASA Astrophysics Data System (ADS)

    Glagolev, Mikhail K.; Vasilevskaya, Valentina V.; Khokhlov, Alexei R.

    2016-07-01

    Impact of mixture composition on self-organization in concentrated solutions of stiff helical and flexible macromolecules was studied by means of molecular dynamics simulation. The macromolecules were composed of identical amphiphilic monomer units but a fraction f of macromolecules had stiff helical backbones and the remaining chains were flexible. In poor solvents the compacted flexible macromolecules coexist with bundles or filament clusters from few intertwined stiff helical macromolecules. The increase of relative content f of helical macromolecules leads to increase of the length of helical clusters, to alignment of clusters with each other, and then to liquid-crystalline-like ordering along a single direction. The formation of filament clusters causes segregation of helical and flexible macromolecules and the alignment of the filaments induces effective liquid-like ordering of flexible macromolecules. A visual analysis and calculation of order parameter relaying the anisotropy of diffraction allow concluding that transition from disordered to liquid-crystalline state proceeds sharply at relatively low content of stiff components.

  8. Induced liquid-crystalline ordering in solutions of stiff and flexible amphiphilic macromolecules: Effect of mixture composition.

    PubMed

    Glagolev, Mikhail K; Vasilevskaya, Valentina V; Khokhlov, Alexei R

    2016-07-28

    Impact of mixture composition on self-organization in concentrated solutions of stiff helical and flexible macromolecules was studied by means of molecular dynamics simulation. The macromolecules were composed of identical amphiphilic monomer units but a fraction f of macromolecules had stiff helical backbones and the remaining chains were flexible. In poor solvents the compacted flexible macromolecules coexist with bundles or filament clusters from few intertwined stiff helical macromolecules. The increase of relative content f of helical macromolecules leads to increase of the length of helical clusters, to alignment of clusters with each other, and then to liquid-crystalline-like ordering along a single direction. The formation of filament clusters causes segregation of helical and flexible macromolecules and the alignment of the filaments induces effective liquid-like ordering of flexible macromolecules. A visual analysis and calculation of order parameter relaying the anisotropy of diffraction allow concluding that transition from disordered to liquid-crystalline state proceeds sharply at relatively low content of stiff components.

  9. Structure, dynamics, and activity of xylanase solvated in binary mixtures of ionic liquid and water.

    PubMed

    Jaeger, Vance W; Pfaendtner, Jim

    2013-01-01

    We have discovered that a family 11 xylanase from Trichoderma longibrachiatum maintains significant activity in low concentrations of the ionic liquids (IL) 1-ethyl-3-methyl-imidazolium acetate ([EMIM][OAc]) or 1-ethyl-3-methyl-imidazolium ethyl sulfate ([EMIM][EtSO4]) in water. In order to understand the mechanisms by which the ionic liquids affect the activity of xylanase, we conducted molecular dynamics simulations of the enzyme in various concentrations of the cosolvent. The simulations show that higher concentrations of ionic liquid correlate with less deviation from the starting crystallographic structure. Dynamic motion of the protein is severely dampened by even the lowest tested concentrations of ionic liquid as measured by root-mean-square fluctuation. Principal component analysis shows that the characteristics of the main modes of enzyme motion are greatly affected by the choice of solvent. Cations become kinetically trapped in the binding pocket, allowing them to act as a competitive inhibitor to the natural substrate. Dynamic light scattering and kinetic studies evaluated the stability of the enzyme in the new solvents. These studies indicate that likely factors in the loss of enzyme activity for this xylanase are the dampening of dynamic motion and kinetic trapping of cations in the binding pocket as opposed to the denaturing of the protein.

  10. Unusual linear dependency of viscosity with temperature in ionic liquid/water mixtures.

    PubMed

    Nanda, R

    2016-09-21

    An unusual linear dependency of viscosity with temperature has been observed in aqueous solutions of 1-octyl-3-methylimidazolium-based ionic liquids because of the ion induced structural transition which leads to the violation of both the Stokes-Einstein and fractional Stokes-Einstein equations, suggesting the presence of dynamic heterogeneity in the system.

  11. Anomalous effective polarity of an air/liquid-mixture interface: a heterodyne-detected electronic and vibrational sum frequency generation study.

    PubMed

    Mondal, Sudip Kumar; Inoue, Ken-ichi; Yamaguchi, Shoichi; Tahara, Tahei

    2015-10-07

    We study the effective polarity of an air/liquid-mixture interface by using interface-selective heterodyne-detected electronic sum frequency generation (HD-ESFG) and vibrational sum frequency generation (HD-VSFG) spectroscopies. With water and N,N-dimethylformamide (DMF) chosen as two components of the liquid mixture, the bulk polarity of the mixture is controlled nearly arbitrarily by the mixing ratio. The effective polarity of the air/mixture interface is evaluated by HD-ESFG with a surface-active solvatochromic molecule used as a polarity indicator. Surprisingly, the interfacial effective polarity of the air/mixture interface increases significantly, when the bulk polarity of the mixture decreases (i.e. when the fraction of DMF increases). Judging from the hydrogen-bond structure at the air/mixture interface clarified by HD-VSFG, this anomalous change of the interfacial effective polarity is attributed to the interface-specific solvation structure around the indicator molecule at the air/mixture interface.

  12. Simultaneous nitrogen and phosphorus recovery from sludge-fermentation liquid mixture and application of the fermentation liquid to enhance municipal wastewater biological nutrient removal.

    PubMed

    Zhang, Chao; Chen, Yinguang

    2009-08-15

    Recently, waste activated sludge (WAS) fermentation for short-chain fatty acids (SCFAs) production has drawn much attention because the waste biosolids produced in wastewater treatment plants (WWTP) can be reused, and the produced SCFAs can be applied to promote biological nutrient removal (BNR). Usually, after WAS fermentation, the fermentation liquid is separated and then the recovery of ammonium and phosphorus, which are released during WAS fermentation, is conducted to prevent the increase of nitrogen and phosphorus loadings to WWTP. As an alternative to the traditional process, this paper investigated the recovery of ammonium and phosphorus in the formation of struvite before sludge-liquid separation, and its positive effecton the following sludge-liquid filtration separation. First, the conditions for ammonium and phosphorus recovery from the WAS fermentation mixture were optimized by response surface methodology (RSM). Then, the effect of ammonium and phosphorus recovery on sludge filtration dewatering was investigated. With ammonium and phosphorus recovery, it was observed that the specific resistance to filtration (SRF), the capillary suction time (CST), and the sludge volume after filtration reduced by 96.9, 99.6, and 88.7%, respectively, compared with no ammonium and phosphorus recovered sludge. Third, the mechanisms for ammonium and phosphorus recovery significantly enhancing sludge dewatering capacity were investigated. The formation of struvite, the neutralization of 5 potential, the increase of magnesium ion, which was added during ammonium and phosphorus recovery, and the decrease of sludge polymeric substance caused the improvement of sludge dewatering. Finally, the fermentation liquid was used as the additional carbon source of BNR, and the nutrient removal efficiency was obviously enhanced.

  13. Marangoni Bursting: Evaporation-Induced Emulsification of Binary Mixtures on a Liquid Layer

    NASA Astrophysics Data System (ADS)

    Keiser, L.; Bense, H.; Colinet, P.; Bico, J.; Reyssat, E.

    2017-02-01

    Adjusting the wetting properties of water through the addition of a miscible liquid is commonly used in a wide variety of industrial processes involving interfaces. We investigate experimentally the evolution of a drop of water and volatile alcohol deposited on a bath of oil: The drop spreads and spontaneously fragments into a myriad of minute droplets whose size strongly depends on the initial concentration of alcohol. Marangoni flows induced by the evaporation of alcohol play a key role in the overall phenomenon. The intricate coupling of hydrodynamics, wetting, and evaporation is well captured by analytical scaling laws. Our scenario is confirmed by experiments involving other combinations of liquids that also lead to this fascinating phenomenon.

  14. An exact solution for the solidification of a liquid slab of binary mixture

    NASA Technical Reports Server (NTRS)

    Antar, B. N.; Collins, F. G.; Aumalia, A. E.

    1986-01-01

    The time dependent temperature and concentration profiles of a one dimensional finite slab of a binary liquid alloy is investigated during solidification. The governing equations are reduced to a set of coupled, nonlinear initial value problems using the method outlined by Meyer. Two methods will be used to solve these equations. The first method uses a Runge-Kutta-Fehlberg integrator to solve the equations numerically. The second method comprises of finding closed form solutions of the equations.

  15. Functionalized copolyimide membranes for the separation of gaseous and liquid mixtures

    PubMed Central

    Schmeling, Nadine; Konietzny, Roman; Sieffert, Daniel; Rölling, Patrick

    2010-01-01

    Summary Functionalized copolyimides continue to attract much attention as membrane materials because they can fulfill the demands for industrial applications. Thus not only good separation characteristics but also high temperature stability and chemical resistance are required. Furthermore, it is very important that membrane materials are resistant to plasticization since it has been shown that this phenomenon leads to a significant increase in permeability with a dramatic loss in selectivity. Plasticization effects occur with most polymer membranes at high CO2 concentrations and pressures, respectively. Plasticization effects are also observed with higher hydrocarbons such as propylene, propane, aromatics or sulfur containing aromatics. Unfortunately, these components are present in mixtures of high commercial relevance and can be separated economically by single membrane units or hybrid processes where conventional separation units are combined with membrane-based processes. In this paper the advantages of carboxy group containing 6FDA (4,4′-hexafluoroisopropylidene diphthalic anhydride) -copolyimides are discussed based on the experimental results for non cross-linked, ionically and covalently cross-linked membrane materials with respect to the separation of olefins/paraffins, e.g. propylene/propane, aromatic/aliphatic separation e.g. benzene/cyclohexane as well as high pressure gas separations, e.g. CO2/CH4 mixtures. In addition, opportunities for implementing the membrane units in conventional separation processes are discussed. PMID:20978620

  16. Transport properties of the binary mixtures of the three organic liquids toluene, methanol, and cyclohexane

    NASA Astrophysics Data System (ADS)

    Lapeira, E.; Gebhardt, M.; Triller, T.; Mialdun, A.; Köhler, W.; Shevtsova, V.; Bou-Ali, M. M.

    2017-03-01

    We report on the measurements of diffusion (D), thermodiffusion (DT), and Soret (ST) coefficients in binary pairs of the ternary system toluene-methanol-cyclohexane using different instrumental techniques: microgravity measurements (SODI/DCMIX2) on the International Space Station, thermogravitational column in combination with sliding symmetric tubes, optical beam deflection, optical digital interferometry, and counter flow cell. The binary systems have large regions where the mixtures are either not miscible or the Soret coefficient is negative. All the coefficients have been measured over a wide composition range with the exception of a miscibility gap. Results from different instruments and literature data are in favorable agreement over a broad composition range. Additionally, we have carefully measured the physical properties and the optical contrast factors (∂n/∂c ) p ,T and (∂n/∂T ) p ,c. The latter ones were also calculated using the Looyenga equation. The measurements in methanol-cyclohexane mixture revealed a decay of the diffusion coefficient when approaching the miscibility gap. We have interpreted this in the spirit of the pseudospinodal concept.

  17. Multicomponent Implant Releasing Dexamethasone

    NASA Astrophysics Data System (ADS)

    Nikkola, L.; Vapalahti, K.; Ashammakhi, N.

    2008-02-01

    Several inflammatory conditions are usually treated with corticosteroids. There are various problems like side effects with traditional applications of steroids, e.g. topical, or systemic routes. Local drug delivery systems have been studied and developed to gain more efficient administration with fewer side effects. Earlier, we reported on developing Dexamethasone (DX) releasing biodegradable fibers. However, their drug release properties were not satisfactory in terms of onset of drug release. Thus, we assessed the development of multicomponent (MC) implant to enhance earlier drug release from such biodegradable fibers. Poly (lactide-co-glycolide) (PLGA) and 2 wt-% and 8 wt-% DX were compounded and extruded with twin-screw extruder to form of fibers. Some of the fibers were sterilized to obtain a change in drug release properties. Four different fiber classes were studied: 2 wt-%, 8 wt-%, sterilized 2 wt-%, and sterilized 8 wt-%. 3×4 different DX-releasing fibers were then heat-pressed to form one multicomponent rod. Half of the rods where sterilized. Drug release was measured from initial fibers and multicomponent rods using a UV/VIS spectrometer. Shear strength and changes in viscosity were also measured. Drug release studies showed that drug release commenced earlier from multicomponent rods than from component fibers. Drug release from multicomponent rods lasted from day 30 to day 70. The release period of sterilized rods extended from day 23 to day 57. When compared to the original component fibers, the drug release from MC rods commenced earlier. The initial shear strength of MC rods was 135 MPa and decreased to 105 MPa during four weeks of immersion in phosphate buffer solution. Accordingly, heat pressing has a positive effect on drug release. After four weeks in hydrolysis, no disintegration was observed.

  18. Developing Mathematical Provisions for Assessment of Liquid Hydrocarbon Emissions in Emergency Situations

    NASA Astrophysics Data System (ADS)

    Zemenkova, M. Yu; Zemenkov, Yu D.; Shantarin, V. D.

