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Sample records for chemical equilibria

  1. New Thermodynamic Paradigm of Chemical Equilibria

    CERN Document Server

    Zilbergleyt, B

    2011-01-01

    The paper presents new thermodynamic paradigm of chemical equilibrium, setting forth comprehensive basics of Discrete Thermodynamics of Chemical Equilibria (DTd). Along with previous results by the author during the last decade, this work contains also some new developments of DTd. Based on the Onsager's constitutive equations, reformulated by the author thermodynamic affinity and reaction extent, and Le Chatelier's principle, DTd brings forward a notion of chemical equilibrium as a balance of internal and external thermodynamic forces (TdF), acting against a chemical system. Basic expression of DTd is the chemical system logistic map of thermodynamic states that ties together energetic characteristics of chemical reaction, occurring in the system, the system shift from "true" thermodynamic equilibrium (TdE), and causing that shift external thermodynamic forces. Solutions to the basic map are pitchfork bifurcation diagrams in coordinates "shift from TdE - growth factor (or TdF)"; points, corresponding to the ...

  2. Phase Equilibria of Stored Chemical Energy Reactants.

    Science.gov (United States)

    1984-07-25

    The reaction of lithium aluminum alloy with water at high temperature is considered in terms of phase equilibria in the system Li-A1-0-H. A...thermodynamic analysis of the system reveals the potential importance of lithium hydride as a reaction product. Major needs for experimental phase equilibria data

  3. Variational principles in chemical equilibria: Complex chemical systems with interacting subsystems

    CERN Document Server

    Zilbergleyt, B

    2010-01-01

    The goal of the paper is to derive a revised condition of global equilibrium in complex chemical systems as variational principle in formalism of recently developed discrete thermodynamics (DTD) of chemical equilibria. In classical approach the problem of complex equilibrium is solved by minimization of the system Gibbs’ free energy subject to logistic constraints. DTD demands any isolated system to comprise smaller subentities, which individual equilibria are based on the balance of internal and external thermodynamic forces, acting against them. The internal forces are equal to the subsystems thermodynamic affinities, while external forces originate from subsystems mutual interactions. Those interactions impose additional constraints on the mother system Gibbs’ free energy minimum. Basic expression of discrete thermodynamics, being multiplied by subsystems deviations from their “true” thermodynamic equilibria, is naturally identical to d’Alembert’s principle. A thermodynamic ve...

  4. A Computer Algebra Approach to Solving Chemical Equilibria in General Chemistry

    Science.gov (United States)

    Kalainoff, Melinda; Lachance, Russ; Riegner, Dawn; Biaglow, Andrew

    2012-01-01

    In this article, we report on a semester-long study of the incorporation into our general chemistry course, of advanced algebraic and computer algebra techniques for solving chemical equilibrium problems. The method presented here is an alternative to the commonly used concentration table method for describing chemical equilibria in general…

  5. Structures and Chemical Equilibria of Some N-Heterocycles Containing Amide Linkages

    Directory of Open Access Journals (Sweden)

    N. H. Abd El Moneim

    2003-05-01

    Full Text Available Structures and chemical equilibria of 5-carboxy-2-thiouracil (1, 5,6-diphenyl-3-hydroxy-1,2,4-triazine (2, 1-phenyl-3-methyl-5-pyrazolone (3 and 2-mercapto-4,6-dimethylpyrimidine hydrochloride (4 are reported. Their electronic transitions are assigned and pK values are evaluated and discussed.

  6. Modeling and Experimental Studies on Phase and Chemical Equilibria in High-Pressure Methanol Synthesis

    NARCIS (Netherlands)

    van Bennekom, Joost G.; Winkelman, Jozef G. M.; Venderbosch, Robertus H.; Nieland, Sebastiaan D. G. B.; Heeres, Hero J.

    2012-01-01

    A solution method was developed to calculate the simultaneous phase and chemical equilibria in high-pressure methanol synthesis (P = 20 MPa, 463

  7. Fast Method for Computing Chemical Potentials and Liquid-Liquid Phase Equilibria of Macromolecular Solutions.

    Science.gov (United States)

    Qin, Sanbo; Zhou, Huan-Xiang

    2016-08-25

    Chemical potential is a fundamental property for determining thermodynamic equilibria involving exchange of molecules, such as between two phases of molecular systems. Previously, we developed the fast Fourier transform (FFT)-based method for Modeling Atomistic Protein-crowder interactions (FMAP) to calculate excess chemical potentials according to the Widom insertion. Intermolecular interaction energies were expressed as correlation functions and evaluated via FFT. Here, we extend this method to calculate liquid-liquid phase equilibria of macromolecular solutions. Chemical potentials are calculated by FMAP over a wide range of molecular densities, and the condition for coexistence of low- and high-density phases is determined by the Maxwell equal-area rule. When benchmarked on Lennard-Jones fluids, our method produces an accurate phase diagram at 18% of the computational cost of the current best method. Importantly, the gain in computational speed increases dramatically as the molecules become more complex, leading to many orders of magnitude in speed up for atomistically represented proteins. We demonstrate the power of FMAP by reporting the first results for the liquid-liquid coexistence curve of γII-crystallin represented at the all-atom level. Our method may thus open the door to accurate determination of phase equilibria for macromolecular mixtures such as protein-protein mixtures and protein-RNA mixtures, that are known to undergo liquid-liquid phase separation, both in vitro and in vivo.

  8. Mass spectrometric and quantum chemical determination of proton water clustering equilibria

    Science.gov (United States)

    Likholyot, Alexander; Lemke, Kono H.; Hovey, Jamey K.; Seward, Terry M.

    2007-05-01

    We report on the thermochemistry of proton hydration by water in the gas phase both experimentally using high-pressure mass spectrometry (HPMS) and theoretically using multilevel G3, G3B3, CBS-Q, CBS-QB3, CBS/QCI-APNO as well as density functional theory (DFT) calculations. Gas phase hydration enthalpies and entropies for protonated water cluster equilibria with up to 7 waters (i.e., n ⩽ 7H 3O +·(H 2O) n) were observed and exhibited non-monotonic behavior for successive hydration steps as well as enthalpy and entropy anomalies at higher cluster rank numbers. In particular, there is a significant jump in the stepwise enthalpies and entropies of cluster formation for n varying from 6 to 8. This behavior can be successfully interpreted using cluster geometries obtained from quantum chemical calculations by considering the number of additional hydrogen bonds formed at each hydration step and simultaneous weakening of ion-solvent interaction with increasing cluster size. The measured total hydration energy for the attachment of the first six water molecules around the hydronium ion was found to account for more than 60% of total bulk hydration free energy.

  9. Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

    Science.gov (United States)

    Marion, G.M.; Kargel, J.S.; Catling, D.C.; Jakubowski, S.D.

    2005-01-01

    solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements. To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO4. 12H2O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic. Copyright ?? 2005 Elsevier Ltd.

  10. Determination of the Tautomeric Equilibria of Pyridoyl Benzoyl -Diketones in the Liquid and Solid State through the use of Deuterium Isotope Effects on 1H and 13C NMR Chemical Shifts and Spin Coupling Constants

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Borisov, Eugeny V.; Lindon, John C.

    2015-01-01

    The tautomeric equilibria for 2-pyridoyl-, 3-pyridoyl-, and 4-pyridoyl-benzoyl methane have been investigated using deuterium isotope effects on 1H and 13C chemical shifts both in the liquid and the solid state. Equilibria are established both in the liquid and the solid state. In addition, in th...

  11. Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

    Science.gov (United States)

    Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

    2007-01-01

    The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent

  12. 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

    Science.gov (United States)

    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

  13. Chemical equilibria model of strontium-90 adsorption and transport in soil in response to dynamic alkaline conditions.

    Science.gov (United States)

    Spalding, B P; Spalding, I R

    2001-01-15

    Strontium-90 is a major hazardous contaminant of radioactive wastewater and its processing sludges at many Department of Energy (DOE) facilities. In the past, such contaminated wastewater and sludge have been disposed in soil seepage pits, lagoons, or cribs often under highly perturbed alkaline conditions (pH > 12) where 90Sr solubility is low and its adsorption to surrounding soil is high. As natural weathering returns these soils to near-neutral or slightly acidic conditions, the adsorbed and precipitated calcium and magnesium phases, in which 90Sr is carried, change significantly in both nature and amounts. No comprehensive computational method has been formulated previously to quantitatively simulate the dynamics of 90Sr in the soil-groundwater environment under such dynamic and wide-ranging conditions. A computational code, the Hydrologic Utility Model for Demonstrating Integrated Nuclear Geochemical Environmental Responses (HUMDINGER), was composed to describe the changing equilibria of 90Sr in soil based on its causative chemical reactions including soil buffering, pH-dependent cation-exchange capacity, cation selectivity, and the precipitation/dissolution of calcium carbonate, calcium hydroxide, and magnesium hydroxide in response to leaching groundwater characteristics including pH, acid-neutralizing capacity, dissolved cations, and inorganic carbonate species. The code includes a simulation of one-dimensional transport of 90Sr through a soil column as a series of soil mixing cells where the equilibrium soluble output from one cell is applied to the next cell. Unamended soil leaching and highly alkaline soil treatments, including potassium hydroxide, sodium silicate, and sodium aluminate, were simulated and compared with experimental findings using large (10 kg) soil columns that were leached with 90Sr-contaminated groundwater after treatment. HUMDINGER's simulations were in good agreement with dynamic experimental observations of soil exchange capacity

  14. Influence of gas phase equilibria on the chemical vapor deposition of graphene.

    Science.gov (United States)

    Lewis, Amanda M; Derby, Brian; Kinloch, Ian A

    2013-04-23

    We have investigated the influence of gas phase chemistry on the chemical vapor deposition of graphene in a hot wall reactor. A new extended parameter space for graphene growth was defined through literature review and experimentation at low pressures (≥0.001 mbar). The deposited films were characterized by scanning electron microscopy, Raman spectroscopy, and dark field optical microscopy, with the latter showing promise as a rapid and nondestructive characterization technique for graphene films. The equilibrium gas compositions have been calculated across this parameter space. Correlations between the graphene films grown and prevalent species in the equilibrium gas phase revealed that deposition conditions associated with a high acetylene equilibrium concentration lead to good quality graphene deposition, and conditions that stabilize large hydrocarbon molecules in the gas phase result in films with multiple defects. The transition between lobed and hexagonal graphene islands was found to be linked to the concentration of the monatomic hydrogen radical, with low concentrations associated with hexagonal islands.

  15. Thermal-chemical-mechanical feedback during fluid-rock interactions: Implications for chemical transport and scales of equilibria in the crust

    Energy Technology Data Exchange (ETDEWEB)

    Dutrow, Barbara

    2008-08-13

    Our research evaluates the hypothesis that feedback amongst thermal-chemical-mechanical processes operative in fluid-rock systems alters the fluid flow dynamics of the system which, in turn, affects chemical transport and temporal and spatial scales of equilibria, thus impacting the resultant mineral textural development of rocks. Our methods include computational experimentation and detailed analyses of fluid-infiltrated rocks from well-characterized terranes. This work focuses on metamorphic rocks and hydrothermal systems where minerals and their textures are utilized to evaluate pressure (P), temperature (T), and time (t) paths in the evolution of mountain belts and ore deposits, and to interpret tectonic events and the timing of these events. Our work on coupled processes also extends to other areas where subsurface flow and transport in porous media have consequences such as oil and gas movement, geothermal system development, transport of contaminants, nuclear waste disposal, and other systems rich in fluid-rock reactions. Fluid-rock systems are widespread in the geologic record. Correctly deciphering the products resulting from such systems is important to interpreting a number of geologic phenomena. These systems are characterized by complex interactions involving time-dependent, non-linear processes in heterogeneous materials. While many of these interactions have been studied in isolation, they are more appropriately analyzed in the context of a system with feedback. When one process impacts another process, time and space scales as well as the overall outcome of the interaction can be dramatically altered. Our goals to test this hypothesis are: to develop and incorporate algorithms into our 3D heat and mass transport code to allow the effects of feedback to be investigated numerically, to analyze fluid infiltrated rocks from a variety of terranes at differing P-T conditions, to identify subtle features of the infiltration of fluids and/or feedback, and

  16. CRYOCHEM, Thermodynamic Model for Cryogenic Chemical Systems: Solid-Vapor and Solid-Liquid-Vapor Phase Equilibria Toward Applications on Titan and Pluto

    Science.gov (United States)

    Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.

    2014-12-01

    Until in-situ measurements can be made regularly on extraterrestrial bodies, thermodynamic models are the only tools to investigate the properties and behavior of chemical systems on those bodies. The resulting findings are often critical in describing physicochemical processes in the atmosphere, surface, and subsurface in planetary geochemistry and climate studies. The extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan introduce huge non-ideality that prevents conventional models from performing adequately. At such conditions, atmospheres as a whole—not components individually—are subject to phase equilibria with their equilibrium solid phases or liquid phases or both. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, the development of which is still in progress, was shown to reproduce the vertical composition profile of Titan's atmospheric methane measured by the Huygens probe (Tan et al., Icarus 2013, 222, 53). Recently, the model was also used to describe Titan's global circulation where the calculated composition of liquid in Ligeia Mare is consistent with the bathymetry and microwave absorption analysis of T91 Cassini fly-by data (Tan et al., 2014, submitted). Its capability to deal with equilibria involving solid phases has also been demonstrated (Tan et al., Fluid Phase Equilib. 2013, 360, 320). With all those previous works done, our attention is now shifting to the lower temperatures in Titan's tropopause and on Pluto's surface, where much technical development remains for CRYOCHEM to assure adequate performance at low temperatures. In these conditions, solid-vapor equilibrium (SVE) is the dominant phase behavior that determines the composition of the atmosphere and the existing ices. Another potential application is for the subsurface phase equilibrium, which also involves liquid, thus three-phase equilibrium: solid-liquid-vapor (SLV). This presentation will discuss the

  17. Quantitative NMR spectroscopy of complex technical mixtures using a virtual reference: chemical equilibria and reaction kinetics of formaldehyde-water-1,3,5-trioxane.

    Science.gov (United States)

    Maiwald, Michael; Grützner, Thomas; Ströfer, Eckhard; Hasse, Hans

    2006-07-01

    Quantitative 1H NMR spectroscopy was used to study chemical equilibria and reaction kinetics of both the formation and decomposition of 1,3,5-trioxane in aqueous formaldehyde solutions. The reaction was homogeneously catalyzed with up to 0.10 g g(-1) sulfuric acid at temperatures between 360 and 383 K so that most of the experiments had to be carried out pressurized. The studied mixtures were complex due to the formation of methylene glycol and poly(oxymethylene) glycols in aqueous formaldehyde and the presence of considerable amounts of ionized species. Most common internal standards are decomposed by the hot sulfuric acid and external standards were not applicable using the flow NMR probe or pressurizable NMR sample tubes. Therefore, for the quantification of the small trioxane signals, a novel procedure was applied, in which electronically generated NMR signals were used as highly stable Virtual References (VR). The NMR decoupler channel with wave-form generator was used as the source of the reference signal, which was irradiated into the probe using the lock coil. Details on the experimental procedure are presented. It is shown that the presented method yields reliable quantitative reaction data for the complex studied mixtures.

  18. Simulation of chemical potentials and phase equilibria in two- and three-dimensional square-well fluids: finite size effects.

    Science.gov (United States)

    Vörtler, Horst L; Schäfer, Katja; Smith, William R

    2008-04-17

    We study the simulation cell size dependence of chemical potential isotherms in subcritical square-well fluids by means of series of canonical ensemble Monte Carlo simulations with increasing numbers of particles, for both three-dimensional bulk systems and two-dimensional planar layers, using Widom-like particle insertion methods. By estimating the corresponding vapor/liquid coexistence densities using a Maxwell-like equal area rule for the subcritical chemical potential isotherms, we are able to study the influence of system size not only on chemical potentials but also on the coexistence properties. The chemical potential versus density isotherms show van der Waals-like loops in the subcritical vapor/liquid coexistence range that exhibit distinct finite size effects for both two- and three-dimensional fluids. Generally, in agreement with recent findings for related studies of Lennard-Jones fluids, the loops shrink with increasing number of particles. In contrast to the subcritical isotherms themselves, the equilibrium vapor/liquid densities show only a weak system size dependence and agree quantitatively with the best-known literature values for three-dimensional fluids. This allows our approach to be used to accurately predict the phase coexistence properties. Our resulting phase equilibrium results for two-dimensional square-well fluids are new. Knowledge concerning finite size effects of square-well systems is important not only for the simulation of thermodynamic properties of simple fluids, but also for the simulation of models of more complex fluids (such as aqueous or polymer fluids) involving square-well interactions.

  19. Learning efficient correlated equilibria

    KAUST Repository

    Borowski, Holly P.

    2014-12-15

    The majority of distributed learning literature focuses on convergence to Nash equilibria. Correlated equilibria, on the other hand, can often characterize more efficient collective behavior than even the best Nash equilibrium. However, there are no existing distributed learning algorithms that converge to specific correlated equilibria. In this paper, we provide one such algorithm which guarantees that the agents\\' collective joint strategy will constitute an efficient correlated equilibrium with high probability. The key to attaining efficient correlated behavior through distributed learning involves incorporating a common random signal into the learning environment.

  20. Phase Equilibria Diagrams Database

    Science.gov (United States)

    SRD 31 NIST/ACerS Phase Equilibria Diagrams Database (PC database for purchase)   The Phase Equilibria Diagrams Database contains commentaries and more than 21,000 diagrams for non-organic systems, including those published in all 21 hard-copy volumes produced as part of the ACerS-NIST Phase Equilibria Diagrams Program (formerly titled Phase Diagrams for Ceramists): Volumes I through XIV (blue books); Annuals 91, 92, 93; High Tc Superconductors I & II; Zirconium & Zirconia Systems; and Electronic Ceramics I. Materials covered include oxides as well as non-oxide systems such as chalcogenides and pnictides, phosphates, salt systems, and mixed systems of these classes.

  1. Chemical Equilibrium, Unit 4: Equilibria in Acid-Base Systems. A Computer-Enriched Module for Introductory Chemistry. Student's Guide and Teacher's Guide.

    Science.gov (United States)

    Settle, Frank A., Jr.

    Presented are the teacher's guide and student materials for one of a series of self-instructional, computer-based learning modules for an introductory, undergraduate chemistry course. The student manual for this acid-base equilibria unit includes objectives, prerequisites, pretest, a discussion of equilibrium constants, and 20 problem sets.…

  2. Amide cis-trans isomerization in aqueous solutions of methyl N-formyl-D-glucosaminides and methyl N-acetyl-D-glucosaminides: chemical equilibria and exchange kinetics.

    Science.gov (United States)

    Hu, Xiaosong; Zhang, Wenhui; Carmichael, Ian; Serianni, Anthony S

    2010-04-07

    Amide cis-trans isomerization (CTI) in methyl 2-deoxy-2-acylamido-d-glucopyranosides was investigated by (1)H and (13)C NMR spectroscopy. Singly (13)C-labeled methyl 2-deoxy-2-formamido-d-glucopyranoside (MeGlcNFm) anomers provided standard (1)H and (13)C chemical shifts and (1)H-(1)H and (13)C-(13)C spin-coupling constants for cis and trans amides that are detected readily in aqueous solution. Equipped with this information, doubly (13)C-labeled methyl 2-deoxy-2-acetamido-d-glucopyranoside (MeGlcNAc) anomers were investigated, leading to the detection and quantification of cis and trans amides in this biologically important aminosugar. In comparison to MeGlcNFm anomers, the percentage of cis amide in aqueous solutions of MeGlcNAc anomers is small ( approximately 23% for MeGlcNFm versus approximately 1.8% for MeGlcNAc at 42 degrees C) but nevertheless observable with assistance from (13)C-labeling. Temperature studies gave thermodynamic parameters DeltaG degrees , DeltaH degrees , and DeltaS degrees for cis-trans interconversion in MeGlcNFm and MeGlcNAc anomers. Cis/trans equilibria depended on anomeric configuration, with solutions of alpha-anomers containing less cis amide than those of beta-anomers. Confirmation of the presence of cis amide in MeGlcNAc solutions derived from quantitative (13)C saturation transfer measurements of CTI rate constants as a function of solution temperature, yielding activation parameters E(act), DeltaG degrees (), DeltaH degrees (), and DeltaS degrees () for saccharide CTI. Rate constants for the conversion of trans to cis amide in MeGlcNFm and MeGlcNAc anomers ranged from 0.02 to 3.59 s(-1) over 31-85 degrees C, compared to 0.24-80 s(-1) for the conversion of cis to trans amide over the same temperature range. Energies of activation ranged from 16-19 and 19-20 kcal/mol for the cis --> trans and trans --> cis processes, respectively. Complementary DFT calculations on MeGlcNFm and MeGlcNAc model structures were conducted to evaluate

  3. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  4. Institutions, Equilibria and Efficiency

    DEFF Research Database (Denmark)

    Competition and efficiency is at the core of economic theory. This volume collects papers of leading scholars, which extend the conventional general equilibrium model in important ways. Efficiency and price regulation are studied when markets are incomplete and existence of equilibria...... membership are evaluated. Core equivalence is shown for bargaining economies. The theory of risk aversion is extended and the relation between risk taking and wealth is experimentally investigated. Other topics include: determinacy in OLG with cash-in-advance constraints, income distribution and democracy...... in such settings is proven under very general preference assumptions. The model is extended to include geographical location choice, a commodity space incorporating manufacturing imprecision and preferences for club-membership, schools and firms. Inefficiencies arising from household externalities or group...

  5. Jump conditions in transonic equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Guazzotto, L.; Betti, R. [Department of Mechanical Engineering, University of Rochester, Rochester, New York 14627 (United States); Jardin, S. C. [Princeton Plasma Physics Laboratory, Princeton, New Jersey 08540 (United States)

    2013-04-15

    In the present paper, the numerical calculation of transonic equilibria, first introduced with the FLOW code in Guazzotto et al.[Phys. Plasmas 11, 604 (2004)], is critically reviewed. In particular, the necessity and effect of imposing explicit jump conditions at the transonic discontinuity are investigated. It is found that 'standard' (low-{beta}, large aspect ratio) transonic equilibria satisfy the correct jump condition with very good approximation even if the jump condition is not explicitly imposed. On the other hand, it is also found that high-{beta}, low aspect ratio equilibria require the correct jump condition to be explicitly imposed. Various numerical approaches are described to modify FLOW to include the jump condition. It is proved that the new methods converge to the correct solution even in extreme cases of very large {beta}, while they agree with the results obtained with the old implementation of FLOW in lower-{beta} equilibria.

  6. A Multistep Equilibria-Redox-Complexation Demonstration to Illustrate Le Chatelier's Principle.

    Science.gov (United States)

    Berger, Tomas G.; Mellon, Edward K.

    1996-01-01

    Describes a process that can be used to illustrate a number of chemical principles including Le Chatelier's principle, redox chemistry, equilibria versus steady state situations, and solubility of species. (JRH)

  7. The effect of chemical treatment on adsorption of natural gas by multi-walled carbon nanotubes: Sorption equilibria and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    Delavar M.

    2012-01-01

    Full Text Available In this study, adsorption of methane as the main constituent of natural gas was firstly studied on the pristine multi-walled carbon nanotubes (MWCNTs and then purification and chemical treatments of MWCNTs was performed to enhance the natural gas adsorption capacity. MWCNTs were chemically treated using different methods in this research. The results revealed that chemical treatment of the MWCNTs in presence of H2SO4/HNO3 acidic mixture in 3:1 volume ratio, enhanced considerably natural gas adsorption capacity (an optimal up to 45 mmol/g at temperature of 298.15 K and the pressure of 50 bar compared to the pristine MWCNTs (about 27 mmol/g at the same operating conditions. This effect can be attributed to the opening of the nanotubes caps with a major alteration in its structural properties due to chemical treatment. The experimental data of adsorption were almost equally well described by Langmuir, Freundlich and Sips equations to determine the model isotherms. The best fit was obtained by the Sips model isotherm with the r-squared value near to unity. Furthermore, using the experimental data obtained in different temperatures the isosteric heat of natural gas adsorption onto pristine MWCNTs was also calculated in the interested range of pressures and temperatures using the thermodynamic-based Clausius-Clapeyron equation from the Sips isotherm model. The results revealed an energetically heterogeneous surface of MWCNTs in natural gas adsorption. Also the natural gas adsorption process was kinetically studied through pseudo-second order and intra-particle diffusion models which indicated the intra-particular diffusion is rate limiting step in adsorption of methane on MWCNTs.

  8. Correct Representation of Conformational Equilibria.

    Science.gov (United States)

    Fulop, F.; And Others

    1983-01-01

    In representing conformational equilibria of compounds having only one chiral center, erroneous formulas showing different antipodes on the two sides of the equilibrium are rare. In contrast, with compounds having two or more chiral centers especially with saturated heterocycles, this erroneous representation occurs frequently in the chemical…

  9. On Uniqueness of coalitional equilibria

    NARCIS (Netherlands)

    Finus, M.; Mouche, van P.H.M.; Rundshagen, B.

    2014-01-01

    For the so-called "new approach" of coalitio formation it is important that coalitional equilibria are unique. Uniqueness comes down to existene and to semi-uniqueness, i.e.\\\\that there exists at most one equilibrium. Although conditions for existence are not problematic, conditions for semi-uniquen

  10. Adsorption equilibria of dimethylnaphthalene isomers

    Energy Technology Data Exchange (ETDEWEB)

    Rota, R.; Morbidelli, M. [Politecnico di Milano (Italy). Dipt. di Chimica Fisica Applicata; Rombi, E.; Monaci, R.; Ferino, I.; Solinas, V. [Univ. di Cagliari (Italy). Dipt. di Scienze Chimiche

    1996-01-01

    Commercial sources of DMNs are the aromatic petroleum fraction of the appropriate boiling range and the coal liquefaction products. Adsorption processes for separating mixtures of dimethylnaphthalene (DMN) isomers are of potential interest for the production of 2,6-DMN. In this work, the adsorption equilibria of liquid mixtures of DMN isomers on zeolites have been investigated experimentally. The separation factors between the various isomers have been found to depend strongly on the composition of the fluid phase. A suitable equilibrium model, based on the adsorbed solution theory, has been developed to describe the multicomponent adsorption equilibria in the entire range of interest. Its performance has been tested using binary and ternary equilibrium data.

  11. Equilibria, Fixed Points, and Complexity Classes

    CERN Document Server

    Yannakakis, Mihalis

    2008-01-01

    Many models from a variety of areas involve the computation of an equilibrium or fixed point of some kind. Examples include Nash equilibria in games; market equilibria; computing optimal strategies and the values of competitive games (stochastic and other games); stable configurations of neural networks; analysing basic stochastic models for evolution like branching processes and for language like stochastic context-free grammars; and models that incorporate the basic primitives of probability and recursion like recursive Markov chains. It is not known whether these problems can be solved in polynomial time. There are certain common computational principles underlying different types of equilibria, which are captured by the complexity classes PLS, PPAD, and FIXP. Representative complete problems for these classes are respectively, pure Nash equilibria in games where they are guaranteed to exist, (mixed) Nash equilibria in 2-player normal form games, and (mixed) Nash equilibria in normal form games with 3 (or ...

  12. Phase equilibria basic principles, applications, experimental techniques

    CERN Document Server

    Reisman, Arnold

    2013-01-01

    Phase Equilibria: Basic Principles, Applications, Experimental Techniques presents an analytical treatment in the study of the theories and principles of phase equilibria. The book is organized to afford a deep and thorough understanding of such subjects as the method of species model systems; condensed phase-vapor phase equilibria and vapor transport reactions; zone refining techniques; and nonstoichiometry. Physicists, physical chemists, engineers, and materials scientists will find the book a good reference material.

  13. Experimental methods for phase equilibria at high pressures.

    Science.gov (United States)

    Dohrn, Ralf; Fonseca, José M S; Peper, Stephanie

    2012-01-01

    Knowledge of high-pressure phase equilibria is crucial in many fields, e.g., for the design and optimization of high-pressure chemical and separation processes, carbon capture and storage, hydrate formation, applications of ionic liquids, and geological processes. This review presents the variety of methods to measure phase equilibria at high pressures and, following a classification, discusses the measurement principles, advantages, challenges, and error sources. Examples of application areas are given. A detailed knowledge and understanding of the different methods is fundamental not only for choosing the most suitable method for a certain task but also for the evaluation of experimental data. The discrepancy between the (sometimes low) true accuracy of published experimental data and the (high) accuracy claimed by authors is addressed. Some essential requirements for the generation of valuable experimental results are summarized.

  14. Motion Control along Relative Equilibria

    DEFF Research Database (Denmark)

    Nordkvist, Nikolaj

    2008-01-01

    The subject of this thesis is control of mechanical systems as they evolve along the steady motions called relative equilibria. These trajectories are of interest in theory and applications and have the characterizing property that the system's body-fixed velocity is constant. For example, constant...... on a Lie group is locally controllable along a relative equilibrium. These conditions subsume the well-known local controllability conditions for equilibrium points. Second, for systems that have fewer controls than degrees of freedom, we present a novel algorithm to control simple mechanical control...

  15. Inefficiency of Nash Equilibria. I

    Science.gov (United States)

    1982-03-12

    continuously for U’ near csEA a’ This also shows that for il close to , D6?’)(X) fl (IW’, f ) - * for a a hence we may assume U0 open.all * 6 A A Furthermore...34 Journal of Economic Theory 22 (1980), 363-376. 14] P. Dubey, A. as-Colell and M. Shubik, "Efficiency Properties of Strategic Market Games: An...Axiomatic Approach," Journal of Economic Theory 22 (1980), 339-362. [5] P. Dubey and J. D. Rogsvski, "Inefficiency of Nash Equilibria: II," forthcoming

  16. Existence of Multiagent Equilibria with Limited Agents

    CERN Document Server

    Bowling, M; 10.1613/jair.1332

    2011-01-01

    Multiagent learning is a necessary yet challenging problem as multiagent systems become more prevalent and environments become more dynamic. Much of the groundbreaking work in this area draws on notable results from game theory, in particular, the concept of Nash equilibria. Learners that directly learn an equilibrium obviously rely on their existence. Learners that instead seek to play optimally with respect to the other players also depend upon equilibria since equilibria are fixed points for learning. From another perspective, agents with limitations are real and common. These may be undesired physical limitations as well as self-imposed rational limitations, such as abstraction and approximation techniques, used to make learning tractable. This article explores the interactions of these two important concepts: equilibria and limitations in learning. We introduce the question of whether equilibria continue to exist when agents have limitations. We look at the general effects limitations can have on agent b...

  17. MHD equilibria with diamagnetic effects

    Science.gov (United States)

    Tessarotto, M.; Zorat, R.; Johnson, J. L.; White, R. B.

    1997-11-01

    An outstanding issue in magnetic confinement is the establishment of MHD equilibria with enhanced flow shear profiles for which turbulence (and transport) may be locally effectively suppressed or at least substantially reduced with respect to standard weak turbulence models. Strong flows develop in the presence of equilibrium E× B-drifts produced by a strong radial electric field, as well as due to diamagnetic contributions produced by steep equilibrium radial profiles of number density, temperature and the flow velocity itself. In the framework of a kinetic description, this generally requires the construction of guiding-center variables correct to second order in the relevant expansion parameter. For this purpose, the Lagrangian approach developed recently by Tessarotto et al. [1] is adopted. In this paper the conditions of existence of such equilibria are analyzed and their basic physical properties are investigated in detail. 1 - M. Pozzo, M. Tessarotto and R. Zorat, in Theory of fusion Plasmas, E.Sindoni et al. eds. (Societá Italiana di Fisica, Editrice Compositori, Bologna, 1996), p.295.

  18. On the topological stability of magnetostatic equilibria

    Science.gov (United States)

    Tsinganos, K. C.; Rosner, R.; Distler, J.

    1984-01-01

    The topological stability of MHD equilibria is investigated by exploring the formal analogy, in the ideal MHD limit, between the topology of magnetic lines of force in coordinate space and the topology of integral surfaces of one- and two-dimensional Hamiltonian systems in phase space. It is demonstrated that in an astrophysical setting, symmetric magnetostatic equilibria satisfying the ideal MHD equations are exceptional. The principal result of the study is that previous infinitesimal perturbation theory calculations can be generalized to include finite-amplitude and symmetry-breaking effects. The effect of the ergodicity of perturbed symmetric equilibria on heat dispersal in magnetically dominated plasmas is discussed.

  19. Inefficient equilibria in transition economy

    Directory of Open Access Journals (Sweden)

    Sergei Guriev

    1999-01-01

    Full Text Available The paper studies a general equilibrium in an economy where all market participants face a bid-ask spread. The spread may be caused by indirect business taxes, middlemen rent-seeking, delays in payments or liquidity constraints or price uncertainty. Wherever it comes from the spread causes inefficiency of the market equilibrium. We discuss some institutions that can decrease the inefficiency. One is second currency (barter exchange in the inter-firm transactions. It is shown that the general equilibrium in an economy with second currency is effective though is still different from Arrow–Debreu equilibrium. Another solution can be introduction of mutual trade credit. In the economy with trade credit there are multiple equilibria that are more efficient than original bid-ask spread but still not as efficient as Arrow–Debreu one, too. The implications for firms' integration and applicability to Russian economy are discussed.

  20. Equilibria in Dynamic Selfish Routing

    Science.gov (United States)

    Anshelevich, Elliot; Ukkusuri, Satish

    In both transportation and communication networks we are faced with “selfish flows”, where every agent sending flow over the network desires to get it to its destination as soon as possible. Such flows have been well studied in time-invariant networks in the last few years. A key observation that must be taken into account in defining and studying selfish flow, however, is that a flow can take a non-negligible amount of time to travel across the network from the source to destination, and that network states like traffic load and congestion can vary during this period. Such flows are called dynamic flows (a.k.a. flows over time). This variation in network state as the flow progresses through the network results in the fundamentally different and significantly more complex nature of dynamic flow equilibria, as compared to those defined in static network settings.

  1. Braided magnetic fields: equilibria, relaxation and heating

    CERN Document Server

    Pontin, D I; Russell, A J B; Hornig, G

    2015-01-01

    We examine the dynamics of magnetic flux tubes containing non-trivial field line braiding (or linkage), using mathematical and computational modelling. The key results obtained from recent modelling efforts are summarised, in the context of testable predictions for the laboratory. We discuss the existence of braided force-free equilibria, and demonstrate that for a field anchored at perfectly-conducting plates, these equilibria exist and contain current sheets whose thickness scales inversely with the braid complexity - as measured for example by the topological entropy. By contrast, for a periodic domain braided exact equilibria typically do not exist, while approximate equilibria contain thin current sheets. In the presence of resistivity, reconnection is triggered at the current sheets and a turbulent relaxation ensues. We discuss the properties of this relaxation, and in particular the existence of constraints that may mean that the final state is not the linear force-free field predicted by Taylor's hypo...

  2. Symmetry transforms for ideal magnetohydrodynamics equilibria.

    Science.gov (United States)

    Bogoyavlenskij, Oleg I

    2002-11-01

    A method for constructing ideal magnetohydrodynamics (MHD) equilibria is introduced. The method consists of the application of symmetry transforms to any known MHD equilibrium [ O. I. Bogoyavlenskij, Phys. Rev. E. 62, 8616, (2000)]. The transforms break the geometrical symmetries of the field-aligned solutions and produce continuous families of the nonsymmetric MHD equilibria. The method of symmetry transforms also allows to obtain MHD equilibria with current sheets and exact solutions with noncollinear vector fields B and V. A model of the nonsymmetric astrophysical jets outside of their accretion disks is developed. The total magnetic and kinetic energy of the jet is finite in any layer c(1)equilibria that model ball lightning with dynamics of plasma inside the fireball.

  3. Nash equilibria via duality and homological selection

    Indian Academy of Sciences (India)

    Arnab Basu; Samik Basu; Mahan MJ

    2014-11-01

    Given a multifunction from to the -fold symmetric product Sym$_{k}(X)$, we use the Dold–Thom theorem to establish a homological selection theorem. This is used to establish existence of Nash equilibria. Cost functions in problems concerning the existence of Nash equilibria are traditionally multilinear in the mixed strategies. The main aim of this paper is to relax the hypothesis of multilinearity. We use basic intersection theory, Poincaré duality in addition to the Dold–Thom theorem.

  4. Network Connection Games with Disconnected Equilibria

    CERN Document Server

    Brandes, Ulrik; Nick, Bobo

    2008-01-01

    In this paper we extend a popular non-cooperative network creation game (NCG) to allow for disconnected equilibrium networks. There are n players, each is a vertex in a graph, and a strategy is a subset of players to build edges to. For each edge a player must pay a cost, and the utility is a trade-off between edge costs and shortest path lengths to all other players. We extend the model to a penalized game (PCG), for which we reduce the penalty counted towards the utility for a pair of disconnected players to a finite value. Our analysis concentrates on existence, structure, and cost of disconnected regular and strong Nash equilibria. Although the PCG is not a potential game, pure Nash equilibria always and pure strong equilibria very often exist. We provide tight conditions under which disconnected (strong) Nash equilibria can evolve. Components of these equilibria must be (strong) Nash equilibria of a smaller NCG. However, in contrast to the NCG, for almost all parameter values no tree is a stable componen...

  5. Effect of temperature on acid-base equilibria in separation techniques. A review.

    Science.gov (United States)

    Gagliardi, Leonardo G; Tascon, Marcos; Castells, Cecilia B

    2015-08-19

    Studies on the theoretical principles of acid-base equilibria are reviewed and the influence of temperature on secondary chemical equilibria within the context of separation techniques, in water and also in aqueous-organic solvent mixtures, is discussed. In order to define the relationships between the retention in liquid chromatography or the migration velocity in capillary electrophoresis and temperature, the main properties of acid-base equilibria have to be taken into account for both, the analytes and the conjugate pairs chosen to control the solution pH. The focus of this review is based on liquid-liquid extraction (LLE), liquid chromatography (LC) and capillary electrophoresis (CE), with emphasis on the use of temperature as a useful variable to modify selectivity on a predictable basis. Simplified models were evaluated to achieve practical optimizations involving pH and temperature (in LLE and CE) as well as solvent composition in reversed-phase LC.

  6. Information Anatomy of Stochastic Equilibria

    Directory of Open Access Journals (Sweden)

    Sarah Marzen

    2014-08-01

    Full Text Available A stochastic nonlinear dynamical system generates information, as measured by its entropy rate. Some—the ephemeral information—is dissipated and some—the bound information—is actively stored and so affects future behavior. We derive analytic expressions for the ephemeral and bound information in the limit of infinitesimal time discretization for two classical systems that exhibit dynamical equilibria: first-order Langevin equations (i where the drift is the gradient of an analytic potential function and the diffusion matrix is invertible and (ii with a linear drift term (Ornstein–Uhlenbeck, but a noninvertible diffusion matrix. In both cases, the bound information is sensitive to the drift and diffusion, while the ephemeral information is sensitive only to the diffusion matrix and not to the drift. Notably, this information anatomy changes discontinuously as any of the diffusion coefficients vanishes, indicating that it is very sensitive to the noise structure. We then calculate the information anatomy of the stochastic cusp catastrophe and of particles diffusing in a heat bath in the overdamped limit, both examples of stochastic gradient descent on a potential landscape. Finally, we use our methods to calculate and compare approximations for the time-local predictive information for adaptive agents.

  7. Effect of the interaction between the chemical and the magnetic ordering on the phase equilibria of iron base alloys%化学有序及磁有序在铁基合金相平衡影响方面的交互作用

    Institute of Scientific and Technical Information of China (English)

    大沼郁雄

    2005-01-01

    It is well known that the magnetic properties such as the Curie temperature TmagC and the mean magnetic moment β of ordered compounds have different values from those of the disordered solutions. For instance, both Tcmag and β of the Ni3 Pt (L12) and NiPt (L10) and Tcmag of the CoPt (L10) and CoPt3 (L12) ordered compounds are strongly depressed due to the ordering compared with those of the metastable disordered Ni-Pt and Co-Pt alloys. On the other hand, the γ-FeNi3(L12) and the α-FeCo (B2) ordered compounds have higher Tcmag and β values comparing with the disordered solution phases, γ (A1) and α (A2), respectively. In consequence, the stability of the ordered phase is depressed or enhanced due to the interaction between the chemical and magnetic ordering caused by the decrease or increase of Tcmag and β values. The purpose of this study is to investigate the effect of the interaction between the chemical and the magnetic ordering on the phase equilibria in the Fe-X(X=Al, Co, Ni, Rh, Si) binary systems.The Gibbs energy of the α(A2), γ(A1) and liquid phases is described by a sub-regular solution approximatior. The ordering contribution to the Gibbs energy ,ΔGmorder, and deviations of magnetic properties, ΔTcmag and Δβ, of the ordered compounds, FeAl(B2), Fe3 Al (D03), FeCo (B2), FeRh (B2), FeSi (B2), Fe3 Si (D03) and FeNi3 (L12) is introduced by the split compound energy formalism. Effect of the interaction between the chemical ordering, B2, D03 and L12 and the magnetic ordering on the phase equilibria will be discussed according to the calculated phase diagrams of the Fe-X binary systems.

  8. Computation of two-fluid, flowing equilibria

    Science.gov (United States)

    Steinhauer, Loren; Kanki, Takashi; Ishida, Akio

    2006-10-01

    Equilibria of flowing two-fluid plasmas are computed for realistic compact-toroid and spherical-tokamak parameters. In these examples the two-fluid parameter ɛ (ratio of ion inertial length to overall plasma size) is small, ɛ ˜ 0.03 -- 0.2, but hardly negligible. The algorithm is based on the nearby-fluids model [1] which avoids a singularity that otherwise occurs for small ɛ. These representative equilibria exhibit significant flows, both toroidal and poloidal. Further, the flow patterns display notable flow shear. The importance of two-fluid effects is demonstrated by comparing with analogous equilibria (e.g. fixed toroidal and poloidal current) for a static plasma (Grad-Shafranov solution) and a flowing single-fluid plasma. Differences between the two-fluid, single-fluid, and static equilibria are highlighted: in particular with respect to safety factor profile, flow patterns, and electrical potential. These equilibria are computed using an iterative algorithm: it employs a successive-over-relaxation procedure for updating the magnetic flux function and a Newton-Raphson procedure for updating the density. The algorithm is coded in Visual Basic in an Excel platform on a personal computer. The computational time is essentially instantaneous (seconds). [1] L.C. Steinhauer and A. Ishida, Phys. Plasmas 13, 052513 (2006).

  9. Instability of Magnetic Equilibria in Barotropic Stars

    CERN Document Server

    Mitchell, J P; Reisenegger, A; Spruit, H; Valdivia, J A; Langer, N

    2014-01-01

    In stably stratified stars, numerical magneto-hydrodynamics simulations have shown that arbitrary initial magnetic fields evolve into stable equilibrium configurations, usually containing nearly axisymmetric, linked poloidal and toroidal fields that stabilize each other. In this work, we test the hypothesis that stable stratification is a requirement for the existence of such stable equilibria. For this purpose, we follow numerically the evolution of magnetic fields in barotropic (and thus neutrally stable) stars, starting from two different types of initial conditions, namely random disordered magnetic fields, as well as linked poloidal-toroidal configurations resembling the previously found equilibria. With many trials, we always find a decay of the magnetic field over a few Alfv\\'en times, never a stable equilibrium. This strongly suggests that there are no stable equilibria in barotropic stars, thus clearly invalidating the assumption of barotropic equations of state often imposed on the search of magneti...

  10. Multiple Equilibria in Noisy Rational Expectations Economies

    DEFF Research Database (Denmark)

    Palvolgyi, Domotor; Venter, Gyuri

    This paper studies equilibrium uniqueness in standard noisy rational expectations economies with asymmetric or differential information a la Grossman and Stiglitz (1980) and Hellwig (1980). We show that the standard linear equilibrium of Grossman and Stiglitz (1980) is the unique equilibrium......-sloping” demand curves, (iv) higher prices leading to future returns that are higher in expectation (price drift) and (v) more positively skewed. Discontinuous equilibria can be arbitrarily close to being fully-revealing. Finally, discontinuous equilibria with the same construction also exist in Hellwig (1980)....

  11. Effect of temperature on acid–base equilibria in separation techniques. A review

    Energy Technology Data Exchange (ETDEWEB)

    Gagliardi, Leonardo G.; Tascon, Marcos; Castells, Cecilia B., E-mail: castells@isis.unlp.edu.ar

    2015-08-19

    Studies on the theoretical principles of acid–base equilibria are reviewed and the influence of temperature on secondary chemical equilibria within the context of separation techniques, in water and also in aqueous-organic solvent mixtures, is discussed. In order to define the relationships between the retention in liquid chromatography or the migration velocity in capillary electrophoresis and temperature, the main properties of acid–base equilibria have to be taken into account for both, the analytes and the conjugate pairs chosen to control the solution pH. The focus of this review is based on liquid–liquid extraction (LLE), liquid chromatography (LC) and capillary electrophoresis (CE), with emphasis on the use of temperature as a useful variable to modify selectivity on a predictable basis. Simplified models were evaluated to achieve practical optimizations involving pH and temperature (in LLE and CE) as well as solvent composition in reversed-phase LC. - Highlights: • The study of theoretical principles of acid–base equilibrium has been reviewed. • The proton transfer process is often present in the analytical separation practice. • The influence of temperature on secondary chemical equilibria is examined. • The focus is laid on liquid chromatography and capillary electrophoresis. • Temperature can be a useful variable to modify selectivity under predictable basis.

  12. Instability of magnetic equilibria in barotropic stars

    Science.gov (United States)

    Mitchell, J. P.; Braithwaite, J.; Reisenegger, A.; Spruit, H.; Valdivia, J. A.; Langer, N.

    2015-02-01

    In stably stratified stars, numerical magnetohydrodynamics simulations have shown that arbitrary initial magnetic fields evolve into stable equilibrium configurations, usually containing nearly axisymmetric, linked poloidal and toroidal fields that stabilize each other. In this work, we test the hypothesis that stable stratification is a requirement for the existence of such stable equilibria. For this purpose, we follow numerically the evolution of magnetic fields in barotropic (and thus neutrally stable) stars, starting from two different types of initial conditions, namely random disordered magnetic fields, as well as linked poloidal-toroidal configurations resembling the previously found equilibria. With many trials, we always find a decay of the magnetic field over a few Alfvén times, never a stable equilibrium. This strongly suggests that there are no stable equilibria in barotropic stars, thus clearly invalidating the assumption of barotropic equations of state often imposed on the search of magnetic equilibria. It also supports the hypothesis that, as dissipative processes erode the stable stratification, they might destabilize previously stable magnetic field configurations, leading to their decay.

  13. Phase equilibria of carbohydrates in polar solvents

    DEFF Research Database (Denmark)

    Jonsdottir, Svava Osk; Rasmussen, Peter

    1999-01-01

    A method for calculating interaction energies and interaction parameters with molecular mechanics methods is extended to predict solid-liquid equilibria (SLE) for saccharides in aqueous solution, giving results in excellent agreement with experimental values. Previously, the method has been shown...

  14. Intermediates and Generic Convergence to Equilibria

    DEFF Research Database (Denmark)

    Freitas, Michael Marcondes de; Wiuf, Carsten; Feliu, Elisenda

    2016-01-01

    Known graphical conditions for the generic or global convergence to equilibria of the dynamical system arising from a reaction network are shown to be invariant under the so-called successive removal of intermediates, a systematic procedure to simplify the network, making the graphical conditions...

  15. Binary Solid-Liquid Phase Equilibria

    Science.gov (United States)

    Ellison, Herbert R.

    1978-01-01

    Indicates some of the information that may be obtained from a binary solid-liquid phase equilibria experiment and a method to write a computer program that will plot an ideal phase diagram to which the experimental results may be compared. (Author/CP)

  16. Study of Phase Equilibria of Petrochemical Fluids using Gibbs Ensemble Monte Carlo Methods

    Science.gov (United States)

    Nath, Shyamal

    2001-03-01

    Knowledge of phase behavior of hydrocarbons and related compounds are highly of interest to chemical and petrochemical industries. For example, design of processes such as supercritical fluid extraction, petroleum refining, enhanced oil recovery, gas treatment, and fractionation of wax products. A precise knowledge of the phase equilibria of alkanes, alkenes and related compounds and their mixtures are required for efficient design of these processes. Experimental studies to understand the related phase equilibria often become unsuitable for various reasons. With the advancement of simulation technology, molecular simulations could provide a useful complement and alternative in the study and description of phase behavior of these systems. In this work we study vapor-liquid phase equilibria of pure hydrocarbons and their mixtures using Gibbs ensemble simulation. Insertion of long and articulated chain molecules are facilitated in our simulations by means of configurational bias and expanded ensemble methods. We use the newly developed NERD force field in our simulation. In this work NERD force field is extended to provide coverage for hydrocarbons with any arbitrary architecture. Our simulation results provide excellent quantitative agreement with available experimental phase equilibria data for both the pure components and mixtures.

  17. Phase equilibria in stratified thin liquid films stabilized by colloidal particles

    OpenAIRE

    Blawzdziewicz, J.; Wajnryb, E.

    2005-01-01

    Phase equilibria between regions of different thickness in thin liquid films stabilized by colloidal particles are investigated using a quasi-two-dimensional thermodynamic formalism. Appropriate equilibrium conditions for the film tension, normal pressure, and chemical potential of the particles in the film are formulated, and it is shown that the relaxation of these parameters occurs consecutively on three distinct time scales. Film stratification is described quantitatively for a hard-spher...

  18. Multiple equilibria in a simple elastocapillary system

    KAUST Repository

    Taroni, Michele

    2012-09-28

    We consider the elastocapillary interaction of a liquid drop placed between two elastic beams, which are both clamped at one end to a rigid substrate. This is a simple model system relevant to the problem of surface-tension-induced collapse of flexible micro-channels that has been observed in the manufacture of microelectromechanical systems (MEMS). We determine the conditions under which the beams remain separated, touch at a point, or stick along a portion of their length. Surprisingly, we show that in many circumstances multiple equilibrium states are possible. We develop a lubrication-type model for the flow of liquid out of equilibrium and thereby investigate the stability of the multiple equilibria. We demonstrate that for given material properties two stable equilibria may exist, and show via numerical solutions of the dynamic model that it is the initial state of the system that determines which stable equilibrium is ultimately reached. © 2012 Cambridge University Press.

  19. Equilibria of Generalized Cut and Choose Protocols

    DEFF Research Database (Denmark)

    Branzei, Simina; Caragiannis, Ioannis; Kurokawa, David

    Classic cake cutting protocols — which fairly allocate a divisible good among agents with heterogeneous preferences — are susceptible to manipulation. Do their strategic outcomes still guarantee fairness? To answer this question we adopt a novel algo rithmic approach, proposing a concrete computa...... the stronger fairness notion of envy-freeness. Finally, we show that under an obliviousness restriction, which still allows the computation of approximately envy-free allocations, GCC protocols are guaranteed to have exact subgame perfect Nash equilibria...

  20. Relative Equilibria in the Spherical, Finite Density 3-Body Problem

    CERN Document Server

    Scheeres, D J

    2016-01-01

    The relative equilibria for the spherical, finite density 3 body problem are identified. Specifically, there are 28 distinct relative equilibria in this problem which include the classical 5 relative equilibria for the point-mass 3-body problem. None of the identified relative equilibria exist or are stable over all values of angular momentum. The stability and bifurcation pathways of these relative equilibria are mapped out as the angular momentum of the system is increased. This is done under the assumption that they have equal and constant densities and that the entire system rotates about its maximum moment of inertia. The transition to finite density greatly increases the number of relative equilibria in the 3-body problem and ensures that minimum energy configurations exist for all values of angular momentum.

  1. Ruthenium redox equilibria: 1. Thermodynamic stability of Ru(III and Ru(IV hydroxides

    Directory of Open Access Journals (Sweden)

    Igor Povar

    2016-04-01

    Full Text Available On the basis of the selected thermodynamic data for Ru(III and Ru(IV compounds in addition to original thermodynamic and graphical approach used in this paper, the thermodynamic stability areas of sparingly soluble hydroxides as well as the repartition of their soluble and insoluble chemical species towards the solution pH and initial concentrations of ruthenium in heterogeneous mixture solid phase–saturated solution have been investigated. By means of the ΔG–pH diagrams, the areas of thermodynamic stability of Ru(III and Ru(IV hydroxides have been established for a number of analytical concentrations in heterogeneous mixtures. The diagrams of heterogeneous and homogeneous chemical equilibria have been used for graphical representation of complex equilibria in aqueous solutions containing Ru(III and Ru(IV. The obtained results, based on the thermodynamic analysis and graphic design of the calculated data in the form of the diagrams of heterogeneous chemical equilibria, are in good agre­ement with the available experimental data.

  2. Exogenous empirical-evidence equilibria in perfect-monitoring repeated games yield correlated equilibria

    KAUST Repository

    Dudebout, Nicolas

    2014-12-15

    This paper proves that exogenous empirical-evidence equilibria (xEEEs) in perfect-monitoring repeated games induce correlated equilibria of the associated one-shot game. An empirical-evidence equilibrium (EEE) is a solution concept for stochastic games. At equilibrium, agents\\' strategies are optimal with respect to models of their opponents. These models satisfy a consistency condition with respect to the actual behavior of the opponents. As such, EEEs replace the full-rationality requirement of Nash equilibria by a consistency-based bounded-rationality one. In this paper, the framework of empirical evidence is summarized, with an emphasis on perfect-monitoring repeated games. A less constraining notion of consistency is introduced. The fact that an xEEE in a perfect-monitoring repeated game induces a correlated equilibrium on the underlying one-shot game is proven. This result and the new notion of consistency are illustrated on the hawk-dove game. Finally, a method to build specific correlated equilibria from xEEEs is derived.

  3. Cycles and Multiple Equilibria in the Market for Durable Lemons

    NARCIS (Netherlands)

    M.C.W. Janssen (Maarten); V.A. Karamychev (Vladimir)

    2000-01-01

    textabstractWe investigate the nature of market failure in a dynamic version of Akerlof (1970) where identical cohorts of a durable good enter the market over time. In the dynamic model, equilibria with qualitatively different properties emerge. Typically, in equilibria of the dynamic model, sellers

  4. A unifying approach to existence of Nash equilibria

    NARCIS (Netherlands)

    Balder, E.J.

    2001-01-01

    An approach initiated in [4] is shown to unify results about the existence of (i) Nash equilibria in games with at most countably many players, (ii) Cournot-Nash equilibrium distributions for large, anonymous games, and (iii) Nash equilibria (both mixed and pure) for continuum games. A new, central

  5. Correlated Equilibria of Classical Strategic Games with Quantum Signals

    CERN Document Server

    La Mura, P

    2003-01-01

    Correlated equilibria are sometimes more efficient than the Nash equilibria of a game without signals. We investigate whether the availability of quantum signals in the context of a classical strategic game may allow the players to achieve even better efficiency than in any correlated equilibrium with classical signals, and find the answer to be positive.

  6. Phase equilibria in the NaF-CdO-NaPO3 system at 873 K and crystal structure and physico-chemical characterizations of the new Na2CdPO4F fluorophosphate

    Science.gov (United States)

    Aboussatar, Mohamed; Mbarek, Aïcha; Naili, Houcine; El-Ghozzi, Malika; Chadeyron, Geneviève; Avignant, Daniel; Zambon, Daniel

    2017-04-01

    Isothermal sections of the diagram representing phase relationships in the NaF-CdO-NaPO3 system have been investigated by solid state reactions and powder X-ray diffraction. This phase diagram investigation confirms the polymorphism of the NaCdPO4 side component and the structure of the ß high temperature polymorph (orthorhombic, space group Pnma and unit cell parameters a=9.3118(2), b=7.0459(1), c=5.1849(1) Å has been refined. A new fluorophosphate, Na2CdPO4F, has been discovered and its crystal structure determined and refined from powder X-ray diffraction data. It exhibits a new 3D structure with orthorhombic symmetry, space group Pnma and unit cell parameters a=5.3731(1), b=6.8530(1), c=12.2691(2) Å. The structure is closely related to those of the high temperature polymorph of the nacaphite Na2CaPO4F and the fluorosilicate Ca2NaSiO4F but differs essentially in the cationic repartition since the structure is fully ordered with one Na site (8d) and one Cd site (4c). Relationships with other Na2MIIPO4F (MII=Mg, Ca, Mn, Fe, Co, Ni) have been examined and the crystal-chemical and topographical analysis of these fluorophosphates is briefly reviewed. IR, Raman, optical and 19F, 23Na, 31P MAS NMR characterizations of Na2CdPO4F have been investigated.

  7. High temperature phase equilibria and phase diagrams

    CERN Document Server

    Kuo, Chu-Kun; Yan, Dong-Sheng

    2013-01-01

    High temperature phase equilibria studies play an increasingly important role in materials science and engineering. It is especially significant in the research into the properties of the material and the ways in which they can be improved. This is achieved by observing equilibrium and by examining the phase relationships at high temperature. The study of high temperature phase diagrams of nonmetallic systems began in the early 1900s when silica and mineral systems containing silica were focussed upon. Since then technical ceramics emerged and more emphasis has been placed on high temperature

  8. Prediction of vapour-liquid equilibria for the kinetic study of processes based on synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Di Serio, M.; Tesser, R.; Cozzolino, M.; Santacesaria, E. [Naples Univ., Napoli (Italy). Dept. of Chemistry

    2006-07-01

    Syngas is normally used in the production of a broad range of chemicals and fuels. In many of these processes multiphase reactors, gas-liquid or gas-liquid-solid are used. Kinetic studies in multiphase systems are often complicated by the non-ideal behaviour of reagents and/or products that are consistently partitioned between the liquid and the vapour phase. Moreover, as often kinetic data are collected in batch conditions for the liquid phase, activity coefficients of the partitioned components can consistently change during the time as a consequence of changing the composition of the reaction mixture. Therefore, it is necessary, in these cases, to known the vapor-liquid equilibria (VLE) in order to collect and to interpret correctly the kinetic data. The description of phase equilibria, at high pressures, is usually performed by means of an EOS (Equation of State) allowing the calculation of fugacity coefficients, for each component, in both phases and determining the partition coefficients but the EOS approach involves the experimental determination of the interaction parameters for all the possible binary system of the mixture. For multicomponent mixtures a complete experimental determination of vapourliquid equilibria is very hard, also considering the high pressure and temperatures used. Some predictive group contribution methods have been recently developed. In this paper, we will describe in detail the application of these methods to the methanol homologation, as an example, with the scope of determining more reliable kinetic parameters for this reaction. (orig.)

  9. TOKAMAK EQUILIBRIA WITH CENTRAL CURRENT HOLES AND NEGATIVE CURRENT DRIVE

    Energy Technology Data Exchange (ETDEWEB)

    CHU, M.S.; PARKS, P.B.

    2002-06-01

    OAK B202 TOKAMAK EQUILIBRIA WITH CENTRAL CURRENT HOLES AND NEGATIVE CURRENT DRIVE. Several tokamak experiments have reported the development of a central region with vanishing currents (the current hole). Straightforward application of results from the work of Greene, Johnson and Weimer [Phys. Fluids, 3, 67 (1971)] on tokamak equilibrium to these plasmas leads to apparent singularities in several physical quantities including the Shafranov shift and casts doubts on the existence of this type of equilibria. In this paper, the above quoted equilibrium theory is re-examined and extended to include equilibria with a current hole. It is shown that singularities can be circumvented and that equilibria with a central current hole do satisfy the magnetohydrodynamic equilibrium condition with regular behavior for all the physical quantities and do not lead to infinitely large Shafranov shifts. Isolated equilibria with negative current in the central region could exist. But equilibria with negative currents in general do not have neighboring equilibria and thus cannot have experimental realization, i.e. no negative currents can be driven in the central region.

  10. Close pairs of relative equilibria for identical point vortices

    DEFF Research Database (Denmark)

    Dirksen, Tobias; Aref, Hassan

    2011-01-01

    Numerical solution of the classical problem of relative equilibria for identical point vortices on the unbounded plane reveals configurations that are very close to the analytically known, centered, symmetrically arranged, nested equilateral triangles. New numerical solutions of this kind are found...... also has this property, and new relative equilibria close to the nested, symmetrically arranged, regular heptagons have been found. The centered regular nonagon is also marginally stable. Again, a new family of close relative equilibria has been found. The closest relative equilibrium pairs occur...

  11. CONSTRUCTING EXAMPLES WITH 5 EQUILIBRIA FOR SYMMETRIC 3 × 2 CES / LES PURE EXCHANGE ECONOMIES

    Institute of Scientific and Technical Information of China (English)

    Huang Hui; Shi Xiaojun; Zhang Shunming

    2012-01-01

    This paper explores the existence of multiple equilibria for symmetric 3 individual,2 good CES / LES pure exchange economies.Analytically,we show that there are no more than 5 equilibria in such economies.The number of equilibria varies from 5 to 3 then to 1.We generalize our analytical results of existence of 1,3,5 equilibria for a wide range of parametrizations.We also provide concrete examples of 1,3,5 equilibria with parameter zones specified.

  12. Study of improved methods for predicting chemical equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Lenz, T.G.; Vaughan, J.D.

    1992-06-01

    The objective of our research has been to develop computational methods that have the capability of accurately predicting equilibrium constants of typical organic reactions in gas and liquid solution phases. We have chosen Diels-Alder reactions as prototypic systems for the investigation, chiefly because there are an adequate number of reported equilibrium constants for the candidate reactions in both gas and solution phases, which data provides a suitable basis for tests of the developed computational methods. Our approach has been to calculate the standard enthalpies of formation ({Delta}H{sub f}{sup 0}) at 298.15K and the standard thermodynamic functions (S{sup 0}, Cp{sup 0}, and (H{sup 0}-H{sub 0}{sup 0})/T) for a range of temperatures for reactants and products, and from these properties to calculate standard enthalpies, entropies, Gibbs free energies, and equilibrium constants ({Delta}H{sub T}{sup 0}, {Delta}S{sub T}{sup 0}, and K{sub a}) at various temperatures for the chosen reaction.

  13. Chemical equilibria in bio sorption; Equilibrios quimicos en bioadsorcion

    Energy Technology Data Exchange (ETDEWEB)

    Romero, A.; Gonzalez, F.; Ballester, A.; Blazquez, M. L.; Munoz, J.A.

    2007-07-01

    An experimental study of bio sorption was carried out using six different kinds of algae and five different heavy metals (cadmium, copper, nickel, lead and zinc). Experimental data fitted very well to langmuir's model and this allowed to predict the behaviour of the biomass under specific working conditions. Using the equations of the model under different initial assumptions, a series of mathematical calculations were done for mono metallic, bimetallic and tri metallic systems. the most complicated calculation is that in which, knowing the initial metal concentration (C{sub 0}), it is necessary to calculate the conditions reached at the equilibrium, this is, q{sub e} and C{sub e}. This assumption is of great interest from the point of view of the actual applicability of the process. However, in this case, it is necessary to solve very complex mathematical equations which, for multi metallic systems, are of degree n+1, where n is the number of ions present in solution. The excellent correlation between experimental and theoretical data demonstrates that the bio sorption process can be modelling. (Author) 18 refs.

  14. An Algorithm for Computing All Berge Equilibria

    Directory of Open Access Journals (Sweden)

    H. W. Corley

    2015-01-01

    Full Text Available An algorithm is presented in this note for determining all Berge equilibria for an n-person game in normal form. This algorithm is based on the notion of disappointment, with the payoff matrix (PM being transformed into a disappointment matrix (DM. The DM has the property that a pure strategy profile of the PM is a BE if and only if (0,…,0 is the corresponding entry of the DM. Furthermore, any (0,…,0 entry of the DM is also a more restrictive Berge-Vaisman equilibrium if and only if each player’s BE payoff is at least as large as the player’s maximin security level.

  15. A molecular-thermodynamic framework for asphaltene-oil equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Wu, J.; Prausnitz, J.M. [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.; Firoozabadi, A. [Reservoir Engineering Research Inst., Palo Alto, CA (United States)

    1997-02-01

    Asphaltene precipitation is a perennial problem in production and refinery of crude oils. To avoid precipitation, it is useful to predict the solubility of asphaltenes in petroleum liquids as a function of temperature, pressure and liquid-phase composition. In the molecular-thermodynamic model presented here, both asphaltenes and resins are represented by pseudo-pure components, and all other components in the solution are represented by a continuous medium which affects interactions among asphaltene and resin particles. The effect of the medium on asphaltene-asphaltene, resin-asphaltene, resin-resin pair interactions is taken into account through its density and molecular-dispersion properties. To obtain expressions for the chemical potential of asphaltene and for the osmotic pressure of an asphaltene-containing solution, the authors use the integral theory of fluids coupled with the SAFT model to allow for asphaltene aggregation and for adsorption of resin on asphaltene particles. With these expressions, a variety of experimental observations can be explained including the effects of temperature, pressure and composition on the phase behavior of asphaltene-containing fluids. For engineering application, the molecular parameters in this model must be correlated to some macroproperties of oil such as density and molecular weight. When such correlations are established, it will be possible to calculate asphaltene-precipitation equilibria at a variety of conditions for realistic systems.

  16. Molecular equilibria and condensation sequences in carbon rich gases

    Science.gov (United States)

    Sharp, C. M.; Wasserburg, G. J.

    1993-01-01

    Chemical equilibria in stellar atmospheres have been investigated by many authors. Lattimer, Schramm, and Grossman presented calculations in both O rich and C rich environments and predicted possible presolar condensates. A recent paper by Cherchneff and Barker considered a C rich composition with PAH's included in the calculations. However, the condensation sequences of C bearing species have not been investigated in detail. In a carbon rich gas surrounding an AGB star, it is often assumed that graphite (or diamond) condenses out before TiC and SiC. However, Lattimer et al. found some conditions under which TiC condenses before graphite. We have performed molecular equilibrium calculations to establish the stability fields of C(s), TiC(s), and SiC(s) and other high temperature phases under conditions of different pressures and C/O. The preserved presolar interstellar dust grains so far discovered in meteorites are graphite, diamond, SiC, TiC, and possibly Al2O3.

  17. Learning Equilibria with Partial Information in Decentralized Wireless Networks

    CERN Document Server

    Rose, Luca; Lasaulce, Samson; Debbah, Mérouane

    2011-01-01

    In this article, a survey of several important equilibrium concepts for decentralized networks is presented. The term decentralized is used here to refer to scenarios where decisions (e.g., choosing a power allocation policy) are taken autonomously by devices interacting with each other (e.g., through mutual interference). The iterative long-term interaction is characterized by stable points of the wireless network called equilibria. The interest in these equilibria stems from the relevance of network stability and the fact that they can be achieved by letting radio devices to repeatedly interact over time. To achieve these equilibria, several learning techniques, namely, the best response dynamics, fictitious play, smoothed fictitious play, reinforcement learning algorithms, and regret matching, are discussed in terms of information requirements and convergence properties. Most of the notions introduced here, for both equilibria and learning schemes, are illustrated by a simple case study, namely, an interfe...

  18. The freedom to choose neutron star magnetic field equilibria

    CERN Document Server

    Glampedakis, Kostas

    2016-01-01

    Our ability to interpret and glean useful information from the large body of observations of strongly magnetised neutron stars rests largely on our theoretical understanding of magnetic field equilibria. We answer the following question: is one free to arbitrarily prescribe magnetic equilibria such that fluid degrees of freedom can balance the equilibrium equations? We examine this question for various models for neutron star matter; from the simplest single-fluid barotrope to more realistic non-barotropic multifluid models with superfluid/superconducting components, muons and entropy. We do this for both axi- and non-axisymmetric equilibria, and in Newtonian gravity and general relativity. We show that, in axisymmetry, the most realistic model allows complete freedom in choosing a magnetic field equilibrium whereas non-axisymmetric equilibria are never completely arbitrary.

  19. Stable equilibria of elliptic roly-poly toys

    Science.gov (United States)

    Hong, Seok-In

    2016-11-01

    As an instructive (gravitational potential) energy approach, we show that the elliptic roly-poly has a richer and more useful profile (including the tilted configuration) of stable equilibria than conventional spherical or cylindrical roly-polys.

  20. Calculation of Liquid Water-Hydrate-Methane Vapor Phase Equilibria from Molecular Simulations

    DEFF Research Database (Denmark)

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas

    2010-01-01

    Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled...... using the TIP4P/ice potential and a united-atom Lennard-Jones potential. respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials. (ii) calculation of the chemical...... potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated...

  1. Existence of General Competitive Equilibria: A Variational Approach

    Directory of Open Access Journals (Sweden)

    G. Anello

    2016-01-01

    Full Text Available We study the existence of general competitive equilibria in economies with agents and goods in a finite number. We show that there exists a Walras competitive equilibrium in all ownership private economies such that, for all consumers, initial endowments do not contain free goods and utility functions are locally Lipschitz quasiconcave. The proof of the existence of competitive equilibria is based on variational methods by applying a theoretical existence result for Generalized Quasi Variational Inequalities.

  2. Supercritical Phase Equilibria Modeling of Glyceride Mixtures and Carbon Dioxide Using the Group Contribution EoS

    Directory of Open Access Journals (Sweden)

    Tiziana Fornari

    2011-01-01

    Experimental data was obtained in a countercurrent packed extraction column at pressures ranging from 16 to 25 MPa and temperatures from 313 to 368 K. The GC-EoS model was applied in a completely predictive manner to simulate the phase equilibria behavior of the multistage separation process. The chemical analysis of the glyceride mixture allowed a significant simplification of its complex composition and thus, a simple and satisfactory simulation of the supercritical extraction process was achieved.

  3. CHEMICALS

    CERN Multimedia

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  4. Unifying dynamical and structural stability of equilibria

    Science.gov (United States)

    Arnoldi, Jean-François; Haegeman, Bart

    2016-09-01

    We exhibit a fundamental relationship between measures of dynamical and structural stability of linear dynamical systems-e.g. linearized models in the vicinity of equilibria. We show that dynamical stability, quantified via the response to external perturbations (i.e. perturbation of dynamical variables), coincides with the minimal internal perturbation (i.e. perturbations of interactions between variables) able to render the system unstable. First, by reformulating a result of control theory, we explain that harmonic external perturbations reflect the spectral sensitivity of the Jacobian matrix at the equilibrium, with respect to constant changes of its coefficients. However, for this equivalence to hold, imaginary changes of the Jacobian's coefficients have to be allowed. The connection with dynamical stability is thus lost for real dynamical systems. We show that this issue can be avoided, thus recovering the fundamental link between dynamical and structural stability, by considering stochastic noise as external and internal perturbations. More precisely, we demonstrate that a linear system's response to white-noise perturbations directly reflects the intensity of internal white-noise disturbance that it can accommodate before becoming stochastically unstable.

  5. The CHEASE code for toroidal MHD equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Luetjens, H. [Ecole Polytechnique, 91 - Palaiseau (France). Centre de Physique Theorique; Bondeson, A. [Chalmers Univ. of Technology, Goeteborg (Sweden). Inst. for Electromagnetic Field Theory and Plasma Physics; Sauter, O. [ITER-San Diego, La Jolla, CA (United States)

    1996-03-01

    CHEASE solves the Grad-Shafranov equation for the MHD equilibrium of a Tokamak-like plasma with pressure and current profiles specified by analytic forms or sets of data points. Equilibria marginally stable to ballooning modes or with a prescribed fraction of bootstrap current can be computed. The code provides a mapping to magnetic flux coordinates, suitable for MHD stability calculations or global wave propagation studies. The code computes equilibrium quantities for the stability codes ERATO, MARS, PEST, NOVA-W and XTOR and for the global wave propagation codes LION and PENN. The two-dimensional MHD equilibrium (Grad-Shafranov) equation is solved in variational form. The discretization uses bicubic Hermite finite elements with continuous first order derivates for the poloidal flux function {Psi}. The nonlinearity of the problem is handled by Picard iteration. The mapping to flux coordinates is carried out with a method which conserves the accuracy of the cubic finite elements. The code uses routines from the CRAY libsci.a program library. However, all these routines are included in the CHEASE package itself. If CHEASE computes equilibrium quantities for MARS with fast Fourier transforms, the NAG library is required. CHEASE is written in standard FORTRAN-77, except for the use of the input facility NAMELIST. CHEASE uses variable names with up to 8 characters, and therefore violates the ANSI standard. CHEASE transfers plot quantities through an external disk file to a plot program named PCHEASE using the UNIRAS or the NCAR plot package. (author) figs., tabs., 34 refs.

  6. Bilinear Relative Equilibria of Identical Point Vortices

    DEFF Research Database (Denmark)

    Aref, H.; Beelen, Peter; Brøns, Morten

    2012-01-01

    -axis and n on the x-axis. We define generating polynomials q(z) and p(z), respectively, for each set of vortices. A second-order, linear ODE for p(z) given q(z) is derived. Several results relating the general solution of the ODE to relative equilibrium configurations are established. Our strongest result......A new class of bilinear relative equilibria of identical point vortices in which the vortices are constrained to be on two perpendicular lines, conveniently taken to be the x- and y-axes of a Cartesian coordinate system, is introduced and studied. In the general problem we have m vortices on the y......, obtained using Sturm’s comparison theorem, is that if p(z) satisfies the ODE for a given q(z) with its imaginary zeros symmetric relative to the x-axis, then it must have at least n−m+2 simple, real zeros. For m=2 this provides a complete characterization of all zeros, and we study this case in some detail...

  7. Applied chemical engineering thermodynamics

    CERN Document Server

    Tassios, Dimitrios P

    1993-01-01

    Applied Chemical Engineering Thermodynamics provides the undergraduate and graduate student of chemical engineering with the basic knowledge, the methodology and the references he needs to apply it in industrial practice. Thus, in addition to the classical topics of the laws of thermodynamics,pure component and mixture thermodynamic properties as well as phase and chemical equilibria the reader will find: - history of thermodynamics - energy conservation - internmolecular forces and molecular thermodynamics - cubic equations of state - statistical mechanics. A great number of calculated problems with solutions and an appendix with numerous tables of numbers of practical importance are extremely helpful for applied calculations. The computer programs on the included disk help the student to become familiar with the typical methods used in industry for volumetric and vapor-liquid equilibria calculations.

  8. Mathematical Model for Multicomponent Adsorption Equilibria Using Only Pure Component Data

    DEFF Research Database (Denmark)

    Marcussen, Lis

    2000-01-01

    A mathematical model for nonideal adsorption equilibria in multicomponent mixtures is developed. It is applied with good results for pure substances and for prediction of strongly nonideal multicomponent equilibria using only pure component data. The model accounts for adsorbent...

  9. Correlation of three-liquid-phase equilibria involving ionic liquids.

    Science.gov (United States)

    Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A

    2016-08-03

    The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results.

  10. The mechanics of rocking stones: equilibria on separated scales

    CERN Document Server

    Domokos, Gábor; Szabó, Tímea

    2011-01-01

    Rocking stones, balanced in counter-intuitive positions have always intrigued geologists. In our paper we explain this phenomenon based on high-precision scans of pebbles which exhibit similar behavior. We construct their convex hull and the heteroclinic graph carrying their equilibrium points. By systematic simplification of the arising Morse-Smale complex in a one-parameter process we show that equilibria occur typically in highly localized groups (flocks), the number of the latter can be reliably observed and determined by hand experiments. Both local and global (micro and macro) equilibria can be either stable or unstable. Most commonly, rocks and pebbles are balanced on stable local equilibria belonging to stable flocks. However, it is possible to balance a convex body on a stable local equilibrium belonging to an unstable flock and this is the intriguing mechanical scenario corresponding to rocking stones. Since outside observers can only reliably perceive flocks, the last described situation will appea...

  11. It takes two to tango: Equilibria in a model of sales

    NARCIS (Netherlands)

    M.R. Baye (Michael); D. Kovenock (Dan); C.G. de Vries (Casper)

    1992-01-01

    textabstractWe show that the Varian model of sales with more than two firms has two types of equilibria: a unique symmetric equilibrium, and a continuum of asymmetric equilibria. In contrast, the 2-firm game has a unique equilibrium that is symmetric. For the n-firm case the asymmetric equilibria im

  12. On the existence and convergence of price equilibria for random economies

    OpenAIRE

    Nummelin, Esa

    2000-01-01

    We study an exchange economy comprising $n$ agents,where the excess demands by the agents are random variables. We show that under certain conditions the set of price equilibria is nonempty. We also prove a theorem concerning the convergence of the random price equilibria toward the price equilibria of an associated “expectation economy.”

  13. Recent progress in the relative equilibria of point vortices — In memoriam Hassan Aref

    DEFF Research Database (Denmark)

    Beelen, Peter; Brøns, Morten; Krishnamurthy, Vikas S.;

    2013-01-01

    Hassan Aref, who sadly passed away in 2011, was one of the world's leading researchers in the dynamics and equilibria of point vortices. We review two problems on the subject of point vortex relative equilibria in which he was engaged at the time of his death: bilinear relative equilibria and the...

  14. Long-range correlations and coherent structures in magnetohydrodynamic equilibria.

    Science.gov (United States)

    Weichman, Peter B

    2012-12-01

    The equilibrium theory of the 2D magnetohydrodynamic equations is derived, accounting for the full infinite hierarchies of conserved integrals. An exact description in terms of two coupled elastic membranes emerges, producing long-ranged correlations between the magnetic and velocity fields. This is quite different from the results of previous variational treatments, which relied on a local product ansatz for the thermodynamic Gibbs distribution. The equilibria display the same type of coherent structures, such as compact eddies and zonal jets, previously found in pure fluid equilibria. Possible consequences of this for recent simulations of the solar tachocline are discussed.

  15. A method of computational magnetohydrodynamics defining stable Scyllac equilibria.

    Science.gov (United States)

    Betancourt, O; Garabedian, P

    1977-02-01

    A computer code has been developed for the numerical calculation of sharp boundary equilibria of a toroidal plasma with diffuse pressure profile. This generalizes earlier work that was done separately on the sharp boundary and diffuse models, and it allows for large amplitude distortions of the plasma in three-dimensional space. By running the code, equilibria that are stable to the so-called m = 1, k = 0 mode have been found for Scyllac, which is a high beta toroidal confinement device of very large aspect ratio.

  16. Ideal MHD beta-limits of poloidally asymmetric equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in ..beta../sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is ..beta../sub critical/ approx. = 6.5%.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  19. Shallow-water vortex equilibria and their stability

    Energy Technology Data Exchange (ETDEWEB)

    Plotka, H; Dritschel, D G, E-mail: hanna@mcs.st-andrews.ac.uk, E-mail: dgd@mcs.st-andrews.ac.uk [School of Mathematics and Statistics, University of St Andrews, North Haugh, St. Andrews KY16 9SS (United Kingdom)

    2011-12-22

    We first describe the equilibrium form and stability of steadily-rotating simply-connected vortex patches in the single-layer quasi-geostrophic model of geophysical fluid dynamics. This model, valid for rotating shallow-water flow in the limit of small Rossby and Froude numbers, has an intrinsic length scale L{sub D} called the 'Rossby deformation length' relating the strength of stratification to that of the background rotation rate. Specifically, L{sub D} = c/f where c={radical}gH is a characteristic gravity-wave speed, g is gravity (or 'reduced' gravity in a two-layer context where one layer is infinitely deep), H is the mean active layer depth, and f is the Coriolis frequency (here constant). We next introduce ageostrophic effects by using the full shallow-water model to generate what we call 'quasi-equilibria'. These equilibria are not strictly steady, but radiate such weak gravity waves that they are steady for all practical purposes. Through an artificial ramping procedure, we ramp up the potential vorticity anomaly of the fluid particles in our quasi-geostrophic equilibria to obtain shallow-water quasi-equilibria at finite Rossby number. We show a few examples of these states in this paper.

  20. From Singularity Theory to Finiteness of Walrasian Equilibria

    DEFF Research Database (Denmark)

    Castro, Sofia B.S.D.; Dakhlia, Sami F.; Gothen, Peter

    The paper establishes that for an open and dense subset of smooth exchange economies, the number of Walrasian equilibria is finite. In particular, our results extend to non-regular economies; it even holds when restricted to the subset of critical ones. The proof rests on concepts from singularit...

  1. On Pure and (approximate) Strong Equilibria of Facility Location Games

    CERN Document Server

    Hansen, Thomas Dueholm

    2008-01-01

    We study social cost losses in Facility Location games, where n selfish agents install facilities over a network and connect to them, so as to forward their local demand (expressed by a non-negative weight per agent). Agents using the same facility share fairly its installation cost, but every agent pays individually a (weighted) connection cost to the chosen location. We study the Price of Stability (PoS) of pure Nash equilibria and the Price of Anarchy of strong equilibria (SPoA), that generalize pure equilibria by being resilient to coalitional deviations. A special case of recently studied network design games, Facility Location merits separate study as a classic model with numerous applications and individual characteristics: our analysis for unweighted agents on metric networks reveals constant upper and lower bounds for the PoS, while an O(ln n) upper bound implied by previous work is tight for non-metric networks. Strong equilibria do not always exist, even for the unweighted metric case. For this cas...

  2. Nanoscale effects on thermodynamics and phase equilibria in oxide systems.

    Science.gov (United States)

    Navrotsky, Alexandra

    2011-08-22

    Because different solid materials (phases) have different surface energies, equilibria among them will be significantly affected by particle size. This Minireview summarizes experimental (calorimetric) data for the surface energies of oxides and discusses shifts in the stability of polymorphs, the thermodynamics of hydration, and oxidation-reduction reactions in nanoscale oxide systems.

  3. QUASI-EQUILIBRIA IN MARKETS WITH NON-CONVEX PREFERENCES.

    Science.gov (United States)

    An upper bound is placed on social divergence from general equilibrium , due to non-convexity of the traders’ preference relations. Existence and significance of certain quasi-equilibria are investigated. If there is a sufficiently large number of traders in the market, the existence of a configuration arbitrarily close to equilibrium is demonstrated. (Author)

  4. Shallow-water vortex equilibria and their stability

    Science.gov (United States)

    Płotka, H.; Dritschel, D. G.

    2011-12-01

    We first describe the equilibrium form and stability of steadily-rotating simply-connected vortex patches in the single-layer quasi-geostrophic model of geophysical fluid dynamics. This model, valid for rotating shallow-water flow in the limit of small Rossby and Froude numbers, has an intrinsic length scale LD called the "Rossby deformation length" relating the strength of stratification to that of the background rotation rate. Specifically, LD = c/f where is a characteristic gravity-wave speed, g is gravity (or "reduced" gravity in a two-layer context where one layer is infinitely deep), H is the mean active layer depth, and f is the Coriolis frequency (here constant). We next introduce ageostrophic effects by using the full shallow-water model to generate what we call "quasi-equilibria". These equilibria are not strictly steady, but radiate such weak gravity waves that they are steady for all practical purposes. Through an artificial ramping procedure, we ramp up the potential vorticity anomaly of the fluid particles in our quasi-geostrophic equilibria to obtain shallow-water quasi-equilibria at finite Rossby number. We show a few examples of these states in this paper.

  5. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald

    2013-01-01

    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  6. Evaluation of a Mathematical Model for Single Component Adsorption Equilibria with Reference to the Prediction of Multicomponent Adsorption Equilibria

    DEFF Research Database (Denmark)

    Krøll, Annette Elisabeth; Marcussen, Lis

    1997-01-01

    An equilibrium equation for pure component adsorption is compared to experiments and to the vacancy solution theory. The investigated equilibrium equation is a special case of a model for prediction of multicomponent adsorption equilibria.The vacancy solution theory for multicomponent systems req...

  7. Dissociation and ionization equilibria of deuterium fluid over a wide range of temperatures and densities

    Energy Technology Data Exchange (ETDEWEB)

    Zaghloul, Mofreh R. [Department of Physics, College of Science, United Arab Emirates University, P.O. Box 15551, Al-Ain (United Arab Emirates)

    2015-06-15

    We investigate the dissociation and ionization equilibria of deuterium fluid over a wide range of temperatures and densities. The partition functions for molecular and atomic species are evaluated, in a statistical-mechanically consistent way, implementing recent developments in the literature and taking high-density effects into account. A new chemical model (free energy function) is introduced in which the fluid is considered as a mixture of diatomic molecules, atoms, ions, and free electrons. Intensive short range hard core repulsion is taken into account together with partial degeneracy of free electrons and Coulomb interactions among charged particles. Samples of computational results are presented as a set of isotherms for the degree of ionization, dissociated fraction of molecules, pressure, and specific internal energy for a wide range of densities and temperatures. Predictions from the present model calculations show an improved and sensible physical behavior compared to other results in the literature.

  8. Drug Distribution: A Guided-Inquiry Laboratory Experiment in Coupled Homogeneous and Heterogeneous Equilibria

    Science.gov (United States)

    Hein, John; Jeannot, Michael

    2001-02-01

    A simple and inexpensive experiment for the study of simultaneous homogeneous and heterogeneous equilibria is described using a common antihistamine drug, diphenhydramine. This experiment gives students an opportunity to study the distribution of a drug in a two-phase system by measuring the concentrations of two chemical species and predicting the others by considering charge balance, mass balance, and equilibrium constant expressions. Furthermore, the acid-dissociation constant and aqueous-organic distribution coefficient can be calculated. The experiment is attractive to students because it represents a simplified model for something experienced in everyday life, namely, drug distribution in the human body. Students also gain experience with two very important analytical techniques, gas chromatography and pH measurement with a glass electrode.

  9. Experimental measurements of vapor-liquid equilibria of the H2O + CO2 + CH4 ternary system

    Science.gov (United States)

    Qin, J.; Rosenbauer, R.J.; Duan, Zhenhao

    2008-01-01

    Reported are the experimental measurements on vapor-liquid equilibria in the H2O + CO2 + CH4 ternary system at temperatures from (324 to 375) K and pressures from (10 to 50) MPa. The results indicate that the CH4 solubility in the ternary mixture is about 10 % to 40 % more than that calculated by interpolation from the Henry's law constants of the binary system, H2O + CH4, and the solubility of CO2 is 6 % to 20 % more than what is calculated by the interpolation from the Henry's law constants of the binary mixture, H 2O + CO2. ?? 2008 American Chemical Society.

  10. Phase diagrams and heterogeneous equilibria a practical introduction

    CERN Document Server

    Predel, Bruno; Pool, Monte

    2004-01-01

    This graduate-level textbook provides an introduction to the practical application of phase diagrams. It is intended for students and researchers in chemistry, metallurgy, mineralogy, and materials science as well as in engineering and physics. Heterogeneous equilibria are described by a minimum of theory illustrated by practical examples and realistic case discussions from the different fields of application. The treatment of the physical and energetic background of phase equilibria leads to the discussion of the thermodynamics of mixtures and the correlation between energetics and composition. Thus, tools for the prediction of energetic, structural, and physical quantities are provided. The authors treat the nucleation of phase transitions, the production and stability of technologically important metastable phases, and metallic glasses. Furthermore, the text also concisely presents the thermodynamics and composition of polymer systems.

  11. Vlasov tokamak equilibria with shearad toroidal flow and anisotropic pressure

    CERN Document Server

    Kuiroukidis, Ap; Tasso, H

    2015-01-01

    By choosing appropriate deformed Maxwellian ion and electron distribution functions depending on the two particle constants of motion, i.e. the energy and toroidal angular momentum, we reduce the Vlasov axisymmetric equilibrium problem for quasineutral plasmas to a transcendental Grad-Shafranov-like equation. This equation is then solved numerically under the Dirichlet boundary condition for an analytically prescribed boundary possessing a lower X-point to construct tokamak equilibria with toroidal sheared ion flow and anisotropic pressure. Depending on the deformation of the distribution functions these steady states can have toroidal current densities either peaked on the magnetic axis or hollow. These two kinds of equilibria may be regarded as a bifurcation in connection with symmetry properties of the distribution functions on the magnetic axis.

  12. Correlated Equilibria in Continuous Games: Characterization and Computation

    Science.gov (United States)

    2008-12-22

    Annals of Mathematics Studies, pages 75 – 86. Princeton University Press, Princeton, NJ, 1953. [9] M. Dresher, S. Karlin, and L. S. Shapley. Polynomial...games. In H. W. Kuhn and A. W. Tucker, editors, Contributions to the Theory of Games I, number 24 in Annals of Mathematics Studies, pages 161 – 180...J. Lipton and E. Markakis. Nash equilibria via polynomial equations. In Proceedings of LATIN, 2004. [18] J. F. Nash. Non-cooperative games. Annals of Mathematics , 54

  13. Approximation of stochastic equilibria for dynamic systems with colored noise

    Energy Technology Data Exchange (ETDEWEB)

    Bashkirtseva, Irina [Ural Federal University, Lenina 51, Ekaterinburg, 620083 (Russian Federation)

    2015-03-10

    We consider nonlinear dynamic systems forced by colored noise. Using first approximation systems, we study dynamics of deviations of stochastic solutions from stable deterministic equilibria. Equations for the stationary second moments of deviations of random states are derived. An application of the elaborated theory to Van der Pol system driven by colored noise is given. A dependence of the dispersion on the time correlation of the colored noise is studied.

  14. Generalized Thermodynamics of Phase Equilibria in Scalar Active Matter

    OpenAIRE

    Solon, Alexandre P.; Stenhammar, Joakim; Cates, Michael E.; Kafri, Yariv; Tailleur, Julien

    2016-01-01

    Motility-induced phase separation (MIPS) arises generically in fluids of self-propelled particles when interactions lead to a kinetic slowdown at high density. Starting from a continuum description of diffusive scalar active matter, we give a general prescription for phase equilibria that amounts, at a hydrodynamics scale, to extremalizing a generalized free energy. We illustrate our approach on two well known models: self-propelled particles interacting either through a density-dependent pro...

  15. Generalized statistical model for multicomponent adsorption equilibria on zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Rota, R.; Gamba, G.; Paludetto, R.; Carra, S.; Morbidelli, M. (Dipartimento di Chimica Fisica Applicata, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (IT))

    1988-05-01

    The statistical thermodynamic approach to multicomponent adsorption equilibria on zeolites has been extended to nonideal systems, through the correction of cross coefficients characterizing the interaction between unlike molecules. Estimation of the model parameters requires experimental binary equilibrium data. Comparisons with the classical model based on adsorbed solution theory are reported for three nonideal ternary systems. The two approaches provide comparable results in the simulation of binary and ternary adsorption equilibrium data at constant temperature and pressure.

  16. Liquid equilibria in the Fe-Ni-Mn system

    Energy Technology Data Exchange (ETDEWEB)

    Schuermann, E. [Technische Univ. Clausthal, Clausthal-Zellerfeld (Germany). Inst. fuer Eisenhuettenkunde und Giessereiwesen; Djurdjevic, M.; Nedeljkovic, L. [Belgrade Univ. (Yugoslavia). Faculty of Technology and Metallurgy

    1997-12-01

    New literature results on the liquid equilibria in the three edge binary systems make necessary a reconsideration and correction of liquidus surfaces of the {gamma} and {delta} solid solutions hitherto outlined in the literature. Therefore, with respect to the critically reinterpreted edge binary systems, the shape of the stable liquidus surface of the {gamma} and {delta} solid solutions has been newly outlined. (orig.) 7 refs.

  17. Relative Equilibria in the Spherical, Finite Density Three-Body Problem

    Science.gov (United States)

    Scheeres, D. J.

    2016-10-01

    The relative equilibria for the spherical, finite density three-body problem are identified. Specifically, there are 28 distinct relative equilibria in this problem which include the classical five relative equilibria for the point-mass three-body problem. None of the identified relative equilibria exist or are stable over all values of angular momentum. The stability and bifurcation pathways of these relative equilibria are mapped out as the angular momentum of the system is increased. This is done under the assumption that they have equal and constant densities and that the entire system rotates about its maximum moment of inertia. The transition to finite density greatly increases the number of relative equilibria in the three-body problem and ensures that minimum energy configurations exist for all values of angular momentum.

  18. On the complexity of Nash dynamics and Sink Equilibria

    CERN Document Server

    Mirrokni, Vahab

    2009-01-01

    Studying Nash dynamics is an important approach for analyzing the outcome of games with repeated selfish behavior of self-interested agents. Sink equilibria has been introduced by Goemans, Mirrokni, and Vetta for studying social cost on Nash dynamics over pure strategies in games. However, they do not address the complexity of sink equilibria in these games. Recently, Fabrikant and Papadimitriou initiated the study of the complexity of Nash dynamics in two classes of games. In order to completely understand the complexity of Nash dynamics in a variety of games, we study the following three questions for various games: (i) given a state in game, can we verify if this state is in a sink equilibrium or not? (ii) given an instance of a game, can we verify if there exists any sink equilibrium other than pure Nash equilibria? and (iii) given an instance of a game, can we verify if there exists a pure Nash equilibrium (i.e, a sink equilibrium with one state)? In this paper, we almost answer all of the above question...

  19. Nash equilibria in multi-agent motor interactions.

    Directory of Open Access Journals (Sweden)

    Daniel A Braun

    2009-08-01

    Full Text Available Social interactions in classic cognitive games like the ultimatum game or the prisoner's dilemma typically lead to Nash equilibria when multiple competitive decision makers with perfect knowledge select optimal strategies. However, in evolutionary game theory it has been shown that Nash equilibria can also arise as attractors in dynamical systems that can describe, for example, the population dynamics of microorganisms. Similar to such evolutionary dynamics, we find that Nash equilibria arise naturally in motor interactions in which players vie for control and try to minimize effort. When confronted with sensorimotor interaction tasks that correspond to the classical prisoner's dilemma and the rope-pulling game, two-player motor interactions led predominantly to Nash solutions. In contrast, when a single player took both roles, playing the sensorimotor game bimanually, cooperative solutions were found. Our methodology opens up a new avenue for the study of human motor interactions within a game theoretic framework, suggesting that the coupling of motor systems can lead to game theoretic solutions.

  20. Solution influence on biomolecular equilibria - Nucleic acid base associations

    Science.gov (United States)

    Pohorille, A.; Pratt, L. R.; Burt, S. K.; Macelroy, R. D.

    1984-01-01

    Various attempts to construct an understanding of the influence of solution environment on biomolecular equilibria at the molecular level using computer simulation are discussed. First, the application of the formal statistical thermodynamic program for investigating biomolecular equilibria in solution is presented, addressing modeling and conceptual simplications such as perturbative methods, long-range interaction approximations, surface thermodynamics, and hydration shell. Then, Monte Carlo calculations on the associations of nucleic acid bases in both polar and nonpolar solvents such as water and carbon tetrachloride are carried out. The solvent contribution to the enthalpy of base association is positive (destabilizing) in both polar and nonpolar solvents while negative enthalpies for stacked complexes are obtained only when the solute-solute in vacuo energy is added to the total energy. The release upon association of solvent molecules from the first hydration layer around a solute to the bulk is accompanied by an increase in solute-solvent energy and decrease in solvent-solvent energy. The techniques presented are expectd to displace less molecular and more heuristic modeling of biomolecular equilibria in solution.

  1. Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.

    Science.gov (United States)

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas; Wierzchowski, Scott; Walsh, Matthew R; Koh, Carolyn A; Sloan, E Dendy; Wu, David T; Sum, Amadeu K

    2010-05-06

    Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.

  2. Acid-Base Chemistry of White Wine: Analytical Characterisation and Chemical Modelling

    OpenAIRE

    Enrico Prenesti; Silvia Berto; Simona Toso; Pier Giuseppe Daniele

    2012-01-01

    A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of car...

  3. Modeling the Thermodynamic and Transport Properties of Decahydronaphthalene/Propane Mixtures: Phase Equilibria, Density, and Viscosity

    Science.gov (United States)

    2011-01-01

    Modeling the Thermodynamic and Transport Properties of Decahydronaphthalene/Propane Mixtures: Phase Equilibria , Density, and Viscosity Nathaniel...Decahydronaphthalene/Propane Mixtures: Phase Equilibria , Density, And Viscosity 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18 Keywords: phase equilibria ; modified Sanchez-Lacombe equation of state

  4. Stability and attractive basins of multiple equilibria in delayed two-neuron networks

    Institute of Scientific and Technical Information of China (English)

    Huang Yu-Jiao; Zhang Hua-Guang; Wang Zhan-Shan

    2012-01-01

    Multiple stability for two-dimensional delayed recurrent neural networks with piecewise linear activation functions of 2r (r ≥ 1) corner points is studied.Sufficient conditions are established for checking the existence of (2r + 1)2 equilibria in delayed recurrent neural networks.Under these conditions,(r + 1)2 equilibria are locally exponentially stable,and (2r + 1)2 - (r + 1)2 - r2 equilibria are unstable.Attractive basins of stable equilibria are estimated,which are larger than invariant sets derived by decomposing state space.One example is provided to illustrate the effectiveness of our results.

  5. Modeling the Thermodynamics of Mixed Organic-Inorganic Aerosols to Predict Water Activities and Phase Equilibria

    Science.gov (United States)

    Zuend, A.; Marcolli, C.; Luo, B.; Peter, T.

    2008-12-01

    Tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behavior. While the thermodynamics of aqueous inorganic systems at atmospheric temperatures are well established, little is known about the physicochemistry of mixed organic-inorganic particles. Salting-out and salting-in effects result from organic-inorganic interactions and are used to improve industrial separation processes. In the atmosphere, they may influence the aerosol phases. Liquid-liquid phase separations into a mainly polar (aqueous) and a less polar organic phase may considerably influence the gas/particle partitioning of semi-volatile substances compared to a single phase estimation. Moreover, the phases present in the aerosol define the reaction medium for heterogeneous and multiphase chemistry occurring in aerosol particles. A correct description of these phases is needed when gas- or cloud-phase reaction schemes are adapted to aerosols. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems. This model allows to compute vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semiempirical middle

  6. Determination of phase equilibria in confined systems by open pore cell Monte Carlo method.

    Science.gov (United States)

    Miyahara, Minoru T; Tanaka, Hideki

    2013-02-28

    We present a modification of the molecular dynamics simulation method with a unit pore cell with imaginary gas phase [M. Miyahara, T. Yoshioka, and M. Okazaki, J. Chem. Phys. 106, 8124 (1997)] designed for determination of phase equilibria in nanopores. This new method is based on a Monte Carlo technique and it combines the pore cell, opened to the imaginary gas phase (open pore cell), with a gas cell to measure the equilibrium chemical potential of the confined system. The most striking feature of our new method is that the confined system is steadily led to a thermodynamically stable state by forming concave menisci in the open pore cell. This feature of the open pore cell makes it possible to obtain the equilibrium chemical potential with only a single simulation run, unlike existing simulation methods, which need a number of additional runs. We apply the method to evaluate the equilibrium chemical potentials of confined nitrogen in carbon slit pores and silica cylindrical pores at 77 K, and show that the results are in good agreement with those obtained by two conventional thermodynamic integration methods. Moreover, we also show that the proposed method can be particularly useful for determining vapor-liquid and vapor-solid coexistence curves and the triple point of the confined system.

  7. A chemical system that mimics decoding operations.

    Science.gov (United States)

    Giansante, Carlo; Ceroni, Paola; Venturi, Margherita; Sakamoto, Junji; Schlüter, A Dieter

    2009-02-23

    The chemical information stored in equilibrium mixtures of molecular species is larger than the sum of information carried by the individual molecules. Protonation equilibria in dilute dichloromethane solution of a shape-persistent macrocycle bearing two 2,2'-bipyridine units and two Coumarin 2 moieties (see figure) can be exploited to mimic decoding operations.

  8. Phase equilibria in the In–Sb–Bi system at 300 ºC

    Directory of Open Access Journals (Sweden)

    DUSKO MINIC

    2006-07-01

    Full Text Available Binary thermodynamic data, successfully used for phase diagram calculations of the binary systems In–Sb, Bi–Sb and In–Bi, were used fort the prediction of phase equilibria in the ternary system In–Sb–Bi at 300 ºC. The predicted equilibria were compared with the results of SEM–EDX analysis.

  9. Looking for multiple equilibria when geography matters : German city growth and the WWII shock

    NARCIS (Netherlands)

    Bosker, Maarten; Brakman, Steven; Garretsen, Harry; Schramm, Marc

    2007-01-01

    Based on the methodology of Davis and Weinstein, we look for multiple equilibria in German city growth. Bytaking the bombing of Germany during WWII as an example of a large, temporary shock, we analyze whether German city growth is characterized by multiple equilibria. In doing so, we allow for spat

  10. On Pure and (approximate) Strong Equilibria of Facility Location Games

    DEFF Research Database (Denmark)

    Hansen, Thomas Dueholm; Telelis, Orestis A.

    2008-01-01

    We study social cost losses in Facility Location games, where n selfish agents install facilities over a network and connect to them, so as to forward their local demand (expressed by a non-negative weight per agent). Agents using the same facility share fairly its installation cost, but every...... networks we prove upper and lower bounds on PoS, while an O(ln n) upper bound implied by previous work is tight for non-metric networks. We also prove a constant upper bound for the SPoA of metric networks when strong equilibria exist. For the weighted game on general networks we prove existence of e...

  11. Anomeric and tautomeric equilibria in D-2-glucosamine Schiff bases

    Science.gov (United States)

    Kołodziej, B.; Grech, E.; Schilf, W.; Kamieński, B.; Makowski, M.; Rozwadowski, Z.; Dziembowska, T.

    2007-11-01

    The structure of some glucosamine Schiff bases has been studied by means of ab initio RHF and DFT calculation and CP/MAS 13C and 15N NMR measurements. The anomeric and tautomeric equilibria in a DMSO solution have been studied by 1H, 13C and 15N NMR spectroscopy. The anomeric composition of D-2-glucosamine Schiff bases in the solid state and in DMSO solution has been shown to depends on the tautomeric form of Schiff bases and electronic properties of substituents on the aromatic ring.

  12. Cryptographically Blinded Games: Leveraging Players' Limitations for Equilibria and Profit

    DEFF Research Database (Denmark)

    Hubacek, Pavel; Park, Sunoo

    2014-01-01

    In this work we apply methods from cryptography to enable mutually distrusting players to implement broad classes of mediated equilibria of strategic games without trusted mediation. Our implementation uses a pre-play 'cheap talk' phase, consisting of non- binding communication between players pr...... prior to play in the original game. In the cheap talk phase, the players run a secure multi-party computation protocol to sample from an equilibrium of a "cryptographically blinded" version of the game, in which actions are encrypted...

  13. Nas-Walras equilibria of a large economy.

    Science.gov (United States)

    Minelli, E; Polemarchakis, H M

    2000-05-09

    Individuals exchange contracts for the delivery of commodities in competitive markets and, simultaneously, act strategically; actions affect utilities across individuals directly or through the payoffs of contracts. This encompasses economies with asymmetric information. Nash-Walras equilibria exist for large economies, even if utility functions are not quasi-concave and choice sets are not convex, which is the case in standard settings; the separation of the purchase from the sale of contracts and the pooling of the deliveries on contracts guarantee that the markets for commodities clear.

  14. Solitonlike solutions of magnetostatic equilibria: Plane-symmetric case

    CERN Document Server

    Yoshino, Hirotaka

    2008-01-01

    We present the plane-symmetric solitonlike solutions of magnetostatic equilibria by solving the nonlinear Grad-Shafranov (GS) equation numerically. The solutions have solitonlike and periodic structures in the $x$ and $y$ directions, respectively, and $z$ is the direction of plane symmetry. Although such solutions are unstable against the numerical iteration, we give the procedure to realize the sufficient convergence. Our result provides the definite answer for the existence of the solitonlike solutions that was questioned in recent years. The method developed in this paper will make it possible to study the axisymmetric solitonlike solutions of the nonlinear GS equation, which could model astrophysical jets with knotty structures.

  15. Liquid-liquid equilibria for ternary polymer mixtures

    Science.gov (United States)

    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.

  16. Application of conformal solution theory to gas-gas equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Tan, P.Y.; Luks, K.D.; Kozak, J.J.

    1971-08-01

    The conformal solution theory (CST) is applied to the problem of gas-gas immiscibility. It is found that the occurrence of this phenomena can be predicted in the system He-Xe; in particular, the calculated critical locus is in satisfactory agreement with the experimental data of de Swaan Arons and Diepen, provided a suitable reference is chosen. Furthermore, using CST as a guide, it was found that criteria could be developed, related to Temkin's criteria, which permit the prediction and classification of the 3 types of gas-gas equilibria known to occur in mixtures of nonpolar molecules. (10 refs.)

  17. On multicomponent adsorption equilibria of xylene mixtures on zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Paludetto, R.; Storti, G.; Gamba, G.; Carra, S.; Morbidelli, M.

    1987-11-01

    Adsorption equilibria of two ternary systems involving m-xylene, p-xylene, and either toluene or isopropylbenzene on zeolite K-Y have been studied. Due to nonideal behavior of the adsorbed phase, m- and p-xylene selectivity is strongly dependent upon composition. In particular, it is found that the addition of a third component can either enhance or depress such selectivity values. Ternary experimental data are well predicted by the developed equilibrium model, whose parameters can be estimated based only on experimental data relative to pure and binary mixtures. Finally, the role of these nonidealities in the equilibrium behavior on the dynamics of adsorption separation columns is discussed.

  18. Conformational equilibria and intrinsic affinities define integrin activation.

    Science.gov (United States)

    Li, Jing; Su, Yang; Xia, Wei; Qin, Yan; Humphries, Martin J; Vestweber, Dietmar; Cabañas, Carlos; Lu, Chafen; Springer, Timothy A

    2017-03-01

    We show that the three conformational states of integrin α5β1 have discrete free energies and define activation by measuring intrinsic affinities for ligand of each state and the equilibria linking them. The 5,000-fold higher affinity of the extended-open state than the bent-closed and extended-closed states demonstrates profound regulation of affinity. Free energy requirements for activation are defined with protein fragments and intact α5β1 On the surface of K562 cells, α5β1 is 99.8% bent-closed. Stabilization of the bent conformation by integrin transmembrane and cytoplasmic domains must be overcome by cellular energy input to stabilize extension. Following extension, headpiece opening is energetically favored. N-glycans and leg domains in each subunit that connect the ligand-binding head to the membrane repel or crowd one another and regulate conformational equilibria in favor of headpiece opening. The results suggest new principles for regulating signaling in the large class of receptors built from extracellular domains in tandem with single-span transmembrane domains.

  19. Phase equilibria in polydisperse nonadditive hard-sphere systems.

    Science.gov (United States)

    Paricaud, Patrice

    2008-08-01

    Colloidal particles naturally exhibit a size polydispersity that can greatly influence their phase behavior in solution. Nonadditive hard-sphere (NAHS) mixtures are simple and well-suited model systems to represent phase transitions in colloid systems. Here, we propose an analytical equation of state (EOS) for NAHS fluid mixtures, which can be straightforwardly applied to polydisperse systems. For positive values of the nonadditivity parameter Delta the model gives accurate predictions of the simulated fluid-fluid coexistence curves and compressibility factors. NPT Monte Carlo simulations of the mixing properties of the NAHS symmetric binary mixture with Delta>0 are reported. It is shown that the enthalpy of mixing is largely positive and overcomes the positive entropy of mixing when the pressure is increased, leading to a fluid-fluid phase transition with a lower critical solution pressure. Phase equilibria in polydisperse systems are predicted with the model by using the density moment formalism [P. Sollich, Adv. Chem. Phys. 116, 265 (2001)]. We present predictions of the cloud and shadow curves for polydisperse NAHS systems composed of monodisperse spheres and polydisperse colloid particles. A fixed nonadditivity parameter Delta > 0 is assumed between the monodisperse and polydisperse spheres, and a Schulz distribution is used to represent the size polydispersity. Polydispersity is found to increase the extent of the immiscibility region. The predicted cloud and shadow curves depend dramatically on the upper cutoff diameter sigmac of the Schulz distribution, and three-phase equilibria can occur for large values of sigmac.

  20. Phase equilibria in model surfactants forming Langmuir monolayers.

    Science.gov (United States)

    Ramírez, E; Santana, A; Cruz, A; López, G E

    2007-12-14

    The study of Langmuir monolayers has generated the attention of researchers because of their unique properties and their not well understood phase equilibrium. These monolayers exhibit interesting phase diagrams where the unusual liquid-liquid equilibrium can be observed for a single component monolayer. Monte Carlo computer simulations in the virtual Gibbs ensemble were used to obtain the phase diagram of Langmuir monolayers. The liquid-vapor and liquid-liquid phase equilibria were considered by constructing the Cailletet-Mathias phase diagrams. By using the Ising model and the rectilinear approximations the identification of the critical properties for both equilibria was determined. These critical parameters were calculated as a function of the strength of the interaction between the surfactant molecules and the aqueous subphase. As a result, we have identified the coexistence between a liquid expanded state (LES)-vapor and the liquid condensed state-LES, in agreement with experimental and theoretical evidence in the literature. We obtained a clear separation of phases and a strong dependence on the strength of the solvent used. Namely, as the interaction between the solvent and the head of the surfactant increases, the critical properties also increase. Equilibrium states were characterized by computing thermodynamic quantities as a function of temperature and solvent strength.

  1. Stability of Hall equilibria in neutron star crusts

    CERN Document Server

    Marchant, Pablo; Valdivia, Juan Alejandro; Hoyos, Jaime H

    2014-01-01

    In the solid crusts of neutron stars, the advection of the magnetic field by the current-carrying electrons, an effect known as Hall drift, should play a very important role as the ions remain essentially fixed (as long as the solid does not break). Although Hall drift preserves the magnetic field energy, it has been argued that it may drive a turbulent cascade to scales at which Ohmic dissipation becomes effective, allowing a much faster decay in objects with very strong fields. On the other hand, it has been found that there are "Hall equilibria", i.e., field configurations that are unaffected by Hall drift. Here, we address the crucial question of the stability of these equilibria through axially symmetric (2D) numerical simulations of Hall drift and Ohmic diffusion, with the simplifying assumption of uniform electron density and conductivity. We demonstrate the 2D-stability of a purely poloidal equilibrium, for which Ohmic dissipation makes the field evolve towards an attractor state through adjacent stab...

  2. Thermodynamic modeling of phase equilibria in magmatic systems: Progress and future directions (Robert Wilhelm Bunsen Medal Lecture)

    Science.gov (United States)

    Ghiorso, Mark S.

    2010-05-01

    Research over the past thirty years has established that thermodynamic modeling is extremely useful for illuminating the production, transport, chemical differentiation, and eruptive potential of magmas. The key to successful modeling of this kind is the formulation of an internally consistent thermodynamic database that includes properties of liquid and solid endmember components, and - most importantly - a cohesive set of models that describe the thermodynamics of mixing of both liquid (± fluid) and mineral solid solutions. Despite numerous successes in the application of thermodynamic modeling to liquid-solid phase equilibria under crustal and upper mantle pressure-temperature conditions, there are critical and relevant areas of application where the models fail to generate useful results. Importantly, these applications include phase equilibria in hornblende- and biotite-bearing magmas and the melting relations of silicate mantle-like bulk compositions at pressures above 3 GPa. Research is underway to address many of these modeling deficiencies. Approaches include (1) the development of new solution models for igneous pyroxenes and garnets, including majoritic garnet components, (2) the reformulation of thermodynamic models for liquid solution properties in order to implement non-deal associative solutions and a more robust equation of state that allows extrapolation of liquid density and free energy to high-pressures, (3) the creation of an experimental program to generate data necessary for the calibration of solution theory for igneous hornblendes and mica, and (4) the use of molecular dynamics simulations to facilitate the creation of a data base of liquid thermochemical properties at high-pressures that will serve as a basis for the calibration of phase equilibria models under Earth-like lower mantle conditions. All of these approaches give hope that in the future it will be possible to compute melting and melt-rock reaction over a much broader range of

  3. Goldilocks and the three inorganic equilibria: how Earth's chemistry and life coevolve to be nearly in tune.

    Science.gov (United States)

    Rickaby, R E M

    2015-03-13

    Life and the chemical environment are united in an inescapable feedback cycle. The periodic table of the elements essential for life has transformed over Earth's history, but, as today, evolved in tune with the elements available in abundance in the environment. The most revolutionary time in life's history was the advent and proliferation of oxygenic photosynthesis which forced the environment towards a greater degree of oxidation. Consideration of three inorganic chemical equilibria throughout this gradual oxygenation prescribes a phased release of trace metals to the environment, which appear to have coevolved with employment of these new chemicals by life. Evolution towards complexity was chemically constrained, and changes in availability of notably Fe, Zn and Cu paced the systematic development of complex organisms. Evolving life repeatedly catalysed its own chemical challenges via the unwitting release of new and initially toxic chemicals. Ultimately, the harnessing of these allowed life to advance to greater complexity, though the mechanism responsible for translating novel chemistry to heritable use remains elusive. Whether a chemical acts as a poison or a nutrient lies both in the dose and in its environmental history.

  4. Social Interactions under Incomplete Information: Games, Equilibria, and Expectations

    Science.gov (United States)

    Yang, Chao

    My dissertation research investigates interactions of agents' behaviors through social networks when some information is not shared publicly, focusing on solutions to a series of challenging problems in empirical research, including heterogeneous expectations and multiple equilibria. The first chapter, "Social Interactions under Incomplete Information with Heterogeneous Expectations", extends the current literature in social interactions by devising econometric models and estimation tools with private information in not only the idiosyncratic shocks but also some exogenous covariates. For example, when analyzing peer effects in class performances, it was previously assumed that all control variables, including individual IQ and SAT scores, are known to the whole class, which is unrealistic. This chapter allows such exogenous variables to be private information and models agents' behaviors as outcomes of a Bayesian Nash Equilibrium in an incomplete information game. The distribution of equilibrium outcomes can be described by the equilibrium conditional expectations, which is unique when the parameters are within a reasonable range according to the contraction mapping theorem in function spaces. The equilibrium conditional expectations are heterogeneous in both exogenous characteristics and the private information, which makes estimation in this model more demanding than in previous ones. This problem is solved in a computationally efficient way by combining the quadrature method and the nested fixed point maximum likelihood estimation. In Monte Carlo experiments, if some exogenous characteristics are private information and the model is estimated under the mis-specified hypothesis that they are known to the public, estimates will be biased. Applying this model to municipal public spending in North Carolina, significant negative correlations between contiguous municipalities are found, showing free-riding effects. The Second chapter "A Tobit Model with Social

  5. Numbers of Relative Equilibria in the Planar Four-Vortex Problem: Some Special Cases

    Science.gov (United States)

    Tsai, Ya-Lun

    2016-11-01

    Three planar four-vortex problems are considered in this paper. In the (3+1) -vortex problem, we study the relative equilibria of the four point vortices when one vortex has zero vorticity and the other three with nonzero vorticities form an equilateral triangle. In the (1+3) -vortex problem, we study the limiting cases of the relative equilibria when one of the four point vortices has fixed nonzero vorticity and other vorticities approach zero. The third problem is the case of vanishing total vorticity. All problems involve two real vorticity parameters. We consider all meaningful pairs of parameters and find there can only be 4, 8, 9 or 10 relative equilibria in the (3+1) -vortex problem, and 8, 10, 12 or 14 relative equilibria in the (1+3) -vortex problem. For the case of zero total vorticity, there are 0, 1 or 2 collinear relative equilibria and 2, 3 or 4 strictly planar relative equilibria. We completely classify parameters according to the different numbers of relative equilibria. For all cases, we reduce them to the problems of counting common zeros in an open region of {{{R}}}2 for polynomial systems with two equations, two variables, and two parameters. We propose a method to count zeros for such type of systems for all parameters in an open region of R2 through symbolic computations. Therefore, all of our results are proved rigorously.

  6. Phase Equilibria and Transition in Mixtures of a Homopolymer and a Block Copolymer. II.

    Science.gov (United States)

    1983-01-26

    AD-A124 929 PHASE EQUILIBRIA AND TRANSITION IN MIXTURES OF A In- NOMOPOLYMER AND’A BLOCK..(U) CINCINNATI UNJY ON DEPT OF MATERIALS SCIENCE AND...REPORT NO. 7 v2 L Phase Equilibria and Transition in Mixtures of a Homopolymer and a Block Copolymer II. The Phase Diagram by R. J. Roe and W. C. Zin...homopolymers as in our systems. The phase equilibria at temperatures above the "pseudo-triple point" BCD can be interpreted in terms of the free energy of

  7. Study of ionic equilibria of indotricarbocyanines in aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Dyadyusha, G.G.; Ishchenko, A.A.; Derevyanko, N.A.; Tolmachev, A.I.

    1982-05-01

    Study of the equilibria in nonpolar solvents is very complicated by the poor solubility of the salt-like dyes. Indotricarbocyanines I and II were found to be fairly soluble in aromatic hydrocarbons for solving these problems by means of electronic spectra. In the present work, their absorption spectra were studied in benzene, toluene, and m-xylene (the absorption spectra were measured on the SF-8 spectrophotometer). It was shown that the dyes studied in these solvents have spectral bands of unusual form of polymethine dyes. At the long wave edge of the spectra of indotricarbocyanines, a distinct band appears, whose intensity is very dependent on the nature of the anion. In the case of perchlorate I, it has a lower intensity, and in the case of iodide II, the intensity is higher.