    2016-10-01

    The paper reviews the development of methodology for calculation of hydrocarbon emissions during seepage and evaporation to monitor the reliability and safety of hydrocarbon storage and transportation. The authors have analyzed existing methods, models and techniques for assessing the amount of evaporated oil. Models used for predicting the material balance of multicomponent two-phase systems have been discussed. The results of modeling the open-air hydrocarbon evaporation from an oil spill are provided and exemplified by an emergency pit. Dependences and systems of differential equations have been obtained to assess parameters of mass transfer from the open surface of a liquid multicomponent mixture.

  19. Mathematical Simulation of Unsteady-State Gas-Liquid Mixture Flow in a Bed-Well System

    NASA Astrophysics Data System (ADS)

    Abbasov, É. M.; Imamaliev, S. A.

    2016-09-01

    Based on theoretical investigations, the influence of various forms of pressure variation at the wellhead with a nonstationary flow of a two-phase fluid in a bed-well system on the character of change in the bottom-hole pressure has been investigated, which makes it possible to determine this pressure from the wellhead operation parameters. The trapezoidal form of the change in pressure is considered as an example. The coupled equations of filtration and the equations describing nonstationary motion of a gas-liquid mixture in a pipeline have been solved jointly. Analytical formulas have been obtained allowing one to determine the bottom-hole pressure from the technological parameters at the wellhead with account for the dynamic connection of the bed-well system at different forms of change in the wellhead pressure. The influence of the wellhead pressure pulsation frequencies on the bottom-hole pressure dynamics has been established.

  20. Theoretical and experimental analysis of a multiphase screw pump, handling gas-liquid mixtures with very high gas volume fractions

    SciTech Connect

    Raebiger, K.; Maksoud, T.M.A.; Ward, J.; Hausmann, G.

    2008-09-15

    In the investigation of the pumping behaviour of multiphase screw pumps, handling gas-liquid mixtures with very high gas volume fractions, theoretical and experimental analyses were performed. A new theoretical screw pump model was developed, which calculates the time-dependent conditions inside the several chambers of a screw pump as well as the exchange of mass and energy between these chambers. By means of the performed experimental analysis, the screw pump model was verified, especially at very high gas volume fractions from 90% to 99%. The experiments, which were conducted with the reference fluids water and air, can be divided mainly into the determination of the steady state pumping behaviour on the one hand and into the analysis of selected transient operating conditions on the other hand, whereas the visualisation of the leakage flows through the circumferential gaps was rounded off the experimental analysis. (author)

  1. Infrared spectroscopy of acetone-methanol liquid mixtures: Hydrogen bond network

    NASA Astrophysics Data System (ADS)

    Max, Jean-Joseph; Chapados, Camille

    2005-01-01

    Acetone and methanol mixtures covering the whole solubility range are studied by Fourier transform infrared attenuated total reflectance spectroscopy. The strong bathochromic shifts observed on methanol OH and acetone CO stretch IR bands are related to hydrogen bonds between these groups. Factor analysis separates the spectra into four acetone and four methanol principal factors. A random molecular model developed for the acetone-water system [Max and Chapados, J. Chem. Phys. 119, 5632 (2003); 120, 6625 (2004)] was modified for the acetone-methanol system. This model, which takes into account H bonds accepted by methanol and acetone, is made up of 12 methanol and 11 acetone species. The 23 species abundances are regrouped according to evolving patterns or spectral similarities to compare them to the eight experimental factors. Methanol acetone mixtures are almost but not exactly random: the methanol oxygen atoms have stronger capacities than acetone to accept H bonds from methanol in the proportion 1.5 to 1. Since oxygen atoms are in excess, all labile hydrogen atoms will form H bonds. As acetone is added to methanol, its OH stretch band blueshifts as the number of accepted H bonds decreases. When methanol gives one H bond and accepts one, an H-bonding network is formed that was coined "chained organization." However, the acetone molecules do not sequester any methanol molecules by breaking or increasing the H-bond methanol network. Similarly, the methanol molecules do not sequester any acetone molecules. Consequently no acetone-methanol complex is formed in the mixtures. Gaussian simulation of the four principal factors in the methanol OH stretch region gave three distinct absorption regimes consisting of the OH stretch bands and their satellites that are identified as MeOH1, MeOH2, and MeOH3 (subscript indicates the number of H, covalent and H bond, which surround the oxygen). These regimes are related to those identified in the water-acetone system as OH2, OH3

  2. Infrared spectroscopy of methanol-hexane liquid mixtures. I. Free OH present in minute quantities

    NASA Astrophysics Data System (ADS)

    Max, Jean-Joseph; Chapados, Camille

    2008-06-01

    Methanol and hexane mixtures covering the whole solubility range are studied by Fourier transform infrared attenuated total reflectance spectroscopy in order to evaluate OH groups that are H-bond-free. The mixtures from 0 to 0.25 and from 0.75 to 1.00 mole fractions form homogeneous solutions, whereas those from 0.25 to 0.75 mole fractions are inhomogeneous, forming two phases. Factor analysis (FA) was used to find out if free OH groups were present. These were found in minute quantities at the lowest mole fraction by evaluating the OH stretch absorption. The bulk of the absorption is due to the greater than 99.9% of hydrogen-bonded methanol molecules, with a band maximum situated at 3340 cm-1. The stretch band of the free OH groups absorbs at 3654 cm-1, with a full width at half maximum of 35 cm-1. The concentration is very weak but constant at less than 5 mM in the mole fraction between 0.252 and 0.067. Below this range, OH concentrations are even smaller. This represents less than 1% of the amount of methanol at the mole fraction of 0.067 (0.543M). Above 0.25 mole fraction, free methanol OH groups are not observed. Since the free OH band is very weak, almost at the noise level, we verified its presence with mixtures of hexanol in hexane. There, we found a similar free OH band with almost the same band characteristics, but with almost three times the concentrations found with methanol, which we attribute to the difference in the hydrocarbon chain length. The present study indicates clearly that solutions of methanol in hexane contain free OH groups but in minute quantities and only in the low methanol concentrations. This situation is much different from that observed in solutions of methanol in CCl4, where free OH groups are clearly observed at all concentrations except at the concentration limits. Whereas in CCl4, methanol is believed to form H-bonded chains, the situation is different in n-hexane: methanol in the low concentration region would form reverse

  3. Perturbed-chain SAFT as a versatile tool for thermodynamic modeling of binary mixtures containing isoquinolinium ionic liquids.

    PubMed

    Domańska, Urszula; Zawadzki, Maciej; Paduszyński, Kamil; Królikowski, Marek

    2012-07-19

    This contribution reports a recapitulation of our experimental and modeling study on thermodynamic behavior of binary systems containing N-alkylisoquinolinium ionic liquids (ILs) based on bis(trifluoromethylsulfonyl)imide anion, [CniQuin][NTf2] (n = 4,6,8). In particular, we report isothermal vapor-liquid equilibrium (VLE) phase diagrams and molar excess enthalpies of mixing (H(E)) for binary mixtures of [C8iQuin][NTf2] IL with various organic solutes including benzene, toluene, thiophene, pyridine, and butan-1-ol. The measured VLE data represented simple homozeotropic behavior with either negative or positive deviations from ideality, depending on polarity of the solute, temperature, and mole fraction of IL. In turn, the obtained data on H(E) were negative and positive for the mixtures containing aromatic hydrocarbons or thiophene and butan-1-ol, respectively, in the whole range of IL's concentration. All of the measured and some previously published data regarding phase behavior of [C8iQuin][NTf2] IL were analyzed and successfully described in terms of perturbed-chain statistical associating fluid theory (PC-SAFT). The methodology used in this work was described by us previously. In general, the proposed modeling results in VLE diagrams, which are in excellent agreement with experimental data. In the case of H(E), the results obtained are good as well but not so satisfactory such as those for VLE. Nevertheless, they seem to be very promising if one take into account the simplicity of the utilized molecular model against significant complexity of IL-based systems. Thus, we concluded that PC-SAFT equation of state can be viewed as a powerful and robust tool for modeling of systems involving ILs.

  4. Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions.

    PubMed

    Sato, Bruno M; de Oliveira, Carolina G; Martins, Clarissa T; El Seoud, Omar A

    2010-02-28

    The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the "complex" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

  5. Probing the acidity of carboxylic acids in protic ionic liquids, water, and their binary mixtures: activation energy of proton transfer.

    PubMed

    Shukla, Shashi Kant; Kumar, Anil

    2013-02-28

    Acidity functions were used to express the ability of a solvent/solution to donate/accept a proton to a solute. The present work accounts for the acidity determination of HCOOH, CH3COOH, and CH3CH2COOH in the alkylimidazolium-based protic ionic liquids (PILs), incorporated with carboxylate anion, water, and in a binary mixture of PIL and water using the Hammett acidity function, H0. A reversal in the acidity trend was observed, when organic acids were transferred from water to PIL. It was emphasized that an increased stabilization offered by PIL cation toward the more basic conjugate anion of organic acid was responsible for this anomalous change in acidity order in PILs, which was absent in water. The greater stabilization of a basic organic anion by PIL cation is discussed in terms of the stable hard–soft acid base (HSAB) pairing. A change in the H0 values of these acids was observed with a change in temperature, and a linear correlation between the ln H0 and 1/T was noted. This relationship points toward the activation energy of proton transfer (E(a,H+)), a barrier provided by the medium during the proton transfer from Brønsted acid to indicator. The H0 function in binary mixtures points to the involvement of pseudosolvent, the behavior of which changes with the nature and concentration of acid. The presence of the maxima/minima in the H0 function is discussed in terms of the synergetic behavior of the pseudosolvent composed of the mixtures of aqueous PILs.

  6. Coaxial probe and apparatus for measuring the dielectric spectra of high pressure liquids and supercritical fluid mixtures

    NASA Astrophysics Data System (ADS)

    Lee, Sung B.; Smith, Richard L.; Inomata, Hiroshi; Arai, Kunio

    2000-11-01

    A probe and apparatus were developed for measuring the dielectric spectra (complex permittivity) of high pressure liquids and supercritical fluid mixtures. The probe consisted a 2.2 mm semirigid coaxial cable that was cut off flat and mounted into a high pressure tube. The apparatus for measuring complex permittivity consisted of the dielectric probe, cell, densimeter, piston for varying the system density at constant composition, and magnetic pump for agitation and recirculation, all of which were housed in a constant temperature air bath. The probe is simple, robust, inexpensive, and further, its design allows for quick connection to high pressure systems. Probe accuracy is estimated to be ±0.5 in ɛ' and ±0.5 in ɛ″ from 200 MHz to 18 GHz based on replicate measurements of calibration and 2σ deviations over the interval. Dielectric spectra were measured over the 200 MHz-20 GHz range for methanol+carbon dioxide mixture at 323.2 K and a pressures up to 18 MPa.

  7. Investigation of the running-in process and friction coefficient under the lubrication of ionic liquid/water mixture

    NASA Astrophysics Data System (ADS)

    Xie, Guoxin; Liu, Shuhai; Guo, Dan; Wang, Quan; Luo, Jianbin

    2009-04-01

    The tribological properties of three different films commonly used in microelectromechanical systems (MEMS) under the lubrication of ionic liquid (IL)/water mixtures with various concentrations in the running-in process have been investigated. Results show that coefficients of friction (COFs) and wear rates for low temperature silicon oxide (LTO)/Si 3N 4 vary in a similar way to the ones for poly-Si/Si 3N 4 under the lubrications of different IL/water mixtures. In contrast, the differences in COFs and wear rates are more significant in that the COFs and wear rates increase dramatically with the decrease in IL/water concentration in the case of self-mated Si 3N 4, while the differences in COFs and wear rates for the two other tribopairs are relatively small when the concentration is changed. The period of the running-in process reduces with the increase in IL/water concentration for all the tribopairs. Effective hydrodynamic lubrication can be found in the case of Si 3N 4/Si 3N 4 tribopair at higher IL/water concentrations without an evident running-in process, however, such a phenomenon cannot be observed for the other two tribopairs. Different wear mechanisms will also be analyzed in this paper.

  8. The direct determination of double bond positions in lipid mixtures by liquid chromatography/in-line ozonolysis/mass spectrometry.

    PubMed

    Sun, Chenxing; Zhao, Yuan-Yuan; Curtis, Jonathan M

    2013-01-31

    The direct determination of double bond positions in unsaturated lipids using in-line ozonolysis-mass spectrometry (O(3)-MS) is described. In this experiment, ozone penetrates through the semi-permeable Teflon AF-2400 tubing containing a flow of a solution of fatty acid methyl esters (FAME). Unsaturated FAME are thus oxidized by the ozone and cleaved at the double bond positions. The ozonolysis products then flow directly into the atmospheric pressure photoionization (APPI) source of a mass spectrometer for analysis. Aldehyde products retaining the methyl ester group are indicative of the double bond positions in unsaturated FAME. For the first time, O(3)-MS is able to couple directly to high performance liquid chromatography (HPLC), making the double bond localization in lipid mixtures possible. The application of LC/O(3)-MS has been demonstrated for a fat sample from bovine adipose tissue. A total of 9 unsaturated FAME including 6 positional isomers were identified unambiguously, without comparison to standards. The in-line ozonolysis reaction apparatus is applicable to most mass spectrometers without instrumental modification; it is also directly compatible with various LC columns. The LC/O(3)-MS method described here is thus a practical, versatile and easy to use new approach to the direct determination of double bond positions in lipids, even in complex mixtures.