  8. Analytical solutions for Tokamak equilibria with reversed toroidal current

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Caroline G. L.; Roberto, M.; Braga, F. L. [Departamento de Fisica, Instituto Tecnologico de Aeronautica, Sao Jose dos Campos, Sao Paulo 12228-900 (Brazil); Caldas, I. L. [Instituto de Fisica, Universidade de Sao Paulo, 05315-970 Sao Paulo, SP (Brazil)

    2011-08-15

    In tokamaks, an advanced plasma confinement regime has been investigated with a central hollow electric current with negative density which gives rise to non-nested magnetic surfaces. We present analytical solutions for the magnetohydrodynamic equilibria of this regime in terms of non-orthogonal toroidal polar coordinates. These solutions are obtained for large aspect ratio tokamaks and they are valid for any kind of reversed hollow current density profiles. The zero order solution of the poloidal magnetic flux function describes nested toroidal magnetic surfaces with a magnetic axis displaced due to the toroidal geometry. The first order correction introduces a poloidal field asymmetry and, consequently, magnetic islands arise around the zero order surface with null poloidal magnetic flux gradient. An analytic expression for the magnetic island width is deduced in terms of the equilibrium parameters. We give examples of the equilibrium plasma profiles and islands obtained for a class of current density profile.

  9. Complex Networks as Nash Equilibria of Navigation Games

    CERN Document Server

    Gulyás, András; Kőrösi, Attila; Rétvári, Gábor; Krioukov, Dmitri

    2014-01-01

    The common sense suggests that networks are not random mazes of purposeless connections, but that these connections are organised so that networks can perform their functions. One common function that many networks perform is targeted transport or navigation. Here with the help of game theory we show that minimalistic networks designed to maximise the navigation efficiency at minimal cost share basic structural properties of real networks. These idealistic networks are Nash equilibria of a network construction game whose purpose is to find an optimal trade-off between the network cost and navigability. They are navigation skeletons that we show are present in the Internet, {\\it E. coli} metabolic network, English word network, US airport network, and the Hungarian road network. The knowledge of these skeletons allows one to identify the minimal number of edges by altering which one can dramatically improve or paralyse the navigation in the network.

  10. Stability of compressible reduced magnetohydrodynamic equilibria - analogy with magnetorotational instability

    CERN Document Server

    Morrison, Philip J; Tronko, Natalia

    2013-01-01

    Stability analyses for equilibria of the compressible reduced magnetohydrodynamics (CRMHD) model are carried out by means of the Energy-Casimir (EC) method. Stability results are compared with those obtained for ideal magnetohydrodynamics (MHD) from the classical {\\delta}W criterion. An identification of the terms in the second variation of the free energy functional for CRMHD with those of {\\delta}W is made: two destabilizing effects present for CRMHD turn out to correspond to the kink and interchange instabilities in usual MHD, while the stabilizing roles of field line bending and compressibility are also identified in the reduced model. Also, using the EC method, stability conditions in the presence of toroidal flow are obtained. A formal analogy between CRMHD and a reduced incompressible model for magnetized rotating disks, due to Julien and Knobloch [EAS Pub. Series, 21, 81 (2006)], is discovered. In light of this analogy, energy stability analysis shows that the condition for magnetorotational instabili...

  11. Axisymmetric equilibria of a gravitating plasma with incompressible flows

    CERN Document Server

    Throumoulopoulos, G N

    2001-01-01

    It is found that the ideal magnetohydrodynamic equilibrium of an axisymmetric gravitating magnetically confined plasma with incompressible flows is governed by a second-order elliptic differential equation for the poloidal magnetic flux function containing five flux functions coupled with a Poisson equation for the gravitation potential, and an algebraic relation for the pressure. This set of equations is amenable to analytic solutions. As an application, the magnetic-dipole static axisymmetric equilibria with vanishing poloidal plasma currents derived recently by Krasheninnikov, Catto, and Hazeltine [Phys. Rev. Lett. {\\bf 82}, 2689 (1999)] are extended to plasmas with finite poloidal currents, subject to gravitating forces from a massive body (a star or black hole) and inertial forces due to incompressible sheared flows. Explicit solutions are obtained in two regimes: (a) in the low-energy regime $\\beta_0\\approx \\gamma_0\\approx \\delta_0 \\approx\\epsilon_0\\ll 1$, where $\\beta_0$, $\\gamma_0$, $\\delta_0$, and $\\...

  12. Boric acid equilibria in near-critical and supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Wofford, W.T.; Gloyna, E.F.; Johnston, K.P. [Univ. of Texas, Austin, TX (United States)

    1998-05-01

    Greater knowledge of acid-base equilibria is crucial to understanding the chemistry of hydrothermal processes including oxidation of organics, corrosion, catalysis, hydrolysis reactions, crystal growth and formation, precipitation of metal complexes and steam power cycles. The pH values of aqueous solutions of boric acid and KOH were measured with the optical indicator 2-naphthol at temperatures from 300 to 380 C. The equilibrium constant K{sub b}{sup {minus}1} for the reaction B(OH){sub 3} + OH{sup {minus}} = B(OH){sub 4}{sup {minus}} was determined from the pH measurements and correlated with a modified Born model. The titration curve for the addition of HCl to sodium borate exhibits strong acid-strong base behavior even at 350 C and 24.1 MPa. At these conditions, aqueous solutions of sodium borate buffer the pH at 9.6 {+-} 0.25.

  13. Multiple equilibria of cross-equatorial Inertial jets

    Institute of Scientific and Technical Information of China (English)

    CHAO JiPing; LIU Fei

    2007-01-01

    Based on the developed Anderson and Moore's theory about cross-equatorial inertial jets and a nonlinear equivalence shallow water model, new universal functions are determined by the characters of the vortical large-scale air flow (atmosphere) or ocean current (ocean) related to the jet, then the potential vorticity and energy conservation equations along the streamline in the cross-equatorial inertial jets can be obtained. Because the governing equations are nonlinear, some limited multiple equilibria of cross-equatorial inertial jets may exist. According to the character of large-scale air flow or ocean current outside the jets, the existent criterion for multiple eqnilibria in cross-equatorial inertial jets is discussed, and two examples for multiple equilibia of nonlinear governing equations are given.

  14. Multiple equilibria of cross-equatorial Inertial jets

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Based on the developed Anderson and Moore’s theory about cross-equatorial inertial jets and a nonlinear equivalence shallow water model, new universal functions are determined by the characters of the vortical large-scale air flow (atmosphere) or ocean current (ocean) related to the jet, then the potential vorticity and energy conservation equations along the streamline in the cross-equatorial in-ertial jets can be obtained. Because the governing equations are nonlinear, some limited multiple equi-libria of cross-equatorial inertial jets may exist. According to the character of large-scale air flow or ocean current outside the jets, the existent criterion for multiple eqnilibria in cross-equatorial inertial jets is discussed, and two examples for multiple equilibia of nonlinear governing equations are given.

  15. Phase equilibria in the Ni-Co-Ga alloy system

    Energy Technology Data Exchange (ETDEWEB)

    Ducher, R. [Department of Materials Science, Graduate School of Engineering, Tohoku University, 6-6-02 Aoba-yama, Sendai 980-8579 (Japan); Kainuma, R. [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Sendai 980-8577 (Japan)], E-mail: kainuma@tagen.tohoku.ac.jp; Ishida, K. [Department of Materials Science, Graduate School of Engineering, Tohoku University, 6-6-02 Aoba-yama, Sendai 980-8579 (Japan)

    2008-10-20

    Phase equilibria among the {alpha} (A1), {alpha}' (L1{sub 2}), {beta} (B2), {delta} (Ni{sub 5}Ga{sub 3}) and {epsilon} (Ni{sub 13}Ga{sub 9}) phases at elevated temperatures and the existing composition region of the martensite phase at room temperature in the Ni-Co side of the Ni-Co-Ga system were examined by electron probe microanalysis (EPMA) using diffusion triples which were fabricated by two-step diffusion coupling. It was confirmed that single-phase regions of the {alpha}, {alpha}' and {beta} phases at 700 and 1000 deg. C exist in a wide composition range parallel to Ni-Co section and that the existing region of the martensite phase at room temperature is also located over a wide range in the {beta} phase along the {beta} + {alpha} (or {alpha}') two-phase region.

  16. Navigable networks as Nash equilibria of navigation games

    Science.gov (United States)

    Gulyás, András; Bíró, József J.; Kőrösi, Attila; Rétvári, Gábor; Krioukov, Dmitri

    2015-07-01

    Common sense suggests that networks are not random mazes of purposeless connections, but that these connections are organized so that networks can perform their functions well. One function common to many networks is targeted transport or navigation. Here, using game theory, we show that minimalistic networks designed to maximize the navigation efficiency at minimal cost share basic structural properties with real networks. These idealistic networks are Nash equilibria of a network construction game whose purpose is to find an optimal trade-off between the network cost and navigability. We show that these skeletons are present in the Internet, metabolic, English word, US airport, Hungarian road networks, and in a structural network of the human brain. The knowledge of these skeletons allows one to identify the minimal number of edges, by altering which one can efficiently improve or paralyse navigation in the network.

  17. Tautomeric equilibria in solutions of 1-methyl-2-phenacylbenzimidazoles

    Science.gov (United States)

    Skotnicka, Agnieszka; Czeleń, Przemysław; Gawinecki, Ryszard

    2017-04-01

    Until now the susceptibility of 1-methyl-2-phenacylbenzimidazoles to the proton transfer has not been carefully examined. There only have been selective trials to recognize tautomeric equilibrium of substituted compounds. Unfortunately, conclusions of these studies are often conflicting. Therefore, the aim of this work was to analyze the influence of the factors affecting the tautomeric processes of substituted 1-methyl-2-phenacylbenzimidazoles in solutions of chloroform by spectroscopic technique of 1H and 13C NMR. Complex equilibria may only take place when molecules of tautomeric species contain multiple basic and/or acidic centres. Analysis of NMR spectra show unequivocally that 1-methyl-2-phenacylbenzimidazoles (ketimine tautomeric form) are in equilibrium with (Z)-2-(1-methyl-1H-benzo[d]imidazol-2yl)-1-phenylethenols (enolimine).

  18. Settling the Complexity of Computing Two-Player Nash Equilibria

    CERN Document Server

    Chen, Xi; Teng, Shang-Hua

    2007-01-01

    We settle a long-standing open question in algorithmic game theory. We prove that Bimatrix, the problem of finding a Nash equilibrium in a two-player game, is complete for the complexity class PPAD Polynomial Parity Argument, Directed version) introduced by Papadimitriou in 1991. This is the first of a series of results concerning the complexity of Nash equilibria. In particular, we prove the following theorems: Bimatrix does not have a fully polynomial-time approximation scheme unless every problem in PPAD is solvable in polynomial time. The smoothed complexity of the classic Lemke-Howson algorithm and, in fact, of any algorithm for Bimatrix is not polynomial unless every problem in PPAD is solvable in randomized polynomial time. Our results demonstrate that, even in the simplest form of non-cooperative games, equilibrium computation and approximation are polynomial-time equivalent to fixed point computation. Our results also have two broad complexity implications in mathematical economics and operations res...

  19. Extended Group Contribution Model for Polyfunctional Phase Equilibria

    DEFF Research Database (Denmark)

    Abildskov, Jens

    -liquid equilibria from data on binary mixtures, composed of structurally simple molecules with a single functional group. More complex is the situation with mixtures composed of structurally more complicated molecules or molecules with more than one functional group. The UNIFAC method is extended to handle...... polyfunctional group situations, based on additional information on molecular structure. The extension involves the addition of second-order correction terms to the existing equation. In this way the current first-order formulation is retained. The second-order concept is developed for mixture properties based....... In chapter 4 parameters are estimated for the first-order UNIFAC model, based on which parameters are estimated for one of the second-order models described in chapter 3. The parameter estimation is based on measured binary data on around 4000 systems, covering 11 C-, H- and O-containing functional groups...

  20. Self-consistent equilibria in cylindrical reversed-field pinch

    Energy Technology Data Exchange (ETDEWEB)

    Lo Surdo, C. [ENEA, Centro Ricerche Frascati, Rome (Italy). Dip. di Energia; Paccagnella, R.; Guo, S. [CNR, Padua (Italy). Istituto Gas Ionizzati

    1995-07-01

    The object of this work is to study the self-consistent magnetofluidstatic equilibria of a 2-region (plasma + gas) reversed-field pinch (RFP) in cylindrical approximation (namely, with vanishing inverse aspect ratio). Differently from what happens in a tokamak, in a RFP a significant part of the plasma current is driven by a dynamo electric field (DEF), in its turn mainly due to plasma turbulence. So, it is worked out a reasonable mathematical model of the above self-consistent equilibria under the following main points it has been: (a) to the lowest order, and according to a standard ansatz, the turbulent DEF say {epsilon}{sup t}, is expressed as a homogeneous transform of the magnetic field B of degree 1, {epsilon}{sup t}=({alpha}) (B), with {alpha}{identical_to}a given 2-nd rank tensor, homogeneous of degree 0 in B and generally depending on the plasma state; (b) {epsilon}{sup t} does not explicitly appear in the plasma energy balance, as it were produced by a Maxwell demon able of extract the corresponding Joule power from the plasma. In particular, it is showed that, if both {alpha} and the resistivity tensor {eta} are isotropic and constant, the magnetic field is force-free with abnormality equal to {alpha}{eta}{sub 0}/{eta}, in the limit of vanishing {beta}; that is, the well-known J.B. Taylor`result is recovered, in this particular conditions, starting from ideas quite different from the usual ones (minimization of total magnetic energy under constrained total elicity). Finally, the general problem is solved numerically under circular (besides cylindrical) symmetry, for simplicity neglecting the existence of gas region (i.e., assuming the plasma in direct contact with the external wall).

  1. Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.

    Science.gov (United States)

    Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K

    2012-12-01

    The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model.

  2. Direct MD simulation of liquid-solid phase equilibria for three-component plasma

    CERN Document Server

    Hughto, J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K

    2012-01-01

    The neutron rich isotope 22Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of 22Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semi analytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two component carbon and oxygen systems. This suggests that small amounts of 22Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Gamma) in our MD simulations compared to the semi analytic ...

  3. The freedom to choose neutron star magnetic field equilibria: Table 1.

    Science.gov (United States)

    Glampedakis, Kostas; Lasky, Paul D.

    2016-12-01

    Our ability to interpret and glean useful information from the large body of observations of strongly magnetized neutron stars rests largely on our theoretical understanding of magnetic field equilibria. We answer the following question: is one free to arbitrarily prescribe magnetic equilibria such that fluid degrees of freedom can balance the equilibrium equations? We examine this question for various models for neutron star matter; from the simplest single-fluid barotrope to more realistic non-barotropic multifluid models with superfluid/superconducting components, muons and entropy. We do this for both axi- and non-axisymmetric equilibria, and in Newtonian gravity and general relativity. We show that, in axisymmetry, the most realistic model allows complete freedom in choosing a magnetic field equilibrium whereas non-axisymmetric equilibria are never completely arbitrary.

  4. Modeling of Vapor-Liquid-Solid Equilibria in Acidic Aqueous Solutions

    DEFF Research Database (Denmark)

    Christensen, Søren Gregers; Thomsen, Kaj

    2003-01-01

    The phase behavior (vapor - liquid equilibria (VLE) and solid - liquid equilibria (SLE)) and thermal properties of aqueous solutions of ions like (K+, Na+, NH4+, Ca2+, Cl-) in the presence of phosphoric acid (H3PO4, H2PO4-, HPO42- ) and nitric acid (HNO3, NO3-) are described by means of the Exten......The phase behavior (vapor - liquid equilibria (VLE) and solid - liquid equilibria (SLE)) and thermal properties of aqueous solutions of ions like (K+, Na+, NH4+, Ca2+, Cl-) in the presence of phosphoric acid (H3PO4, H2PO4-, HPO42- ) and nitric acid (HNO3, NO3-) are described by means...

  5. Exact nonlinear analytic Vlasov-Maxwell tangential equilibria with arbitrary density and temperature profiles

    CERN Document Server

    Mottez, F

    2003-01-01

    The tangential layers are characterized by a bulk plasma velocity and a magnetic field that are perpendicular to the gradient direction. They have been extensively described in the frame of the Magneto-Hydro-Dynamic (MHD) theory. But the MHD theory does not look inside the transition region if the transition has a size of a few ion gyroradii. A series of kinetic tangential equilibria, valid for a collisionless plasma is presented. These equilibria are exact analytical solutions of the Maxwell-Vlasov equations. The particle distribution functions are sums of an infinite number of elementary functions parametrized by a vector potential. Examples of equilibria relevant to space plasmas are shown. A model for the deep and sharp density depletions observed in the auroral zone of the Earth is proposed. Tangential equilibria are also relevant for the study of planetary environments and of remote astrophysical plasmas.

  6. Calculation of Binary Adsorption Equilibria: Hydrocarbons and Carbon Dioxide on Activated Carbon

    DEFF Research Database (Denmark)

    Marcussen, Lis; Krøll, A.

    1999-01-01

    Binary adsorption equilibria are calculated by means of a mathematical model for multicomponent mixtures combined with the SPD (Spreading Pressure Dependent) model for calculation of activity coefficients in the adsorbed phase. The model has been applied successfully for the adsorption of binary ...... mixtures of hydrocarbons and carbon dioxide on activated carbons. The model parameters have been determined, and the model has proven to be suited for prediction of adsorption equilibria in the investigated systems....

  7. Solid Phase Equilibria in the Pi-Ga-As and Pt-Ga-Sb Systems

    Science.gov (United States)

    1988-07-22

    OFFICE OF NAVAL RESEARCH Research Contract N00014-87-K-0014 R&T Code 413E026---01 AD-A 198 654 TECHNICAL REPORT No. 9 SOLID PHASE EQUILIBRIA IN THE...Classtcation) UNCLASSLFIED: Tech.Rept.#9 SOLID PHASE EQUILIBRIA IN T11: Pt-Ga-As AND Pt-Ga-Sb SYST’IS 12 PERSONAL AuTiOR(S) C.T. Tsai and R.S. Williats 13a TYPE

  8. Calculation of Phase Equilibria Based on the Levenberg-Marquardt Method

    Institute of Scientific and Technical Information of China (English)

    Ruijie ZHANG; Lei LI; Zhongwei CHEN; Zhi HE; Wanqi JIE

    2005-01-01

    The Levenberg-Marquardt method, the best algorithm to obtain the least-square solution of nonlinear equations, is applied to calculate the stable phase equilibria. It can get the best combination between robustness and speed of the calculations. Its application to ternary Al-Si-Mg system is executed in detail. The calculated phase equilibria agree well with the experimental results. Furthermore, the Levenberg-Marquardt method is not sensitive to the initial values.

  9. Thermodynamic characteristics of protolytic equilibria in aqueous solutions of glycyl peptides

    Science.gov (United States)

    Gridchin, S. N.

    2016-11-01

    Protolytic equilibria in aqueous solutions of glycyl-DL-serine, glycyl-DL-threonine, and glycyl-DL-valine are investigated by means of potentiometry and calorimetry. Dissociation constants and heat effects of the above dipeptides are determined. Standard thermodynamic characteristics (p K°, Δdis G°, Δdis H°, Δdis S°) of the investigated equilibria are calculated. The obtained results are compared to corresponding data on relative compounds.

  10. Durability of cement-based materials: modeling of the influence of physical and chemical equilibria on the microstructure and the residual mechanical properties; Durabilite des materiaux cimentaires: modelisation de l'influence des equilibres physico-chimiques sur la microstructure et les proprietes mecaniques residuelles

    Energy Technology Data Exchange (ETDEWEB)

    Guillon, E

    2004-09-15

    A large part of mechanical and durability characteristics of cement-based materials comes from the performances of the hydrated cement, cohesive matrix surrounding the granular skeleton. Experimental studies, in situ or in laboratory, associated to models, have notably enhanced knowledge on the cement material and led to adapted formulations to specific applications or particularly aggressive environments. Nevertheless, these models, developed for precise cases, do not permit to specifically conclude for other experimental conclusions. To extend its applicability domain, we propose a new evolutive approach, based on reactive transport expressed at the microstructure scale of the cement. In a general point of view, the evolution of the solid compounds of the cement matrix, by dissolutions or precipitations, during chemical aggressions can be related to the pore solution evolution, and this one relied to the ionic exchanges with the external environment. By the utilization of a geochemical code associated to a thermodynamical database and coupled to a 3D transport model, this approach authorizes the study of all aggressive solution. The approach has been validated by the comparison of experimental observations to simulated degradations for three different environments (pure water, mineralized water, seawater) and on three different materials (CEM I Portland cement with 0.25, 0.4 and 0.5 water-to cement ratio). The microstructural approach permits also to have access to mechanical properties evolutions. During chemical aggressions, the cement matrix evolution is traduced in a microstructure evolution. This one is represented from 3D images similarly to the models developed at NIST (National Institute of Standards and Technology). A new finite-element model, validated on previous tests or models, evaluates the stiffness of the cement paste, using as a mesh these microstructures. Our approach identifies and quantifies the major influence of porosity and its spatial

  11. Comparison of electron drift waves in numerical and analytical tokamak equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Rafiq, T; Anderson, J; Persson, M [Department of Electromagnetics and Euratom/VR Association, Chalmers University of Technology, S-41296 Goeteborg (Sweden)

    2004-01-01

    In this paper, we demonstrate the importance of the details of the equilibria on the stability of electron drift waves. A comparison of electrostatic electron drift waves in numerical and analytical tokamak equilibria is presented in fully three-dimensional circular and non-circular tokamaks. The numerical equilibria are obtained using the variational moments equilibrium code and the analytical equilibria used is the generalized s-alpha model. An eigenvalue equation for the model is derived using the ballooning mode formalism and solved numerically using a standard shooting technique. The stability and the localization of the electron drift wave is found to be strongly dependent on the local shear of the magnetic field. Large values of the local shear are found to be stabilizing. A disagreement in the results is found between analytical and numerical equilibria at aspect ratios of typical tokamaks, suggesting that the latter approach should be used in the transport calculations. The effects of the local shaping of the magnetic surfaces are complicated and can be both stabilizing and destabilizing, depending on the details of the equilibria.

  12. Dynamical Behaviors of Multiple Equilibria in Competitive Neural Networks With Discontinuous Nonmonotonic Piecewise Linear Activation Functions.

    Science.gov (United States)

    Nie, Xiaobing; Zheng, Wei Xing

    2016-03-01

    This paper addresses the problem of coexistence and dynamical behaviors of multiple equilibria for competitive neural networks. First, a general class of discontinuous nonmonotonic piecewise linear activation functions is introduced for competitive neural networks. Then based on the fixed point theorem and theory of strict diagonal dominance matrix, it is shown that under some conditions, such n -neuron competitive neural networks can have 5(n) equilibria, among which 3(n) equilibria are locally stable and the others are unstable. More importantly, it is revealed that the neural networks with the discontinuous activation functions introduced in this paper can have both more total equilibria and locally stable equilibria than the ones with other activation functions, such as the continuous Mexican-hat-type activation function and discontinuous two-level activation function. Furthermore, the 3(n) locally stable equilibria given in this paper are located in not only saturated regions, but also unsaturated regions, which is different from the existing results on multistability of neural networks with multiple level activation functions. A simulation example is provided to illustrate and validate the theoretical findings.

  13. Liquid-liquid equilibria for ternary polymer mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Suk Yung [Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University, Seoul 133-791 (Korea, Republic of); Bae, Young Chan, E-mail: ycbae@hanyang.ac.kr [Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2011-01-24

    Graphical abstract: We developed a molecular thermodynamic model for multicomponent systems and discribed the phase equilibrium for ternary polymer mixtures by using the model parameters obtained from the binary systems. Research highlights: {yields} Model parameters were obtained from the binary systems. {yields} The obtained parameters were directly used to predict the ternary data. {yields} The undetermined parameters were used to correlate the ternary data. {yields} The proposed model agreed well with the experimental data. - Abstract: 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.

  14. Phase equilibria in the Ni-Fe-Ga alloy system

    Energy Technology Data Exchange (ETDEWEB)

    Ducher, R. [Department of Materials Science, Graduate School of Engineering, Tohoku University, 6-6-02 Aoba-yama, Sendai 980-8579 (Japan); Kainuma, R. [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Sendai 980-8577 (Japan)], E-mail: kainuma@tagen.tohoku.ac.jp; Ishida, K. [Department of Materials Science, Graduate School of Engineering, Tohoku University, 6-6-02 Aoba-yama, Sendai 980-8579 (Japan)

    2008-09-08

    The phase equilibria, A2/B2 and B2/L2{sub 1} (or D0{sub 3}) order-disorder transitions and martensitic transformation on the Ni-Fe side of the Ni-Fe-Ga system were examined by electron probe microanalysis (EPMA) and differential scanning calorimetric (DSC) measurement. The equilibrium compositions of interrelations mainly among the {alpha} (A2), {beta} (B2), {beta}' (L2{sub 1} or D0{sub 3}), {gamma} (A1) and {gamma}' (L1{sub 2}) phases were determined using diffusion triples which were fabricated by two-step diffusion coupling. It was confirmed that a bcc single-phase region composed of {alpha}, {beta} and {beta}' at 850-1000 deg. C exists in a wide composition range and that the critical temperature of the B2/L2{sub 1} order-disorder transformation in the Fe{sub 3}Ga-Ni{sub 3}Ga pseudo-binary section gradually increases with increasing Ni content. The existing composition region of the martensite phase at room temperature was also determined by the diffusion triple method.

  15. Bifurcations and selection of equilibria in a simple cosymmetric model of filtrational convection.

    Science.gov (United States)

    Govorukhin, V. N.; Yudovich, V. I.

    1999-06-01

    A three-dimensional set of ordinary differential equations that constitutes a simple abstract model of Darcy convection is investigated. The model reproduces a number of effects that are typical for dynamic systems with nontrivial cosymmetry. Nontrivial cosymmetry can give rise to a continuous family of equilibria where, in this case, the equilibrium stability spectrum varies along the family. The family of equilibria and its stability are examined analytically, and special bifurcations that occur in the system are investigated. It is shown that discrete and continual symmetries, called "flash symmetries," can be present in the system for certain parameter values. Computer experiments on the selection of equilibria in the symmetric and cosymmetric cases have been carried out. They showed that, for initial points that are far enough from a cycle of equilibria, the neighborhood of a single equilibrium is established in the case of cosymmetry, but all the equilibria are equivalent in the case of symmetry. The authors hope that these results, as well as the formulation of the problems and the approach to their solution, will serve as a sample in the investigation of more complex systems in mathematical physics. (c) 1999 American Institute of Physics.

  16. Study of phase equilibria in the CO(NH2)2-KH2PO4-K2HPO4-H2O system at 25°C using an optimized method of cross sections

    Science.gov (United States)

    Noskov, M. N.; Mazunin, S. A.

    2015-06-01

    Phase equilibria are studied in ternary contouring systems and in the CO(NH2)2-KH2PO4-K2HPO4-H2O quaternary system at 25°C using an optimized method of cross sections. It is found that an incongruent chemical compound forms between the components of a system with the composition 2KH2PO4 · K2HPO4. The compositions of eutonic and peritonic solutions and the solid phases saturating them are determined. The lines of monovariant equilibria and the crystallization surface of potassium dihydrogen phosphate are studied. The location of the eutonic and peritonic solutions and monovariant equilibrium lines near the plane are shown.

  17. Phase Equilibria and Magnetic Phases in the Ce-Fe-Co-B System

    Directory of Open Access Journals (Sweden)

    Tian Wang

    2016-12-01

    Full Text Available Ce-Fe-Co-B is a promising system for permanent magnets. A high-throughput screening method combining diffusion couples, key alloys, Scanning Electron Microscope/Wavelength Dispersive X-ray Spectroscope (SEM/WDS, and Magnetic Force Microscope (MFM is used in this research to understand the phase equilibria and to explore promising magnetic phases in this system. Three magnetic phases were detected and their homogeneity ranges were determined at 900 °C, which were presented by the formulae: Ce2Fe14−xCoxB (0 ≤ x ≤ 4.76, CeCo4−xFexB (0 ≤ x ≤ 3.18, and Ce3Co11−x FexB4 (0 ≤ x ≤ 6.66. The phase relations among the magnetic phases in this system have been studied. Ce2(Fe, Co14B appears to have stronger magnetization than Ce(Co, Fe4B and Ce3(Co, Fe11B4 from MFM analysis when comparing the magnetic interactions of selected key alloys. Also, a non-magnetic CeCo12−xFexB6 (0 ≤ x ≤ 8.74 phase was detected in this system. A boron-rich solid solution with Ce13FexCoyB45 (32 ≤ x ≤ 39, 3 ≤ y ≤ 10 chemical composition was also observed. However, the crystal structure of this phase could not be found in the literature. Moreover, ternary solid solutions ε1 (Ce2Fe17−xCox (0 ≤ x ≤ 12.35 and ε2 (Ce2Co17−xFex (0 ≤ x ≤ 3.57 were found to form between Ce2Fe17 and Ce2Co17 in the Ce-Fe-Co ternary system at 900 °C.

  18. PHASE EQUILIBRIA INVESTIGATION OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 9. CALCULATION OF THERMODYNAMIC QUANTITIES FROM PHASE DIAGRAMS

    Science.gov (United States)

    The thermodynamic fundamentals relating phase equilibria in binary and ternary systems to the thermodynamic properties of the phases are reviewed and...system demonstrate the application of the equations for extracting thermodynamic data from phase diagrams and also for the prediction of phase equilibria .

  19. Development and testing of a new apparatus for the measurement of high-pressure low-temperature phase equilibria

    DEFF Research Database (Denmark)

    Fonseca, José M.S.; von Solms, Nicolas

    2012-01-01

    A new apparatus for the study of high-pressure phase equilibria at low temperatures using an analytical method was designed, assembled and tested. The apparatus was specially developed for the study of multi-phase equilibria in systems containing hydrocarbons, water and hydrate inhibitors...

  20. Lagrangian relative equilibria for a gyrostat in the three-body problem: bifurcations and stability

    Energy Technology Data Exchange (ETDEWEB)

    Guirao, Juan L G; Vera, Juan A, E-mail: juan.garcia@upct.e, E-mail: juanantonio.vera@upct.e [Departamento de Matematica Aplicada y EstadIstica, Universidad Politecnica de Cartagena, Hospital de Marina, 30203 Cartagena, Region de Murcia (Spain)

    2010-05-14

    In this paper we consider the non-canonical Hamiltonian dynamics of a gyrostat in the frame of the three-body problem. Using geometric/mechanic methods we study the approximate dynamics of the truncated Legendre series representation of the potential of an arbitrary order. Working in the reduced problem, we study the existence of relative equilibria that we refer to as Lagrange type following the analogy with the standard techniques. We provide necessary and sufficient conditions for the linear stability of Lagrangian relative equilibria if the gyrostat morphology form is close to a sphere. Thus, we generalize the classical results on equilibria of the three-body problem and many results on them obtained by the classic approach for the case of rigid bodies.

  1. A note on relative equilibria in a rotating shallow water layer

    KAUST Repository

    Ait Abderrahmane, Hamid

    2013-05-08

    Relative equilibria of two and three satellite vortices in a rotating shallow water layer have been recorded via particle image velocimetry (PIV) and their autorotation speed was estimated. This study shows that these equilibria retain the fundamental characteristics of Kelvin\\'s equilibria, and could be adequately described by the classical idealized point vortex theory. The same conclusion can also be inferred using the experimental dataset of Bergmann et al. (J. Fluid Mech., vol. 679, 2011, pp. 415-431; J. Fluid Mech., vol. 691, 2012, pp. 605-606) if the assigned field\\'s contribution to pattern rotation is included. © 2013 Cambridge University Press.

  2. Non-existence of Normal Tokamak Equilibria with Negative Central Current

    Energy Technology Data Exchange (ETDEWEB)

    G.W. Hammett; S.C. Jardin; B.C. Stratton

    2003-02-18

    Recent tokamak experiments employing off-axis, non-inductive current drive have found that a large central current hole can be produced. The current density is measured to be approximately zero in this region, though in principle there was sufficient current-drive power for the central current density to have gone significantly negative. Recent papers have used a large aspect-ratio expansion to show that normal MHD equilibria (with axisymmetric nested flux surfaces, non-singular fields, and monotonic peaked pressure profiles) can not exist with negative central current. We extend that proof here to arbitrary aspect ratio, using a variant of the virial theorem to derive a relatively simple integral constraint on the equilibrium. However, this constraint does not, by itself, exclude equilibria with non-nested flux surfaces, or equilibria with singular fields and/or hollow pressure profiles that may be spontaneously generated.

  3. A dynamical view of different solution paradigms in two-person symmetric games: Nash vs co-action equilibria

    CERN Document Server

    Sasidevan, V

    2015-01-01

    The study of games and their equilibria is central to developing insights for understanding many socio-economic phenomena. Here we present a dynamical systems view of the equilibria of two-person, payoff-symmetric games. In particular, using this perspective, we discuss the differences between two solution concepts for such games - namely, those of Nash equilibrium and co-action equilibrium. For the Nash equilibrium, we show that the dynamical view can provide an equilibrium refinement, selecting one equilibrium among several possibilities, thereby solving the issue of multiple equilibria that appear in some games. We illustrate in detail this dynamical perspective by considering three well known 2-person games namely the Prisoner's Dilemma, game of Chicken and the Stag-Hunt. We find that in all of these cases, co-action equilibria tends to correspond to `nicer' strategies than those corresponding to Nash equilibria.

  4. Exotic equilibria of Harary graphs and a new minimum degree lower bound for synchronization

    KAUST Repository

    Canale, Eduardo A.

    2015-02-01

    © 2015 AIP Publishing LLC. This work is concerned with stability of equilibria in the homogeneous (equal frequencies) Kuramoto model of weakly coupled oscillators. In 2012 [R. Taylor, J. Phys. A: Math. Theor. 45, 1-15 (2012)], a sufficient condition for almost global synchronization was found in terms of the minimum degree-order ratio of the graph. In this work, a new lower bound for this ratio is given. The improvement is achieved by a concrete infinite sequence of regular graphs. Besides, non standard unstable equilibria of the graphs studied in Wiley et al. [Chaos 16, 015103 (2006)] are shown to exist as conjectured in that work.

  5. Existence of three-dimensional ideal-magnetohydrodynamic equilibria with current sheets

    Energy Technology Data Exchange (ETDEWEB)

    Loizu, J. [Max-Planck-Institut für Plasmaphysik, D-17491 Greifswald (Germany); Princeton Plasma Physics Laboratory, PO Box 451, Princeton, New Jersey 08543 (United States); Hudson, S. R.; Bhattacharjee, A.; Lazerson, S. [Princeton Plasma Physics Laboratory, PO Box 451, Princeton, New Jersey 08543 (United States); Helander, P. [Max-Planck-Institut für Plasmaphysik, D-17491 Greifswald (Germany)

    2015-09-15

    We consider the linear and nonlinear ideal plasma response to a boundary perturbation in a screw pinch. We demonstrate that three-dimensional, ideal-MHD equilibria with continuously nested flux-surfaces and with discontinuous rotational-transform across the resonant rational-surfaces are well defined and can be computed both perturbatively and using fully nonlinear equilibrium calculations. This rescues the possibility of constructing MHD equilibria with current sheets and continuous, smooth pressure profiles. The results predict that, even if the plasma acts as a perfectly conducting fluid, a resonant magnetic perturbation can penetrate all the way into the center of a tokamak without being shielded at the resonant surface.

  6. A comparison of Nash equilibria analysis and agent-based modelling for power markets

    Energy Technology Data Exchange (ETDEWEB)

    Krause, T.; Andersson, G. [EEH Power Systems Laboratory, ETH Zuerich, (Switzerland); Beck, E.V.; Cherkaoui, R.; Germond, A. [LRE Laboratoire de Reseaux Electriques, EPFL-STI-LRE, Lausanne (Switzerland); Ernst, D. [Universitede Liege, Institut Montefiore Batiment B28, Liege (Belgium)

    2006-11-15

    In this paper we compare Nash equilibria analysis and agent-based modelling for assessing the market dynamics of network-constrained pool markets. Power suppliers submit their bids to the market place in order to maximize their payoffs, where we apply reinforcement learning as a behavioral agent model. The market clearing mechanism is based on the locational marginal pricing scheme. Simulations are carried out on a benchmark power system. We show how the evolution of the agent-based approach relates to the existence of a unique Nash equilibrium or multiple equilibria in the system. Additionally, the parameter sensitivity of the results is discussed. (author)

  7. Exotic equilibria of Harary graphs and a new minimum degree lower bound for synchronization

    Energy Technology Data Exchange (ETDEWEB)

    Canale, Eduardo A., E-mail: ecanale@pol.una.py [Facultad Politénica, UNA, Asunción (Paraguay); Monzón, Pablo, E-mail: monzon@fing.edu.uy [School of Engineering, UDELAR, Montevideo 11300 (Uruguay)

    2015-02-15

    This work is concerned with stability of equilibria in the homogeneous (equal frequencies) Kuramoto model of weakly coupled oscillators. In 2012 [R. Taylor, J. Phys. A: Math. Theor. 45, 1–15 (2012)], a sufficient condition for almost global synchronization was found in terms of the minimum degree–order ratio of the graph. In this work, a new lower bound for this ratio is given. The improvement is achieved by a concrete infinite sequence of regular graphs. Besides, non standard unstable equilibria of the graphs studied in Wiley et al. [Chaos 16, 015103 (2006)] are shown to exist as conjectured in that work.

  8. Words or Pictures: A Comparison of Written and Pictorial Explanations of Physical and Chemical Equilibria

    Science.gov (United States)

    Akaygun, Sevil; Jones, Loretta L.

    2014-01-01

    The features of a concept or principle an individual chooses to highlight in an explanation or description may be related to the medium of communication used. Different aspects of understanding can be revealed through words and through drawings. This two-part exploratory study examined the differences between explanations of physical and chemical…

  9. Study of improved methods for predicting chemical equilibria. Progress report, January 1, 1990--June 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Lenz, T.G.; Vaughan, J.D.

    1992-06-01

    The objective of our research has been to develop computational methods that have the capability of accurately predicting equilibrium constants of typical organic reactions in gas and liquid solution phases. We have chosen Diels-Alder reactions as prototypic systems for the investigation, chiefly because there are an adequate number of reported equilibrium constants for the candidate reactions in both gas and solution phases, which data provides a suitable basis for tests of the developed computational methods. Our approach has been to calculate the standard enthalpies of formation ({Delta}H{sub f}{sup 0}) at 298.15K and the standard thermodynamic functions (S{sup 0}, Cp{sup 0}, and (H{sup 0}-H{sub 0}{sup 0})/T) for a range of temperatures for reactants and products, and from these properties to calculate standard enthalpies, entropies, Gibbs free energies, and equilibrium constants ({Delta}H{sub T}{sup 0}, {Delta}S{sub T}{sup 0}, and K{sub a}) at various temperatures for the chosen reaction.

  10. Study of improved methods for predicting chemical equilibria. Final report, January 1, 1990--March 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Lenz, T.G.; Vaughan, J.D.

    1993-09-01

    Objective was to develop computational methods for equilibrium constants of Diels-Alder reactions in gas and liquid solution phases. Approach was to calculate standard enthalpies of formation at 298 K and standard thermodynamic functions for a range of temperatures for reactants and products, and then to calculate standard enthalpies, entropies, Gibbs free energies, and equilibrium constants at various temperatures.

  11. Prediction of Pure Component Adsorption Equilibria Using an Adsorption Isotherm Equation Based on Vacancy Solution Theory

    DEFF Research Database (Denmark)

    Marcussen, Lis; Aasberg-Petersen, K.; Krøll, Annette Elisabeth

    2000-01-01

    An adsorption isotherm equation for nonideal pure component adsorption based on vacancy solution theory and the Non-Random-Two-Liquid (NRTL) equation is found to be useful for predicting pure component adsorption equilibria at a variety of conditions. The isotherm equation is evaluated successfully...... adsorption systems, spreading pressure and isosteric heat of adsorption are also calculated....

  12. Analysis of statistical thermodynamic model for binary protein adsorption equilibria on cation exchange adsorbent

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xiaopeng; SU Xueli; SUN Yan

    2007-01-01

    A study of nonlinear competitive adsorption equilibria of proteins is of fundamental importance in understanding the behavior of preparative chromatographic separation.This work describes the nonlinear binary protein adsorption equilibria on ion exchangers by the statistical thermodynamic (ST) model.The single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin(BSA)on SP Sepharose FF were determined by batch adsorption experiments in 0.05 mol/L sodium acetate buffer at three pH values(4.5,5.0 and 5.5)and three NaCl concentrations(0.05,0.10 and 0.15 mol/L)at pH 5.0.The ST model was found to depict the effects of pH and ionic strength on the single-component equilibria well,with model parameters depending on the pH and ionic strength.Moreover,the ST model gave acceptable fitting to the binary adsorption data with the fltted singlecomponent model parameters,leading to the estimation of the binary ST model parameter.The effects of pH and ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories.Results demonstrate the availability of the ST model for describing nonlinear competitive protein adsorption equilibria in the presence of two proteins.

  13. Reflexivity, expectations feedback and almost self-fulfilling equilibria: economic theory, empirical evidence and laboratory experiments

    NARCIS (Netherlands)

    Hommes, C.

    2013-01-01

    We discuss recent work on bounded rationality and learning in relation to Soros’ principle of reflexivity and stress the empirical importance of non-rational, almost selffulfilling equilibria in positive feedback systems. As an empirical example, we discuss a behavioral asset pricing model with hete

  14. Ternary liquid–liquid equilibria for mixtures of toluene + n-heptane + an ionic liquid

    NARCIS (Netherlands)

    Meindersma, G. Wytze; Podt, Anita J.G.; Haan, de André B.

    2006-01-01

    This research has been focused on a study of sulfolane and four ionic liquids as solvents in liquid–liquid extraction. Liquid–liquid equilibria data were obtained for mixtures of (sulfolane or 4-methyl-N-butylpyridinium tetrafluoroborate ([mebupy]BF4) or 1-ethyl-3-methylimidazolium ethylsulfate ([em

  15. Vapor-Liquid-Solid Equilibria of Sulfur Dioxide in Aqueous Electrolyte Solutions

    DEFF Research Database (Denmark)

    Pereda, Selva; Thomsen, Kaj; Rasmussen, Peter

    2000-01-01

    The Extended UNIQUAC model for electrolyte systems, combined with the Soave-Redlich-Kwong equation of state is used to describe the complex vapor-liquid-solid equilibria of sulfur dioxide in electrolyte solutions. Model parameters based on 1500 experimental data points are presented. The paramete...

  16. Dynamics of parabolic equations via the finite element method I. Continuity of the set of equilibria

    Science.gov (United States)

    Figueroa-López, R. N.; Lozada-Cruz, G.

    2016-11-01

    In this paper we study the dynamics of parabolic semilinear differential equations with homogeneous Dirichlet boundary conditions via the discretization of finite element method. We provide an appropriate functional setting to treat this problem and, as a first step, we show the continuity of the set of equilibria and of its linear unstable manifolds.

  17. A numerical algorithm to find all feedback Nash equilibria in scalar affine quadratic differential games

    NARCIS (Netherlands)

    Engwerda, Jacob

    2015-01-01

    This note deals with solving scalar coupled algebraic Riccati equations. These equations arise in finding linear feedback Nash equilibria of the scalar N-player affine quadratic differential game. A numerical procedure is provided to compute all the stabilizing solutions. The main idea is to reformu

  18. Transport and Phase Equilibria Properties for Steam Flooding of Heavy Oils

    Energy Technology Data Exchange (ETDEWEB)

    Gabitto, Jorge; Barrufet, Maria

    2001-12-18

    The objectives of this research included experimental determination and rigorous modeling and computation of phase equilibria, volumetric, and transport properties of hydrocarbon/CO2/water mixtures at pressures and temperatures typical of steam injection processes for thermal recovery of heavy oils.

  19. The Representation of Highly Non-Ideal Phase Equilibria Using Computer Graphics.

    Science.gov (United States)

    Charos, Georgios N.; And Others

    1986-01-01

    Previous work focused on use of computer graphics in teaching thermodynamic phase equilibria for classes I and II. Extends this work to include the considerably more non-ideal phase behavior shown by classes III, IV, and V. Student and instructor response has been overwhelmingly positive about the approach. (JN)

  20. Vapor-Liquid Equilibria Using the Gibbs Energy and the Common Tangent Plane Criterion

    Science.gov (United States)

    Olaya, Maria del Mar; Reyes-Labarta, Juan A.; Serrano, Maria Dolores; Marcilla, Antonio

    2010-01-01

    Phase thermodynamics is often perceived as a difficult subject with which many students never become fully comfortable. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based…

  1. Phase equilibria in the Ag-Au-In system at 500°C

    Science.gov (United States)

    Ptashkina, E. A.; Romanova, A. G.; Pavlenko, A. S.; Kabanova, E. G.; Kuznetsov, V. N.

    2017-02-01

    Phase equilibria in Ag-Au-In system at 500°C are investigated by means of electron microscopy, electron probe microanalysis, and X-ray powder diffraction. The part of the system's isothermal cross section with an indium content of up to 50 at % is constructed.

  2. New investigation of phase equilibria in the system Al-Cu-Si.

    Science.gov (United States)

    Ponweiser, Norbert; Richter, Klaus W

    2012-01-25

    The phase equilibria and invariant reactions in the system Al-Cu-Si were investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and electron probe micro analysis (EPMA). Isothermal phase equilibria were investigated within two isothermal sections. The isothermal section at 500 °C covers the whole ternary composition range and largely confirms the findings of previous phase diagram investigations. The isothermal section at 700 °C describes phase equilibria only in the complex Cu-rich part of the phase diagram. A new ternary compound τ was found in the region between (Al,Cu)-γ(1) and (Cu,Si)-γ and its solubility range was determined. The solubility of Al in κ-CuSi was found to be extremely high at 700 °C. In contrast, no ternary solubility in the β-phase of Cu-Al was found, although this phase is supposed to form a complete solid solution according to previous phase diagram assessments. Two isopleths, at 10 and 40 at.% Si, were investigated by means of DTA and a partial ternary reaction scheme (Scheil diagram) was constructed, based on the current work and the latest findings in the binary systems Al-Cu and Cu-Si. The current study shows that the high temperature equilibria in the Cu-rich corner are still poorly understood and additional studies in this area would be favorable.

  3. Modelling of phase equilibria of glycol ethers mixtures using an association model

    DEFF Research Database (Denmark)

    Garrido, Nuno M.; Folas, Georgios; Kontogeorgis, Georgios

    2008-01-01

    Vapor-liquid and liquid-liquid equilibria of glycol ethers (surfactant) mixtures with hydrocarbons, polar compounds and water are calculated using an association model, the Cubic-Plus-Association Equation of State. Parameters are estimated for several non-ionic surfactants of the polyoxyethylene ...

  4. Simulation of the high-pressure phase equilibria of hydrocarbon-water/brine systems

    DEFF Research Database (Denmark)

    Zuo, You-Xiang; Stenby, Erling Halfdan; Guo, Tian-Min

    1996-01-01

    The major objectives of this work are: (1) extend the modified Patel-Teja (MPT) equation of state proposed for aqueous electrolyte systems (Zuo and Guo, 1991) to describe the liquid-liquid and vapor-liquid-liquid equilibria of hydrocarbon-water/brine systems through introducing an unconventional ...

  5. New investigation of phase equilibria in the system Al–Cu–Si

    Science.gov (United States)

    Ponweiser, Norbert; Richter, Klaus W.

    2012-01-01

    The phase equilibria and invariant reactions in the system Al–Cu–Si were investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and electron probe micro analysis (EPMA). Isothermal phase equilibria were investigated within two isothermal sections. The isothermal section at 500 °C covers the whole ternary composition range and largely confirms the findings of previous phase diagram investigations. The isothermal section at 700 °C describes phase equilibria only in the complex Cu-rich part of the phase diagram. A new ternary compound τ was found in the region between (Al,Cu)-γ1 and (Cu,Si)-γ and its solubility range was determined. The solubility of Al in κ-CuSi was found to be extremely high at 700 °C. In contrast, no ternary solubility in the β-phase of Cu–Al was found, although this phase is supposed to form a complete solid solution according to previous phase diagram assessments. Two isopleths, at 10 and 40 at.% Si, were investigated by means of DTA and a partial ternary reaction scheme (Scheil diagram) was constructed, based on the current work and the latest findings in the binary systems Al–Cu and Cu–Si. The current study shows that the high temperature equilibria in the Cu-rich corner are still poorly understood and additional studies in this area would be favorable. PMID:22287828

  6. Adsorption of Halogenated Hydrocarbons from Gaseous Streams by Amberlite XAD-4 Resin and Activated Carbon: Equilibria

    NARCIS (Netherlands)

    Rexwinkel, G.; Heesink, A.B.M.; Swaaij, van W.P.M.

    1999-01-01

    Single-solute adsorption equilibria have been measured for the adsorption of the gaseous solutes chloroform, chlorobenzene, and 1,1,1-trichloroethane onto Amberlite XAD-4 resin. For 1,1,1-trichloroethane the adsorption equilibrium has also been measured with activated carbon Norit ROW 0.8 SUPRA as a

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

    DEFF Research Database (Denmark)

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

    2004-01-01

    Two algorithms for evaluating liquid-liquid equilibria (LLE) for binary and ternary polymer solutions are presented. The binary algorithm provides the temperature versus concentration cloud-point curve at fixed pressure, whereas the ternary algorithm provides component 1 versus component 2...

  8. The nucleation rate surfaces design over diagram of phase equilibria and their applications for computational chemistry

    Science.gov (United States)

    Anisimov, M. P.

    2016-12-01

    One can find in scientific literature a pretty fresh idea of the nucleation rate surfaces design over the diagrams of phase equilibria. That idea looks like profitable for the nucleation theory development and for various practical applications where predictions of theory have no high enough accuracy for today. The common thermodynamics has no real ability to predict parameters of the first order phase transition. Nucleation experiment can be provided in very local nucleation conditions even the nucleation takes place from the critical line (in two-component case) down to the absolute zero temperature limit and from zero nucleation rates at phase equilibria up to the spinodal conditions. Theory predictions have low reliability as a rule. The computational chemistry has chance to make solution of that problem easier when a set of the used axiomatic statements will adapt enough progressive assumptions [1]. Semiempirical design of the nucleation rate surfaces over diagrams of phase equilibria have a potential ability to provide a reasonable quality information on nucleation rate for each channel of nucleation. Consideration and using of the nucleation rate surface topologies to optimize synthesis of a given phase of the target material can be available when data base on nucleation rates over diagrams of phase equilibria will be created.

  9. High-pressure fluid-phase equilibria: Experimental methods and systems investigated (2000-2004)

    DEFF Research Database (Denmark)

    Dohrn, Ralf; Peper, Stephanie; Fonseca, José

    2010-01-01

    -vapor-liquid equilibria, critical points, the solubility of high-boiling substances in supercritical fluids, the solubility of gases in liquids and the solubility (sorption) of volatile components in polymers are included. For the systems investigated, the reference, the temperature and pressure range of the data...

  10. Synthetic methods in phase equilibria: A new apparatus and error analysis of the method

    DEFF Research Database (Denmark)

    Fonseca, José; von Solms, Nicolas

    2014-01-01

    A new apparatus for the study of high-pressure phase equilibria using a synthetic method is described. The apparatus was especially developed for the study of solubilities of gases in condensed phases, at temperatures ranging from 243 K to 353 K and pressures up to 20 MPa. The quality of the equi...

  11. Control Algorithms Along Relative Equilibria of Underactuated Lagrangian Systems on Lie Groups

    DEFF Research Database (Denmark)

    Nordkvist, Nikolaj; Bullo, F.

    2008-01-01

    We present novel algorithms to control underactuated mechanical systems. For a class of invariant systems on Lie groups, we design iterative small-amplitude control forces to accelerate along, decelerate along, and stabilize relative equilibria. The technical approach is based upon a perturbation...

  12. Transport and phase equilibria of benzene in FAU type zeolites

    Science.gov (United States)

    Saravanan, Chandra

    We have studied lattice models for self-diffusion of benzene in FAU type zeolites, to explore the effect of the thermodynamics of confined fluids on the transport properties of molecules in zeolites. Our model assumes that benzene molecules are located near Na+ ions in supercages, and in 12-ring windows separating adjacent supercages, respectively. The study was performed in three stages. First, to disentangle the effect of a vapor-liquid phase equilibria on diffusion in zeolites, the transport of benzene in Na-Y is modeled in the absence of attractive guest-guest interactions. The loading dependence of diffusion coefficient, Dtheta, at a constant temperature, referred to as a diffusion isotherm, is modeled with site-blocking effects using a mean field theory (MFT) that yields, Dq=16kq a2q, where atheta ≅ 11 A is the mean intercage jump length and 1/ktheta is the mean supercage residence time. A completely analytical expression is derived to calculate ktheta. The MFT is tested using a mean field approximation (MFA) where ktheta and atheta are calculated from kinetic Monte Carlo simulations yielding excellent qualitative agreement. Further calculations are performed to test MFA by calculating "exact" diffusion coefficients from mean square displacement (MSD) calculations also yielding excellent qualitative agreement. Next, by including guest-guest attractive interactions, we have performed lattice grand canonical Monte Carlo simulations of benzene adsorption in Na-X zeolite to determine whether strongly confined benzene molecules exhibit subcritical properties. We observe a phase transition from low to high density of adsorbed benzene, analogous to vapor-liquid equilibrium, at temperatures as high as 300 K and above. By performing thermodynamic integration to construct the coexistence curve, we obtain a critical point for benzene in Na-X at Tc = 370 +/- 20 K, thetac = 0.45 +/- 0.05 fractional coverage. We suggest that careful adsorption experiments should be

  13. On Eulerian equilibria in K-order approximation of the gyrostat in the three-body problem

    Directory of Open Access Journals (Sweden)

    J. A. Vera

    2006-01-01

    the main result of this work, the number of Eulerian equilibria in an approximate dynamics of order k for k≥1 is independent of the order of truncation of the potential if the gyrostat S0 is close to the sphere. The instability of Eulerian equilibria is proven for any approximate dynamics if the gyrostat is close to the sphere. In this way, we generalize the classical results on equilibria of the three-body problem and many of those obtained by other authors using more classic techniques for the case of rigid bodies.

  14. Thermodynamic analysis and phase equilibria investigation in Pb−Zn−Ag system

    Directory of Open Access Journals (Sweden)

    Mitovski Aleksandra M.

    2010-01-01

    Full Text Available Physico-chemical processes that take place during the refining process in the extractive metallurgy of lead, are connected with ternary Pb−Zn−Ag system, which is necessary to study from the theoretical practical and aspects. Such investigation is important from production point of view, because of the phenomena that occur during desilvering of lead which is one of the important stages during lead refining process. Process of lead desilvering binds to ternary system Pb−Zn−Ag, which was the reason for numerous investigations, both from thermodynamic point of view and in terms of testing and determining the phase diagram, bearing in mind the theoretical, and practical importance of knowledge about the processes which are going in investigated system. The paper presents the results of thermodynamic analysis and investigation of phase equilibria of the Pb−Zn−Ag ternary system using the method of thermodynamic predictions and phase diagrams calculations, respectively, and the experimental results of metalography obtained by optical microscopy. Phase diagram of the vertical section Pb−Zn80Ag20 is presented, obtained by CALPHAD calculation methodology, and using PANDAT thermodynamic software, compared to experimental results obtained by DTA analysis. The results show a pronounced break in solubility, which is characteristic for the whole ternary Pb−Zn−Ag system. Also, it can be noticed that the thermodynamic properties follow the behavior of this system, which is expressed through positive deviation of Raoult’s law, pointing to the lack of lead affinity compared to the other two components in the system. The optical microscopy results of the investigated system show the following: - Sample L1 (weight% Pb = 98: the structure of the observed section shows double eutectic (Pbsol+Zn−Agsol which lies in the base of the primary crystals of lead (Pbsol - Samples L2−L5: the structure consists of a dual eutectic (Pbsol+Zn−Agsol and

  15. Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

    Science.gov (United States)

    Filiberto, Justin; Wood, Justin; Loan, Le; Dasgupta, Rajdeep; Shimizu, Nobumichi; Treiman, Allan H.

    2010-01-01

    Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future

  16. Study of monoprotic acid-base equilibria in aqueous micellar solutions of nonionic surfactants using spectrophotometry and chemometrics.

    Science.gov (United States)

    Babamoradi, Hamid; Abdollahi, Hamid

    2015-10-05

    Many studies have shown the distribution of solutes between aqueous phase and micellar pseudo-phase in aqueous micellar solutions. However, spectrophotometric studies of acid-base equilibria in these media do not confirm such distribution because of the collinearity between concentrations of chemical species in the two phases. The collinearity causes the number of detected species to be equal to the number of species in a homogenous solution that automatically misinterpreted as homogeneity of micellar solutions, therefore the collinearity is often neglected. This interpretation is in contradiction to the distribution theory in micellar media that must be avoided. Acid-base equilibrium of an indicator was studied in aqueous micellar solutions of a nonionic surfactant to address the collinearity using UV/Visible spectrophotometry. Simultaneous analysis (matrix augmentation) of the equilibrium and solvation data was applied to eliminate the collinearity from the equilibrium data. A model was then suggested for the equilibrium that was fitted to the augmented data to estimate distribution coefficients of the species between the two phases. Moreover, complete resolution of concentration and spectral profiles of species in each phase was achieved.

  17. PHASE EQUILIBRIA INVESTIGATIONS OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 2. EFFECT OF RHENIUM AND ALUMINUM ADDITIONS ON THE METAL-RICH EQUILIBRIA IN THE TITANIUM-MOLYBDENIUM-CARBON AND TITANIUM-NIOBIUM-CARBON SYSTEMS

    Science.gov (United States)

    The solid state phase equilibria of the metal-rich regions of the Titanium-Molybdenum-Carbon and Titanium-Niobium-Carbon systems with up to 12 At...Rhenium and 10 At.% Aluminum additions, respectively, have been determined on hot pressed, heat treated, and in part arc melted alloys. The phase ... equilibria in the metal-rich regions, with these additions, is practically unchanged over that of the ternary Titanium-Molybdenum-Carbon and Titanium

  18. Phase equilibria of carbon dioxide and methane gas-hydrates predicted with the modified analytical S-L-V equation of state

    Directory of Open Access Journals (Sweden)

    Span Roland

    2012-04-01

    Full Text Available Gas-hydrates (clathrates are non-stoichiometric crystallized solutions of gas molecules in the metastable water lattice. Two or more components are associated without ordinary chemical union but through complete enclosure of gas molecules in a framework of water molecules linked together by hydrogen bonds. The clathrates are important in the following applications: the pipeline blockage in natural gas industry, potential energy source in the form of natural hydrates present in ocean bottom, and the CO2 separation and storage. In this study, we have modified an analytical solid-liquid-vapor equation of state (EoS [A. Yokozeki, Fluid Phase Equil. 222–223 (2004] to improve its ability for modeling the phase equilibria of clathrates. The EoS can predict the formation conditions for CO2- and CH4-hydrates. It will be used as an initial estimate for a more complicated hydrate model based on the fundamental EoSs for fluid phases.