  9. Nanostructural organization in carbon disulfide/ionic liquid mixtures: Molecular dynamics simulations and optical Kerr effect spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, Peng; Voth, Gregory A.; Xiao, Dong; Hines, Larry G.; Bartsch, Richard A.; Quitevis, Edward L.

    2011-07-01

    In this paper, the nanostructural organization and subpicosecond intermolecular dynamics in the mixtures of CS2 and the room temperature ionic liquid (IL) 1-pentyl-3-methylimidazolium bis{(trifluoromethane)sulfonyl}amide ([C5mim][NTf2]) were studied as a function of concentration using molecular dynamics (MD) simulations and optical heterodyne-detected Raman-induced Kerr effect spectroscopy. At low CS2 concentrations (<10 mol.% CS2/IL), the MD simulations indicate that the CS2 molecules are localized in the nonpolar domains. In contrast, at higher concentrations (≥10 mol.% CS2/IL), the MD simulations show aggregation of the CS2 molecules. The optical Kerr effect (OKE) spectra of the mixtures are interpreted in terms of an additivity model with the components arising from the subpicosecond dynamics of CS2 and the IL. Comparison of the CS2-component with the OKE spectra of CS2 in alkane solvents is consistent with CS2 mainly being localized in the nonpolar domains, even at high CS2 concentrations, and the local CS2 concentration being higher than the bulk CS2 concentration.

  10. Hydrophilic interaction liquid chromatography-electrospray ionization-tandem mass spectrometry of a complex mixture of native and oxidized phospholipids.

    PubMed

    Losito, I; Facchini, L; Diomede, S; Conte, E; Megli, F M; Cataldi, T R I; Palmisano, F

    2015-11-27

    A mixture of native and oxidized phospholipids (PLs), generated by the soybean lipoxygenase type V-catalyzed partial oxidation of a lipid extract obtained from human platelets, was analyzed by Hydrophilic Interaction Liquid Chromatography-ElectroSpray Ionization-Tandem Mass Spectrometry (HILIC-ESI-MS/MS). The complexity of the resulting mixture was remarkable, considering that the starting lipid extract, containing (as demonstrated in a previous study) about 130 native PLs, was enriched with enzymatically generated hydroperoxylated derivatives and chemically generated hydroxylated forms of PLs bearing polyunsaturated side chains. Nonetheless, the described analytical approach proved to be very powerful; indeed, focusing on phosphatidylcolines (PCs), the most abundant PL class in human platelets, about fifty different native/oxidized species could be identified in a single HILIC-ESI-MS/MS run. Low-energy collision induced dissociation tandem MS (CID-MS/MS) experiments on chromatographically separated species showed single neutral losses of H2O2 and H2O to be typical fragmentation pathways of hydroperoxylated PCs, whereas a single H2O loss was observed for hydroxylated ones. Moreover, diagnostic losses of n-hexanal or n-pentanol were exploited to recognize PCs hydroperoxylated on the last but five carbon atom of a ɷ-6 polyunsaturated side chain. Despite the low resolution of the 3D ion trap mass analyzer used, the described HILIC-ESI-MS/MS approach appears very promising for the identification of oxidized lipids in oxidatively stressed complex biological systems.

  11. Densities and vapor-liquid equilibria in binary mixtures formed by propyl methanoate + ethanol, + propan-1-ol, and + butan-1-ol at 160.0 kPa

    SciTech Connect

    Falcon, J.; Ortega, J.; Gonzalez, E.

    1996-07-01

    Densities and excess volumes were determined at 298.15 K for propyl methanoate + ethanol, + propan-1-ol, and + butan-1-ol. The results of those quantities were then correlated to get the concentrations of vapor-liquid equilibrium obtained isobarically at 160 kPa for the same mixtures. Two mixtures show azeotropes: for propyl methanoate (1) + ethanol (2), x{sub 1} = 0.443 at T = 358.7 K; and for propyl methanoate (1) + propan-1-ol (2), x{sub 1} = 0.762 at T = 368.2 K. The mixtures are thermodynamically consistent, and the predictions made using several group-contribution models are satisfactory.

  12. Anomalous waves in gas-liquid mixtures near gas critical point in Gardner equation approximation

    NASA Astrophysics Data System (ADS)

    Gasenko, V. G.

    2016-10-01

    The waves in a bubbled incompressible liquid with Van der Waals gas in a bubbles being near critical points is considered in a frame of Gardner equation. It is shown that both coefficients on quadratic and cubic nonlinear terms in Gardner equation change the sign near gas critical point and it results the anomalous waves: negative and limited solitons, kinks, antikinks and breathers. The dynamics and interactions of these waves was studied numerically by high accuracy Fourier methods with periodically boundary conditions. In particular it is revealed that limited solitons always arise from initial distribution with a few identical soliton's pair and stand stable in their form after numerous interactions.

  13. Microscopic self-dynamics in liquid hydrogen and in its mixtures with deuterium

    NASA Astrophysics Data System (ADS)

    Colognesi, D.; Celli, M.; Neumann, M.; Zoppi, M.

    2004-12-01

    We have measured the dynamic structure factor of liquid parahydrogen, pure and mixed with deuterium, in various thermodynamic conditions using incoherent inelastic neutron scattering. The experiments were carried out on TOSCA-II, a new time-of-flight, inverse-geometry, crystal-analyzer spectrometer. After an accurate data reduction, the high-energy parts of the neutron spectra recorded in backward scattering were studied through the modified Young and Koppel model, from which the mean kinetic energy values for a hydrogen molecule were estimated. In addition the low-energy parts of the neutron spectra recorded in forward scattering were analyzed in the framework of the Gaussian approximation and fitted through a Levesque-Verlet model for the velocity autocorrelation function. Thus various physical quantities are determined and compared with accurate path integral Monte Carlo simulations. Despite the excellent quality of these fits, the velocity autocorrelation functions derived from the forward-scattering data appear totally unable to properly describe the backward-scattering ones. These findings prove an unquestionable breakdown of the Gaussian approximation in semiquantum liquids. The present results appear of great interest and suggest further investigation on the limits of the widely used Gaussian approximation.

  14. The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

    SciTech Connect

    Johnson, Steven

    1999-02-12

    The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

  15. Controlling hydrolysis reaction rates with binary ionic liquid mixtures by tuning hydrogen-bonding interactions.

    PubMed

    Weber, Cameron C; Masters, Anthony F; Maschmeyer, Thomas

    2012-02-16

    The ability of a binary ionic liquid (IL) system consisting of a phosphonium transition state analogue (TSA) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([BMIM][NTf(2)]) to accelerate the rate of the well-studied hydrolysis of a tert-alkyl picolinium salt by influencing the solvent structure was investigated. A significant rate enhancement was observed in the presence of the TSA; however, comparison with other cations illustrated that this enhancement was not unique to the chosen TSA. Instead, the rate enhancements were correlated with the dilution of hydrogen bonding by the added cations. This phenomenon was further examined by the use of 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ([BMMIM][NTf(2)]) as a cosolvent and the use of Reichardt's dye to measure the extent of hydrogen bonding on solutes in these systems. The rate increases are rationalized in terms of weaker hydrogen bonding from the solvent system to water.

  16. High performance liquid chromatography study of complex oxygenated alkane mixtures from organic aerosols

    NASA Astrophysics Data System (ADS)

    Kalafut-Pettibone, Alicia J.; Klems, Joseph P.; McGivern, W. Sean

    2013-05-01

    The composition of secondary organic aerosol particles is of primary importance both in identifying particle sources and in determining physical parameters, such as cloud condensation nucleus propensity. Further, measurements of composition are valuable in determining the chemistry of formation and aging. In this work, we describe the application of a recently-developed derivatization technique to a complex synthetic organic aerosol derived from the photolysis of 1-iodooctane. The technique utilizes high-performance liquid chromatography (HPLC) coupled to both ultravioletvisible (UV/VIS) spectroscopy and tandem mass spectrometry (MS-MS) to determine the overall distribution of hydroxyl (OH), non-acid carbonyl (C=O), and carboxylic acid (COOH) moieties as well as the specific identities of chromatographically separated products. This composition data will then be used to constrain models of the particle formation mechanisms.

  17. Rapid hydrogen hydrate growth from non-stoichiometric tuning mixtures during liquid nitrogen quenching.

    PubMed

    Grim, R Gary; Kerkar, Prasad B; Sloan, E Dendy; Koh, Carolyn A; Sum, Amadeu K

    2012-06-21

    In this study the rapid growth of sII H(2) hydrate within 20 min of post formation quenching towards liquid nitrogen (LN(2)) temperature is presented. Initially at 72 MPa and 258 K, hydrate samples would cool to the conditions of ~60 MPa and ~90 K after quenching. Although within the stability region for H(2) hydrate, new hydrate growth only occurred under LN(2) quenching of the samples when preformed hydrate "seeds" of THF + H(2) were in the presence of unconverted ice. The characterization of hydrate seeds and the post-quenched samples was performed with confocal Raman spectroscopy. These results suggest that quenching to LN(2) temperature, a common preservation technique for ex situ hydrate analysis, can lead to rapid unintended hydrate growth. Specifically, guest such as H(2) that may otherwise need sufficiently long induction periods to nucleate, may still experience rapid growth through an increased kinetic effect from a preformed hydrate template.

  18. The structure of graphene oxide membranes in liquid water, ethanol and water-ethanol mixtures.

    PubMed

    Talyzin, Alexandr V; Hausmaninger, Tomas; You, Shujie; Szabó, Tamás

    2014-01-07

    The structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate the absence of "negative thermal expansion" and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are a distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed of the same graphene oxide flakes.

  19. Transient liquid-phase sintering using silver and tin powder mixture for die bonding

    NASA Astrophysics Data System (ADS)

    Fujino, Masahisa; Narusawa, Hirozumi; Kuramochi, Yuzuru; Higurashi, Eiji; Suga, Tadatomo; Shiratori, Toshiyuki; Mizukoshi, Masataka

    2016-04-01

    In this research, we develop transient liquid-phase bonding by uniaxial pressing using a Ag-Sn system. The Ag-Sn system was fabricated using Ag and Sn fine powder paste at optimized the proportions. The die bonding was performed for Cu substrates and metalized Si chips, and the sintering process was analyzed by cross-sectional observation. Die shear strength of bonded specimens was also measured. As a result, Ag-Sn completely formed a solid solution, also, Sn and Cu from substrates formed an intermetallic compound. The die shear strength was approximately 40 MPa obtained at 50 wt % Ag proportion of paste at 260, 280, and 300 °C sintering.

  20. Liquid gallium-lead mixture spinodal, binodal, and excess thermodynamic properties

    NASA Astrophysics Data System (ADS)

    Grosdidier, B.; Osman, S. M.; Ben Abdellah, A.

    2008-07-01

    A statistical mechanical based theory is developed for incorporating the effect of the long-range forces in Ga-Pb alloy. In particular, the simplified random-phase approximation is employed in conjunction with the Grosdidier [Phys. Rev. B 72, 024207 (2005)] model for GaGa and PbPb interactions while a suitable nonadditive pair potential is introduced between unlike atoms. We present analytical expressions for the equation of state and for the concentration fluctuations SCC(0) , and then the role of the nonadditivity parameter is established by consulting the empirical critical parameters of the spinodal curve. It becomes possible to deduce the behavior of different thermodynamic functions such as Gibbs energy of mixing, excess Gibbs energy, isobaric heat capacity, and SCC(0) in the vicinity of the liquid-liquid critical point and under extremely high pressure. The impact of temperature and pressure on segregation, and compound-forming tendencies is also investigated. Moreover, the immiscibility gap of the alloy is calculated and compared with the empirical results. The results suggest that: (i) the nonadditivity of the potential tails plays a dominant role in the determination of the spinodal curve, (ii) SCC(0) is a very sensitive function in triggering the chemical short-range order, and (iii) the segregation or phase separation in Ga-Pb alloy is an outcome of the temperature dependence of the energy mismatch parameter. In conclusion, the present equation of state is sufficiently accurate that it provides a binodal curve, an excess Gibbs energy of mixing and isobaric heat capacity in quantitatively good agreement with the empirical results.

  1. The inactivation of Chlorella spp. with dielectric barrier discharge in gas-liquid mixture

    NASA Astrophysics Data System (ADS)

    Song, Dan; Sun, Bing; Zhu, Xiaomei; Yan, Zhiyu; Liu, Hui; Liu, Yongjun

    2013-03-01

    The inactivation of Chlorella spp. with high voltage and frequency pulsed dielectric barrier discharge in hybrid gas-liquid reactor with a suspension electrode was studied experimentally. In the hybrid gas-liquid reactor, a steel plate was used as high voltage electrode while a quartz plate as a dielectric layer, another steel plate placing in the aqueous solution worked as a whole ground electrode. A suspension electrode is installed near the surface of solution between high voltage and ground electrode to make the dielectric barrier discharge uniform and stable, the discharge gap was between the quartz plate and the surface of the water. The effect of peak voltage, treatment time, the initial concentration of Chlorella spp. and conductivity of solution on the inactivation rate of Chlorella spp. was investigated, and the inactivation mechanism of Chlorella spp. preliminarily was studied. Utilizing this system inactivation of Chlorella spp., the inactivation rate increased with increasing of peak voltage, treatment time and electric conductivity. It was found that the inactivation rate of Chlorella spp. arrived at 100% when the initial concentration was 4 × 106 cells mL-1, and the optimum operation condition required a peak voltage of 20 kV, a treatment time of 10 min and a frequency of 7 kHz. Though the increasing of initial concentration of the Chlorella spp. contributed to the addition of interaction probability between the Chlorella spp. and O3, H2O2, high-energy electrons, UV radiation and other active substances, the total inactivation number raise, but the inactivation rate of the Chlorella spp. decreased.