  19. Ternary liquid-liquid equilibria of dimethyl carbonate + 2-propanol + water system at 303.15 and 313.15 K

    Science.gov (United States)

    Ginting, Rizqy Romadhona; Mustain, Asalil; Tetrisyanda, Rizki; Gunardi, Ignatius; Wibawa, Gede

    2015-12-01

    In this work, liquid-liquid equilibria data of dimethyl carbonate (DMC) + 2-propanol + water system were accurately determined at 303.15 and 313.15 K using stirred and jacketed equilibrium cell under atmospheric pressure. The reliabilities of the experimental data were confirmed using Bachman-Brown correlation giving r-squared value of 0.9993 and 0.9983 at 303.15 and 313.15 K, respectively. Experimental data obtained in this work exhibit Treybal's Type I ternary phase behavior. The selectivity and distribution coefficient of DMC increases with addition of DMC concentration in the organic phase. On the other hand, the effect of temperature to phase boundary was found to be not significant. The data were correlated well using the Non-Random Two Liquid (NRTL) and Universal Quasi-Chemical (UNIQUAC) activity coefficient models with root-mean-square deviation of 1.5% and 1.3%, respectively.

  20. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    Science.gov (United States)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  1. Study on Osmotic Pressure and Liquid-Liquid Equilibria for Micelle, Colloid and Microemulsion Systems by Yukawa Potential

    Institute of Scientific and Technical Information of China (English)

    FU,Dong(付东); LU,Jiu-Fang(陆九芳); WU,Wei(吴畏); Li,Yi-Gui(李以圭)

    2004-01-01

    An equation of state (EOS) was established to study the osmotic pressure and liquid-liquid equilibria for micelle,colloid and microemulsion systems. The Carnahan-Starling equation was used for the hard sphere repulsion. The Yukawa potential was used to describe both the attractive dispersion and the double-layer repulsion. By using the established EOS, the osmotic pressures for charged colloid, uncharged micelle, uncharged and weakly charged microemuslion, the phase equilibria for uncharged micelle and charged colloid systems were studied.

  2. Experimental investigation of undesired stable equilibria in pumpkin shape super-pressure balloon designs

    Science.gov (United States)

    Schur, W. W.

    2004-01-01

    Excess in skin material of a pneumatic envelope beyond what is required for minimum enclosure of a gas bubble is a necessary but by no means sufficient condition for the existence of multiple equilibrium configurations for that pneumatic envelope. The very design of structurally efficient super-pressure balloons of the pumpkin shape type requires such excess. Undesired stable equilibria in pumpkin shape balloons have been observed on experimental pumpkin shape balloons. These configurations contain regions with stress levels far higher than those predicted for the cyclically symmetric design configuration under maximum pressurization. Successful designs of pumpkin shape super-pressure balloons do not allow such undesired stable equilibria under full pressurization. This work documents efforts made so far and describes efforts still underway by the National Aeronautics and Space Administration's Balloon Program Office to arrive on guidance on the design of pumpkin shape super-pressure balloons that guarantee full and proper deployment.

  3. GLOBAL ANALYSIS OF SIS EPIDEMIC MODEL WITH A SIMPLE VACCINATION AND MULTIPLE ENDEMIC EQUILIBRIA

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    An SIS epidemic model with a simple vaccination is investigated in this article.The efficiency of vaccine, the disease-related death rate and population dynamics are also considered in this model. The authors find two threshold R0 and Rc (Rc may not exist).There is a unique endemic equilibrium for R0 > 1 or Rc = R0; there are two endemic equilibria for Rc < R0 < 1; and there is no endemic equilibrium for R0 < Rc < 1. When Rc exists, there is a backward bifurcation from the disease-free equilibrium for R0 = 1.They analyze the stability of equilibria and obtain the globally dynamic behaviors of the model. The results acquired in this article show that an accurate estimation of the efficiency of vaccine is necessary to prevent and controll the spread of disease.

  4. Rapidly convergent algorithms for 3-D tandem and stellarator equilibria in the paraxial approximation

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, B.

    1984-04-01

    Tandem and stellarator equilibria at high ..beta.. have proved hard to compute and the relaxation methods of Bauer et al., Chodura and Schluter, Hirshman, Strauss, and Pearlstein et al. have been slow to converge. This paper reports an extension of the low-..beta.. analytic method of Pearlstein, Kaiser, and Newcomb to arbitrary ..beta.. for tandem mirrors which converges in 10 to 20 iterations. Extensions of the method to stellarator equilibria are proposed and are very close to the analytic method of Johnson and Greene - the stellarator expansion. Most of the results of all these calculations can be adequately described by low-..beta.. approximations since the MHD stability limits occur at low ..beta... The tandem mirror, having weak curvature and a long central cell, allows finite Larmor radius effects to eliminate most ballooning modes and offers the possibility of really high average ..beta... This is the interest in developing such three-dimensional numerical algorithms.

  5. Protonation Equilibria of L-Aspartic, Citric and Succinic Acids in Anionic Micellar Media

    Directory of Open Access Journals (Sweden)

    P. Srinivasa Rao

    2009-01-01

    Full Text Available The impact of sodium lauryl sulphate (SLS on the protonation equilibria of L-aspartic acid, citric acid and succinic acid has been studied in various concentrations (0.5-2.5% w/v of SLS solution maintaining an ionic strength of 0.16 mol dm-3 at 303 K. The protonation constants have been calculated with the computer program MINIQUAD75 and the best fit models have been calculated based on statistical parameters. The trend of log values of step-wise protonation constants with mole fraction of the medium has been explained based on electrostatic and non-electrostatic forces operating on the protonation equilibria. The effects of errors on the protonation constants have also been presented.

  6. Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation-reduction equilibria.

    Science.gov (United States)

    Navrotsky, Alexandra; Ma, Chengcheng; Lilova, Kristina; Birkner, Nancy

    2010-10-08

    Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature.

  7. Further work on experimental plagioclase equilibria and the Skaergaard liquidus temperature

    DEFF Research Database (Denmark)

    Thy, Peter; Lesher, Charles E.; Tegner, Christian

    2013-01-01

    Equilibria between plagioclase and ferrobasaltic melt in low-pressure, dry melting experiments can be demonstrated near the liquidus. Further analyses of melting experiments using optimized beam conditions reveals that previous data for understanding the Skaergaard intrusion potentially suffered...... data set provides tighter bounds on experimental plagioclase composition and documents composition-dependent partitioning of Na and Ca between plagioclase and melt. Application of the results to modeling the Skaergaard requires only minor adjustments to the previously proposed liquidus temperatures...

  8. Calculation of phase equilibria of the Ag-In-Sb system by the calphad method

    Directory of Open Access Journals (Sweden)

    Borisov Ivana I.

    2007-01-01

    Full Text Available The ternary Ag-In-Sb system is a promising candidate for use as a Pb-free solder. The results of phase equilibria calculation by the CALPHAD method are presented in this study. The isothermal section at 400°C was calculated using optimized thermodynamic parameters of the constitutive binary systems. Calculated vertical sections from the indium and antimony corners were compared with the DTA results from this study and from the literature.

  9. Equation-of-State Modeling of Phase Equilibria in Petroleum Fluids

    DEFF Research Database (Denmark)

    Jørgensen, Marianne

    1996-01-01

    The Soave-Redlich-Kwong (SRK) equation of state was used to investigate and develop several aspects of the modeling of natural petroleum fluids.A new method was presented for numerical evaluation of PVT experiments. This method was used in the estimation of binary interaction parameters. A comphr...... that exists for mixtures of CO2 and crude oils. Good results are obtained, and a tuning procedure is proposed for improved representation of the three phase equilibria....

  10. Multiple Equilibria in a Single-Column Model of the Tropical Atmosphere

    CERN Document Server

    Sobel, Adam H; Bacmeister, Julio T

    2007-01-01

    A single-column model run under the weak temperature gradient approximation, a parameterization of large-scale dynamics appropriate for the tropical atmosphere, is shown to have multiple stable equilibria. Under conditions permitting persistent deep convection, the model has a statistically steady state in which such convection occurs, as well as an extremely dry state in which convection does not occur. Which state is reached depends on the initial moisture profile.

  11. Control algorithms along relative equilibria of underactuated Lagrangian systems on Lie groups

    DEFF Research Database (Denmark)

    Nordkvist, Nikolaj; Bullo, Francesco

    2007-01-01

    We present novel algorithms to control underactuated mechanical systems. For a class of invariant systems on Lie groups, we design iterative small-amplitude control forces to accelerate along, decelerate along, and stabilize relative equilibria. The technical approach is based upon a perturbation...... analysis and the design of inversion primitives and composition methods. We illustrate the algorithms on an underactuated planar rigid body and on a satellite with two thrusters....

  12. Thermal analysis and prediction of phase equilibria in ternary Pb-Zn-Ag system

    OpenAIRE

    2011-01-01

    Ternary Pb-Zn-Ag system is typical for some physicochemical processes going on in refining phase in the extractive metallurgy of lead. Therefore, investigation of mentioned system is important from both theoretical and practical research of the phenomena occurring during the lead desilverizing process. The results of experimental investigation using differential thermal analysis (DTA) and thermodynamic calculation of phase equilibria in Pb-Zn-Ag system according to CALPHAD method, in th...

  13. Phase equilibria in carbon dioxide expanded solvents: Experiments and molecular simulations.

    Science.gov (United States)

    Houndonougbo, Yao; Jin, Hong; Rajagopalan, Bhuma; Wong, Kean; Kuczera, Krzysztof; Subramaniam, Bala; Laird, Brian

    2006-07-06

    We present complementary molecular simulations and experimental results of phase equilibria for carbon dioxide expanded acetonitrile, methanol, ethanol, acetone, acetic acid, toluene, and 1-octene. The volume expansion measurements were done using a high-pressure Jerguson view cell. Molecular simulations were performed using the Gibbs ensemble Monte Carlo method. Calculations in the canonical ensemble (NVT) were performed to determine the coexistence curve of the pure solvent systems. Binary mixtures were simulated in the isobaric-isothermal distribution (NPT). Predictions of vapor-liquid equilibria of the pure components agree well with experimental data. The simulations accurately reproduced experimental data on saturated liquid and vapor densities for carbon dioxide, methanol, ethanol, acetone, acetic acid, toluene, and 1-octene. In all carbon dioxide expanded liquids (CXL's) studied, the molecular simulation results for the volume expansion of these binary mixtures were found to be as good as, and in many cases superior to, predictions based on the Peng-Robinson equation of state, demonstrating the utility of molecular simulation in the prediction of CXL phase equilibria.

  14. Stability of the relative equilibria of a rigid body in a J2 gravity field

    CERN Document Server

    Wang, Yue; Xu, Shijie

    2014-01-01

    The motion of a point mass in the J2 problem is generalized to that of a rigid body in a J2 gravity field. Different with the original J2 problem, the gravitational orbit-rotation coupling of the rigid body is considered in this generalized problem. The linear stability of the classical type of relative equilibria of the rigid body, which have been obtained in our previous paper, is studied in the framework of geometric mechanics with the second-order gravitational potential. Non-canonical Hamiltonian structure of the problem, i.e., Poisson tensor, Casimir functions and equations of motion, are obtained through a Poisson reduction process by means of the symmetry of the problem. The linear system matrix at the relative equilibria is given through the multiplication of the Poisson tensor and Hessian matrix of the variational Lagrangian. Based on the characteristic equation of the linear system matrix, the conditions of linear stability of the relative equilibria are obtained. With the stability conditions obta...

  15. 3D low-beta magnetized plasma equilibria from external shaping

    Science.gov (United States)

    Hassam, A.; Tenbarge, J.; Landreman, M.; Dorland, W.; Sengupta, W.

    2016-10-01

    A 3D nonlinear dissipative MHD code is in development to allow relaxation to low-beta MHD equilibrium inside a shaped 3D conducting boundary with prescribed conserved axial magnetic flux and no external current. Formation of magnetic islands is expected. Heat sources would be eventually introduced to allow the possibility of non-stationary convection depending on the stability properties of the accessible MHD equilibria. The initial development will be done using the code UMHD. The initial emphasis will be on recovering expected physics in simpler 3D geometries. A primary objective is to minimize numerical boundary noise. In particular, codes which specify the normal magnetic field B.n on bounding surfaces are prone to noise generation. We plan to shape the boundary to conform to the desired field shape so that B.n is zero on the boundary. Non-orthogonal coordinates will be chosen to effect this. We will test noise reduction within the tangential field approach. Results obtained to date support this conjecture. Initial results from simple 2D code equilibria have been verified against analytic solution of equilibria in weak shaping. Initial results also recover the expected features of the Hahm- Kulsrud island formation solution. Work supported by US DOE.

  16. Magma genesis, plate tectonics, and chemical differentiation of the Earth

    OpenAIRE

    Wyllie, Peter J.

    1988-01-01

    Magma genesis, migration, and eruption have played prominent roles in the chemical differentiation of the Earth. Plate tectonics has provided the framework of tectonic environments for different suites of igneous rocks and the dynamic mechanisms for moving masses of rock into melting regions. Petrology is rooted in geophysics. Petrological and geophysical processes are calibrated by the phase equilibria of the materials. The geochemistry of basalts and mantle xenoliths demonstrates that the m...

  17. TERNARY PHASE EQUILIBRIA IN TRANSITION METAL-BORON-CARBON-SILICON SYSTEMS. PART 4. THERMOCHEMICAL CALCULATIONS, VOLUME 3. COMPUTATIONAL APPROACH TO THE CALCULATION OF TERNARY PHASE DIAGRAMS

    Science.gov (United States)

    The general conditional equations which govern the phase equilibria in three-component systems are presented. Using the general conditional equations...a general method has been developed to precalculate the phase equilibria in three-component systems from first principle using computer technique...The method developed has been applied to several model examples and the system Ta-Hf-C. The phase equilibria in three-component systems calculated

  18. TERNARY PHASE EQUILIBRIA IN TRANSITION METAL-BORON-CARBON-SILICON SYSTEMS. PART II. TERNARY SYSTEMS. VOLUME XVI. V-NB-C SYSTEM,

    Science.gov (United States)

    Phase equilibria in the ternary system vanadium-niobium-carbon from 800C through the melting ranges of the cubic monocarbide solid solutions were...established on the basis of X-ray, melting point and metallographic studies. The phase equilibria above 1400C are presented in a three-dimensional...temperature-composition constitutional diagram, since the phase equilibria below 1400C were not thoroughly investigated due to kinetic problems. Vanadium

  19. Redox Equilibria of Chromium in Calcium Silicate Base Melts

    Science.gov (United States)

    Mirzayousef-Jadid, A.-M.; Schwerdtfeger, Klaus

    2009-08-01

    The oxidation state of chromium has been determined at 1600 °C in CaO-SiO2-CrO x melts with CaO/SiO2 ratios (mass pct) of 0.66, 0.93, and 1.10, and 0.15 to 3.00 pct Cr2O3 (initial). A few experiments were also carried out with CaO-SiO2-Al2O3-CrO x melts at 1430 °C. The slag samples were equilibrated with gas phases of controlled oxygen pressure. Two techniques were applied to determine the oxidation state: thermogravimetry and quenching of the samples with subsequent wet chemical analysis. In the low-oxygen pressure range, the chromium is mainly divalent. In the high-oxygen pressure range, it is trivalent and hexavalent. It was found that the Cr3+/Cr2+ and Cr6+/Cr3+ ratios depend on oxygen pressure at a constant CaO/SiO2 ratio and a constant content of total chromium, according to the ideal law of mass action. According to the respective chemical reactions, these ratios change proportional to p_{{{text{O}}2 }}{}^{1/4} or p_{{{text{O}}_{ 2} }}{}^{3/4}, respectively. They also increase with increasing basicity. The data are used to compute the fractions of the different ions in the melt. There is a certain range of oxygen pressure in which all three valence states, Cr2+, Cr3+, and Cr6+, coexist. The color of the solidified slag samples is described and is explained with the help of transmission spectra.

  20. Phase transitions and connectivity in three-dimensional vortex equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Akao, J.H.

    1994-05-01

    The statistical mechanics of collections of closed self avoiding vortex loops on a lattice are studied. The system is related to the vortex form of the three dimensional XY model and to lattice vortex equilibrium models of turbulence. The system exhibits vortex connectivity and screening effects, and models in vorticity variables the superfluid transition. The equilibrium states of the system are simulated by a grand canonical Monte Carlo method. A set of geometric transformations for self-avoiding loops is developed. The numerical method employs histogram sampling techniques and utilizes a modification to the Metropolis flow which enhances efficiency. Results are given for a region in the temperature-chemical potential plane, where the chemical potential is related to the vortex fugacity. A line of second order transitions is identified at low temperature. The transition is shown to be a percolation threshold at which connected vortex loops of infinite size appear in the system. The nature of the transition supports the assumption that the lambda transition in bulk superfluid helium is driven by vortices. An asymptotic analysis is performed for the energy and entropy scaling of the system as functions of the system size and the lattice spacing. These estimates indicate that the infinite temperature line is a phase boundary between small scale fractal vortices and large scale smooth vortices. A suggestion is made that quantum vortices have uniform structure on the scale of the lattice spacing and lie in the positive temperature regime, while classical vortices have uniform structure on the scale of the domain and lie in the negative temperature regime.

  1. Phase equilibria, crystal structure and properties of complex oxides in the Nd2O3-SrO-CoO system

    Science.gov (United States)

    Aksenova, T. V.; Efimova, T. G.; Lebedev, O. I.; Elkalashy, Sh. I.; Urusova, A. S.; Cherepanov, V. A.

    2017-04-01

    The phase equilibria in the ½Nd2O3-SrO-CoO system were systematically studied at 1373 K in air. The intermediate phases formed in the ½Nd2O3-SrO-CoO system at 1373 K in air are: Nd1-xSrxCoO3-δ (0.0≤x≤0.5 with orthorhombic structure, sp. gr. Pbnm and 0.6≤x≤0.95 whose structure was detected as cubic according to XRD sp. gr. Pm3m, but shown to be tetragonal by TEM due to the oxygen vacancy ordering), Nd2-ySryCoO4-δ (0.6≤y≤1.1 with tetragonal K2NiF4-type structure, sp. gr. I4/mmm) and Nd2-zSrzO3 (0.0≤z≤0.15 with hexagonal structure, sp. gr. P-3m1). The unit cell parameters for the single phase samples were refined by the Rietveld analysis. The changes of oxygen content in Nd1-xSrxCoO3-δ (0.6≤x≤0.95) and Ruddlesden-Popper oxide Nd2-ySryCoO4-δ were examined by TGA. All were found to be oxygen deficient phases. High-temperature dilatometry allows calculating the thermal expansion coefficient and evaluating the chemical expansion coefficient at high temperature. The projection of isothermal-isobaric phase diagram for the Nd-Sr-Co-O system at 1373 K in air to the compositional triangle of metallic components has been constructed. The phase equilibria in the studied Nd-Sr-Co-O system were compared to La-Sr-Co-O and Nd-M-Co-O (M=Ca and Ba).

  2. Application of the cubic-plus-association equation of state to mixtures with polar chemicals and high pressures

    DEFF Research Database (Denmark)

    Folas, Georgios; Kontogeorgis, Georgios; Michelsen, Michael Locht

    2006-01-01

    was given to low pressures and liquid-liquid equilibria. In this work, CPA is applied to two classes of mixtures containing polar chemicals for which high-pressure data are available: acetone-containing systems and dimethyl ether mixtures. They are of both scientific and industrial importance. Moreover, CPA...... is applied to high-pressure solid-liquid equilibria (SLE) for alcohol-alkane mixtures. In the case of acetone-hydrocarbon mixtures, satisfactory results are achieved if acetone is allowed to self-associate. Satisfactory high-pressure acetone-water vapor-liquid equilibrium (VLE) is obtained, comparable...

  3. Displacement of estimates of chemical equilibrium constants at breaking of determinancy of independent variables of equilibrium system regression models

    Energy Technology Data Exchange (ETDEWEB)

    Nikolaeva, L.S.; Prikhod' ko, N.V.; Evseev, A.M.; Rozen, A.M.; Kolychev, A.E.; Gontar, B.G. (Moskovskij Gosudarstvennyj Univ. (USSR). Khimicheskij Fakul' tet)

    1982-07-01

    Using as an example regression models of extraction systems HNO/sub 3/-TBP-H/sub 2/O, UO/sub 2/(NO/sub 3/)/sub 2/-TBP-H/sub 2/O it has been shown that disregard of errors of the controlled (independent) variables 3% measurement error of UO/sub 2/(NO/sub 3/)/sub 2/ equilibrium concentration and 3% error of the determination of HNO/sub 3/ activity coefficient results in the displacement of evaluations of certain equilibria constants and leads to incorrect conclusion on the mechanism of chemical equilibria.

  4. Biogas generation in landfills. Equilibria, rates and yields

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, M.

    1997-05-01

    Landfilling in `cells` has become more common in recent years. Different waste streams are guided to different cells, among which the biocell is a landfill designed for biogas production. In this thesis, the dependence of biogas generation on waste composition was investigated. Six 8,000 m{sup 3} test cells, with contents ranging from mainly commercial waste to pure domestic waste and equipped with gas extraction systems and bottom plastic liners, were monitored for seven years. Great emphasis was given to the characterization of conversion processes and governing mechanism in the topics of bio-energetics, kinetics and capacities. A thermodynamic model, in which the oxidations of volatile fatty acids (VFA) (2chemical oxygen demand, N, P and K were quantified. Biomass pools were estimated from methane yields, growth yield coefficients, and bacterial mineral contents. However, results from commercial waste test cells showed that the assimilation of P exceeded the refuse content, which suggests the turnover of microbial biomass and questions the notion of nutritional limitation. In sum, the results showed that the advantages of a reduced content of readily biodegradable material, achieved by guidance or pretreatment, encompass several aspects of the performance. 84 refs, 6 figs, 1 tab

  5. Transferable potentials for phase equilibria-coarse-grain description for linear alkanes.

    Science.gov (United States)

    Maerzke, Katie A; Siepmann, J Ilja

    2011-04-07

    Coarse-grain potentials allow one to extend molecular simulations to length and time scales beyond those accesssible to atomistic representations of the interacting system. Since the coarse-grain potentials remove a large number of interaction sites and, hence, a large number of degrees of freedom, it is generally assumed that coarse-grain potentials are not transferable to different systems or state points (temperature and pressure). Here we apply lessons learned from the parametrization of transferable atomistic potentials to develop a systematic procedure for the parametrization of transferable coarse-grain potentials. In particular, we apply an iterative Boltzmann optimization for the determination of the bonded interactions for coarse-grain beads belonging to the same molecule and separated by one or two coarse-grain bonds and parametrize the nonbonded interactions by fitting to the vapor-liquid coexistence curves computed for selected molecules represented by the TraPPE-UA (transferable potentials for phase equilibria-united atom) force field. This approach is tested here for linear alkanes where parameters for C(3)H(7) end segments and for C(3)H(6) middle segments of the TraPPE-CG (transferable potentials for phase equilibria-coarse grain) force field are determined and it is shown that these parameters yield quite accurate vapor-liquid equilibria for neat n-hexane to n-triacontane and for the binary mixture of n-hexane and n-hexatriacontane. In addition, the position of the first peak in various radial distribution functions and the coordination number for the first solvation shell are well reproduced by the TraPPE-CG force field, but the first peaks are too high and narrow.

  6. Phase equilibria, structure and properties of Y-Ba ceramic

    Energy Technology Data Exchange (ETDEWEB)

    Shamrai, V.F.; Efimov, Yu.V.; Karpinskii, O.G.; Babareko, A.A.; Leitus, G.M.; Frolova, T.M.; Myasnikova, E.A.; Postnikov, A.M.; Savel' yeva, M.E.; Lipikhin, Yu.L. (A.A. Baikov Inst. of Metallurgy, Academy of Sciences, Moscow (USSR))

    1990-05-01

    XRD, microscopy, chemical and activation analysis, together with measurement of Tc and some other properties, have been used to study changes in phase composition, microstructure, crystal structure, texture and composition-property diagrams of high temperature Y-Ba superconductors (single-crystal and polycrystalline specimens and cold-rolled strips) with variations in preparation, heat treatment, deformation and temperature. When prepared by conventional solid state reactions, specimens of the Y-Ba ceramic are generally polyphase (orthorhombic superconducting 123 phase, 2115 phase, sometimes BaCuO{sub 2}, and residual amounts of the initial oxides). The non-equilibrium specimens also contain Y{sub x}Ba{sub y}O{sub z}-type phases. Homogeneous single-phase (as shown by XRD) specimens of the 123-type phase with Tc=88-92 K (containing under 2-5 vol.% second phase, predominantly 2115) are obtained by repeated wet grinding, mixing and solid state annealing at 920-930degC, in air and under oxygen, of the initial mixture of oxides, including BaO{sub 2}. The manner in which the lattice periods of the orthorhombic 123 phase (Tc=92 K) vary with temperature displays an anomaly near Tc that correlates with the thermal behaviour of the Debye temperature. The lattice parameters of a YBa{sub 2}Cu{sub 3}O{sub 6.6} orthorhombic crystal have been studied at 91 and 293 K to ascertain the occupancy of the oxygen positions. Cooling the orthorhombic crystals involves the compression of the triple layers formed by two sheets of CuO{sub 5} pyramids, with their vertices facing the Cu1-O1-Cu1 chains. The compression is mainly due to a reduction in the Cu1-O2 distance. Centrally located in the ''a'' edges, the oxygen atoms may ''trigger'' the interchain interaction. Rolling of the 123 phase powder and strip with the addition of a plasticizer causes brittle cleavage of the crystals and gives rise to the (001) (110) basal texture.

  7. Thermodynamic modeling of phase equilibria of semi-clathrate hydrates of CO2, CH4, or N2+tetra-n-butylammonium bromide aqueous solution

    DEFF Research Database (Denmark)

    Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique

    2012-01-01

    Prediction of phase equilibria of semi-clathrate hydrates has been very rarely investigated in the literature. In this work, a thermodynamic model is proposed for representation/prediction of phase equilibria of semi-clathrate hydrates of the CO2, CH4, or N2+tetra-n-butylammonium bromide (TBAB...

  8. Comparison of two association models (Elliott-Suresh-Donohue and simplified PC-SAFT) for complex phase equilibria of hydrocarbon-water and amine-containing mixtures

    DEFF Research Database (Denmark)

    Grenner, Andreas; Schmelzer, Jürgen; von Solms, Nicolas;

    2006-01-01

    Two Wertheim-based association models, the simplified PC-SAFT and the Elliott-Suresh-Donohue (ESD) equation of state, are compared in this work for the description of vapor-liquid equilibria (VLE) and liquid-liquid equilibria (LLE) in binary systems of aniline, cyclohexylamine (CHA), hydrocarbons...

  9. Investigation of the Phase Equilibria and Interfacial Properties for Non-polar Fluids

    Institute of Scientific and Technical Information of China (English)

    付东; 赵毅

    2005-01-01

    A self-consistent density-functional theory (DFT) was applied to investigate the phase behavior and interfacial properties of non-polar fluids. For the bulk phases, the theory was reduced to the statistical associating fluid theory(SAFF) that provides accurate descriptions of vapor-liquid phase diagrams below the critical region. The phase diagrams in the critical region were corrected by the renormalization group theory (RGT). The density profile in the surface was obtained by minimizing the grand potential. With the same set of molecular parameters, both the phase equilibria and the interfacial properties of non-polar fluids were investigated satisfactorily.

  10. Multistep Hybrid Iterations for Systems of Generalized Equilibria with Constraints of Several Problems

    Directory of Open Access Journals (Sweden)

    Lu-Chuan Ceng

    2014-01-01

    Full Text Available We first introduce and analyze one multistep iterative algorithm by hybrid shrinking projection method for finding a solution of the system of generalized equilibria with constraints of several problems: the generalized mixed equilibrium problem, finitely many variational inclusions, the minimization problem for a convex and continuously Fréchet differentiable functional, and the fixed-point problem of an asymptotically strict pseudocontractive mapping in the intermediate sense in a real Hilbert space. We prove strong convergence theorem for the iterative algorithm under suitable conditions. On the other hand, we also propose another multistep iterative algorithm involving no shrinking projection method and derive its weak convergence under mild assumptions.

  11. Isobaric vapor-liquid equilibria in the system methyl propanoate + n-butyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Susial, P.; Ortega, J. (Univ. de Las Palmas de Gran Canaria, Canary Islands (Spain). Lab. de Termodinamica y Fisicoquimica)

    1993-10-01

    Isobaric vapor-liquid equilibria were determined at 74.66, 101.32, and 127.99 kPa for binary mixtures containing methyl propanoate + n-butyl alcohol by using a dynamic still with vapor and liquid circulation. No azeotrope was detected. The data were found to be thermodynamically consistent according to the point to point test. Application of the group-contribution models ASOG, UNIFAC, and modified UNIFAC to the activity coefficients at the three pressures studied gives average errors of less than 10%, 11%, and 3%, respectively.

  12. Phase equilibria in the Ti-rich corner of the Ti-Si-Sn system

    Energy Technology Data Exchange (ETDEWEB)

    Bulanova, M.; Soroka, A.; Zheltov, P.; Vereshchaka, V.; Meleshevich, K. [Natsional`na Akademyiya Nauk Ukrayini, Kiev (Ukraine). Inst. of Problems in Materials Science

    1999-07-01

    Using differential thermal, X-ray, metallographic and electron microprobe analyses phase equilibria in Ti-rich corner of the Ti-Si-Sn system were studied. Projections of solidus and liquidus surfaces, isothermal section at 1300 C and isopleth at 90 at.% Ti were constructed. It was shown that in the concentration interval studied at the solidus and 1300 C temperatures the Ti{sub 5}(Si, Sn){sub 3} (Z) phase coexists with left angle {beta}-Ti right angle ({beta}). The liquidus surface is characterised by the fields of {beta} and Z primary crystallisation, resulting in a monovariant L <=> {beta} + Z eutectic. (orig.) 8 refs.

  13. New results concerning the stability of equilibria of a delay differential equation modeling leukemia

    CERN Document Server

    Ion, Anca Veronica

    2010-01-01

    The paper is devoted to the study of stability of equilibrium solutions of a delay differential equation that models leukemia. The equation was previously studied in [5] and [6], where the emphasis is put on the numerical study of periodic solutions. Some stability results for the equilibria are also presented in these works, but they are incomplete and contain some errors. Our work aims to complete and to bring corrections to those results. Both Lyapunov first order approximation method and second Lyapunov method are used.

  14. Gas equilibria in Cerro Prieto geothermal field, B.C., Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Portugal, E.; Barragan, R.M.; Izquierdo, G. [Inst. de Investigaciones Electricas, Morelos (Mexico); Leon, J. de [Comision Federal de Electricidad, Mexicali B.C. (Mexico)

    2003-07-01

    Gas equlibria methods involving fischer-tropsch-pyrite-magnetite; and fischer-tropsch-pyrite-hematite-pyrite-magnetite reactions were used to evaluate reservoir temperature and a mass steam fraction in Cerro Prieto geothermal field. These approaches have been applied in some selected producing wells from four areas under exploitation. The results show good correlation for both equilibria methods; however fischer-tropsch; pyrite-magnetite reactions provide the best estimation of the physical reservoir parameters. The main processes found for Cerro Prieto IV area are lateral vapor contribution and the inflow of hotter and deeper fluid with high liquid saturation. (orig.)

  15. Time-Preference Heterogeneity and Multiplicity of Equilibria in Two-Group Bargaining

    Directory of Open Access Journals (Sweden)

    Daniel Cardona

    2016-05-01

    Full Text Available We consider a multilateral bargaining game in which the agents can be classified into two groups according to their instantaneous preferences. In one of these groups there is one agent with a different discount factor. We analyze how this time-preference heterogeneity may generate multiplicity of equilibria. When such an agent is sufficiently more patient than the rest, there is an equilibrium in which her group-mates make the same proposal as the members of the other group. Thus, in heterogeneous groups the presence of more patient members may reduce the utility of its members.

  16. Thermal analysis and prediction of phase equilibria in ternary Pb-Zn-Ag system

    Directory of Open Access Journals (Sweden)

    Živković D.

    2011-01-01

    Full Text Available Ternary Pb-Zn-Ag system is typical for some physicochemical processes going on in refining phase in the extractive metallurgy of lead. Therefore, investigation of mentioned system is important from both theoretical and practical research of the phenomena occurring during the lead desilverizing process. The results of experimental investigation using differential thermal analysis (DTA and thermodynamic calculation of phase equilibria in Pb-Zn-Ag system according to CALPHAD method, in the sections with Zn:Ag mass ratio equal to 90:10, 70:30 and 50:50, are presented in this paper.

  17. Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates

    Science.gov (United States)

    Minor, D. B.; Roth, R. S.; Parker, H. S.; Brower, W. S.

    1977-01-01

    The phase equilibria relations and crystal chemistry of portions of the Rb2O-Nb2O5 and Rb2O-Ta2O5 systems were investigated for structures potentially useful as ionic conductors. A hexagonal tungsten bronze-type (HTB) structure was found in both systems as well as three hexagonal phases with mixed HTB-pyrochlore type structures. Ion exchange experiments between various alkali ions are described for several phases. Unit cell dimensions and X-ray diffraction powder patterns are reported.

  18. Hydrate phase equilibria of CO2+N2+aqueous solution of THF, TBAB or TBAF system

    DEFF Research Database (Denmark)

    Sfaxi, Imen Ben Attouche; Durand, Isabelle; Lugo, Rafael

    2014-01-01

    We report hydrate dissociation conditions of CO2 (15 and 30mol%)+N2 (85 and 70mol%) in the presence of aqueous solutions of THF, TBAB or TBAF. The concentrations of TBAB and TBAF in the aqueous solutions are 5wt% and 9wt% while THF concentration in aqueous solution is 3mol%. Two different...... experimental techniques including isochoric pressure search method and a DSC method are used to measure the hydrate dissociation conditions. A comparison is finally made with the literature data. It is expected that this study provides better understanding of hydrate phase equilibria associated with CO2...... capture. © 2014 Elsevier Ltd....

  19. Mathematical modelling of complex equilibria taking into account experimental data on activities of components

    Energy Technology Data Exchange (ETDEWEB)

    Nikolaeva, L.S.; Evseev, A.M.; Rozen, A.M.; Bobytev, A.P.; Kir' yanov, Yu.A. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1981-09-01

    The extraction systems, the application of which is possible when reprocessing irradiated nuclear fuels are considered. It is shown that the selection of the component activities as the observed properties of the system (responses) provides a possibility to model the equilibria using methods of the regression analysis. The mathematical model of nitric acid extraction with tributyl phosphate is presented. The data on the composition of the complexes in the system studied, obtained by the method of mathematical modelling, are confirmed with the study of the IR spectra of the extracts.

  20. Relative Equilibria in the Four-Vortex Problem with Two Pairs of Equal Vorticities

    Science.gov (United States)

    Hampton, Marshall; Roberts, Gareth E.; Santoprete, Manuele

    2014-02-01

    We examine in detail the relative equilibria in the planar four-vortex problem where two pairs of vortices have equal strength, that is, Γ 1= Γ 2=1 and Γ 3= Γ 4= m where is a parameter. One main result is that, for m>0, the convex configurations all contain a line of symmetry, forming a rhombus or an isosceles trapezoid. The rhombus solutions exist for all m but the isosceles trapezoid case exists only when m is positive. In fact, there exist asymmetric convex configurations when mmodern and computational algebraic geometry.

  1. Stability of relative equilibria of point vortices on a sphere and symplectic integrators

    Energy Technology Data Exchange (ETDEWEB)

    Marsden, J.E.; Pekarsky, S. [California Institute of Technology, Pasadena, CA (United States); Shkoller, S. [California Institute of Technology, Pasadena, CA (United States); Los Alamos National Lab., Los Alamos, NM (United States)

    1999-12-01

    This paper analyzes the dynamics of {nu} point vortices moving on a sphere from the point of view of geometric mechanics. The formalism is developed for the general case of {nu} vortices, and the details are provided for the (integrable) case {nu}=3. Stability of relative equilibria is analyzed by the energy-momentum method. Explicit criteria for stability of different configurations with generic and non-generic momenta are obtained. In each case, a group of transformations is specified, such that motion in the original phase space is stable module this group. Finally, the construction of a symplectic-momentum integrator for vortex dynamics on a sphere is outlined.

  2. Liquid-vapor phase equilibria and the thermodynamic properties of 2-methylpropanol- n-alkyl propanoate solutions

    Science.gov (United States)

    Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.

    2016-08-01

    The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).

  3. Advantages of ion-based mole fractions for describing phase equilibria in ionic liquids: application to gas solubility.

    Science.gov (United States)

    Longinotti, María Paula; Alvarez, Jorge L; Japas, M Laura

    2009-03-19

    Despite the obvious ionic character of ionic liquids (ILs), previous studies of phase equilibria in these media were formulated implicitly assuming a "molecular" behavior of the ionic solvent. In this work, a more appropriate thermodynamic treatment is applied to describe the solubility of gases in ILs. According to our results, if the concentration is expressed on an ionic basis, solutions of simple gases in ILs display rather small deviations from ideal behavior in wide composition ranges, whereas deviations are larger when the solvent is considered as an anion-cation pair. The present thermodynamic formulation also accounts for the observed solid-liquid phase equilibria of molecular and IL binary mixtures.

  4. Joint Sensing and Power Allocation in Nonconvex Cognitive Radio Games: Quasi-Nash Equilibria

    Science.gov (United States)

    Pang, Jong-Shi; Scutari, Gesualdo

    2013-05-01

    In this paper, we propose a novel class of Nash problems for Cognitive Radio (CR) networks composed of multiple primary users (PUs) and secondary users (SUs) wherein each SU (player) competes against the others to maximize his own opportunistic throughput by choosing jointly the sensing duration, the detection thresholds, and the vector power allocation over a multichannel link. In addition to power budget constraints, several (deterministic or probabilistic) interference constraints can be accommodated in the proposed general formulation, such as constraints on the maximum individual/aggregate (probabilistic) interference tolerable from the PUs. To keep the optimization as decentralized as possible, global interference constraints, when present, are imposed via pricing; the prices are thus additional variables to be optimized. The resulting players' optimization problems are nonconvex and there are price clearance conditions associated with the nonconvex global interference constraints to be satisfied by the equilibria of the game, which make the analysis of the proposed game a challenging task; none of classical results in the game theory literature can be successfully applied. To deal with the nonconvexity of the game, we introduce a relaxed equilibrium concept, the Quasi-Nash Equilibrium (QNE), and study its main properties, performance, and connection with local Nash equilibria. Quite interestingly, the proposed game theoretical formulations yield a considerable performance improvement with respect to current centralized and decentralized designs of CR systems, which validates the concept of QNE.

  5. CASTOR3D: linear stability studies for 2D and 3D tokamak equilibria

    Science.gov (United States)

    Strumberger, E.; Günter, S.

    2017-01-01

    The CASTOR3D code, which is currently under development, is able to perform linear stability studies for 2D and 3D, ideal and resistive tokamak equilibria in the presence of ideal and resistive wall structures and coils. For these computations ideal equilibria represented by concentric nested flux surfaces serve as input (e.g. computed with the NEMEC code). Solving an extended eigenvalue problem, the CASTOR3D code takes simultaneously plasma inertia and wall resistivity into account. The code is a hybrid of the CASTOR_3DW stability code and the STARWALL code. The former is an extended version of the CASTOR and CASTOR_FLOW code, respectively. The latter is a linear 3D code computing the growth rates of resistive wall modes in the presence of multiply-connected wall structures. The CASTOR_3DW code, and some parts of the STARWALL code have been reformulated in a general 3D flux coordinate representation that allows to choose between various types of flux coordinates. Furthermore, the implemented many-valued current potentials in the STARWALL part allow a correct treatment of the m  =  0, n  =  0 perturbation. In this paper, we outline the theoretical concept, and present some numerical results which illustrate the present status of the code and demonstrate its numerous application possibilities.

  6. Artificial multiple criticality and phase equilibria: an investigation of the PC-SAFT approach.

    Science.gov (United States)

    Yelash, Leonid; Müller, Marcus; Paul, Wolfgang; Binder, Kurt

    2005-11-01

    The perturbed-chain statistical associating fluid theory (PC-SAFT) is studied for a wide range of temperature, T, pressure, p, and (effective) chain length, m, to establish the generic phase diagram of polymers according to this theory. In addition to the expected gas-liquid coexistence, two additional phase separations are found, termed "gas-gas" equilibrium (at very low densities) and "liquid-liquid" equilibrium (at densities where the system is expected to be solid already). These phase separations imply that in one-component polymer systems three critical points occur, as well as equilibria of three fluid phases at triple points. However, Monte Carlo simulations of the corresponding system yield no trace of the gas-gas and liquid-liquid equilibria, and we conclude that the latter are just artefacts of the PC-SAFT approach. Using PC-SAFT to correlate data for polybutadiene melts, we suggest that discrepancies in modelling the polymer density at ambient temperature and high pressure can be related to the presumably artificial liquid-liquid phase separation at lower temperatures. Thus, particular care is needed in engineering applications of the PC-SAFT theory that aims at predicting properties of macromolecular materials.

  7. Phase transformations and phase equilibria in the Co-Sn-Ti system in the crystallization interval

    Science.gov (United States)

    Fartushna, Iu.; Bulanova, M.; Ayral, R. M.; Tedenac, J. C.; Meleshevich, K.

    2016-12-01

    The Co-Sn-Ti system was studied in the crystallization interval (below 50 at% Sn) by the methods of Scanning Electron Microscopy, microprobe analysis, Differential Thermal Analysis, X-ray diffraction. The liquidus and solidus projections and the melting diagram were constructed. Only Co2TiSn(τ1) ternary compound (Heusler phase-L12) was found in equilibria with the liquid in the concentration interval studied. Taking into account our recent data, the liquidus projection is characterized by the fields of primary crystallization of (βTi), (Co), binary-based phases Ti3Sn, Ti2Sn, Ti5Sn3, Ti6Sn5, Ti2Co, TiCo, TiCo2 (c), TiCo2 (h), TiCo3, βCo3Sn2, CoSn and ternary τ1. The solidus projection is characterized by thirteen three-phase fields, which result from invariant four-phase equilibria, five are of eutectic type (E) and eight of transition type (U) and the existence of one more region Ti2Sn3+βCoSn3+(Sn) in the solidus projection is discussed.

  8. Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

    Science.gov (United States)

    Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

    2009-04-23

    In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

  9. Phase equilibria and modeling of pyridinium-based ionic liquid solutions.

    Science.gov (United States)

    Domańska, Urszula; Królikowski, Marek; Ramjugernath, Deresh; Letcher, Trevor M; Tumba, Kaniki

    2010-11-25

    The phase diagrams of the ionic liquid (IL) N-butyl-4-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide ([BM(4)Py][NTf(2)]) with water, an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol), an aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), an alkane (n-hexane, n-heptane, n-octane), or cyclohexane have been measured at atmospheric pressure using a dynamic method. This work includes the characterization of the synthesized compound by water content and also by differential scanning calorimetry. Phase diagrams for the binary systems of [BM(4)Py][NTf(2)] with all solvents reveal eutectic systems with regards to (solid-liquid) phase equilibria and show immiscibility in the liquid phase region with an upper critical solution temperature (UCST) in most of the mixtures. The phase equilibria (solid, or liquid-liquid) for the binary systems containing aliphatic hydrocarbons reported here exhibit the lowest solubility and the highest immiscibility gap, a trend which has been observed for all ILs. The reduction of experimental data has been carried out using the nonrandom two-liquid (NRTL) correlation equation. The phase diagrams reported here have been compared with analogous phase diagrams reported previously for systems containing the IL N-butyl-4-methylpyridinium tosylate and other pyridinium-based ILs. The influence of the anion of the IL on the phase behavior has been discussed.

  10. Stable bootstrap-current driven equilibria for low aspect ratio tokamaks

    Energy Technology Data Exchange (ETDEWEB)

    Miller, R.L.; Lin-Liu, Y.R.; Turnbull, A.D.; Chan, V.S. [General Atomics, San Diego, CA (United States); Pearlstein, L.D. [Lawrence Livermore National Lab., CA (United States); Sauter, O.; Villard, L. [Ecole Polytechnique Federale, Lausanne (Switzerland). Centre de Recherche en Physique des Plasma (CRPP)

    1996-09-01

    Low aspect ratio tokamaks can potentially provide a high ratio of plasma pressure to magnetic pressure {beta} and high plasma current I at a modest size, ultimately leading to a high power density compact fusion power plant. For the concept to be economically feasible, bootstrap current must be a major component of the plasma. A high value of the Troyon factor {beta}{sub N} and strong shaping are required to allow simultaneous operation at high {beta} and high bootstrap current fraction. Ideal magnetohydrodynamic stability of a range of equilibria at aspect 1.4 is systematically explored by varying the pressure profile and shape. The pressure and current profiles are constrained in such a way as to assure complete bootstrap current alignment. Both {beta}{sub N} and {beta} are defined in terms of the vacuum toroidal field. Equilibria with {beta} {sub N}{>=}8 and {beta} {approx_equal}35% to 55% exist which are stable to n = {infinity} ballooning modes, and stable to n = 0,1,2,3 kink modes with a conducting wall. The dependence of {beta} and {beta}{sub N} with respect to aspect ratio is also considered. (author) 9 figs., 14 refs.

  11. Phase equilibria of the system methane-ethane from temperature scaling Gibbs Ensemble Monte Carlo simulation

    Science.gov (United States)

    Zhang, Zhigang; Duan, Zhenhao

    2002-10-01

    A new technique of temperature scaling method combined with the conventional Gibbs Ensemble Monte Carlo simulation was used to study liquid-vapor phase equilibria of the methane-ethane (CH 4-C 2H 6) system. With this efficient method, a new set of united-atom Lennard-Jones potential parameters for pure C 2H 6 was found to be more accurate than those of previous models in the prediction of phase equilibria. Using the optimized potentials for liquid simulations (OPLS) potential for CH 4 and the potential of this study for C 2H 6, together with a simple mixing rule, we simulated the equilibrium compositions and densities of the CH 4-C 2H 6 mixtures with accuracy close to experiments. The simulated data are supplements to experiments, and may cover a larger temperature-pressure-composition space than experiments. Compared with some well-established equations of state such as Peng-Robinson equation of state (PR-EQS), the simulated results are found to be closer to experiments, at least in some temperature and pressure ranges.

  12. Theories of multiple equilibria and weather regimes : A critical reexamination. II - Baroclinic two-layer models

    Science.gov (United States)

    Cehelsky, Priscilla; Tung, Ka Kit

    1987-01-01

    Previous results based on low- and intermediate-order truncations of the two-layer model suggest the existence of multiple equilibria and/or multiple weather regimes for the extratropical large-scale flow. The importance of the transient waves in the synoptic scales in organizing the large-scale flow and in the maintenance of weather regimes was emphasized. The result shows that multiple equilibria/weather regimes that are present in lower-order models examined disappear when a sufficient number of modes are kept in the spectral expansion of the solution to the governing partial differential equations. Much of the chaotic behavior of the large-scale flow that is present in intermediate-order models is now found to be spurious. Physical reasons for the drastic modification are offered. A peculiarity in the formulation of most existing two-layer models is noted that also tends to exaggerate the importance of baroclinic processes and increase the degree of unpredictability of the large-scale flow.

  13. Experimental vapor-liquid equilibria data for binary mixtures of xylene isomers

    Directory of Open Access Journals (Sweden)

    W.L. Rodrigues

    2005-09-01

    Full Text Available Separation of aromatic C8 compounds by distillation is a difficult task due to the low relative volatilities of the compounds and to the high degree of purity required of the final commercial products. For rigorous simulation and optimization of this separation, the use of a model capable of describing vapor-liquid equilibria accurately is necessary. Nevertheless, experimental data are not available for all binaries at atmospheric pressure. Vapor-liquid equilibria data for binary mixtures were isobarically obtained with a modified Fischer cell at 100.65 kPa. The vapor and liquid phase compositions were analyzed with a gas chromatograph. The methodology was initially tested for cyclo-hexane+n-heptane data; results obtained are similar to other data in the literature. Data for xylene binary mixtures were then obtained, and after testing, were considered to be thermodynamically consistent. Experimental data were regressed with Aspen Plus® 10.1 and binary interaction parameters were reported for the most frequently used activity coefficient models and for the classic mixing rules of two cubic equations of state.

  14. Adsorption of Halogenated Hydrocarbons from Aqueous Solutions by Wetted and Nonwetted Hydrophobic and Hydrophilic Sorbents:  Equilibria

    NARCIS (Netherlands)

    Rexwinkel, G.; Heesink, A.B.M.; Swaaij, van W.P.M.

    1999-01-01

    Single-solute adsorption equilibria of 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethene, trans-1,2-dichloroethene, chloroform, 2,4-dichorophenol, and dichloromethane dissolved in water have been measured, using both wetted and nonwetted hydrophobic Amberlite XAD-4 resin at 20 °C. The re

  15. Modeling phase equilibria for acid gas mixtures using the CPA equation of state. Part II: Binary mixtures with CO2

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios; Michelsen, Michael Locht;

    2011-01-01

    In Part I of this series of articles, the study of H2S mixtures has been presented with CPA. In this study the phase behavior of CO2 containing mixtures is modeled. Binary mixtures with water, alcohols, glycols and hydrocarbons are investigated. Both phase equilibria (vapor–liquid and liquid...

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

    NARCIS (Netherlands)

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

    2009-01-01

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

  17. Phase and extraction equilibria in water-polyethyleneglycol ethers of monoethanolamides of synthetic fatty acid-ammonium chloride systems

    Science.gov (United States)

    Lesnov, A. E.; Golovkina, A. V.; Kudryashova, O. S.; Denisova, S. A.

    2016-08-01

    Phase equilibria in layering systems of water, polyethyleneglycol ethers of monoethanolamides of synthetic fatty acids (SFAs) (synthamide-5), and ammonium chloride are studied. The possibility of using such systems for the liquid extraction of metal ions is evaluated. The effect the nature of salting-out agents has on the processes of segregation of the systems has been considered.

  18. Stability of the classical type of relative equilibria of a rigid body in the J2 problem

    CERN Document Server

    Wang, Yue

    2013-01-01

    The motion of a point mass in the J2 problem is generalized to that of a rigid body in a J2 gravity field. The linear and nonlinear stability of the classical type of relative equilibria of the rigid body, which have been obtained in our previous paper, are studied in the framework of geometric mechanics with the second-order gravitational potential. Non-canonical Hamiltonian structure of the problem, i.e., Poisson tensor, Casimir functions and equations of motion, are obtained through a Poisson reduction process by means of the symmetry of the problem. The linear system matrix at the relative equilibria is given through the multiplication of the Poisson tensor and Hessian matrix of the variational Lagrangian. Based on the characteristic equation of the linear system matrix, the conditions of linear stability of the relative equilibria are obtained. The conditions of nonlinear stability of the relative equilibria are derived with the energy-Casimir method through the projected Hessian matrix of the variationa...

  19. The investigation of variable nernst equilibria on isolated neurons and coupled neurons forming discrete and continuous networks

    Science.gov (United States)

    Meier, Stephen R.

    Since the introduction of the Hodgkin-Huxley equations, used to describe the excitation of neurons, the Nernst equilibria for individual ion channels have assumed to be constant in time. Recent biological recordings call into question the validity of this assumption. Very little theoretical work has been done to address the issue of accounting for these non-static Nernst equilibria using the Hodgkin-Huxley formalism. This body of work incorporates non-static Nernst equilibria into the generalized Hodgkin-Huxley formalism by considering the first-order effects of the Nernst equation. It is further demonstrated that these effects are likely dominate in neurons with diameters much smaller than that of the squid giant axon and permeate important information processing regions of the brain such as the hippocampus. Particular results of interest include single-cell bursting due to the interplay of spatially separated neurons, pattern formation via spiral waves within a soliton-like regime, and quantifiable shifts in the multifractality of hippocampal neurons under the administration of various drugs at varying dosages. This work provides a new perspective on the variability of Nernst equilibria and demonstrates its utility in areas such as pharmacology and information processing.

  20. Solid–liquid equilibria for binary and ternary systems with the Cubic-Plus-Association (CPA) equation of state

    DEFF Research Database (Denmark)

    Fettouhi, André; Thomsen, Kaj

    2010-01-01

    A systematic investigation of the CPA model's performance within solid-liquid equilibria (SLE) in binary mixtures (methane + ethane, methane + heptane, methane + benzene, methane + CO2, ethane + heptane, ethane + CO2, 1-propanol + 1,4-dioxane, ethanol + water, 2-propanol + water) is presented...

  1. Acid-base chemistry of white wine: analytical characterisation and chemical modelling.

    Science.gov (United States)

    Prenesti, Enrico; Berto, Silvia; Toso, Simona; Daniele, Pier Giuseppe

    2012-01-01

    A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids) with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture), ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic "wine" especially adapted for testing.

  2. Acid-Base Chemistry of White Wine: Analytical Characterisation and Chemical Modelling

    Directory of Open Access Journals (Sweden)

    Enrico Prenesti

    2012-01-01

    Full Text Available A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria. Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture, ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic “wine” especially adapted for testing.

  3. Solid-Phase Equilibria in the Au-As, Au-Ga-Sb, Au-In-As, and Au-In-Sb Ternaries.

    Science.gov (United States)

    1986-02-28

    AD6i5 469 SOLID- PHASE EQUILIBRIA IN THE Ru-As AU-GA-SB AU-IN-AS- 1/17 AND AU-IN-SB TERNAR (U) CALIFORNIA UNIV LOS ANGELES DEPT OF CHEMISTRY AND...REPORT & PERIOD COVERED SOLID- PHASE EQUILIBRIA IN THE Au-Ga-As, Au-Ga-Sb Thchnical Report Au-In-As, and Au-In-Sb TEARIEIS S. PERFORMING ORG. REPORT NUMBER...CLASSIFICATION OF THIS PAGEMI*n Does Entepd) 4./ lie- . .- - - - - -- -- Solid Phase Equilibria in the Au-Ga-As, Au-Ga-Sb, Au-In-As, and Au-In-Sb Ternaries C

  4. Thermodynamic modelling of phase equilibria in Al–Ga–P–As system

    Indian Academy of Sciences (India)

    S Acharya; J P Hajra

    2005-04-01

    A generalized thermodynamic expression of the liquid Al–Ga–P–As alloys is used in conjunction with the solid solution model in determining the solid–liquid equilibria at 1173 K and 1273 K. The liquid solution model contains thirtyseven parameters. Twentyfour of them pertain to those of the six constituent binaries, twelve refer to the specific ternary interactions. Additionally the liquid solution model also contains a specific quaternary interaction parameter. The latter has been evaluated here based on the experimental data available in the literature. The present research shows an excellent agreement between the derived and experimental values at 1173 K and 1273 K for the system. The article also presents a comparison between the evaluated values with those based on the regular solution model for the liquid alloys.

  5. Local equilibria and state transfer of charged classical particles on a helix in an electric field

    CERN Document Server

    Plettenberg, J; Zampetaki, A V; Schmelcher, P

    2016-01-01

    We explore the effects of a homogeneous external electric field on the static properties and dynamical behavior of two charged particles confined to a helix. In contrast to the field-free setup which provides a separation of the center-of-mass and relative motion, the existence of an external force perpendicular to the helix axis couples the center-of-mass to the relative degree of freedom leading to equilibria with a localized center of mass. By tuning the external field various fixed points are created and/or annihilated through different bifurcation scenarios. We provide a detailed analysis of these bifurcations based on which we demonstrate a robust state transfer between essentially arbitrary equilibrium configurations of the two charges that can be induced by making the external force time-dependent.

  6. EFFECT OF PROFILES AND SHAPE ON IDEAL STABILITY OF ADVANCED TOKAMAK EQUILIBRIA

    Energy Technology Data Exchange (ETDEWEB)

    MAKOWSKI,MA; CASPER,TA; FERRON,JR; TAYLOR,TS; TURNBULL,AD

    2003-08-01

    OAK-B135 The pressure profile and plasma shape, parameterized by elongation ({kappa}), triangularity ({delta}), and squareness ({zeta}), strongly influence stability. In this study, ideal stability of single null and symmetric, double-null, advanced tokamak (AT) configurations is examined. All the various shapes are bounded by a common envelope and can be realized in the DIII-D tokamak. The calculated AT equilibria are characterized by P{sub 0}/

    {approx} 2.0-4.5, weak negative central shear, high q{sub min} (> 2.0), high bootstrap fraction, an H-mode pedestal, and varying shape parameters. The pressure profile is modeled by various polynomials together with a hyperbolic tangent pedestal, consistent with experimental observations. Stability is calculated with the DCON code and the resulting stability boundary is corroborated by GATO runs.

  7. [Phase equilibria in water-defatted milk proteins-carboxymethylcellulose sodium salt systems].

    Science.gov (United States)

    Glotova, Iu K; Pavlovskaia, G E; Lashko, N P; Antonov, Iu A; Tolstoguzov, V B

    1993-01-01

    Phase equilibria in water mixtures of skimmed milk with sodium salt of carboxymethylcellulose (CMC) was studied using two degrees of CMC polymerization (500 and 200) and substitution (0.8 and 0.5). The increase of the polymerization degree from 200 to 500 resulted in a higher protein yield in the protein phase, while the decrease of the substitution degree from 0.8 to 0.5 caused a noticeable decrease of asymmetry of phase diagrams. The phase separation was accompanied by ion exchange: potassium and calcium ions were mainly found in the protein phase. The highest yield of milk protein into the protein phase was 85% at a CMC concentration of 0.7%. The main protein component of the polysaccharide phase was alpha-lactalbumin.

  8. Free-boundary ideal MHD stability of W7-X divertor equilibria

    Science.gov (United States)

    Nührenberg, C.