  2. General Model for Multicomponent Ablation Thermochemistry

    NASA Technical Reports Server (NTRS)

    Milos, Frank S.; Marschall, Jochen; Rasky, Daniel J. (Technical Monitor)

    1994-01-01

    A previous paper (AIAA 94-2042) presented equations and numerical procedures for modeling the thermochemical ablation and pyrolysis of thermal protection materials which contain multiple surface species. This work describes modifications and enhancements to the Multicomponent Ablation Thermochemistry (MAT) theory and code for application to the general case which includes surface area constraints, rate limited surface reactions, and non-thermochemical mass loss (failure). Detailed results and comparisons with data are presented for the Shuttle Orbiter reinforced carbon-carbon oxidation protection system which contains a mixture of sodium silicate (Na2SiO3), silica (SiO2), silicon carbide (SiC), and carbon (C).

  3. Coexistence of two liquid crystalline phases in dihydrosphingomyelin and dioleoylphosphatidylcholine binary mixtures.

    PubMed

    Kinoshita, Masanao; Matsumori, Nobuaki; Murata, Michio

    2014-05-01

    Recently, DHSM, a minor constituent in naturally occurring SMs, was indicated to form a raft-like ordered phase more effectively than a naturally occurring form of SM because DHSM has greater potential to induce the intermolecular hydrogen bond. In order to examine the influence of the DHSM-induced hydrogen bond on the phase segregation, the thermal phase behavior of stearoyl-DHSM/DOPC binary bilayers was examined using calorimetry and fluorescence observation and compared with that of SSM/DOPC binary bilayers. Results revealed that the DHSM/DOPC bilayers undergo phase segregation between two L(α) phases within a limited compositional range. On the other hand, apparent phase separation was not observed above main transition temperature in SSM/DOPC mixtures. Our monolayer measurements showed that the lipid packing of DHSM is less perturbed than that of SSM by the addition of small amount of DOPC, indicating a stronger hydrogen bond between DHSM molecules. Therefore, in DHSM/DOPC binary bilayers, DHSM molecules may locally accumulate to form a DHSM-rich domain due to a DHSM-induced hydrogen bond. On the other hand, excess accumulation of DHSM should be prevented because the difference in the curvature between DHSM and DOPC assemblies causes elastic constraint at the domain boundary between the DHSM-rich and DOPC-rich domains. Competition between the energetic advantages provided by formation of the hydrogen bond and the energetic disadvantage conferred by elastic constraints likely results in L(α)/L(α) phase separation within a limited compositional range.

  4. Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

    PubMed

    Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

    2012-02-02

    The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

  5. Vapor-liquid critical surface of ternary difluoromethane + pentafluoroethane + 1,1,1,2-tetrafluoroethane (R-32/125/134a) mixtures

    SciTech Connect

    Higashi, Y.

    1999-09-01

    The plane of vapor-liquid criticality for ternary refrigerant mixtures of difluoromethane (R-32) + pentafluoroethane (R-125) + 1,1,1,2-tetrafluoroethane (R-134a) was determined from data on the vapor-liquid coexistence curve near the mixture critical points. The composition (mass percentage) of the mixtures studied were 23% R-32 + 25% R-125 + 52% R-134a (R-407C). 25% R-32 + 15% R-125 + 60% R-134a (R-407E), and 20% R-32 + 40% R-125 + 40% R-134a (R-407A). The critical temperature of each mixture was determined by observation of the disappearance of the meniscus. The critical density of each mixture was determined on the basis of meniscus disappearance level and the intensity of the critical opalescence. The uncertainties of the temperature, density, and composition measurements are estimated as {+-}10mK, {+-}5kg{center_dot}m{sup {minus}3}, and {+-}0.05%, respectively. In addition, predictive methods for the critical parameters of R-32/125/134a mixtures are discussed.

  6. Proton-transfer reactions of acridine in water-containing ionic-liquid-rich mixtures.

    PubMed

    Kumar, Vinod; Pandey, Ashish; Pandey, Siddharth

    2013-12-02

    To assess the potential of ionic liquids (ILs) as a solubilizing media that facilitates proton-transfer reactions, acridine prototropism is investigated using UV/Vis molecular absorbance as well as steady-state and time-resolved fluorescence with different ILs in the presence of a small amount of dilute acid or base. It is found that protonation and deprotonation of acridine, when dissolved in different ILs, can be triggered by the addition of a small amount of dilute aqueous HCl and NaOH, respectively, in both the ground and excited states, irrespective of the identity of the IL. However, the amount of dilute acid/base needed to protonate/deprotonate acridine dissolved in different ILs is found to vary from one IL to another. Steady-state fluorescence measurements also imply the presence of interactions between the acidic proton(s) of IL cation and excited acridine. The interconversion of neutral and protonated acridine, as well as the presence of a weakly fluorescent complex between excited acridine and the acidic proton(s) of the IL cation, is further corroborated by the parameters recovered from the fitting of the excited-state intensity-decay data. It is established that ILs as solubilizing media readily support facile proton transfer in both ground and excited states.

  7. Interactions in Water-Ionic Liquid Mixtures: Comparing Protic and Aprotic Systems.

    PubMed

    Reid, Joshua E S J; Gammons, Richard J; Slattery, John M; Walker, Adam J; Shimizu, Seishi

    2017-01-26

    The sensitivity of ionic liquids (ILs) to water affects their physical and chemical properties, even at relatively low concentrations, yet the structural thermodynamics of protic IL- (PIL-) water systems at low water concentrations still remains unclear. Using the rigorous Kirkwood-Buff theory of solutions, which can quantify the interactions between species in IL-water systems solely from thermodynamic data, we have shown the following: (1) Between analogous protic and aprotic ILs (AILs), the AIL cholinium bis(trifluoromethanesulfonyl)imide ([Ch][NTf2]) shows stronger interactions with water at low water concentrations, with the analogous PIL N,N-dimethylethanolammonium bis(trifluoromethanesulfonyl)imide ([DMEtA][NTf2]) having stronger water-ion interactions at higher water contents, despite water-ion interactions weakening with increasing water content in both systems. (2) Water has little effect on the average ion-ion interactions in both protic and aprotic ILs, aside from the AIL [Ch][NTf2], which shows a strengthening of ion-ion interactions with increasing water content. (3) Self-association of water in both PIL-water systems leading to the presence of large aggregates of water in IL-rich compositions has been inferred. Water-water interactions in [DMEtA][NTf2] were found to be similar to those of dialkylimidazolium AILs, whereas these interactions were much larger in the PIL N,N-dimethylethanolammonium propionate ([DMEtA][Pr]), attributed to the change in anion-water interactions.

  8. Influence of vibration on diffusion in liquid mixtures on-board the international space station

    NASA Astrophysics Data System (ADS)

    Parsa, Aram

    Experiments on-board the International Space Station experience a convective flow due to the oscillatory g-jitters induced by several sources such as crew activities, mechanical systems, thrusters firing, spacecraft docking, etc. Although g-jitter seems to have a major impact on diffusion-related experiments in Space, very few experimental studies have addressed this topic. This study examined the effect of oscillatory g-jitters on transport processes (fluid flow, heat transfer and mass transfer). Cubic rigid cells filled with water and isopropanol at different concentrations were subjected to thermal gradients and forced vibrations. The cells were exposed to different levels of vibration in terms of frequency and amplitude, which were applied perpendicular to the temperature gradient. The full transient Navier Stokes equations coupled with the mass and heat transfer formulas were solved numerically using the control volume technique. The physical properties of the fluid mixture such as the density were determined using two different models. The effect of different levels of vibration on the flow was analysed and the results were compared in a benchmark study with other scientific groups. The effect of the diffusion coefficients variation and other physical properties on the temperature and concentration distribution was compared to those results obtained with constant diffusion coefficients. Results show that use of variable physical properties in the modelling produces different flow patterns and component concentration. By examining different flow patterns, it was found that the effect of using variable coefficients is much more significant in the cases with high Rayleigh vibration that result in strong flow when compared with numerical analysis using constant variables. The numerical analysis was also performed for the actual experiment on board the International Space Station. The same trend was seen for both the numerical and experimental results. However

  9. Influence of Trace Elements Mixture on Bacterial Diversity and Fermentation Characteristics of Liquid Diet Fermented with Probiotics under Air-Tight Condition

    PubMed Central

    Liu, Xiaolan; Wang, Chengwei; Lu, Wei

    2014-01-01

    Cu2+, Zn2+, Fe2+ and I− are often supplemented to the diet of suckling and early weaning piglets, but little information is available regarding the effects of different Cu2+, Zn2+, Fe2+ and I− mixtures on bacteria growth, diversity and fermentation characteristics of fermented liquid diet for piglets. Pyrosequencing was performed to investigate the effect of Cu2+, Zn2+, Fe2+ and I− mixtures on the diversity, growth and fermentation characteristics of bacteria in the liquid diet fermented with Bacillus subtilis and Enterococcus faecalis under air-tight condition. Results showed that the mixtures of Cu2+, Zn2+, Fe2+ and I− at different concentrations promoted Bacillus growth, increased bacterial diversity and lactic acid production and lowered pH to about 5. The importance of Cu2+, Zn2+, Fe2+ and I− is different for Bacillus growth with the order Zn2+> Fe2+>Cu2+> I− in a 21-d fermentation and Cu2+>I−>Fe2+>Zn2+ in a 42-d fermentation. Cu2+, Zn2+, Fe2+ and I− is recommended at a level of 150, 60, 150 and 0.6 mg/kg respectively for the production of fermented liquid diet with Bacillus subtilis. The findings improve our understanding of the influence of trace elements on liquid diet fermentation with probiotics and support the proper use of trace elements in the production of fermented liquid diet for piglets. PMID:25486254

  10. Influence of trace elements mixture on bacterial diversity and fermentation characteristics of liquid diet fermented with probiotics under air-tight condition.

    PubMed

    He, Yuyong; Chen, Zhiyu; Liu, Xiaolan; Wang, Chengwei; Lu, Wei

    2014-01-01

    Cu2+, Zn2+, Fe2+ and I- are often supplemented to the diet of suckling and early weaning piglets, but little information is available regarding the effects of different Cu2+, Zn2+, Fe2+ and I- mixtures on bacteria growth, diversity and fermentation characteristics of fermented liquid diet for piglets. Pyrosequencing was performed to investigate the effect of Cu2+, Zn2+, Fe2+ and I- mixtures on the diversity, growth and fermentation characteristics of bacteria in the liquid diet fermented with Bacillus subtilis and Enterococcus faecalis under air-tight condition. Results showed that the mixtures of Cu2+, Zn2+, Fe2+ and I- at different concentrations promoted Bacillus growth, increased bacterial diversity and lactic acid production and lowered pH to about 5. The importance of Cu2+, Zn2+, Fe2+ and I- is different for Bacillus growth with the order Zn2+> Fe2+>Cu2+> I- in a 21-d fermentation and Cu2+>I->Fe2+>Zn2+ in a 42-d fermentation. Cu2+, Zn2+, Fe2+ and I- is recommended at a level of 150, 60, 150 and 0.6 mg/kg respectively for the production of fermented liquid diet with Bacillus subtilis. The findings improve our understanding of the influence of trace elements on liquid diet fermentation with probiotics and support the proper use of trace elements in the production of fermented liquid diet for piglets.

  11. Molecular dynamics simulations of the structure of the graphene-ionic liquid/alkali salt mixtures interface.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Lynden-Bell, Ruth M; Varela, Luis M

    2014-07-14

    We performed molecular dynamics simulations of mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate with lithium tetrafluoroborate and potassium tetrafluoroborate between two charged and uncharged graphene walls, in order to analyze the structure of the well-known formation of layers that takes place on liquids under confinement. For this purpose, we studied the molecular density profiles, free energy profiles for bringing lithium and potassium cations from the bulk mixture to the graphene wall and the orientational distributions of imidazolium rings within the first adsorbed layer as a function of salt concentration and electrode potential. The charge densities in the electrodes were chosen to be zero and ±1 e nm(-2), and the salt molar percentages were %salt = 0, 10 and 25. We found that the layered structure extends up to 1-2 nm, where the bulk behaviour is recovered. In addition, whereas for the neutral surface the layers are composed of both ionic species, increasing the electrode potential, the structure changes to alternating cationic and anionic layers leading to an overcompensation of the charge of the previous layer. We also calculated the distribution of angles of imidazolium rings near neutral and charged graphene walls, finding a limited influence of the added salt. In addition, the average tilt of the imidazolium ring within the first layer goes from 36° with respect to a normal vector to the uncharged graphene wall to 62° in the presence of charged walls. The free energy profiles revealed that lithium and potassium ions are adsorbed on the negative surface only for the highest amount of salt, since the free energy barriers for approaching this electrode are considerably higher than kBT.