    2016-07-01

    Plasma configurations describing the stellarator experiment Wendelstein 7-X (W7-X) are computationally established taking into account the geometry of the test-divertor unit and the high-heat-flux divertor which will be installed in the vacuum chamber of the device (Gasparotto et al 2014 Fusion Eng. Des. 89 2121). These plasma equilibria are computationally studied for their global ideal magnetohydrodynamic (MHD) stability properties. Results from the ideal MHD stability code cas3d (Nührenberg 1996 Phys. Plasmas 3 2401), stability limits, spatial structures and growth rates are presented for free-boundary perturbations. The work focusses on the exploration of MHD unstable regions of the W7-X configuration space, thereby providing information for future experiments in W7-X aiming at an assessment of the role of ideal MHD in stellarator confinement.

  9. Experimental investigation of phase equilibria in the Nb-Si-Ta ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jian; Wang, Cuiping; Yao, Jun; Yang, Shuiyuan; Zhan Shi; Liu, Xingjun [Xiamen Univ. (China). Dept. of Materials Science and Engineering; Xiamen Univ. (China). Fujian Provincial Key Laboratory of Materials Genome; Kang, Yongwang [Beijing Institute of Aeronautical Materials (China). Science and Technology on Advanced High Temperature Structural Materials Lab.

    2016-12-15

    The phase equilibria in the Nb-Si-Ta ternary system at 1 373 K, 1 473 K and 1 573 K were investigated by means of back-scattered electron imaging, electron probe microanalysis and X-ray diffraction. The isothermal sections at 1 373 K, 1 473 K and 1 573 K consist of two three-phase regions and seven two-phase regions, without any ternary compounds. The compounds of NbSi{sub 2} and TaSi{sub 2}, αNb{sub 5}Si{sub 3} and αTa{sub 5}Si{sub 3} form continuous solid solutions, respectively. The solubilities of Nb in Ta{sub 3}Si and Ta{sub 2}Si phases are extremely large, whereas the solubility of Si in the β(Nb, Ta) phase is relatively small.

  10. An alternative method of constructing axisymmetric toroidal equilibria with nonparallel flow

    Science.gov (United States)

    Kuiroukidis, Ap; Throumoulopoulos, G. N.

    2016-11-01

    An alternative method based on an inverse aspect ratio (ɛ) expansion which reduces the axisymmetric equilibrium problem to a set of ODEs containing terms of arbitrary order in ɛ is employed to solve a generalized Grad-Shafranov equation with incompressible sheared flow nonparallel to the magnetic field. The method is applied to construct equilibria with either circular magnetic surfaces and reversed magnetic shear or D-shaped magnetic surfaces and normal magnetic shear. From the former equilibrium, it turns out that the electric field results in an increase of the reversed magnetic shear, thus indicating potential synergetic effects of the sheared flow and the magnetic shear in the formation of an internal transport barrier in consistent with experimental evidence.

  11. MTDATA and the Prediction of Phase Equilibria in Oxide Systems: 30 Years of Industrial Collaboration

    Science.gov (United States)

    Gisby, John; Taskinen, Pekka; Pihlasalo, Jouni; Li, Zushu; Tyrer, Mark; Pearce, Jonathan; Avarmaa, Katri; Björklund, Peter; Davies, Hugh; Korpi, Mikko; Martin, Susan; Pesonen, Lauri; Robinson, Jim

    2016-09-01

    This paper gives an introduction to MTDATA, Phase Equilibrium Software from the National Physical Laboratory (NPL), and describes the latest advances in the development of a comprehensive database of thermodynamic parameters to underpin calculations of phase equilibria in large oxide, sulfide, and fluoride systems of industrial interest. The database, MTOX, has been developed over a period of thirty years based upon modeling work at NPL and funded by industrial partners in a project co-ordinated by Mineral Industry Research Organisation. Applications drawn from the fields of modern copper scrap smelting, high-temperature behavior of basic oxygen steelmaking slags, flash smelting of nickel, electric furnace smelting of ilmenite, and production of pure TiO2 via a low-temperature molten salt route are discussed along with calculations to assess the impact of impurities on the uncertainty of fixed points used to realize the SI unit of temperature, the kelvin.

  12. Implementation of Hamada principle in calculations of nested 3-D equilibria

    Science.gov (United States)

    Zakharov, Leonid E.

    2015-12-01

    > Plasma confinement is based on the use of nested toroidal magnetic surfaces. In axisymmetric configurations the nestedness is provided by the existence of a flux function describing the magnetic surfaces explicitly. In the case of a three-dimensional magnetic field, the nested surfaces represent an exception. More typically, magnetic islands are formed on the resonant surfaces. The islands could degrade the plasma performance. The rigorous condition for the existence of nested surfaces without islands was formulated by Hamada (Nucl. Fusion, vol. 2, 1962, pp. 23-37) but was not implemented directly into numerical codes used, for example, for designing the stellarator configurations. This paper introduces a method of implementation of the Hamada principle in numerical algorithms. The proposed approach allows for simple linearized equilibrium equations (LEE) and potentially very efficient three-dimensional calculations of nested equilibria.

  13. A software for the estimation of binding parameters of biochemical equilibria based on statistical probability model.

    Science.gov (United States)

    Fisicaro, E; Braibanti, A; Sambasiva Rao, R; Compari, C; Ghiozzi, A; Nageswara Rao, G

    1998-04-01

    An algorithm is proposed for the estimation of binding parameters for the interaction of biologically important macromolecules with smaller ones from electrometric titration data. The mathematical model is based on the representation of equilibria in terms of probability concepts of statistical molecular thermodynamics. The refinement of equilibrium concentrations of the components and estimation of binding parameters (log site constant and cooperativity factor) is performed using singular value decomposition, a chemometric technique which overcomes the general obstacles due to near singularity. The present software is validated with a number of biochemical systems of varying number of sites and cooperativity factors. The effect of random errors of realistic magnitude in experimental data is studied using the simulated primary data for some typical systems. The safe area within which approximate binding parameters ensure convergence has been reported for the non-self starting optimization algorithms.

  14. Biomass conversions in subcritical and supercritical water: driving force, phase equilibria, and thermodynamic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Feng, W.; Kooi, H.J. van der; Swaan Arons, J. de [Physical Chemistry and Molecular Thermodynamics, Delft University of Technology, Delft (Netherlands)

    2004-07-01

    Two biomass conversion processes have been studied: hydrothermal upgrading (HTU) under subcritical water conditions; supercritical water gasification (SCWG) in supercritical water. For the design of the two biomass conversion processes, the following contributions of thermodynamics have been presented: phase behaviour and phase equilibria in the reactor and separators; indication of the favourable operation conditions and the trends in product distribution for the conversion reactions; construction of heat exchange network and exergy analysis. A wide variety of fluids have been dealt with, from small molecules to large molecules, including non-polar and polar substances. The statistical association fluids theory (SAFT) equation of state has been applied to calculate the mass distribution in different phases and to estimate the entropy and enthalpy values for different mass streams. (author)

  15. Liquid-Liquid equilibria of the water-acetic acid-butyl acetate system

    Directory of Open Access Journals (Sweden)

    E. Ince

    2002-04-01

    Full Text Available Experimental liquid-liquid equilibria of the water-acetic acid-butyl acetate system were studied at temperatures of 298.15± 0.20, 303.15± 0.20 and 308.15± 0.20 K. Complete phase diagrams were obtained by determining solubility and tie-line data. The reliability of the experimental tie-line data was ascertained by using the Othmer and Tobias correlation. The UNIFAC group contribution method was used to predict the observed ternary liquid-liquid equilibrium (LLE data. It was found that UNIFAC group interaction parameters used for LLE did not provide a good prediction. Distribution coefficients and separation factors were evaluated for the immiscibility region.

  16. High-pressure Phase Equilibria for Binary Ethanol System Containing Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    High-pressure phase behavior of supercritical (SC) CO2+ethanol system was investigated at 333.2 K, 348.2 K, 353.2 K, 368.2 K, 413.2 K and 453.2 K and pressure from 2.0 MPa to 14.3 MPa. The measurement was carried out in a cylindrical autoclave with a moveable piston and a window for adjustment and observation of phase equilibria at given T and p. The samples were taken from two coexisting phases and were analyzed to obtain their compositions. It is shown that the solubility of SC CO2 in ethanol increases drastically with pressures at the given temperature, but the content of ethanol in CO2-rich phase increase faintly.

  17. The Swelling Equilibria of N-isopropylacrylamide Based Hydrogel in Aqueous Solution of Ethanol

    Institute of Scientific and Technical Information of China (English)

    许小平; HUETHERAndreas; MAURERGerd

    2003-01-01

    N-isopropylacrylamide (NIPAAm) was used to synthesize NIPAAm homopolymer (nonionized) and NIPAAm-sodium methacrylate copolymer (ionized). The swelling equilibria for both gels were obtained in aqueous solution of ethanol with concentration ranging from 0 to 100%(by mass) at 25℃. The swollen gel in water shrank first with the addition of a small amount of ethanol and then reswelled with further addition of ethanol showing not only a discontinuous volume phase transition but also a typical reentrant phenomenon. A thermodynamic model based on the UNIQUAC with the "free-volume" contribution was applied to correlate and predict the swelling behavior of the poly(NIPAAM)-gels in ethanol-water mixture.

  18. Applications of the IAPWS-95 formulation in fluid inclusion and mineral-fluid phase equilibria

    Directory of Open Access Journals (Sweden)

    Lanlan Shi

    2012-01-01

    Full Text Available The IAPWS-95 formulation explicit in Helmholtz free energy proposed by Wagner and Pruβ (2002 is the best equation of state of water, from which all thermodynamic properties can be obtained over a wide T–p range from 273.16 to 1273 K and from 0 to 1000 MPa with experimental accuracy. This paper reports the applications of the IAPWS-95 formulation in fluid inclusion and mineral-water phase equilibria. A reliable and highly efficient calculation method is presented for the saturated properties of water so that the formulation can be conveniently applied in the study of fluid inclusion, such as calculating homogenization pressures, homogenization densities (or molar volumes, volume fractions and isochores. Meanwhile, the univariant curves of some mineral-dehydration reactions are calculated based on the IAPWS-95 formulation. The computer code of the IAPWS-95 formulation can be obtained from the corresponding author.

  19. Phase Equilibria Measurement of Binary Mixture for the Propoxylated Neopentyl Glycol Diacrylate in Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Byun, Hun-Soo [Chonnam National University, Yeosu (Korea, Republic of)

    2016-04-15

    Experimental data are reported on the phase equilibrium of propoxylated neopentyl glycol diacrylate in supercritical carbon dioxide. Phase equilibria data were measured in static method at a temperature of (313.2, 333.2, 353.2, 373.2 and 393.2) K and at pressures up to 27.82 MPa. At a constant pressure, the solubility of propoxylated neopentyl glycol diacrylate for the (carbon dioxide + propoxylated neopentyl glycol diacrylate) system increases as temperature increases. The (carbon dioxide + propoxylated neopentyl glycol diacrylate) system exhibits type-I phase behavior. The experimental result for the (carbon dioxide + propoxylated neopentyl glycol diacrylate) system is correlated with Peng- Robinson equation of state using mixing rule. The critical property of propoxylated neopentyl glycol diacrylate is predicted with Joback and Lyderson method.

  20. Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system

    Science.gov (United States)

    De Guire, Mark R.; Prasanna, T. R. S.; Kalonji, Gretchen; O'Handley, Robert C.

    1987-01-01

    Two novel ternary compounds are noted in the present study of 1000 C solid-state equilibria in the Fe-Co-P-O system's Fe2O3-FePO4-Co3(Po4)2-CoO region: CoFe(PO4)O, which undergoes incongruent melting at 1130 C, and Co3Fe4(PO4)6, whose incongruent melting occurs at 1080 C. The liquidus behavior-related consequences of rapidly solidified cobalt ferrite formation from cobalt ferrite-phosphate melts are discussed with a view to spinel formation. It is suggested that quenching from within the spinel-plus-liquid region may furnish an alternative to quenching a homogeneous melt.

  1. Solid-liquid phase equilibria of the Gaussian core model fluid.

    Science.gov (United States)

    Mausbach, Peter; Ahmed, Alauddin; Sadus, Richard J

    2009-11-14

    The solid-liquid phase equilibria of the Gaussian core model are determined using the GWTS [J. Ge, G.-W. Wu, B. D. Todd, and R. J. Sadus, J. Chem. Phys. 119, 11017 (2003)] algorithm, which combines equilibrium and nonequilibrium molecular dynamics simulations. This is the first reported use of the GWTS algorithm for a fluid system displaying a reentrant melting scenario. Using the GWTS algorithm, the phase envelope of the Gaussian core model can be calculated more precisely than previously possible. The results for the low-density and the high-density (reentrant melting) sides of the solid state are in good agreement with those obtained by Monte Carlo simulations in conjunction with calculations of the solid free energies. The common point on the Gaussian core envelope, where equal-density solid and liquid phases are in coexistence, could be determined with high precision.

  2. Extension of the transferable potentials for phase equilibria force field to dimethylmethyl phosphonate, sarin, and soman.

    Science.gov (United States)

    Sokkalingam, Nandhini; Kamath, Ganesh; Coscione, Maria; Potoff, Jeffrey J

    2009-07-30

    The transferable potentials for phase equilibria force field is extended to dimethylmethylphosphonate (DMMP), sarin, and soman by introducing a new interaction site representing the phosphorus atom. Parameters for the phosphorus atom are optimized to reproduce the liquid densities at 303 and 373 K and the normal boiling point of DMMP. Calculations for sarin and soman are performed in predictive mode, without further parameter optimization. Vapor-liquid coexistence curves, critical properties, vapor pressures and heats of vaporization are predicted over a wide range of temperatures with histogram reweighting Monte Carlo simulations in the grand canonical ensemble. Excellent agreement with experiment is achieved for all compounds, with unsigned errors of less than 1% for vapor pressures and normal boiling points and under 5% for heats of vaporization and liquid densities at ambient conditions.

  3. Phase equilibria in fluid mixtures at high pressures - The He-CH4 system.

    Science.gov (United States)

    Streett, W. B.; Erickson, A. L.; Hill, J. L. E.

    1972-01-01

    An experimental study of phase equilibria in the He-CH4 system has been carried out over the temperature range 95 to 290 K and at pressures to 10,000 atm. The experimental results consist of equilibrium phase composition for twenty-eight isotherms in the region of coexistence of two fluid phases, together with the pressure-temperature trace of the three-phase boundary at which a CH4-rich solid phase is in equilibrium with the two fluid phases. The system exhibits a fluid-fluid phase separation which persists to temperatures and pressures beyond the range of this experiment. These findings are relevant to problems of deep atmosphere and interior structures in the outer planets.-

  4. Phase equilibria in fluid mixtures at high pressures: The He-CH4 system

    Science.gov (United States)

    Streett, W. B.; Erickson, A. L.; Hill, J. L. E.

    1972-01-01

    An experimental study of phase equilibria in the He-CH4 system was carried out over the temperature range 95 to 290 K and at pressures to 10,000 atm. The experimental results consist of equilibrium phase composition for twenty-eight isotherms in the region of coexistence of two fluid phases, together with the pressure-temperature trace of the three-phase boundary at which a CH4-rich solid phase is in equilibrium with the two fluid phases. The system exhibits a fluid-fluid phase separation which persists to temperatures and pressures beyond the range of this experiment. These results, together with those recently obtained for other binary systems, provide information about the form of phase diagrams for binary gas mixtures in the region of pressure induced phase transitions at high pressures. These findings are relevant to problems of deep atmosphere and interior structures in the outer planets.

  5. Biomolecular simulations with the transferable potentials for phase equilibria: extension to phospholipids.

    Science.gov (United States)

    Bhatnagar, Navendu; Kamath, Ganesh; Potoff, Jeffrey J

    2013-08-29

    The Transferable Potentials for Phase Equilibria (TraPPE) is extended to zwitterionic and charged lipids including phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylserine (PS), and phosphatidylglycerol (PG). The performance of the force field is validated through isothermal-isobaric ensemble (NPT) molecular dynamics simulations of hydrated lipid bilayers performed with the aforementioned head groups combined with saturated and unsaturated alkyl tails containing 12-18 carbon atoms. The effects of water model and sodium ion parameters on the performance of the lipid force field are determined. The predictions of the TraPPE force field for the area per lipid, bilayer thickness, and volume per lipid are within 1-5% of experimental values. Key structural properties of the bilayer, such as order parameter splitting in the sn-2 chain and X-ray form factors, are found to be in close agreement with experimental data.

  6. Hydration energies of deprotonated amino acids from gas phase equilibria measurements.

    Science.gov (United States)

    Wincel, Henryk

    2008-08-01

    Singly hydrated clusters of deprotonated amino acids were studied using an electrospray high-pressure mass spectrometer equipped with a pulsed ion-beam reaction chamber. Thermochemical data, DeltaH(o), DeltaS(o), and DeltaG(o), for the hydration reaction [AA - H](-) + H(2)O = [AA - H](-).(H(2)O) were obtained from gas-phase equilibria determinations for AA = Gly, Ala, Val, Pro, Phe, Lys, Met, Trp, Gln, Arg, and Asp. The hydration free-energy changes are found to depend significantly on the side-chain substituents. The water binding energy in [AA - H](-).(H(2)O) increases with the gas-phase acidity of AA. The anionic hydrogen bond strengths in [AA - H](-).(H(2)O) are compared with those of the cationic bonds in the corresponding AAH(+).(H(2)O) systems.

  7. Phase equilibria of the magnesium sulfate-water system to 4 kbars

    Science.gov (United States)

    Hogenboom, D. L.; Kargel, J. S.; Ganasan, J. P.; Lee, L.

    1993-01-01

    Magnesium sulfate is the most abundant salt in carbonaceous chondrites, and it may be important in the low-temperature igneous evolution and aqueous differentiation of icy satellites and large chondritic asteroids. Accordingly, we are investigating high-pressure phase equilibria in MgSO4-H2O solutions under pressures up to four kbars. An initial report was presented two years ago. This abstract summarizes our results to date including studies of solutions containing 15.3 percent, 17 percent, and 22 percent MgSO4. Briefly, these results demonstrate that increasing pressure causes the eutectic and peritectic compositions to shift to much lower concentrations of magnesium sulfate, and the existence of a new low-density phase of magnesium sulfate hydrate.

  8. Mie potentials for phase equilibria calculations: application to alkanes and perfluoroalkanes.

    Science.gov (United States)

    Potoff, Jeffrey J; Bernard-Brunel, Damien A

    2009-11-05

    Transferable united-atom force fields, based on n - 6 Lennard-Jones potentials, are presented for normal alkanes and perfluorocarbons. It is shown that by varying the repulsive exponent the range of the potential can be altered, leading to improved predictions of vapor pressures while also reproducing saturated liquid densities to high accuracy. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the vapor liquid coexistence curves, vapor pressures, heats of vaporization, and critical points for normal alkanes methane through tetradecane, and perfluorocarbons perfluoromethane through perfluorooctane. For all molecules studied, saturated liquid densities are reproduced to within 1% of experiment. Vapor pressures for normal alkanes and perfluorocarbons were predicted to within 3% and 6% of experiment, respectively. Calculations performed for binary mixture vapor-liquid equilibria for propane + pentane show excellent agreement with experiment, while slight deviations are observed for the ethane + perfluoroethane mixture.

  9. High-pressure Phase Equilibria for Binary Ethanol System Containing Supercriticai CO2

    Institute of Scientific and Technical Information of China (English)

    朱虎刚; 田宜灵; 陈丽; 秦颖; 冯季军

    2001-01-01

    High-pressure phase behavior of supercritical (SC) CO2+ethanol system was investigated at 333.2 K,348.2K, 353.2K, 368.2K, 413.2K and 453.2K and pressure from 2.0MPa to 14.3MPa. The measurement was carried out in a cylindrical autoclave with a moveable piston and a window for adjustment and observation of phase equilibria at given T and p. The samples were taken from two coexisting phases and were analyzed to obtain their compositions. It is shown that the solubility of SC CO2 in ethanol increases drastically with pressures at the given temperature, but the content of ethanol in CO2-rich phase increase faintly.

  10. Optical trapping by Laguerre-Gaussian beams: Symmetries, stability and equilibria

    CERN Document Server

    Kiselev, Alexei D

    2016-01-01

    We use the T-matrix formalism in combination with the method of far-field matching to evaluate the optical force exerted by Laguerre-Gaussian (LG) light beams on a spherical (Mie) particle. For both non-vortex and optical vortex LG beams, the theoretical results are used to analyze the optical-force-induced dynamics of the scatterer near the trapping points represented by the equilibrium (zero-force) positions. The regimes of linearized dynamics are described in terms of the stiffness matrix spectrum and the damping constant of the ambient medium. For the purely azimuthal LG beams, the dynamics is found to be locally non-conservative and is characterized by the presence of conditionally stable equilibria (unstable zero-force points that can be stabilized by the ambient damping). The effects related to the Mie resonances that under certain conditions manifest themselves as the points changing the trapping properties of the particles are discussed.

  11. On the scarcity of solutions of the equations of magnetohydrodynamic equilibria with flow

    Energy Technology Data Exchange (ETDEWEB)

    Nunez, Manuel [Departamento de Analisis Matematico, Universidad de Valladolid, 47005 Valladolid (Spain)], E-mail: mnjmhd@am.uva.es

    2008-06-16

    While particular analytic solutions to the equations of axisymmetric MHD equilibria with flow are known, it is not clear what possible choosing of the free parameters of the equation of the magnetic flux will yield a solution. The most important of these is the poloidal stream function. We show that for a given flow to be able to yield an equilibrium, the flow itself must satisfy an analogous equation to the generalized Grad-Shafranov one. The problem therefore turns out to be how common are solutions to this type of equations. It is shown that in a natural space of functions, the set of these solutions is contained within a manifold of infinite codimension: extremely small by any criteria. Hence the class of flows for which an equilibrium, even defined only locally and irrespective of boundary conditions, may be found, is highly constrained.

  12. Influence of somatic cell count on mineral content and salt equilibria of milk

    Directory of Open Access Journals (Sweden)

    Primo Mariani

    2010-01-01

    Full Text Available Aim of this research was to study the effect of somatic cell count on mineral content and salt equilibria at the level of quarter milk samples. Ten Italian Friesian cows, in which two homologous quarters (front quarters in 1 cow, rear quarters in 6 cows and both rear and front quarters in 3 cows were characterised by a milk SCC400,000 cells/mL (HC-milk, respectively, were selected. Cows were milked at quarter level during the morning milking and a single sample was collected from each selected quarter, thus, 26 quarter milk samples were collected. Compared to LC-milk, HC-milk was characterised by a lower content of phosphorus and potassium and by a higher content of both sodium and chloride. The equilibrium of calcium, phosphorus and magnesium between the colloidal and soluble phase of milk and the mineralisation degree of the casein micelles, were not different between HC and LC milk.

  13. Stability of Relative Equilibria in the Planar N-Vortex Problem

    CERN Document Server

    Roberts, Gareth E

    2013-01-01

    We study the linear and nonlinear stability of relative equilibria in the planar N-vortex problem, adapting the approach of Moeckel from the corresponding problem in celestial mechanics. After establishing some general theory, a topological approach is taken to show that for the case of positive circulations, a relative equilibrium is linearly stable if and only if it is a nondegenerate minimum of the Hamiltonian restricted to a level surface of the angular impulse (moment of inertia). Using a criterion of Dirichlet's, this implies that any linearly stable relative equilibrium with positive vorticities is also nonlinearly stable. Two symmetric families, the rhombus and the isosceles trapezoid, are analyzed in detail, with stable solutions found in each case.

  14. Semistability of Nonlinear Systems Having a Continuum of Equilibria and Time-Varying Delays

    CERN Document Server

    Hui, Qing

    2010-01-01

    In this paper, we develop a semistability analysis framework for nonlinear systems with time-varying delays with applications to stability analysis of multiagent dynamic networks with consensus protocols in the presence of unknown heterogeneous time-varying delays along the communication links. We show that for such a nonlinear system having a continuum of equilibria, if the system asymptotically converges to a constant time-delay system and this new system is semistable, then the original time-varying delay system is semistable, provided that the delays are just bounded, not necessarily differentiable. In proving our results, we extend the limiting equation approach to the time-varying delay systems and also develop some new convergence results for functional differential equations.

  15. Simulated annealing for three-dimensional low-beta reduced MHD equilibria in cylindrical geometry

    CERN Document Server

    Furukawa, M

    2016-01-01

    Simulated annealing (SA) is applied for three-dimensional (3D) equilibrium calculation of ideal, low-beta reduced MHD in cylindrical geometry. The SA is based on the theory of Hamiltonian mechanics. The dynamical equation of the original system, low-beta reduced MHD in this study, is modified so that the energy changes monotonically while preserving the Casimir invariants in the artificial dynamics. An equilibrium of the system is given by an extremum of the energy, therefore SA can be used as a method for calculating ideal MHD equilibrium. Previous studies demonstrated that the SA succeeds to lead to various MHD equilibria in two dimensional rectangular domain. In this paper, the theory is applied to 3D equilibrium of ideal, low-beta reduced MHD. An example of equilibrium with magnetic islands, obtained as a lower energy state, is shown. Several versions of the artificial dynamics are developed that can effect smoothing.

  16. Effect of pressure on conformational equilibria of liquid 1-chloropropane and 1-bromopropane

    Science.gov (United States)

    Katō, Minoru; Taniguchi, Yoshihiro

    1990-09-01

    The effects of pressure on conformational equilibria of liquid 1-chloropropane and 1-bromopropane has been measured up to 2.5 kbar by Raman spectroscopy. Pressure effects on relative integrated intensities of the carbon-halogen stretching vibration of the two conformers show that both gauche conformers increase when compressed. The volume changes of the trans to the gauche are -1.1±0.2 and -1.2±0.2 cm3 /mol for 1-chloro- and 1-bromopropanes at 20 °C, respectively. The volume changes are mainly due to the solvation volumes as shown from calculation of the van der Waals volumes. The solvation volume cannot be accounted for by the quadrupole-induced electrostatic interactions in liquids. The solvation volume arises from local intermolecular interactions.

  17. Strong and Weak Convergence Criteria of Composite Iterative Algorithms for Systems of Generalized Equilibria

    Directory of Open Access Journals (Sweden)

    Lu-Chuan Ceng

    2014-01-01

    Full Text Available We first introduce and analyze one iterative algorithm by using the composite shrinking projection method for finding a solution of the system of generalized equilibria with constraints of several problems: a generalized mixed equilibrium problem, finitely many variational inequalities, and the common fixed point problem of an asymptotically strict pseudocontractive mapping in the intermediate sense and infinitely many nonexpansive mappings in a real Hilbert space. We prove a strong convergence theorem for the iterative algorithm under suitable conditions. On the other hand, we also propose another iterative algorithm involving no shrinking projection method and derive its weak convergence under mild assumptions. Our results improve and extend the corresponding results in the earlier and recent literature.

  18. Solid—Liquid Equilibria of Several Binary and Ternary Systems Containing Meleic Anhydride

    Institute of Scientific and Technical Information of China (English)

    MAPeisheng; CHENMingming; 等

    2002-01-01

    Solid-liquid equilibria(SLE) of three binary systems and seven ternary systems containing maleic anhydride(MA) are measured by visual method. The experimental data are compared with the calculated ones with modified universal quasichemical functional group activity coefficient(UNIFAC) method in which the interaction parameters between groups come from two sources,dortmund data bank (DDB), if there′s any,and correlations based on our former presented experimental SLE data of twenty binary systems.New groups of MA,ACCOO group,COO group,>C=O group and cy-CH2 group are defined and the SLE data of maleic anhydride in isopropyl acetate in literature are cited in order to assess the new interaction parameters,correlated with Wilson equation and the λh equation.The modified UNIFAC method with these new regressed interaction parameters is also used to predict other three binary systems containing maleic anhydride.

  19. From one-dimensional fields to Vlasov equilibria: Theory and application of Hermite polynomials

    CERN Document Server

    Allanson, O; Troscheit, S; Wilson, F

    2016-01-01

    We consider the theory and application of a solution method for the inverse problem in collisionless equilibria, namely that of calculating a Vlasov-Maxwell equilibrium for a given macroscopic (fluid) equilibrium. Using Jeans' Theorem, the equilibrium distribution functions are expressed as functions of the constants of motion, in the form of a Maxwellian multiplied by an unknown function of the canonical momenta. In this case it is possible to reduce the inverse problem to inverting Weierstrass transforms, which we achieve by using expansions over Hermite polynomials. A sufficient condition on the pressure tensor is found which guarantees the convergence and the boundedness of the candidate solution, when satisfied. This condition is obtained by elementary means, and it is clear how to put it into practice. We also argue that for a given pressure tensor for which our method applies, there always exists a positive distribution function solution for a sufficiently magnetised plasma. Illustrative examples of th...

  20. Power Allocation Games in Interference Relay Channels: Existence Analysis of Nash Equilibria

    CERN Document Server

    Belmega, E V

    2011-01-01

    We consider a network composed of two interfering point-to-point links where the two transmitters can exploit one common relay node to improve their individual transmission rate. Communications are assumed to be multi-band and transmitters are assumed to selfishly allocate their resources to optimize their individual transmission rate. The main objective of this paper is to show that this conflicting situation (modeled by a non-cooperative game) has some stable outcomes, namely Nash equilibria. This result is proved for three different types of relaying protocols: decode-and-forward, estimate-and-forward, and amplify-and-forward. We provide additional results on the problems of uniqueness, efficiency of the equilibrium, and convergence of a best-response based dynamics to the equilibrium. These issues are analyzed in a special case of the amplify-and-forward protocol and illustrated by simulations in general.

  1. Rotational equilibria by Lagrangian variational principle: toward multi-dimensional stellar evolutions

    CERN Document Server

    Yasutake, Nobutoshi; Yamada, Shoichi

    2016-01-01

    We have developed a new formulation to obtain self-gravitating, axisymmetric configurations in permanent rotation. The formulation is based on the Lagrangian variational principle with a triangulated mesh. It treats not only barotropic but also baroclinic equations of state. We compare the various stellar equilibria obtained by our new scheme with those by Hachisu's self-consistent field scheme for the barotropic case, and those by Fujisawa's self-consistent field scheme for the baroclinic case. Included in these rotational configurations are those with shellular-type rotations, which are commonly assumed in the evolution calculation of rotating stars. Although radiation processes, convections and meridional flows have not been taken into account in this study, we have in mind the application of this method to the two-dimensional evolution calculations of rotating stars, for which the Lagrangian formulation is best suited.

  2. MTDATA and the Prediction of Phase Equilibria in Oxide Systems: 30 Years of Industrial Collaboration

    Science.gov (United States)

    Gisby, John; Taskinen, Pekka; Pihlasalo, Jouni; Li, Zushu; Tyrer, Mark; Pearce, Jonathan; Avarmaa, Katri; Björklund, Peter; Davies, Hugh; Korpi, Mikko; Martin, Susan; Pesonen, Lauri; Robinson, Jim

    2017-02-01

    This paper gives an introduction to MTDATA, Phase Equilibrium Software from the National Physical Laboratory (NPL), and describes the latest advances in the development of a comprehensive database of thermodynamic parameters to underpin calculations of phase equilibria in large oxide, sulfide, and fluoride systems of industrial interest. The database, MTOX, has been developed over a period of thirty years based upon modeling work at NPL and funded by industrial partners in a project co-ordinated by Mineral Industry Research Organisation. Applications drawn from the fields of modern copper scrap smelting, high-temperature behavior of basic oxygen steelmaking slags, flash smelting of nickel, electric furnace smelting of ilmenite, and production of pure TiO2 via a low-temperature molten salt route are discussed along with calculations to assess the impact of impurities on the uncertainty of fixed points used to realize the SI unit of temperature, the kelvin.

  3. The vapour-liquid equilibria of several binary systems of fluorocarbons and hydrocarbons. Pt. 2

    Energy Technology Data Exchange (ETDEWEB)

    Kramp, S. [Inst. fuer Physikalische Chemie, Univ. Goettingen (Germany); Wagner, H.G. [Inst. fuer Physikalische Chemie, Univ. Goettingen (Germany)

    1995-06-01

    The vapour-liquid equilibria of the binary systems perfluoromethylcyclohexane-pentafluorobenzene, benzene-pentafluorobenzene, benzene-methylperfluorobutanoate and perfluoromethylcyclohexane-methylperfluorobutanoate have been measured at 333.07 K and 343.12 K using a dynamic circulation still of the Sieg-Roeck type. The thermodynamic consistency of the measurements was tested by two different methods. New UNIFAC interaction parameters [1] were calculated for the following groups: ACH-ACF, ACF-CF{sub 2}, CF{sub 2}-COO, ACCH{sub 2}-ACF, ACH-CF{sub 2}. The abbreviations stand for the following increments: ACH = aromatic CH group, ACF = aromatic CF group, CF{sub 2} = aliphatic CF{sub 2} group, COO = ester group and ACCH{sub 2} = side chain CH group. (orig.)

  4. Kinetic simulations of the lowest-order unstable mode of relativistic magnetostatic equilibria

    CERN Document Server

    Nalewajko, Krzysztof; Yuan, Yajie; East, William E; Blandford, Roger D

    2016-01-01

    We present the results of particle-in-cell numerical pair plasma simulations of relativistic 2D magnetostatic equilibria known as the 'ABC' fields. In particular, we focus on the lowest-order unstable configuration consisting of two minima and two maxima of the magnetic vector potential. Breaking of the initial symmetry leads to exponential growth of the electric energy and to the formation of two current layers, which is consistent with the picture of 'X-point collapse' first described by Syrovatskii. Magnetic reconnection within the layers heats a fraction of particles to very high energies. After the saturation of the linear instability, the current layers are disrupted and the system evolves chaotically, diffusing the particle energies in a stochastic second-order Fermi process leading to the formation of power-law energy distributions. The power-law slopes harden with the increasing mean magnetization, but they are significantly softer than those produced in simulations initiated from Harris-type layers....

  5. Phase Equilibria of Water/CO2 and Water/n-Alkane Mixtures from Polarizable Models.

    Science.gov (United States)

    Jiang, Hao; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2017-02-16

    Phase equilibria of water/CO2 and water/n-alkane mixtures over a range of temperatures and pressures were obtained from Monte Carlo simulations in the Gibbs ensemble. Three sets of Drude-type polarizable models for water, namely the BK3, GCP, and HBP models, were combined with a polarizable Gaussian charge CO2 (PGC) model to represent the water/CO2 mixture. The HBP water model describes hydrogen bonds between water and CO2 explicitly. All models underestimate CO2 solubility in water if standard combining rules are used for the dispersion interactions between water and CO2. With the dispersion parameters optimized to phase compositions, the BK3 and GCP models were able to represent the CO2 solubility in water, however, the water composition in CO2-rich phase is systematically underestimated. Accurate representation of compositions for both water- and CO2-rich phases cannot be achieved even after optimizing the cross interaction parameters. By contrast, accurate compositions for both water- and CO2-rich phases were obtained with hydrogen bonding parameters determined from the second virial coefficient for water/CO2. Phase equilibria of water/n-alkane mixtures were also studied using the HBP water and an exponenial-6 united-atom n-alkanes model. The dispersion interactions between water and n-alkanes were optimized to Henry's constants of methane and ethane in water. The HBP water and united-atom n-alkane models underestimate water content in the n-alkane-rich phase; this underestimation is likely due to the neglect of electrostatic and induction energies in the united-atom model.

  6. Spectroscopic studies on U(VI)-salicylate complex formation with multiple equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Cha, W.; Cho, H.R.; Jung, E.C.; Park, K.K.; Kim, W.H.; Song, K. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of). Nuclear Chemistry Research Div.

    2012-07-01

    This study investigates multiple equilibria related to the formation of the U(VI)-salicylate complex in a pH range of 3.0-5.5 using UV-Vis absorption and fluorescence measurement techniques. The absorbance changes at the characteristic charge-transfer bands of the complex were monitored, and the results indicated the presence of multiple equilibria and the formation of both 1:1 and 1:2 (U(VI):salicylate) complexes possessing bi-dentate chelate structures. The determined step-wise formation constants (log K{sub 1:1} and log K{sub 1:2}) are as follows: 12.5 {+-} 0.1 and 11.4 {+-} 0.2 for salicylate, 11.2 {+-} 0.1 and 10.1 {+-} 0.2 for 5-sulfosalicylate, and 12.4 {+-} 0.1 and 11.4 {+-} 0.1 for 2,6-dihydroxybenzoate, respectively. The molar absorptivities of the complexes are also provided. Furthermore, time-resolved laser-induced luminescence spectra of U(VI) species demonstrate the presence of both a dynamic and static quenching process upon the addition of a salicylate ligand. Particularly for the luminescent hydroxouranyl species, a strong static quenching effect is observed. The results suggest that both the UO{sub 2}(HSal){sup +} and the U(VI)-Sal chelate complexes serve as ground-state complexes that induce static quenching. The Stern-Volmer parameters were derived based on the measured luminescent intensity and lifetime data. The static quenching constants (log K{sub S}) obtained are 3.3 {+-} 0.1, 4.9 {+-} 0.1, and 4.4 {+-} 0.1 for UO{sub 2}{sup 2+}, (UO{sub 2}){sub 2}(OH){sub 2}{sup 2+} and (UO{sub 2}){sub 3}(OH){sub 5}{sup +}, respectively. (orig.)

  7. Chemical Emergencies

    Science.gov (United States)

    When a hazardous chemical has been released, it may harm people's health. Chemical releases can be unintentional, as in the case of an ... the case of a terrorist attack with a chemical weapon. Some hazardous chemicals have been developed by ...

  8. Studies on tautomerism in tetrazole: comparison of Hartree Fock and density functional theory quantum chemical methods

    Science.gov (United States)

    Mazurek, A. P.; Sadlej-Sosnowska, N.

    2000-11-01

    A comparison of the ab initio quantum chemical methods: Hartree-Fock (HF) and hybrid density functional theory (DFT)/B3LYP for the treatment of tautomeric equilibria both in the gas phase and in the solution is made. The solvent effects were investigated in terms of the self-consistent reaction field (SCRF). Ionization potentials (IP), calculated by DFT/B3LYP, are also compared with those calculated previously within the HF frame.

  9. Petrology, phase equilibria and monazite geochronology of granulite-facies metapelites from deep drill cores in the Ordos Block of the North China Craton

    Science.gov (United States)

    He, Xiao-Fang; Santosh, M.; Bockmann, Kiara; Kelsey, David E.; Hand, Martin; Hu, Jianmin; Wan, Yusheng

    2016-10-01

    Among the various Precambrian crustal blocks in the North China Craton (NCC), the geology and evolution of the Ordos Block remain largely enigmatic due to paucity of outcrop. Here we investigate granulite-facies metapelites obtained from deep-penetrating drill holes in the Ordos Block and report petrology, calculated phase equilibria and in-situ monazite LA-ICP-MS geochronology. The rocks we studied are two samples of cordierite-bearing garnet-sillimanite-biotite metapelitic gneisses and one graphite-bearing, two-mica granitic gneiss. The peak metamorphic age from LA-ICP-MS dating of monazite in all three samples is in the range of 1930-1940 Ma. The (U + Pb)-Th chemical ages through EPMA dating reveals that monazite occurring as inclusions in garnet are older than those in the matrix. Calculated metamorphic phase diagrams for the cordierite-bearing metapelite suggest peak P-T conditions ca. 7-9 kbar and 775-825 °C, followed by decompression and evolution along a clockwise P-T path. Our petrologic and age data are consistent with those reported from the Khondalite Belt in the Inner Mongolia Suture Zone in the northern part of the Ordos Block, suggesting that these granulite-facies metasediments represent the largest Paleoproterozoic accretionary belt in the NCC.

  10. An energy stable evolution method for simulating two-phase equilibria of multi-component fluids at constant moles, volume and temperature

    KAUST Repository

    Kou, Jisheng

    2016-02-25

    In this paper, we propose an energy-stable evolution method for the calculation of the phase equilibria under given volume, temperature, and moles (VT-flash). An evolution model for describing the dynamics of two-phase fluid system is based on Fick’s law of diffusion for multi-component fluids and the Peng-Robinson equation of state. The mobility is obtained from diffusion coefficients by relating the gradient of chemical potential to the gradient of molar density. The evolution equation for moles of each component is derived using the discretization of diffusion equations, while the volume evolution equation is constructed based on the mechanical mechanism and the Peng-Robinson equation of state. It is proven that the proposed evolution system can well model the VT-flash problem, and moreover, it possesses the property of total energy decay. By using the Euler time scheme to discretize this evolution system, we develop an energy stable algorithm with an adaptive choice strategy of time steps, which allows us to calculate the suitable time step size to guarantee the physical properties of moles and volumes, including positivity, maximum limits, and correct definition of the Helmhotz free energy function. The proposed evolution method is also proven to be energy-stable under the proposed time step choice. Numerical examples are tested to demonstrate efficiency and robustness of the proposed method.

  11. Progress in study on phase equilibria of salt-water systems%水盐体系相平衡研究进展

    Institute of Scientific and Technical Information of China (English)

    张杰; 史学伟; 赵双良; 宋兴福; 于建国

    2016-01-01

    水盐体系相平衡与相图是无机盐化工的理论基础,对水盐体系相平衡的研究可为盐湖盐类资源的综合开发利用提供理论支持。从水盐体系相平衡实验和理论研究两个方面,综述了近期国内外相关研究进展及研究方法。重点介绍了稳定相平衡和介稳相平衡体系相图测定方法及特点,概述了相区间和结晶类型变化的影响因素;从热力学模型法、统计力学理论和分子模拟3个方面介绍了水盐体系相平衡的理论研究思路及基于液-固化学势平衡的研究现状,并讨论了3类方法在相平衡研究上的可能发展方向。最后总结了该领域的一些研究热点,并对水盐体系相平衡的研究趋势作了展望。%The phase equilibria and phase diagrams of salt-water systems constitute the theoretical basis for chemical industry of inorganic salts. The fundamental studies on the phase equilibrium can provide firm support for the comprehensive development and utilization of salt lake salt resources. In this paper, the recent domestic and international research advances and methods on phase equilibria of slat-water systems from both experimental and theoretical perspectives are summarized. In particular, the experimental methods on the determination of phase diagrams for stable and metastable phase equilibrium systems as well as the factors which cause the change of phase interval and solid crystal type are presented. In addition, based on the up-to-date theoretical methods including thermodynamic models, statistical mechanics theories and computer simulations, the outline of their principles, current situations and possible extensions toward the investigation of stable and metastable phase equilibrium systems are introduced. Finally, the research hotspots in this domain are discussed along with the expectations on the future development.

  12. Relative equilibria of full dynamics of a rigid body with gravitational orbit-attitude coupling in a uniformly rotating second degree and order gravity field

    Science.gov (United States)

    Wang, Yue; Xu, Shijie

    2014-12-01

    The motion of a rigid body in a uniformly rotating second degree and order gravity field is a good model for the gravitationally coupled orbit-attitude motion of a spacecraft in the close proximity of an asteroid. The relative equilibria of this full dynamics model are investigated using geometric mechanics from a global point of view. Two types of relative equilibria are found based on the equilibrium conditions: one is the Lagrangian relative equilibria, at which the circular orbit of the rigid body is in the equatorial plane of the central body; the other is the non-Lagrangian relative equilibria, at which the circular orbit is parallel to but not in the equatorial plane of central body. The existences of the Lagrangian and non-Lagrangian relative equilibria are discussed numerically with respect to the parameters of the gravity field and the rigid body. The effect of the gravitational orbit-attitude coupling is especially assessed. The existence region of the Lagrangian relative equilibria is given on the plane of the system parameters. Numerical results suggest that the negative C 20 with a small absolute value and a negative C 22 with a large absolute value favor the existence of the non-Lagrangian relative equilibria. The effect of the gravitational orbit-attitude coupling of the rigid body on the existence of the non-Lagrangian relative equilibria can be positive or negative, which depends on the harmonics C 20 and C 22, and the angular velocity of the rotation of the gravity field.

  13. Free Energy Minimization Calculation of Complex Chemical Equilibria. Reduction of Silicon Dioxide with Carbon at High Temperature.

    Science.gov (United States)

    Wai, C. M.; Hutchinson, S. G.

    1989-01-01

    Discusses the calculation of free energy in reactions between silicon dioxide and carbon. Describes several computer programs for calculating the free energy minimization and their uses in chemistry classrooms. Lists 16 references. (YP)

  14. Phase equilibria of molecular fluids via hybrid Monte Carlo Wang-Landau simulations: applications to benzene and n-alkanes.

    Science.gov (United States)

    Desgranges, Caroline; Delhommelle, Jerome

    2009-06-28

    In recent years, powerful and accurate methods, based on a Wang-Landau sampling, have been developed to determine phase equilibria. However, while these methods have been extensively applied to study the phase behavior of model fluids, they have yet to be applied to molecular systems. In this work, we show how, by combining hybrid Monte Carlo simulations in the isothermal-isobaric ensemble with the Wang-Landau sampling method, we determine the vapor-liquid equilibria of various molecular fluids. More specifically, we present results obtained on rigid molecules, such as benzene, as well as on flexible chains of n-alkanes. The reliability of the method introduced in this work is assessed by demonstrating that our results are in excellent agreement with the results obtained in previous work on simple fluids, using either transition matrix or conventional Monte Carlo simulations with a Wang-Landau sampling, and on molecular fluids, using histogram reweighting or Gibbs ensemble Monte Carlo simulations.

  15. First principles calculation of L2{sub 1}+A2 coherent equilibria in the Fe-Al-Ti system

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, Paula R., E-mail: pralonso@cnea.gov.a [Departamento de Materiales (GIDAT-CAC), Comision Nacional de Energia Atomica, Avda. General Paz 1499, B1650KNA San Martin, Pcia. Buenos Aires (Argentina); Instituto Sabato, Universidad Nacional de San Martin, Avda. General Paz 1499, B1650KNA San Martin, Pcia. Buenos Aires (Argentina); Gargano, Pablo H. [Departamento de Materiales (GIDAT-CAC), Comision Nacional de Energia Atomica, Avda. General Paz 1499, B1650KNA San Martin, Pcia. Buenos Aires (Argentina); Instituto Sabato, Universidad Nacional de San Martin, Avda. General Paz 1499, B1650KNA San Martin, Pcia. Buenos Aires (Argentina); Ramirez-Caballero, Gustavo E.; Balbuena, Perla B. [Department of Chemical Engineering, Texas A and M University, College Station, TX 77843 (United States); Rubiolo, Gerardo H. [Departamento de Materiales (GIDAT-CAC), Comision Nacional de Energia Atomica, Avda. General Paz 1499, B1650KNA San Martin, Pcia. Buenos Aires (Argentina); Instituto Sabato, Universidad Nacional de San Martin, Avda. General Paz 1499, B1650KNA San Martin, Pcia. Buenos Aires (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnologicas (CONICET), Avda Rivadavia 1917, C1033AAJ Ciudad Autonoma de Buenos Aires (Argentina)

    2009-10-01

    By combining first-principles density functional total energy calculations and statistical mechanics the ground state and the phase equilibria at finite temperatures of the ternary system Fe-Al-Ti have been investigated. Total energy calculations have been performed by means of the Wien 2k code to establish the ground state energetic. A cluster expansion method was therewith used to describe solid solutions. At several chosen finite temperatures the cluster variation method in the irregular tetrahedron approximation was employed in order to calculate the iron rich ternary bcc equilibria. It is confirmed that there are two kinds of phase separations of the bcc phase, A2+L2{sub 1} and B2+L2{sub 1}.

  16. The “maturation” of milk for Parmigiano- Reggiano cheesemaking: effects on mineral equilibria and technological properties

    OpenAIRE

    Mariani, P; Vecchia, P; A. Tambini; Pecorari, M; Franceschi, P.; A. Summer; M. Malacarne; Formaggioni, P.

    2010-01-01

    The “maturation” of milk for Parmigiano-Reggiano cheese is characterised by natural creaming process: the full cream milk is placed in large flat vats, for about 10-12 hours, to obtain the gravity separation of milk fat. The modifications of mineral equilibria and technological properties of milk during the “maturation” phase, were studied. To this aim 24 full cream (FC) milk samples and the corresponding partially skimmed (PS) milk, by natural creaming, were analysed....

  17. Thermodynamic characteristics of acid-base equilibria of DL-α-alanyl-DL-norleucine in aqueous solutions at 298 K

    Science.gov (United States)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Bychkova, S. A.; Skvortsov, I. A.

    2015-09-01

    Protolytic equilibria in aqueous solutions of DL-α-alanyl-DL-norleucine are studied via potentiometry and calorimetry. Measurements are made at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (against a background of potassium nitrate). The thermodynamic characteristics (p K, Δ G, Δ H, Δ S) of the stepwise dissociation of the dipeptide both in aqueous-salt solutions and in standard solution are obtained for the first time.

  18. EXPERIMENTAL PHASE EQUILIBRIA OF SELECTED BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 4. THE PHASE DIAGRAM W-B-C

    Science.gov (United States)

    system and the mutual solubilities between carbide and boride phases are small. The solid state sections (򒾐C) are characterized by two- phase ... equilibria existing between the phase pairs W2B + W2C, W2B + WC, WC + WB, WB + C, W2B5 + C, W2B5 + B4C, and WB approximately 4 + B4C. The two-phase

  19. Isotropic-nematic phase equilibria of hard-sphere chain fluids-Pure components and binary mixtures.

    Science.gov (United States)

    Oyarzún, Bernardo; van Westen, Thijs; Vlugt, Thijs J H

    2015-02-14

    The isotropic-nematic phase equilibria of linear hard-sphere chains and binary mixtures of them are obtained from Monte Carlo simulations. In addition, the infinite dilution solubility of hard spheres in the coexisting isotropic and nematic phases is determined. Phase equilibria calculations are performed in an expanded formulation of the Gibbs ensemble. This method allows us to carry out an extensive simulation study on the phase equilibria of pure linear chains with a length of 7 to 20 beads (7-mer to 20-mer), and binary mixtures of an 8-mer with a 14-, a 16-, and a 19-mer. The effect of molecular flexibility on the isotropic-nematic phase equilibria is assessed on the 8-mer+19-mer mixture by allowing one and two fully flexible beads at the end of the longest molecule. Results for binary mixtures are compared with the theoretical predictions of van Westen et al. [J. Chem. Phys. 140, 034504 (2014)]. Excellent agreement between theory and simulations is observed. The infinite dilution solubility of hard spheres in the hard-sphere fluids is obtained by the Widom test-particle insertion method. As in our previous work, on pure linear hard-sphere chains [B. Oyarzún, T. van Westen, and T. J. H. Vlugt, J. Chem. Phys. 138, 204905 (2013)], a linear relationship between relative infinite dilution solubility (relative to that of hard spheres in a hard-sphere fluid) and packing fraction is found. It is observed that binary mixtures greatly increase the solubility difference between coexisting isotropic and nematic phases compared to pure components.

  20. Performance of predictive models in phase equilibria of complex associating systems: PC-SAFT and CEOS/GE

    OpenAIRE

    Bender, N.; P. B. Staudt; Soares, R.P.; Cardozo,N. S. M.

    2013-01-01

    Cubic equations of state combined with excess Gibbs energy predictive models (like UNIFAC) and equations of state based on applied statistical mechanics are among the main alternatives for phase equilibria prediction involving polar substances in wide temperature and pressure ranges. In this work, the predictive performances of the PC-SAFT with association contribution and Peng-Robinson (PR) combined with UNIFAC (Do) through mixing rules are compared. Binary and multi-component systems involv...

  1. Thermodynamic Modeling of Multi-phase Solid–Liquid Equilibria in Industrial-Grade Oils and Fats

    DEFF Research Database (Denmark)

    Hjorth, Jeppe Lindegaard; Miller, Rasmus L.; Woodley, John M.

    2015-01-01

    Compositional thermodynamic phase separation is investigated for industrial-grade vegetable oils with complex compositions. Solid–liquid equilibria have been calculated by utilizing the Margules 2-suffix activity-coefficient model in combination with minimization of the Gibb’s free energy of the ...... because many different oil mixtures can be evaluated quickly with respect to specific properties, prior to more time-consuming experimental evaluation....

  2. Isobaric (vapor + liquid) equilibria of 1-ethyl-3-methylimidazolium ethylsulfate plus (propionaldehyde or valeraldehyde): Experimental data and prediction

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez, Victor H. [School of Chemical Engineering, University of Campinas (UNICAMP), Av. Albert Einstein 500, 13083-852 Campinas, SP (Brazil); Mattedi, Silvana [Chemical Engineering Department, Polytechnic School, Federal University of Bahia (UFBA), R. Aristides Novis 2, 40210-630 Salvador, BA (Brazil); Aznar, Martin, E-mail: maznar@feq.unicamp.b [School of Chemical Engineering, University of Campinas (UNICAMP), Av. Albert Einstein 500, 13083-852 Campinas, SP (Brazil)

    2011-06-15

    Research highlights: We report density, refraction index, and VLE for (propionaldehyde or valeraldehyde) + [emim][EtSO{sub 4}]. The Peng-Robinson + Wong-Sandler + COSMO-SAC model was used to predict density and VLE. The densities were predicted with deviations below than 2.3%. The experimental VLE was predicted with deviations below than 1.6%. - Abstract: This paper reports the density, refraction index, and (vapor + liquid) equilibria (VLE) for binary systems {l_brace}aldehyde + 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO{sub 4}]){r_brace}: {l_brace}propionaldehyde + [emim][EtSO{sub 4}]{r_brace} and {l_brace}valeraldehyde + [emim][EtSO{sub 4}]{r_brace}. The uncertainties for the temperature, pressure, and compositions measurements for the phase equilibria are {+-}0.1 K, {+-}0.01 kPa and {+-}0.0004, respectively. A qualitative analysis of the variation of the properties with changes in solvent and temperature was performed. The Peng-Robinson equation of state (PR EoS), coupled with the Wong-Sandler mixing rule (WS), is used to describe the experimental data. To calculate activity coefficients we used three different models: NRTL, UNIQUAC, and COSMO-SAC. Since the predictive liquid activity coefficient model COSMO-SAC is used in the Wong-Sandler mixing rule, the resulting thermodynamic model is a completely predictive one. The prediction results for the density and for the (vapor + liquid) equilibria have a deviation lower than 2.3% and 1.6%, respectively. The (vapor + liquid) equilibria predictions show a good description for the propionaldehyde system and only a qualitative description for the valeraldehyde system.

  3. Petrogenesis of Mt. Baker basalts (Cascade arc): Constraints from thermobarometry, phase equilibria, trace elements and isotopes

    Science.gov (United States)

    Mullen, E. K.; McCallum, I. S.

    2010-12-01

    Primitive arc basalts provide information on sub-arc mantle compositions and processes. The relative abundance of basalts in the Cascade arc decreases northward, and basalts are rare in the most northerly segment of the arc (Garibaldi belt) where the Mt. Baker volcanic field (MBVF) is located. Following reconstruction of the compositions of the primary basalts at MBVF (olivine addition ± plag subtraction), we have applied phase equilibria and forward-modeled trace element abundances and isotope ratios to obtain petrogenetic constraints. The most primitive lavas are the Sulphur Cr, Lk Shannon, and Park Butte basalts and the Hogback, Tarn Plateau, and Cathedral Crag basaltic andesites, ranging from 716 to 10 ka. Most erupted peripheral to the major centers. Spinel/olivine and Fe-Ti oxide oxybarometry indicate redox states of ~QFM + 1 corresponding to Fe3+/ΣFe = 0.20. Mg# ranges from 51 to 71. The lavas are medium-K and similar to calc-alkaline basalts and high-Mg basaltic andesites from the High Cascades. MBVF basalts have higher MgO and lower CaO and Al2O3 than typical CAB and HAOT, grading to alkalic compositions with TiO2 and Na2O of up to 1.65 and 5.4 wt%, respectively (Sulphur Cr). Phenocryst contents are 5 to 33% (plag + olivine ± cpx) and the lavas are holo- or hypocrystalline with glass contents of up to 15%. The whole rocks are close to equilibrium with olivine cores (range Fo 87-68). Plagioclase cores range from An 88-68. Reconstructed primary basalt compositions give liquidus T and P values (from olivine-liquid equilibria and silica activities) ranging from 1280°C and 1 GPa (Tarn Plateau) to 1350°C and 1.4 GPa (Sulphur Cr), corresponding to the upper mantle above the core of the mantle wedge. These estimates take into account the 1 to 3 wt% initial H2O contents of the basalts calculated using plagioclase cores. Phase equilibria of the primary basalts indicate a similar pressure range of 1-2 GPa and indicate a residual mantle assemblage of harzburgite

  4. The Influenza M2 Ectodomain Regulates the Conformational Equilibria of the Transmembrane Proton Channel: Insights from Solid-State Nuclear Magnetic Resonance.

    Science.gov (United States)

    Kwon, Byungsu; Hong, Mei

    2016-09-27

    The influenza M2 protein is the target of the amantadine family of antiviral drugs, and its transmembrane (TM) domain structure and dynamics have been extensively studied. However, little is known about the structure of the highly conserved N-terminal ectodomain, which contains epitopes targeted by influenza vaccines. In this study, we synthesized an M2 construct containing the N-terminal ectodomain and the TM domain, to understand the site-specific conformation and dynamics of the ectodomain and to investigate the effect of the ectodomain on the TM structure. We incorporated (13)C- and (15)N-labeled residues into both domains and measured their chemical shifts and line widths using solid-state nuclear magnetic resonance. The data indicate that the entire ectodomain is unstructured and dynamic, but the motion is slower for residues closer to the TM domain. (13)C line shapes indicate that this ecto-TM construct undergoes fast uniaxial rotational diffusion, like the isolated TM peptide, but drug binding increases the motional rates of the TM helix while slowing the local motion of the ectodomain residues that are close to the TM domain. Moreover, (13)C and (15)N chemical shifts indicate that the ectodomain shifts the conformational equilibria of the TM residues toward the drug-bound state even in the absence of amantadine, thus providing a molecular structural basis for the lower inhibitory concentration of full-length M2 compared to that of the ectodomain-truncated M2. We propose that this conformational selection may result from electrostatic repulsion between negatively charged ectodomain residues in the tetrameric protein. Together with the recent study of the M2 cytoplasmic domain, these results show that intrinsically disordered extramembrane domains in membrane proteins can regulate the functionally relevant conformation and dynamics of the structurally ordered TM domains.

  5. Measurement and modeling of high-pressure (vapor + liquid) equilibria of (CO{sub 2} + alkanol) binary systems

    Energy Technology Data Exchange (ETDEWEB)

    Bejarano, Arturo; Gutierrez, Jorge E. [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Araus, Karina A. [Departamento de Ingenieria Quimica y Bioprocesos, Pontificia Universidad Catolica de Chile, Avda. Vicuna Mackenna 4860, Macul, Santiago (Chile); Fuente, Juan C. de la, E-mail: juan.delafuente@usm.c [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Centro Regional de Estudios en Alimentos Saludables, Blanco 1623, Valparaiso (Chile)

    2011-05-15

    Research highlights: (Vapor + liquid) equilibria of three (CO{sub 2} + C{sub 5} alcohol) binary systems were measured. Complementary data are reported at (313, 323 and 333) K and from (2 to 11) MPa. No liquid immiscibility was observed at the temperatures and pressures studied. Experimental data were correlated with the PR-EoS and the van de Waals mixing rules. Correlation results showed relative deviations {<=}8 % (liquid) and {<=}2 % (vapor). - Abstract: Complementary isothermal (vapor + liquid) equilibria data are reported for the (CO{sub 2} + 3-methyl-2-butanol), (CO{sub 2} + 2-pentanol), and (CO{sub 2} + 3-pentanol) binary systems at temperatures of (313, 323, and 333) K, and at pressure range of (2 to 11) MPa. For all (CO{sub 2} + alcohol) systems, it was visually monitored that there was no liquid immiscibility at the temperatures and pressures studied. The experimental data were correlated with the Peng-Robinson equation of state using the quadratic mixing rules of van der Waals with two adjustable parameters. The calculated (vapor + liquid) equilibria compositions were found to be in good agreement with the experimental data with deviations for the mole fractions <8% and <2% for the liquid and vapor phase, respectively.

  6. A THEORETICAL STUDY ON THE MULTIPLE EQUILIBRIA OF TROPICAL ATMOSPHERE AND THEIR RELATION TO THE ONSET OF THE SUMMER MONSOON

    Institute of Scientific and Technical Information of China (English)

    ZHAO Nan; DING Yi-hui; Masaaki Takahashi; SHEN Xin-yong

    2006-01-01

    Multiple equilibria and their stability in tropical atmosphere are investigated through β -plane barotropic models with consideration of heating and dissipation. We have derived the solutions of the model equations corresponding to the multiple equilibria or the steady flows first, and then establish the criteria for the stability of steady flow by use of the Liapunov direct Method. When these criteria are applied to the solutions of equilibria obtained, stable flows, which are closely related to the different patterns of quasi-stationary circulation in the tropical region, are found. The configurations of these stable flows and the shift between two of them as season changes provide quite reasonable explanations to many fundamental problems of tropical circulation features such as the catastrophe mechanism of the onset and the break-active cycle of the Asian summer monsoon. It follows that the onset or the abrupt transition of the Asian summer monsoon could be attributed to the multiple equilibrium property of the tropical circulation resulted from the advective nonlinearity, which provide another explanation among others.

  7. Measurement and modeling of high-pressure (vapour + liquid) equilibria of (CO{sub 2} + alcohol) binary systems

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, Jorge E.; Bejarano, Arturo [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Fuente, Juan C. de la, E-mail: juan.delafuente@usm.c [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Centro Regional de Estudios en Alimentos Saludables, Blanco 1623, Valparaiso (Chile)

    2010-05-15

    An apparatus based on a static-analytic method assembled in this work was utilized to perform high pressure (vapour + liquid) equilibria measurements with uncertainties estimated at <5%. Complementary isothermal (vapour + liquid) equilibria results are reported for the (CO{sub 2} + 1-propanol), (CO{sub 2} + 2-methyl-1-propanol), (CO{sub 2} + 3-methyl-1-butanol), and (CO{sub 2} + 1-pentanol) binary systems at temperatures of (313, 323, and 333) K, and at pressure range of (2 to 12) MPa. For all the (CO{sub 2} + alcohol) systems, it was visually monitored to insure that there was no liquid immiscibility at the temperatures and pressures studied. The experimental results were correlated with the Peng-Robinson equation of state using the quadratic mixing rules of van der Waals with two adjustable parameters. The calculated (vapour + liquid) equilibria compositions were found to be in good agreement with the experimental values with deviations for the mol fractions <0.12 and <0.05 for the liquid and vapour phase, respectively.

  8. High-pressure phase equilibria for the carbon dioxide + 3-pentanol and carbon dioxide + 3-pentanol + water systems

    Energy Technology Data Exchange (ETDEWEB)

    Lee, H.S.; Mun, S.Y.; Lee, H. [Korea Advanced Inst. of Science and Technology, Taejon (Korea, Republic of). Dept. of Chemical Engineering

    1999-05-01

    High-pressure vapor-liquid equilibria for the binary carbon dioxide + 3-pentanol system were measured at 313.2 K. The phase equilibrium apparatus used in this work was of the circulation type in which the coexisting phases were recirculated, on-line sampled, and analyzed. The critical pressure and corresponding mole fraction of carbon dioxide at 313.2 K were found to be 8.22 MPa and 0.974, respectively, for this binary system. The phase equilibria for the ternary carbon dioxide + 3-pentanol + water system were also measured at 313.2 K and pressures of 2.00, 4.00, 6.00, 8.00, and 8.25 MPa. This ternary system showed the liquid-liquid-vapor (LLV) phase behavior over the range of pressure up to the critical pressure of 8.25 MPa. The binary equilibrium data were all reasonably well-correlated with the Redlich-Kwong, Soave-Redlich-Kwong, Peng-Robinson, and Patel-Teja equations of state incorporated with the eight different mixing rules: the van der Waals, Panagiotopoulos-Reic, and six modified Huron-Vidal mixing rules with UNIQUAC parameters. For the prediction of high-pressure phase equilibria for the systems containing carbon dioxide and alcohols, the SRK-MHV2 might reproduce many features of the measured behavior although further tests are needed with other systems.

  9. Use of reconstructed 3D VMEC equilibria to match effects of toroidally rotating discharges in DIII-D

    Science.gov (United States)

    Wingen, A.; Wilcox, R. S.; Cianciosa, M. R.; Seal, S. K.; Unterberg, E. A.; Hanson, J. M.; Hirshman, S. P.; Lao, L. L.; Logan, N. C.; Paz-Soldan, C.; Shafer, M. W.

    2017-01-01

    A technique for tokamak equilibrium reconstructions is used for multiple DIII-D discharges, including L-mode and H-mode cases when weakly 3D fields ≤ft(δ B/B˜ {{10}-3}\\right) are applied. The technique couples diagnostics to the non-linear, ideal MHD equilibrium solver VMEC, using the V3FIT code, to find the most likely 3D equilibrium based on a suite of measurements. It is demonstrated that V3FIT can be used to find non-linear 3D equilibria that are consistent with experimental measurements of the plasma response to very weak 3D perturbations, as well as with 2D profile measurements. Observations at DIII-D show that plasma rotation larger than 20 krad s-1 changes the relative phase between the applied 3D fields and the measured plasma response. Discharges with low averaged rotation (10 krad s-1) and peaked rotation profiles (40 krad s-1) are reconstructed. Similarities and differences to forward modeled VMEC equilibria, which do not include rotational effects, are shown. Toroidal phase shifts of up to {{30}\\circ} are found between the measured and forward modeled plasma responses at the highest values of rotation. The plasma response phases of reconstructed equilibra on the other hand match the measured ones. This is the first time V3FIT has been used to reconstruct weakly 3D tokamak equilibria.

  10. Effect of Resonant Magnetic Perturbations on 3D equilibria in the MST RFP

    Science.gov (United States)

    Munaretto, Stefano

    2015-11-01

    The orientation of 3D, stellarator-like equilibria in the MST RFP can now be controlled with application of an m = 1 RMP. This has led to greatly improved diagnosis, revealing enhancements in both the central electron temperature and density. Coupled to a recent advance in the V3FIT code, reconstructions of the 3D equilibria have also been dramatically improved. The RMP also inhibits the generation of high-energy >20 keV electrons that is otherwise common with the 3D state. This state occurs when the normally broad spectrum of core-resonant m = 1 tearing modes condenses, with the innermost resonant mode growing to large amplitude, reaching ~ 8% of the axisymmetric field strength. This occurs in plasmas of sufficiently large Lundquist number ~ IpTe3/2, and the duration of the state is maximized with zero applied Bt (infinite toroidal beta). As the dominant mode grows, eddy current in MST's conducting shell slows the mode's rotation. This leads to locking of the 3D structure, but with an orientation that varies randomly shot to shot, making diagnosis difficult. An m = 1 RMP can now be applied with an array of saddle coils at the vertical insulated cut in the shell. With an amplitude br/B ~ 10% and a tailored temporal waveform, the RMP can force the 3D structure into any desired orientation relative to MST's diagnostics. A recent advance in V3FIT allows calculation of the substantial helical image current flowing in MST's shell, which has in turn allowed self-consistent utilization of both external and internal (Faraday rotation) measurements of the magnetic field. The ORBIT code predicts reduced stochasticity and improved confinement of high-energy electrons within the 3D structure. The suppression of these electrons by the m = 1 RMP may reflect a change to the central magnetic topology. The generation of these electrons is unaffected by non-resonant perturbations, such as m = 3. Supported by the US DOE.

  11. Chemical reactions confined within carbon nanotubes.

    Science.gov (United States)

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N

    2016-08-22

    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors.

  12. Thermodynamic models for vapor-liquid equilibria of nitrogen + oxygen + carbon dioxide at low temperatures

    Science.gov (United States)

    Vrabec, Jadran; Kedia, Gaurav Kumar; Buchhauser, Ulrich; Meyer-Pittroff, Roland; Hasse, Hans

    2009-02-01

    For the design and optimization of CO 2 recovery from alcoholic fermentation processes by distillation, models for vapor-liquid equilibria (VLE) are needed. Two such thermodynamic models, the Peng-Robinson equation of state (EOS) and a model based on Henry's law constants, are proposed for the ternary mixture N 2 + O 2 + CO 2. Pure substance parameters of the Peng-Robinson EOS are taken from the literature, whereas the binary parameters of the Van der Waals one-fluid mixing rule are adjusted to experimental binary VLE data. The Peng-Robinson EOS describes both binary and ternary experimental data well, except at high pressures approaching the critical region. A molecular model is validated by simulation using binary and ternary experimental VLE data. On the basis of this model, the Henry's law constants of N 2 and O 2 in CO 2 are predicted by molecular simulation. An easy-to-use thermodynamic model, based on those Henry's law constants, is developed to reliably describe the VLE in the CO 2-rich region.

  13. A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways.

    Science.gov (United States)

    Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

    2009-12-15

    Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann's approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thus possible equilibrium precipitation pathways can be evaluated by calculating the evolution of surface charge, particle size and/or interfacial energy during the ongoing reaction. The approach includes the use of the Kelvin's law to express the influence of particle size on the solubility constant of precipitates, the use of Nernst's law to calculate surface potentials from solubility calculations and relate this to experimentally measured zeta potentials. Calcium carbonate precipitation and zeta potential measurements of well characterised high purity calcite have been used as a model system to validate the calculated values. The clarification of the change in zeta potential on titration illustrates the power of this approach as a tool for reaction pathway prediction and hence knowledge based tailoring of precipitation reactions.

  14. Kinetic Simulations of the Lowest-order Unstable Mode of Relativistic Magnetostatic Equilibria

    Science.gov (United States)

    Nalewajko, Krzysztof; Zrake, Jonathan; Yuan, Yajie; East, William E.; Blandford, Roger D.

    2016-08-01

    We present the results of particle-in-cell numerical pair plasma simulations of relativistic two-dimensional magnetostatic equilibria known as the “Arnold-Beltrami-Childress” fields. In particular, we focus on the lowest-order unstable configuration consisting of two minima and two maxima of the magnetic vector potential. Breaking of the initial symmetry leads to exponential growth of the electric energy and to the formation of two current layers, which is consistent with the picture of “X-point collapse” first described by Syrovatskii. Magnetic reconnection within the layers heats a fraction of particles to very high energies. After the saturation of the linear instability, the current layers are disrupted and the system evolves chaotically, diffusing the particle energies in a stochastic second-order Fermi process, leading to the formation of power-law energy distributions. The power-law slopes harden with the increasing mean magnetization, but they are significantly softer than those produced in simulations initiated from Harris-type layers. The maximum particle energy is proportional to the mean magnetization, which is attributed partly to the increase of the effective electric field and partly to the increase of the acceleration timescale. We describe in detail the evolving structure of the dynamical current layers and report on the conservation of magnetic helicity. These results can be applied to highly magnetized astrophysical environments, where ideal plasma instabilities trigger rapid magnetic dissipation with efficient particle acceleration and flares of high-energy radiation.

  15. Phase equilibria in the Ti-rich corner of the Ti-Si-Al system

    Energy Technology Data Exchange (ETDEWEB)

    Bulanova, M. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Problem Materialovedeniya; Tretyachenko, L. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Problem Materialovedeniya; Golovkova, M. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Problem Materialovedeniya

    1997-03-01

    By the methods of differential thermal, X-ray, microscopy and electron microprobe analysis phase equilibria in the Ti-rich corner of the Ti-Si-Al system were studied. Projections of solidus and liquidus surfaces as well as an isothermal section at 1300 C were constructed. It was shown that at the solidus and 1300 C Ti{sub 5} (Si,Al){sub 3} (Z) phase coexists with all of the Ti-Al-based phases, resulting in wide two-phase ({beta} + Z, {alpha} + Z, {gamma} + Z) and narrow three-phase ({alpha} + {beta} + Z, {alpha} + {gamma} + Z) regions. The last two ones result from invariant four-phase peritectic and eutectic reactions, respectively. Coordinates of peritectic (U{sub 1}) and eutectic (E) points were determined to be: U{sub 1} - 1420 C, {approx}49Ti-4Si-47Al; E-1415 C, 48Ti-4Si-48Al. The solidus surface has its temperature maximum at 1545 C corresponding to the invariant pseudobinary eutectic L <=> {beta} + Z with eutectic point at 65Ti-8Si-27Al. The isopleth at 10 at.% Si is given. The shape of the Ti{sub 5} (Si,Al){sub 3} homogeneity range is discussed. (orig.)

  16. DETERMINATION OF SOLID-LIQUID EQUILIBRIA DATA FOR MIXTURES OF HEAVY HYDROCARBONS IN A LIGHT SOLVENT

    Energy Technology Data Exchange (ETDEWEB)

    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. Study of extended MHD effects on interchange modes in spheromak equilibria

    Science.gov (United States)

    Howell, E. C.; Sovinec, C. R.

    2014-10-01

    A study of extended MHD effects on linear interchange modes is performed using the NIMROD code [Sovinec & King JCP 2010]. A linear cylindrical equilibrium model is adapted from [Jardin NF 1982] to allow finite toroidal current at the edge. These equilibria are representative of SSPX discharges where currents are driven on the open field to keep the safety factor above 1/2 across the profile [McLean et al., POP 2006]. These spheromaks have weak magnetic shear, and interchange stability is an important consideration. The Suydam parameter, D, is scaled to study resistive and ideal interchange modes. The calculated MHD growth rate increases with D. The resistive interchange scaling γ ~η 1 / 3 is observed for D <1/4 . Calculations using the full extended MHD model are performed for a range of hall parameters Λ. This model includes gyro-viscosity, the hall term, equilibrium diamagnetic flows, and the cross-field diamagnetic heat flux. Two fluid effects in the full model are always destabilizing at large Λ. However, some cases exhibit a range of Λ where the growth rate for the full model is reduced relative to the MHD growth rate. Work supported by US DOE.

  18. Phase Equilibria of the Fe-Ni-Sn Ternary System at 270°C

    Science.gov (United States)

    Huang, Tzu-Ting; Lin, Shih-Wei; Chen, Chih-Ming; Chen, Pei Yu; Yen, Yee-Wen

    2016-12-01

    The Fe-42 wt.% Ni alloy, also known as a 42 invar alloy (Alloy 42), is used as a lead-frame material because its thermal expansion coefficient is much closer to Si substrate than Cu or Ni substrates. In order to enhance the wettability between the substrate and solder, the Sn layer was commonly electroplated onto the Alloy 42 surface. A clear understanding of the phase equilibria of the Fe-Ni-Sn ternary system is necessary to ensure solder-joint reliability between Sn and Fe-Ni alloys. To determine the isothermal section of the Fe-Ni-Sn ternary system at 270°C, 26 Fe-Ni-Sn alloys with different compositions were prepared. The experimental results confirmed the presence of the Fe3Ni and FeNi phases at 270°C. Meanwhile, it observed that the isothermal section of the Fe-Ni-Sn ternary system was composed of 11 single-phase regions, 19 two-phase regions and nine tie-triangles. Moreover, no ternary compounds were found in the Fe-Ni-Sn system at 270°C.

  19. Phase equilibria of haloalkanes dissolved in ethylsulfate- or ethylsulfonate-based ionic liquids.

    Science.gov (United States)

    Deive, Francisco J; Rodríguez, Ana; Pereiro, Ana B; Shimizu, Karina; Forte, Paulo A S; Romão, Carlos C; Canongia Lopes, José N; Esperança, José M S S; Rebelo, Luís P N

    2010-06-03

    The temperature-composition phase diagrams of 40 binary mixtures composed of a haloalkane dissolved in either 1-ethyl-3-methylimidazolium ethylsulfate or 1-ethyl-3-methylimidazolium ethylsulfonate were measured from ambient temperature to the boiling point temperature of the solute. The coexistence curves corresponding to liquid-liquid equilibria (LLE) boundaries were visually determined and the experimental results have been correlated using either the nonrandom two-liquid (NRTL) model or a set of empirical equations capable of describing the corresponding upper critical solution temperatures (UCSTs) loci. The different types of LLE behavior were discussed in terms of the type of ionic liquid solvent, the alkyl-chain length of the solute, and the type and pattern of halogen substitution present in the haloalkane. Auxiliary simulation data (obtained by ab initio or by molecular dynamics methods) were used to corroborate some of the experimental findings. Also, they correlate in a semiquantitative way the observed LLE behavior with the dipole moments of the different solutes.

  20. Phase equilibria of the Sn–Si–Ti system at 900 and 1200 °C

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ya; Dong, Zhen; Peng, Haoping; Wu, Changjun; Wang, Jianhua; Su, Xuping, E-mail: sxping@cczu.edu.cn

    2015-09-05

    Highlights: • The isothermal sections of the Sn–Si–Ti system at 900 and 1200 °C were determined. • Ternary intermediate phase τ, with a tetragonal W{sub 5}Si{sub 3}-type structure, can be stable up to at least 1200 °C. • Eleven three-phase equilibria were determined at each temperature. - Abstract: Phase relations in the ternary Sn–Si–Ti system were established for the whole composition range for two temperatures, 900 and 1200 °C, by X-ray powder diffraction, scanning electron microscopy and energy dispersive spectroscopic. The results indicate that the previously reported compound τ is the only ternary intermediate phase, which can be stable up to at least 1200 °C and remains a tetragonal W{sub 5}Si{sub 3}-type structure. No Si solubility was found in Ti{sub 6}Sn{sub 5} phase, and no Sn solubility was found in the Si–Ti binary phases except for Ti{sub 5}Si{sub 3} at either temperature.

  1. Experimental investigation and thermodynamic assessment of phase equilibria in the Nb–Si–Zr ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Li, J.; Guo, Y.H. [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China); Yang, S.Y.; Shi, Z.; Wang, C.P. [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China); Research Center of Materials Design and Applications, Xiamen University, Xiamen 361005 (China); Liu, X.J., E-mail: lxj@xmu.edu.cn [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China); Research Center of Materials Design and Applications, Xiamen University, Xiamen 361005 (China)

    2015-09-05

    Highlights: • The sections of Nb–Si–Zr system at 1373, 1473 and 1573 K were determined. • Large solubilities of Nb in αZr{sub 5}Si{sub 4}, Zr{sub 3}Si{sub 2} and Zr{sub 2}Si phases were observed. • The thermodynamic assessment of Nb–Si–Zr ternary system was carried out. - Abstract: In this study, the phase equilibria of Nb–Si–Zr at 1373 K, 1473 K and 1573 K were experimentally determined by means of back-scattered electron (BSE), electron probe microanalysis (EPMA) and X-ray diffraction (XRD). The results show that there were five three-phase regions and sixteen two-phase regions in the studied isothermal sections, and no any ternary compounds were found. The solubility of Si in the Nb–Zr side is very small. Large solubilities of Nb in αZr{sub 5}Si{sub 4}, Zr{sub 3}Si{sub 2} and Zr{sub 2}Si phases were observed, otherwise the solubilities of Nb in ZrSi{sub 2}, αZrSi and Zr{sub 3}Si phases are relatively small. Based on the present experimental results, the thermodynamic assessment of Nb–Si–Zr system was carried out using the CALPHAD (Calculation of Phase Diagrams) method. The current calculated phase diagrams are in reasonable agreement with the present experimental data.

  2. Phase equilibria in the ternary In-Ni-Sn system at 700 °C.

    Science.gov (United States)

    Schmetterer, C; Zemanova, A; Flandorfer, H; Kroupa, A; Ipser, H

    2013-04-01

    The phase equilibria of the ternary system In-Ni-Sn were investigated experimentally at 700 °C using X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron micro probe analysis (EMPA) and energy dispersive X-ray spectroscopy (EDX). A corresponding isothermal section was established based on these results. This particular temperature was chosen because it allowed obtaining reliable results within reasonable time. The existence of the ternary phase InNi6Sn5 was confirmed whereas the ternary compound In2NiSn, reported earlier in literature, was found to be part of a large solid solution field based on binary InNi. The ternary solubility of the binary phases was established, and continuous solid solutions were found between the isostructural phases Ni3Sn LT and InNi3 as well as between Ni3Sn2 HT and InNi2. In addition, this isothermal section could be well reproduced by CALPHAD modelling. The resulting calculated isotherm at 700 °C is presented, too, and compared with the experimental results.

  3. Phase equilibria and modeling of ammonium ionic liquid, C2NTf2, solutions.

    Science.gov (United States)

    Domańska, Urszula; Marciniak, Andrzej; Królikowski, Marek

    2008-01-31

    Novel quaternary ammonium ionic liquid, ethyl(2-hydroxyethyl)dimethylammonium bis(trifluomethylsulfonyl)imide (C2NTf2), has been prepared from N,N-dimethylethanolamine as a substrate. The paper includes a specific basic characterization of the synthesized compound by NMR and the basic thermophysical properties: the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition determined by the differential scanning calorimetry (DSC), temperature of decomposition, and water content. The density of the new compound was measured. The solid-liquid or liquid-liquid phase equilibria of binary mixtures containing {C2NTf2+water or an alcohol (propan-1-ol, butan-1-ol, hexan-1-ol, octan-1-ol, decan-1-ol), aromatic hydrocarbons (benzene, toluene), aliphatic hydrocarbons (n-hexane, n-octane), dimethylsulfoxide (DMSO), or tetrahydrofuran (THF)} have been measured by a dynamic method in a wide range of temperatures from 230 to 430 K. These data were correlated by means of the nonrandom two-liquid (NRTL) equation utilizing temperature-dependent parameters derived from the solid-liquid or liquid-liquid equilibrium. From the solubility results, the negative value of the partition coefficient of ionic liquid in binary system octan-1-ol/water (log P) at 298.15 K has been calculated.

  4. New Computational Approach to Determine Liquid-Solid Phase Equilibria of Water Confined to Slit Nanopores.

    Science.gov (United States)

    Kaneko, Toshihiro; Bai, Jaeil; Yasuoka, Kenji; Mitsutake, Ayori; Zeng, Xiao Cheng

    2013-08-13

    We devise a new computational approach to compute solid-liquid phase equilibria of confined fluids. Specifically, we extend the multibaric-multithermal ensemble method with an anisotropic pressure control to achieve the solid-liquid phase equilibrium for confined water inside slit nanopores (with slit width h ranging from 5.4 Å to 7.2 Å). A unique feature of this multibaric-multithermal ensemble is that the freezing points of confined water can be determined from the heat-capacity peaks. The new approach has been applied to compute the freezing point of two monolayer ices, namely, a high-density flat rhombic monolayer ice (HD-fRMI) and a high-density puckered rhombic monolayer ice (HD-pRMI) observed in our simulation. We find that the liquid-to-solid transition temperature (or the freezing point) of HD-pRMI is dependent on the slit width h, whereas that of HD-fRMI is nearly independent of the h.

  5. Postperovskite phase equilibria in the MgSiO3-Al2O3 system.

    Science.gov (United States)

    Tsuchiya, Jun; Tsuchiya, Taku

    2008-12-09

    We investigate high-P,T phase equilibria of the MgSiO(3)-Al(2)O(3) system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh(2)O(3)(II) phase, present calculations demonstrate that (i) dissolving Al(2)O(3) tends to decrease the postperovskite transition pressure of MgSiO(3) but the effect is not significant ( approximately -0.2 GPa/mol% Al(2)O(3)); (ii) Al(2)O(3) produces the narrow perovskite+postperovskite coexisting P,T area (approximately 1 GPa) for the pyrolitic concentration (x(Al2O3) approximately 6 mol%), which is sufficiently responsible to the deep-mantle D'' seismic discontinuity; (iii) the transition would be smeared (approximately 4 GPa) for the basaltic Al-rich composition (x(Al2O3) approximately 20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh(2)O(3)(II) with increasing the Al concentration involving small displacements of the Mg-site cations.

  6. Experimental investigation of the phase equilibria in the Co-Fe-Ti ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Chaohui; Chen, Chong; Peng, Yingbiao; Du, Yong; Li, Kun [Central South Univ., State Key of Powder Metallurgy, Changsha (China); Lu, Xingxu [Central South Univ., State Key of Powder Metallurgy, Changsha (China); Central South Univ., School of Materials Science and Engineering, Changsha (China)

    2015-08-15

    Phase equilibria in the Co-Fe-Ti ternary system were investigated by means of the equilibrated alloy method with X-ray powder diffraction and electron probe microanalysis. No ternary compounds were found. The experimental results indicated the existence of seven two-phase and one three-phase regions at 600 C, five two-phase and two three-phase regions at 800 C, and six two-phase and two three-phase regions at 950 C. The solubility of Co in TiFe{sub 2} was determined to be larger than 54 at.% at all investigated temperatures, and the solubilities of Fe in TiCo{sub 3} and Ti{sub 2}Co showed an appreciable increase with increasing temperature. The three-phase equilibrium in the Ti-rich corner at 800 C was revealed to be ((β-Ti) + Ti(Fe, Co) + Ti{sub 2}Co) rather than ((α-Ti) + Ti(Fe, Co) + Ti{sub 2}Co) reported in previous investigations. Based on the experimental data obtained in the present work, three isothermal sections at 600, 800 and 950 C were established.

  7. Experimental investigation of phase equilibria in the Co-Ni-Zr ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xingjun; Yang, Shuiyuan; Yu, Wenjie; Wang, Cuiping [Xiamen Univ. (China). Fujian Key Laboratory of Materials Genome; Xiong, Huaping; Cheng, Yaoyong; Wu, Xin [Beijing Institute of Aeronautical Materials (China). Div. of Welding and Forging

    2016-10-15

    The phase equilibria of the Co-Ni-Zr ternary system at 1 000 C, 1 100 C and 1 200 C were experimentally investigated by means of back-scattered electron imaging, electron probe microanalysis and X-ray diffraction on the equilibrated ternary alloys. In this study, no ternary compound is found. The (αCo, Ni) phase region extends from the Ni-rich corner to the Co-rich corner with small solubility of Zr at three sections. At 1 000 C and 1 100 C, Ni{sub 5}Zr, Co{sub 2}Zr and Ni{sub 10}Zr{sub 7} phases have large solid solution ranges, but Ni{sub 10}Zr{sub 7} phase disappears at 1 200 C. The Ni{sub 7}Zr{sub 2}, NiZr, Co{sub 11}Zr{sub 2}, Co{sub 23}Zr{sub 6} and CoZr phases exhibit nearly linear compounds in the studied sections, and have large composition ranges. Additionally, some differences in phase relationship exist among the above three isothermal sections.

  8. Thermodynamic Models for Vapor-Liquid Equilibria of Nitrogen+Oxygen+Carbon Dioxide at Low Temperatures

    CERN Document Server

    Vrabec, J; Buchhauser, U; Meyer-Pittroff, R; Hasse, H

    2009-01-01

    For the design and optimization of CO2 recovery from alcoholic fermentation processes by distillation, models for vapor-liquid equilibria (VLE) are needed. Two such thermodynamic models, the Peng-Robinson equation of state (EOS) and a model based on Henry's law constants, are proposed for the ternary mixture N2+O2+CO2. Pure substance parameters of the Peng-Robinson EOS are taken from the literature, whereas the binary parameters of the Van der Waals one-fluid mixing rule are adjusted to experimental binary VLE data. The Peng-Robinson EOS describes both binary and ternary experimental data well, except at high pressures approaching the critical region. A molecular model is validated by simulation using binary and ternary experimental VLE data. On the basis of this model, the Henry's law constants of N2 and O2 in CO2 are predicted by molecular simulation. An easy-to-use thermodynamic model, based on those Henry's law constants, is developed to reliably describe the VLE in the CO2-rich region.

  9. Collision Index and Stability of Elliptic Relative Equilibria in Planar {n} -body Problem

    Science.gov (United States)

    Hu, Xijun; Ou, Yuwei

    2016-06-01

    It is well known that a planar central configuration of the {n} -body problem gives rise to solutions where each particle moves on a specific Keplerian orbit while the totality of the particles move on a homographic motion. When the eccentricity {e} of the Keplerian orbit belongs in {[0,1)} , following Meyer and Schmidt, we call such solutions elliptic relative equilibria (shortly, ERE). In order to study the linear stability of ERE in the near-collision case, namely when {1-e} is small enough, we introduce the collision index for planar central configurations. The collision index is a Maslov-type index for heteroclinic orbits and orbits parametrised by half-lines that, according to the definition given by Hu and Portaluri (An index theory for unbounded motions of Hamiltonian systems, Hu and Portaluri (2015, preprint)), we shall refer to as half-clinic orbits and whose definition in this context, is essentially based on a blow up technique in the case {e=1} . We get the fundamental properties of collision index and approximation theorems. As applications, we give some new hyperbolic criteria and prove that, generically, the ERE of minimal central configurations are hyperbolic in the near-collision case, and we give a detailed analysis of Euler collinear orbits in the near-collision case.

  10. Modification of Peng Robinson EOS for modelling (vapour + liquid) equilibria with electrolyte solutions

    Energy Technology Data Exchange (ETDEWEB)

    Baseri, Hadi [School of Chemical, Gas and Petroleum Engineering, Semnan University, Semnan 35196-45399 (Iran, Islamic Republic of); Lotfollahi, Mohammad Nader, E-mail: mnlotfollahi@semnan.ac.ir [School of Chemical, Gas and Petroleum Engineering, Semnan University, Semnan 35196-45399 (Iran, Islamic Republic of)

    2011-10-15

    Highlights: > Extended PR-EOS was presented for VLE of H{sub 2}O/Salt/CO{sub 2} systems at high pressure. > The proposed EPR-EOS is based upon contributions to the Helmholtz energy. > Born, Margules, and Debye-Huckel or mean spherical approximation terms were used. > Two different mixing rules Panagiotopoulos and Reid and Kwak and Mansoori (KM) were used. > A combination of KM mixing rule with DH term results more accurate VLE results. - Abstract: A modification of the extended Peng-Robinson equation of state (PR-EOS) is presented to describe the (vapour + liquid) equilibria of systems containing water and salts. The modification employs three additional terms including a Born term, a Margules term and two terms separately used for estimation of the long-range electrostatic interactions (the Debye-Huckel (DH) or the mean spherical approximation (MSA) terms). Effects of two mixing rules, first, the Panagiotopoulos and Reid mixing rule (PR) and, second, the Kwak and Mansoori mixing rule (KM), on the final values of VLE calculations are also investigated. The results show that the KM mixing rule is more appropriate than the PR mixing rule. The proposed equation of state is used to calculate the (vapour + liquid) equilibrium (VLE) of the systems containing (water + sodium sulphate + carbon dioxide) and (water + sodium chloride + carbon dioxide) at high pressure. The comparison of calculated results with the experimental data shows that a combination of KM mixing rule with the DH term results a more accurate VLE values.

  11. Water equilibria and management using a two-volume model of a polymer electrolyte fuel cell

    Science.gov (United States)

    Karnik, Amey Y.; Stefanopoulou, Anna G.; Sun, Jing

    In this paper, we introduce a modified interpretation of the water activity presented in Springer et al. [T.E. Springer, T.A. Zawodzinski, S. Gottesfeld, Polymer electrolyte fuel cell model, J. Electrochem. Soc. 138 (8) (1991) 2334-2342]. The modification directly affects the membrane water transport between the anode and the cathode (two electrodes) of the polymer electrolyte membrane (PEM) fuel cell in the presence of liquid water inside the stack. The modification permits calibration of a zero-dimensional isothermal model to predict the flooding and drying conditions in the two electrodes observed at various current levels [D. Spernjak, S. Advani, A.K. Prasad, Experimental investigation of liquid water formation and transport in a transparent single-serpentine PEM fuel cell, in: Proceedings of the Fourth International Conference on Fuel Cell Science, Engineering and Technology (FUELCELL2006-97271), June 2006]. Using this model the equilibria of the lumped water mass in the two electrodes are analyzed at various flow conditions of the stack to determine stable and unstable (liquid water growth) operating conditions. Two case studies of water management through modification of cathode inlet humidification and anode water removal are then evaluated using this model. The desired anode water removal and the desired cathode inlet humidification are specified based upon (i) the water balance requirements, (ii) the desired conditions in the electrodes, and (iii) the maximum membrane transport at those conditions.

  12. Relative Equilibria in the Four-Vortex Problem with Two Pairs of Equal Vorticities

    CERN Document Server

    Hampton, Marshall; Santoprete, Manuele

    2012-01-01

    We examine in detail the relative equilibria in the four-vortex problem where two pairs of vortices have equal strength, that is, \\Gamma_1 = \\Gamma_2 = 1 and \\Gamma_3 = \\Gamma_4 = m where m is a nonzero real parameter. One main result is that for m > 0, the convex configurations all contain a line of symmetry, forming a rhombus or an isosceles trapezoid. The rhombus solutions exist for all m but the isosceles trapezoid case exists only when m is positive. In fact, there exist asymmetric convex configurations when m < 0. In contrast to the Newtonian four-body problem with two equal pairs of masses, where the symmetry of all convex central configurations is unproven, the equations in the vortex case are easier to handle, allowing for a complete classification of all solutions. Precise counts on the number and type of solutions (equivalence classes) for different values of m, as well as a description of some of the bifurcations that occur, are provided. Our techniques involve a combination of analysis and mod...

  13. The Impact of Prophage on the Equilibria and Stability of Phage and Host

    Science.gov (United States)

    Yu, Pei; Nadeem, Alina; Wahl, Lindi M.

    2016-11-01

    In this paper, we present a bacteriophage model that includes prophage, that is, phage genomes that are incorporated into the host cell genome. The general model is described by an 18-dimensional system of ordinary differential equations. This study focuses on asymptotic behaviour of the model, and thus the system is reduced to a simple six-dimensional model, involving uninfected host cells, infected host cells and phage. We use dynamical system theory to explore the dynamic behaviour of the model, studying in particular the impact of prophage on the equilibria and stability of phage and host. We employ bifurcation and stability theory, centre manifold and normal form theory to show that the system has multiple equilibrium solutions which undergo a series of bifurcations, finally leading to oscillating motions. Numerical simulations are presented to illustrate and confirm the analytical predictions. The results of this study indicate that in some parameter regimes, the host cell population may drive the phage to extinction through diversification, that is, if multiple types of host emerge; this prediction holds even if the phage population is likewise diverse. This parameter regime is restricted, however, if infecting phage are able to recombine with prophage sequences in the host cell genome.

  14. Fast Three Dimensional Reconstruction of Magnetohydrodynamic Equilibria in Plasma Confinement Devices

    Science.gov (United States)

    Seal, S. K.; Cianciosa, M. R.; Hirshman, S. P.; Wingen, A.; Wilcox, R. S.; Unterberg, E. A.

    2016-10-01

    High-fidelity reconstruction of plasma equilibria in confinement devices like stellarators and tokamaks with external three dimensional (3D) fields is computationally very expensive and routinely requires days, even weeks, to complete using serial approaches. Here, we present the performance results of coupling the 3D plasma reconstruction code, V3FIT, with PARVMEC, the recently developed parallel version of VMEC. We present the parallel design of this coupled software along with a scalability analysis to identify its performance bottlenecks. Dependence of its scalability limits on model parameters is derived. These analyses are supported by scaling studies on over 6,000 processor cores of a Cray XC30 supercomputer. PARVMEC, which dominates the total runtime of the reconstruction procedure, is shown to deliver speedup improvements of over one to two orders of magnitude, depending on whether the equilibrium computations are carried out in a free or fixed boundary mode. The overall speedup of the coupled reconstruction code is shown to deliver over 40X improvement enabling fusion scientists to carry out high-fidelity 3D plasma reconstruction analyses in only a few hours instead of in days/weeks for the first time. This work was supported by the U.S. D.O.E. contract DE-AC05-00OR22725.

  15. Fusion burn equilibria sensitive to the ratio between energy and helium transport

    Science.gov (United States)

    Jakobs, Merlijn; Lopes Cardozo, Niek; Jaspers, Roger

    2014-12-01

    An analysis of the burn equilibria of fusion reactors of the tokamak family is presented. The global (zero-dimensional) analysis is self-consistent in that it takes into account the dependence of the energy confinement on the variables of the burning plasma, such as temperature and density. Universal burn contours are presented for a selection of commonly used scaling laws for energy confinement. It is shown that the output power of a fusion reactor is to good approximation inversely proportional to the particle confinement time, due to the choking effect of the accumulation of helium, the ash of the fusion reaction. It is further shown that, whereas a fusion reactor requires a minimum energy confinement time to ignite, the output power reaches a maximum for an energy confinement that lies about 30% above this minimum. Further improvement of confinement will lower the output, although in some cases the β limit will be the limiting factor. Given that for maximum performance density the confinement and fuel mix are best chosen to be optimal, the particle confinement is proposed as an attractive parameter for burn control.

  16. Theory of equilibria of elastic braids with applications to DNA supercoiling

    Science.gov (United States)

    van der Heijden, Gert; Starostin, Eugene

    2014-03-01

    Motivated by supercoiling of DNA and other filamentous structures, we formulate a new theory for equilibria of 2-braids, i.e., structures formed by two elastic rods winding around each other in continuous contact and subject to a local interstrand interaction. Unlike in previous work no assumption is made on the shape of the contact curve. Rather, this shape is solved for. The theory is developed in terms of a moving frame of directors attached to one of the strands with one of the directors pointing to the position of the other strand. The constant-distance constraint is automatically satisfied by the introduction of what we call braid strains. The price we pay is that the potential energy involves arclength derivatives of these strains, thus giving rise to a second-order variational problem. The Euler-Lagrange equations for this problem give balance equations for the overall braid force and moment referred to the moving frame as well as differential equations that can be interpreted as effective constitutive relations encoding the effect that the second strand has on the first as the braid deforms under the action of end loads. Both open braid and closed braid solutions (links and knots) are computed and current applications to DNA supercoiling are discussed. Research supported by EPSRC and HFSP.

  17. Extracellular mercury sequestration by exopolymeric substances produced by Yarrowia spp.: Thermodynamics, equilibria, and kinetics studies.

    Science.gov (United States)

    Oyetibo, Ganiyu Oladunjoye; Miyauchi, Keisuke; Suzuki, Hitoshi; Ishikawa, Satoru; Endo, Ginro

    2016-12-01

    Exopolymeric substances (EPS) produced by highly mercury-resistant strains of the yeast Yarrowia spp. (Idd1 and Idd2) were isolated and studied for their mercury binding potential. Excellent yield (approximately 0.3 g EPS per gram biomass) of soluble EPS in medium with 3% glucose was observed in the Yarrowia cultures 7 day post-inoculation. A gram dry weight of the EPS consists mainly of carbohydrates (0.4 g), protein (0.3-0.4 g), uronic acid (0.02 g), and nucleic acids (0.002 g). Mercury interactions with the biopolymer were measured as uptake kinetics from a simulated aquatic system and modelled with thermodynamics and calculated mass action equilibria. The EPS forms a complex with Hg(2+) in water with small activation energy (≤2 kJ mol(-1)), achieving about 30 mg Hg(2+) adsorption per gram dry weight of EPS. The adsorption models confirmed complexation of Hg(2+) by the EPS via heterogeneous multilayer adsorption that obey second-order kinetics at constant rate of 4.0 and 8.1 mg g(-1) min(-1). The EPS used chemisorption as rate-limiting step that controls the uptake of Hg(2+) from aquatic systems during micro-precipitation as bio-removal strategy. The EPS are promising biotechnological tools to design bioreactors for treatment of mercury-rich industrial wastewater.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-10

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

  19. Does an irreversible chemical cycle support equilibrium?

    CERN Document Server

    Banerjee, Kinshuk

    2013-01-01

    The impossibility of attaining equilibrium for cyclic chemical reaction networks with irreversible steps is apparently due to a divergent entropy production rate. A deeper reason seems to be the violation of the detailed balance condition. In this work, we discuss how the standard theoretical framework can be adapted to include irreversible cycles, avoiding the divergence. With properly redefined force terms, such systems are also seen to reach and sustain equilibria that are characterized by the vanishing of the entropy production rate, though detailed balance is not maintained. Equivalence of the present formulation with Onsager's original prescription is established for both reversible and irreversible cycles, with a few adjustments in the latter case. Further justification of the attainment of true equilibrium is provided with the help of the minimum entropy production principle. All the results are generalized for an irreversible cycle comprising of N number of species.

  20. Chemical Sciences Division annual report, 1990

    Energy Technology Data Exchange (ETDEWEB)

    1991-08-01

    This report contains sections on the following topics: photochemistry of materials in the stratosphere, energy transfer and structural studies of molecules on surfaces, crossed molecular beams, molecular interactions, theory of atomic and molecular collision processes, selective photochemistry, photodissociation of free radicals, physical chemistry with emphasis on thermodynamic properties, chemical physics at the high photon energies, high-energy atomic physics, atomic physics, high-energy oxidizers and delocalized-electron solids, catalytic hydrogenation of CO, transition metal-catalyzed conversion of CO, NO, H{sub 2}, and organic molecules to fuels and petrochemicals, formation of oxyacids of sulfur from SO{sub 2}, potentially catalytic and conducting polyorganometallics, actinide chemistry, and molecular thermodynamics for phase equilibria in mixtures.

  1. On the Mathematical Structure of Balanced Chemical Reaction Networks Governed by Mass Action Kinetics

    CERN Document Server

    van der Schaft, Arjan; Jayawardhana, Bayu

    2011-01-01

    Motivated by recent progress on the interplay between graph theory, dynamics, and systems theory, we revisit the analysis of chemical reaction networks described by mass action kinetics. For reaction networks possessing a thermodynamic equilibrium we derive a compact formulation exhibiting at the same time the structure of the complex graph and the stoichiometry of the network, and which admits a direct thermodynamical interpretation. This formulation allows us to easily characterize the set of equilibria and their stability properties. Furthermore, we develop a framework for interconnection of chemical reaction networks. Finally we discuss how the established framework leads to a new approach for model reduction.

  2. Modelling of associating mixtures for applications in the oil & gas and chemical industries

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Folas, Georgios; Muro Sunè, Nuria

    2007-01-01

    -alcohol (glycol)-alkanes and certain acid and amine-containing mixtures. Recent results include glycol-aromatic hydrocarbons including multiphase, multicomponent equilibria and gas hydrate calculations in combination with the van der Waals-Platteeuw model. This article will outline some new applications...... of the model of relevance to the petroleum and chemical industries: high pressure vapor-liquid and liquid-liquid equilibrium in alcohol-containing mixtures, mixtures with gas hydrate inhibitors and mixtures with polar and hydrogen bonding chemicals including organic acids. Some comparisons with conventional...

  3. Chemical reaction network approaches to Biochemical Systems Theory.

    Science.gov (United States)

    Arceo, Carlene Perpetua P; Jose, Editha C; Marin-Sanguino, Alberto; Mendoza, Eduardo R

    2015-11-01

    This paper provides a framework to represent a Biochemical Systems Theory (BST) model (in either GMA or S-system form) as a chemical reaction network with power law kinetics. Using this representation, some basic properties and the application of recent results of Chemical Reaction Network Theory regarding steady states of such systems are shown. In particular, Injectivity Theory, including network concordance [36] and the Jacobian Determinant Criterion [43], a "Lifting Theorem" for steady states [26] and the comprehensive results of Müller and Regensburger [31] on complex balanced equilibria are discussed. A partial extension of a recent Emulation Theorem of Cardelli for mass action systems [3] is derived for a subclass of power law kinetic systems. However, it is also shown that the GMA and S-system models of human purine metabolism [10] do not display the reactant-determined kinetics assumed by Müller and Regensburger and hence only a subset of BST models can be handled with their approach. Moreover, since the reaction networks underlying many BST models are not weakly reversible, results for non-complex balanced equilibria are also needed.

  4. Chemical speciation code CHEMSPEC and its applications

    Institute of Scientific and Technical Information of China (English)

    WANG XiangYun; CHEN Tao; LIU ChunLi

    2009-01-01

    The adsorption and migration behavior of a radionuclide in geological media heavily depends on its chemical forms in a given chemical environment.In order to predict the temporal and spatial distribution of radionuclides around a disposal site when its canister is damaged,it is necessary to develop coupled chemical speciation-solute transport models and relevant software.For that reason,we wrote a new chemical speciation program CHEMSPEC.In this paper,the principles and structure of CHEMSPEC are briefly described,and the strategy and algorithms that were used in this code are interpreted in some detail,such as the measures adopted to prevent divergence in iteratively solving the mass balance equations,the "predictor-corrector" algorithm for calculation of the number and quantities of solid species formed,and the alternate use of "freezing" and "defreezing" oxidation states in handling of co-existent redox and precipitation equilibria.Four examples are given to illustrate CHEMSPEC's features and capabilities.

  5. Chemical speciation code CHEMSPEC and its applications

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The adsorption and migration behavior of a radionuclide in geological media heavily depends on its chemical forms in a given chemical environment.In order to predict the temporal and spatial distribution of radionuclides around a disposal site when its canister is damaged,it is necessary to develop coupled chemical speciation-solute transport models and relevant software.For that reason,we wrote a new chemical speciation program CHEMSPEC.In this paper,the principles and structure of CHEMSPEC are briefly described,and the strategy and algorithms that were used in this code are interpreted in some detail,such as the measures adopted to prevent divergence in iteratively solving the mass balance equations,the "predictor-corrector" algorithm for calculation of the number and quantities of solid species formed,and the alternate use of "freezing" and "defreezing" oxidation states in handling of co-existent redox and precipitation equilibria.Four examples are given to illustrate CHEMSPEC’s features and capabilities.

  6. Calculation of continuum damping of Alfvén eigenmodes in tokamak and stellarator equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Bowden, G. W.; Hole, M. J. [Plasma Theory and Modelling, Research School of Physics and Engineering, Australian National University, Acton 2601, Australian Capital Territory (Australia); Könies, A. [Max-Planck-Institut für Plasmaphysik, EURATOM-Association, D-17491 Greifswald (Germany)

    2015-09-15

    In an ideal magnetohydrodynamic (MHD) plasma, shear Alfvén eigenmodes may experience dissipationless damping due to resonant interaction with the shear Alfvén continuum. This continuum damping can make a significant contribution to the overall growth/decay rate of shear Alfvén eigenmodes, with consequent implications for fast ion transport. One method for calculating continuum damping is to solve the MHD eigenvalue problem over a suitable contour in the complex plane, thereby satisfying the causality condition. Such an approach can be implemented in three-dimensional ideal MHD codes which use the Galerkin method. Analytic functions can be fitted to numerical data for equilibrium quantities in order to determine the value of these quantities along the complex contour. This approach requires less resolution than the established technique of calculating damping as resistivity vanishes and is thus more computationally efficient. The complex contour method has been applied to the three-dimensional finite element ideal MHD Code for Kinetic Alfvén waves. In this paper, we discuss the application of the complex contour technique to calculate the continuum damping of global modes in tokamak as well as torsatron, W7-X and H-1NF stellarator cases. To the authors' knowledge, these stellarator calculations represent the first calculation of continuum damping for eigenmodes in fully three-dimensional equilibria. The continuum damping of global modes in W7-X and H-1NF stellarator configurations investigated is found to depend sensitively on coupling to numerous poloidal and toroidal harmonics.

  7. HIGH PRESSURE VAPOR-LIQUID EQUILIBRIA OF PALM FATTY ACIDS DISTILLATES-CARBON DIOXIDE SYSTEM

    Directory of Open Access Journals (Sweden)

    Nélio T. MACHADO

    1997-12-01

    Full Text Available Vapor-Liquid equilibria of palm fatty acids distillates/carbon dioxide system has been investigated experimentally at temperatures of 333, 353, and 373 K and pressures of 20, 23, 26, and 29 MPa using the static method. Experimental data for the quasi-binary system palm fatty acids distillates/carbon dioxide has been correlated with Redlich-Kwong-Aspen equation of state. Modeling shows good agreement with experimental data. Selectivity obtained indicates that supercritical carbon dioxide is a reasonable solvent for separating saturated (palmitic acid and unsaturated (oleic+linoleic acids fatty acids from palm fatty acids distillates in a continuous multistage countercurrent column.Foi investigado experimentalmente o equilíbrio líquido-vapor para o sistema Destilado Ácido de Óleo de Palma (PFAD/Dióxido de Carbono, nas temperaturas de 333, 353 e 373 K e pressões de 20, 23, 26 e 29 MPa, usando-se o método estático. Os dados experimentais do sistema pseudo-binário PFAD/CO2 foram correlacionados com a equação de estado de Redlich-Kwong do pacote computacional ASPEN. O modelo reproduz bem os resultados experimentais. A seletividade obtida indica que o CO2 supercrítico é um solvente razoável para a separação em coluna multi-estágio e contínua, do ácido graxo saturado (ácido palmítico daqueles insaturados (ácido oleico e ácido linoleico contidos no PFAD.

  8. Liquid-Liquid Phase Equilibria and Interactions between Droplets in Water-in-Oil Microemulsions.

    Science.gov (United States)

    Yin, Tianxiang; Wang, Mingjie; Tao, Xiaoyi; Shen, Weiguo

    2016-12-20

    The liquid-liquid phase equilibria of [water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-decane] with the molar ratio w0 of water to AOT being 37.9 and [water/AOT/ethoxylated-2,5,8,11-tetramethyl-6-dodecyne-5,8-diol(Dynol-604)/n-decane] with w0 = 37.9 and the mole fraction α of Dynol-604 in the total surfactants being 0.158 were measured in this study. From the data collected in the critical region, the critical exponent β corresponding to the width of the coexistence curve was determined, which showed good agreement with the 3D-Ising value. A thermodynamic approach based on the Carnahan-Starling-van der Waals type equation was proposed to describe the coexistence curves and to deduce the interaction properties between droplets in the microemulsions. The interaction enthalpies were found to be positive for the studied systems, which evidenced that the entropy effect dominated the phase separations as the temperature increased. The addition of Dynol-604 into the (water/AOT/n-decane) microemulsion resulted in the decrease in the critical temperature and the interaction enthalpy. Combining the liquid-liquid equilibrium data for (water/AOT/n-decane) microemulsions with various w0 values determined previously, it was shown that the interaction enthalpy decreased with w0 and tended to change its sign at low w0, which coincided with the results from the isothermal titration calorimetry investigation. All of these behaviors were interpreted by the effects of entropy and enthalpy and their competition, which resulted from the release of solvent molecules entrapped in the interface of microemulsion droplets and were dependent on the rigidity of the surfactant layers and the size of the droplet.

  9. Phase Equilibria of the Ce-Mg-Zn Ternary System at 300 °C

    Directory of Open Access Journals (Sweden)

    Ahmad Mostafa

    2014-05-01

    Full Text Available The isothermal section of the Ce-Mg-Zn system at 300 °C was experimentally established in the full composition range via diffusion multiple/couples and key alloys. Annealed key alloys were used to confirm the phase equilibria obtained by diffusion multiple/couples and to determine the solid solubility ranges. Spot analysis was carried out, using wavelength dispersive X-ray spectroscopy (WDS, to identify the composition of the observed phases. The composition profiles were obtained using WDS line-scans across the diffusion zones. X-ray diffraction (XRD was performed to identify the phases in the annealed alloys and to confirm the WDS results. Eight ternary compounds, in the Ce-Mg-Zn isothermal section at 300 °C, were observed from 45–80 at.% Zn. These are: τ1 (Ce6Mg3Zn19, τ2 (CeMg29Zn25, τ3 (Ce2Mg3Zn3, τ4 (CeMg3Zn5, τ5 (CeMg7Zn12, τ6 (CeMg2.3−xZn12.8+x; 0 ≤ x ≤ 1.1, τ7 (CeMgZn4 and τ8 (Ce(Mg1−yZny11; 0.096 ≤ y ≤ 0.43. The ternary solubility of Zn in the Ce-Mg compounds was found to increase with a decrease in Mg concentration. Accordingly, the ternary solid solubility of Zn in CeMg12 and CeMg3 was measured as 5.6 and 28.4 at.% Zn, respectively. Furthermore, the CeMg and CeZn showed a complete solid solubility. The complete solubility was confirmed by a diffusion couple made from alloys containing CeMg and CeZn compounds.

  10. Phase equilibria in the Co–Ti–V system at 873 K

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, G.J., E-mail: gjzhoumike@163.com [School of Mechanical Engineering, Hunan Institute of Science and Technology, Yue-yang, Hunan 414006 (China); Tang, J.G. [School of Materials Science and Engineering, Central South University, Chang-Sha, Hunan 410083 (China); Zhou, Y.; An, W.K.; Cai, An.H. [School of Mechanical Engineering, Hunan Institute of Science and Technology, Yue-yang, Hunan 414006 (China)

    2014-07-25

    Highlights: • The 873 K isothermal section of Co–Ti–V ternary system is determined. • Nine three-phase equilibria are experimentally measured. • All of Co–V and Co–Ti binary phases show large ternary solubility. • The maximum solid solubility of Ti, Co, V in binary phases is determined. - Abstract: The isothermal section of the Co–Ti–V ternary system at 873 K has been investigated by means of diffusion triple together with electron probe microanalysis technique. Series of tie lines and tie-triangles have been determined and the isothermal section at 873 K has been established, and nine three-phase fields have been figured out. It is found that VCo{sub 3}, VCo, TiCo{sub 3}, TiCo{sub 2}(h), TiCo{sub 2}(c) and TiCo have range of homogeneity at 873 K, and the V{sub 3}Co and Ti{sub 2}Co are line compounds. The solid solubility of Ti in VCo{sub 3}, VCo and V{sub 3}Co is about 5.2 at.% Ti, 8.8 at.% Ti and 6.9 at.% Ti, and that of V in TiCo{sub 3}, TiCo{sub 2}(h), TiCo{sub 2}(c), TiCo and Ti{sub 2}Co is about 6.1 at.% V, 3.7 at.% V, 3.0 at.% V, 9.3 at.% V and 6.6 at.% V, respectively.

  11. Conformational equilibria in monomeric alpha-synuclein at the single-molecule level.

    Directory of Open Access Journals (Sweden)

    Massimo Sandal

    2008-01-01

    Full Text Available Human alpha-Synuclein (alphaSyn is a natively unfolded protein whose aggregation into amyloid fibrils is involved in the pathology of Parkinson disease. A full comprehension of the structure and dynamics of early intermediates leading to the aggregated states is an unsolved problem of essential importance to researchers attempting to decipher the molecular mechanisms of alphaSyn aggregation and formation of fibrils. Traditional bulk techniques used so far to solve this problem point to a direct correlation between alphaSyn's unique conformational properties and its propensity to aggregate, but these techniques can only provide ensemble-averaged information for monomers and oligomers alike. They therefore cannot characterize the full complexity of the conformational equilibria that trigger the aggregation process. We applied atomic force microscopy-based single-molecule mechanical unfolding methodology to study the conformational equilibrium of human wild-type and mutant alphaSyn. The conformational heterogeneity of monomeric alphaSyn was characterized at the single-molecule level. Three main classes of conformations, including disordered and "beta-like" structures, were directly observed and quantified without any interference from oligomeric soluble forms. The relative abundance of the "beta-like" structures significantly increased in different conditions promoting the aggregation of alphaSyn: the presence of Cu2+, the pathogenic A30P mutation, and high ionic strength. This methodology can explore the full conformational space of a protein at the single-molecule level, detecting even poorly populated conformers and measuring their distribution in a variety of biologically important conditions. To the best of our knowledge, we present for the first time evidence of a conformational equilibrium that controls the population of a specific class of monomeric alphaSyn conformers, positively correlated with conditions known to promote the formation of

  12. PHASE EQUILIBRIA INVESTIGATION OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART IV. THE EFFECT OF MOLYBDENUM AND TUNGSTEN ON THE SUBCARBIDE SOLUTIONS IN THE VANADIUM-TANTALUM-CARBON AND NIOBIUM-TANTALUM-CARBON SYSTEMS.

    Science.gov (United States)

    The phase equilibria investigations described in this report are in direct support of Air Force sponsored cutting tool research programs. The...the high temperature phase equilibria of possible alloy combinations is, therefore, a prerequisite for the fabrication of even test alloys. (Author)

  13. Phase equilibria modeling of methanol-containing systems with the CPA and sPC-SAFT equations of state

    DEFF Research Database (Denmark)

    Tybjerg, Peter Chr. V.; Kontogeorgis, Georgios; Michelsen, Michael Locht

    2010-01-01

    Proper representation at various conditions of phase equilibria of methanol-containing mixtures (with hydrocarbons, water, etc.) is Important for oil flow assurance purposes In this work two association equations of state. CPA and sPC-SAFT, are applied to methanol-containing mixtures The purpose...... density, enthalpy of vaporization and compressibility factor data at e used Methanol-alkane vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE) data. water-methanol VLE as well as water-methanol-hydrocarbon LLE are considered. It is concluded that the two association equations of state...