  12. Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

    PubMed

    Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

    2015-01-01

    Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

  13. Heat transfer and lethality considerations in aseptic processing of liquid/particle mixtures: a review.

    PubMed

    Ramaswamy, H S; Awuah, G B; Simpson, B K

    1997-04-01

    Consumer awareness and demand for nutritious yet inexpensive food products call for innovative processing techniques that have both safety and quality as primary objectives. These challenges appear to have been met by aseptic processing techniques, especially for liquid and high-acid foods. However, the extension of aseptic processing principles to low-acid foods containing discrete particles in viscous sauces has not been approved by regulatory agencies, particularly in North America. This apparent limitation is due primarily to the lack of adequate temperature monitoring devices to keep track of particles in dynamic motion, as well as to the residence time distribution of particles flowing in the continuous heat-hold-cool sections of the aseptic processing system. These problems have prompted active research to describe the phenomenal behavior of particulates through sound mathematical modeling and computer simulators. The accuracy of mathematical models depends heavily on how accurate input parametric values are. These parameters include the thermophysical properties of the carrier fluid and particles, as well as the aseptic processing system characteristics in relation to residence time distribution and the fluid-to-particle interfacial heat transfer coefficient. Apparently, several contradictory findings have been reported in the literature with respect to the effect of various processing parameters on the above-mentioned input parametric values. The need therefore arises for more collaborative studies involving the industry and academia. This review brings to perspective, the current status on the aseptic processing of particulate foods with respect to the critical processing parameters which affect the fluid-to-particle convective heat transfer coefficient associated with particulate laden products.

  14. Lyotropic liquid crystal to soft mesocrystal transformation in hydrated salt-surfactant mixtures.

    PubMed

    Albayrak, Cemal; Barım, Gözde; Dag, Ömer

    2013-10-25

    Hydrated CaCl2, LiI, and MgCl2 salts induce self-assembly in nonionic surfactants (such as C12H25(OCH2CH2)10OH) to form lyotropic liquid-crystalline (LLC) mesophases that undergo a phase transition to a new type of soft mesocrystal (SMC) under ambient conditions. The SMC samples can be obtained by aging the LLC samples, which were prepared as thin films by spin-coating, dip-coating, or drop-casting of a clear homogenized solution of water, salt, and surfactant over a substrate surface. The LLC mesophase exists up to a salt/surfactant mole ratio of 8, 10, and 4 (corresponding to 59, 68, and 40 wt% salt/surfactant) in the CaCl2, LiI, and MgCl2 mesophases, respectively. The SMC phase can transform back to a LLC mesophase at a higher relative humidity. The phase transformations have been monitored using powder X-ray diffraction (PXRD), polarized optical microscopy (POM), and FTIR techniques. The LLC mesophases only diffract at small angles, but the SMCs diffract at both small and wide angles. The broad surfactant features in the FTIR spectra of the LLC mesophases become sharp and well resolved upon SMC formation. The unit cell of the mesophases expands upon SMC transformation, in which the expansion is largest in the MgCl2 and smallest in the CaCl2 systems. The POM images of the SMCs display birefringent textures with well-defined edges, similar to crystals. However, the surface of the crystals is highly patterned, like buckling patterns, which indicates that these crystals are quite soft. This unusual phase behavior could be beneficial in designing new soft materials in the fields of phase-changing materials and mesostructured materials, and it demonstrates the richness of the phase behavior in the salt-surfactant mesophases.

  15. A new method for measuring the dynamic surface tension of complex-mixture liquid drops

    SciTech Connect

    Zhang, X.; Harris, M.T.; Basaran, O.A.

    1994-06-29

    A simple and accurate technique has been developed for measuring dynamic surface tension. The new technique is based on growing a drop at the end of a fine capillary into another immiscible fluid and can follow the changes in tension at a freshly formed interface during its entire period of evolution. When the relative importance of the surface tension force is large compared to gravitational and viscous forces, shapes of growing drops are sections of spheres and the difference in pressure between the interior and the exterior of the drop {triangle}p is related to the surface tension {sigma} and the radius of curvature R by the static Young-Laplace formula {triangle}p = 2{sigma}/R. In contrast to related work, the new technique can determine the surface tension of an interface with a surface age of a few to tens of milliseconds by measuring transient drop shapes and pressures in 1/6 to 1 millisecond. The capabilities of the new method are demonstrated by performing tension measurements on liquid systems that do not exhibit dynamic surface tension as well as ones that exhibit significant dynamic tension effects. Tension measurements made with surfactant-laden solutions show that variation of surface tension is nonmonotonic in time. In such systems, the dynamic behavior of surface tension is shown to depend upon both the rate of interfacial dilatation and that of surfactant transport. A maximum in the surface tension is attained when the lowering of the surfactant concentration on the drop interface due to its dilatation is balanced by the addition of fresh surfactant to the interface by convection and diffusion.

  16. Photophysics of 3,3'-diethyloxadicarbocyanine iodide (DODCI) in ionic liquid micelle and binary mixtures of ionic liquids: effect of confinement and viscosity on photoisomerization rate.

    PubMed

    Ghosh, Surajit; Mandal, Sarthak; Banerjee, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

    2012-08-09

    The dynamics of photoisomerization of 3,3'-diethyloxadicarbocyanine iodide (DODCI) has been investigated inside micellar environment formed by a surfactant-like ionic liquid, 1-butyl-3-methylimidazolium octyl sulfate ([C(4)mim][C(8)SO(4)]) and also in binary mixture of another ionic liquid, N,N,N-trimethyl-N-propyl ammonium bis(trifluoromethanesulfonyl) imide, ([N(3111)][Tf(2)N]) with methanol, acetonitrile, and n-propanol by using steady-state and picosecond time-resolved fluorescence spectroscopy. The entrapment of DODCI into the [C(4)mim][C(8)SO(4)] micellar environment led to the enhanced fluorescence intensity along with ~13 nm red shift in the emission maxima. A sharp increase in the fluorescence quantum yield (Φ) and the lifetime (τ(f)) near the critical micelle concentration (cmc) range is observed followed by saturation at higher concentration. As a result of partitioning of the probe molecules in the micellar phase from water, the nonradiative rate constant (k(nr)) of DODCI decreases 2.7 times than in water. The retardation of isomerization rate is due to high microviscosity of the micellar system compared to bulk water. In order to understand how the rate of isomerization depends on polarity as well as viscosity, we have measured isomerization rate in neat [N(3111)][Tf(2)N] and its mixtures with polar solvents, like methanol, acetonitrile, and n-propanol. The addition of methanol and n-propanol increases the polarity, but viscosity of the medium decreases. The nonradiative rate constant that represents the rate of photoisomerization decreases with the addition of the polar solvent in [N(3111)][Tf(2)N]. Complete analysis of all the experimental results indicate that viscosity is the sole parameter that regulates the rate of photoisomerization. Temperature-dependent k(nr) are used to determine the activation energy (E(a)) in 100 mM [C(4)mim][C(8)SO(4)] solution and neat [N(3111)][Tf(2)N] system.

  17. Enhanced CO2 capture in binary mixtures of 1-alkyl-3-methylimidazolium tricyanomethanide ionic liquids with water.

    PubMed

    Romanos, George E; Zubeir, Lawien F; Likodimos, Vlassis; Falaras, Polycarpos; Kroon, Maaike C; Iliev, Boyan; Adamova, Gabriela; Schubert, Thomas J S

    2013-10-10

    Absorption of carbon dioxide and water in 1-butyl-3-methylimidazoliun tricyanomethanide ([C4C1im][TCM]) and 1-octyl-3-methylimidazolium tricyanomethanide ([C8C1im][TCM]) ionic liquids (ILs) was systematically investigated for the first time as a function of the H2O content by means of a gravimetric system together with in-situ Raman spectroscopy, excess molar volume (V(E)), and viscosity deviation measurements. Although CO2 absorption was marginally affected by water at low H2O molar fractions for both ILs, an increase of the H2O content resulted in a marked enhancement of both the CO2 solubility (ca. 4-fold) and diffusivity (ca. 10-fold) in the binary [C(n)C1im][TCM]/H2O systems, in contrast to the weak and/or detrimental influence of water in most physically and chemically CO2-absorbing ILs. In-situ Raman spectroscopy on the IL/CO2 systems verified that CO2 is physically absorbed in the dry ILs with no significant effect on their structural organization. A pronounced variation of distinct tricyanomethanide Raman modes was disclosed in the [C(n)C1im][TCM]/H2O mixtures, attesting to the gradual disruption of the anion-cation coupling by the hydrogen-bonded water molecules to the [TCM](-) anions, in accordance with the positive excess molar volumes and negative viscosity deviations for the binary systems. Most importantly, CO2 absorption in the ILs/H2O mixtures at high water concentrations revealed that the [TCM](-) Raman modes tend to restore their original state for the heavily hydrated ILs, in qualitative agreement with the intriguing nonmonotonous transients of CO2 absorption kinetics unveiled by the gravimetric measurements for the hybrid solvents. A molecular exchange mechanism between CO2 in the gas phase and H2O in the liquid phase was thereby proposed to explain the enhanced CO2 absorption in the hybrid [C(n)C1im][TCM]//H2O solvents based on the subtle competition between the TCM-H2O and TCM-CO2 interactions, which renders these ILs very promising for CO2

  18. Li+ solvation and transport properties in ionic liquid/lithium salt mixtures: a molecular dynamics simulation study.

    PubMed

    Li, Zhe; Smith, Grant D; Bedrov, Dmitry

    2012-10-25

    Molecular dynamics simulations of N-methyl-N-propylpyrrolidinium (pyr(13)) bis(trifluoromethanesulfonyl)imide (Ntf(2)) ionic liquid [pyr(13)][Ntf(2)] mixed with [Li][Ntf(2)] salt have been conducted using a polarizable force field. Mixture simulations with lithium salt mole fractions between 0% and 33% at 363 and 423 K yield densities, ion self-diffusion coefficients, and ionic conductivities in very good agreement with available experimental data. In all investigated electrolytes, each Li(+) cation was found to be coordinated, on average, by 4.1 oxygen atoms from surrounding anions. At lower concentrations (x ≤ 0.20), the Li(+) cation was found to be, on average, coordinated by slightly more than three Ntf(2) anions with two anions contributing a single oxygen atom and one anion contributing two oxygen atoms to Li(+) coordination. At the highest [Li][Ntf(2)] concentration, however, there were, on average, 3.5 anions coordinating each Li(+) cation, corresponding to fewer bidendate and more monodentate anions in the Li(+) coordination sphere. This trend is due to increased sharing of anions by Li(+) at higher salt concentrations. In the [pyr(13)][Ntf(2)]/[Li][Ntf(2)] electrolytes, the ion diffusivity is significantly smaller than that in organic liquid electrolytes due to not only the greater viscosity of the solvent but also the formation of clusters resulting from sharing of anions by Li(+) cations. The ionic conductivity of the electrolytes was found to decrease with increasing salt concentration, with the effect being greater at the higher temperature. Finally, we found that the contribution of Li(+) to ionic conductivity does not increase proportionally to Li(+) concentration but saturates at higher doping levels.

  19. Diverging Thermodynamic Derivatives Associated with Heterogeneous Chemical Equilibrium in a Binary Liquid Mixture with a Consolute Point

    NASA Astrophysics Data System (ADS)

    Hu, B.; Baird, J. K.; Alvarez, P. K.; Melton, K. C.; Barlow, D. A.; Richey, R. D.

    2014-05-01

    The solubilities of tin(II) oxide, copper(II) oxide, and cobalt(II) oxide have been determined in the liquid mixture, isobutyric acid + water, along the critical isopleth. When plotted in van't Hoff form with versus , the solubility measurements, , lie on a straight line for values of the temperature, , which are sufficiently in excess of the critical solution temperature, In the case of SnO, the dissolution reaction is exothermic, and the slope of the van't Hoff plot diverges toward positive infinity as In the case of both CuO and CoO, the dissolution reaction is endothermic, and the slope of the van't Hoff plot diverges toward negative infinity as Analysis of these ternary, heterogeneous equilibria using finite dimensional vector space stoichiometry theory shows that each contains two linearly independent components. According to the Gibbs phase rule, two-phase equilibria of this type can be described by two fixed, intensive variables, which are accounted for by the temperature and the pressure, respectively. The Gibbs-Helmholtz equation and the principle of critical-point universality can be combined to predict under conditions of fixed temperature and pressure that when dissolution is exothermic, should diverge toward positive infinity in the critical region, while when dissolution is endothermic, should diverge toward negative infinity. Our experiments include examples confirming both these predictions.

  20. Molecular interactions in the ionic liquid emim acetate and water binary mixtures probed via NMR spin relaxation and exchange spectroscopy.

    PubMed

    Allen, Jesse J; Bowser, Sage R; Damodaran, Krishnan

    2014-05-07

    Interactions of ionic liquids (ILs) with water are of great interest for many potential IL applications. 1-Ethyl-3-methylimidazolium (emim) acetate, in particular, has shown interesting interactions with water including hydrogen bonding and even chemical exchange. Previous studies have shown the unusual behavior of emim acetate when in the presence of 0.43 mole fraction of water, and a combination of NMR techniques is used herein to investigate the emim acetate-water system and the unusual behavior at 0.43 mole fraction of water. NMR relaxometry techniques are used to describe the effects of water on the molecular motion and interactions of emim acetate with water. A discontinuity is seen in nuclear relaxation behavior at the concentration of 0.43 mole fraction of water, and this is attributed to the formation of a hydrogen bonded network. EXSY measurements are used to determine the exchange rates between the H2 emim proton and water, which show a complex dependence on the concentration of the mixture. The findings support and expand our previous results, which suggested the presence of an extended hydrogen bonding network in the emim acetate-water system at concentrations close to 0.50 mole fraction of H2O.

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

    PubMed

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

    2014-05-01

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

  2. Simultaneous determination of acetaminophen, guaifenesin, pseudoephedrine, pholcodine, and paraben preservatives in cough mixture by high-performance liquid chromatography.

    PubMed

    Carnevale, L

    1983-02-01

    The separation and simultaneous determination, by high-performance liquid chromatography, of acetaminophen (I), guaifenesin (II), pseudoephedrine hydrochloride (III), and pholcodine (IV), together with a series of parabens (methyl to butyl, V-VIII) in a cough mixture, has been demonstrated using a chemically bonded octadecylsilane stationary phase with a mobile phase of methanol-water-acetic acid (45:55:2) containing the ion-pairing agent octanesulfonic acid. Retention volumes for the active ingredients were 3.8 ml, 5.4 ml, 9.4 ml, and 15.6 ml for compounds I-IV, respectively. Corrected retention volumes for the parabens [5.4 ml for methyl (V), 9.6 ml for ethyl (VI), 18.5 ml for propyl (VII), and 37.9 ml for butyl (VIII)] showed an exponential relationship with chain length of the esterifying alcohols. Excipients did not interfere with the estimation of any of the compounds, hence pretreatment of the sample was unnecessary. Average recoveries of the active ingredients and of the parabens from laboratory prepared samples were essentially 100% of theoretical with standard deviations of 1.7, 0.3, 1.5, 0.3, 0.3, 3.3, 0.7, and 2.7% for I-VIII, respectively.

  3. A microscale electrospray interface for on-line, capillary liquid chromatography/tandem mass spectrometry of complex peptide mixtures.

    PubMed

    Davis, M T; Stahl, D C; Hefta, S A; Lee, T D

    1995-12-15

    A microcapillary liquid chromatography (HPLC) system designed for the gradient elution of peptide and protein samples at flow rates < 1 microL/min has been coupled to a triple-sector quadrupole mass spectrometer via a simple sheathless electrospray interface (microspray). The microspray interface used a flame-drawn, uncoated, fused silica needle with tip outer diameters in the range of 15-20 microm and an opening less than 5 microm in diameter. Online sample filtration to prevent clogging of the drawn needle was accomplished by using a hydrophilic PVDF membrane filter integrated into the needle assembly. The spray potential (0.5-1 kV) was applied directly to the sample stream through the capillary union. Stable electrospray conditions were obtained over the full range of the gradient (0-90% acetonitrile in water) and was generally independent of flow rate. Both off-line and online analyses of proteins and peptide digest mixtures were performed at sample levels less than 10 fmol. HPLC parameters could be optimized for either rapid LC/MS analysis or enhanced performance in LC/MS/MS experiments by modulation of the eluting peak widths. Additionally, flow could be greatly reduced as selected components pass through the interface to prolong the time available to collect mass spectral data. The reduced spectral background and peak width manipulation facilitated the acquisition of peptide production spectra (MS/MS) using real-time, automated instrument control procedures.

  4. Mechanics of Turbulence of Multicomponent Gases

    NASA Astrophysics Data System (ADS)

    Marov, Mikhail Ya.; Kolesnichenko, Aleksander V.

    2002-02-01

    Turbulence in multicomponent reacting gas mixtures is an important mechanism underlying numerous natural phenomena closely related to the study of our space environment. This book develops a new mathematical approach for modelling multicomponent gas turbulence that adequately describes the combined processes of dynamics and heat and mass transfer when chemical kinetics and turbulent mixing are equally important. The developed models include the evolutionary transfer equations for the single-point second correlation moments of turbulent fluctuations of thermohydrodynamical parameters. The phenomenological approach to the closure problem in hydrodynamic equations of mean motion at the level of the first order moments is based on the thermodynamics of irreversible processes and enables defining relationships in a more general form as compared to those conventionally deduced using the mixing path concept. Based on the developed approach, turbulent exchange factors for a planetary upper atmosphere are evaluated, and a turbulent model of a protoplanetary accretion gas-dust disk involving heat and mass transfer and coagulation is also considered. As compared to previously published books on the problem of turbulence, this book deals, for the first time, with the complicated models of reacting gas mixtures. It is intended for graduate and postgraduate students in the fields of fluid gas dynamics, astrophysics, space physics, planetary sciences, and aeronomy, and especially for those dealing with computer modelling of the processes in such natural media. The book may also be of interest to specialists in the relevant fields of ecology, engineering, and material processing.

  5. On the transition between two-phase and single-phase interface dynamics in multicomponent fluids at supercritical pressures

    NASA Astrophysics Data System (ADS)

    Dahms, Rainer N.; Oefelein, Joseph C.

    2013-09-01

    A theory that explains the operating pressures where liquid injection processes transition from exhibiting classical two-phase spray atomization phenomena to single-phase diffusion-dominated mixing is presented. Imaging from a variety of experiments have long shown that under certain conditions, typically when the pressure of the working fluid exceeds the thermodynamic critical pressure of the liquid phase, the presence of discrete two-phase flow processes become diminished. Instead, the classical gas-liquid interface is replaced by diffusion-dominated mixing. When and how this transition occurs, however, is not well understood. Modern theory still lacks a physically based model to quantify this transition and the precise mechanisms that lead to it. In this paper, we derive a new model that explains how the transition occurs in multicomponent fluids and present a detailed analysis to quantify it. The model applies a detailed property evaluation scheme based on a modified 32-term Benedict-Webb-Rubin equation of state that accounts for the relevant real-fluid thermodynamic and transport properties of the multicomponent system. This framework is combined with Linear Gradient Theory, which describes the detailed molecular structure of the vapor-liquid interface region. Our analysis reveals that the two-phase interface breaks down not necessarily due to vanishing surface tension forces, but due to thickened interfaces at high subcritical temperatures coupled with an inherent reduction of the mean free molecular path. At a certain point, the combination of reduced surface tension, the thicker interface, and reduced mean free molecular path enter the continuum length scale regime. When this occurs, inter-molecular forces approach that of the multicomponent continuum where transport processes dominate across the interfacial region. This leads to a continuous phase transition from compressed liquid to supercritical mixture states. Based on this theory, a regime diagram for

  6. Determination of multicomponent contents in Calculus bovis by ultra-performance liquid chromatography-evaporative light scattering detection and its application for quality control.

    PubMed

    Kong, Weijun; Jin, Cheng; Xiao, Xiaohe; Zhao, Yanling; Liu, Wei; Li, Zulun; Zhang, Ping

    2010-06-01

    A fast ultra-performance liquid chromatography-evaporative light scattering detection (UPLC-ELSD) method was established for simultaneous quantification of seven components in natural Calculus bovis (C. bovis) and its substitutes or spurious breeds. On a Waters Acquity UPLC BEH C(18) column, seven analytes were efficiently separated using 0.2% aqueous formic acid-acetonitrile as the mobile phase in a gradient program. The evaporator tube temperature of ELSD was set at 100 degrees C with the nebulizing gas flow-rate of 1.9 L/min. The results showed that this established UPLC-ELSD method was validated to be sensitive, precise and accurate with the LODs of seven analytes at 2-11 ng, and the overall intra-day and inter-day variations less than 3.0%. The recovery of the method was in the range of 97.8-101.6%, with RSD less than 3.0%. Further results of PCA on the contents of seven investigated analytes suggested that compounds of cholic acid, deoxycholic acid and chenodeoxycholic acid or cholesterol should be added as chemical markers to UPLC analysis of C. bovis samples for quality control and to discriminate natural C. bovis sample and its substitutes or some spurious breeds, then normalize the use of natural C. bovis and ensure its clinical efficacy.

  7. Segregation by Complementarity of nanoDNA based on Liquid Crystal Ordering and Centrifugation

    NASA Astrophysics Data System (ADS)

    Smith, Gregory; Tsai, Ethan; Robins, T.; Khodaghulyan, Armond; Zanchetta, Giuliano; Fraccia, Tommaso; Bellini, Tommaso; Walba, David; Clark, Noel

    2012-02-01

    Nanometer length DNA segments ( <20 base pair long) that are complementary can duplex and condense to make liquid crystal phases at concentrations >˜500 mg/mL This nanoDNA duplexing combined with order-disorder phase separation offers a means of sequestering molecules in mixtures of different DNA sequences based on their degree of complementarity. Here we show that isotropic and liquid crystalline phases, comprising respectively single strands and duplexes in multi-component nanoDNA solutions, can be physically separated by liquid crystal condensation followed by centrifugation.

  8. Criteria for Modeling in LES of Multicomponent Fuel Flow

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Selle, Laurent

    2009-01-01

    A report presents a study addressing the question of which large-eddy simulation (LES) equations are appropriate for modeling the flow of evaporating drops of a multicomponent liquid in a gas (e.g., a spray of kerosene or diesel fuel in air). The LES equations are obtained from the direct numerical simulation (DNS) equations in which the solution is computed at all flow length scales, by applying a spatial low-pass filter. Thus, in LES the small scales are removed and replaced by terms that cannot be computed from the LES solution and instead must be modeled to retain the effect of the small scales into the equations. The mathematical form of these models is a subject of contemporary research. For a single-component liquid, there is only one LES formulation, but this study revealed that for a multicomponent liquid, there are two non-equivalent LES formulations for the conservation equations describing the composition of the vapor. Criteria were proposed for selecting the multicomponent LES formulation that gives the best accuracy and increased computational efficiency. These criteria were applied in examination of filtered DNS databases to compute the terms in the LES equations. The DNS databases are from mixing layers of diesel and kerosene fuels. The comparisons resulted in the selection of one of the multicomponent LES formulations as the most promising with respect to all criteria.

  9. Structural origin of proton mobility in a protic ionic liquid/imidazole mixture: insights from computational and experimental results.

    PubMed

    Yaghini, Negin; Gómez-González, Víctor; Varela, Luis M; Martinelli, Anna

    2016-08-17

    The structure, dynamics, and phase behavior of a binary mixture based on the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide (C2HImTFSI) and imidazole are investigated by (1)H NMR spectroscopy, vibrational spectroscopy, diffusion NMR, calorimetric measurements, and molecular dynamics simulations. Particular attention is given to the nature of the H-bonds established and the consequent occurrence of the Grotthuss mechanism of proton transfer. We find that due to their structural similarity, the imidazolium cation and the imidazole molecule behave as interchangeable and competing sites of interaction for the TFSI anion. All investigated properties, that is the phase behavior, strength of ion-ion and ion-imidazole interactions, number of specific H-bonds, density, and self-diffusivity, are composition dependent and show trend changes at mole fractions of imidazole (χ) approximately equal to 0.2 and 0.5. Beyond χ = 0.8 imidazole is not miscible in C2HImTFSI at room temperature. We find that at the equimolar composition (χ ≈ 0.5) a structural transition occurs from an ionic network mainly stabilized by coulombic forces to a mixed phase held together by site specific H-bonds. The same composition also marks a steeper decrease in density and increase in diffusivity, resulting from the preference of imidazole molecules to H-bond to each other in a chain-like manner. As a result of these structural features the Grotthuss mechanism of proton transfer is less favored at the equimolar composition where H-bonds are too stable. By contrast, the Grotthuss mechanism is more pronounced in the low concentration range where imidazole acts as a base pulling the proton of the imidazolium cation. At high imidazole concentrations the contribution from the vehicular mechanism dominates.

  10. Liquid chromatographic determination of sitagliptin either alone or in ternary mixture with metformin and sitagliptin degradation product.

    PubMed

    El-Bagary, Ramzia I; Elkady, Ehab F; Ayoub, Bassam M

    2011-07-15

    Two reversed-phase liquid chromatographic (RP-LC) methods have been developed for the determination of sitagliptin phosphate monohydrate (STG). The first method comprised the determination of STG alone in bulk and plasma; and in its pharmaceutical preparation. This method was based on isocratic elution of STG using a mobile phase consisting of potassium dihydrogen phosphate buffer pH (7.8)-acetonitrile (70:30, v/v) at a flow rate of 1 mL min(-1) with flourometric detection. The flourometric detector was operated at 267 nm for excitation and 575 nm for emission. In the second method, the simultaneous determination of STG and metformin (MET) in the presence of sitagliptin alkaline degradation product (SDP) has been developed. In this method, the ternary mixture of STG, MET and SDP was separated using a mobile phase consisting of potassium dihydrogen phosphate buffer pH (4.6)-acetonitrile-methanol (30:50:20, v/v/v) at a flow rate of 1 mL min(-1) with UV detection at 220 nm. Chromatographic separation in the two methods was achieved on a Symmetry(®) Waters C18 column (150 mm×4.6 mm, 5 μm). Linearity, accuracy and precision were found to be acceptable over the concentration ranges of 0.25-200 μg mL(-1) for STG with the first method and 5-160 μg mL(-1), 25-800 μg mL(-1) for STG and MET, respectively with the second method. The optimized methods were validated and proved to be specific, robust and accurate for the quality control of the cited drugs in pharmaceutical preparations.