  14. Modeling the vapor-liquid equilibria of polymer-solvent mixtures: Systems with complex hydrogen bonding behavior

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2009-01-01

    The vapor–liquid equilibria of binary polymer–solvent systems was modeled using the Non-Random Hydrogen Bonding (NRHB) model. Mixtures of poly(ethylene glycol), poly(propylene glycol), poly(vinyl alcohol) and poly(vinyl acetate) with various solvents were investigated, while emphasis was put...... on hydrogen bonding systems, in which functional groups of the polymer chain can self-associate or cross-associate with the solvent molecules. Effort has been made to explicitly account for all hydrogen bonding interactions. The results reveal that the NRHB model offers a flexible approach to account...... the complexity of the examined systems....

  15. Evaluation of the truncated perturbed chain-polar statistical associating fluid theory for complex mixture fluid phase equilibria

    DEFF Research Database (Denmark)

    Karakatsani, Eirini; Kontogeorgis, Georgios; Economou, Ioannis

    2006-01-01

    Perturbed chain-statistical associating fluid theory (PC-SAFT) was extended rigorously to polar fluids based on the theory of Stell and co-workers [Mol. Phys. 1977, 33, 987]. The new PC-PSAFT was simplified to truncated PC-PSAFT (tPC-PSAFT) so that it can be practical for real polar fluid thermod...... pressures are calculated. Comparisons against PC-SAFT calculations are made. It is shown that tPC-PSAFT is an accurate model for polar fluid mixture phase equilibria....

  16. Experimental determination and prediction of (solid+liquid) phase equilibria for binary mixtures of heavy alkanes and fatty acids

    Science.gov (United States)

    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.

  17. Solid-Liquid Equilibria for Many-component Mixtures Using Cubic-Plus-Association (CPA) equation of state

    DEFF Research Database (Denmark)

    Fettouhi, André; Thomsen, Kaj

    2010-01-01

    In the creation of liquefied natural gas the formation of solids play a substantial role, hence detailed knowledge is needed about solid-liquid equilibria (SLE). In this abstract we shortly summarize the work we have carried out at CERE over the past year with SLE for many-component mixtures using...... the Cubic-Plus-Association (CPA) equation of state. Components used in this work are highly relevant to the oil and gas industry and include light and heavy hydrocarbons, alcohols, water and carbon dioxide....

  18. (Ternary liquid + liquid) equilibria for (water + acetone + {alpha}-pinene, or {beta}-pinene, or limonene) mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaoli [Department of Chemistry and Chemical Engineering, Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192 (Japan); Tamura, Kazuhiro, E-mail: tamura@t.kanazawa-u.ac.j [Department of Chemistry and Chemical Engineering, Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192 (Japan)

    2010-11-15

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

  19. Chemical use

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This is a summary of research and activities related to chemical use on Neal Smith National Wildlife Refuge between 1992 and 2009. The chemicals used on the Refuge...

  20. Chemical Reactors.

    Science.gov (United States)

    Kenney, C. N.

    1980-01-01

    Describes a course, including content, reading list, and presentation on chemical reactors at Cambridge University, England. A brief comparison of chemical engineering education between the United States and England is also given. (JN)

  1. Phase equilibria in the P(2)O(5)-CaO-CaF(2)-NaF-H(2)O quinary system and the formation of apatite

    Science.gov (United States)

    Martin, Roger Isaac

    Phase equilibria among calcium phosphates in the Hsb3POsb4-Ca(OH)sb2-Hsb2O ternary system were determined as a basis for research in the formation of hydroxyapatite, a biomaterial. The acidic portion of the ternary diagram was established. Ca(Hsb2POsb4)sb2 was not stable for temperatures below 100sp°C. The experimental and theoretical dissolution paths of Ca(Hsb2POsb4)sb2{*}Hsb2O were compared. It is possible for the initial dissolution of Ca(Hsb2POsb4)sb2{*}Hsb2O to supersaturate the system with respect to hydroxyapatite because Ca(Hsb2POsb4)sb2{*}Hsb2O is "twice" incongruently soluble. Hydroxyapatite composition is variable with a Ca/P ratio ranging from 1.5 to 1.67. Hydroxyapatite formation from acid-base reactions of CaHPOsb4 and Casb4(POsb4)sb2O was investigated for composition at the terminal limits. The total heats-of-reaction (Delta Hsb{r}) were determined to be 261.3 and 320 kJ/mol for the formation of calcium deficient and stoichiometric hydroxyapatite, respectively. Activation energies of 84.7 and 87.4 kJ/mol were calculated for the formation of calcium deficient and stoichiometric hydroxyapatite, respectively. Heats-of-formation (Delta Hsb{f}) for Casb4(POsb4)sb2O and Casb9HPOsb4(POsb4)sb5OH were calculated to be -4764.1 and -1207.7 kJ/mol, respectively. The effects of magnesium on hydroxyapatite formation in vitro from CaHPOsb4 and Casb4(POsb4)sb2O at 37.4sp°C were investigated. Magnesium is a biological agent with 0.78 mM concentrations in blood. Magnesium inhibited nucleation for 1 mM concentrations and above for a 5 liquid-to-solids ratio. However, a 5 mM concentration of MgClsb2 slightly accelerated the growth rate. The activity of magnesium is approximately 6% of its concentration. Therefore the inorganic chemical activity of magnesium may not significantly inhibit the formation of bioapatites. Phase equilibria in the Psb2Osb5-CaO-CaFsb2-Hsb2O system at 37.4sp°C was determined and dental fluorosis explained. Fluoroapatite dissolves

  2. Reversed-phase ion-pair liquid chromatographic method for determination of reaction equilibria involving ionic species: exemplification of the method using ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions.

    Science.gov (United States)

    Sato, Emiko; Miya, Seiko; Saitoh, Kazunori; Saito, Shingo; Shibukawa, Masami

    2011-02-18

    A reversed-phase ion-pair liquid chromatographic method is presented for the determination of reaction equilibria involving ionic species of the same charge sign as reactant and product compounds. It has been demonstrated that ion-exchange chromatography or reversed-phase ion-pair chromatography is a useful tool for the determination of equilibrium constants of chemical reactions involving ionic species such as metal complexation reactions. Previous work with these methods has been based on the assumption that the limiting retention factors of the reactant and product species are constant independent of concentration of the chemical species (X) in the mobile phase, which reacts with the analyte compound. However, when all the reactant and product species are ions of the same charge sign as that of the species X, it is virtually impossible to apply these methods to the equilibrium constant determination because the retention factors of both the reactant and product species may depend on the concentration of X. In this study, an alternative approach was developed that estimates the limiting retention factors of ionic species from the dependence of the retention factor on the ionic strength of the mobile phase. Ligand substitution reactions of ethylenediaminetetraacetatochromium(III) ion with acetate and phosphate ions were used as model reactions to test this method. The equilibrium constants determined by this method are in good agreement with those obtained by a UV-visible spectrophotometric method.

  3. First-principles calculation of phase equilibria and phase separation of the Fe-Ni alloy system

    Institute of Scientific and Technical Information of China (English)

    Ying Chen; Shuichi Iwata; Tetsuo Mohri

    2006-01-01

    Theoretical investigation of the phase equilibria of the Fe-Ni alloy has been performed by combining the FLAPW total energy calculations and the Cluster Variation Method through the Cluster Expansion Method. The calculations have proved the stabilization of the L12 phase at 1:3 stoichiometry, which is in agreement with the experimental result,and predicted the existence of L10 as a stable phase below 550 K; this L10 phase has been missing in the conventional phasediagram. The calculations are extended to the Fe-rich region that is characterized by a wide range phase separation and has drawn considerable attention because of the intriguing Invar property associated with a Fe concentration of 65%. To reveal the origin of the phase separation, a P-V curve in an entire concentration range is derived by the second derivative of free energy functional of the disordered phase with respect to the volume. The calculation confirmed that the phase separation is caused by the breakdown of the mechanical-stability criterion. The newly calculated phase separation line combined with the L10 and L12 order-disordered phase boundaries provides phase equilibria in the wider concentration range of the system. Furthermore, a coefficient of thermal expansion (CTE) is attempted by incorporating the thermal vibration effect through harmonic approximation of the Debye-Gruneisen model. The Invar behavior has been reproduced, and the origin of this anomalous volume change has been discussed.

  4. Leveraging Gibbs Ensemble Molecular Dynamics and Hybrid Monte Carlo/Molecular Dynamics for Efficient Study of Phase Equilibria.

    Science.gov (United States)

    Gartner, Thomas E; Epps, Thomas H; Jayaraman, Arthi

    2016-11-08

    We describe an extension of the Gibbs ensemble molecular dynamics (GEMD) method for studying phase equilibria. Our modifications to GEMD allow for direct control over particle transfer between phases and improve the method's numerical stability. Additionally, we found that the modified GEMD approach had advantages in computational efficiency in comparison to a hybrid Monte Carlo (MC)/MD Gibbs ensemble scheme in the context of the single component Lennard-Jones fluid. We note that this increase in computational efficiency does not compromise the close agreement of phase equilibrium results between the two methods. However, numerical instabilities in the GEMD scheme hamper GEMD's use near the critical point. We propose that the computationally efficient GEMD simulations can be used to map out the majority of the phase window, with hybrid MC/MD used as a follow up for conditions under which GEMD may be unstable (e.g., near-critical behavior). In this manner, we can capitalize on the contrasting strengths of these two methods to enable the efficient study of phase equilibria for systems that present challenges for a purely stochastic GEMC method, such as dense or low temperature systems, and/or those with complex molecular topologies.

  5. Body-fixed orbit-attitude hovering at equilibria near an asteroid using non-canonical Hamiltonian structure

    CERN Document Server

    Wang, Yue

    2014-01-01

    Orbit-attitude hovering of a spacecraft at the natural relative equilibria in the body-fixed frame of a uniformly rotating asteroid is discussed in the framework of the full spacecraft dynamics, in which the spacecraft is modeled as a rigid body with the gravitational orbit-attitude coupling. In this hovering model, both the position and attitude of the spacecraft are kept to be stationary in the asteroid body-fixed frame. A Hamiltonian structure-based feedback control law is proposed to stabilize the relative equilibria of the full dynamics to achieve the orbit-attitude hovering. The control law is consisted of two parts: potential shaping and energy dissipation. The potential shaping is to make the relative equilibrium a minimum of the modified Hamiltonian on the invariant manifold by modifying the potential artificially. With the energy-Casimir method, it is shown that the unstable relative equilibrium can always be stabilized in the Lyapunov sense by the potential shaping with sufficiently large feedback ...

  6. Phase Equilibria of the Ternary Sn-Zn-Co System at 250°C and 500°C

    Science.gov (United States)

    Wang, Chao-hong; Huang, Sheng-en; Huang, Po-yen

    2015-12-01

    The isothermal sections of the ternary Sn-Zn-Co system (IMCs) are very limited. For the phase equilibria at 250°C, two ternary IMCs, T1 and T2, were found, whose compositions were Sn-25 at.%Zn-25 at.%Co and Sn-15 at.%Zn-41 at.%Co, respectively. For the phase equilibria at 500°C, in addition to the T2 phase, another ternary IMC, namely T3 (Sn-18 at.%Zn-37 at.%Co), was also found. Moreover, the phase stability of the T1 and T3 phases was investigated at temperatures of 260°C to 400°C in detail. The equilibrium phase was the T1 phase below 300°C, and changed to the T3 phase at 400°C. The crystal structures of these three ternary IMCs were also studied. The T1 phase has a cubic structure ( Pm3m), and the T2 and T3 phases are orthorhombic in space group Cmcm and Pnma, respectively.

  7. Analysis of the expected density of internal equilibria in random evolutionary multi-player multi-strategy games.

    Science.gov (United States)

    Duong, Manh Hong; Han, The Anh

    2016-12-01

    In this paper, we study the distribution and behaviour of internal equilibria in a d-player n-strategy random evolutionary game where the game payoff matrix is generated from normal distributions. The study of this paper reveals and exploits interesting connections between evolutionary game theory and random polynomial theory. The main contributions of the paper are some qualitative and quantitative results on the expected density, [Formula: see text], and the expected number, E(n, d), of (stable) internal equilibria. Firstly, we show that in multi-player two-strategy games, they behave asymptotically as [Formula: see text] as d is sufficiently large. Secondly, we prove that they are monotone functions of d. We also make a conjecture for games with more than two strategies. Thirdly, we provide numerical simulations for our analytical results and to support the conjecture. As consequences of our analysis, some qualitative and quantitative results on the distribution of zeros of a random Bernstein polynomial are also obtained.

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

    Directory of Open Access Journals (Sweden)

    Lozano, L. J.

    2005-10-01

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

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

  9. Statistical equilibria of the coupled barotropic flow and shallow water flow on a rotating sphere

    Science.gov (United States)

    Ding, Xueru

    The motivation of this research is to build equilibrium statistical models that can apply to explain two enigmatic phenomena in the atmospheres of the solar system's planets: (1) the super-rotation of the atmospheres of slowly-rotating terrestrial planets---namely Venus and Titan, and (2) the persistent anticyclonic large vortex storms on the gas giants, such as the Great Red Spot (GRS) on Jupiter. My thesis is composed of two main parts: the first part focuses on the statistical equilibrium of the coupled barotropic vorticity flow (non-divergent) on a rotating sphere; the other one has to do with the divergent shallow water flow rotating sphere system. The statistical equilibria of these two systems are simulated in a wide range of parameter space by Monte Carlo methods based on recent energy-relative enstrophy theory and extended energy-relative enstrophy theory. These kind of models remove the low temperatures defect in the old classical doubly canonical energy-enstrophy theory which cannot support any phase transitions. The other big difference of our research from previous work is that we work on the coupled fluid-sphere system, which consists of a rotating high density rigid sphere, enveloped by a thin shell of fluid. The sphere is considered to have infinite mass and angular momentum; therefore, it can serve as a reservoir of angular momentum. Unlike the fluid sphere system itself, the coupled fluid sphere system allows for the exchange of angular momentum between the atmosphere and the solid planet. This exchange is the key point in any model that is expected to capture coherent structures such as the super-rotation and GRS-like vortices problems in planetary atmospheres. We discovered that slowly-rotating planets can have super-rotation at high energy state. All known slowly-rotating cases in the solar system---Venus and Titan---have super-rotation. Moreover, we showed that the anticyclonicity in the GRS-like structures is closely associated with the

  10. Predicting mixed-gas adsorption equilibria on activated carbon for precombustion CO2 capture.

    Science.gov (United States)

    García, S; Pis, J J; Rubiera, F; Pevida, C

    2013-05-21

    We present experimentally measured adsorption isotherms of CO2, H2, and N2 on a phenol-formaldehyde resin-based activated carbon, which had been previously synthesized for the separation of CO2 in a precombustion capture process. The single component adsorption isotherms were measured in a magnetic suspension balance at three different temperatures (298, 318, and 338 K) and over a large range of pressures (from 0 to 3000-4000 kPa). These values cover the temperature and pressure conditions likely to be found in a precombustion capture scenario, where CO2 needs to be separated from a CO2/H2/N2 gas stream at high pressure (~1000-1500 kPa) and with a high CO2 concentration (~20-40 vol %). Data on the pure component isotherms were correlated using the Langmuir, Sips, and dual-site Langmuir (DSL) models, i.e., a two-, three-, and four-parameter model, respectively. By using the pure component isotherm fitting parameters, adsorption equilibrium was then predicted for multicomponent gas mixtures by the extended models. The DSL model was formulated considering the energetic site-matching concept, recently addressed in the literature. Experimental gas-mixture adsorption equilibrium data were calculated from breakthrough experiments conducted in a lab-scale fixed-bed reactor and compared with the predictions from the models. Breakthrough experiments were carried out at a temperature of 318 K and five different pressures (300, 500, 1000, 1500, and 2000 kPa) where two different CO2/H2/N2 gas mixtures were used as the feed gas in the adsorption step. The DSL model was found to be the one that most accurately predicted the CO2 adsorption equilibrium in the multicomponent mixture. The results presented in this work highlight the importance of performing experimental measurements of mixture adsorption equilibria, as they are of utmost importance to discriminate between models and to correctly select the one that most closely reflects the actual process.

  11. Selective adsorption and phase equilibria of confined fluids: Density-functional theory and Monte Carlo simulation

    Science.gov (United States)

    Sowers, Susanne Lynn

    1997-11-01

    Microporous sorbents such as carbons, silicas and aluminas are used commercially in a variety of separation, purification and selective reaction applications. A detailed study of the effects of the porous material characteristics on the adsorption equilibrium properties such as selectivity and phase equilibria of fluid mixtures can enhance our understanding of adsorption on a molecular level. Such knowledge will improve our utilization of such adsorbents and provide a tool for directing the future of tailoring sorbents for particular separation processes. The effect of pore size, shape and pressure on the selective adsorption of trace pollutants from an inert gas was studied using prototype mixtures of Lennard-Tones (LJ) N2/CCl4, CF4, and SO2. Both nonlocal density functional theory (DFT) and grand canonical Monte Carlo (GCMC) molecular simulations were used in order to investigate the validity of the theory, which is much quicker and easier to use. Our results indicate that there is an optimal pore size and shape for which the pollutant selectivity is greatly enhanced. In many industrial adsorption processes relative humidity can greatly affect the life of an adsorbent bed, as seen in breakthrough curves. Therefore, the influence of water vapor on the selective adsorption of CCl4 from a mixture of N2/CCl4/H20 in activated carbon was studied using GCMC simulations. The equilibrium adsorption properties are found to be dependent upon both the density of active sites on the pore walls and the relative humidity. Liquid-liquid transitions in porous materials are of interest in connection with oil recovery, lubrication, coating technology and pollution control. The results of a study on the effect of confinement on the liquid-liquid equilibrium of binary LJ mixtures using DFT are compared with those of molecular simulation and experiments. Our findings show that the phase coexistence for the confined mixture is in general decreased and shifted toward the component which

  12. High temperature phase equilibria studies in the Bi-Sr-Ca-Cu-O-Ag system

    Energy Technology Data Exchange (ETDEWEB)

    Margulies, Lawrence

    1999-11-08

    A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi-Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO{sub 2}). A liquid immiscibility region between oxide and Ag liquids in the 8--98 at% range was found above 900 C. Two eutectics were found in the Bi2212-Ag pseudobinary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15 C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO{sub 2} range studied. The stability of these solid phases were found to be highly sensitive to PO{sub 2}, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by the significant thermal gradients and lack of full bulk sampling which is inherent in conventional HTXRD designs. In part 2, a new furnace design compatible with synchrotron radiation sources is introduced to address these problems. This design allows for full bulk sampling in a low thermal gradient environment using Debye-Scherrer transmission geometry. Sample spinning is also introduced in the design to eliminate preferred orientation and incomplete powder averaging and allow for quantitative phase analysis and structural refinement. Studies on model systems are presented to demonstrate the capabilities for high resolution structural studies (Al{sub 2}O{sub 3}) and time resolved phase transformation studies (SrCO{sub 3}). Finally, the Bi2212 system is examined to confirm the quenching results

  13. NATO Advanced Study Institute on Advances in Chemical Reaction Dynamics

    CERN Document Server

    Capellos, Christos

    1986-01-01

    This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys­ tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidati...

  14. Experimental study and modelling of competitive adsorption equilibria of aromatics in liquid phase on X and Y faujasites; Etude experimentale et modelisation des equilibres d'adsorption competitive d'aromatiques en phase liquide sur des faujasites X et Y

    Energy Technology Data Exchange (ETDEWEB)

    Tournier, H.

    2000-10-13

    The separation of p-xylene from C{sub 8} aromatics is performed industrially by selective adsorption on zeolitic molecular sieves. The aim of this work is to study and model adsorption equilibria of C{sub 8} and C{sub 10} aromatics on X and Y zeolites. The experimental data are obtained by an entirely automated equipment allowing to work in a large range of temperature (50 deg. C - 250 deg. C). With this equipment, we can follow the evolution of the composition of the liquid phase and determine the composition of the adsorbed phase at equilibrium by a mass balance calculation and with an inert component. Two analytical techniques are used to determine the composition of the liquid phase: (1) a classical method using a gas chromatograph (GC) allowed to measure selectivities in the concentration range (3%-97%) in a component; (2) an original method based on the use and on the measure of {sup 13}C labelled xylenes was developed to investigate the ranges of strongly contrasting concentrations [0-3%] and [97%-100%] in a component, which are representative of high purity domains. Lastly, three thermodynamic models are used to describe the adsorption equilibria: the Langmuir-Freundlich model, the quasi-chemical model and the statistical model. The last model is the more interesting, because it is based on physical considerations. A new statistical model has been developed with taking into account some observations coming from adsorption phenomenon in zeolites. (author)

  15. The New Low Value for the Second Dissociation Constant for H2S: Its History, Its Best Value, and Its Impact on the Teaching of Sulfide Equilibria.

    Science.gov (United States)

    Myers, Rollie J.

    1986-01-01

    Discusses the historical development of a new value of the second dissociation constant (K2) for hydrogen sulfide (H2S). Describes the differences between the traditional high values for K2. Suggests modification of teaching about sulfide equilibria in light of the new low value for K2. (TW)

  16. Modelling the phase equilibria of multicomponent mixtures containing CO2, alkanes, water, and/or alcohols using the quadrupolar CPA equation of state

    DEFF Research Database (Denmark)

    Bjørner, Martin Gamel; Kontogeorgis, Georgios

    2016-01-01

    In this work, a quadrupolar cubic plus association (qCPA) equation of state is evaluated for its ability to predict the phase equilibria of multicomponent mixtures containing CO2 and alkanes, alcohols, and/or water. A single binary interaction parameter is employed in qCPA for all binary...

  17. Random-lattice models and simulation algorithms for the phase equilibria in two-dimensional condensed systems of particles with coupled internal and translational degrees of freedom

    DEFF Research Database (Denmark)

    Nielsen, Morten; Miao, Ling; Ipsen, John Hjorth;

    1996-01-01

    In this work we concentrate on phase equilibria in two-dimensional condensed systems of particles where both translational and internal degrees of freedom are present and coupled through microscopic interactions, with a focus on the manner of the macroscopic coupling between the two types...

  18. Vapor Pressure Plus: An Experiment for Studying Phase Equilibria in Water, with Observation of Supercooling, Spontaneous Freezing, and the Triple Point

    Science.gov (United States)

    Tellinghuisen, Joel

    2010-01-01

    Liquid-vapor, solid-vapor, and solid-liquid-vapor equilibria are studied for the pure substance water, using modern equipment that includes specially fabricated glass cells. Samples are evaporatively frozen initially, during which they typically supercool to -5 to -10 [degrees]C before spontaneously freezing. Vacuum pumping lowers the temperature…

  19. Vapor-liquid (VLE) and liquid-liquid (LLE) phase equilibria calculations for polystyrene plus methyleyclohexane and polystyrene plus cyclohexane solutions

    DEFF Research Database (Denmark)

    Wilczura-Wachnik, H.; Jonsdottir, Svava Osk

    2006-01-01

    This paper presents the vapor-liquid (VLE) and liquid-liquid (LLE) phase equilibria predictions for polystyrene in two theta solvents: cyclohexane and methylcyclohexane. VLE calculations were performed with the Elbro free volume method and a modified version of the PC-SAFT method, as well...

  20. Oxygen equilibria and ligand binding kinetics of erythrocruorins from two burrowing polychaetes of different modes of life, Marphysa sanguinea and Diopatra cuprea

    DEFF Research Database (Denmark)

    Weber, Roy E.; Bonaventura, J.; Sullivan, B.;

    1978-01-01

    Oxygen equilibria, ligand-binding kinetics and some other physicochemical properties are reported for erythrocruorins of two intertidal polychaetes:Marphysa sanguinea, which inhabits simple, relatively stagnant burrows, andDiopatra cuprea, which inhabits impermeable, parchment-like tubes that are...

  1. An Introduction to Multivariate Curve Resolution-Alternating Least Squares: Spectrophotometric Study of the Acid-Base Equilibria of 8-Hydroxyquinoline-5-Sulfonic Acid

    Science.gov (United States)

    Rodriguez-Rodriguez, Cristina; Amigo, Jose Manuel; Coello, Jordi; Maspoch, Santiago

    2007-01-01

    A spectrophotometric study of the acid-base equilibria of 8-hydroxyquinoline-5-sulfonic acid to describe the multivariate curve resolution-alternating least squares algorithm (MCR-ALS) is described. The algorithm provides a lot of information and hence is of great importance for the chemometrics research.

  2. Equation of state modeling of the phase equilibria of asymmetric CO2+n-alkane binary systems using mixing rules cubic with respect to mole fraction

    DEFF Research Database (Denmark)

    Cismondi, Martin; Mollerup, Jørgen M.; Zabaloy, Marcelo S.

    2010-01-01

    Both the equation of state (EOS) and the quadratic mixing rules proposed by van der Waals towards the end of the XIX century were enormous contributions to the understanding and modeling of fluids phase behavior. They set the basis for a consistent and useful representation of phase equilibria...

  3. Aluminum Deoxidation Equilibria in Liquid Iron: Part III—Experiments and Thermodynamic Modeling of the Fe-Mn-Al-O System

    Science.gov (United States)

    Paek, Min-Kyu; Do, Kyung-Hyo; Kang, Youn-Bae; Jung, In-Ho; Pak, Jong-Jin

    2016-10-01

    Deoxidation equilibria in high-Mn- and high-Al-alloyed liquid steels were studied over the entire Fe-Mn-Al composition range by both experiments and thermodynamic modeling. Effect of Mn on the Al deoxidation equilibria in liquid iron was measured by the different experimental techniques depending on the Al content. In order to confirm the reproducibility of the experimental results, the deoxidation experiments were carried out reversibly from high oxygen state by addition of Al as a deoxidizer, and from low oxygen state by addition of Fe2O3 or MnO as an oxygen source. For the Al-rich side, CaO flux was added on top of liquid iron in order to remove suspended Al2O3 inclusions in the melt. Based on the present experimental result and available critically evaluated literature data, the Al deoxidation equilibria in Fe-Mn-Al-O liquid alloy were thermodynamically modeled. The Modified Quasichemical Model was used in order to take into account a strong short-range ordering of atoms in molten state. Deoxidation equilibria and inclusion stability diagram for entire Fe-Mn-Al melt were successfully reproduced by the present model.

  4. Surprising Impact of Remote Groups on the Folding-Unfolding and Dimer-Chain Equilibria of Bifunctionl H-Bonding Unimers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Rui; Cheng, Shuang; Baker, Erin Shammel; Smith, Richard D.; Zeng, Xiao Cheng; Gong, Bing

    2016-01-28

    Oligoamide 1, consisting of two H-bonding units linked by a trimethylene linker, was previously found to form a very stable, folded dimer. In this work, replacing the side chains and end groups of 1 led to derivatives that show the surprising impact of end groups on the folding and dimer-chain equilibria of the resultant molecules.

  5. Isothermal Vapor-liquid Equilibria for the Binary Mixtures of 3-Methylpentane with Ethylene Glycol Monopropyl Ether and Ethylene Glycol Isopropyl Ether

    Energy Technology Data Exchange (ETDEWEB)

    Hyeong, Seonghoon; Jang, Sunghyun; Kim, Hwayong [Seoul National University, Seoul (Korea, Republic of)

    2015-02-15

    Isothermal vapor liquid equilibria for the binary system of 3-methylpentane with ethylene glycol monopropyl ether (C{sub 3}E{sub 1}) and ethylene glycol isopropyl ether (iC{sub 3}E{sub 1}) were measured at 303.15, 318.15, and 333.15K. In our previous work, phase equilibria for the binary system of C{sub 3}E{sub 1} mixtures were investigated according to the chain length of alkane, alcohol or those isomer. But in this study, we discussed the different effect of C{sub 3}E{sub 1} and its isomer, iC{sub 3}E{sub 1}, on the phase equilibria. The measured systems were correlated with a Peng-Robinson equation of state (PR EOS) combined with Wong-Sandler mixing rule for the vapor phase, and NRTL, UNIQUAC, and Wilson activity coefficient models for the liquid phase. All the measured systems showed good agreement with the correlation results. And it was found that the phase equilibria showed very little difference between the iC{sub 3}E{sub 1} mixture system and the C{sub 3}E{sub 1} mixture system.

  6. Concordant chemical reaction networks and the Species-Reaction Graph.

    Science.gov (United States)

    Shinar, Guy; Feinberg, Martin

    2013-01-01

    In a recent paper it was shown that, for chemical reaction networks possessing a subtle structural property called concordance, dynamical behavior of a very circumscribed (and largely stable) kind is enforced, so long as the kinetics lies within the very broad and natural weakly monotonic class. In particular, multiple equilibria are precluded, as are degenerate positive equilibria. Moreover, under certain circumstances, also related to concordance, all real eigenvalues associated with a positive equilibrium are negative. Although concordance of a reaction network can be decided by readily available computational means, we show here that, when a nondegenerate network's Species-Reaction Graph satisfies certain mild conditions, concordance and its dynamical consequences are ensured. These conditions are weaker than earlier ones invoked to establish kinetic system injectivity, which, in turn, is just one ramification of network concordance. Because the Species-Reaction Graph resembles pathway depictions often drawn by biochemists, results here expand the possibility of inferring significant dynamical information directly from standard biochemical reaction diagrams.

  7. Measurement of liquid-liquid equilibria for condensate + glycol and condensate + glycol + water systems

    DEFF Research Database (Denmark)

    Riaz, Muhammad; Kontogeorgis, Georgios; Stenby, Erling Halfdan

    2011-01-01

    Today's oil and gas production requires the application of various chemicals in large amounts. To evaluate the effects of those chemicals on the environment, it is of crucial importance to know how much of the chemicals are discharged via produced water and how much is dissolved in the crude oil....... The ultimate objective of this work is to develop a predictive thermodynamic model for the mutual solubility of oil, water, and polar chemicals. But for the development and validation of the model, experimental data are required. This work presents new experimental liquid-liquid equilibrium (LLE) data for 1......,2-ethanediol (MEG) + condensate and MEG + water + condensate systems at temperatures from (275 to 323) K at atmospheric pressure. The condensate used in this work is a stabilized natural gas condensate from an offshore field in the North Sea. Compositional analysis of the natural gas condensate was carried out...

  8. Chemical sensors

    Science.gov (United States)

    Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

    1991-07-02

    Sensors responsive to small changes in the concentration of chemical species are disclosed. The sensors comprise a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment. They are operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical response. 9 figures.

  9. Degree of Chemical Non-equilibrium in Central Au-Au Collisions at RHIC energies

    CERN Document Server

    Tawfik, Abdel Nasser; Habashy, D M; Mohamed, M T; Abbas, Ehab

    2014-01-01

    We investigate the difference between hadron resonance gas (HRG) calculations for chemical freeze-out parameters at fully and partly chemical equilibria. To this end, the results are compared with the particle ratios measured in central Au-Au collisions at a wide range of nucleon-nucleon center-of-mass energies, \\hbox{$\\sqrt{s_{NN}}=7.7-200 $GeV} as offered by the STAR experiment. We restrict the discussion to STAR, because of large statistics and overall homogeneity of STAR measurements (one detector) against previous experiments. We find that the matter produced at these energies is likely in fully chemical equilibrium, which is consistent with recent lattice QCD results. The possible improvements by partial chemical equilibrium ($\\gamma_S\

  10. Kinetic study of radiation-reaction-limited particle acceleration during the relaxation of unstable force-free equilibria

    CERN Document Server

    Yuan, Yajie; Zrake, Jonathan; East, William E; Blandford, Roger D

    2016-01-01

    Many powerful and variable gamma-ray sources, including pulsar wind nebulae, active galactic nuclei and gamma-ray bursts, seem capable of accelerating particles to gamma-ray emitting energies efficiently over very short time scales. These are likely due to rapid dissipation of electromagnetic energy in a highly magnetized, relativistic plasma. In order to understand the generic features of such processes, we have investigated simple models based on relaxation of unstable force-free magnetostatic equilibria. In this work, we make the connection between the corresponding plasma dynamics and the expected radiation signal, using 2D particle-in-cell simulations that self-consistently include synchrotron radiation reaction. We focus on the lowest order unstable force-free equilibrium in a 2D periodic box. We find that rapid variability, with modest apparent radiation efficiency as perceived by a fixed observer, can be produced during the evolution of the instability. The "flares" are accompanied by an increased pol...

  11. Breakup of a transient wetting layer in polymer blend thin films: unification with 1D phase equilibria.

    Science.gov (United States)

    Coveney, Sam; Clarke, Nigel

    2013-09-20

    We show that lateral phase separation in polymer blend thin films can proceed via the formation of a transient wetting layer which breaks up to give a laterally segregated film. We show that the growth of lateral inhomogeneities at the walls in turn causes the distortion of the interface in the transient wetting layer. By addressing the 1D phase equilibria of a polymer blend thin film confined between selectively attracting walls, we show that the breakup of a transient wetting layer is due to wall-blend interactions; there are multiple values of the volume fraction at the walls which solve equilibrium boundary conditions. This mechanism of lateral phase separation should be general.

  12. Liquid/gas and liquid/liquid phase equilibria of the system water/bovine serum albumin.

    Science.gov (United States)

    Antonov, Yurij; Eckelt, John; Sugaya, Rei; Wolf, Bernhard A

    2013-05-09

    The thermodynamic behavior of the system H2O/BSA was studied at 25 °C within the entire composition range: vapor pressure measurements via head space sampling gas chromatography demonstrate that the attainment of equilibria takes more than one week. A miscibility gap was detected via turbidity and the coexisting phases were analyzed. At 6 °C the two phase region extends from ca. 34 to 40 wt % BSA; it shrinks upon heating. The polymer rich phase is locally ordered, as can be seen under the optical microscope using crossed polarizers. The Flory-Huggins theory turns out to be inappropriate for the modeling of experimental results. A phenomenological expression is employed which uses three adjustable parameters and describes the vapor pressures quantitatively; it also forecasts the existence of a miscibility gap.

  13. Phase equilibria and liquid phase epitaxy growth of PbSnSeTe lattice matched to PbSe

    Science.gov (United States)

    Mccann, Patrick J.; Fonstad, Clifton G.; Fuchs, Jacob; Feit, Ze'ev

    1987-01-01

    The necessary phase diagram data for growing lattice-matched layers of PbSnSeTe on PbSe are presented. Solid compounds of Pb(1-x)Sn(x)Se(1-y)Te(y) lattice-matched to PbSe were grown from liquid melts consisting of (Pb/1-x/Sn/x/)(1-z)(Se/1-y/Te/y/)(z); phase equilibria data were determined together with liquidus data for values of x(liquid) from 0 to 40 percent and y(liquid) from 0 to 40 percent for temperatures between 450 and 540 C. It was found that relatively large amounts of Te must be added to the melt to achieve lattice matching because of its low segregation coefficient relative to Se. A significant lattice-pulling effect was discovered for the 5-percent Sn case, and a similar effect is expected for the 10- and 20-percent Sn cases.

  14. Optimized Mie potentials for phase equilibria: Application to noble gases and their mixtures with n-alkanes.

    Science.gov (United States)

    Mick, Jason R; Soroush Barhaghi, Mohammad; Jackman, Brock; Rushaidat, Kamel; Schwiebert, Loren; Potoff, Jeffrey J

    2015-09-21

    Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions.

  15. Performance of predictive models in phase equilibria of complex associating systems: PC-SAFT and CEOS/GE

    Directory of Open Access Journals (Sweden)

    N. Bender

    2013-03-01

    Full Text Available Cubic equations of state combined with excess Gibbs energy predictive models (like UNIFAC and equations of state based on applied statistical mechanics are among the main alternatives for phase equilibria prediction involving polar substances in wide temperature and pressure ranges. In this work, the predictive performances of the PC-SAFT with association contribution and Peng-Robinson (PR combined with UNIFAC (Do through mixing rules are compared. Binary and multi-component systems involving polar and non-polar substances were analyzed. Results were also compared to experimental data available in the literature. Results show a similar predictive performance for PC-SAFT with association and cubic equations combined with UNIFAC (Do through mixing rules. Although PC-SAFT with association requires less parameters, it is more complex and requires more computation time.

  16. Phase equilibria, crystal structure and oxygen content of intermediate phases in the Y-Ba-Co-O system

    OpenAIRE

    A.S. Urusova; Cherepanov, V. A.; Aksenova, T. V.; Gavrilova, L. Y.; Kiselev, E. A.

    2013-01-01

    The phase equilibria in the Y-Ba-Co-O system were systematically studied at 1373 K in air. The intermediate phases formed in the Y-Ba-Co-O system at 1373 K in air were: YBaCo2O5+δ, YBaCo4O 7 and BaCo1-yYyO3-δ (0.09≤y≤0.42). It was shown that YBaCo2O5+δ possesses tetragonal structure with the 3ap×3a p×2ap superstructure (sp. gr. P4/mmm). High-temperature X-ray diffraction analysis of the YBaCo2O 5+δ in the temperature range from 298 K up to 1073 K under Po2=0.21 atm has not shown any phase tra...

  17. The human homolog of a candidate mouse t complex responder gene: conserved motifs and evolution with punctuated equilibria.

    Science.gov (United States)

    Islam, S D; Pilder, S H; Decker, C L; Cebra-Thomas, J A; Silver, L M

    1993-12-01

    The mouse Tcp-10 gene has been established as a molecular candidate for the t complex responder locus which plays a central role in the transmission ratio distortion phenotype expressed by males heterozygous for a t haplotype. Here we describe a comparison of the mouse and human TCP10 coding sequences. The results show that whole exons have been added or eliminated from the transcripts expressed in each species, suggesting an evolutionary process of punctuated equilibria for this gene. Two of the polypeptide regions that are most conserved between the two species contain specific peptide motifs. The conserved C-terminal region contains a unique nonapeptide repeat of unknown function and the conserved N-terminal region contains a pair of leucine zippers within a region that shows additional similarity to the coiled-coil regions of various cytosolic polypeptides. These results are discussed in terms of the possible function of the TCP10 protein.

  18. Phase equilibria in the Mg-rich corner of the Mg-Zn-La system at 350℃

    Institute of Scientific and Technical Information of China (English)

    LI Hongxiao; REN Yuping; HUANG Mingli; CHEN Qin; HAO Shiming

    2006-01-01

    The phase equilibria in the Mg-rich corner of the Mg-Zn-La system at 350℃ have been investigated by scanning electron microscopy, X-ray diffraction, and electron probe microanalysis. It has been shown that the linear compound (Mg,Zn)17La2 existed in the Mg-Zn-La system at 350℃. The linear compound (so-called T phase) was with the C-centred orthorhombic crystal structure induced by the solution of significant quantities of the third element. The three-phase region α(Mg) + MgZn(La) + T and the two-phase region composed of the α(Mg) and the linear-compound T phase existed in the Mg-rich corner of the Mg-Zn-La system at 350℃.

  19. Equilibria and kinetics for pH-dependent axial ligation of bromomethyl(aquo)cobaloxime by aliphatic amine ligands

    Indian Academy of Sciences (India)

    M Bhoopal; N Ravi Kumar Reddy; S Satyanarayana

    2003-04-01

    Kinetics and equilibria of axial ligation of bromomethyl(aquo) cobaloxime by a series of straight chain primary amines (methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine), cycloamines (cyclopentylamine, cyclohexylamine, cycloheptylamine) and secondary amines (N,N-dimethylamine, N,N-diethylamine) have been measured as functions of pH by spectrophotometric technique in aqueous solution, ionic strength 1 M (KCl) at 25°C. The rate of substitution of H2O varies with the Ka of incoming ligand, thus establishing nucleophilic participation of the ligand in the transition state. Binding and kinetic data are interpreted based on the basicity and steric influence of the entering ligand. To compare the rate constants of the entering ligands, pH independent second-order rate constants (on) are calculated.

  20. Prediction of vapor-liquid equilibria for the alcohol + glycerol systems using UNIFAC and modified UNIFAC (Dortmund)

    Science.gov (United States)

    Hartanto, Dhoni; Mustain, Asalil; Nugroho, Febry Dwi

    2017-03-01

    The vapor-liquid equilibria for eight systems of alcohols + glycerol at 101.325 kPa have been predicted in this study using UNIFAC and Modified UNIFAC (Dortmund) group contribution methods. The investigated alcohols were methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol. In order to study the accuracy of both contribution methods, the predicted data obtained from both approaches were compared to the experimental data from the literature. The prediction accuracy using modified UNIFAC (Dortmund) give better results compared to the UNIFAC method for (ethanol, 1-propanol, 2-propanol and 1-butanol) + glycerol but UNIFAC method show better accuracy for methanol + glycerol system. In addition, the influences of carbon chain length on the phase behaviours of alcohol + glycerol systems were also discussed as well.

  1. Chemical intolerance

    DEFF Research Database (Denmark)

    Dantoft, Thomas Meinertz; Andersson, Linus; Nordin, Steven;

    2015-01-01

    Chemical intolerance (CI) is a term used to describe a condition in which the sufferer experiences a complex array of recurrent unspecific symptoms attributed to low-level chemical exposure that most people regard as unproblematic. Severe CI constitutes the distinguishing feature of multiple...... chemical sensitivity (MCS). The symptoms reported by CI subjects are manifold, involving symptoms from multiple organs systems. In severe cases of CI, the condition can cause considerable life-style limitations with severe social, occupational and economic consequences. As no diagnostic tools for CI...

  2. Hazardous Chemicals

    Centers for Disease Control (CDC) Podcasts

    2007-04-10

    Chemicals are a part of our daily lives, providing many products and modern conveniences. With more than three decades of experience, The Centers for Disease Control and Prevention (CDC) has been in the forefront of efforts to protect and assess people's exposure to environmental and hazardous chemicals. This report provides information about hazardous chemicals and useful tips on how to protect you and your family from harmful exposure.  Created: 4/10/2007 by CDC National Center for Environmental Health.   Date Released: 4/13/2007.

  3. Detection of interstellar DNC - Difficulties of chemical equilibrium hypothesis for enrichment

    Science.gov (United States)

    Godfrey, P. D.; Brown, R. D.; Gunn, H. I.; Blackman, G. L.; Storey, J. W. V.

    1977-01-01

    The J = 1-0 transition of DNC at 76.3058 GHz has been observed in emission in NGC 2264. Comparison with previous observations of HN(C-13) indicates that deuterium is enriched in DNC similarly to the enrichment reported for DCO(+) in this source. The DNC/HNC ratio is estimated to be about 1/24. The results cannot readily be interpreted in terms of chemical equilibria relating to the formation of DNC. It is suggested that the explanation must be sought in isotope effects on rates of formation of interstellar molecules.

  4. Phase Equilibria Constraints on Relations of Ore-bearing Intrusionswith Flood Basalts in the Panxi Region, Southwestern China

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhaochong; HAO Yanli; AI Yu; LI Ying; ZHAO Li

    2009-01-01

    There are two types of temporally and spatially associated intrusions within the Emeishan large igneous province (LIP); namely, small uitramafic subvolcanic sills that host magmatic Cu-Ni-Platinum Group Element (PGE)-bearing sulfide deposits and large mafic layered intrusions that host giant Ti-V magnetite deposits in the Panxi region. However, except for their coeval ages, the genetic relations between the ore-bearing intrusions and extrusive rocks are poorly understood. Phase equilibria analysis (Q-PI-OI-Opx-Cpx system) has been carried out to elucidate whether ore-bearing Panzhihua, Xinjie and Limahe intrusions are co-magmatic with the picrites and flood basalts (including high-Ti, low-Ti and alkali basalts), respectively. In this system, the parental magma can be classified as silica-undersaturated olivine basalt and silica-saturated tholeiite. The equivalents of the parental magma of the Xinjie and Limahe peridotites and picrites and iow-Ti basalts are silica-undersaturated, whereas the Limahe gabbro-diorites and high-Ti basalts are silica-saturated. In contrast, the Panzhihua intrusion appears to be alkali character. Phase equilibria relations clearly show that the magmas that formed the Panzhihua intrusion and high-Ti basalts cannot be co-magmatic as there is no way to derive one liquid from another by fractional crystallization. On the other hand, the Panzhihua intrusion appears to be related to Permian alkali intrusions in the region, but does not appear to be related to the alkali basalts recognized in the Longzhoushan lava stratigraphy. Comparably, the Limabe intrusion appears to be a genetic relation to the picrites, whereas the Xinjie intrusion may be genetically related to be low-Ti basaits. Additionally, the gabbro-diorites and peridotites of the Limahe intrusion are not co-magmatic, and the former appears to be derived liquid from high-Ti basalts.

  5. Experimental study of the phase equilibria in the Mg–Zn–Ag ternary system at 300 °C

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jian, E-mail: jian.wang@polymtl.ca [Center for Research in Computational Thermochemistry (CRCT), Department of Chemical Engineering, École Polytechnique, Montréal, Québec H3C 3A7 (Canada); Zhang, Yi-Nan [Department of Mechanical Engineering, Concordia University, 1455 De Maisonneuve Blvd. West, Montreal, Quebec H3G 1M8 (Canada); Hudon, Pierre; Jung, In-Ho [Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, Quebec H3A 0C5 (Canada); Medraj, Mamoun [Department of Mechanical Engineering, Concordia University, 1455 De Maisonneuve Blvd. West, Montreal, Quebec H3G 1M8 (Canada); Department of Mechanical and Materials Engineering, Masdar Institute, Masdar City, P.O. Box 54224, Abu Dhabi (United Arab Emirates); Chartrand, Patrice [Center for Research in Computational Thermochemistry (CRCT), Department of Chemical Engineering, École Polytechnique, Montréal, Québec H3C 3A7 (Canada)

    2015-08-05

    Highlights: • The phase equilibria of Mg–Zn–Ag system at 300 °C were determined. • A bcc continuous ternary solid solution forms between MgAg (bcc-B2) and AgZn (bcc-A2) was determined. • The extended solid solubilities of the sub-binary compounds were also determined. - Abstract: The phase equilibria in the Mg–Zn–Ag ternary system at 300 °C were investigated using three diffusion couples and 35 key samples. Scanning electron microscopy (SEM) equipped with energy-dispersive spectroscope (EDS) and X-ray diffraction (XRD) techniques were used for homogeneity ranges and crystal structure determination. Large solid solubility limits, due to substitution among Mg, Zn and Ag atoms in Mg{sub 3}Ag and MgZn{sub 2} phases, were observed in the present work. Solid solubility limits of Ag and Zn in the hcp (Mg) phase were found to be less than 1 at.%. The extended solid solubilities of the Mg{sub 12}Zn{sub 13}, Mg{sub 2}Zn{sub 3}, MgZn{sub 2} (C14), Mg{sub 2}Zn{sub 11}, Ag{sub 5}Zn{sub 8} and hcp (AgZn{sub 3}) sub-binary compounds were also determined in the Mg–Zn–Ag ternary system. In addition, a bcc continuous ternary solid solution forms between MgAg (bcc-B2) and AgZn (bcc-A2) at 300 °C.

  6. Quaternary liquid/liquid equilibria of sodium sulfate, sodium sulfite and water with two solvents: Acetone and 2-propanol

    Energy Technology Data Exchange (ETDEWEB)

    Schiozer, A.L.

    1994-03-01

    Aqueous solutions of sodium sulfate and sodium sulfite are produced from sodium carbonate in flue-gas scrubbers; recovery of these salts often requires multi-effect evaporators; however, a new energy-efficient unit operation called extractive crystallization has been shown to have reduced energy costs. In this process, an organic solvent is added to the aqueous salt solution to precipitate salt. Acetone is a suitable solvent for this process, better than 2-propanol. Liquid/liquid/solid equilibria for ternary systems containing a salt, water, and an organic solvent were measured. Systems investigated were sodium sulfite/water/acetone and sodium sulfite/water/2-propanol. Experiments were conducted at salt saturation covering a temperature range between the lower consolute temperature and 48.6{degrees}C. In the attempt to improve the extractive crystallization process for recovery of sodium sulfate from flue-gas scrubbers, attention was given to a feed containing a mixture of sodium sulfite and sodium sulfate. Liquid-liquid equilibria for quaternary systems containing two salts, water, and an organic solvent were experimentally determined at 35{degrees}C. The systems investigated were sodium sulfate/sodium sulfite/water/acetone and sodium sulfate/sodium sulfite/water/2propanol. The systems were studied at three salt ratios. For each salt ratio, experiments were conducted starting at saturation, water was then added until the one-phase region was reached. Mixtures of the two salts proved to have a small disadvantage relative to the 100 % sulfate feed process. Therefore, a sulfate-based extractive crystallization process is recommended.

  7. Monte Carlo simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB): Pressure and temperature effects for the solid phase and vapor-liquid phase equilibria.

    Science.gov (United States)

    Rai, Neeraj; Bhatt, Divesh; Siepmann, J Ilja; Fried, Laurence E

    2008-11-21

    The transferable potentials for phase equilibria (TraPPE) force field was extended to nitro and amino substituents for aromatic rings via parametrization to the vapor-liquid coexistence curves of nitrobenzene and aniline, respectively. These groups were then transferred to model 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Without any further parametrization to solid state data, the TraPPE force field is able to predict TATB's unit cell lengths and angles at 295 K with mean unsigned percentage errors of 0.3% and 1.8% and the specific density within 0.5%. These predictions are comparable in accuracy to the GRBF model [Gee et al., J. Chem. Phys. 120, 7059 (2004)] that was parametrized directly to TATB's solid state properties. Both force fields are able to reproduce the pressure dependence of TATB's unit cell volume, but they underestimate its thermal expansion. Due to its energetic nature and unusually large cohesive energy, TATB is not chemically stable at temperature in its liquid range. Gibbs ensemble simulations allow one to determine TATB's vapor-liquid coexistence curve at elevated temperatures and the predicted critical temperature and density for the TraPPE and GRBF model are 937+/-8 and 1034+/-8 K, and 0.52+/-0.02 and 0.50+/-0.02 gcm(3), respectively.

  8. 用重整化群理论研究硬核Asakura-Oosawa流体的相平衡%Study on the Phase Equilibria of Hard Core Asakura-Oosawa Fluids with Renormalization-group Theory

    Institute of Scientific and Technical Information of China (English)

    付东

    2004-01-01

    An analytical equation of state (EOS) for hard core Asakura-Oosawa (AO) fluid is established by combining the AO potential, the first-order perturbation theory and the radial distribution function (RDF) for the hard sphere fluid. The phase equilibria are studied by using the renormalization-group (RG) theory. The obtained results agree well with the simulation data. Investigation shows that the attractive range parameter plays an important role in the phase equilibria for AO fluid.

  9. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    studies of catalytic chemical reactions in dense and supercritical carbon dioxide have been complemented by the theoretical calculations of phase equilibria using advanced thermodynamic models. In the recent years, the use of compressed carbon dioxide as innovative, non-toxic and non-flammable, cheap...... is discussed more extensively. Heterogeneously catalysed hydrogenation reactions are considered to be quite well studied and established. However, the catalyst performance can alter significantly when the reaction is performed in carbon dioxide medium. This effect was studied with the example of the selective...... the selective hydrogenation of unsaturated aldehydes in carbon dioxide medium. It was found that supported tungstosilicic acid catalysts and acidic resin Amberlyst-15 are very effective for performing aldol reactions. The positive influence of temperature and CO2-content on catalyst activity was studied...

  10. Calcium, Strontium and Barium Homogeneous Catalysts for Fine Chemicals Synthesis.

    Science.gov (United States)

    Sarazin, Yann; Carpentier, Jean-François

    2016-12-01

    The large alkaline earths (Ae), calcium, strontium and barium, have in the past 15 years yielded a brand new generation of heteroleptic molecular catalysts for the production of fine chemicals. However, the integrity of these complexes is often plagued by ligand redistribution equilibria in solution. This personal account retraces the paths followed in our research group towards the design of stable heteroleptic alkalino-earth complexes, including the use of intramolecular noncovalent Ae···H-Si and Ae···F-C interactions. Their implementation as homogenous precatalysts for reactions such as the intramolecular and intermolecular hydroamination and hydrophosphination of activated alkenes, the hydrophosphonylation of ketones, and the dehydrogenative coupling of amines and hydrosilanes that enable the efficient and controlled formations of CP, CN, or SiN σ-bonds, is presented in a synthetic perspective that highlights their overall outstanding catalytic performance.

  11. Phase equilibria calculation of LaI3-MI (M=Na, K, Cs) binary systems

    Institute of Scientific and Technical Information of China (English)

    WANG Yu; SHAO Guoquan; LI Shaobo; SUN Yimin; QIAO Zhiyu

    2009-01-01

    The Gibbs energies of liquid phases in the LaI3-MI (M=Na, K, Cs) systems were described by the modified quasi-chemical model. From the measured phase equilibrium data of these binary systems, a set of thermodynamic functions were optimized by using the CAL-PHAD technique. The enthalpy of mixing and the interaction parameter of the liquid phase were predicted from known data for the LaI3-MI systems.

  12. A New General System of Generalized Nonlinear Mixed Composite-Type Equilibria and Fixed Point Problems with an Application to Minimization Problems

    Directory of Open Access Journals (Sweden)

    Pongsakorn Sunthrayuth

    2012-01-01

    Full Text Available We introduce a new general system of generalized nonlinear mixed composite-type equilibria and propose a new iterative scheme for finding a common element of the set of solutions of a generalized equilibrium problem, the set of solutions of a general system of generalized nonlinear mixed composite-type equilibria, and the set of fixed points of a countable family of strict pseudocontraction mappings. Furthermore, we prove the strong convergence theorem of the purposed iterative scheme in a real Hilbert space. As applications, we apply our results to solve a certain minimization problem related to a strongly positive bounded linear operator. Finally, we also give a numerical example which supports our results. The results obtained in this paper extend the recent ones announced by many others.

  13. Solid-Liquid Equilibria of Musk Ketone, Musk Xylene and 1,3-Dimethyl-2,4-Dinitro-5-Tert-Butyl Benzene

    Institute of Scientific and Technical Information of China (English)

    曲红梅; 白鹏; 杨志才; 余国琮

    2004-01-01

    The solid-liquid equilibria of musk ketone + musk xylene, musk xylene+1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutectics. Moreover the melting points and the fusion enthalpies of musk ketone, musk xylene and 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are also measured by the DSC. These solid-liquid equilibrium data and the heats of fusion are reported for the first time. Then UNIFAC model is used to correlate the solid-liquid equilibrium data.It is shown that the solid-liquid equilibria of musk systems can be predicted bv the UNIFAC model.

  14. Extension of LCVM-type mixing rule to three-parameter equations of state for vapor-liquid equilibria of mixtures

    Institute of Scientific and Technical Information of China (English)

    HAN Xiao-hong; CHEN Guang-ming; WANG Qin; CUI Xiao-long

    2005-01-01

    In this paper, the LCVM mixing rule is extended to the multi-parameter equations of state by combining infinite-pressure and zero-pressure mixing rule models. The new LCVM-type mixing rule, coupled with Patel-Teja equation of state(EOS) is applied for vapor-liquid equilibria of different polar and non-polar systems in which the NRTL activity coefficient model is used to calculate the excess Gibbs free energy. The tested results agree well with existing experimental data within a wide range of temperatures and pressures. In comparison with the Van der Waals mixing rule, the new mixing rule gives much better correlations for the vapor-liquid equilibria of non-polar and polar systems.

  15. Chemical Mahjong

    Science.gov (United States)

    Cossairt, Travis J.; Grubbs, W. Tandy

    2011-01-01

    An open-access, Web-based mnemonic game is described whereby introductory chemistry knowledge is tested using mahjong solitaire game play. Several tile sets and board layouts are included that are themed upon different chemical topics. Introductory tile sets can be selected that prompt the player to match element names to symbols and metric…

  16. Chemical dispersants

    NARCIS (Netherlands)

    Rahsepar, Shokouhalsadat; Smit, Martijn P.J.; Murk, Albertinka J.; Rijnaarts, Huub H.M.; Langenhoff, Alette A.M.

    2016-01-01

    Chemical dispersants were used in response to the Deepwater Horizon oil spill in the Gulf of Mexico, both at the sea surface and the wellhead. Their effect on oil biodegradation is unclear, as studies showed both inhibition and enhancement. This study addresses the effect of Corexit on oil biodeg

  17. Fac-mer equilibria of coordinated iminodiacetate (ida2-) in ternary CuII(ida)(H-1B)- complex formation (B = imidazole, benzimidazole) in aqueous solution

    Indian Academy of Sciences (India)

    Susmita Bandyopadhyay; G N Mukherjee

    2003-08-01

    pH potentiometric and spectrophotometric investigations on the complex formation equilibria of CuII with iminodiacetate (ida2-) and heterocyclic N-bases, viz. imidazole and benzimidazole (B), in aqueous solution in binary and ternary systems using different molar ratios of the reactants indicated the formation of complexes of the types, Cu(ida), Cu(ida)(OH)-, (ida)Cu(OH)Cu(ida)-, Cu(B)2+, Cu(H-1B)+, Cu(ida)(H-1B)-, (ida)Cu(B)Cu(ida) and (ida)Cu(H-1B)Cu(ida)-. Formation constants of the complexes at 25 ± 1° at a fixed ionic strength, = 0.1 mol dm-3 (NaNO3) in aqueous solution were evaluated and the complex formation equilibria were elucidated with the aid of speciation curves. Departure of the experimental values of the reproportionation constants (log Cu) of ternary Cu(ida)(H-1B)- complexes from the statistically expected values, despite their formation in appreciable amounts at equilibrium, were assigned to fac(f)-mer(m) equilibria of the ida2- ligand coordinated to CuII, as the N-heterocyclic donors, (H-1B)-, coordinate trans- to the N-(ida2-) atom in the binary Cu(ida) complex to form the ternary Cu(ida) (H-1B)- complexes.