  11. A capillary liquid chromatography method for benzalkonium chloride determination as a component or contaminant in mixtures of biocides.

    PubMed

    Prieto-Blanco, M C; Argente-García, A; Campíns-Falcó, P

    2016-01-29

    A method for quantifying benzalkonium chloride (BAK), an alkyl dimethyl benzyl ammonium compound, in several biocides formulations is proposed. A tertiary amine like N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine (TA) and a straight-chain alkyl ammonium compound like trimethyl-tetradecyl ammonium chloride (TMTDAC), have been employed as trade surfactants besides BAK. Two capillary analytical columns with different polarities are tested: inertsil CN-3 capillary column (150mm×0.5mm i.d., 3μm particle diameter) and a non endcapped Zorbax C18 capillary column (35mm×0.5mm i.d., 5μm particle diameter). This latter column provided the best separation of the BAK homologues in less than 12min using acetonitrile:acetate buffer (50mM, pH 5) 85:15 at 20μLmin(-1). The proposed method combines on-line in-tube solid-phase microextraction (IT-SPME) coupled to capillary liquid chromatography (CapLC) and UV diode array detection. Matrix effect was present when TA were in excess to BAK. If TMTDAC is the co-biocide, matrix effect is always present. A decreasing of analytical response mainly for C12-BAK homologue was found using both chromatographic columns. The charged amount of mixture in the system was the most important parameter for obtaining reliable results. 1mL was the on line processed sample volume optimum for concentrations lower than 35μgmL(-1) of total surfactants. LODs were 0.03μgmL(-1) and 0.006μgmL(-1) for C12-BAK and C14-BAK, respectively. This method is also of use to evaluate the unwanted presence of BAK in biocide formulations due to industrial processes.

  12. Thermodynamic properties of liquid 3He- 4He mixtures at zero pressure for temperatures below 250 mK and 3He concentrations below 8%

    NASA Astrophysics Data System (ADS)

    Kuerten, J. G. M.; Castelijns, C. A. M.; de Waele, A. T. A. M.; Gijsman, H. M.

    We calculated the thermodynamic quantities of dilute liquid 3He- 4He mixtures, starting from experimental values of the specific heat and the osmotic pressure. The calculations are confined to temperatures below 250 mK and 3He concentrations below 8% at zero pressure. Some results are especially useful for dilution refrigeration. Contrary to the calculations previously performed by Radebaugh, our results are in good agreement with the experimental date on both the osmotic pressure and the osmotic enthalpy.

  13. New insight into the nanostructure of ionic liquids: a small angle X-ray scattering (SAXS) study on liquid tri-alkyl-methyl-ammonium bis(trifluoromethanesulfonyl)amides and their mixtures.

    PubMed

    Pott, Tanja; Méléard, Philippe

    2009-07-14

    We report a small angle X-ray scattering study on the liquid phase of a series of room temperature ionic liquids and their binary mixtures. The ionic liquids studied belong to the tri-alkyl-methyl-ammonium family with bis(trifluoromethanesulfonyl)amide as the anion and were studied as a function of alkyl chain length. These ionic liquids were found to exhibit marked nanoscale ordering in their isotropic liquid state as judged from the small angle X-ray scattering. The observed structural ordering is of supramolecular order and depends strongly on the length of the cation hydrophobic side chain. Moreover, the data can be analyzed on the basis of a disordered smectic A phase, consisting of strongly interdigitated bilayers that sequester the ionic liquid into polar and hydrophobic regions. These findings were also found to be consistent with density data of these molten salts. Additionally, we demonstrate that this experimentally observed nanostructuring can further be fine-tuned using binary mixtures.

  14. Investigation of the local structure of mixtures of an ionic liquid with polar molecular species through molecular dynamics: cluster formation and angular distributions.

    PubMed

    Carrete, Jesús; Méndez-Morales, Trinidad; Cabeza, Óscar; Lynden-Bell, Ruth M; Gallego, Luis J; Varela, Luis M

    2012-05-24

    In this work, we used molecular dynamics simulations to analyze in detail the spatial distributions of the different constituents in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate with three polar molecular species: water and two alcohols of different chain lengths (methanol and ethanol). In particular, we report results regarding the influence of the chosen species and its concentration on the formation of ionic and molecular clusters over the whole miscibility range, as well as on the angular distribution of polar molecules around the anion and the cation in these systems. Both analyses showed that addition of a molecular species breaks down the polar network of the pure ionic liquid in clusters whose mean size decreases progressively as more molecules are added. At very high concentrations of the molecular species, the ions are found to be isolated in mixtures with water and methanol, but they tend to form pairs in ethanol. In mixtures with water we identified large clusters that form a water network at very high water concentrations, while at low water concentrations polar molecules tend to form smaller aggregates. In contrast, in mixtures with alkanols there is no evidence of the formation of large alcohol clusters at any concentration. Spatial order in alcohol was also studied by means of the Kirkwood G factor, reaching the conclusion that the angular correlations which appear in pure alcohols due to dipole interactions are destroyed by the ionic liquid, even when present only in tiny amounts.

  15. Study of the Vapor-Liquid Coexistence Curve and the Critical Curve for Nonazeotropic Refrigerant Mixture R152a + R114 System

    NASA Astrophysics Data System (ADS)

    Kabata, Yasuo; Higashi, Yukihiro; Uematsu, Masahiko; Watanabe, Koichi

    Measurements of the vapor-liquid coexistence curve in the critical region for the refrigerant mixture of R152a (CH3CHF2: 1, l-difluoroethane) +R 114 (CCIF2CCIF2 :1, 2-dichloro-1, 1, 2, 2-tetrafluoroethane) system were made by visual observation of the disappearance of the meniscus at the vapor-liquid interface within an optical cell. Forty-eight saturated densities along the vapor-liquid coexistence curve between 204 and 861 kg·m-3 for five different compositions of 10, 20, 50, 80 and 90 wt% R 152a were obtained in the temperature range 370 to 409 K. The experimental errors of temperature, density, and mass fraction were estimated within ±10mK, ±0.5% and +0.05 %, respectively. On the basis of these measurements, the critical parameters of five different compositions for the R 152a +R 114 system were determined in consideration of the meniscus disappearance level as well as intensity of the critical opalescence. In accordance with the previous results of three other refrigerant mixtures, i.e., R 12 +R 22 system, R 22 +R 114 system and R 13B1 + R 114 system, the coexistence curve and critical curve on the temperature-density diagram for binary refrigerant mixtures were discussed. In addition, correlations of its composition dependence for this system were proposed.

  16. Hygroscopicity of internally mixed multi-component aerosol particles of atmospheric relevance

    NASA Astrophysics Data System (ADS)

    Liu, Qifan; Jing, Bo; Peng, Chao; Tong, Shengrui; Wang, Weigang; Ge, Maofa

    2016-01-01

    The hygroscopic properties of two water-soluble organic compounds (WSOCs) relevant to urban haze pollution (phthalic acid and levoglucosan) and their internally mixtures with inorganic salts (ammonium sulfate and ammonium nitrate) are investigated using a hygroscopicity tandem differential mobility analyzer (H-TDMA) system. The multi-component particles uptake water gradually in the range 5-90% relative humidity (RH). The experimental results are compared with the thermodynamic model predictions. For most mixtures, Extended Aerosol Inorganic Model (E-AIM) predictions agree well with the measured growth factors. The hygroscopic growth of mixed particles can be well described by the Zdanovskii-Stokes-Robinson (ZSR) relation as long as the mixed particles are completely liquid. ZSR calculations underestimate the water uptake of mixed particles at moderate RH due to the partial dissolution of ammonium sulfate in the organic and ammonium nitrate solution in this RH region. The phase of ammonium nitrate in the initial dry particles changes dramatically with the composition of mixtures. The presence of organics in the mixed particles can inhibit the crystallization of ammonium nitrate during the drying process and results in water uptake at low RH (RH < 60%). These results demonstrate that certain representative WSOCs can substantially influence the hygroscopicity of inorganic salts and overall water uptake of particles.

  17. Performance tests of R-22 and R-32/R-125/R-134a mixture for baseline air conditioning and liquid over-feeding operations

    SciTech Connect

    Mei, V.C.; Chen, F.C.; Chen, D.T.; HuangFu, E.P.

    1995-12-31

    Much experimental and theoretical analysis of potential R-22 replacements has been accomplished. However, published information regarding the experimental analysis of any off-the-shelf air conditioners with a potential R-22 replacement at realistic operating conditions is still rare. This type of work could be useful because it would provide baseline data for comparing the performance of R-22 and its potential replacement at drop-in conditions. In this study, an off-the-shelf window air conditioners was tested at Air Conditioning and Refrigeration Institute (ARI)-rated indoor conditions and at different ambient temperatures, include the ARI-rated outdoor condition, with R-22 and with its potential replacement, a ternary mixture of R-32(30%)/R-125(10%)/R-134a(60%) (the ternary mixture). A test rig was built that provided for baseline operation and for the option of operating the system with a flooded evaporator by means of liquid overfeeding (LOF). The test results indicated that the cooling capacity of the ternary mixture was 7.7% less than that of R-22 at 95 F ambient for baseline operation. The cooling capacity for both refrigerants improved when a flooded evaporator, or LOF, was used. For LOF operation, the cooling capacity of the ternary mixture was only 1.1% less than that of R-22. The ternary mixture had slightly higher compressor discharge pressure, a lower compressor discharge temperature, slightly lower compressor power consumption, and a higher compressor high/low pressure ratio.

  18. Applications of the Simple Multi-Fluid Model to Correlations of the Vapor-Liquid Equilibrium of Refrigerant Mixtures Containing Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Akasaka, Ryo

    This study presents a simple multi-fluid model for Helmholtz energy equations of state. The model contains only three parameters, whereas rigorous multi-fluid models developed for several industrially important mixtures usually have more than 10 parameters and coefficients. Therefore, the model can be applied to mixtures where experimental data is limited. Vapor-liquid equilibrium (VLE) of the following seven mixtures have been successfully correlated with the model: CO2 + difluoromethane (R-32), CO2 + trifluoromethane (R-23), CO2 + fluoromethane (R-41), CO2 + 1,1,1,2- tetrafluoroethane (R-134a), CO2 + pentafluoroethane (R-125), CO2 + 1,1-difluoroethane (R-152a), and CO2 + dimethyl ether (DME). The best currently available equations of state for the pure refrigerants were used for the correlations. For all mixtures, average deviations in calculated bubble-point pressures from experimental values are within 2%. The simple multi-fluid model will be helpful for design and simulations of heat pumps and refrigeration systems using the mixtures as working fluid.

  19. Extraction of S- and N-Compounds from the Mixture of Hydrocarbons by Ionic Liquids as Selective Solvents

    PubMed Central

    Gabrić, Beata; Sander, Aleksandra; Cvjetko Bubalo, Marina; Macut, Dejan

    2013-01-01

    Liquid-liquid extraction is an alternative method that can be used for desulfurization and denitrification of gasoline and diesel fuels. Recent approaches employ different ionic liquids as selective solvents, due to their general immiscibility with gasoline and diesel, negligible vapor pressure, and high selectivity to sulfur- and nitrogen-containing compounds. For that reason, five imidazolium-based ionic liquids and one pyridinium-based ionic liquid were selected for extraction of thiophene, dibenzothiophene, and pyridine from two model solutions. The influences of hydrodynamic conditions, mass ratio, and number of stages were investigated. Increasing the mass ratio of ionic liquid/model fuel and multistage extraction promotes the desulfurization and denitrification abilities of the examined ionic liquids. All selected ionic liquids can be reused and regenerated by means of vacuum evaporation. PMID:23843736

  20. Equations of state for strongly nonideal fluid mixtures: application of the local-composition concept

    SciTech Connect

    Whiting, W.B.; Prausnitz, J.M.

    1981-04-01

    A new model has been developed for calculation of fluid-phase equilibria of asymmetric mixtures. This local-composition model extends the quasi-chemical theory of Guggenheim (known to correlate well liquid-state activity coefficients) to fluids of all densities. The model can be applied to any equation of state, contains only one new adjustable parameter per binary pair, and can be extended to multicomponent mixtures of large and small molecules by use of the surface areas of the molecules. Although the local-composition model is a nonrandomness approach, all randomness boundary conditions are met. Significant improvement over the random-mixing model is shown for the prediction of vapor-liquid equilibria of methane/water and ethane/water systems.

  1. Virial coefficients, thermodynamic properties, and fluid-fluid transition of nonadditive hard-sphere mixtures

    NASA Astrophysics Data System (ADS)

    Santos, Andrés; López de Haro, Mariano; Yuste, Santos B.

    2010-05-01

    Different theoretical approaches for the thermodynamic properties and the equation of state for multicomponent mixtures of nonadditive hard spheres in d dimensions are presented in a unified way. These include the theory by Hamad, our previous formulation, the original MIX1 theory, a recently proposed modified MIX1 theory, as well as a nonlinear extension of the MIX1 theory proposed in this paper. Explicit expressions for the compressibility factor, Helmholtz free energy, and second, third, and fourth virial coefficients are provided. A comparison is carried out with recent Monte Carlo data for the virial coefficients of asymmetric mixtures and with available simulation data for the compressibility factor, the critical consolute point, and the liquid-liquid coexistence curves. The merits and limitations of each theory are pointed out.