  18. Asymmetric kinetic equilibria: Generalization of the BAS model for rotating magnetic profile and non-zero electric field

    Science.gov (United States)

    Dorville, Nicolas; Belmont, Gérard; Aunai, Nicolas; Dargent, Jérémy; Rezeau, Laurence

    2015-09-01

    Finding kinetic equilibria for non-collisional/collisionless tangential current layers is a key issue as well for their theoretical modeling as for our understanding of the processes that disturb them, such as tearing or Kelvin Helmholtz instabilities. The famous Harris equilibrium [E. Harris, Il Nuovo Cimento Ser. 10 23, 115-121 (1962)] assumes drifting Maxwellian distributions for ions and electrons, with constant temperatures and flow velocities; these assumptions lead to symmetric layers surrounded by vacuum. This strongly particular kind of layer is not suited for the general case: asymmetric boundaries between two media with different plasmas and different magnetic fields. The standard method for constructing more general kinetic equilibria consists in using Jeans theorem, which says that any function depending only on the Hamiltonian constants of motion is a solution to the steady Vlasov equation [P. J. Channell, Phys. Fluids (1958-1988) 19, 1541 (1976); M. Roth et al., Space Sci. Rev. 76, 251-317 (1996); and F. Mottez, Phys. Plasmas 10, 1541-1545 (2003)]. The inverse implication is however not true: when using the motion invariants as variables instead of the velocity components, the general stationary particle distributions keep on depending explicitly of the position, in addition to the implicit dependence introduced by these invariants. The standard approach therefore strongly restricts the class of solutions to the problem and probably does not select the most physically reasonable. The BAS (Belmont-Aunai-Smets) model [G. Belmont et al., Phys. Plasmas 19, 022108 (2012)] used for the first time the concept of particle accessibility to find new solutions: considering the case of a coplanar-antiparallel magnetic field configuration without electric field, asymmetric solutions could be found while the standard method can only lead to symmetric ones. These solutions were validated in a hybrid simulation [N. Aunai et al., Phys. Plasmas (1994-present) 20

  19. Asymmetric kinetic equilibria: Generalization of the BAS model for rotating magnetic profile and non-zero electric field

    Energy Technology Data Exchange (ETDEWEB)

    Dorville, Nicolas, E-mail: nicolas.dorville@lpp.polytechnique.fr; Belmont, Gérard; Aunai, Nicolas; Dargent, Jérémy; Rezeau, Laurence [LPP, Ecole Polytechnique, CNRS, UPMC, Université Paris Sud, Palaiseau (France)

    2015-09-15

    Finding kinetic equilibria for non-collisional/collisionless tangential current layers is a key issue as well for their theoretical modeling as for our understanding of the processes that disturb them, such as tearing or Kelvin Helmholtz instabilities. The famous Harris equilibrium [E. Harris, Il Nuovo Cimento Ser. 10 23, 115–121 (1962)] assumes drifting Maxwellian distributions for ions and electrons, with constant temperatures and flow velocities; these assumptions lead to symmetric layers surrounded by vacuum. This strongly particular kind of layer is not suited for the general case: asymmetric boundaries between two media with different plasmas and different magnetic fields. The standard method for constructing more general kinetic equilibria consists in using Jeans theorem, which says that any function depending only on the Hamiltonian constants of motion is a solution to the steady Vlasov equation [P. J. Channell, Phys. Fluids (1958–1988) 19, 1541 (1976); M. Roth et al., Space Sci. Rev. 76, 251–317 (1996); and F. Mottez, Phys. Plasmas 10, 1541–1545 (2003)]. The inverse implication is however not true: when using the motion invariants as variables instead of the velocity components, the general stationary particle distributions keep on depending explicitly of the position, in addition to the implicit dependence introduced by these invariants. The standard approach therefore strongly restricts the class of solutions to the problem and probably does not select the most physically reasonable. The BAS (Belmont-Aunai-Smets) model [G. Belmont et al., Phys. Plasmas 19, 022108 (2012)] used for the first time the concept of particle accessibility to find new solutions: considering the case of a coplanar-antiparallel magnetic field configuration without electric field, asymmetric solutions could be found while the standard method can only lead to symmetric ones. These solutions were validated in a hybrid simulation [N. Aunai et al., Phys. Plasmas (1994-present

  20. Supply-demand equilibria and the size-number trade-off in spatially structured recreational fisheries.

    Science.gov (United States)

    Wilson, Kyle L; Cantin, Ariane; Ward, Hillary G M; Newton, Eric R; Mee, Jonathan A; Varkey, Divya A; Parkinson, Eric A; Post, John R

    2016-06-01

    Recreational fishing effort varies across complex inland landscapes (e.g., lake-districts) and appears influenced by both angler preferences and qualities of the fishery resource, like fish size and abundance. However, fish size and abundance have an ecological trade-off within a population, thereby structuring equal-quality isopleths expressing this trade-off across the fishing landscape. Since expressed preferences of recreational anglers (i.e., site-selection of high-quality fishing opportunities among many lakes) can be analogous to optimal foraging strategies of natural predators, adopting such concepts can aid in understanding scale-dependence in fish-angler interactions and impacts of fishing across broad landscapes. Here, we assumed a fish supply-angler demand equilibria and adapted a novel bivariate measure of fishing quality based on fish size and catch rates to assess how recreational anglers influence fishing quality among a complex inland landscape. We then applied this metric to evaluate (1) angler preferences for caught and released fish compared to harvested fish, (2) the nonlinear size-numbers trade-off with uncertainty in both traits, and (3) the spatial-scale of the equilibria across 62 lakes and four independent management regions in British Columbia's (BC) rainbow trout Oncorhynchus mykiss fishery. We found anglers had low preference for caught and released fish (~10% of the value compared to harvested fish), which modified anglers' perception of fishing quality. Hence, fishing quality and angler effort was not influenced simply by total fish caught, but largely by harvested fish catch rates. Fishing quality varied from BC's northern regions (larger fish and more abundant) compared to southern regions (smaller fish and less abundant) directly associated with a 2.5 times increase in annual fishing effort in southern regions, suggesting that latent fishing pressure can structure the size-numbers trade-off in rainbow trout populations. The

  1. Quantifying geological uncertainty in metamorphic phase equilibria modelling; a Monte Carlo assessment and implications for tectonic interpretations

    Directory of Open Access Journals (Sweden)

    Richard M. Palin

    2016-07-01

    Full Text Available Pseudosection modelling is rapidly becoming an essential part of a petrologist's toolkit and often forms the basis of interpreting the tectonothermal evolution of a rock sample, outcrop, or geological region. Of the several factors that can affect the accuracy and precision of such calculated phase diagrams, “geological” uncertainty related to natural petrographic variation at the hand sample- and/or thin section-scale is rarely considered. Such uncertainty influences the sample's bulk composition, which is the primary control on its equilibrium phase relationships and thus the interpreted pressure–temperature (P–T conditions of formation. Two case study examples—a garnet–cordierite granofels and a garnet–staurolite–kyanite schist—are used to compare the relative importance that geological uncertainty has on bulk compositions determined via (1 X-ray fluorescence (XRF or (2 point counting techniques. We show that only minor mineralogical variation at the thin-section scale propagates through the phase equilibria modelling procedure and affects the absolute P–T conditions at which key assemblages are stable. Absolute displacements of equilibria can approach ±1 kbar for only a moderate degree of modal proportion uncertainty, thus being essentially similar to the magnitudes reported for analytical uncertainties in conventional thermobarometry. Bulk compositions determined from multiple thin sections of a heterogeneous garnet–staurolite–kyanite schist show a wide range in major-element oxides, owing to notable variation in mineral proportions. Pseudosections constructed for individual point count-derived bulks accurately reproduce this variability on a case-by-case basis, though averaged proportions do not correlate with those calculated at equivalent peak P–T conditions for a whole-rock XRF-derived bulk composition. The main discrepancies relate to varying proportions of matrix phases (primarily mica relative to

  2. Phase equilibria study of the binary systems (1-butyl-3-methylimidazolium thiocyanate ionic liquid + organic solvent or water).

    Science.gov (United States)

    Domańska, Urszula; Laskowska, M; Pobudkowska, Aneta

    2009-05-07

    (Solid + liquid) phase equilibria (SLE) for the binary systems, ionic liquid (IL) 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN] with an alcohol (1-octanol, 1-nonanol, 1-decanol, 1-undecanol, or 1-dodecanol) or water, and (liquid + liquid) phase equilibria (LLE) for the binary systems of [BMIM][SCN] with an alkane (n-hexane, n-heptane, n-octane, n-nonane, or n-decane), benzene, an alkylbenzenes (toluene or ethylbenzene), tetrahydrofuran (THF), cycloalkanes (cyclohexane or cycloheptane), or ethers (di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether, n-butylmethyl ether, tert-butylmethyl ether (MTBE), or tert-butylethyl ether (ETBE)) have been determined at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from 250 to 430 K. In the case of systems IL + alkane, cycloalkane, or ether, the mutual immiscibility with an upper critical solution temperature (UCST) was detected, and in the systems of IL + benzene, alkylbenzene, or THF, the mutual immiscibility with a lower critical solution temperature (LCST) was observed. UV-vis spectroscopy was used to determine the very small compositions of the IL in the n-hexane (about 2 x 10(-5) IL mole fraction), benzene (about 2 x 10(-3) IL mole fraction), cyclohexane (about 2 x 10(-5) IL mole fraction), and THF (about 1.2 x 10(-2) IL mole fraction). For the binary systems containing alcohol, it was noticed that with increasing chain length of an alcohol, the solubility decreases. The basic thermal properties of the pure IL, that is, the glass-transition temperature as well as the heat capacity at the glass-transition temperature, have been measured using a differential scanning microcalorimetry technique (DSC). Decomposition of the IL was detected by the simultaneous TG/DTA experiments. Well-known UNIQUAC, Wilson, and NRTL equations have been used to correlate the experimental SLE data sets for alcohols and water. For the systems containing immiscibility gaps {IL + alkane

  3. Interest of thermochemical data bases linked to complex equilibria calculation codes for practical applications

    Energy Technology Data Exchange (ETDEWEB)

    Cenerino, G. [CEA Centre d`Etudes de Fontenay-aux-Roses, 92 (France). Dept. de Protection de l`Environnement et des Installations; Chevalier, P.Y.; Fischer, E. [Thermodata, 38 -Saint-Martin-d`Heres (France); Marbeuf, A. [Centre National de la Recherche Scientifique (CNRS), 92 - Meudon-Bellevue (France). Lab. de Magnetisme et de Physique du Solide; Frenk, A. [Ecole Polytechnique Federale, Lausanne (Switzerland); Vahlas, C. [Laboratoire Marcel Mathieu, Centre Helioparc, 64 - Pau (France)

    1992-12-31

    Since 1974, Thermodata has been working on developing an Integrated Information System in Inorganic Chemistry. A major effort was carried on the thermochemical data assessment of both pure substances and multicomponent solution phases. The available data bases are connected to powerful calculation codes (GEMINI = Gibbs Energy Minimizer), which allow to determine the thermodynamical equilibrium state in multicomponent systems. The high interest of such an approach is illustrated by recent applications in as various fields as semi-conductors, chemical vapor deposition, hard alloys and nuclear safety. (author). 26 refs., 6 figs.

  4. Ruthenium redox equilibria 1. Thermodynamic stability of Ru(III) and Ru(IV) hydroxides

    OpenAIRE

    Igor Povar; Oxana Spinu

    2016-01-01

    On the basis of the selected thermodynamic data for Ru(III) and Ru(IV) compounds in addition to original thermodynamic and graphical approach used in this paper, the thermodynamic stability areas of sparingly soluble hydroxides as well as the repartition of their soluble and insoluble chemical species towards the solution pH and initial concentrations of ruthenium in heterogeneous mixture solid phase–saturated solution have been investigated. By means of the ΔG–pH diagrams, the areas of therm...

  5. Liquid-Liquid Equilibria of Ternary Systems cis-1,2-Dimethylcyclohexane+Toluene+Sulfolane☆

    Institute of Scientific and Technical Information of China (English)

    Xiaoyan Sun; Shuguang Xiang

    2014-01-01

    Liquid–Liquid Equilibrium (LLE) data for three Ternary Systems comprising cis-1,2-dimethylcyclohexane+toluene+sulfolane were measured at 298.15, 313.15 and 328.15 K under atmospheric pressure. The phase di-agrams for the ternary systems were presented. The reliability of the experiment data was tested using the Othmer–Tobias correlation. The LLE data were then correlated with the universal functional activity coefficient for liquid–liquid systems (UNIF-LL) and non-random two liquid using dataset 2 (NRTL/2) activity coefficient models to obtain the binary interaction parameters as programmed by the Aspen Plus simulation. The results showed that the experimental data were satisfactorily represented by both the UNIF-LL and the NRTL/2 models as revealed from the very smal values of the root mean square error and the absolute deviation in composition. © 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. Al rights reserved.

  6. A Modified Mixing Rule for PSRK Model and Application for the Prediction of Vapor-Liquid Equilibria of Polymer Solutions

    Institute of Scientific and Technical Information of China (English)

    李敏; 王利生; J.Gmehling

    2004-01-01

    To extend the PSRK (predictive Soave-Redlich-Kwong equation of state) model to vapor-liquid equilibria of polymer solutions, a new EOS-gE mixing rule is applied in which the term ∑xiln(b/bi) in the PSRK mixing rule for the parameter a, and the combinatorial part in the original universal functional activity coefficient (UNIFAC) model are cancelled. To take into account the free volume contribution to the excess Gibbs energy in polymer solution, a quadratic mixing rule for the cross co-volume bij with an exponent equals to 1/2 is applied [bij1/2=1/2(bi1/2+bj1/2)]. The literature reported Soave-Redlich-Kwong equation of state (SRK EOS) parameters of i3 - 2- pure polymer are employed. The PSRK model with the modified mixing rule is used to predict the vapor-liquid equilibrium (VLE) of 37 solvent-polymer systems over a large range of temperature and pressure with satisfactory results.

  7. Phase equilibria constraints on pre-eruptive magma storage conditions for the 1956 eruption of Bezymianny Volcano, Kamchatka, Russia

    Science.gov (United States)

    Shcherbakov, Vasily D.; Neill, Owen K.; Izbekov, Pavel E.; Plechov, Pavel Yu.

    2013-08-01

    Phase equilibria experiments were performed on andesites from the catastrophic 1956 eruption of Bezymianny Volcano, Kamchatka, Russia, to determine pre-eruptive magma storage conditions. Fifteen experiments were conducted under water-saturated conditions, with oxygen fugacity equal to the Ni-NiO oxygen buffer, at temperatures between 775 and 1100 °C and pressures between 50 and 200 MPa. Simultaneous amphibole and plagioclase crystallization is reproduced at ≤ 850 °C and ≥ 200 MPa. The simultaneous crystallization temperature range of the plagioclase-clinopyroxene-orthopyroxene-Fe-Ti oxide assemblage increases with decreasing pressure, from 840 to 940 °C at 150 MPa to 940-1020 °C at 50 MPa. Melt inclusion compositions in plagioclase phenocrysts and matrix glass match experimental melt compositions reproduced at 50-100 MPa and ≤ 50 MPa, respectively. Presence of the silica phase in groundmass and mature amphibole breakdown rims suggests that magma has been stored at ca. 3 km depth prior to the final ascent for at least 40 days. Syn-eruptive ascent led to decompression-driven crystallization, which caused a temperature increase from 850-900 °C to 950-1000 °C.

  8. High-Temperature Phase Equilibria of Duplex Stainless Steels Assessed with a Novel In-Situ Neutron Scattering Approach

    Science.gov (United States)

    Pettersson, Niklas; Wessman, Sten; Hertzman, Staffan; Studer, Andrew

    2017-01-01

    Duplex stainless steels are designed to solidify with ferrite as the parent phase, with subsequent austenite formation occurring in the solid state, implying that, thermodynamically, a fully ferritic range should exist at high temperatures. However, computational thermodynamic tools appear currently to overestimate the austenite stability of these systems, and contradictory data exist in the literature. In the present work, the high-temperature phase equilibria of four commercial duplex stainless steel grades, denoted 2304, 2101, 2507, and 3207, with varying alloying levels were assessed by measurements of the austenite-to-ferrite transformation at temperatures approaching 1673 K (1400 °C) using a novel in-situ neutron scattering approach. All grades became fully ferritic at some point during progressive heating. Higher austenite dissolution temperatures were measured for the higher alloyed grades, and for 3207, the temperature range for a single-phase ferritic structure approached zero. The influence of temperatures in the region of austenite dissolution was further evaluated by microstructural characterization using electron backscattered diffraction of isothermally heat-treated and quenched samples. The new experimental data are compared to thermodynamic calculations, and the precision of databases is discussed.

  9. New insight into phase equilibria involving imidazolium bistriflamide ionic liquids and their mixtures with alcohols and water.

    Science.gov (United States)

    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.

  10. Transferable potentials for phase equilibria-united atom description of five- and six-membered cyclic alkanes and ethers.

    Science.gov (United States)

    Keasler, Samuel J; Charan, Sophia M; Wick, Collin D; Economou, Ioannis G; Siepmann, J Ilja

    2012-09-13

    While the transferable potentials for phase equilibria-united atom (TraPPE-UA) force field has generally been successful at providing parameters that are highly transferable between different molecules, the polarity and polarizability of a given functional group can be significantly perturbed in small cyclic structures, which limits the transferability of parameters obtained for linear molecules. This has motivated us to develop a version of the TraPPE-UA force field specifically for five- and six-membered cyclic alkanes and ethers. The Lennard-Jones parameters for the methylene group obtained from cyclic alkanes are transferred to the ethers for each ring size, and those for the oxygen atom are common to all compounds for a given ring size. However, the partial charges are molecule specific and parametrized using liquid-phase dielectric constants. This model yields accurate saturated liquid densities and vapor pressures, critical temperatures and densities, normal boiling points, heat capacities, and isothermal compressibilities for the following molecules: cyclopentane, tetrahydrofuran, 1,3-dioxolane, cyclohexane, oxane, 1,4-dioxane, 1,3-dioxane, and 1,3,5-trioxane. The azeotropic behavior and separation factor for the binary mixtures of 1,3-dioxolane/cyclohexane and ethanol/1,4-dioxane are qualitively reproduced.

  11. Standard state Gibbs energies of hydration of hydrocarbons at elevated temperatures as evaluated from experimental phase equilibria studies

    Science.gov (United States)

    Plyasunov, Andrey V.; Shock, Everett L.

    2000-08-01

    Experimental results of phase equilibria studies at elevated temperatures for more than twenty hydrocarbon-water systems were uniformly correlated within the framework of the Peng-Robinson-Stryjek-Vera equation of state in combination with simple mixing rules. This treatment allows evaluation of the Gibbs energy of hydration for many alkanes, 1-alkenes, cycloalkanes (derivatives of cyclohexane) and alkylbenzenes up to 623 K at saturated water vapor pressure and up to 573 K at 50 MPa. Results for homologous series show regular changes with increasing carbon number, and confirm the applicability of the group contribution approach to the Gibbs energy of hydration of hydrocarbons at elevated temperatures. The temperature dependence of group contributions to the Gibbs energy of hydration were determined for CH 3, CH 2, and CH in aliphatic hydrocarbons; C=C and H for alkenes; c-CH 2 and c-CH in cycloalkanes; and CH ar and C ar in alkylbenzenes (or aromatic hydrocarbons). Close agreement between calculated and experimental results suggests that this approach provides reasonable estimates of Gibbs energy of hydration for many alkanes, 1-alkenes, alkyl cyclohexanes and alkylbenzenes at temperatures up to 623 K and pressures up to 50 MPa.

  12. Implications of climate variability for the detection of multiple equilibria and for rapid transitions in the atmosphere-vegetation system

    Energy Technology Data Exchange (ETDEWEB)

    Bathiany, S. [Max Planck Institute for Meteorology, Hamburg (Germany); Claussen, M. [Max Planck Institute for Meteorology, Hamburg (Germany); Universitaet Hamburg, Meteorologisches Institut, Hamburg (Germany); Fraedrich, K. [Universitaet Hamburg, Meteorologisches Institut, Hamburg (Germany)

    2012-05-15

    Paleoclimatic records indicate a decline of vegetation cover in the Western Sahara at the end of the African Humid Period (about 5,500 years before present). Modelling studies have shown that this phenomenon may be interpreted as a critical transition that results from a bifurcation in the atmosphere-vegetation system. However, the stability properties of this system are closely linked to climate variability and depend on the climate model and the methods of analysis. By coupling the Planet Simulator (PlaSim), an atmosphere model of intermediate complexity, with the simple dynamic vegetation model VECODE, we assess previous methods for the detection of multiple equilibria, and demonstrate their limitations. In particular, a stability diagram can yield misleading results because of spatial interactions, and the system's steady state and its dependency on initial conditions are affected by atmospheric variability and nonlinearities. In addition, we analyse the implications of climate variability for the abruptness of a vegetation decline. We find that a vegetation collapse can happen at different locations at different times. These collapses are possible despite large and uncorrelated climate variability. Because of the nonlinear relation between vegetation dynamics and precipitation the green state is initially stabilised by the high variability. When precipitation falls below a critical threshold, the desert state is stabilised as variability is then also decreased. (orig.)

  13. Kinetics and equilibria for the axial ligation of bromomethyl (aqua)cobaloxime with pyridines - Isolation characterization and DNA binding

    Indian Academy of Sciences (India)

    Kotha Laxma Reddy; K Ashwini Kumar; N Ravi Kumar Reddy; Penumaka Nagababu; A Panasa Reddy; S Satyanarayana

    2009-11-01

    The kinetics and equilibria for the axial ligation of pyridine and substituted pyridines to bromomethyl(aqua)cobaloxime have been measured spectrophotometrically in aqueous solutions of ionic strength 1.0 M (KC1) at 25°C as a function of H. The binding constants and rate of formation increase in the order 4-NH2Py 4-EtPy > 4-MePy > Py > 2-NH2Py > 2-EtPy. The data have been interpreted based on the basicity of the ligand, -back bonding from Co(III) → L and hard and soft interactions. The rate of substitution of H2O varies with the pKa of the incoming ligand, thus establishing the existence of nucleophilic participation of the ligand in the transition state. We have investigated the DNA binding of bromomethyl(aqua)cobaloxime with DNA. Bromomethyl(ligand)cobaloximes were isolated and characterized by elemental analysis, IR and NMR (1H, 13C) spectra.

  14. Equilibria and Free Vibration of a Two-Pulley Belt-Driven System with Belt Bending Stiffness

    Directory of Open Access Journals (Sweden)

    Jieyu Ding

    2014-01-01

    Full Text Available Nonlinear equilibrium curvatures and free vibration characteristics of a two-pulley belt-driven system with belt bending stiffness and a one-way clutch are investigated. With nonlinear dynamical tension, the transverse vibrations of the translating belt spans and the rotation motions of the pulleys and the accessory shaft are coupled. Therefore, nonlinear piecewise discrete-continuous governing equations are established. Considering the bending stiffness of the translating belt spans, the belt spans are modeled as axially moving beams. The pattern of equilibria is a nontrivial solution. Furthermore, the nontrivial equilibriums of the dynamical system are numerically determined by using two different approaches. The governing equations of the vibration near the equilibrium solutions are derived by introducing a coordinate transform. The natural frequencies of the dynamical systems are studied by using the Galerkin method with various truncations and the differential and integral quadrature methods. Moreover, the convergence of the Galerkin truncation is investigated. Numerical results reveal that the study needs 16 terms after truncation in order to determine the free vibration characteristics of the pulley-belt system with the belt bending stiffness. Furthermore, the first five natural frequencies are very sensitive to the bending stiffness of the translating belt.

  15. Mixed-ligand complex formation equilibria of CuII with biguanide in presence of glycine as the auxiliary ligand

    Indian Academy of Sciences (India)

    Tannistha Roy Barman; G N Mukherjee

    2006-09-01

    Equilibrium study on the mixed ligand complex formation of CuII with biguanide(Bg) and glycine (HG), indicated the formation of the complexes: Cu(Bg)2+, Cu(Bg)$_{2}^{2+}$, Cu(Bg-H)(Bg)+, Cu(Bg-H)2, Cu(Bg)(OH)+, Cu(Bg-H)(OH); Cu(G)+, Cu(G)(OH), Cu(G)2; Cu(G)(Bg)+, Cu(G)(Bg-H); (G)Cu(Bg)Cu(G)2+, (G)Cu(Bg-H)Cu(G)+, and (G)Cu(Bg-2H)Cu(G). From the deprotonation constants of coordinated biguanide (Bg) in the complexes Cu(Bg)(OH)+, Cu(Bg-H)(Bg)+ and Cu(G)(Bg)+, the Lewis basicities of the coordinated ligand species (Bg-H)-, OH- and glycinate (G-) were found to be of the order: (Bg-H)- >> OH- > G-. Bridging (N1-N4, N2-N5) tetradentate mode of coordination by biguanide species Bg, (Bg-H)- and (Bg-2H)2- was indicated from the occurrence of biguanide-bridged dinuclear mixed ligand complexes (G)Cu(Bg)Cu(G)2+, (G)Cu(Bg-H)Cu(G)+, (G)Cu(Bg-2H)Cu(G) in the complexation equilibria.

  16. PD-FiTE - an efficient method for calculating gas / liquid equilibria in atmospheric aerosol particles

    Science.gov (United States)

    Topping, D.; Lowe, D.; McFiggans, G.; Barley, M.

    2009-04-01

    Assessing the impact of atmospheric aerosol particles on the environment requires adequate representation of appropriate key processes within large scale models. In the absence of primary particulate material, interactions between the atmospheric gaseous components and particles means that the chemical nature of the particles is largely determined by the availability of condensable gaseous material, such as sulphuric and nitric acids, and by the ambient environmental conditions. Gas to particle mass transfer of semi-volatile components,driven by a difference in equilibrium and actual partial pressures above an aerosol particle, is an important factor in determining the evolving chemical composition of the particle and is necessary for predicting aerosol loading and composition. The design of an appropriate framework required for parameterizations of key variables is challenging. These thermodynamic frameworks are often numerically very complex, resulting in significant computational expense. Three dimensional chemical and aerosol transport models demand that computational expense be kept at a minimum,resulting in a trade-off between accuracy and efficiency. To calculate the equilibrium vapour pressure above a solution requires treatment of solution nonideality. This is manifest through activity coefficients of components pertinent to each condensing specie. However, activity coefficients are complex functions of the solution composition. Parameterisation of activity coefficients provides the main focus of this work largely because reducing the numerical complexity whilst retaining a good level of accuracy is very challenging. The approach presented here, the hybrid Partial Derivative Fitted Taylor Expansion (PDFiTE) (Topping et al 2008), builds on previously reported work, with an aim to derive parameters for an accurate and computationally efficient framework through coupling with a complex thermodynamic model. Such a reduction in complexity is important as it is

  17. Global existence and asymptotic stability of equilibria to reaction-diffusion systems

    Science.gov (United States)

    Wang, Rong-Nian; Tang, Zhong Wei

    2009-06-01

    In this paper, we study weakly coupled reaction-diffusion systems in unbounded domains of {\\bb R}^2 or {\\bb R}^3 , where the reaction terms are sums of quasimonotone nondecreasing and nonincreasing functions. Such systems are more complicated than those in many previous publications and little is known about them. A comparison principle and global existence, and boundedness theorems for solutions to these systems are established. Sufficient conditions on the nonlinearities, ensuring the positively Ljapunov stability of the zero solution with respect to H2-perturbations, are also obtained. As samples of applications, these results are applied to an autocatalytic chemical model and a concrete problem, whose nonlinearities are nonquasimonotone. Our results are novel. In particular, we present a solution to an open problem posed by Escher and Yin (2005 J. Nonlinear Anal. Theory Methods Appl. 60 1065-84).

  18. Modelling of phase equilibria and related properties of mixtures involving lipids

    DEFF Research Database (Denmark)

    Cunico, Larissa

    Many challenges involving physical and thermodynamic properties in the production of edible oils and biodiesel are observed, such as availability of experimental data and realiable prediction. In the case of lipids, a lack of experimental data for pure components and also for their mixtures in open...... literature was observed, what makes it necessary to development reliable predictive models from limited data. One of the first steps of this project was the creation of a database containing properties of mixtures involved in tasks related to process design, simulation, and optimization as well as design...... of chemicals based products. This database was combined with the existing lipids database of pure component properties. To contribute to the missing data, measurements of isobaric vapour-liquid equilibrium (VLE) data of two binary mixtures at two different pressures were performed using Differential Scanning...

  19. The prediction of borate mineral equilibria in natural waters: Application to Searles Lake, California

    Science.gov (United States)

    Felmy, Andrew R.; Weare, John H.

    1986-12-01

    The chemical equilibrium model of HARVIEet al. (1984) has been extended to include borate species. The model is based upon the semi-empirical equations of PITZER (1973) and coworkers and is valid to high ionic strength (≈14 m) and high borate concentration. Excellent agreement with the existing emf, isopiestic and solubility data in the system (Na-K-Ca-Mg-H-Cl-SO4-CO2-B(OH)4-H2O) is obtained. Calculated mineral solubilities are in general within 10% of their experimental values, even at high ionic strengths. The model was applied to the multicomponent, high ionic strength (I ~ 10) and high borate concentration (BT ~ 0.5 m) Searles Lake evaporite deposit. Utilizing the chemical composition of the interstitial brine, the model predicts equilibrium between the brine and only those minerals which are known to be in contact with the brine. These calculations clearly demonstrate the applicability of the model to high ionic strength, high borate concentration natural waters. The model was also utilized to calculate the mineral sequences which should result from evaporation of the major source of water for Searles Lake, the Owens River. The geochemical conditions necessary for the formation of the most recent mud and saline units are examined. The final results indicate that the mineral sequences found in the most recent saline unit in Searles Lake can be produced by evaporation of a water close in composition to present Owens River water, provided primary dolomite formation is delayed and back reaction between the Parting Mud and the Upper Salt is inhibited.

  20. Temperature and pressure based NMR studies of detergent micelle phase equilibria.

    Science.gov (United States)

    Alvares, Rohan; Gupta, Shaan; Macdonald, Peter M; Prosser, R Scott

    2014-05-29

    Bulk thermodynamic and volumetric parameters (ΔGmic°, ΔHmic°, ΔSmic°, ΔCp,mic°, ΔVmic°, and Δκmic°) associated with the monomer–micelle equilibrium, were directly determined for a variety of common detergents [sodium n-dodecyl sulfate (SDS), n-dodecyl phosphocholine (DPC), n-dodecyl-β-d-maltoside (DDM), and 7-cyclohexyl-1-heptyl phosphocholine (CyF)] via 1H NMR spectroscopy. For each temperature and pressure point, the critical micelle concentration (cmc) was obtained from a single 1H NMR spectrum at a single intermediate concentration by referencing the observed chemical shift to those of pure monomer and pure micellar phases. This permitted rapid measurements of the cmc over a range of temperatures and pressures. In all cases, micelle formation was strongly entropically favored, while enthalpy changes were all positive, with the exception of SDS, which exhibited a modestly negative enthalpy of micellization. Heat capacity changes were also characteristically negative, while partial molar volume changes were uniformly positive, as expected for an aggregation process dictated by hydrophobic effects. Isothermal compressibility changes were found to be consistent with previous measurements using other techniques. Thermodynamic measurements were also related to spectroscopic studies of topology and micelle structure. For example, paramagnetic effects resulting from the addition of dioxygen provided microscopic topological details concerning the hydrophobicity gradient along the detergent chains within their respective micelles as detected by 1H NMR. In a second example, combined 13C and 1H NMR chemical shift changes arising from application of high pressure, or upon micellization, of CyF provided site-specific details regarding micelle topology. In this fashion, bulk thermodynamics could be related to microscopic topological details within the detergent micelle.

  1. Chemical carcinogenesis

    Directory of Open Access Journals (Sweden)

    Paula A. Oliveira

    2007-12-01

    Full Text Available The use of chemical compounds benefits society in a number of ways. Pesticides, for instance, enable foodstuffs to be produced in sufficient quantities to satisfy the needs of millions of people, a condition that has led to an increase in levels of life expectancy. Yet, at times, these benefits are offset by certain disadvantages, notably the toxic side effects of the chemical compounds used. Exposure to these compounds can have varying effects, ranging from instant death to a gradual process of chemical carcinogenesis. There are three stages involved in chemical carcinogenesis. These are defined as initiation, promotion and progression. Each of these stages is characterised by morphological and biochemical modifications and result from genetic and/or epigenetic alterations. These genetic modifications include: mutations in genes that control cell proliferation, cell death and DNA repair - i.e. mutations in proto-oncogenes and tumour suppressing genes. The epigenetic factors, also considered as being non-genetic in character, can also contribute to carcinogenesis via epigenetic mechanisms which silence gene expression. The control of responses to carcinogenesis through the application of several chemical, biochemical and biological techniques facilitates the identification of those basic mechanisms involved in neoplasic development. Experimental assays with laboratory animals, epidemiological studies and quick tests enable the identification of carcinogenic compounds, the dissection of many aspects of carcinogenesis, and the establishment of effective strategies to prevent the cancer which results from exposure to chemicals.A sociedade obtém numerosos benefícios da utilização de compostos químicos. A aplicação dos pesticidas, por exemplo, permitiu obter alimento em quantidade suficiente para satisfazer as necessidades alimentares de milhões de pessoas, condição relacionada com o aumento da esperança de vida. Os benefícios estão, por

  2. Chemical cosmology

    CERN Document Server

    Boeyens, Jan CA

    2010-01-01

    The composition of the most remote objects brought into view by the Hubble telescope can no longer be reconciled with the nucleogenesis of standard cosmology and the alternative explanation, in terms of the LAMBDA-Cold-Dark-Matter model, has no recognizable chemical basis. A more rational scheme, based on the chemistry and periodicity of atomic matter, opens up an exciting new interpretation of the cosmos in terms of projective geometry and general relativity. The response of atomic structure to environmental pressure predicts non-Doppler cosmical redshifts and equilibrium nucleogenesis by alp

  3. Physical-chemical conditions of ore deposition

    Science.gov (United States)

    Barton, P.B.

    1981-01-01

    Ore deposits form under a wide range of physical and chemical conditions, but those precipitating from hot, aqueous fluids-i.e. the hydrothermal deposits-form generally below 700??C and at pressures of only 1 or 2 kbar or less. Natural aqueous fluids in rocks may extract metal and sulfur from a variety of rock types or may acquire them as a residual heritage from a crystallizing silicate magma. Ore-forming hydrothermal fluids never appear as hot springs (except in deep, submarine situations) because they boil, mix with surface waters, and cool, thereby losing their ore-bearing ability before reaching the surface. Mineral systems function as chemical buffers and indicators just as buffers and indicators function in a chemical laboratory. By reading the record written in the buffer/indicator assemblages of minerals one can reconstruct many aspects of the former chemical environment. By studying the record of changing conditions one may deduce information regarding the processes functioning to create the succession of chemical environments and the ore deposits they represent. The example of the OH vein at Creede, Colorado, shows a pH buffered by the K-feldspar + muscovite + quartz assemblage and the covariation of S2 and O2 buffered by the assemblage chlorite + pyrite + quartz. Boiling of the ore fluid led to its oxidation to hematite-bearing assemblages and simultaneously produced an intensely altered, sericitic capping over the vein in response to the condensation of vapors bearing acidic components. The solubility of metals as calculated from experimental and theoretical studies of mineral solubility appears too low by at least one or two powers of ten to explain the mineralization at Creede. In contrast to Creede where the mineral stabilities all point to a relatively consistent chemistry, the Mississippi Valley type deposits present a puzzle of conflicting chemical clues that are impossible to reconcile with any single equilibrium situation. Thus we must

  4. Physical-chemical conditions of ore deposition

    Science.gov (United States)

    Barton, Paul B.

    Ore deposits form under a wide range of physical and chemical conditions, but those precipitating from hot, aqueous fluids-i.e. the hydrothermal deposits-form generally below 700°C and at pressures of only 1 or 2 kbar or less. Natural aqueous fluids in rocks may extract metal and sulfur from a variety of rock types or may acquire them as a residual heritage from a crystallizing silicate magma. Ore-forming hydrothermal fluids never appear as hot springs (except in deep, submarine situations) because they boil, mix with surface waters, and cool, thereby losing their ore-bearing ability before reaching the surface. Mineral systems function as chemical buffers and indicators just as buffers and indicators function in a chemical laboratory. By reading the record written in the buffer/indicator assemblages of minerals one can reconstruct many aspects of the former chemical environment. By studying the record of changing conditions one may deduce information regarding the processes functioning to create the succession of chemical environments and the ore deposits they represent. The example of the OH vein at Creede, Colorado, shows a pH buffered by the K-feldspar + muscovite + quartz assemblage and the covariation of S 2 and O 2 buffered by the assemblage chlorite + pyrite + quartz. Boiling of the ore fluid led to its oxidation to hematite-bearing assemblages and simultaneously produced an intensely altered, sericitic capping over the vein in response to the condensation of vapors bearing acidic components. The solubility of metals as calculated from experimental and theoretical studies of mineral solubility appears too low by at least one or two powers of ten to explain the mineralization at Creede. In contrast to Creede where the mineral stabilities all point to a relatively consistent chemistry, the Mississippi Valley type deposits present a puzzle of conflicting chemical clues that are impossible to reconcile with any single equilibrium situation. Thus we must

  5. Illinois basin coal fly ashes. 2. Equilibria relationships and qualitative modeling of ash-water reactions

    Science.gov (United States)

    Roy, W.R.; Griffin, R.A.

    1984-01-01

    Alkaline and acidic Illinois Basin coal fly ash samples were each mixed with deionized water and equilibrated for about 140 days to simulate ash ponding environments. Common to both equilibrated solutions, anhydrite solubility dominated Ca2+ activities, and Al3+ activities were in equilibrium with both matrix mullite and insoluble aluminum hydroxide phases. Aqueous silica activities were controlled by both mullite and matrix silicates. The pH of the extract of the acidic fly ash was 4.1 after 24 h but increased to a pH value of 6.4 as the H2SO4, assumed to be adsorbed to the particle surfaces, was exhausted by the dissolution of matrix iron oxides and aluminosilicates. The activities of aqueous Al3+ and iron, initially at high levels during the early stages of equilibration, decreased to below analytical detection limits as the result of the formation of insoluble Fe and Al hydroxide phases. The pH of the extract of the alkaline fly ash remained above a pH value of 10 during the entire equilibration interval as a result of the hydrolysis of matrix oxides. As with the acidic system, Al3+ activities were controlled by amorphous aluminum hydroxide phases that began to form after about 7 days of equilibration. The proposed mechanisms and their interrelations are discussed in addition to the solubility diagrams used to deduce these relationships. ?? 1984 American Chemical Society.

  6. Transferable force field for carboxylate esters: application to fatty acid methylic ester phase equilibria prediction.

    Science.gov (United States)

    Ferrando, Nicolas; Lachet, Véronique; Boutin, Anne

    2012-03-15

    In this work, a new transferable united-atoms force field for carboxylate esters is proposed. All Lennard-Jones parameters are reused from previous parametrizations of the AUA4 force field, and only a unique set of partial electrostatic charges is introduced for the ester chemical function. Various short alkyl-chain esters (methyl acetate, ethyl acetate, methyl propionate, ethyl propionate) and two fatty acid methylic esters (methyl oleate and methyl palmitate) are studied. Using this new force field in Monte Carlo simulations, we show that various pure compound properties are accurately predicted: saturated liquid densities, vapor pressures, vaporization enthalpies, critical properties, liquid-vapor surface tensions. Furthermore, a good accuracy is also obtained in the prediction of binary mixture pressure-composition diagrams, without introducing empirical binary interaction parameters. This highlights the transferability of the proposed force field and gives the opportunity to simulate mixtures of industrial interest: a demonstration is performed through the simulation of the methyl oleate + methanol mixture involved in the purification sections of biodiesel production processes.

  7. 化工分离中相平衡研究进展%Recent progress in the study of phase equilibria in chemical engineering separation

    Institute of Scientific and Technical Information of China (English)

    李群生; 郭凡

    2014-01-01

    相平衡是分离过程的理论基础,对化工分离过程中的理论研究和工业应用具有极为重要的价值.本文在介绍了汽-液相平衡热力学模型及固-液相平衡测定方法的基础上,综述了近年来以离子液体为溶剂的汽-液相平衡以及激光动态监测法固-液相平衡的研究进展,介绍了典型物系的相平衡研究近况,并在最后提出了几点对未来化工分离中相平衡重点研究方向的看法.

  8. An NMR and ab initio quantum chemical study of acid-base equilibria for conformationally constrained acidic alpha-amino acids in aqueous solution

    DEFF Research Database (Denmark)

    Nielsen, Peter Aadal; Jaroszewski, Jerzy W.; Norrby, Per-Ola

    2001-01-01

    The protonation states of a series of piperidinedicarboxylic acids (PDAs), which are conformationally constrained acidic alpha -amino acids, have been studied by C-13 NMR titration in water. The resulting data have been correlated with theoretical results obtained by HF/6-31+G* calculations using...

  9. Chemical Analyses

    Science.gov (United States)

    Bulluck, J. W.; Rushing, R. A.

    1994-01-01

    As a preliminary study on the effects of chemical aging of polymer materials MERL and TRI have examined two polymeric materials that are typically used for offshore umbilical applications. These two materials were Tefzel, a copolymer of ethylene and tetrafluoroethylene, and Coflon, polyvinylidene fluoride. The Coflon specimens were cut from pipe sections and exposed to H2S at various temperatures and pressures. One of these specimens was tested for methane permeation, and another for H2S permeation. The Tefzel specimens were cut from .05 mm sheet stock material and were exposed to methanol at elevated temperature and pressure. One of these specimens was exposed to methanol permeation for 2 days at 100 C and 2500 psi. An additional specimen was exposed to liquid methanol for 3 days at 150 C and 15 Bar. Virgin specimens of each material were similarly prepared and tested.

  10. Subsolidus phase equilibria and magnetic characterization of the pyrochlore in the Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub x} system

    Energy Technology Data Exchange (ETDEWEB)

    Egorysheva, A.V., E-mail: anna_egorysheva@rambler.ru [Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991 (Russian Federation); Ellert, O.G. [Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991 (Russian Federation); Maksimov, Yu.V. [Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991 (Russian Federation); Volodin, V.D.; Efimov, N.N.; Novotortsev, V.M. [Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991 (Russian Federation)

    2013-12-05

    Highlights: •We have constructed the isothermal section of the system Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub x}. •Ternary compound formation is limited to pyrochlore, which forms a solid solution region. •The phase diagram points out that 7–25% of Bi-positions are occupied with Fe{sup 3+}. •The Mossbauer data confirmed that Fe{sup 3+} ions enter the Bi-positions. •Magnetic measurements revealed spin-glass magnetic transition at 9 K. -- Abstract: The subsolidus phase equilibria of the Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub x} system have been investigated by X-ray powder diffraction. The isothermal section of the system at 775–800 °C has been constructed. It can be represented by 9 phase assemblage triangles. Ternary compound formation is limited to pyrochlore which forms a substantial solid solution region of Bi-deficient compositions relative to Bi{sub 2}FeSbO{sub 7}. As follows from the phase diagram, approximately 7–25% of Bi positions in pyrochlore may be occupied with Fe{sup 3+} ions that was confirmed by Mossbauer data. Magnetic measurements were carried out on the pyrochlore specimen of quasi-chemical formula (Bi{sub 1.8}Fe{sub 0.2})(FeSb)O{sub 7}. The existence of the strong short-range antiferromagnetic superexchange interactions and spin-glass magnetic transition at around 9 K were revealed.

  11. The “maturation” of milk for Parmigiano- Reggiano cheesemaking: effects on mineral equilibria and technological properties

    Directory of Open Access Journals (Sweden)

    P. Mariani

    2010-04-01

    Full Text Available The “maturation” of milk for Parmigiano-Reggiano cheese is characterised by natural creaming process: the full cream milk is placed in large flat vats, for about 10-12 hours, to obtain the gravity separation of milk fat. The modifications of mineral equilibria and technological properties of milk during the “maturation” phase, were studied. To this aim 24 full cream (FC milk samples and the corresponding partially skimmed (PS milk, by natural creaming, were analysed. PS milk evidenced higher values of both colloidal Ca/casein (+4.28%; P£0.01 and colloidal P/casein (+4.02%; P£0.01 ratios than FC milk. An increase of pH (+0.028; P£0.01 and titratable acidity (+0.03 °SH/50ml; P£0.01 was observed during the milk “maturation”. The PS milk was characterised by a higher milk clotting time (r (+7.91%; P£0.01 and a lower curd firmness (a30 (−16.75%; P£0.01 than FC milk. Concerning rheological properties, PS milk curd was characterised by higher values of both resistance to compression (+14.82%; P£0.01 and resistance to cut (+15.12%; P£0.01 than FC milk. The variations of milk characteristics observed in PS milk seems to indicate a structural modification of the native micelle during the “maturation” phase; this feature contributed to variations of rennet-coagulation and rheological properties observed in PS milk.

  12. Phase Equilibria, Microstructure, and High-Temperature Strength of TiC-Added Mo-Si-B Alloys

    Science.gov (United States)

    Miyamoto, Shimpei; Yoshimi, Kyosuke; Ha, Seong-Ho; Kaneko, Takahiro; Nakamura, Junya; Sato, Tetsuya; Maruyama, Kouichi; Tu, Rong; Goto, Takashi

    2013-05-01

    TiC was added to Mo-Si-B alloys using a conventional Ar arc-melting technique, and the phase equilibria, microstructure evolution, and high-temperature strength at 1673 K (1400 °C) were investigated. The primary phase changed to Mo solid solution (Moss), Mo5SiB2 (T2), or TiC depending on the composition. Following the primary phase solidification, a Moss + TiC, Moss + T2, or Moss + T2 + TiC + Mo2C eutectic reaction took place as the secondary solidification step. In some alloys, Moss + T2 + TiC and Moss + T2 + Mo2C eutectic reactions were present as higher-order solidification steps. After annealing at 2073 K (1800 °C) for 24 hours, Moss, T2, TiC, and Mo2C coexisted stably with microstructural coarsening. The coarsening rate was much faster in an alloy with no TiC dispersion, suggesting that TiC has a strong pinning effect on the grain boundary and interface migration. Compression tests conducted at 1673 K (1400 °C) revealed strength properties of almost all the alloys that were better than those of the Mo-Hf-C alloy (MHC). Alloy densities were 9 g/cm3 or less, which is lighter than pure Mo and MHC (≥10 g/cm3) and competitive with Ni-base superalloys. TiC-added Mo-Si-B alloys are promising candidates for ultrahigh-temperature materials beyond Ni-base superalloys.

  13. An LFER study of the protolytic equilibria of 4-aryl-2,4-dioxobutanoic acids in aqueous solutions

    Directory of Open Access Journals (Sweden)

    TATJANA Z. VERBIC

    2007-12-01

    Full Text Available The protolytic equilibria of 13 4-aryl-2,4-dioxobutanoic acids (ADKs were spectrophotometrically studied in aqueous solutions in the pH range 1–9 at 25±1 °C and an ionic strength of 0.1 mol l-1 (NaCl, with the exception of the 4-OH- derivative which was also potentiometrically studied in the pH range 7–10 at 25±1 °C and an ionic strength of 0.1 mol l-1 (NaCl. In solution, the compounds simultaneously exist in one diketo and two enolic forms; therefore, the determined acidity constants (pKa1 1.87–2.29, pKa2 6.63–8.13 and pKa3(4-OH- 9.52 represent system macro constants. The 1H-NMR spectrum of the basic compound (4-phenyl-2,4-dioxobutanoic acid (25 °C, pD 5.0 proved the existence of all tautomeric forms. Using the extended Hammett relation, the determined pKa values were correlated with literature σ values. The predicted pKa values were in fair accordance with the experimentally observed ones. Molecular, monoanionic and dianionic forms of the basic compound were optimized by the semi-empirical molecular orbital PM6 method using the implicit water solvation model (COSMO. The obtained geometries were used to explain the quality of the LFER models.

  14. Kinetic Study of Radiation-reaction-limited Particle Acceleration During the Relaxation of Unstable Force-free Equilibria

    Science.gov (United States)

    Yuan, Yajie; Nalewajko, Krzysztof; Zrake, Jonathan; East, William E.; Blandford, Roger D.

    2016-09-01

    Many powerful and variable gamma-ray sources, including pulsar wind nebulae, active galactic nuclei and gamma-ray bursts, seem capable of accelerating particles to gamma-ray emitting energies efficiently over very short timescales. These are likely due to the rapid dissipation of electromagnetic energy in a highly magnetized, relativistic plasma. In order to understand the generic features of such processes, we have investigated simple models based on the relaxation of unstable force-free magnetostatic equilibria. In this work, we make the connection between the corresponding plasma dynamics and the expected radiation signal, using 2D particle-in-cell simulations that self-consistently include synchrotron radiation reactions. We focus on the lowest order unstable force-free equilibrium in a 2D periodic box. We find that rapid variability, with modest apparent radiation efficiency as perceived by a fixed observer, can be produced during the evolution of the instability. The “flares” are accompanied by an increased polarization degree in the high energy band, with rapid variation in the polarization angle. Furthermore, the separation between the acceleration sites and the synchrotron radiation sites for the highest energy particles facilitates acceleration beyond the synchrotron radiation reaction limit. We also discuss the dynamical consequences of the radiation reaction, and some astrophysical applications of this model. Our current simulations with numerically tractable parameters are not yet able to reproduce the most dramatic gamma-ray flares, e.g., from the Crab Nebula. Higher magnetization studies are promising and will be carried out in the future.

  15. Computing the Stackelberg/Nash equilibria using the extraproximal method: Convergence analysis and implementation details for Markov chains games

    Directory of Open Access Journals (Sweden)

    Trejo Kristal K.

    2015-06-01

    Full Text Available In this paper we present the extraproximal method for computing the Stackelberg/Nash equilibria in a class of ergodic controlled finite Markov chains games. We exemplify the original game formulation in terms of coupled nonlinear programming problems implementing the Lagrange principle. In addition, Tikhonov’s regularization method is employed to ensure the convergence of the cost-functions to a Stackelberg/Nash equilibrium point. Then, we transform the problem into a system of equations in the proximal format. We present a two-step iterated procedure for solving the extraproximal method: (a the first step (the extra-proximal step consists of a “prediction” which calculates the preliminary position approximation to the equilibrium point, and (b the second step is designed to find a “basic adjustment” of the previous prediction. The procedure is called the “extraproximal method” because of the use of an extrapolation. Each equation in this system is an optimization problem for which the necessary and efficient condition for a minimum is solved using a quadratic programming method. This solution approach provides a drastically quicker rate of convergence to the equilibrium point. We present the analysis of the convergence as well the rate of convergence of the method, which is one of the main results of this paper. Additionally, the extraproximal method is developed in terms of Markov chains for Stackelberg games. Our goal is to analyze completely a three-player Stackelberg game consisting of a leader and two followers. We provide all the details needed to implement the extraproximal method in an efficient and numerically stable way. For instance, a numerical technique is presented for computing the first step parameter (λ of the extraproximal method. The usefulness of the approach is successfully demonstrated by a numerical example related to a pricing oligopoly model for airlines companies.

  16. Phase equilibria study of the binary systems (N-hexylisoquinolinium thiocyanate ionic liquid + organic solvent or water).

    Science.gov (United States)

    Królikowska, Marta; Karpińska, Monika; Zawadzki, Maciej

    2012-04-12

    Liquid-liquid phase equilibria (LLE) of binary mixtures containing a room-temperature ionic liquid N-hexylisoquinolinium thiocyanate, [HiQuin][SCN] with an aliphatic hydrocarbon (n-hexane, n-heptane), aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), cyclohexane, thiophene, water, and 1-alcohol (1-ethanol, 1-butanol, 1-hexanol, 1-octanol, 1-decanol) have been determined using a dynamic method from room temperature to the boiling-point of the solvent at ambient pressure. N-hexylisoquinolinium thiocyanate, [HiQuin][SCN] has been synthesized from N-hexyl-isoquinolinium bromide as a substrate. Specific basic characterization of the new compound including NMR spectra, elementary analysis, and water content have been done. The density and viscosity of pure ionic liquid were determined over a wide temperature range from 298.15 to 348.15 K. The mutual immiscibility with an upper critical solution temperature (UCST) for the binary systems {IL + aliphatic hydrocarbon, cyclohexane, or water} was detected. In the systems of {IL + aromatic hydrocarbon or thiophene} an immiscibility gap with a lower critical solution temperature (LCST) was observed. Complete miscibility in the liquid phase, over a whole range of ionic liquid mole fraction, was observed for the binary mixtures containing IL and an 1-alcohol. For the tested binary systems with immiscibility gap {IL + aliphatic hydrocarbon, aromatic hydrocarbon, cyclohexane, thiophene, or water}, the parameters of the LLE correlation have been derived using the NRTL equation. The basic thermal properties of the pure IL, that is, the glass-transition temperature as well as the heat capacity at the glass-transition temperature, have been measured using a differential scanning microcalorimetry technique (DSC). Decomposition of the IL was detected by simultaneous thermogravimetric/differential thermal analysis (TG/DTA) experiments.

  17. Phase equilibria and structural investigations in the Ni-poor part of the system Al-Ge-Ni.

    Science.gov (United States)

    Reichmann, Thomas L; Duarte, Liliana I; Effenberger, Herta S; Leinenbach, Christian; Richter, Klaus W

    2012-09-01

    The ternary phase diagram Al-Ge-Ni was investigated between 0 and 50 at.% Ni by a combination of differential thermal analysis (DTA), powder- and single-crystal X-ray diffraction (XRD), metallography and electron probe microanalysis (EPMA). Ternary phase equilibria and accurate phase compositions of the equilibrium phases were determined within two partial isothermal sections at 400 and 700 °C, respectively. The two binary intermediate phases AlNi and Al3Ni2 were found to form extended solid solutions with Ge in the ternary. Three new ternary phases were found to exist in the Ni-poor part of the phase diagram which were designated as τ1 (oC24, CoGe2-type), τ2 (at approximately Al67.5Ge18.0Ni14.5) and τ3 (cF12, CaF2-type). The ternary phases show only small homogeneity ranges. While τ1 was investigated by single crystal X-ray diffraction, τ2 and τ3 were identified from their powder diffraction pattern. Ternary phase reactions and melting behaviour were studied by means of DTA. A total number of eleven invariant reactions could be derived from these data, which are one ternary eutectic reaction, six transition reactions, three ternary peritectic reactions and one maximum. Based on the measured DTA values three vertical sections at 10, 20 and 35 at.% Ni were constructed. Additionally, all experimental results were combined to a ternary reaction scheme (Scheil diagram) and a liquidus surface projection.

  18. Transferable potentials for phase equilibria. 10. Explicit-hydrogen description of substituted benzenes and polycyclic aromatic compounds.

    Science.gov (United States)

    Rai, Neeraj; Siepmann, J Ilja

    2013-01-10

    The explicit-hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to various substituted benzenes through the parametrization of the exocyclic groups -F, -Cl, -Br, -C≡N, and -OH and to polycyclic aromatic hydrocarbons through the parametrization of the aromatic linker carbon atom for multiple rings. The linker carbon together with the TraPPE-EH parameters for aromatic heterocycles constitutes a force field for fused-ring heterocycles. Configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to compute vapor-liquid coexistence curves for fluorobenzene; chlorobenzene; bromobenzene; di-, tri-, and hexachlorobenzene isomers; 2-chlorofuran; 2-chlorothiophene; benzonitrile; phenol; dihydroxybenzene isomers; 1,4-benzoquinone; naphthalene; naphthalene-2-carbonitrile; naphthalen-2-ol; quinoline; benzo[b]thiophene; benzo[c]thiophene; benzoxazole; benzisoxazole; benzimidazole; benzothiazole; indole; isoindole; indazole; purine; anthracene; and phenanthrene. The agreement with the limited experimental data is very satisfactory, with saturated liquid densities and vapor pressures reproduced to within 1.5% and 15%, respectively. The mean unsigned percentage errors in the normal boiling points, critical temperatures, and critical densities are 0.9%, 1.2%, and 1.4%, respectively. Additional simulations were carried out for binary systems of benzene/benzonitrile, benzene/phenol, and naphthalene/methanol to illustrate the transferability of the developed potentials to binary systems containing compounds of different polarity and hydrogen-bonding ability. A detailed analysis of the liquid-phase structures is provided for selected neat systems and binary mixtures.

  19. Conformational Dynamics and Binding Free Energies of Inhibitors of BACE-1: From the Perspective of Protonation Equilibria.

    Directory of Open Access Journals (Sweden)

    M Olivia Kim

    2015-10-01

    Full Text Available BACE-1 is the β-secretase responsible for the initial amyloidogenesis in Alzheimer's disease, catalyzing hydrolytic cleavage of substrate in a pH-sensitive manner. The catalytic mechanism of BACE-1 requires water-mediated proton transfer from aspartyl dyad to the substrate, as well as structural flexibility in the flap region. Thus, the coupling of protonation and conformational equilibria is essential to a full in silico characterization of BACE-1. In this work, we perform constant pH replica exchange molecular dynamics simulations on both apo BACE-1 and five BACE-1-inhibitor complexes to examine the effect of pH on dynamics and inhibitor binding properties of BACE-1. In our simulations, we find that solution pH controls the conformational flexibility of apo BACE-1, whereas bound inhibitors largely limit the motions of the holo enzyme at all levels of pH. The microscopic pKa values of titratable residues in BACE-1 including its aspartyl dyad are computed and compared between apo and inhibitor-bound states. Changes in protonation between the apo and holo forms suggest a thermodynamic linkage between binding of inhibitors and protons localized at the dyad. Utilizing our recently developed computational protocol applying the binding polynomial formalism to the constant pH molecular dynamics (CpHMD framework, we are able to obtain the pH-dependent binding free energy profiles for various BACE-1-inhibitor complexes. Our results highlight the importance of correctly addressing the binding-induced protonation changes in protein-ligand systems where binding accompanies a net proton transfer. This work comprises the first application of our CpHMD-based free energy computational method to protein-ligand complexes and illustrates the value of CpHMD as an all-purpose tool for obtaining pH-dependent dynamics and binding free energies of biological systems.

  20. Re-investigation of phase equilibria in the system Al-Cu and structural analysis of the high-temperature phase η1-Al1-δCu.

    Science.gov (United States)

    Ponweiser, Norbert; Lengauer, Christian L; Richter, Klaus W

    2011-11-01

    The phase equilibria and reaction temperatures in the system Al-Cu were re-investigated by a combination of optical microscopy, powder X-ray diffraction (XRD) at ambient and elevated temperature, differential thermal analysis (DTA) and scanning electron microscopy (SEM). A full description of the phase diagram is given. The phase equilibria and invariant reactions in the Cu-poor part of the phase diagram could be confirmed. The Cu-rich part shows some differences in phase equilibria and invariant reactions compared to the known phase diagram. A two phase field was found between the high temperature phase η1 and the low temperature phase η2 thus indicating a first order transition. In the ζ1/ζ2 region of the phase diagram recent findings on the thermal stability could be widely confirmed. Contrary to previous results, the two phase field between δ and γ1 is very narrow. The results of the current work indicate the absence of the high temperature β0 phase as well as the absence of a two phase field between γ1 and γ0 suggesting a higher order transition between γ1 and γ0. The structure of γ0 (I-43m, Cu5Zn8-type) was confirmed by means of high-temperature XRD. Powder XRD was also used to determine the structure of the high temperature phase η1-Al1-δCu. The phase is orthorhombic (space group Cmmm) and the lattice parameters are a = 4.1450(1) Å, b = 12.3004(4) Å and c = 8.720(1) Å; atomic coordinates are given.