  2. A decoupled energy stable scheme for a hydrodynamic phase-field model of mixtures of nematic liquid crystals and viscous fluids

    NASA Astrophysics Data System (ADS)

    Zhao, Jia; Yang, Xiaofeng; Shen, Jie; Wang, Qi

    2016-01-01

    We develop a linear, first-order, decoupled, energy-stable scheme for a binary hydrodynamic phase field model of mixtures of nematic liquid crystals and viscous fluids that satisfies an energy dissipation law. We show that the semi-discrete scheme in time satisfies an analogous, semi-discrete energy-dissipation law for any time-step and is therefore unconditionally stable. We then discretize the spatial operators in the scheme by a finite-difference method and implement the fully discrete scheme in a simplified version using CUDA on GPUs in 3 dimensions in space and time. Two numerical examples for rupture of nematic liquid crystal filaments immersed in a viscous fluid matrix are given, illustrating the effectiveness of this new scheme in resolving complex interfacial phenomena in free surface flows of nematic liquid crystals.

  3. Vapor-Liquid Equilibrium in the Mixture 1,1,1-Trichloroethane C2H3Cl3 + C6H10O Cyclohexanone (EVLM1111, LB5638_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,1,1-Trichloroethane C2H3Cl3 + C6H10O Cyclohexanone (EVLM1111, LB5638_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  4. Temperature-driven mixing-demixing behavior of binary mixtures of the ionic liquid choline bis(trifluoromethylsulfonyl)imide and water.

    PubMed

    Nockemann, Peter; Binnemans, Koen; Thijs, Ben; Parac-Vogt, Tatjana N; Merz, Klaus; Mudring, Anja-Verena; Menon, Preethy Chirukandath; Rajesh, Ravindran Nair; Cordoyiannis, George; Thoen, Jan; Leys, Jan; Glorieux, Christ

    2009-02-05

    The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point=30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility properties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). 1H NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G+/G-. These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

  5. Liquid-vapor phase diagram and surface properties in oppositely charged colloids represented by a mixture of attractive and repulsive Yukawa potentials.

    PubMed

    Chapela, Gustavo A; del Río, Fernando; Alejandre, José

    2013-02-07

    The liquid-vapor phase diagrams of equal size diameter σ binary mixtures of screened potentials have been reported for several ranges of interaction using Monte Carlo simulation methods [J. B. Caballero, A. M. Puertas, A. Ferńandez-Barbero, F. J. de las Nieves, J. M. Romero-Enrique, and L. F. Rull, J. Chem. Phys. 124, 054909 (2006); A. Fortini, A.-P. Hynninen, and M. Dijkstra, J. Chem. Phys. 125, 094502 (2006)]. Both works report controversial results about the stability of the phase diagram with the inverse Debye screening length κ. Caballero found stability for values of κσ up to 20 while Fortini reported stability for κσ up to 20 while Fortini reported stability for κσ ≤ 4. In this work a spinodal decomposition process where the liquid and vapor phases coexist through an interface in a slab geometry is used to obtain the phase equilibrium and surface properties using a discontinuous molecular dynamics simulations for mixtures of equal size particles carrying opposite charge and interacting with a mixture of attractive and repulsive Yukawa potentials at different values of κσ. An crude estimation of the triple point temperatures is also reported. The isothermal-isobaric method was also used to determine the phase stability using one phase simulations. We found that liquid-vapor coexistence is stable for values of κσ > 20 and that the critical temperatures have a maximum value at around κσ = 10, in agreement with Caballero et al. calculations. There also exists a controversy about the liquid-vapor envelope stability of the pure component attractive Yukawa model which is also discussed in the text. In addition, details about the equivalence between continuous and discontinuous molecular dynamics simulations are given, in the Appendix, for Yukawa and Lennard-Jones potentials.

  6. Liquid-vapor phase diagram and surface properties in oppositely charged colloids represented by a mixture of attractive and repulsive Yukawa potentials

    NASA Astrophysics Data System (ADS)

    Chapela, Gustavo A.; del Río, Fernando; Alejandre, José

    2013-02-01

    The liquid-vapor phase diagrams of equal size diameter σ binary mixtures of screened potentials have been reported for several ranges of interaction using Monte Carlo simulation methods [J. B. Caballero, A. M. Puertas, A. Ferńandez-Barbero, F. J. de las Nieves, J. M. Romero-Enrique, and L. F. Rull, J. Chem. Phys. 124, 054909 (2006), 10.1063/1.2159481; A. Fortini, A.-P. Hynninen, and M. Dijkstra, J. Chem. Phys. 125, 094502 (2006), 10.1063/1.2335453]. Both works report controversial results about the stability of the phase diagram with the inverse Debye screening length κ. Caballero found stability for values of κσ up to 20 while Fortini reported stability for κσ up to 20 while Fortini reported stability for κσ ⩽ 4. In this work a spinodal decomposition process where the liquid and vapor phases coexist through an interface in a slab geometry is used to obtain the phase equilibrium and surface properties using a discontinuous molecular dynamics simulations for mixtures of equal size particles carrying opposite charge and interacting with a mixture of attractive and repulsive Yukawa potentials at different values of κσ. An crude estimation of the triple point temperatures is also reported. The isothermal-isobaric method was also used to determine the phase stability using one phase simulations. We found that liquid-vapor coexistence is stable for values of κσ > 20 and that the critical temperatures have a maximum value at around κσ = 10, in agreement with Caballero et al. calculations. There also exists a controversy about the liquid-vapor envelope stability of the pure component attractive Yukawa model which is also discussed in the text. In addition, details about the equivalence between continuous and discontinuous molecular dynamics simulations are given, in the Appendix, for Yukawa and Lennard-Jones potentials.

  7. Relationship between composition of mixture charged and that in circulation in an auto refrigerant cascade and a J-T refrigerator operating in liquid refrigerant supply mode

    NASA Astrophysics Data System (ADS)

    Sreenivas, Bura; Nayak, H. Gurudath; Venkatarathnam, G.

    2017-01-01

    The composition of the refrigerant mixture in circulation during steady state operation of J-T and allied refrigerators is not the same as that charged due to liquid hold up in the heat exchangers and phase separators, as well as the differential solubility of different refrigerant components in the compressor lubricating oil. The performance of refrigerators/liquefiers operating on mixed refrigerant cycles is dependent on the mixture composition. It is therefore important to charge the right mixture that results in an optimum composition in circulation during steady state operation. The relationship between the charged and circulating composition has been experimentally studied in a J-T refrigerator operating in the liquid refrigerant supply (LRS) mode and an auto refrigerant cascade refrigerator (with a phase separator) operating in the gas refrigerant supply (GRS) mode. The results of the study are presented in this work. The results show that the method presented earlier for J-T refrigerators operating in GRS mode is also applicable in the case of refrigerators studied in this work.

  8. A COSMO-RS based guide to analyze/quantify the polarity of ionic liquids and their mixtures with organic cosolvents.

    PubMed

    Palomar, José; Torrecilla, José S; Lemus, Jesús; Ferro, Víctor R; Rodríguez, Francisco

    2010-02-28

    A COSMO-RS descriptor (S(sigma-profile)) has been used in quantitative structure-property relationship (QSPR) studies by a neural network (NN) for the prediction of empirical solvent polarity E(T)(N) scale of neat ionic liquids (ILs) and their mixtures with organic solvents. S(sigma-profile) is a two-dimensional quantum chemical parameter which quantifies the polar electronic charge of chemical structures on the polarity (sigma) scale. Firstly, a radial basis neural network exact fit (RBNN) is successfully optimized for the prediction of E(T)(N), the solvatochromic parameter of a wide variety of neat organic solvents and ILs, including imidazolium, pyridinium, ammonium, phosphonium and pyrrolidinium families, solely using the S(sigma-profile) of individual molecules and ions. Subsequently, a quantitative structure-activity map (QSAM), a new concept recently developed, is proposed as a valuable tool for the molecular understanding of IL polarity, by relating the E(T)(N) polarity parameter to the electronic structure of cations and anions given by quantum-chemical COSMO-RS calculations. Finally, based on the additive character of the S(sigma-profile) descriptor, we propose to simulate the mixture of IL-organic solvents by the estimation of the S(sigma-profile)(Mixture) descriptor, defined as the weighted mean of the S(sigma-profile) values of the components. Then, the E(T)(N) parameters for binary solvent mixtures, including ILs, are accurately predicted using the S(sigma-profile)(Mixture) values from the RBNN model previously developed for pure solvents. As result, we obtain a unique neural network tool to simulate, with similar reliability, the E(T)(N) polarity of a wide variety of pure ILs as well as their mixtures with organic solvents, which exhibit significant positive and negative deviations from ideality.

  9. Rotational Diffusion of Charged and Nondipolar Solutes in Ionic Liquid-Organic Solvent Mixtures: Evidence for Stronger Specific Solute-Solvent Interactions in Presence of Organic Solvent.

    PubMed

    Prabhu, Sugosh R; Dutt, G B

    2015-08-20

    Rotational diffusion of a charged solute, rhodamine 110 (R110), and a nondipolar solute, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP), has been investigated in ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]) and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([BMIM][FAP]), with 0.8 mole fraction of dibenzyl ether (DBE). This study has been undertaken to find out how specific interactions between the solute and the ionic liquid are affected upon dilution with a nondipolar solvent. It has been observed that at a given viscosity (η) and temperature (T), the reorientation times of R110 increase by 40-60% in the ionic liquid-organic solvent mixtures compared to ones in the corresponding neat ionic liquids. In the case of DMDPP, the influence of DBE is less pronounced, and its reorientation times increase by 25-50% at a given η/T. The addition of DBE weakens the numerous interactions prevailing between the cations and the anions of the ionic liquids, which results in stronger specific interactions between the solutes and the constituent ions, consequently leading to slower rotation of the solutes.

  10. Molecular Dynamics Simulation Study of the Capacitive Performance of a Binary Mixture of Ionic Liquids near an Onion-like Carbon Electrode.

    PubMed

    Li, Song; Feng, Guang; Fulvio, Pasquale F; Hillesheim, Patrick C; Liao, Chen; Dai, Sheng; Cummings, Peter T

    2012-09-06

    An equimolar mixture of 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C3mpy][Tf2N]), 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide ([C4mpip][Tf2N]) was investigated by classic molecular dynamics (MD) simulation. Differential scanning calorimetry (DSC) measurements verified that the binary mixture exhibited lower glass transition temperature than either of the pure room-temperature ionic liquids (RTILs). Moreover, the binary mixture gave rise to higher conductivity than the neat RTILs at lower temperature range. In order to study its capacitive performance in supercapacitors, simulations were performed of the mixture, and the neat RTILs used as electrolytes near an onion-like carbon (OLC) electrode at varying temperatures. The differential capacitance exhibited independence of the electrical potential applied for three electrolytes, which is in agreement with previous work on OLC electrodes in a different RTILs. Positive temperature dependence of the differential capacitance was observed, and it was dominated by the electrical double layer (EDL) thickness, which is for the first time substantiated in MD simulation.

  11. The simultaneous determination of active ingredients in cough-cold mixtures by isocratic reversed-phase ion-pair high-performance liquid chromatography.

    PubMed

    Lau, O W; Chan, K; Lau, Y K; Wong, W C

    1989-01-01

    A simple, rapid and accurate method for the simultaneous determination of active ingredients in cough-cold mixtures using isocratic reversed-phase ion-pair high-performance liquid chromatography has been developed. It involves the use of an octadecylsilane column as the stationary phase with methanol, water, tetrahydrofuran, phosphoric acid mixtures as mobile phase including sodium dioctylsulphosuccinate as the ion-pair agent. The pH of the mobile phase was adjusted to 4.6 by means of phosphoric acid and ammonium hydroxide solutions. The proposed method involves the simple dilution of the samples with the mobile phase and the addition of metoclopramide hydrochloride as the internal standard. The active ingredients under investigation were chlorpheniramine, codeine, diphenhydramine, ephedrine, ethylmorphine, phenylephrine, phenylpropanolamine and pholcodine, which exist as various combinations in cough-cold mixtures. The optimum composition of the mobile phase and the optimum flow rate were determined and are reported. The method was applied to the determination of active ingredients in seven commercially available cough-cold mixtures.

  12. Two-photon Laurdan studies of the ternary lipid mixture DOPC:SM:cholesterol reveal a single liquid phase at sphingomyelin:cholesterol ratios lower than 1.

    PubMed

    Carravilla, Pablo; Nieva, José L; Goñi, Félix M; Requejo-Isidro, Jose; Huarte, Nerea

    2015-03-10

    The ternary lipid mixture DOPC:eggSM:cholesterol in excess water has been studied in the form of giant unilamellar vesicles using two-photon fluorescence microscopy. Previous publications based on single-photon fluorescence microscopy had reported heterogeneous phase behavior (phase coexistence) in the region of the triangular phase diagram corresponding to SM:cholesterol molar ratios <1. We have examined this region by two-photon microscopy of Laurdan-labeled mixtures and have found that, under our conditions, only a single liquid phase exists. We have shown that macroscopic phase separation in the above region can be artifactually induced by one-photon excitation of the fluorescent probes and ensuing photooxidation and is prevented using two-photon excitation. The main effect of increasing the concentration of cholesterol in mixtures containing 30 mol % SM was to increase the rigidity of the disordered domains. Increasing the concentration of SM in